KR102181876B1 - Manufacturing method of composite resin composition using waste separator for secondary battery - Google Patents

Manufacturing method of composite resin composition using waste separator for secondary battery Download PDF

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KR102181876B1
KR102181876B1 KR1020190057957A KR20190057957A KR102181876B1 KR 102181876 B1 KR102181876 B1 KR 102181876B1 KR 1020190057957 A KR1020190057957 A KR 1020190057957A KR 20190057957 A KR20190057957 A KR 20190057957A KR 102181876 B1 KR102181876 B1 KR 102181876B1
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composite resin
separator
waste
polyolefin
separation membrane
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KR1020190057957A
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Korean (ko)
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김호주
하현수
강창기
강민성
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강창기
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/10Making granules by moulding the material, i.e. treating it in the molten state
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • H01M50/414Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417Polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04Disintegrating plastics, e.g. by milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50Details of extruders
    • B29C48/505Screws
    • B29C48/64Screws with two or more threads
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • H01M2/1653
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/443Particulate material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B2017/001Pretreating the materials before recovery
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04Disintegrating plastics, e.g. by milling
    • B29B2017/0424Specific disintegrating techniques; devices therefor
    • B29B2017/0468Crushing, i.e. disintegrating into small particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04Polymers of ethylene
    • B29K2023/06PE, i.e. polyethylene
    • B29K2023/0658PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683UHMWPE, i.e. ultra high molecular weight polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12Thermoplastic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26Scrap or recycled material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Abstract

The present invention relates to a method for preparing a composite resin composition by regenerating a waste separator of a secondary battery, coated with ceramic particles on one surface or both surfaces thereof. Particularly, the present invention relates to a method for preparing a composite resin composition including the steps of: i) a pretreatment step in which the waste separator of a secondary battery coated with ceramic particles is pulverized and compressed/pulverized to a smaller volume; ii) mixing and melting the pretreated waste separator material with a polyolefin-based material having high flowability, other modifiers and additives, kneading the mixture homogeneously, and extruding the mixture; and iii) processing the extruded product in the form of pellets. According to the present invention, there is provided a cost-efficient, highly efficient and eco-friendly method which can produce a composite resin composition having a novel composition and useful for various purposes from ceramic particle-coated separator scraps generated during the manufacture of a secondary battery and defected separators to be discarded.

Description

이차전지 폐분리막을 이용한 복합수지 조성물의 제조 방법{Manufacturing method of composite resin composition using waste separator for secondary battery}Manufacturing method of composite resin composition using waste separator for secondary battery}

본 발명은 단면 또는 양면에 세라믹입자로 코팅된 이차전지 폐분리막을 재생하여 복합수지 조성물을 제조하는 방법, 및 이런 방법으로 제조된 새로운 조성의 복합수지 조성물에 관한 것이다.The present invention relates to a method for manufacturing a composite resin composition by regenerating a waste separator for secondary batteries coated with ceramic particles on one side or both sides, and to a composite resin composition of a new composition prepared by this method.

리튬 이차전지는 지금까지 상용화되어 있는 이차전지 가운데 가장 성능이 우수한 전지 중 하나로 인정받고 있다. 이러한 우수성으로 인하여 핸드폰, PC, 각종 전동공구 등 소형화 및 경량화가 요구되는 각종 전기 제품들의 전원으로 널리 이용되고 있으며, 또한 최근에는 전기자동차에 대한 용도로 적용이 확대되고 있다. 이들 용도로 사용하기 위해서, 더욱 용량이 크고, 수명이 길고, 또한 안정성이 높은 리튬이온 이차전지의 개발이 요청되고 있다. 그래서 리튬 이차전지의 성능을 개선하기 위한 노력들이 계속 진행되고 있으며, 특히 양극과 음극을 분리시켜 단락을 막아주는 분리막에 대한 연구가 활발하다.Lithium secondary batteries are recognized as one of the most excellent batteries among secondary batteries commercially available so far. Due to such excellence, it is widely used as a power source for various electric products that require miniaturization and weight reduction, such as mobile phones, PCs, and various power tools, and has recently been expanded to use for electric vehicles. In order to be used for these purposes, the development of a lithium ion secondary battery having a larger capacity, longer life, and high stability is required. Therefore, efforts to improve the performance of lithium secondary batteries are continuing, and in particular, research on a separator that separates the anode and the cathode to prevent short circuit is actively conducted.

종래에 광범위하게 사용되고 있는 폴리올레핀(polyolefine) 계열의 분리막은 고온 열적 안정성과 물리적 강도가 취약하여 150℃의 온도에서 1시간 정도 노출 시 열 수축률이 50 ~ 90%로 발생하여 격리막의 기능을 상실하게 되며, 또한 외부 충격시 내부 단락이 일어날 가능성이 높은 문제점이 있었다. 이러한 문제점을 보완하기 위하여 최근에 보편적으로 채택되고 있는 기술이 세라믹 코팅이다. Polyolefine-based separators, which have been widely used in the past, have poor thermal stability and physical strength at high temperatures, so when exposed to a temperature of 150℃ for about 1 hour, heat shrinkage occurs at 50 to 90%, and the function of the separator is lost. In addition, there is a problem in that there is a high possibility that an internal short circuit occurs when an external impact occurs. In order to compensate for this problem, ceramic coating is a technology that has been widely adopted in recent years.

예컨대, 국내 특허등록 제10-739337호, 제10-754746호, 제10-858214호 및 국내 특허공개 제10-2010-28009호, 제10-2011-35847호에는 폴리올레핀계 다공성 기재의 적어도 일면에다 무기물 입자와 고분자 바인더로 이루어진 코팅액을 도포하여 다공성 활성층을 형성하는 유기/무기 복합세라믹 코팅 분리막이 제안되어 있다. 상기 특허들에 소개된 세라믹 코팅 분리막은 세라믹 코팅층이 없는 통상적인 분리막에 비해 열적 안정성이 월등히 개선된 것으로 보고되어 있다. 또한, 국내 특허공개 제10-2014-0048138호에서는 무기 필러 대신 유기 필러를 사용함으로써 소수성 입자의 제조를 통해 수분을 제어하는 하는 것도 제안되어 있다.For example, Korean Patent Registration Nos. 10-739337, 10-754746, 10-858214, and Korean Patent Publication Nos. 10-2010-28009 and 10-2011-35847 cover at least one side of a polyolefin-based porous substrate. An organic/inorganic composite ceramic coating separator has been proposed in which a coating solution composed of inorganic particles and a polymeric binder is applied to form a porous active layer. It has been reported that the ceramic-coated separator introduced in the above patents has significantly improved thermal stability compared to a conventional separator without a ceramic coating layer. In addition, Korean Patent Publication No. 10-2014-0048138 proposes to control moisture through the production of hydrophobic particles by using an organic filler instead of an inorganic filler.

하지만, 이러한 이차전지의 특성을 높이기 위한 복잡한 코팅 과정 중 불량품의 발생율이 높아지고 있으며, 최종 제품에서의 높은 요구물성을 달성하지 못하여 사용 불가한 스크랩 발생도 증가하는 추세이다.However, the incidence of defective products is increasing during the complicated coating process for enhancing the characteristics of such secondary batteries, and the generation of unusable scraps is also increasing due to the failure to achieve high required properties in the final product.

최근에 사용되는 고성능 분리막의 경우, 주로 초고분자량 폴리에틸렌을 사용하여 파라핀계 오일을 가공조제로 압출하여 오일이 포함된 시트를 제조, 냉각 고화하여 상분리시킨 후 이축 연신을 통해 공극을 형성하고 메틸렌클로라이드를 이용하여 Oil을 제거하는 단계를 통해서 분리막 원단을 제조하고 있으며, 내열성 및 특성을 높이기 위한 방안으로 세라믹 등의 소재를 단면 또는 양면에 코팅하여 제조하고 있다.In the case of a recently used high-performance separator, a sheet containing oil is prepared by extruding paraffinic oil as a processing aid using mainly ultra-high molecular weight polyethylene, cooling and solidifying, and phase separation, forming voids through biaxial stretching, and methylene chloride. Separator fabric is manufactured through the step of removing oil by using, and as a method to increase heat resistance and properties, materials such as ceramic are coated on one side or both sides.

코팅 분리막 제조공정은 매우 복잡하고 요구 특성이 까다롭기 때문에 품질 균일성이 떨어지는 엣지부의 경우 스크랩이 되며, 생산된 코팅 분리막에서도 최종 규격에 만족하지 못하여 사용할 수 없는 경우도 다수 발생되고 있으나, 점도가 매우 높은 초고분자량 폴리에틸렌에 매우 높은 함량의 세라믹 코팅 입자가 포함된 형태이기 때문에 일반적인 방법으로 재생이 불가하여 이전까지는 모두 폐기물로 고려되어 소각 또는 매립의 과정을 통해 처리됨으로써 고가의 처리 비용이 발생되고 환경적인 부담도 높은 현실이었다.Since the manufacturing process of the coating separator is very complex and the required characteristics are difficult, the edge part with poor quality uniformity becomes scrap, and there are many cases that the produced coating separator cannot be used because the final standard is not satisfied, but the viscosity is very high. Since ultra-high molecular weight polyethylene contains very high content of ceramic coating particles, it cannot be recycled in a general way. Until now, all of them were considered wastes and processed through incineration or landfill, resulting in expensive treatment costs and environmental burden. It was also high reality.

