KR20180070142A - Thermosetting resin composition for improving self-extinguishing performance for battery module for battery pack of electric vehicle - Google Patents
Thermosetting resin composition for improving self-extinguishing performance for battery module for battery pack of electric vehicle Download PDFInfo
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- H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
- H01M50/258—Modular batteries; Casings provided with means for assembling
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Abstract
Description
본 발명은 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물에 관한 것으로, 보다 상세하게는 중국 인증규격인 GBT31467.3의 요구성능중 하나인 파이어 버닝(Fire Burning) 시험시 배터리 폭발이 없고 2분내 자기소화 성능을 만족할 수 있도록 개발된 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물에 관한 것이다.The present invention relates to a thermosetting resin composition for improving the self-extinguishing performance of a battery module for an electric vehicle, and more particularly, to a fire-burning test The present invention relates to a thermosetting resin composition for improving self-extinguishing performance for manufacturing a battery module for a battery pack of an electric vehicle, which is developed to satisfy self-extinguishing performance within two minutes without battery explosion.
전세계적으로 전기자동차의 수요가 증가하고 있고, 특히 중국은 국가적인 차원의 전폭적 지원에 힘입어 비약적으로 성장하고 있으며, 가장 큰 시장이다.Demand for electric vehicles is increasing worldwide, and China is growing rapidly, supported by full support from the national level, and is the largest market.
이러한 전기자동차 시장의 성장에 따라 소비자의 요구사항도 함께 증대하여 각국의 완성차 업체에서도 이와 같은 소비자의 요구사항을 반영하기 위해 노력하고 있는데 주된 요구사항중 하나로 연비 개선을 들 수 있다.As the electric vehicle market grows, the demands of consumers increase as well, and the automakers in each country are striving to reflect these consumer requirements. One of the main requirements is fuel efficiency improvement.
특히, 전기자동차(HEV, PHEV, EV, 수소연료전지차 등)의 경우 1회 충전으로 주행가능한 거리를 높이기 위해 차량의 중량절감, 배터리 용량증대 등 많은 부분에 있어 연구 및 투자를 집중하고 있다.In particular, in the case of electric vehicles (HEV, PHEV, EV, hydrogen fuel cell vehicle, etc.), research and investment are concentrated on many aspects such as weight saving of the vehicle and increase of the battery capacity.
이와 같이 전기자동차의 중량 절감을 위해 부품단위별로도 경량화소재를 적용하려는 시도가 활발하게 이루어지고 있다.In order to reduce the weight of electric vehicles, attempts have been actively made to apply lightweight materials to individual parts.
그럼에도 불구하고, 중국시장에서는 그 외 중요한 조건중 하나라 제품의 연소시험, 특히 자기소화 성능 시험을 만족해야만 차량 판매가 가능하다.Nonetheless, it is one of the other important conditions in the Chinese market. It is possible to sell a vehicle only if the product satisfies the combustion test, especially the self-extinguishing performance test.
이러한 연소시험 관련한 중국 인증규격은 GBT31467.3(Lithium-ion Traction Battery Pack and System for electric vehicles Safety Requirements and test methods)로서, 이는 도 1의 예시와 같이 800-900℃의 열원에 테스트 대상품을 투입하되 60초 동안 간접가열한 후 70초 동안 직접가열하는 형태로 약 130초 동안 직간접 가열한 상태에서 취출했을 때 배터리셀들이 폭발하지 않아야 하고, 또한 2분내 자소성(자기소화성)이 있어야 할 것을 규정한 규격이다.The Chinese certification standard related to this combustion test is GBT31467.3 (Lithium-ion Traction Battery Pack and System for electric vehicles safety requirements and test methods) It is stipulated that the battery cells should not explode when they are directly or indirectly heated for about 130 seconds in the form of direct heating for 60 seconds after indirect heating for 60 seconds and self-extinguishing (self-extinguishing) within 2 minutes It is one standard.
또한, 유사한 인증규격으로 유럽의 경우에는 ECE R-100을 규정하고 있다.In addition, ECE R-100 is defined for similar certification standards in Europe.
이와 관련하여 스틸이나 알루미늄은 융점이 매우 높기 때문에 상기 인증규격에서 문제가 되지 않지만 중량 및 원가 측면에서 합성수지(플라스틱) 보다 상대적으로 현저히 높아 경쟁력에서 밀리므로 결국 합성수지를 통한 고강도, 경량화가 이루어지고 있어 상기 인증규격 만족과 관련하여 문제가 발생한다.Steel or aluminum has a very high melting point, so it is not a problem in the above certification standards, but it is relatively higher than synthetic resin (plastic) in terms of weight and cost, There is a problem with the satisfaction of the certification standard.
