KR101013827B1 - Heat-Expandable Flame-Retardant Polyolefin Resin Composition and Panel Using the Same - Google Patents

Heat-Expandable Flame-Retardant Polyolefin Resin Composition and Panel Using the Same Download PDF

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KR101013827B1
KR101013827B1 KR1020080117328A KR20080117328A KR101013827B1 KR 101013827 B1 KR101013827 B1 KR 101013827B1 KR 1020080117328 A KR1020080117328 A KR 1020080117328A KR 20080117328 A KR20080117328 A KR 20080117328A KR 101013827 B1 KR101013827 B1 KR 101013827B1
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polyolefin resin
flame retardant
weight
resin composition
thermally expandable
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KR20100058789A (en
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이순종
김기수
최원준
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주식회사 유니언스
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Priority to PCT/KR2009/006993 priority patent/WO2010062113A2/en
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Abstract

본 발명은 폴리올레핀수지 15 내지 40중량부, 무기 난연제 60 내지 80중량부 및 열팽창성 마이크로캡슐 0.2 내지 5중량부를 포함하는 열팽창성 난연 폴리올레핀 수지 조성물 및 이를 이용한 난연성 복합패널에 관한 것이다. The present invention relates to a heat-expandable flame retardant polyolefin resin composition comprising 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant, and 0.2 to 5 parts by weight of thermally expandable microcapsules, and a flame retardant composite panel using the same.

본 발명에 따른 조성물을 이용하여 제조된 난연성 복합패널은 요구되는 난연성이 유지되면서도 경량화되는 효과를 갖는다.The flame retardant composite panel manufactured using the composition according to the present invention has the effect of being lightweight while maintaining the required flame retardancy.

폴리올레핀수지, 난연성, 복합패널, 열팽창 마이크로 캡슐 Polyolefin resin, flame retardant, composite panel, thermal expansion microcapsules

Description

열팽창성 난연 폴리올레핀수지 조성물 및 이를 이용한 난연성 복합패널{Heat-Expandable Flame-Retardant Polyolefin Resin Composition and Panel Using the Same}Heat-expandable flame-retardant polyolefin resin composition and panel using the same

본 발명은 열팽창성 난연 폴리올레핀수지 조성물 및 이를 이용한 난연성 복합패널에 관한 것으로서, 더욱 상세하게는 폴리올레핀 수지, 무기 난연제 및 열팽창성 마이크로캡슐을 포함하는 열팽창성 난연 폴리올레핀수지 조성물과 이를 이용하여 제조된 복합패널에 관한 것이다. The present invention relates to a thermally expandable flame retardant polyolefin resin composition and a flame retardant composite panel using the same, and more particularly, to a thermally expandable flame retardant polyolefin resin composition comprising a polyolefin resin, an inorganic flame retardant, and a thermally expandable microcapsule, and a composite panel prepared using the same. It is about.

일반적으로 건축 내외장재로 사용되는 알루미늄복합패널은 알루미늄, 접착층, 심재(폴리에틸렌수지), 접착층 및 알루미늄이 순차적으로 형성된 다층 구조를 갖는다. 상기 다층구조는 고가인 알루미늄 원판의 사용을 줄이기 위해 얇은 알루미늄, 바람직하게는 0.5mm 이하의 두께를 갖는 알루미늄판을 구비한 후 심재로서 저렴한 플라스틱 소재를 알루미늄판에 접착시키도록 구성된다.In general, aluminum composite panels used as interior and exterior building materials have a multilayer structure in which aluminum, an adhesive layer, a core material (polyethylene resin), an adhesive layer, and aluminum are sequentially formed. The multi-layered structure is configured to have a thin aluminum plate, preferably 0.5 mm or less, in order to reduce the use of expensive aluminum discs, and then to adhere the inexpensive plastic material to the aluminum plate as a core material.

이러한 알루미늄복합패널의 일례로서, 일본특허공개 평2-63734호 및 일본특허공개 평2-63735호에는 심재인 폴리에틸렌수지의 연속 압출방식에 의한 알루미늄 복합패널의 제조방법이 개시되어 있다. 그러나 전술한 알루미늄복합패널의 제조방법은 접착층을 구성하는 접착성 수지와 심재인 폴리에틸렌수지를 공압출하는 방법으로 개량되었다. As an example of such an aluminum composite panel, Japanese Patent Laid-Open No. 2-63734 and Japanese Patent Laid-Open No. 2-63735 disclose a method for producing an aluminum composite panel by a continuous extrusion method of polyethylene resin, which is a core material. However, the manufacturing method of the above-described aluminum composite panel has been improved by the method of co-extrusion of the adhesive resin constituting the adhesive layer and polyethylene resin which is a core material.

여기서, 상기 공압출 방법은 심재로 사용되는 재료의 흐름성이 중요하며, 흐름성이 좋지 않을 경우 접착층과 흐름이 불균일하고, 압출 부하상승에 따른 연속적인 생산이 곤란하게 되며, 흐름성이 과다하게 좋을 경우 압출다이와 폴리싱롤 사이에 열 처짐 현상이 발생하여 폴리싱롤에서의 뱅크형성이 불균일해져 제품의 두께편차뿐만 아니라 접착층이 균일하게 도포되지 않는 문제점 등이 발생된다. Here, in the coextrusion method, the flowability of the material used as the core material is important, and if the flowability is not good, the adhesive layer and the flow are uneven, and continuous production is difficult due to the increase in the extrusion load, and the flowability is excessively increased. In this case, a heat deflection phenomenon may occur between the extrusion die and the polishing roll, resulting in uneven bank formation in the polishing roll, and a problem in that the adhesive layer is not uniformly applied as well as thickness deviation of the product.

이와 같은 방법으로 제조되는 종래의 알루미늄복합패널의 심재로 사용되는 폴리에틸렌수지는 가볍고 가격이 저렴할 뿐만 아니라, 물성이 우수하여 다양한 용도로 사용되고 있으나, 재료 자체가 가연성이 높아 그 사용범위가 제한적이었다. Polyethylene resin, which is used as a core material of the conventional aluminum composite panel manufactured by the above method, is not only light and inexpensive, but also has excellent physical properties and is used for various purposes, but the material itself is highly flammable and its use range is limited.

이러한 문제점을 극복하기 위하여 무기 난연제인 수산화마그네슘 및/또는 수산화알루미늄과 같은 무기 난연제를 수지조성물에 혼합시켜 상기 무기 난연제를 포함하는 수지조성물로 제조된 제품에 충분한 난연성을 부여하고 있다.In order to overcome this problem, inorganic flame retardants such as magnesium hydroxide and / or aluminum hydroxide, which are inorganic flame retardants, are mixed with a resin composition to impart sufficient flame retardancy to a product made of a resin composition including the inorganic flame retardant.

그 일례로서, 대한민국등록특허 10-0680822호에는 폴리올레핀수지 15 내지 35중량%, 무기 난연제 60 내지 80중량% 및 경량필러 0 내지 15중량%를 포함하는 비할로겐계 난연성 폴리올레핀 수지조성물이 개시되어 있다. As an example, Korean Patent No. 10-0680822 discloses a non-halogen flame retardant polyolefin resin composition including 15 to 35% by weight of a polyolefin resin, 60 to 80% by weight of an inorganic flame retardant, and 0 to 15% by weight of a light filler.