이에, 본 발명자들은 이차전지 제조과정 중 발생하는 단면 또는 양면에 코팅된 분리막 스크랩 및 불량품인 단면 또는 양면에 코팅된 폐분리막을 이용하여 다양한 용도로 적용될 수 있는 새로운 복합수지 조성물을 제공하면서, 동시에 경제적이고 효율적이며 환경친화적인 공정을 통해 가공성 문제를 해결한 방법을 개발함으로써, 본 발명을 완성하였다.Accordingly, the present inventors provide a new composite resin composition that can be applied for various purposes by using a separator scrap coated on one side or both sides during the manufacturing process of a secondary battery and a waste separator coated on one side or both sides, which is a defective product, while at the same time The present invention has been completed by developing a method that solves the processability problem through an efficient, environmentally friendly process.

본 발명의 목적은 단면 또는 양면에 세라믹 입자로 코팅된 이차전지 폐분리막을 분쇄 및 부피를 작게 압축 분쇄하는 전처리하는 공정; 폴리올레핀계 소재, 기타 개질제 및 첨가제와 혼합하여 용융 혼련 및 압출하는 공정; 및 펠릿 형태로 가공하는 공정;을 포함하는, 세라믹 입자로 코팅된 이차전지 폐분리막을 재생하여 복합수지 조성물을 제조하는 방법을 제공하는 것이다.An object of the present invention is a pretreatment process of pulverizing a waste separator for secondary batteries coated with ceramic particles on one side or both sides and compressing the volume to a small size; Melt-kneading and extruding by mixing with a polyolefin-based material, other modifiers and additives; And it is to provide a method for manufacturing a composite resin composition by regenerating a waste separator for secondary batteries coated with ceramic particles, including;

본 발명의 또다른 목적은 단면 또는 양면에 세라믹입자로 코팅된 이차전지 폐분리막과 폴리올레핀계 수지, 및 선택적으로 개질제 또는 첨가제 중 어느 하나 이상을 포함하는 복합수지 조성물을 제공하는 것이다. Another object of the present invention is to provide a composite resin composition comprising a waste separator for secondary batteries coated with ceramic particles on one side or both sides, a polyolefin resin, and optionally any one or more of a modifier or additive.

상기 목적을 달성하기 위하여, 본 발명은In order to achieve the above object, the present invention

i) 단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막을 분쇄한 후 부피를 작게 압축 분쇄하는 전처리 단계; i) a pretreatment step of pulverizing the waste separator for secondary batteries coated with ceramic particles on one or both sides and then compressing and pulverizing the volume to a small size;

ii) 전처리된 폐분리막 소재를 폴리올레핀계 수지, 개질제 및 첨가제와 혼합한 후, 용융, 혼련 및 압출하는 단계; 및ii) mixing the pretreated waste separation membrane material with a polyolefin-based resin, a modifier and an additive, and then melting, kneading and extruding; And

iii) 압출물을 펠릿 형태로 가공하는 단계;를 포함하는,iii) processing the extrudate into a pellet form; containing,

세라믹 입자가 코팅된 이차전지용 폐분리막을 재생하여 복합수지 조성물을 제조하는 방법을 제공한다.It provides a method of manufacturing a composite resin composition by regenerating a waste separator for a secondary battery coated with ceramic particles.

또한, 본 발명은 In addition, the present invention

상기 복합수지 조성물을 제조하는 방법의 전처리 단계에서 In the pretreatment step of the method for preparing the composite resin composition

i-a) 폐분리막 조각을 오픈(Open) 형태의 밀롤을 통하여 압착시키는 방법, 또는 i-a) A method of compressing a piece of waste separation membrane through an open mill roll, or

i-b) 폐분리막 조각을 압출기에 투입하여 덩어리(Lump) 형태로 제조하는 방법 중 어느 하나를 수행하는 방법을 제공한다.i-b) Provides a method of performing any one of the methods of manufacturing a waste separation membrane piece into a lump form by putting it into an extruder.

또한, 본 발명은 In addition, the present invention

상기 복합수지 조성물을 제조하는 방법의 용융, 혼련 및 압출 단계에서 In the melting, kneading and extrusion steps of the method for preparing the composite resin composition

ii-a) 분쇄된 폐분리막 소재를 가압형 니더에 투입하여 1차로 가압 용융시킨 후, 폴리올레핀계 소재, 및 선택적으로 개질제 또는 첨가제 중 어느 하나 이상을 추가로 가압형 니더에 투입하여 가압 용융하여 고르게 혼련한 다음, 압출하는 방법, 또는 ii-a) Put the pulverized waste separation membrane material into a pressurized kneader and first press-melt it, then add a polyolefin-based material, and optionally any one or more of a modifier or additive to a pressurized kneader, and pressurize to melt it evenly. Kneading and then extruding, or

ii-b) 분쇄된 폐분리막 소재, 폴리올레핀계 중합체, 및 선택적으로 개질제 또는 첨가제 중 어느 하나 이상을 혼련한 후, 2축 압출기(Twin Screw Extruder)에 투입하여 용융 압출하는 방법 어느 하나를 수행하는 방법을 제공한다.ii-b) After kneading any one or more of the pulverized waste separation membrane material, a polyolefin-based polymer, and optionally a modifier or additive, it is introduced into a twin screw extruder to melt-extrusion. Provides.

또한, 본 발명은 In addition, the present invention

상기 본 발명에 따른 제조 방법으로 제조된 세라믹 입자로 단면 또는 양면에 코팅된 이차전지 폐분리막이 포함된 펠릿 형태의 새로운 재생 복합수지 조성물을 제공한다.It provides a new recycled composite resin composition in the form of a pellet including a waste separator for secondary batteries coated on one side or both sides with ceramic particles prepared by the manufacturing method according to the present invention.

또한, 본 발명은 In addition, the present invention

단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막으로부터 분쇄 및 부피를 작게 압축 분쇄로 전처리된 폐분리막 소재 10 ~ 99 중량%; 및, 폴리올레핀계 수지 1 ~ 90 중량%;를 포함하는, 복합수지 조성물을 제공한다.10 to 99% by weight of a waste separator material pretreated by crushing and compacting the volume from the waste separator for secondary batteries coated with ceramic particles on one or both sides; And, 1 to 90% by weight of a polyolefin-based resin; it provides a composite resin composition containing.

또한, 본 발명은 In addition, the present invention

상기 복합수지 조성물에 개질제 0 ~ 50 중량% 또는 첨가제 0 ~ 30 중량% 중 어느 하나 이상을 더 포함하는 복합수지 조성물을 제공한다.It provides a composite resin composition further comprising any one or more of 0 to 50% by weight of the modifier or 0 to 30% by weight of the additive to the composite resin composition.

또한, 본 발명은 In addition, the present invention

상기 본 발명에 따른 복합수지 조성물을 포함하는 파이프, 기어 또는 인조잔디를 제공한다.It provides a pipe, gear or artificial turf comprising the composite resin composition according to the present invention.

아울러, 본 발명은 In addition, the present invention

상기 본 발명에 따른 복합수지 조성물을 포함하는 자동차 내/외장재, 생활용품, 산업용 자재 또는 건축용 자재를 제공한다. It provides interior/exterior materials for automobiles, household goods, industrial materials, or construction materials comprising the composite resin composition according to the present invention.

본 발명은 세라믹 입자가 단면 또는 양면에 코팅된 이차전지 폐분리막으로부터 새로운 복합수지 조성물을 만드는 방법은 이차전지 제조과정 중 발생하는 코팅 분리막 스크랩 및 불량품인 코팅 폐분리막을 이용하여 적절한 폴리올계핀계 수지, 개질제 및 첨가제를 최적 조성으로 투입하여 새로운 복합수지 조성물을 만드는 경제적이고 효율적이며 친환경적인 방법을 제공한다.The present invention relates to a method of making a new composite resin composition from a secondary battery waste separator coated on one side or both sides of the ceramic particles, using a coated separator scrap generated during the manufacturing process of a secondary battery and a defective coated waste separator using a suitable polyol-based fin resin, It provides an economical, efficient and eco-friendly method of making a new composite resin composition by adding modifiers and additives in an optimal composition.

본 발명에 따른 새로운 복합수지 조성물은 기존의 다양한 가공법으로 자동차 내/외장재, 생활용품, 산업용, 건축용 등의 다양한 분야에서 기존의 복합소재를 대체할 수 있는 경제성이 우수하고 물성이 우수한 신소재로의 적용 가능하다.The new composite resin composition according to the present invention is applied to a new material with excellent economical properties and excellent physical properties that can replace the existing composite material in various fields such as automobile interior/exterior materials, household goods, industrial, and construction using various existing processing methods. It is possible.