이때, 합성수지로는 열가소성수지와 열경화성수지 모두 사용될 수 있지만, 열가소성수지는 약 700℃ 정도의 화염에서 용융되어 버리기 때문에 자기소화성이 없어 요구성능을 만족시킬 수 없을 뿐만 아니라 배터리팩의 내부 수밀성을 만족시킬 수 없고, 열경화성수지 그 중에서도 특히 SMC(유리섬유가 함유된 불포화폴리에스테르)는 치수안정성도 우수하고 비중이 스틸 대비 낮기 때문에 배터리팩 내부 보호를 위한 커버 소재로 각광 받고 있지만 중국 인증규격 및 유럽 인증규격인 2분내 자기소화성을 갖추기 위해서는 다량의 난연제 함유가 필요하기 때문에 가격이 상승하는 요인이 되어 경쟁력을 떨어뜨리는 한계에 봉착해 있는 상태이다.At this time, both the thermoplastic resin and the thermosetting resin can be used as the synthetic resin, but since the thermoplastic resin is melted in the flame of about 700 ° C, the self-extinguishing property is not available and the required performance can not be satisfied. In particular, SMC (unsaturated polyester containing glass fiber) has excellent dimensional stability and low specific gravity compared with steel, so it is widely regarded as a cover material for protecting the inside of battery pack. However, In order to have self-extinguishing ability within 2 minutes, it is necessary to contain a large amount of flame retardant, which causes a rise in the price, and thus it is in a state of limiting the competitiveness.
본 발명은 상술한 바와 같은 종래 기술상의 제반 문제점들을 감안하여 이를 해결하고자 창출된 것으로, 전기자동차용 배터리팩을 구성하는 패터리모듈 제조시 최소한의 난연제를 사용하면서도 중국 인증규격인 GBT31467.3의 요구성능중 하나인 파이어 버닝(Fire Burning) 시험시 배터리 폭발이 없고 2분내 자기소화 성능을 만족할 수 있도록 하여 제조비용 절감에 기여하여 가격경쟁력을 증대시킨 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물을 제공함에 그 주된 목적이 있다.The present invention has been made in view of the above-mentioned problems in the prior art, and it is an object of the present invention to provide a battery module for an electric vehicle, which uses a minimum amount of flame retardant in manufacturing a battery module, The self-extinguishing performance for the battery module for the battery pack of an electric vehicle which contributes to the reduction of the manufacturing cost and the price competitiveness by allowing the battery explosion to be satisfied in the fire burning test which is one of the performance, There is a main purpose of providing a thermosetting resin composition for improvement.
본 발명은 상기한 목적을 달성하기 위한 수단으로, 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물로서, 상기 열경화성수지 조성물은 열경화성수지 17-20중량%, 저수축제 13-15중량%, 충진제 15-20중량%, 증점제 1-3중량%, 난연제 4-25중량%, 기타 이형제 및 경화제 각각 0.5-1중량% 및 나머지 화이버(Fiber)로 이루어진 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물을 제공한다.A thermosetting resin composition for improving self-extinguishing performance for manufacturing a battery module for a battery pack of an electric vehicle, the thermosetting resin composition comprising 17 to 20% by weight of a thermosetting resin, 13 to 20% by weight of a water- 15 to 20 weight% of a filler, 1 to 3 weight% of a thickener, 4 to 25 weight% of a flame retardant, 0.5 to 1 weight% of each of a releasing agent and a curing agent, and the remaining fibers. A thermosetting resin composition for improving self-extinguishing performance for manufacturing a battery module for a battery pack is provided.
이때, 상기 열경화성수지는 불포화폴리에스테르 수지 또는 비닐에스터 수지 또는 에폭시 수지인 것에도 그 특징이 있다.At this time, the thermosetting resin is also characterized by being an unsaturated polyester resin, a vinyl ester resin or an epoxy resin.
또한, 상기 저수축제는 BS(styrene-butadiene-styrene), PS(Polystyrene), PVAc(Polyvinyl Acetate), PMMA(Polymethylmethacrylate), PE(polyethylene), PS/PVAc 코폴리머 중에서 선택된 어느 하나인 것에도 그 특징이 있다.The water-reducing agent may be any one selected from among styrene-butadiene-styrene (BS), polystyrene (PS), polyvinyl acetate (PVAc), polymethylmethacrylate (PMMA), polyethylene (PE) .
또한, 상기 충진제는 탄산칼슘을 사용하고, 상기 증점제는 산화마그네슘인 것에도 그 특징이 있다.Also, calcium carbonate is used as the filler, and magnesium oxide is used as the thickener.