전술한 조성물은 압출가공성이 개선되긴 하였으나, 난연성 유지를 위한 무기 난연제의 함량이 높고, 경량필러를 사용하였음에도 불구하고 비중이 약 1.3 내지 1.7정도로서 폴리에틸렌수지에 비하여 비중이 높아 상기 조성물을 이용하여 제조된 난연성 알루미늄복합패널의 생산비가 증가되는 문제점이 있다. Although the above-mentioned composition has improved extrusion processability, although the content of the inorganic flame retardant for maintaining flame retardancy is high, and a light weight filler is used, the specific gravity is about 1.3 to 1.7, and the specific gravity is higher than that of the polyethylene resin prepared using the composition. There is a problem that the production cost of the flame retardant aluminum composite panel is increased.

이에, 본 발명자들은 전술한 문제점을 극복하기 위한 수지조성물과 알루미늄복합패널의 제조방법에 대하여 지속적으로 연구하던 중 종래의 난연 폴리올레핀수지 조성물에 열팽창 마이크로캡슐을 첨가함으로써 열에 의하여 팽창할 수 있는 난연 수지 조성물을 얻을 수 있다는 점과 이를 압출 시 적절하게 열팽창성 마이크로캡슐을 열팽창시켜 발포효과를 제공으로써 이를 심재로 사용하게 되면 저비중의 알루미늄복합패널을 제조할 수 있을 것이라는 점을 착안하여 한국산업규격인 KS F5660-1 에 따른 준불연 이상의 저 비중 복합패널을 완성하기에 이르렀다.Accordingly, the present inventors continue to study the resin composition and the method for manufacturing the aluminum composite panel to overcome the above problems, flame retardant resin composition that can be expanded by heat by adding thermal expansion microcapsules to the conventional flame retardant polyolefin resin composition KS, the Korean industrial standard, can be produced by considering that it can be obtained by using the core material as a core material by thermally expanding the thermally expandable microcapsules during extrusion and providing a foaming effect. The company has completed a low specific gravity composite panel in accordance with F5660-1.

본 발명은 전술한 문제점을 극복하기 위해 도출된 것으로서, 열팽창성 마이크로캡슐을 발포시켜 비중을 낮추고, 난연제의 사용량을 감소시켜 경량화 하면서도 요구되는 난연성을 유지하도록 하여 취급용이성 뿐만 아니라 비용을 절감할 수 있도록 하는 열팽창성 난연 폴리올레핀수지 조성물 및 이를 이용한 난연성 복합패널을 제공한다. The present invention has been derived to overcome the above-mentioned problems, foaming the thermally expandable microcapsules to lower the specific gravity, to reduce the amount of flame retardant used to maintain the required flame retardancy while reducing the ease of handling as well as cost It provides a thermally expandable flame retardant polyolefin resin composition and a flame retardant composite panel using the same.

본 발명은 상기 과제를 해결하기 위한 수단으로서, 폴리올레핀수지 15 내지 40중량부, 무기 난연제 60 내지 80중량부 및 열팽창성 마이크로캡슐 0.2 내지 5중량부를 포함하는 열팽창성 난연 폴리올레핀 수지 조성물을 제공한다. The present invention provides a thermally expandable flame retardant polyolefin resin composition comprising 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant, and 0.2 to 5 parts by weight of thermally expandable microcapsules as a means for solving the above problems.

본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, 열팽창성 난연 폴리올레핀수지 조성물이 포함된 난연성 복합패널을 제공한다. The present invention provides another flame-retardant composite panel containing a heat-expandable flame-retardant polyolefin resin composition as another means for solving the above problems.

본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, The present invention is another means for solving the above problems,

전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지, 60 내지 80중량부의 무기 난연제 및 0.2 내지 5중량부의 열팽창성 마이크로캡슐을 혼합 시켜 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계; 및 Preparing a thermally expandable flame retardant polyolefin resin composition by mixing 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant, and 0.2 to 5 parts by weight of thermally expandable microcapsules relative to the total resin composition; And

상기 열팽창성 난연 폴리올레핀 수지조성물을 발포한 뒤 금속판재와 접착시키는 단계를 포함하는 난연성 복합패널의 제조방법을 제공한다. It provides a method for producing a flame-retardant composite panel comprising the step of foaming the thermally expandable flame-retardant polyolefin resin composition and then bonding to a metal plate.

본 발명에 따르면, 열팽창성 마이크로캡슐을 발포시켜 비중을 낮추고, 부피당 난연 수지조성물의 사용량을 감소시켜 경량화 하면서도 요구되는 난연성을 유지하도록 하여 취급용이성 뿐만 아니라 비용을 절감할 수 있는 효과를 가진다. According to the present invention, it is possible to reduce the specific gravity by foaming the thermally expandable microcapsules, to reduce the amount of the flame retardant resin composition per volume to maintain the required flame retardancy while reducing weight, as well as ease of handling and cost.

본 발명은 폴리올레핀수지 15 내지 40중량부, 무기 난연제 60 내지 80 중량부 및 열팽창성 마이크로캡슐 0.2 내지 5중량부를 포함하는 열팽창성 난연 폴리올레핀 수지 조성물에 관한 것이다.The present invention relates to a heat-expandable flame retardant polyolefin resin composition comprising 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant and 0.2 to 5 parts by weight of thermally expandable microcapsules.

본 발명에 따른 열팽창성 난연 폴리올레핀 수지 조성물에 있어서, 상기 “난연”이란 방염 및 내염을 의미한다. In the thermally expandable flame retardant polyolefin resin composition according to the present invention, the term "flame retardant" means flame and flame resistant.

본 발명에 따른 폴리올레핀수지는 폴리에틸렌수지 및 에틸렌공중합체의 혼합물, 폴리에틸렌수지 및 열가소성고무의 혼합물 또는 이들의 혼합물을 의미하는 것으로서, 그 사용량은 전체 열팽창성 난연 폴리올레핀 수지조성물 100중량부에 대하여 15 내지 40중량부를 포함하는 것이 바람직하다.The polyolefin resin according to the present invention refers to a mixture of polyethylene resin and ethylene copolymer, a mixture of polyethylene resin and thermoplastic rubber, or a mixture thereof, the amount of which is 15 to 40 based on 100 parts by weight of the total thermally expandable flame retardant polyolefin resin composition. It is preferred to include parts by weight.

이때, 상기 폴리올레핀수지의 사용량이 15중량부 미만이면 열팽창성 마이크로캡슐의 함량이 높게 되어 압출 가공이 곤란해질 우려가 있고, 40중량부를 초과하면 난연성이 부족하여 요구되는 난연성, 바람직하게는 KS F5660-1에 정하고 있는 준불연성을 갖지 못할 우려가 있다.In this case, when the amount of the polyolefin resin is less than 15 parts by weight, the thermally expandable microcapsules may be high, which may make extrusion difficult. If the amount of the polyolefin resin exceeds 40 parts by weight, the flame retardancy may be insufficient, preferably KS F5660-. There is a possibility that the semi-combustibility set in 1 may not be obtained.

이에, 본 발명에 따른 폴리올레핀수지를 구성하는 폴리에틸렌수지, 에틸렌 공중합체 및/또는 열가소성고무의 조성비에 있어서, 상기 폴리에틸렌수지는 적어도 전체 폴리올레핀수지 100중량부에 대하여 20 내지 80중량부를 포함하고, 이를 제외한 조성, 예를 들면 에틸렌공중합체 및/또는 열가소성고무는 나머지 100중량부의 조성량을 갖도록 첨가되는 것이 바람직하다.Thus, in the composition ratio of the polyethylene resin, ethylene copolymer and / or thermoplastic rubber constituting the polyolefin resin according to the present invention, the polyethylene resin includes at least 20 to 80 parts by weight based on 100 parts by weight of the total polyolefin resin, except The composition, for example ethylene copolymer and / or thermoplastic rubber, is preferably added to have the composition amount of the remaining 100 parts by weight.