특히, 본 발명에 따른 새로운 복합수지 조성물은 폐분리막을 활용함으로써 원가를 낮추고 포름알데히드의 자극성 냄새 발현이 없으며, 우수한 인장강도, 탁월한 충격강도를 가지고 있어 상대적으로 낮은 내열성으로 인해 내열성이 크게 요구되지 않는 용도의 경우 폴리아세탈을 대체할 수 있다.In particular, the new composite resin composition according to the present invention lowers the cost by using a waste separator, does not develop a stimulating odor of formaldehyde, and has excellent tensile strength and excellent impact strength, so that heat resistance is not largely required due to relatively low heat resistance. For use, it can replace polyacetal.

도 1은 본 발명에 따른 이차전지 폐 코팅 분리막을 재생하여 복합수지 조성물을 제조하는 방법을 보여주는 그림이다.1 is a diagram showing a method of manufacturing a composite resin composition by regenerating a waste coating separator for a secondary battery according to the present invention.

이하에서 본 발명에 대해 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은The present invention

i) 단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막을 분쇄한 후 부피를 작게 압축 분쇄하는 전처리 단계; i) a pretreatment step of pulverizing the waste separator for secondary batteries coated with ceramic particles on one or both sides and then compressing and pulverizing the volume to a small size;

ii) 전처리된 폐분리막 소재를 폴리올레핀계 수지, 개질제 및 첨가제와 혼합한 후, 용융, 혼련 및 압출하는 단계; 및ii) mixing the pretreated waste separation membrane material with a polyolefin-based resin, a modifier and an additive, and then melting, kneading and extruding; And

iii) 압출물을 펠릿 형태로 가공하는 단계;를 포함하는,iii) processing the extrudate into a pellet form; containing,

세라믹 입자가 코팅된 이차전지용 폐분리막을 재생하여 복합수지 조성물을 제조하는 방법을 제공한다.It provides a method of manufacturing a composite resin composition by regenerating a waste separator for a secondary battery coated with ceramic particles.

상기 제조 방법에 있어서, 상기 단계 i)은 코팅 분리막이 연속된 Film 형태 또는 얇고 면적이 넓은 불규칙 조각 형태로 존재하여 재생을 위한 공정 투입이 매우 어렵기 때문에, 적절하게 분쇄/압착 또는 압출기에 투입하여 Lump 형태로 제조한 후 분쇄를 통해 이종 원료와의 혼련 또는 후공정을 용이한 특성을 부여하기 위한 단계이다. In the above manufacturing method, in step i), since the coating separator is in the form of a continuous film or in the form of thin and wide irregular pieces, it is very difficult to input the process for regeneration. This is a step to give easy characteristics for kneading or post-processing with different raw materials through pulverization after manufacturing in a lump shape.

상기 단계 i)의 폐분리막은 초고분자량 폴리에틸렌(ultrahigh molecular weight polyethylene, UHMWPE)을 사용한 분리막 원단을 이용한 단면 또는 양면에 세라믹 코팅을 진행하는 공정 중 발생하는 스크랩 또는 불량품인 것이 바람직하다.The waste separation membrane of step i) is preferably a scrap or defective product generated during the process of performing ceramic coating on one side or both sides using a separator fabric using ultrahigh molecular weight polyethylene (UHMWPE).

상기 단계 i)의 전처리 단계는 The pretreatment step of step i) is

i-a) 폐분리막 조각을 오픈(Open) 형태의 밀롤을 통하여 압착시키는 방법, 또는 i-a) A method of compressing a piece of waste separation membrane through an open mill roll, or

i-b) 폐분리막 조각을 압출기에 투입하여 덩어리(Lump) 형태로 제조하는 방법 중 어느 하나를 수행하는 것이 바람직하다.i-b) It is preferable to perform any one of the methods of manufacturing a lump form by putting a piece of waste separation membrane into an extruder.

이때, 상기 i-b)에서 압출기는 Feeding Zone이 개조된 압출기인 것이 바람직하다. At this time, the extruder in i-b) is preferably an extruder with a modified Feeding Zone.

상기 제조 방법에 있어서, 상기 단계 ii)는 초고분자량 폴리에틸렌 및 고함량의 세라믹소재의 혼합물로 단독으로는 가공성 확보가 불가능하기 때문에, 이후 단계인 압출 펠릿화 공정 및 후가공이 가능하도록 가공성을 부여하기 위해 최적화된 분자량과 적절한 함량의 폴리올레핀계 소재, 기타 개질제 및 첨가제와 혼합, 용융하여 고르게 혼련하고 압출하는 것을 통해 용이한 가공과 함께 목적하고자 하는 특성을 부여하기 위한 단계이다. In the above manufacturing method, step ii) is a mixture of ultra-high molecular weight polyethylene and a high content ceramic material, and since it is impossible to secure processability alone, in order to impart workability so that the subsequent steps of extrusion pelletization and post-processing are possible. This is a step to provide the desired properties along with easy processing by mixing, melting and evenly mixing and extruding polyolefin-based materials with an optimized molecular weight and appropriate content, other modifiers and additives.

코팅 분리막에 사용되는 원단의 주요 성분인 초고분자량폴리에틸렌의 고점도로 인하여 단독으로는 용융 압출이 불가하다는 사실과, 또한 코팅 소재로 사용되는 세라믹의 함량이 원단에 사용된 초고분자량폴리에틸렌 100 중량부 대비 20 내지 200 중량부의 매우 높은 함량으로 존재하여 용융 상태에서 흐름성을 매우 저해함으로써 재생을 불가능하게 한다는 사실을 통해, 재생 공정 중, 저점도의 펠릿 또는 분체 형태의 폴리올레핀계 수지를 균일하게 혼합할 경우 용융 점도가 낮아져 가공이 용이하게 할 수 있다. 하지만, 분리막 원단에 사용된 초고분자량 폴리에틸렌의 점도가 매우 높기 때문에 저점도의 폴리올레핀계 수지를 혼합 후 일반적인 압출 가공의 경우 너무 큰 점도 차이로 인하여 서로 균일하게 섞이는 것이 어려워 일반적인 압출 가공이 불가능하기 때문에, 점도가 크게 상이한 초고분자량폴리에틸렌, 폴리올레핀계 수지 및 고함량의 세라믹 복합물을 균일하게 혼합하여 가공성을 개선할 수 있는 하기 두 가지 방안의 용융, 혼련 및 압출 단계를 적용하는 것이 필요하다. The fact that melt extrusion alone is not possible due to the high viscosity of ultra-high molecular weight polyethylene, the main component of the fabric used in the coating separator, and the content of ceramic used as a coating material is compared to 100 parts by weight of ultra-high molecular weight polyethylene used in the fabric. Due to the fact that it is present in a very high content of to 200 parts by weight, which impairs flowability in the molten state, making regeneration impossible, melting when uniformly mixing a polyolefin-based resin in the form of low viscosity pellets or powder during the regeneration process Since the viscosity is lowered, processing can be facilitated. However, since the viscosity of the ultra-high molecular weight polyethylene used for the membrane fabric is very high, in the case of general extrusion processing after mixing a polyolefin-based resin of low viscosity, it is difficult to mix uniformly with each other due to a too large difference in viscosity, so general extrusion processing is impossible. It is necessary to apply the following two methods of melting, kneading, and extrusion steps, which can improve processability by uniformly mixing ultra-high molecular weight polyethylene, polyolefin-based resins and ceramic composites having a high content of different viscosities.

상기 단계 ii)의 용융, 혼련 및 압출 단계는 The melting, kneading and extrusion steps of step ii)

ii-a) 분쇄된 폐분리막 소재를 가압형 니더에 투입하여 1차로 가압 용융시킨 후, 폴리올레핀계 소재, 및 선택적으로 개질제 또는 첨가제 중 어느 하나 이상을 추가로 가압형 니더에 투입하여 가압 용융하여 고르게 혼련한 다음, 압출하는 방법, 또는 ii-a) Put the pulverized waste separation membrane material into a pressurized kneader and first press-melt it, then add a polyolefin-based material, and optionally any one or more of a modifier or additive to a pressurized kneader, and pressurize to melt it evenly. Kneading and then extruding, or

ii-b) 분쇄된 폐분리막 소재, 폴리올레핀계 중합체, 및 선택적으로 개질제 또는 첨가제 중 어느 하나 이상을 혼련한 후, 2축 압출기(Twin Screw Extruder)에 투입하여 용융 압출하는 방법 어느 하나를 수행하는 것이 바람직하다.ii-b) After kneading any one or more of the pulverized waste separation membrane material, a polyolefin-based polymer, and optionally a modifier or additive, it is injected into a twin screw extruder to melt-extrusion. desirable.