또한, 상기 이형제는 스테아린산아연이고, 상기 경화제는 TBPB(T-Butyl-peroxy Benzoate) 또는 TBIC(TriButyl Isopropyl mono peroxy Carbonate)인 것에도 그 특징이 있다.Also, the release agent is zinc stearate, and the curing agent is TBPB (T-Butyl-peroxy Benzoate) or TBIC (TriButyl Isopropyl Mono Peroxy Carbonate).
또한, 상기 화이버(Fiber)는 유리섬유, 카본섬유, 아라미드 섬유 중 어느 하나인 것에도 그 특징이 있다.The fiber is also characterized by being any one of glass fiber, carbon fiber and aramid fiber.
또한, 상기 난연제는 수산화알루미늄(ATH), 인/질소 복합화합물, DBDPE(DecaBromodiphenyl Ethane), 삼산화안티몬 중에서 선택된 어느 하나 또는 둘 이상 혼합사용하는 것에도 그 특징이 있다.Further, the flame retardant is also characterized by using one or more selected from among aluminum hydroxide (ATH), phosphorus / nitrogen compound, DBDPE (deca bromodiphenyl ethane) and antimony trioxide.
또한, 상기 난연제는 수산화알루미늄:인/질소 복합화합물이 1:2의 중량비로 혼합된 것을 사용하는 것에도 그 특징이 있다.Further, the flame retardant is also characterized in that aluminum hydroxide: phosphorus / nitrogen complex compound is mixed at a weight ratio of 1: 2.
상기 난연제는 인/질소 복합화합물:DBDPE(DecaBromodiphenyl Ethane),:삼산화안티몬이 1:3:1의 중량비로 혼합된 것을 사용하는 것에도 그 특징이 있다.The flame retardant is also characterized in that a mixture of phosphorus / nitrogen compound: DBDPE (deca bromodiphenyl ethane), antimony trioxide in a weight ratio of 1: 3: 1 is used.
또한, 상기 난연제는 DBDPE(DecaBromodiphenyl Ethane),:삼산화안티몬이 3:1 또는 4:1의 중량비로 혼합된 것을 사용하는 것에도 그 특징이 있다.Further, the flame retardant is also characterized by using DBPE (deca bromodiphenyl ethane): antimony trioxide in a weight ratio of 3: 1 or 4: 1.
또한, 상기 난연제는 산화알루미늄:DBDPE(DecaBromodiphenyl Ethane),:삼산화알루미늄이 17:4:1의 중량비로 혼합된 것을 사용하는 것에도 그 특징이 있다.Further, the flame retardant is also characterized by using a mixture of aluminum oxide: DBDPE (deca bromodiphenyl ethane): aluminum trioxide in a weight ratio of 17: 4: 1.
또한, 상기 난연제는 수산화알루미늄:DBDPE(DecaBromodiphenyl Ethane),:삼산화알루미늄이 30:3:1의 중량비로 혼합된 것을 사용하는 것에도 그 특징이 있다.Further, the flame retardant is also characterized by using aluminum hydroxide: DBDPE (deca bromodiphenyl ethane): aluminum trioxide in a weight ratio of 30: 3: 1.
본 발명에 따르면, 전기자동차용 배터리팩을 구성하는 배터리모듈 제조시 최소한의 난연제를 사용하면서도 중국 인증규격인 GBT31467.3의 요구성능중 하나인 파이어 버닝(Fire Burning) 시험시 배터리 폭발이 없고 2분내 자기소화 성능을 만족할 수 있도록 하여 제조비용 절감에 기여하는 효과를 얻을 수 있다.According to the present invention, there is no explosion of the battery during the fire burning test, which is one of the requirements of GBT31467.3, which is a Chinese certification standard, while using a minimum amount of flame retardant in manufacturing a battery module constituting a battery pack for an electric vehicle, The self-extinguishing performance can be satisfied and the effect of contributing to the reduction of the manufacturing cost can be obtained.
도 1은 전기자동차용 배터리모듈과 관련된 중국 인증규격인 GBT31467.3의 시험예를 보인 예시도이다.
도 2는 본 발명에 따른 열경화성수지 조성물로 제조된 배터리셀 커버의 실험 전후 상태를 보인 실제 사진이다.
도 3은 본 발명에 따른 열경화성수지 조성물에 포함되는 난연제의 함량에 따른 자기소화 실험예를 보인 예시도이다.FIG. 1 is an exemplary view showing a test example of a Chinese certification standard GBT31467.3 related to a battery module for an electric vehicle.
FIG. 2 is a photograph showing the state before and after the experiment of the battery cell cover made of the thermosetting resin composition according to the present invention. FIG.