여기서, 상기 폴리에틸렌수지의 함량이 20중량부 미만이면 제조되는 수지조성물의 가열변형 온도 및 굴곡강도가 낮아질 우려가 있고, 80중량부를 초과하면 유연성이 감소되어 굴곡 시 크랙이 발생되고, 가공 시 열 처짐 현상이 발생하여 뱅크 불균일에 의한 심재의 접착불량 및 두께편차가 발생될 우려가 있다.Here, if the content of the polyethylene resin is less than 20 parts by weight, the heat deformation temperature and bending strength of the resin composition to be produced may be lowered. If the content of the polyethylene resin exceeds 80 parts by weight, the flexibility is reduced, cracking occurs during bending, and heat sagging during processing. The phenomenon occurs and there is a fear that adhesion failure and thickness deviation of the core material due to bank unevenness may occur.

상기 폴리에틸렌수지는 저밀도 폴리에틸렌수지(LDPE), 극저밀도 폴리에틸렌(VLDPE) 또는 선형 저밀도 폴리에틸렌수지(LLDPE)가 단독 또는 혼합되어 사용될 수 있으며, 그 양은 전체 폴리올레핀수지 100중량부에 대하여 20 내지 80중량부를 포함하는 것이 바람직하고, 그 밀도는 0.89 내지 0.929g/cm3, 용융지수는 10 내지 60g/10분의 범위를 갖는 것이 바람직하다.The polyethylene resin may be used alone or mixed with low density polyethylene resin (LDPE), ultra low density polyethylene (VLDPE) or linear low density polyethylene resin (LLDPE), the amount of which includes 20 to 80 parts by weight based on 100 parts by weight of the total polyolefin resin It is preferable that the density is 0.89 to 0.929 g / cm 3 , and the melt index is preferably in the range of 10 to 60 g / 10 minutes.

이때, 상기 용융지수가 10g/10분 미만이면 압출 가공성이 용이하지 않을 우려가 있고, 60g/10분을 초과하면 열 처짐 현상이 발생되어 뱅크 형성이 불균일해질 우려가 있다.At this time, if the melt index is less than 10g / 10 minutes, extrusion workability may not be easy, and if it exceeds 60g / 10 minutes, there is a fear that heat deflection occurs, the bank formation is uneven.

상기 에틸렌 공중합체는 에틸렌-프로필렌 공중합체, 에틸렌-옥텐 공중합체, 에틸렌-부텐 공중합체, 에틸렌-헥센 공중합체, 에틸렌비닐아세테이트, 에틸렌에틸아크릴레이트, 에틸렌메틸아크릴레이트 또는 이들로부터 선택된 적어도 하나 이상 을 의미하는 것으로서, 상기 전체폴리올레핀수지 100중량부에 대하여 20 내지 80중량부로 포함되는 폴리에틸렌수지의 나머지 100중량부로 포함되는 것이 바람직하다. The ethylene copolymer may be at least one selected from ethylene-propylene copolymer, ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene vinyl acetate, ethylene ethyl acrylate, ethylene methyl acrylate or these. Meaning, it is preferably included in the remaining 100 parts by weight of the polyethylene resin contained in 20 to 80 parts by weight relative to 100 parts by weight of the total polyolefin resin.

상기 열가소성고무는 SBS(styrene-butadiene-styrene 공중합체), SIS(styrene-isoprene-styrene 공중합체)와 이들의 수소첨가 제품인 SEBS[styrene-ethylene-butylene-styrene 공중합체], SEPS[styrene-ethylene-propylene-styrene 공중합] 및 HSBR[Hydrogenated styrene-butadiene rubber], EPDM[ethylene-propylene-diene monomer]/폴리올레핀수지의 동적가교물로 이루어진 군으로부터 선택되는 적어도 하나 이상을 의미하는 것으로서, 그 사용량은 상기 전체 폴리올레핀수지 100중량부에 대하여 20 내지 80중량부로 포함되는 폴리에틸렌수지의 나머지 100중량부로 포함되는 것이 바람직하다. The thermoplastic rubber is SBS (styrene-butadiene-styrene copolymer), SIS (styrene-isoprene-styrene copolymer) and their hydrogenated products SEBS [styrene-ethylene-butylene-styrene copolymer], SEPS [styrene-ethylene- propylene-styrene copolymerization] and HSBR [Hydrogenated styrene-butadiene rubber] and EPDM [ethylene-propylene-diene monomer] / polyolefin resins of at least one selected from the group consisting of a dynamic crosslinking, the amount of the use It is preferably included in the remaining 100 parts by weight of the polyethylene resin contained in 20 to 80 parts by weight relative to 100 parts by weight of the polyolefin resin.

본 발명에 따른 무기 난연제는 전체 수지조성물 100중량부에 대하여 60 내지 80중량부, 바람직하게는 65 내지 75중량부를 포함하는 것이 바람직하다. 사용 가능한 난연제로는 당업자에게 통상적으로 알려진 난연제라면 어떠한 것을 사용하여도 무방하지만, 바람직하게는 수산화마그네슘, 수산화알루미늄 및 탄산마그네슘을 단독 또는 혼합하여 사용할 수 있으며, 입자크기는 1 내지 60㎛, 비표면적(BET) 0.4 내지 35m2/g인 것이 바람직하다. The inorganic flame retardant according to the present invention preferably contains 60 to 80 parts by weight, preferably 65 to 75 parts by weight, based on 100 parts by weight of the total resin composition. As the flame retardant that can be used, any flame retardant known to those skilled in the art may be used, but preferably magnesium hydroxide, aluminum hydroxide and magnesium carbonate may be used alone or in combination, and the particle size is 1 to 60 µm, specific surface area. (BET) It is preferable that it is 0.4-35m <2> / g.

여기서, 상기 무기 난연제의 함량이 60중량부 미만이면 난연성이 감소, 예를 들면 KS F5660-1에서 정하고 있는 준불연 이하로 감소될 우려가 있고, 그 함량이 80중량부를 초과하면 압출부하 상승으로 인한 가공성이 용이하지 않을 뿐 아니라 열팽창 시 뱅크가 불균일해져 최적 목적물을 제조하는 것이 곤란해질 우려가 있다.Here, if the content of the inorganic flame retardant is less than 60 parts by weight, the flame retardancy may be reduced, for example, less than the quasi-non-flammable specified in KS F5660-1, if the content exceeds 80 parts by weight due to the increase in extrusion load Not only the workability is easy but also the bank becomes uneven during thermal expansion, making it difficult to manufacture the optimum target.

본 발명에 따른 열팽창성 마이크로캡슐은 수지조성물에 포함되어 열을 가했을 때 부피가 팽창하여 발포되어 비중을 감소시키기 위해 사용하는 것으로서, 상기 열팽창성 마이크로캡슐이 전술한 목적으로 사용된다면 어떠한 것을 사용하여도 무방하지만, 바람직하게는 니트릴계 공중합체로 구성된 3 내지 50㎛ 크기의 고분자 쉘 내에 액체탄화수소가 포함되는 것이 바람직하다. The thermally expandable microcapsules according to the present invention are used to reduce the specific gravity by expanding and foaming when the volume is expanded and applied to the resin composition, and the thermally expandable microcapsules may be used if the thermally expandable microcapsules are used for the aforementioned purpose. However, it is preferable that the liquid hydrocarbon is contained in the polymer shell having a size of 3 to 50 μm, preferably composed of a nitrile copolymer.

상기 니트릴계 공중합체는 아크릴로니크릴 공중합체, 메타크릴로니트릴 공중합체, 알파-클로로아크릴로니트릴 공중합체, 알파-에톡시아크릴로니트릴 공중합체, 푸마로니트릴 공중합체 또는 이들로부터 선택된 적어도 하나 이상인 것이 바람직하다.The nitrile copolymer is at least one selected from acrylonitrile copolymer, methacrylonitrile copolymer, alpha-chloroacrylonitrile copolymer, alpha-ethoxyacrylonitrile copolymer, fumaronitrile copolymer or these It is preferable.