상기 ii-a)의 고온 가압 니딩 방법은 50℃ 내지 300℃, 적절하게는 100℃ 내지 250℃, 더 적절하게는 150℃ 내지 200℃의 고온에서 먼저 전처리된 코팅분리막 스크랩을 0.1 내지 0.8MPa, 적절하게는 0.3 내지 0.7MPa, 더욱 적절하게는 0.4 내지 0.6MPa로 5 내지 30분간 가압 용융한 후 후가공에서의 가공성 확보 및 특성 부여를 위해 MI 0.01~100g/10분(190℃, 2.16kg)수준의 저분자량 폴리올레핀계 수지 및 첨가제/개질제를 추가한 후 동일 조건에서 추가로 5내지 30분간 고르게 혼련한 다음, 고르게 혼련된 혼합물 덩어리를 150 내지 250℃의 온도에서 Single 내지 Twin Screw Extruder를 이용하여 원형 다이스를 통해 스트렌드 형태로 압출하는 방법으로 수행될 수 있다.The high-temperature pressurization kneading method of ii-a) is 0.1 to 0.8 MPa of coating separator scrap pretreated first at a high temperature of 50°C to 300°C, preferably 100°C to 250°C, more preferably 150°C to 200°C, Appropriately 0.3 to 0.7 MPa, more suitably 0.4 to 0.6 MPa, after 5 to 30 minutes of pressure melting, MI 0.01 to 100 g/10 minutes (190° C., 2.16 kg) for securing processability and imparting properties in post-processing After adding the low molecular weight polyolefin resin and additives/modifiers, knead evenly for 5 to 30 minutes under the same conditions, and then mix the evenly kneaded mixture mass at a temperature of 150 to 250℃ using a single or twin screw extruder. It can be performed by extruding in a strand form through a die.

상기 ii-b)의 Twin Screw Extruder를 이용한 용융 혼합 방법은 분쇄된 폐분리막 소재와 유동성이 우수한 폴리올레핀계 중합체 및 개질제/첨가제를 건조 상태에서 텀블러 믹서 등의 혼련 장치를 이용하여 1차 상온에서 균일하게 혼련한 후 혼합된 원료를 혼련성을 높인 스크류 구성을 가지는 Twin Screw Extruder에 투입, 압출을 통하여 150내지 250℃, 적절하게는 150 내지 200℃의 온도에서 용융 혼련한 다음, 용융 혼련된 압출물을 원형 홀을 가진 다이스를 통해 스트렌드 형태로 압출하는 방법으로 수행될 수 있다.In the melt mixing method using the Twin Screw Extruder of ii-b), the pulverized waste separation membrane material, the polyolefin-based polymer with excellent fluidity, and the modifier/additive are uniformly mixed at the primary room temperature using a kneading device such as a tumbler mixer. After kneading, the mixed raw material is put into a twin screw extruder having a screw configuration with improved kneading properties, and melt-kneaded at a temperature of 150 to 250°C, preferably 150 to 200°C through extrusion, and then melt-kneaded extrudates. It can be performed by extruding in a strand form through a die having a circular hole.

상기 단계 ii)의 폴리올레핀계 수지는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리메틸펜텐(PMP), 폴리부텐-1(PB-1), 폴리올레핀 엘라스토머(POE), 폴리이소부틸렌(PIB), 에틸렌프로필렌고무(EPR), 에틸렌프로필렌디엔고무(EPDM) 및 이들의 조합으로 이루어진 군으로부터 선택된 어느 하나인 것이 바람직하다.The polyolefin resin of step ii) is polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyolefin elastomer (POE), polyisobutylene (PIB). , Ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), and a combination thereof is preferably any one selected from the group consisting of.

상기 폴리에틸렌(PE)은 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 선형저밀도폴리에틸렌(LLDPE) 및 에틸렌계 공중합체로서 에틸렌 및 C3 내지 C10 알파-올레핀 중 적어도 하나로부터 유도된 공중합체 및 이들의 조합으로 이루어진 군으로부터 선택된 것으로, 용융지수가 0.01 ~ 300g/10분(190℃, 2.16kg), 적절하게는 0.1 ~ 200g/분, 더욱 적절하게는 1 ~ 100g/분인 것이 바람직하다.The polyethylene (PE) is a high-density polyethylene (HDPE), a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE) and an ethylene-based copolymer, a copolymer derived from at least one of ethylene and C3 to C10 alpha-olefins, and combinations thereof As selected from the group consisting of, it is preferred that the melt index is 0.01 to 300 g/10 minutes (190° C., 2.16 kg), preferably 0.1 to 200 g/min, more preferably 1 to 100 g/min.

상기 폴리프로필렌(PP)는 Homo PP, Random PP, Block PP, 아이소탁틱 폴리프로필렌(iPP), 신디오탁틱 폴리프로필렌(sPP), 고용융강도 폴리프로필렌(HMS-PP) 및 프로필렌계 공중합체로서 프로필렌 및 C2 또는 C4 내지 C10 알파-올레핀 중 적어도 하나로부터 유도된 공중합체 및 이들의 조합으로 이루어진 군으로부터 선택된 것으로, 용융지수가 0.01 ~ 300g/10분(230℃, 2.16kg), 적절하게는 0.1 ~ 200g/분, 더욱 적절하게는 1 ~ 100g/분인 것이 바람직하다.The polypropylene (PP) is Homo PP, Random PP, Block PP, isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), high melt strength polypropylene (HMS-PP), and propylene-based copolymer as propylene And a copolymer derived from at least one of C2 or C4 to C10 alpha-olefin and a combination thereof, and a melt index of 0.01 to 300 g/10 minutes (230° C., 2.16 kg), preferably 0.1 to It is preferably 200 g/min, more preferably 1 to 100 g/min.

상기 단계 ii)에서 별도로 특정 목적을 위하여 상기 조성 외 개질제를 0 ~ 50 중량% 및/또는 첨가제 0 ~ 30 중량%를 추가할 수 있다.In step ii), 0 to 50% by weight and/or 0 to 30% by weight of a modifier other than the above composition may be added separately for a specific purpose.

상기 개질제는 폴리에틸렌 왁스(PE Wax), 아탁틱 폴리프로필렌(APP), 아크릴계 공중합체, 무수말레인산계 공중합체, EPR, TAFMER, 또는 Ethylene Octane/Butene Copolymer 등을 포함할 수 있다.The modifier may include polyethylene wax (PE Wax), atactic polypropylene (APP), acrylic copolymer, maleic anhydride copolymer, EPR, TAFMER, or Ethylene Octane/Butene Copolymer.

상기 첨가제는 페놀계 산화방지제, 인계산화방지제, 스테아린산염, 하이드로탈사이트, 안료, 착색제, 충전제(휘스커, 목분, 리그닌, 전분, 천연 및 합성 실리카, 마스네슘 삼수산화물, 알루미늄 삼수산화물, 탄산칼슘, 카올린, 탄산마그네슘, 이산화티타늄, 대전방지제, 난연제, 슬립제, 블록방지 첨가제, 항미생물제, 핵제 등을 포함할 수 있다.The additives include phenolic antioxidants, phosphorus antioxidants, stearates, hydrotalcite, pigments, colorants, fillers (whisker, wood flour, lignin, starch, natural and synthetic silica, magnesium trihydroxide, aluminum trihydroxide, calcium carbonate, Kaolin, magnesium carbonate, titanium dioxide, antistatic agents, flame retardants, slip agents, anti-blocking additives, antimicrobial agents, nucleating agents, and the like may be included.

이때, 복합수지에서 발생할 수 있는 냄새(코팅분리막 내 존재하는 Binder 성분)를 제거하기 위해 Zeolite 지지체에 VOC 제거물질을 담지한 제품을 0.01 내지 10 중량부를 별도로 투입하는 것도 가능하다.At this time, it is also possible to separately add 0.01 to 10 parts by weight of the product carrying the VOC removal material on the Zeolite support in order to remove the odor (binder component present in the coating separator) that may occur in the composite resin.

상기 제조 방법에 있어서, 상기 단계 iii)의 펠릿 가공 단계는 스트랜드 형태로 압출된 압출물을 공기 중 또는 냉각수를 이용하여 냉각 고화한 후 회전 커터를 이용하여 펠릿 형태로 제조하는 단계이다.In the above manufacturing method, the pellet processing step of step iii) is a step of cooling and solidifying the extruded product in the form of strands in air or using cooling water, and then producing a pellet form using a rotary cutter.

또한, 본 발명은 In addition, the present invention

단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막으로부터 분쇄 및 부피를 작게 압축 분쇄로 전처리된 폐분리막 소재 10 ~ 99 중량%; 및, 폴리올레핀계 수지 1 ~ 90 중량%;를 포함하는, 복합수지 조성물을 제공한다.10 to 99% by weight of a waste separator material pretreated by crushing and compacting the volume from the waste separator for secondary batteries coated with ceramic particles on one or both sides; And, 1 to 90% by weight of a polyolefin-based resin; it provides a composite resin composition containing.

상기 복합수지 조성물은 상기 본 발명에 따른 제조방법으로 제조되는 것이 바람직하다.It is preferable that the composite resin composition is prepared by the method according to the present invention.

상기 복합수지 조성물은 2종 이상의 혼합물로 제조된 것으로 용융지수는 0.05 ~ 100g/10분(190℃, 2.16kg) 수준인 것이 바람직하다.The composite resin composition is made of a mixture of two or more, and the melt index is preferably 0.05 to 100 g/10 minutes (190° C., 2.16 kg).