FIG. 3 is a view showing an example of a self-extinguishing experiment according to the content of the flame retardant contained in the thermosetting resin composition according to the present invention.
이하에서는, 첨부도면을 참고하여 본 발명에 따른 바람직한 실시예를 보다 상세하게 설명하기로 한다.Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명 설명에 앞서, 이하의 특정한 구조 내지 기능적 설명들은 단지 본 발명의 개념에 따른 실시예를 설명하기 위한 목적으로 예시된 것으로, 본 발명의 개념에 따른 실시예들은 다양한 형태로 실시될 수 있으며, 본 명세서에 설명된 실시예들에 한정되는 것으로 해석되어서는 아니된다.Before describing the present invention, the following specific structural or functional descriptions are merely illustrative for the purpose of describing an embodiment according to the concept of the present invention, and embodiments according to the concept of the present invention may be embodied in various forms, And should not be construed as limited to the embodiments described herein.
또한, 본 발명의 개념에 따른 실시예는 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있으므로, 특정 실시예들은 도면에 예시하고 본 명세서에 상세하게 설명하고자 한다. 그러나, 이는 본 발명의 개념에 따른 실시예들을 특정한 개시 형태에 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경물, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.In addition, since the embodiments according to the concept of the present invention can make various changes and have various forms, specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the embodiments according to the concept of the present invention are not intended to limit the present invention to specific modes of operation, but include all modifications, equivalents and alternatives falling within the spirit and scope of the present invention.
본 발명에 따른 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물은 열경화성수지 17-20중량%, 저수축제 13-15중량%, 충진제 15-20중량%, 증점제 1-3중량%, 난연제 4-25중량%, 기타 이형제 및 경화제 각각 0.5-1중량% 및 나머지 화이버(Fiber)로 이루어진다.The thermosetting resin composition for improving the self-extinguishing performance for the battery module for the battery pack of an electric vehicle according to the present invention comprises 17 to 20% by weight of a thermosetting resin, 13 to 15% by weight of a water-reducing agent, 15 to 20% by weight of a filler, 4 to 25% by weight of a flame retardant, 0.5 to 1% by weight of each of a releasing agent and a curing agent, and the remaining fiber.
이때, 상기 열경화성수지는 여러 종류 중에서도 내열성을 강화시킬 수 있는 불포화폴리에스테르 수지, 비닐에스터 수지, 에폭시 수지 중에서 선택된 어느 하나를 사용한다.At this time, any one selected from among unsaturated polyester resins, vinyl ester resins and epoxy resins which can enhance heat resistance among various kinds of thermosetting resins is used.
이 중에서 불포화폴리에스테르 수지는 액상수지에 촉매, 촉진제만 가해도 용도에 따라 상온 성형이 가능할 정도로 성형성이 우수하고 무엇보다도 비중이 작아 경량화가 가능한 장점이 있으며 특히, 인장강도, 충격강도가 동일 중량 대비 금속재료에 버금갈 정도로 우수한 장점이 있고, 나아가 내열성이 우수하다.Among them, the unsaturated polyester resin is advantageous in that it can be molded at room temperature depending on the application even if only a catalyst and a promoter are added to the liquid resin. In addition, the unsaturated polyester resin is advantageous in that the specific gravity is small, It is advantageous in that it is comparable to the contrast metal material, and furthermore, the heat resistance is excellent.
또한, 비닐에스터(=비닐에스테르) 수지는 에폭시 수지에 아크릴 산류를 반응시켜 스티렌에 용해한 수지로서 기계적 강도와 내식성이 매우 뛰어나고 연신율도 우수하며, 특히 내열성이 우수한 장점이 있다.The vinyl ester (= vinyl ester) resin is a resin which is obtained by reacting an epoxy resin with acrylic acid to dissolve in styrene, and has excellent mechanical strength and corrosion resistance, excellent elongation, and excellent heat resistance.
뿐만 아니라, 에폭시 수지는 에폭시기를 2개 이상 갖고 있는 것을 경화시킨 것으로, 기계적 성질과 내열성이 매우 우수한 장점이 있다.In addition, an epoxy resin has two or more epoxy groups cured and has excellent mechanical properties and heat resistance.
그리고, 상기 저수축제는 성형시 수치를 안정화시키기 위한 것으로서, SBS(styrene-butadiene-styrene), PS(Polystyrene), PVAc(Polyvinyl Acetate), PMMA(Polymethylmethacrylate), PE(polyethylene), PS/PVAc 코폴리머 중에서 선택된 어느 하나를 사용할 수 있다.In addition, the above-mentioned water-saving fusing agent is used for stabilizing the numerical value at the time of molding, and it is preferable to use styrene-butadiene-styrene (SBS), polystyrene (PS), polyvinyl acetate (PVAc), polymethylmethacrylate (PMMA) May be used.