본 발명에 따른 열팽창성 마이크로캡슐의 팽창개시온도는 폴리올레핀수지의 융점 이상인 것이 바람직하며, 열팽창성 마이크로캡슐의 최대팽창온도는 150 내지 220℃인 것이 바람직하다. The expansion start temperature of the thermally expandable microcapsules according to the present invention is preferably higher than the melting point of the polyolefin resin, and the maximum expansion temperature of the thermally expandable microcapsules is preferably 150 to 220 ° C.

여기서 상기 열팽창성 마이크로캡슐의 팽창개시온도는 폴리올레핀수지의 융점 이상인 것이 바람직하다. 폴리올레핀수지는 종류에 따라 각각 다른 값의 융점을 가지므로, 상기 열팽창성 마이크로캡슐도 사용하는 폴리올레핀수지에 따라 다른 팽창개시온도를 가지게 되나 90 내지 120℃의 온도범위인 것이 바람직하다. 상기 팽창개시온도가 폴리올레핀수지의 융점보다 낮으면 열팽창성 마이크로캡슐이 조기팽창하여 본 발명에 따른 조성물을 얻을 수 없다.The expansion start temperature of the thermally expandable microcapsules is preferably at least the melting point of the polyolefin resin. Since the polyolefin resin has a different melting point depending on the type, the thermally expandable microcapsules also have different expansion start temperatures depending on the polyolefin resin to be used. However, the polyolefin resin preferably has a temperature range of 90 to 120 ° C. If the expansion start temperature is lower than the melting point of the polyolefin resin, the thermally expandable microcapsules prematurely expand to obtain a composition according to the present invention.

한편 최대팽창온도는 열팽창성 마이크로캡슐이 압출기 내에서 2분 체류시 완 전히 팽창할 때의 온도를 의미한다. 상기 열팽창성 마이크로캡슐의 최대팽창온도는 150 내지 220℃인 것이 바람직하다. 상기 최대팽창온도가 150℃ 미만이면 본 발명의 폴리올레핀수지 조성물 제조 시 열팽창성 마이크로캡슐의 조기팽창 가능성 때문에 폴리올레핀수지 조성물의 혼합을 위한 혼련장치에서의 혼련시간이 짧아져 균일한 혼합물을 얻기 어려워질 우려가 있으며, 균일한 폴리올레핀수지 조성물을 얻었다 하더라도 폴리올레핀수지 조성물을 압출하는 압출기 통과 시에 조기 팽창하여 수축되므로 발포효과를 얻기 어려워질 우려가 있다. The maximum expansion temperature, on the other hand, refers to the temperature at which the thermally expandable microcapsules fully expand after 2 minutes of residence in the extruder. The maximum expansion temperature of the thermally expandable microcapsules is preferably 150 to 220 ° C. If the maximum expansion temperature is less than 150 ℃ due to the possibility of premature expansion of thermally expandable microcapsules in the production of the polyolefin resin composition of the present invention, the kneading time in the kneading apparatus for mixing the polyolefin resin composition is shortened, it is difficult to obtain a uniform mixture Even if a uniform polyolefin resin composition is obtained, there is a concern that it is difficult to obtain a foaming effect because it expands prematurely and contracts during the passage of an extruder for extruding the polyolefin resin composition.

또한 최대팽창온도에서 혼련장치 또는 압출기내에서의 체류시간이 너무 길어지면 마이크로캡슐내의 기체 투과손실로 수축하게 되어 발포효과가 떨어질 우려가 있다. 본 발명의 열팽창성 난연 폴리올레핀조성물을 얻기 위해서는 혼련장치내부에서 조기 팽창이 일어나지 않도록 하여야 한다. In addition, if the residence time in the kneading apparatus or the extruder is too long at the maximum expansion temperature, there is a fear that the foaming effect is reduced by shrinkage due to gas permeation loss in the microcapsules. In order to obtain the thermally expandable flame retardant polyolefin composition of the present invention, it is necessary to prevent premature expansion in the kneading apparatus.

본 발명에 따른 열팽창성 마이크로캡슐의 함량은 전체 수지조성물 100 중량부에 대하여 0.2 내지 5중량부, 바람직하게는 0.5 내지 3중량부를 포함하는 것이 좋다.The content of the thermally expandable microcapsules according to the present invention may include 0.2 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the total resin composition.

상기 마이크로캡슐의 함량이 0.2중량부 미만이면 비중감소 효과가 감소될 우려가 있고, 5중량부를 초과하면 비중감소효과가 미미할 뿐 아니라, 폴리싱 롤에서 뱅크형성이 곤란하여 복합패널, 특정적으로 알루미늄복합패널 제조 시 접착불량 및 두께편차를 발생시킬 우려가 있다. When the content of the microcapsules is less than 0.2 parts by weight, the specific gravity reduction effect may be reduced. When the content of the microcapsules exceeds 5 parts by weight, the specific gravity reduction effect may be insignificant. When manufacturing the panel, there is a possibility of generating poor adhesion and thickness deviation.

한편, 본 발명에 따른 열팽창성 난연 폴리올레핀 수지조성물은 전술한 성분이외에 산화방지제, 가공조제, 유/무기발포제, 필러분산제 및/또는 제습제 등을 추 가로 첨가할 수 있으며, 그 첨가량은 특별히 한정되지 않지만 소량인 것이 좋다.On the other hand, the heat-expandable flame-retardant polyolefin resin composition according to the present invention may further add an antioxidant, processing aid, organic / inorganic foaming agent, filler dispersant and / or dehumidifying agent in addition to the above components, the addition amount is not particularly limited. Small amount is good.

본 발명은 또한 열팽창성 난연 폴리올레핀수지 조성물이 포함된 난연성 복합패널에 관한 것이다. The invention also relates to a flame retardant composite panel comprising a thermally expandable flame retardant polyolefin resin composition.

상기 복합패널은 금속판재/접착층/폴리올레핀수지 조성물/접착층/금속판재의 구조로 이루어진다. The composite panel is made of a metal plate / adhesive layer / polyolefin resin composition / adhesive layer / metal plate structure.

이 때, 금속판재는 알루미늄, 아연 또는 티타늄으로 이루어진 성분을 단독 또는 2종 이상 구성 제조된 합금(alloy)을 사용하는 것이 바람직하다.At this time, it is preferable that the metal sheet material is an alloy made of a single or two or more components composed of aluminum, zinc or titanium.

또한 접착층에 사용되는 접착제는 특별히 한정되지 않지만, 핫멜트 접착제로서 에틸렌 비닐 아세테이트, 폴리에스테르, 폴리에틸렌, 폴리우레탄, 폴리프로필렌, SIS, 또는 폴리아미드를 단독 또는 혼합하여 이루어진 수지를 사용하는 것이 바람직하다.Moreover, although the adhesive agent used for an adhesive layer is not specifically limited, It is preferable to use resin which consists of ethylene vinyl acetate, polyester, polyethylene, a polyurethane, a polypropylene, SIS, or polyamide individually or mixed as a hot melt adhesive.

본 발명은 또한, The present invention also provides

전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지, 60 내지 80중량부의 무기 난연제 및 0.2 내지 5중량부의 열팽창성 마이크로캡슐을 혼합 시켜 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계; 및 Preparing a thermally expandable flame retardant polyolefin resin composition by mixing 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant, and 0.2 to 5 parts by weight of thermally expandable microcapsules relative to the total resin composition; And

상기 열팽창성 난연 폴리올레핀수지 조성물을 발포한 뒤 금속판재와 접착시키는 단계를 포함하는 난연성 복합패널의 제조방법에 관한 것이다.It relates to a method for manufacturing a flame retardant composite panel comprising the step of adhering the thermally expandable flame retardant polyolefin resin composition and then bonding to a metal plate.