상기 폐분리막은 초고분자량 폴리에틸렌(ultrahigh molecular weight polyethylene, UHMWPE)을 사용한 분리막 원단을 이용한 단면 또는 양면에 세라믹 코팅을 진행하는 공정 중 발생하는 스크랩 또는 불량품인 것이 바람직하고, 상기 스크랩 또는 불량품은 0.001 ~ 10g/10분(190℃, 2.16kg) 수준의 용융지수를 가지는 것이 바람직하다.The waste separation membrane is preferably a scrap or defective product generated during the process of ceramic coating on one side or both sides using a separation membrane fabric made of ultrahigh molecular weight polyethylene (UHMWPE), and the scrap or defective product is 0.001 to 10 g It is desirable to have a melt index of /10 minutes (190°C, 2.16kg).

상기 폴리올레핀계 수지는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리메틸펜텐(PMP), 폴리부텐-1(PB-1), 폴리올레핀 엘라스토머(POE), 폴리이소부틸렌(PIB), 에틸렌프로필렌고무(EPR), 에틸렌프로필렌디엔고무(EPDM) 및 이들의 조합으로 이루어진 군으로부터 선택된 어느 하나인 것이 바람직하다.The polyolefin resin is polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyolefin elastomer (POE), polyisobutylene (PIB), ethylene propylene rubber. It is preferably any one selected from the group consisting of (EPR), ethylene propylene diene rubber (EPDM), and combinations thereof.

상기 폴리에틸렌(PE)은 고밀도폴리에틸렌(HDPE), 저밀도폴리에틸렌(LDPE), 선형저밀도폴리에틸렌(LLDPE) 및 에틸렌계 공중합체로서 에틸렌 및 C3 내지 C10 알파-올레핀 중 적어도 하나로부터 유도된 공중합체 및 이들의 조합으로 이루어진 군으로부터 선택된 것으로, 용융지수가 0.01 ~ 300g/10분(190℃, 2.16kg), 적절하게는 0.1 ~ 200g/분, 더욱 적절하게는 1 ~ 100g/분인 것이 바람직하다.The polyethylene (PE) is a high-density polyethylene (HDPE), a low-density polyethylene (LDPE), a linear low-density polyethylene (LLDPE) and an ethylene-based copolymer, a copolymer derived from at least one of ethylene and C3 to C10 alpha-olefins, and combinations thereof As selected from the group consisting of, it is preferred that the melt index is 0.01 to 300 g/10 minutes (190° C., 2.16 kg), preferably 0.1 to 200 g/min, more preferably 1 to 100 g/min.

상기 폴리프로필렌(PP)는 Homo PP, Random PP, Block PP, 아이소탁틱 폴리프로필렌(iPP), 신디오탁틱 폴리프로필렌(sPP), 고용융강도 폴리프로필렌(HMS-PP) 및 프로필렌계 공중합체로서 프로필렌 및 C2 또는 C4 내지 C10 알파-올레핀 중 적어도 하나로부터 유도된 공중합체 및 이들의 조합으로 이루어진 군으로부터 선택된 것으로, 용융지수가 0.01 ~ 300g/10분(230℃, 2.16kg), 적절하게는 0.1 ~ 200g/분, 더욱 적절하게는 1 ~ 100g/분인 것이 바람직하다.The polypropylene (PP) is Homo PP, Random PP, Block PP, isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), high melt strength polypropylene (HMS-PP), and propylene-based copolymer as propylene And a copolymer derived from at least one of C2 or C4 to C10 alpha-olefin and a combination thereof, and a melt index of 0.01 to 300 g/10 minutes (230° C., 2.16 kg), preferably 0.1 to It is preferably 200 g/min, more preferably 1 to 100 g/min.

상기 복합수지 조성물은 상기 조성 외 개질제를 0 ~ 50 중량% 및/또는 첨가제 0 ~ 30 중량%를 추가할 수 있다.The composite resin composition may add 0 to 50% by weight and/or 0 to 30% by weight of a modifier other than the above composition.

상기 개질제는 폴리에틸렌 왁스(PE Wax), 아탁틱 폴리프로필렌(APP), 아크릴계 공중합체, 무수말레인산계 공중합체, EPR, TAFMER, 또는 Ethylene Octane/Butene Copolymer 등을 포함할 수 있다.The modifier may include polyethylene wax (PE Wax), atactic polypropylene (APP), acrylic copolymer, maleic anhydride copolymer, EPR, TAFMER, or Ethylene Octane/Butene Copolymer.

상기 첨가제는 페놀계 산화방지제, 인계산화방지제, 스테아린산염, 하이드로탈사이트, 안료, 착색제, 충전제(휘스커, 목분, 리그닌, 전분, 천연 및 합성 실리카, 마스네슘 삼수산화물, 알루미늄 삼수산화물, 탄산칼슘, 카올린, 탄산마그네슘, 이산화티타늄, 대전방지제, 난연제, 슬립제, 블록방지 첨가제, 항미생물제, 핵제 등을 포함할 수 있다.The additives include phenolic antioxidants, phosphorus antioxidants, stearates, hydrotalcite, pigments, colorants, fillers (whisker, wood flour, lignin, starch, natural and synthetic silica, magnesium trihydroxide, aluminum trihydroxide, calcium carbonate, Kaolin, magnesium carbonate, titanium dioxide, antistatic agents, flame retardants, slip agents, anti-blocking additives, antimicrobial agents, nucleating agents, and the like may be included.

이때, 복합수지에서 발생할 수 있는 냄새(코팅분리막 내 존재하는 Binder 성분)를 제거하기 위해 Zeolite 지지체에 VOC 제거물질을 담지한 제품을 0.01 내지 10 중량부를 별도로 투입하는 것도 가능하다.At this time, it is also possible to separately add 0.01 to 10 parts by weight of the product carrying the VOC removal material on the Zeolite support in order to remove the odor (binder component present in the coating separator) that may occur in the composite resin.

또한, 본 발명은 In addition, the present invention

상기 본 발명에 따른 복합수지 조성물을 포함하는 파이프, 기어 또는 인조잔디를 제공한다.It provides a pipe, gear or artificial turf comprising the composite resin composition according to the present invention.

아울러, 본 발명은 In addition, the present invention

상기 본 발명에 따른 복합수지 조성물을 포함하는 자동차 내/외장재, 생활용품, 산업용 자재 또는 건축용 자재를 제공한다. It provides interior/exterior materials for automobiles, household goods, industrial materials, or construction materials comprising the composite resin composition according to the present invention.

본 발명에 따른 복합수지 조성물은 원가측면에서 매우 경쟁력이 우수하며, 양호한 가공성 및 물성으로 파이프, 기어, 인조잔디에 최적으로 적용할 수 있으나, 본 발명의 용도는 상기 기술된 것에 한정되는 것은 아니며, 자동차 내/외장재, 생활용품, 산업용, 건축용 등 여러 방면에서 다양한 용도로 적용 가능하다. The composite resin composition according to the present invention is very competitive in terms of cost, and can be optimally applied to pipes, gears, and artificial turf with good processability and physical properties, but the use of the present invention is not limited to those described above, It can be applied for various purposes in various fields such as interior/exterior materials for automobiles, household goods, industrial use, and construction.

본 발명에 따른 복합수지 조성물은 폴리아세탈수지의 물성과 비교할 때 상대적으로 낮은 용융온도에 의한 내열성 측면에서 다소 떨어지지만, 양호한 기계적 강도, 매우 탁월한 충격강도, 낮은 마찰계수, 낮은 성형수축율 및 흡수율, 우수한 화학적 성질을 나타냄을 확인할 수 있으므로, 폴리아세탈이 적용 되는 자동차 부품, 기어, 베어링 등 다양한 용도 중 내열성이 크게 요구되지 않는 경우 대체하여 적용 가능하다.The composite resin composition according to the present invention is somewhat inferior in terms of heat resistance due to a relatively low melting temperature compared to the physical properties of the polyacetal resin, but has good mechanical strength, very excellent impact strength, low coefficient of friction, low molding shrinkage and water absorption, and excellent Since it can be confirmed that it shows chemical properties, it can be applied as a substitute if heat resistance is not required among various uses such as automobile parts, gears, bearings, etc. to which polyacetal is applied.

이하, 본 발명의 이해를 돕기 위하여 실시예를 들어 상세하게 설명하기로 한다. 다만, 하기의 실시예는 본 발명의 내용을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to aid understanding of the present invention. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

<< 실시예Example 1> 1>

후공정을 위한 전처리 공정으로 분쇄된 분리막 스크랩 작은 조각을 Open 형태의 밀롤을 통하여 압축하여 부피를 감소시킨 후 크러셔에 넣어 작은 조각으로 분쇄하였다. As a pretreatment process for the post-process, small pieces of the pulverized separator scrap were compressed through an open type mill roll to reduce the volume, and then put into a crusher and crushed into small pieces.