또한, 상기 충진제는 일종의 무기필러로서, 기계적 강도를 보강하고, 내열성을 강화시키기 위해 첨가되며, 탄산칼슘을 사용한다.In addition, the filler is an inorganic filler, which is added to reinforce the mechanical strength and enhance the heat resistance, and calcium carbonate is used.
아울러, 상기 증점제는 점탄성 조정제, 즉 점도를 조절하기 위해 첨가되는 것으로, 성형성을 좋게 하기 위한 것이다. 본 발명에서는 KYOWMAG(Magnesium Oxide)를 사용한다.In addition, the thickening agent is added to adjust the viscoelasticity adjusting agent, i.e., the viscosity, so as to improve the moldability. In the present invention, KYOWMAG (Magnesium Oxide) is used.
나아가, 상기 난연제는 본 발명에서 가장 중요한 성분이며, 기존과 달리 소량 사용하면서도 자기소화 능력을 높일 수 있는 성분들로 구성된다.Further, the flame retardant is the most important component in the present invention, and it consists of components that can be used in small amounts but increase the self-extinguishing ability.
이러한 난연제로는 수산화알루미늄(ATH), 인/질소 복합화합물, DBDPE(DecaBromodiphenyl Ethane), 삼산화안티몬 중에서 선택된 어느 하나를 사용함이 바람직하나, 이들을 일정비율로 혼합사용하는 것이 가장 효과적이다.As such a flame retardant, it is preferable to use any one selected from among aluminum hydroxide (ATH), phosphorus / nitrogen compound, DBDPE (deca bromodiphenyl ethane) and antimony trioxide, and it is most effective to mix them at a certain ratio.
이때, 난연제의 혼합예는 수산화알루미늄:인/질소 복합화합물이 1:2의 중량비로 혼합된 것, 혹은 인/질소 복합화합물:DBDPE:삼산화안티몬이 1:3:1의 중량비로 혼합된 것, DBDPE:삼산화안티몬이 3:1 또는 4:1의 중량비로 혼합된 것, 수산화알루미늄:DBDPE:삼산화알루미늄이 17:4:1의 중량비로 혼합된 것, 수산화알루미늄:DBDPE:삼산화알루미늄이 30:3:1의 중량비로 혼합된 것 중 어느 하나를 사용하는 것이 가장 큰 자기소화 효과를 얻을 수 있다.In this case, examples of mixing the flame retardant include a mixture of aluminum hydroxide: phosphorus / nitrogen composite compound in a weight ratio of 1: 2, or a phosphorus / nitrogen composite compound: DBDPE: antimony trioxide in a weight ratio of 1: 3: DBDPE: a mixture of antimony trioxide in a weight ratio of 3: 1 or 4: 1, aluminum hydroxide: DBDPE: aluminum trioxide in a weight ratio of 17: 4: 1, aluminum hydroxide: DBDPE: : 1, it is possible to obtain the greatest self-extinguishing effect.
여기에서, 수산화알루미늄은 알루미늄의 수산화물로 양쪽성 수산화물이며, 섬유(Fiber) 속에 채우면 방수성이 커지고 저발연성을 갖기 때문에 본 발명에서는 필수적으로 화이버(Fiber)를 주요 조성중 하나로 포함해야 하며, 가공기계의 부식성이 작고 전기절연성이 우수하여 대표적인 난연제로 활용되고 있다.Here, aluminum hydroxide is a hydroxide of aluminum and is an amphoteric hydroxide. When it is filled in a fiber, it is waterproof and has low ductility. Therefore, in the present invention, it is essential to include fiber as one of main constituents, Is small and has excellent electrical insulation, and is used as a typical flame retardant.
그리고, 인/질소 복합화합물은 연소시 열분해되어 H3PO4를 생성하여 탈수탄화 작용에 의해 고체 숯을 생성하고, 이 숯이 산소와 열의 확산을 차단하며, 화염전단으로부터 또는 화염전단에 연소성 분해생성물의 확산을 차단하게 된다. 이때 생긴 H3PO4는 다시 열분해되어 PO라디칼을 생성하며 연소중 연쇄반응을 일으키는 H라디칼 또는 OH라디칼을 안정화시키게 된다. 따라서, 이 복합화합물은 저유해성, 저발열성, 저부식성, 내열성 측면에서 모두를 만족시키는 효과적인 자기소화성을 갖추고 있다고 봐야 한다.The phosphorus / nitrogen composite compound is pyrolyzed at the time of combustion to generate H 3 PO 4 to generate solid char by dehydration carbonization, and this charcoal blocks the diffusion of oxygen and heat, and the combustion decomposition is carried out from the flame front or flame front Thereby preventing diffusion of the product. The resulting H 3 PO 4 is again pyrolyzed to form PO radicals and stabilize H radicals or OH radicals that cause chain reactions during combustion. Therefore, this compound should be considered to have an effective self-extinguishing property which satisfies both low toxicity, low pyrogenicity, low corrosion resistance and heat resistance.