상기 열팽창성 난연 폴리올레핀수지 조성물을 제조하는 단계는 폴리올레핀수지, 무기 난연제 및 열팽창성 마이크로캡슐을 혼합시키는 것으로서, 이러한 목적을 위한 혼합이라면 특별히 한정되지 않지만, 바람직하게는 용융 혼련시켜 혼합시키는 것이 좋다.The step of preparing the thermally expandable flame retardant polyolefin resin composition is to mix the polyolefin resin, the inorganic flame retardant and the thermally expandable microcapsules, if the mixing for this purpose is not particularly limited, it is preferably melt kneaded and mixed.

이때, 상기 열팽창성 난연 폴리올레핀수지 조성물은 전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지, 60 내지 80중량부의 무기 난연제 및 02 내지 5중량부의 열팽창성 마이크로캡슐로 이루어지는 것이 바람직하다. In this case, the thermally expandable flame retardant polyolefin resin composition is preferably composed of 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant and 02 to 5 parts by weight of thermally expandable microcapsules relative to the total resin composition weight.

또한 열팽창성 난연 폴리올레핀수지 조성물은 혼합 장치, 바람직하게는 혼련 장치를 이용하여 제조되는 것이 좋다.In addition, the thermally expandable flame-retardant polyolefin resin composition is preferably produced using a mixing device, preferably a kneading device.

상기 혼련 장치로는 당업계에서 통상적으로 사용되는 것이라면 특별히 한정되지 않지만, 이축압출기, 부스니더, 연속믹서, 밴버리믹서 또는 니더를 사용하는 것이 바람직하며, 특히 밴버리믹서 또는 니더믹서를 사용하는 것이 바람직하다.The kneading apparatus is not particularly limited as long as it is commonly used in the art, but it is preferable to use a twin screw extruder, a bus kneader, a continuous mixer, a Banbury mixer, or a kneader, and in particular, a Banbury mixer or a Kneader mixer is preferably used. .

상기 혼련 장치의 온도는 90 내지 150℃로 유지되는 것이 좋다.The temperature of the kneading apparatus is preferably maintained at 90 to 150 ℃.

특정 양례로서, 상기 열팽창성 난연 폴리올레핀수지 조성물을 제조하는 단계는 As a specific example, the step of preparing the thermally expandable flame retardant polyolefin resin composition

전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지 및 60 내지 80중량부의 무기 난연제를 90 내지 120℃의 온도범위에서 혼합 시키는 혼합 단계; 및 A mixing step of mixing 15 to 40 parts by weight of polyolefin resin and 60 to 80 parts by weight of an inorganic flame retardant relative to the total resin composition in a temperature range of 90 to 120 ° C .; And

상기 폴리올레핀수지 및 무기 난연제의 혼합물에 0.2 내지 5중량부의 열팽창성 마이크로캡슐을 투입하여 120 내지 150℃의 온도범위에서 혼합시켜 열팽창성 난 연 폴리올레핀 수지조성물을 제조하는 단계로 이루어지는 것이 더 바람직하다. More preferably, 0.2 to 5 parts by weight of thermally expandable microcapsules are added to the mixture of the polyolefin resin and the inorganic flame retardant, and mixed at a temperature range of 120 to 150 ° C. to prepare a thermally expandable flame retardant polyolefin resin composition.

상기 혼합단계는 폴리올레핀수지 및 무기 난연제를 혼합시키는 것으로서, 이러한 목적을 위한 혼합단계라면 특별히 한정되지 않지만, 바람직하게는 용융 혼련시켜 혼합시키는 것이 좋다.The mixing step is to mix the polyolefin resin and the inorganic flame retardant, if the mixing step for this purpose is not particularly limited, but preferably melt kneaded and mixed.

이때, 상기 혼합물은 전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지 및 60 내지 80중량부의 무기 난연제로 이루어지는 것이 바람직하다. At this time, the mixture is preferably made of 15 to 40 parts by weight of polyolefin resin and 60 to 80 parts by weight of inorganic flame retardant based on the total resin composition weight.

또한 상기 혼합물은 혼합 장치, 바람직하게는 혼련 장치를 이용하여 혼합되는 것이 좋으며, 상기 혼련 장치의 온도는 90 내지 120℃로 유지되는 것이 좋다.In addition, the mixture is preferably mixed using a mixing device, preferably a kneading device, the temperature of the kneading device is preferably maintained at 90 to 120 ℃.

상기 열팽창성 난연 폴리올레핀수지 조성물을 제조하는 단계는 상기 혼합단계의 혼합물, 특히 용융 혼련된 폴리올레핀수지 및 무기 난연제의 혼합물에 열팽창성 마이크로캡슐을 첨가한다. 이때 열팽창성 마이크로캡슐은 0.2 내지 5중량부 첨가하는 것이 좋다. The step of preparing the thermally expandable flame retardant polyolefin resin composition adds thermally expandable microcapsules to the mixture of the mixing step, in particular a mixture of melt kneaded polyolefin resin and an inorganic flame retardant. At this time, the thermally expandable microcapsules are preferably added in an amount of 0.2 to 5 parts by weight.

상기 열팽창성 마이크로캡슐의 첨가시 상기 폴리올레핀수지 및 무기 난연제의 혼합물의 온도는 90 내지 120℃인 것이 바람직하며, 상기 폴리올레핀수지 및 무기 난연제의 혼합물에 열팽창성 마이크로캡슐을 투입한 후 120 내지 150℃의 온도범위에서 더 혼합한다. When the thermally expandable microcapsules are added, the temperature of the mixture of the polyolefin resin and the inorganic flame retardant is preferably 90 to 120 ° C., and the thermally expandable microcapsules are added to the mixture of the polyolefin resin and the inorganic flame retardant to 120 to 150 ° C. Mix more in the temperature range.

상기 폴리올레핀수지 조성물의 혼합은 혼련장치에서 이루어질 수 있는 바, 이러한 경우 조기 발포가 일어나지 않도록 하는 것이 매우 중요하다.The mixing of the polyolefin resin composition can be made in the kneading apparatus, in which case it is very important to prevent the early foaming.

본 발명에 따른 난연성 복합패널을 제조하는 단계는 상기 혼련된 열팽창성 난연 폴리올레핀수지 조성물을 발포한 뒤 금속판재와 접착시킨다.In the manufacturing of the flame retardant composite panel according to the present invention, the kneaded thermally expandable flame retardant polyolefin resin composition is foamed and then bonded to a metal sheet.

상기 난연성 복합패널의 제조시 온도범위는 150 내지 220℃를 갖는 것이 바람직하다. In the manufacture of the flame retardant composite panel, the temperature range is preferably 150 to 220 ℃.

상기 열팽창성 난연 폴리올레핀수지 조성물을 발포시키는 장치로는 당업계에서 통상적으로 사용되는 것이라면 특별히 한정되지 않지만, 티-다이 및 단축 압출기를 이용하는 것이 바람직하다.The apparatus for foaming the thermally expandable flame retardant polyolefin resin composition is not particularly limited as long as it is commonly used in the art, but it is preferable to use a tee-die and a single screw extruder.

이때, 상기 단축압출기의 L/D(압출기 실린더 길이/실린더 직경)는 8 내지 24가 바람직하고, 스크류 압축비는 1.1:1 내지 2.5:1 인 것이 바람직하다. At this time, the L / D (extruder cylinder length / cylinder diameter) of the single screw extruder is preferably 8 to 24, the screw compression ratio is preferably 1.1: 1 to 2.5: 1.