크러셔에서 분쇄된 작은 조각의 원료를 가압 니더에 넣고 온도 180℃에서 0.55MPa의 가압 하 압축 니딩 작업을 5분간 실시하여 용융반죽 형태로 제조하였다.A small piece of raw material crushed in a crusher was put into a pressure kneader, and compression kneading was performed for 5 minutes under pressure of 0.55 MPa at a temperature of 180° C. to prepare a molten dough form.

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 30 중량부 대비 MI 0.035, Density 0.957의 고밀도폴리에틸렌 수지1(대한유화 F600) 펠렛 60 중량부와 MI 0.85, Density 0.956의 고밀도폴리에틸렌 수지2(대한유화 E308) 10 중량부를 가압 니더에 추가로 투입한 후 온도 200℃에서 0.55MPa의 가압 하 압축 니딩 작업을 추가로 20분간 실시하여 혼합물 덩어리를 제조하였다.High-density polyethylene resin 1 (Daehan Emulsion F600) pellet 60 parts by weight and 60 parts by weight of MI 0.85, density 0.956 high density polyethylene resin 2 (Daehan Emulsion) compared to 30 parts by weight of melt-kneaded coating separator scrap in the form of melt dough E308) 10 parts by weight of the pressure kneader was additionally added, and a compression kneading operation under pressure of 0.55 MPa at a temperature of 200° C. was performed for an additional 20 minutes to prepare a mixture mass.

혼합물 덩어리는 L/D 40, 40Ø 동방향 Twin Screw Extruder를 이용하여 실린더 온도 200℃에서 압출하여 스트렌드를 형성시키고 냉각수가 담겨있는 수조에서 냉각 고화시킨 후 회전 커터를 이용하여 길이 5 mm의 펠릿으로 제조하였다.The mixture mass is extruded at a cylinder temperature of 200℃ using an L/D 40, 40Ø twin screw extruder to form a strand, cooled and solidified in a water bath containing cooling water, and then into pellets with a length of 5 mm using a rotary cutter. Was prepared.

팰렛화된 수지 조성물을 150톤 형체력의 사출성형기로 시편을 제조하였다.Specimens were prepared from the pelletized resin composition by an injection molding machine having a clamping force of 150 tons.

<< 실시예Example 2> 2>

후공정을 위한 전처리 공정으로 분쇄된 분리막 스크랩 작은 조각을 Feeding Zone이 개조된 압출기에 투입하여 200℃에서 용융시켜 Lump 형태로 제조한 후 냉각시키고, 냉각된 덩어리를 크러셔에 넣고 작은 조각으로 분쇄한 것 외에, 이후 과정은 상기 <실시예 1>과 동일하게 수행하였다.As a pretreatment process for post-processing, small pieces of pulverized separator scrap are put into an extruder with a modified Feeding Zone, melted at 200°C, manufactured in a lump shape, cooled, and then cooled, put in a crusher, and crushed into small pieces. In addition, the subsequent process was performed in the same manner as in <Example 1>.

<< 실시예Example 3> 3>

후공정을 위한 전처리 공정은 상기 <실시예 1>과 동일한 방법으로 작은 조각으로 분쇄하였다.The pretreatment process for the post process was pulverized into small pieces in the same manner as in <Example 1>.

분쇄된 코팅분리막 스크랩 30 중량부 대비 MI 0.035, Density 0.957의 고 100 중량의 고밀도폴리에틸렌 수지1(대한유화 F600) 펠렛 60 중량부와 MI 0.85, Density 0.956의 고밀도폴리에틸렌 수지2(대한유화 E308) 10 중량부를 범버리믹서에 넣고 상온에서 40 rpm으로 10분간 교반하여 균일하게 혼합하였다.Compared to 30 parts by weight of pulverized coating separator scrap, 60 parts by weight of high-density polyethylene resin 1 (Daehan Emulsification F600) pellet with MI 0.035, density 0.957 and 60 parts by weight of high-density polyethylene resin 2 (Daehan Emulsion E308) with MI 0.85 and Density 0.956 10 parts by weight The part was put in a Bumbury mixer, and stirred for 10 minutes at 40 rpm at room temperature to uniformly mix.

혼합물을 L/D 40, 40Ø 동방향 Twin Screw Extruder의 Hopper로 투입한 후 실린더 온도 200℃로 압출하여 스트렌드를 형성시키고 냉각수가 담겨있는 수조에서 냉각 고화시킨 후 회전 커터를 이용하여 길이 5 mm의 펠릿으로 제조한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.After inserting the mixture into the hopper of the L/D 40, 40Ø twin screw extruder in the same direction, extruding it at a cylinder temperature of 200℃ to form a strand, cooling and solidifying it in a water tank containing cooling water, and then using a rotary cutter In addition to being prepared as a pellet, it was carried out in the same manner as in <Example 1>.

<< 실시예Example 4> 4>

후공정을 위한 전처리 공정은 상기 <실시예 2?와 동일하게 작은 조각으로 분쇄하였고, 이후 과정은 상기 <실시예 3>과 동일하게 수행하였다.The pretreatment process for the post-process was pulverized into small pieces in the same manner as in <Example 2?>, and the subsequent process was performed in the same manner as in <Example 3>.

<< 실시예Example 5> 5>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 70 중량부 대비 MI 0.85, Density 0.956의 고밀도폴리에틸렌 수지3(대한유화 M690) 펠렛 30 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.In addition to the addition of 30 parts by weight of high-density polyethylene resin 3 (Daehan Emulsification M690) pellets with MI 0.85 and density 0.956 compared to 70 parts by weight of melt-kneaded coating separator scrap that is put into a pressure kneader and uniformly mixed, the < It was carried out in the same manner as in Example 1>.

<< 실시예Example 6> 6>

상기 <실시예 2>에서 제조된 복합수지 조성물 펠렛 30 중량부와 고밀도폴리에틸렌1 70 중량부를 드라이블렌딩을 통해 균일 혼합한 후 150톤 형체력의 사출성형기로 시편을 제조한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.In addition to uniformly mixing 30 parts by weight of the composite resin composition pellets prepared in <Example 2> with 70 parts by weight of high-density polyethylene 1 through dry blending, a specimen was prepared by an injection molding machine having a clamping force of 150 tons, and the <Example 1 Performed in the same manner as >.

<< 실시예Example 7> 7>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 30 중량부 대비 MI 22(190℃), Density 0.914의 선형저밀도폴리에틸렌수지(롯데케미칼 UJ900) 펠렛 70 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.Addition of 70 parts by weight of linear low-density polyethylene resin (Lotte Chemical UJ900) pellets with MI 22 (190℃) and density 0.914 compared to 30 parts by weight of molten-kneaded coating separator scrap into a pressurized kneader and uniformly mixed In addition, it was carried out in the same manner as in <Example 1>.

<< 실시예Example 8> 8>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 30 중량부 대비 MI 22(190℃), Density 0.914의 저밀도폴리에틸렌수지(롯데케미칼 XJ700) 펠렛 70 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.In addition to the addition of 70 parts by weight of low-density polyethylene resin (Lotte Chemical XJ700) pellets of MI 22 (190℃) and density 0.914 compared to 30 parts by weight of melt-kneaded coating separator scrap that is put into a pressurized kneader and uniformly mixed , It was carried out in the same manner as in <Example 1>.

<< 실시예Example 9> 9>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 20 중량부 대비 MI 45(230℃), Density 0.91의 폴리프로필렌수지 Homo PP (대한유화 HJ4045) 펠렛 70 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.Addition of 70 parts by weight of polypropylene resin Homo PP (Daehan Emulsion HJ4045) pellets with MI 45 (230℃) and density 0.91 compared to 20 parts by weight of melt-kneaded coating separator scrap that is put into a pressurized kneader and uniformly mixed In addition, it was carried out in the same manner as in <Example 1>.

<< 실시예Example 10> 10>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 20 중량부 대비 MI 28(230℃), Density 0.91의 폴리프로필렌수지 Random PP (대한유화 RJ6428) 펠렛 70 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.Addition of 70 parts by weight of polypropylene resin Random PP (Daehan Emulsion RJ6428) pellets with MI 28 (230℃) and density 0.91 compared to 20 parts by weight of melt-kneaded coating separation membrane scrap into a pressurized kneader and uniformly mixed In addition, it was carried out in the same manner as in <Example 1>.

<< 실시예Example 11> 11>

가압 니더에 투입되어 용융반죽 형태화된 코팅분리막 스크랩 20 중량부 대비 MI 30(230℃), Density 0.907의 폴리프로필렌수지(대한유화 SB9230) 펠렛 70 중량부를 가압 니더에 추가로 넣고 균일 혼합한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.In addition to the addition of 70 parts by weight of polypropylene resin (Daehan Emulsion SB9230) pellets of MI 30 (230°C) and density 0.907 compared to 20 parts by weight of melt-kneaded coating separation membrane scrap added to the pressurized kneader and uniformly mixing , Was carried out in the same manner as in <Example 1>.