또한, DBDPE는 대표적인 브롬계 난연제로서 열경화성수지 및 섬유(Fiber)와의 결합을 통한 내열성, 저발열성을 강화시켜 자기 소화기능을 현저히 향상시키는 특성이 있다.In addition, DBDPE is a representative brominated flame retardant, which has the property of significantly enhancing the self-extinguishing function by strengthening heat resistance and low exothermicity through bonding with thermosetting resin and fiber.
뿐만 아니라, 삼산화안티몬은 저독성이면서 특히 열경화성수지와 결합에 의한 난연 상승효과가 매우 큰 것으로 알려져 있다. 다만, 단독 사용보다는 다른 난연제들과 일정비율로 복합사용할 때 그 효과가 매우 큰 것으로 실험상 확인되었기에 본 발명에서는 기존의 단독사용과 달리 다른 난연제들과 일정비율로 혼합사용하도록 구성된다.In addition, it is known that antimony trioxide has a low toxicity and a very high synergistic effect of flame retardancy due to bonding with a thermosetting resin. However, since it has been experimentally confirmed that the effect is very large when the flame retardant is used in combination with other flame retardants at a certain ratio, the present invention is configured to mix the flame retardants at a certain ratio with the other flame retardants.
특히, 각 난연재들이 상술한 중량비율 범위로 조합될 때 상보기능에 의해 열경화성수지 및 섬유와의 결합성이 증대되면서 자기소화 기능을 극대화시키게 된다.In particular, when the respective flame retardants are combined in the weight ratio range described above, the complementary function increases the bonding property between the thermosetting resin and the fiber, thereby maximizing the self-extinguishing function.
그리고, 이형제는 성형 후 이형성을 좋게 하기 위한 것으로 스테아린산아연이 바람직하며, 경화제는 경화를 촉진하기 위한 것으로 TBPB(T-Butyl-peroxy Benzoate)와 같은 일반경화제는 물론 TBIC(TriButyl Isopropyl mono peroxy Carbonate)와 같은 속경화제도 사용할 수 있다.The release agent is preferably zinc stearate in order to improve the releasing property after molding. The curing agent is used for accelerating the curing. It is not only a general curing agent such as TBPB (T-Butyl-peroxy Benzoate) but also TBIC (TriButyl Isopropyl Mono Peroxy Carbonate) The same fast curing agent can be used.
또한, 화이버(Fiber)는 난연재들의 침투 결합을 통해 자기소화성을 강화시키기 위해 첨가되는 것으로, 유리섬유, 카본섬유, 아라미드 섬유 중 어느 하나를 사용할 수 있다.Fiber is added to reinforce self-extinguishing property through penetration bonding of flame retardants, and any one of glass fiber, carbon fiber and aramid fiber can be used.
이러한 조성으로 이루어진 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물을 성형하여 도 2의 (a)와 같은 전기자동차용 배터리셀 커버(100)를 만들었으며, 이를 투입가이드(200) 상에 올려 놓고 화염쪽으로 이동시켜 중국 인증규격에서 요구하는 파이어 버닝(Fire Burning) 시험을 실시한 결과, 도 2의 (b)와 같이 2분내 자기소화 성능을 나타냄을 확인할 수 있었다.A
이것은 종래 열가소성수지가 난연제를 포함하더라도 중국 인증시험인 GBT규격을 만족할 수 없었던 이유로 130초간 직/간접으로 70-800℃의 열원에서 열가소성 수지는 용융되어 버리기 때문에 용융되는 순간부터 열원이 배터리팩에 직접적으로 영향을 주게 되지만, 본 발명의 경우는 열경화성, 특히 SMC 소재는 용융되는 것이 아니라 타기만 할 뿐 형체는 그대로 유지하기 때문에 배터리팩에 열원이 직접적으로 영향을 주지 못하도록 막아 주는 특징을 갖게 된다.This is because the thermoplastic resin is melted in a heat source of 70-800 ° C directly or indirectly for 130 seconds because the conventional thermoplastic resin contains a flame retardant but can not satisfy the GBT standard of Chinese certification test. Therefore, In the case of the present invention, however, the thermosetting material, especially the SMC material, is not melted but retains the shape only by burning, thereby preventing the heat source from directly affecting the battery pack.