상기 L/D가 8미만, 스크류 압축비가 1.1:1 미만이 되면 압출량이 불균일해질 우려가 있고, L/D가 24를 초과하면 체류시간이 길어져 조기발포의 가능성이 높아질 우려가 있으며, 스크류 압축비가 2.5:1를 초과하면 압출부하 상승 및 전단력 상승에 의한 발열로 온도 조정이 어렵게 되어 균일하게 발포된 복합패널의 심재를 형성하기 어렵게 될 우려가 있다. If the L / D is less than 8 and the screw compression ratio is less than 1.1: 1, the extrusion amount may be uneven. If the L / D is more than 24, the residence time may be long and the possibility of premature foaming may be increased. If it exceeds 2.5: 1, it is difficult to control the temperature due to the heat generated by the increase in the extrusion load and the increase in the shear force, thereby making it difficult to form the core material of the uniformly foamed composite panel.

또한 압출기 내부의 발열을 최대한 억제하기 위하여 스크류 내부에 냉매를 순환시키는 것이 좋다.In addition, it is preferable to circulate the refrigerant inside the screw in order to minimize the heat generated inside the extruder.

본 발명에 따른 티-다이에서는 3층 구조로 공압출 되는 데, 중간층에는 본 발명에 따른 폴리올레핀수지 조성물이, 그 상하로는 접착성 수지가 함께 3층 구조로 압출된다.In the T-die according to the present invention, a co-extrusion is carried out in a three-layer structure. The polyolefin resin composition according to the present invention is extruded in an intermediate layer, and the adhesive resin is extruded together in a three-layer structure.

발포된 수지 조성물은 롤에 투입되어 금속판재와 접착되는 바, 이때 사용하는 롤은 당업계에서 사용하는 통상적인 롤을 사용할 수 있으며, 캘린더 롤을 사용하는 것이 바람직하다. The foamed resin composition is put into a roll and adhered to the metal plate, and the roll used here may be a conventional roll used in the art, and it is preferable to use a calender roll.

이때 발포된 수지 조성물은 롤에 투입되어 상하단에서 함께 투입되는 금속판재와 접착됨으로써 저비중의 난연성 복합패널이 된다.At this time, the foamed resin composition is put into a roll and adhered to the metal plate material which is put together at the upper and lower ends to form a low specific gravity flame retardant composite panel.

상기 금속판재는 알루미늄, 아연 또는 티타늄으로 이루어진 성분을 단독 또는 2종 이상 구성 제조된 합금(alloy)을 사용하는 것이 바람직하고 알루미늄을 사용하는 것이 보다 바람직하다.It is preferable to use an alloy made of a single or two or more components composed of aluminum, zinc, or titanium, and more preferably, the metal sheet.

이하에서 실시예를 통하여 본 발명을 구체적으로 설명하기로 한다. 그러나 하기의 실시예는 오로지 본 발명을 구체적으로 설명하기 위한 것으로 이들 실기예에 의해 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention by these practical examples.

먼저 본 발명에 따른 실시예를 설명하기에 앞서, 하기 실시예에 의하여 제조되는 물질의 물성측정 방법을 설명하면 다음과 같다.First, prior to explaining the embodiment according to the present invention, the physical property measurement method of the material produced by the following example will be described.

[물성측정 방법][Measurement of physical properties]

1) 비중 : ASTM D1505 1) Specific Gravity: ASTM D1505

니더 혼련장치에서 구성 성분들을 혼련한 후 얻은 조성물 샘플을 압출기 투입 전에 채취하여 비중을 측정하였고, 이어서 압출기를 통과하여 팽창(발포)된 후 이를 심재로 하여 제조된 복합패널의 심재의 비중을 측정하여 비교하였다. 한편 혼련장치에서의 조기 발포 유무를 판별하기 위하여 마이크로캡슐이 첨가되지 않은 비교 실시예1의 난연 조성물의 비중 1.57을 기준으로 하여 비교하였고 육안검사도 병 행하였다.The composition samples obtained after kneading the components in the kneader kneading apparatus were taken before the extruder was input and the specific gravity thereof was measured. Then, the specific gravity of the core material of the composite panel manufactured using the core material after being expanded (foamed) through the extruder was measured. Compared. On the other hand, to determine the presence of premature foaming in the kneading apparatus was compared based on the specific gravity 1.57 of the flame retardant composition of Comparative Example 1 without the addition of microcapsules and visual inspection was also performed.

2) 압출시험 2) extrusion test

니더에서 조성물을 혼련한 후 공압출 방식에 의한 복합패널 제조 장치에서 압출 발포하여 저비중의 난연성 복합패널을 제조 하였다. 이때, 발포균일성 및 캘린더 롤에서의 뱅크의 균일성 등을 관찰하였다. After kneading the composition in the kneader and extrusion foamed in a composite panel manufacturing apparatus by a coextrusion method to produce a low specific gravity flame-retardant composite panel. At this time, the uniformity of foam and the uniformity of the bank in a calender roll were observed.

이때, 알루미늄 판재의 두께는 4mm로서 판재 양 층의 합금두께는 각각 0.5mm이고 접착층을 포함한 심재의 두께는 3mm로 구성된다.At this time, the thickness of the aluminum plate is 4mm, the thickness of the alloy of the plate both layers are 0.5mm and the thickness of the core including the adhesive layer is composed of 3mm.

발포균일성 및 뱅크균일성 평가기준 - ○: 양호, △: 보통, X: 불량Evaluation criteria for foam uniformity and bank uniformity-○: Good, △: Normal, X: Poor

여기서, 사용된 압출기 사양 및 온도조건은 다음과 같다.Here, the extruder specifications and temperature conditions used are as follows.

(1) 압출기 사양(1) extruder specification

- 주압출기-Main extruder

L/D=12, 실린더 직경=180mm, 스크류 압축비=1.2:1, 티-다이 폭=1250mmL / D = 12, cylinder diameter = 180mm, screw compression ratio = 1.2: 1, tee-die width = 1250mm

- 부압출기Sub-extruder

L/D=30, 실린더 직경=60mm, 스크류 압축비=1.9:1 L / D = 30, cylinder diameter = 60mm, screw compression ratio = 1.9: 1

(2) 압출조건(2) Extrusion condition

- 주압출기(열팽창성 난연 폴리올레핀수지)-Main extruder (thermally expandable flame retardant polyolefin resin)

온도; C1/C2/C3/스크린체인저/어댑터/피드블록= 170/180/190/195/195/195℃Temperature; C1 / C2 / C3 / Screen Changer / Adapter / Feedblock = 170/180/190/195/195/195 ℃

- 부압출기(접착성수지)-Sub-extruder (adhesive resin)

온도; C1/C2/C3/C4/어댑터= 130/150/170/190/190℃Temperature; C1 / C2 / C3 / C4 / Adapter = 130/150/170/190/190 ℃

- 티-다이 온도= 195℃T-die temperature = 195 ° C

3) 난연성3) flame retardant

제조된 알루미늄복합패널로 시편을 제작하여 다음과 같은 난연 성능을 평가하였다.The specimens were fabricated using the manufactured aluminum composite panel, and the following flame resistance was evaluated.

- 관련규격: KS F5660-1 준불연 기준-Related standards: KS F5660-1 semi-non-combustible

시험체에 50KW/㎡의 복사열을 가한 후 10분간 총발열량이 8MJ/㎡ 이하이며, 10분간 최대방출률이 10초 이상 200kW/㎡ 을 초과하지 않아야 하고, 10분간의 가열 후 시험체를 관통하는 구멍이 없어야 한다.After applying 50KW / ㎡ radiant heat to the test body, the total heat generation amount is less than 8MJ / ㎡ for 10 minutes, the maximum emission rate should not exceed 200kW / ㎡ for more than 10 seconds for 10 minutes, and there should be no hole through the test body after 10 minutes of heating. do.