<< 비교예Comparative example 1> 1>

분쇄된 코팅분리막 스크랩 100 중량부만으로 가압 니딩한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.Except for pressing and kneading only 100 parts by weight of the pulverized coating separator scrap, it was carried out in the same manner as in <Example 1>.

<< 비교예Comparative example 2> 2>

가압 니딩 공정 진행 시 온도를 상온에서 작업한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.When the pressure kneading process proceeds, the temperature was performed in the same manner as in <Example 1>, except that the temperature was operated at room temperature.

<< 비교예Comparative example 3> 3>

후공정을 위한 전처리 공정이 없이 분리막 스크랩 작은 조각을 그대로 이용한 것 외에, 상기 <실시예 3>과 동일하게 수행하였다.Aside from using a small piece of separator scrap as it is without a pretreatment process for the post-process, it was carried out in the same manner as in <Example 3>.

<< 비교예Comparative example 4> 4>

고밀도폴리에틸렌 수지1(대한유화 F600) 펠렛 100 중량부를 직접 150톤 형체력의 사출성형기로 시편을 제조한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.A sample was prepared in the same manner as in <Example 1>, except that 100 parts by weight of high-density polyethylene resin 1 (Daehan Emulsion F600) pellets were directly prepared by an injection molding machine having a clamping force of 150 tons.

<< 비교예Comparative example 5> 5>

폴리프로필렌수지(대한유화 SB9230) 펠렛 100 중량부를 직접 150톤 형체력의 사출성형기로 시편을 제조한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.A sample was prepared in the same manner as in <Example 1>, except that 100 parts by weight of polypropylene resin (Daehan Petrochemical SB9230) pellets were directly prepared by an injection molding machine having a clamping force of 150 tons.

<< 비교예Comparative example 6> 6>

폴리아세탈수지(한국엔지니어링플라스틱 KEPITAL F20-30) 펠렛 100 중량부를 직접 150톤 형체력의 사출성형기로 시편을 제조한 것 외에, 상기 <실시예 1>과 동일하게 수행하였다.A sample was prepared in the same manner as in <Example 1>, except that 100 parts by weight of polyacetal resin (Korea Engineering Plastics KEPITAL F20-30) pellets were directly prepared by an injection molding machine having a clamping force of 150 tons.

<< 실험예Experimental example 1> 1>

상기 <실시예 1 ~ 11> 및 <비교예 1 ~ 6>에서 제조된 시편에 대해, 시편상 세라믹입자의 분산성 비교를 위해 사출물의 표면상태를 비교하였고, 물성은 시편 제조 후 23℃, 50%의 항온항습하에 48hr Aging후 측정하였다. For the specimens prepared in the <Examples 1 to 11> and <Comparative Examples 1 to 6>, the surface conditions of the extruded product were compared to compare the dispersibility of the ceramic particles on the specimen, and the physical properties were 23°C and 50 It was measured after 48 hours of aging under constant temperature and humidity of %.

물성측정방법은 ASTM 규격에서 규정한 시험방법에 의거하였다. 구체적으로, 용융지수(Melt Index, MI)는 ASTM D1238에 의거하여 190℃, 2.16 kg 하중 하에 측정하였고, 밀도(Density)는 ASTM D1505 방법에 따라 측정하였으며, 굴곡탄성률(Flexural Modulus)은 ASTM D790 방법에 따라 측정하였고, 인장강도(Tensile Strength) 및 신율(Elongation)은 ASTM D638 방법에 따라 측정하였으며, 경도(Hardness)는 ASTM D785 방법에 따라 측정하였다.The physical property measurement method was based on the test method specified in the ASTM standard. Specifically, the melt index (MI) was measured under a load of 190°C and 2.16 kg according to ASTM D1238, and the density was measured according to the ASTM D1505 method, and the flexural modulus was measured by the ASTM D790 method. It was measured according to, and tensile strength (Tensile Strength) and elongation (Elongation) were measured according to the ASTM D638 method, and hardness (Hardness) was measured according to the ASTM D785 method.

시료sample 고밀도
폴리에틸렌 1
(HDPE)
High density
Polyethylene 1
(HDPE)
고밀도
폴리에틸렌 2
(HDPE)
High density
Polyethylene 2
(HDPE)
고밀도
폴리에틸렌 3
(HDPE)
High density
Polyethylene 3
(HDPE)
선형저밀도
폴리에틸렌
(LLDPE)
Linear low density
Polyethylene
(LLDPE)
저밀도
폴리에틸렌
(LDPE)
Low density
Polyethylene
(LDPE)
폴리프로필렌
(Homo PP)
Polypropylene
(Homo PP)
폴리프로필렌
(Random PP)
Polypropylene
(Random PP)
폴리프로필렌
(Block PP)
Polypropylene
(Block PP)
폴리아세탈
(POM)
Polyacetal
(POM)
용융지수 (2.16kg)
(g/10min)
Melt Index (2.16kg)
(g/10min)
0.035
(190℃)
0.035
(190℃)
0.85
(190℃)
0.85
(190℃)
12
(190℃)
12
(190℃)
22
(190℃)
22
(190℃)
22
(190℃)
22
(190℃)
45
(230℃)
45
(230℃)
28
(230℃)
28
(230℃)
30
(230℃)
30
(230℃)
9
(190℃)
9
(190℃)
밀도
(g/cm3)
density
(g/cm 3 )
0.9570.957 0.9560.956 0.9620.962 0.9140.914 0.9140.914 0.910.91 0.910.91 0.910.91 1.411.41
굴곡탄성율(kgf/cm2)Flexural modulus (kgf/cm 2 ) 10,00010,000 9,0009,000 12,00012,000 2,3502,350 950950 21,00021,000 12,00012,000 15,00015,000 25,50025,500 충격강도
(kgf.cm/cm, 23℃)
Impact strength
(kgf.cm/cm, 23℃)
55 >50>50 >50>50 NBNB NBNB 33 66 1010 6.56.5
인장강도
(kgf/cm2)
The tensile strength
(kgf/cm 2 )
280280 250250 400400 7575 9090 400400 330330 290290 650650
열변형온도(℃)Heat deflection temperature (℃) 7474 6969 6262 -- -- 140140 -- 131131 100100 제품명 product name 대한유화(주)
F600
Korea Petrochemical Co., Ltd.
F600
대한유화(주)
E308
Korea Petrochemical Co., Ltd.
E308
대한유화(주)
M690
Korea Petrochemical Co., Ltd.
M690
롯데케미칼
UJ900
Lotte chemical
UJ900
롯데케미칼
XJ700
Lotte chemical
XJ700
대한유화(주)
HJ4045
Korea Petrochemical Co., Ltd.
HJ4045
대한유화(주)
RJ6428
Korea Petrochemical Co., Ltd.
RJ6428
대한유화(주)
SB9230
Korea Petrochemical Co., Ltd.
SB9230
KEP
K20-03
KEP
K20-03

Figure 112019050552955-pat00001
Figure 112019050552955-pat00001

O : 작업성 양호, △ : 작업성이 떨어져 연속 작업 불가, X : 작업성이 매우 불량하여 시편제조 불가O: Good workability, △: Unable to continuous work due to poor workability, X: Unable to manufacture specimen due to very poor workability

상기 표 2의 물성 결과에 나타난 바와 같이, 코팅분리막 스크랩을 후가공이 용이하도록 전처리를 통해 작은 조각으로 제조한 후 적절한 분자량의 폴리에틸렌 및 폴리프로필렌과 가압 니딩 방식 또는 상온 교반 후 Twin Screw Extruder를 통한 압출 시 양호한 가공성을 확보할 수 있으며, 펠릿화를 함으로써 후속 가공 공정에서 용이한 사용이 가능함을 확인하였다.As shown in the physical property results in Table 2 above, the coating separator scrap is prepared into small pieces through pretreatment to facilitate post-processing, and then extruded through a twin screw extruder after stirring with appropriate molecular weight polyethylene and polypropylene and pressure kneading method or room temperature stirring. It was confirmed that good processability can be secured, and easy use in subsequent processing steps is possible by pelletizing.

Figure 112020055367114-pat00003

내약품성은 ◎>○>△>X의 순으로 저하됨을 뜻함
Figure 112020055367114-pat00003

Means that chemical resistance decreases in the order of ◎>○>△>X

삭제delete

내마모성은 Sand Slurry 방법으로 Weight Loss를 측정하며, 실시예5=100 기준(상대값), 수치가 낮을수록 우수Wear resistance is measured by the Sand Slurry method, weight loss, Example 5 = 100 criteria (relative value), the lower the value, the better

상기 표 3의 물성 결과에 나타난 바와 같이, 코팅분리막 스크랩을 이용하여 제조한 <실시예 6> 조성의 복합수지는 폴리아세탈수지의 물성과 비교할 때 상대적으로 낮은 용융온도에 의한 내열성 측면에서 다소 떨어지지만, 양호한 기계적 강도, 매우 탁월한 충격강도, 낮은 마찰계수, 낮은 성형 수축율 및 흡수율, 우수한 화학적 성질을 나타냄을 확인할 수 있었다.As shown in the physical property results of Table 3, the composite resin of the composition of <Example 6> prepared using the coating separator scrap is slightly inferior in terms of heat resistance due to a relatively low melting temperature compared to the physical properties of the polyacetal resin. , Good mechanical strength, very excellent impact strength, low coefficient of friction, low molding shrinkage and water absorption, and excellent chemical properties.