좀 더 구체적으로, 본 발명에 따른 난연제의 기능이 충분히 발휘되었는지를 확인하기 위해 난연제를 4중량%, 10중량%, 25중량%로 변화시켜 가면서 2분내 자기소화성이 나타나는지 확인하였으며, 이를 도 3에 나타내었다.More specifically, in order to confirm whether or not the function of the flame retardant according to the present invention was sufficiently exhibited, it was confirmed that the self-extinguishing property appeared within 2 minutes while changing the flame retardant to 4 wt%, 10 wt%, and 25 wt% Respectively.
참고로, 난연제 3% 첨가시에는 자기 소화에 걸리는 시간이 4분을 넘겼기 때문에 본 발명에서는 자료로 포함시키기 않았다.For reference, the addition of 3% of the flame retardant agent did not include the data in the present invention because the time required for self-extinguishing exceeded 4 minutes.
뿐만 아니라, 난연제를 25중량% 초과하여 첨가하면 난연성을 더 증대되겠지만, 그 만큼 비용이 증가함은 물론 그외에 제품 성형성, 유동성, 가공성 등의 측면을 저해하므로 가장 최적의 범위로 한정함이 바람직하다.In addition, if the flame retardant is added in an amount exceeding 25% by weight, the flame retardancy will be further increased. However, the cost is increased, and furthermore, the moldability, fluidity and workability are deteriorated. Do.
이때, 열경화성수지 조성물은 불포화폴리에스테르 수지 20중량%, PMMA 13중량%, 탄산칼슘 15중량%, MgO 3중량%, 스테아린산아연 및 TBPB 각각 1중량% 및 나머지 유리섬유로 조성하였고, 난연제는 4중량%, 10중량%, 25중량%가 각각 함유된 것을 제조하여 시료를 3개씩 2세트 준비하여 각 시료에 대해 2번씩 테스트하였으며, 특히 난연제는 수산화알루미늄:인/질소 복합화합물이 1:2의 중량비로 혼합된 것을 사용하였고.At this time, the thermosetting resin composition was composed of 20 wt% of unsaturated polyester resin, 13 wt% of PMMA, 15 wt% of calcium carbonate, 3 wt% of MgO, 1 wt% of zinc stearate and TBPB, %, 10 wt.% And 25 wt.%, Respectively, and two sets of three samples were prepared and tested twice for each sample. In particular, the flame retardant was prepared by mixing aluminum hydroxide: phosphorus / Were used.
중국 인증규격에 따른 시험결과, 도 3에서와 같이, 난연제가 4중량% 함유된 경우에는 테스트 1에서는 1분 40초만에 자소(자기소화)되었고 테스트 2에서는 1분 38초만에 자소되었다.As shown in FIG. 3, when the flame retardant was contained at 4% by weight in the test according to the Chinese certification standard, the flame was self-extinguished only at 1 minute and 40 seconds in Test 1 and at 1 minute and 38 seconds in Test 2.
자소 시간이 걸리기는 했지만, 모두 2분 이내에 자소되었기 때문에 인증규격은 만족시켰다.Though it took time, it was all within 2 minutes, so the certification standard was satisfied.
또한, 난연제가 10중량% 및 25중량% 함유된 경우에는 양자 모두 2번의 테스트시 취출과 동시에 즉시 소화되었다.Further, when the flame retardant was contained at 10% by weight and 25% by weight, both of them were immediately extinguished at the time of two tests and immediately digested.
이로써, 본 발명에 따른 열경화성수지 조성물을 통해 자기소화 특성을 확보할 수 있음을 확인하였다.Thus, it was confirmed that the self-extinguishing property can be secured through the thermosetting resin composition according to the present invention.
100: 배터리셀 커버 200: 투입가이드100: Battery cell cover 200: Inlet guide
Claims (12)
상기 열경화성수지 조성물은 열경화성수지 17-20중량%, 저수축제 13-15중량%, 충진제 15-20중량%, 증점제 1-3중량%, 난연제 4-25중량%, 기타 이형제 및 경화제 각각 0.5-1중량% 및 나머지 화이버(Fiber)로 이루어진 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
A thermosetting resin composition for improving self-extinguishing performance for manufacturing a battery module for a battery pack of an electric vehicle,
Wherein the thermosetting resin composition comprises 17 to 20% by weight of a thermosetting resin, 13 to 15% by weight of a water reducing agent, 15 to 20% by weight of a filler, 1 to 3% by weight of a thickener, 4 to 25% by weight of a flame retardant, Wherein the thermoplastic resin composition is a thermosetting resin composition for improving the self extinguishing performance of a battery module for a battery pack of an electric vehicle.