- ASTM D2863에 의거하여 산소지수(Oxygen Index)를 평가함-Evaluate Oxygen Index according to ASTM D2863

<실시예 1>&Lt; Example 1 >

전체 수지조성물 중량 기준으로 선형 저밀도 폴리에틸렌(LLDPE, MI=20, 비중=0.924)[JL210, SK에너지(주),대한민국] 15중량부와 메탈로센 폴리올레핀 수지[인게이지(Engage) 8200, 다우케미칼, 미국] 15중량부로 이루어진 폴리올레핀수지 및 무기 난연제인 수산화마그네슘[DG-800,International Powder Engineering Co. 중국] 69.5중량부를 온도가 120℃로 맞춰져 있는 110리터 용량의 니더 믹서[화인기 계, 대한민국]에 넣은 후 약 100℃에 이르면 열팽창성 마이크로캡슐[MSH-500, 송본유지제약(주), 일본] 0.5중량부를 첨가하여 125℃에 이를 때까지 용융 혼련 시켜 열팽창성 난연 폴리올레핀 수지조성물을 제조하였다.(표1참조)15 parts by weight of linear low density polyethylene (LLDPE, MI = 20, specific gravity = 0.924) [JL210, SK Energy, Korea] and metallocene polyolefin resin [Engage 8200, Dow Chemical] , USA] 15 parts by weight of polyolefin resin and magnesium hydroxide inorganic flame retardant [DG-800, International Powder Engineering Co., Ltd.]. China] 69.5 parts by weight is placed in a 110 liter kneader mixer [Fine-based, Korea] whose temperature is set at 120 ° C., and the thermally expandable microcapsules [MSH-500, Songbon Yuji Pharmaceutical Co., Ltd., Japan] 0.5 parts by weight was added and melt kneaded until the temperature reached 125 ° C., thereby preparing a thermally expandable flame retardant polyolefin resin composition (see Table 1).

그 다음, 티-다이가 부착되어 있는 180mm 단축 압출기[화인기계, 대한민국]를 통과시켜 팽창(발포)시킨 후 캘린더 롤에 투입하여 상 하단에서 투입되는 알루미늄패널과 분당 2.4 미터의 속도로 알루미늄복합패널을 제조하였다.Next, it expands (expands) through a 180mm single screw extruder [Fine Machinery, South Korea] with a T-die, and puts it in a calender roll, and puts it on the upper and lower aluminum composite panels at a speed of 2.4 meters per minute. Was prepared.

그 결과, 발포 전 조성물의 비중이 1.58 이었고 조기발포는 관찰되지 않았으며, 이를 발포시켜 얻은 알루미늄복합패널 심재의 비중이 1.16 으로서 비중이 크게 감소하였다. 난연성은 산소지수가 54이었고 KS F5660-1에서 정하는 준불연 기준을 만족하였다. 또한 압출 시 발포 균일성 및 뱅크형성이 양호한 것으로 나타났다. 이를 정리하면 표2와 같았다. As a result, the specific gravity of the composition before foaming was 1.58 and no early foaming was observed, and the specific gravity of the aluminum composite panel core material obtained by foaming was 1.16, which greatly decreased the specific gravity. The flame retardancy was 54 in oxygen index and the quasi nonflammable standard set in KS F5660-1 was satisfied. It was also shown that the foam uniformity and banking during extrusion were good. This is summarized in Table 2.

<실시예 2><Example 2>

실시예 1과 동일한 방법으로 실시하되, 실시예 1의 폴리에틸렌수지와 무기 난연제의 비를 유지하면서 열팽창성 마이크로캡슐의 함량을 1 중량부 첨가하였다(표1참조).It carried out in the same manner as in Example 1, but added 1 part by weight of the thermally expandable microcapsules while maintaining the ratio of the polyethylene resin and the inorganic flame retardant of Example 1 (see Table 1).

그 결과, 발포 전 조성물의 비중이 1.57 이고 조기발포는 발견되지 않았다. 심재의 비중이 0.96 으로서 거의 폴리에틸렌수지와 유사하였고, 난연성은 산소지수가 52.5 으로서 KS F5660-1에서 정하는 준불연 기준을 합격하였다. 발포균일성 및 뱅크형성이 양호한 것으로 나타났다. 이를 정리하면 표2와 같았다.As a result, the specific gravity of the composition before foaming was 1.57 and no early foaming was found. The core material had a specific gravity of 0.96, which was almost similar to that of polyethylene resin, and its flame retardancy was 52.5, which passed the quasi-non-combustible standard of KS F5660-1. Foam uniformity and bank formation were found to be good. This is summarized in Table 2.

<실시예 3><Example 3>

실시예 1과 동일한 방법으로 실시하되, 실시예 1의 폴리에틸렌수지와 무기 난연제의 비를 유지하면서 열팽창성 마이크로캡슐 의 함량을 3 중량부 첨가하였다(표1참조).It carried out in the same manner as in Example 1, but added 3 parts by weight of the thermally expandable microcapsules while maintaining the ratio of the polyethylene resin and the inorganic flame retardant of Example 1 (see Table 1).

그 결과, 발포 전 조성물의 비중이 1.55 이고 조기발포는 관찰되지 않았다. 심재의 비중이 0.84로서 폴리에틸렌수지보다 낮았다. 산소지수는 52 이었고, 준불연 기준을 합격하였다. 반면 발포균일성이 다소 떨어지고 뱅크형성이 약간 불균일한 특성은 있었으나, 제품 제조에는 큰 문제가 발생하지 않았다. 이를 정리하면 표2와 같았다. As a result, the specific gravity of the composition before foaming was 1.55 and no early foaming was observed. Core specific gravity was 0.84, lower than polyethylene resin. The oxygen index was 52 and passed the semi-non-combustible standard. On the other hand, although the foam uniformity was somewhat inferior and the bank formation was slightly nonuniform, there was no big problem in manufacturing the product. This is summarized in Table 2.

<비교실시예 1>Comparative Example 1

실시예 1과 동일한 방법으로 실시하되, 열팽창성 마이크로갭슐을 첨가하지 않았다(표1참조).The same procedure as in Example 1 was carried out except that the thermally expandable microcapsules were not added (see Table 1).

그 결과, 알루미늄복합패널의 심재 비중이 1.58로 폴리에틸렌수지 0.924에 비하여 상당히 높았다. 반면, 난연성은 산소지수가 54, KS F5660-1에서 정하는 준불연 기준을 만족하였다. 또한 캘린더 롤에서의 뱅크형성은 양호하였다. 이를 정리하면 표2와 같았다.As a result, the specific gravity of the core material of the aluminum composite panel was 1.58, which was significantly higher than that of the polyethylene resin 0.924. On the other hand, the flame retardancy satisfies the quasi-non-flammability criteria set by 54, KS F5660-1. Moreover, bank formation in the calender roll was favorable. This is summarized in Table 2.

<비교실시예 2>Comparative Example 2

실시예 1과 동일한 방법으로 실시하되, 실시예 1의 폴리에틸렌수지와 무기 난연제의 비를 유지하면서 열팽창성 마이크로캡슐의 함량을 6 중량부 첨가하였다(표1참조).It carried out in the same manner as in Example 1, but added 6 parts by weight of the thermally expandable microcapsules while maintaining the ratio of the polyethylene resin and the inorganic flame retardant of Example 1 (see Table 1).

그 결과, 발포 전 조성물의 비중이 1.53 으로서 조기발포가 일어나진 않았으나, 티-다이에서 압출되어 나올 때, 너무 불균일하여 뱅크형성이 거의 불가능하였다. 따라서 알루미늄복합패널 제조에 실패하였다. 이를 정리하면 표2와 같았다. As a result, early foaming did not occur as the specific gravity of the composition before foaming was 1.53, but when it was extruded out of the tee-die, it was too uneven to form a bank almost impossible. Therefore, it failed to manufacture aluminum composite panel. This is summarized in Table 2.

열팽창성 난연 폴리올레핀수지 조성물의 조성(중량부)Composition of thermally expandable flame retardant polyolefin resin composition (parts by weight) LLDPELLDPE 1)메탈로센 폴리올레핀 수지 1) metallocene polyolefin resin 2)수산화마그네슘 2) magnesium hydroxide 3)열팽창성 마이크로캡슐 3) Thermally expandable microcapsules 실시예1Example 1 1515 1515 69.569.5 0.50.5 실시예2Example 2 1515 14.514.5 69.569.5 1One 실시예3Example 3 1515 12.512.5 69.569.5 33 비교예1Comparative Example 1 1515 15.515.5 69.569.5 00 비교예2Comparative Example 2 1515 9.59.5 69.569.5 66

여기서here

상기 LLDPE의 MI=20이고 비중=0.924, [JL210, SK에너지(주),대한민국]이며, MI = 20 and specific gravity of LLDPE = 0.924, [JL210, SK Energy, Korea],

1)은 메탈로센 폴리올레핀 수지[인게이지(Engage) 8200, 다우케미칼, 미국],1) is a metallocene polyolefin resin (Engage 8200, Dow Chemical, USA),

2)는 수산화마그네슘[DG-800,International Powder Engineering Co. 중국],2) magnesium hydroxide [DG-800, International Powder Engineering Co. China],

3)은 열팽창성 마이크로캡슐[MSH-500, 송본유지제약(주), 일본]이다. 3) is a thermally expandable microcapsule [MSH-500, Songbon Oil Holding Co., Japan].

본 발명의 실시예 및 비교실시예에 따른 조성물의 물성Physical Properties of Compositions According to Examples and Comparative Examples of the Present Invention 발포전조성물 비중Specific gravity of foaming composition 조기발포Early foaming 심재 비중Heart rate 산소지수Oxygen index KS F5660 -1KS F5660 -1 균일성Uniformity 뱅크형성Bank formation 실시예1Example 1 1.581.58 ×× 1.161.16 5454 합격pass 실시예2Example 2 1.571.57 ×× 0.960.96 52.552.5 합격pass 실시예3Example 3 1.551.55 ×× 0.840.84 5252 합격pass 비교예1Comparative Example 1 1.581.58 5454 합격pass 비교예2Comparative Example 2 1.531.53 ×× -- -- -- ×× ××

표 2에 나타낸 바와 같이, 열팽창성 마이크로캡슐을 첨가하여 발포시키면, 첨가하지 않았을 때에 비하여 현저히 비중이 감소되며, 반면에 난연성은 거의 감소되지 않음을 알 수 있었다. 이와 같이 난연성을 거의 유지하면서도 비중을 폴리에틸렌수지와 유사 내지는 그 이하로도 낮출 수 있음을 알 수 있었다. As shown in Table 2, it was found that when foamed by adding the thermally expandable microcapsules, the specific gravity was significantly reduced compared to that when not added, while the flame retardancy was hardly reduced. As such, it was found that specific gravity can be lowered to similar or less than polyethylene resin while maintaining almost flame retardancy.

이상에서 설명한 바와 같이, 본 발명이 속하는 기술분야의 당업자는 본 발명이 그 기술적 사상이나 필수적 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적인 것이 아닌 것으로서 이해해야만 한다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위의 의미 및 범위 그리고 그 등가개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.As described above, those skilled in the art will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. Therefore, the above-described embodiments are to be understood as illustrative in all respects and not as restrictive. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the appended claims and equivalent concepts thereof are included in the scope of the present invention rather than the above detailed description.

Claims (18)

전체 수지조성물 중량 대비 15 내지 40중량부의 폴리올레핀수지, 60 내지 80중량부의 무기 난연제 및 0.2 내지 5 중량부의 열팽창성 마이크로캡슐을 혼합 시켜 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계; 및Preparing a thermally expandable flame retardant polyolefin resin composition by mixing 15 to 40 parts by weight of polyolefin resin, 60 to 80 parts by weight of inorganic flame retardant, and 0.2 to 5 parts by weight of thermally expandable microcapsules relative to the total weight of the resin composition; And 상기 열팽창성 난연 폴리올레핀 수지조성물을 발포한 뒤 금속판재와 접착시키는 단계를 포함하는 난연성 복합패널의 제조방법.Method of manufacturing a flame-retardant composite panel comprising the step of foaming the thermally expandable flame-retardant polyolefin resin composition and then bonding to a metal plate. 제 1 항에 있어서, The method of claim 1, 상기 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계가 90 내지 150℃의 온도범위에서 이루어지는 것을 특징으로 하는 난연성 복합패널의 제조방법.The method of producing a thermally expandable flame-retardant polyolefin resin composition is a method of producing a flame-retardant composite panel, characterized in that made in the temperature range of 90 to 150 ℃. 제 1 항에 있어서, The method of claim 1, 상기 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계가The step of preparing the thermally expandable flame retardant polyolefin resin composition 전체 수지조성물 중량 대비 15 내지 40 중량부의 폴리올레핀수지 및 60 내지 80 중량부의 무기 난연제를 90 내지 120℃의 온도범위에서 혼합 시키는 단계; 및Mixing 15 to 40 parts by weight of polyolefin resin and 60 to 80 parts by weight of an inorganic flame retardant with respect to the total resin composition in a temperature range of 90 to 120 ° C; And 상기 폴리올레핀수지 및 무기 난연제의 혼합물에 0.2 내지 5 중량부의 열팽창성 마이크로캡슐을 투입하여 120 내지 150℃의 온도범위에서 혼합시켜 열팽창성 난연 폴리올레핀 수지조성물을 제조하는 단계를 포함하는 것을 특징으로 하는 난연성 복합패널의 제조방법.A flame retardant composite comprising the steps of preparing a thermally expandable flame retardant polyolefin resin composition by adding 0.2-5 parts by weight of thermally expandable microcapsules to a mixture of the polyolefin resin and an inorganic flame retardant and mixing at a temperature range of 120 to 150 ° C. Method of manufacturing the panel. 제 1 항에 있어서, The method of claim 1, 상기 혼합된 열팽창성 난연 폴리올레핀 수지조성물을 발포한 뒤 금속판재와 접착시키는 단계가 150 내지 220℃의 온도범위에서 이루어지는 것을 특징으로 하는 난연성 복합패널의 제조방법.And foaming the mixed thermally expandable flame retardant polyolefin resin composition and adhering to the metal sheet in a temperature range of 150 to 220 ° C. 제 1 항에 있어서, The method of claim 1, 상기 발포는 단축 압출기 및 티-다이를 이용하는 것을 특징으로 하는 난연성 복합패널의 제조방법.The foaming method of producing a flame retardant composite panel, characterized in that using a single-screw extruder and tee-die. 제 5 항에 있어서, The method of claim 5, 상기 단축압출기의 L/D가 8내지 24이고, 스크류 압축비가 1.1:1 내지 2.5:1 인 것을 특징으로 하는 난연성 복합패널의 제조방법.L / D of the single screw extruder is 8 to 24, the screw compression ratio of 1.1: 1 to 2.5: 1 manufacturing method of a flame retardant composite panel. 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete
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