상기 열경화성수지는 불포화폴리에스테르 수지 또는 비닐에스터 수지 또는 에폭시 수지인 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the thermosetting resin is an unsaturated polyester resin, a vinyl ester resin, or an epoxy resin. The thermosetting resin composition for improving the self-extinguishing performance of a battery module for a battery pack of an electric vehicle.
상기 저수축제는 BS(styrene-butadiene-styrene), PS(Polystyrene), PVAc(Polyvinyl Acetate), PMMA(Polymethylmethacrylate), PE(polyethylene), PS/PVAc 코폴리머 중에서 선택된 어느 하나인 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the water-reducing agent is any one selected from styrene-butadiene-styrene (BS), polystyrene (PS), polyvinyl acetate (PVAc), polymethylmethacrylate (PMMA), polyethylene (PE) A thermosetting resin composition for improving self extinguishing performance for manufacturing a battery module for a battery pack.
상기 충진제는 탄산칼슘을 사용하고, 상기 증점제는 산화마그네슘인 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the filler is calcium carbonate, and the thickener is magnesium oxide. The thermosetting resin composition for improving the self-extinguishing performance of a battery module for an electric vehicle battery pack.
상기 이형제는 스테아린산아연이고, 상기 경화제는 TBPB(T-Butyl-peroxy Benzoate) 또는 TBIC(TriButyl Isopropyl mono peroxy Carbonate)인 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the releasing agent is zinc stearate and the curing agent is TBPB or TBIC (tri-butyl isopropyl mono peroxy carbonate). The thermosetting resin for improving the self-extinguishing performance for the battery module for the battery pack of an electric vehicle Composition.
상기 화이버(Fiber)는 유리섬유, 카본섬유, 아라미드 섬유 중 어느 하나인 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the fiber is one of glass fiber, carbon fiber, and aramid fiber. The thermosetting resin composition for improving the self-extinguishing performance for manufacturing the battery module for a battery pack of an electric vehicle.
상기 난연제는 수산화알루미늄(ATH), 인/질소 복합화합물, DBDPE(DecaBromodiphenyl Ethane), 삼산화안티몬 중에서 선택된 어느 하나 또는 둘 이상 혼합사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the flame retardant is one or more selected from aluminum hydroxide (ATH), phosphorus / nitrogen compound, DBDPE (deca bromodiphenyl ethane) and antimony trioxide. (EN) A thermosetting resin composition for improvement.
상기 난연제는 수산화알루미늄:인/질소 복합화합물이 1:2의 중량비로 혼합된 것을 사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the flame retardant is a mixture of aluminum hydroxide: phosphorus / nitrogen composite compound at a weight ratio of 1: 2. The thermosetting resin composition for improving the fire extinguishing performance of a battery module for an electric vehicle.
상기 난연제는 인/질소 복합화합물:DBDPE(DecaBromodiphenyl Ethane),:삼산화안티몬이 1:3:1의 중량비로 혼합된 것을 사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the flame retardant is a mixture of phosphorus / nitrogen compound: DBDPE (deca bromodiphenyl ethane) and antimony trioxide in a weight ratio of 1: 3: 1. / RTI >
상기 난연제는 DBDPE(DecaBromodiphenyl Ethane),:삼산화안티몬이 3:1 또는 4:1의 중량비로 혼합된 것을 사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the flame retardant is a mixture of DBDPE (Deca Bromodiphenyl Ethane) and antimony trioxide in a weight ratio of 3: 1 or 4: 1, and a thermosetting resin composition for improving self-extinguishing performance for manufacturing a battery module for an electric vehicle .
상기 난연제는 산화알루미늄:DBDPE(DecaBromodiphenyl Ethane),:삼산화알루미늄이 17:4:1의 중량비로 혼합된 것을 사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.
The method according to claim 1,
Wherein the flame retardant is a mixture of aluminum oxide, DBDPE (Deca Bromodiphenyl Ethane), and aluminum trioxide in a weight ratio of 17: 4: 1, and the thermosetting resin for improving the self extinguishing performance Composition.
상기 난연제는 수산화알루미늄:DBDPE(DecaBromodiphenyl Ethane),:삼산화알루미늄이 30:3:1의 중량비로 혼합된 것을 사용하는 것을 특징으로 하는 전기자동차의 배터리팩용 배터리모듈 제조를 위한 자기소화 성능 개선용 열경화성수지 조성물.The method according to claim 1,
Wherein the flame retardant is a mixture of aluminum hydroxide, DBDPE (Deca Bromodiphenyl Ethane) and aluminum trioxide in a weight ratio of 30: 3: 1, and the thermosetting resin for improving the self extinguishing performance Composition.
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