엔지니어링플라스틱으로 많이 적용되고 있는 폴리아세탈 수지의 경우 인장강도, 충격강도, 내마모성이 뛰어나고 마찰 저항이 적으며 내열성이 우수한 특징으로 자동차 부품, 기어, 베어링 등 다양한 용도에 적용되고 있으나, 높은 원료 가격과 포름알데히드의 자극성 냄새 발현문제로 인해 그 적용에 제약이 있는데, 본 발명에서 제시된 새로운 복합수지 조성물의 경우, 폐분리막을 활용함으로써 원가를 낮추고 포름알데히드의 자극성 냄새 발현이 없으며, 우수한 인장강도, 탁월한 충격강도를 가지고 있어 상대적으로 낮은 내열성으로 인해 내열성이 크게 요구되지 않는 용도의 경우 폴리아세탈을 대체할 수 있는 충분한 가능성을 제공한다.Polyacetal resin, which is widely applied as engineering plastic, has excellent tensile strength, impact strength, abrasion resistance, low friction resistance, and excellent heat resistance, so it is applied to various uses such as automobile parts, gears, bearings, etc., but high raw material price and form The application of the new composite resin composition presented in the present invention is limited due to the occurrence of irritating odor of aldehyde.In the case of the novel composite resin composition presented in the present invention, the cost is lowered by using a waste separator, and there is no irritating odor of formaldehyde. Because of its relatively low heat resistance, it provides sufficient possibility to replace polyacetal for applications where heat resistance is not required.

Claims (12)

i) 단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막을 분쇄한 후 부피를 작게 압축 분쇄하는 전처리 단계;
ii) 전처리된 폐분리막 소재를 폴리올레핀계 수지, 개질제 및 첨가제와 혼합한 후, 용융, 혼련 및 압출하는 단계; 및
iii) 압출물을 펠릿 형태로 가공하는 단계;를 포함하고,
여기서,
상기 단계 i)의 전처리 단계는
i-a) 폐분리막 조각을 오픈(Open) 형태의 밀롤을 통하여 압착시키는 방법, 또는
i-b) 폐분리막 조각을 압출기에 투입하여 덩어리(Lump) 형태로 제조하는 방법 중 어느 하나를 수행하고,
상기 단계 ii)의 폴리올레핀계 수지는 폴리에틸렌(PE), 폴리프로필렌(PP), 폴리메틸펜텐(PMP), 폴리부텐-1(PB-1), 폴리올레핀 엘라스토머(POE), 폴리이소부틸렌(PIB), 에틸렌프로필렌고무(EPR), 에틸렌프로필렌디엔고무(EPDM) 및 이들의 조합으로 이루어진 군으로부터 선택된 어느 하나이고, 0.01 ~ 300g/10분(190 ~ 230℃, 2.16kg) 수준의 용융지수를 가지고,
상기 단계 ii)의 용융, 혼련 및 압출 단계는
분쇄된 폐분리막 소재를 가압형 니더에 투입하여 1차로 가압 용융시킨 후, 폴리올레핀계 수지, 개질제 및 첨가제를 가압형 니더에 투입하여 가압 용융하여 고르게 혼련한 다음, 압출하는 방법으로 수행하는 것을 특징으로 하는,
세라믹 입자가 코팅된 이차전지용 폐분리막 재생에 의한 복합수지 펠릿의 제조 방법.
i) a pretreatment step of pulverizing the waste separator for secondary batteries coated with ceramic particles on one or both sides and then compressing and pulverizing the volume to a small size;
ii) mixing the pretreated waste separation membrane material with a polyolefin-based resin, a modifier and an additive, and then melting, kneading and extruding; And
iii) processing the extrudate into a pellet form; including,
here,
The pretreatment step of step i) is
ia) A method of compressing the waste separation membrane piece through an open mill roll, or
ib) Injecting a piece of waste separation membrane into an extruder to perform any one of the methods of manufacturing a lump form,
The polyolefin resin of step ii) is polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyolefin elastomer (POE), polyisobutylene (PIB). , Ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), and any one selected from the group consisting of a combination thereof, and has a melt index of 0.01 to 300 g/10 minutes (190 to 230°C, 2.16 kg),
The melting, kneading and extrusion steps of step ii)
The pulverized waste separation membrane material is put into a pressurized kneader and firstly melted under pressure, and then polyolefin-based resin, modifier and additives are put into a pressurized kneader, melted under pressure, and then kneaded evenly, and then extruded. doing,
Method for producing composite resin pellets by recycling a waste separator for secondary batteries coated with ceramic particles.
청구항 제1항에 있어서,
상기 단계 i)의 폐분리막은 초고분자량 폴리에틸렌(ultrahigh molecular weight polyethylene, UHMWPE)을 사용한 분리막 원단을 이용한 단면 또는 양면에 세라믹 코팅을 진행하는 공정 중 발생하는 스크랩 또는 불량품인 것을 특징으로 하는 복합수지 펠릿의 제조 방법.
The method of claim 1,
The waste separator of step i) is a scrap or defective product generated during the process of ceramic coating on one side or both sides using a separator fabric made of ultrahigh molecular weight polyethylene (UHMWPE). Manufacturing method.
삭제delete 삭제delete 삭제delete 청구항 제1항에 있어서,
상기 단계 iii)의 펠릿 가공 단계는
스트랜드 형태로 압출된 압출물을 공기 중 또는 냉각수를 이용하여 냉각 고화한 후 회전 커터를 이용하여 펠릿 형태로 제조하는 것을 특징으로 하는 복합수지 펠릿의 제조 방법.
The method of claim 1,
The pellet processing step of step iii)
A method for producing composite resin pellets, characterized in that the extruded product in the form of strands is cooled and solidified in air or using cooling water, and then made into pellets using a rotary cutter.
단면 또는 양면에 세라믹 입자가 코팅된 이차전지용 폐분리막으로부터 분쇄 및 부피를 작게 압축 분쇄로 전처리된 폐분리막 소재 10 ~ 99 중량%; 및
폴리올레핀계 수지 1 ~ 90 중량%를 포함하는 복합수지 펠릿으로서,
여기서,
상기 전처리된 폐분리막 소재는
i-a) 폐분리막 조각을 오픈(Open) 형태의 밀롤을 통하여 압착시키는 방법, 또는
i-b) 폐분리막 조각을 압출기에 투입하여 덩어리(Lump) 형태로 제조하는 방법 중 어느 하나로 수행된 것이고,
상기 폴리올레핀계 수지는
폴리에틸렌(PE), 폴리프로필렌(PP), 폴리메틸펜텐(PMP), 폴리부텐-1(PB-1), 폴리올레핀 엘라스토머(POE), 폴리이소부틸렌(PIB), 에틸렌프로필렌고무(EPR), 에틸렌프로필렌디엔고무(EPDM) 및 이들의 조합으로 이루어진 군으로부터 선택된 어느 하나이고, 0.01 ~ 300g/10분(190 ~ 230℃, 2.16kg) 수준의 용융지수를 가지고,
상기 복합수지 펠릿은,
분쇄된 폐분리막 소재를 가압형 니더에 투입하여 1차로 가압 용융시킨 후, 폴리올레핀계 수지, 개질제 및 첨가제를 가압형 니더에 투입하여 가압 용융하여 고르게 혼련한 다음, 압출하여 제조된 것을 특징으로 하는,
복합수지 펠릿.
10 to 99% by weight of a waste separator material pretreated by crushing and compacting the volume from the waste separator for secondary batteries coated with ceramic particles on one or both sides; And
A composite resin pellet containing 1 to 90% by weight of a polyolefin resin,
here,
The pretreated waste separation membrane material
ia) A method of compressing the waste separation membrane piece through an open mill roll, or
ib) It is carried out in any one of the methods of manufacturing a lump form by putting a piece of waste separation membrane into an extruder,
The polyolefin resin is
Polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polybutene-1 (PB-1), polyolefin elastomer (POE), polyisobutylene (PIB), ethylene propylene rubber (EPR), ethylene It is any one selected from the group consisting of propylene diene rubber (EPDM) and a combination thereof, and has a melt index of 0.01 to 300 g/10 minutes (190 to 230°C, 2.16 kg),
The composite resin pellet,
The pulverized waste separation membrane material is put into a pressurized kneader and firstly melted under pressure, and then polyolefin-based resin, modifier and additives are put into a pressurized kneader, melted under pressure, and evenly kneaded, and then extruded.
Composite resin pellets.
청구항 제7항에 있어서,
상기 폐분리막은 초고분자량 폴리에틸렌(ultrahigh molecular weight polyethylene, UHMWPE)을 사용한 분리막 원단을 이용한 단면 또는 양면에 세라믹 코팅을 진행하는 공정 중 발생하는 스크랩 또는 불량품이고, 0.001 ~ 10g/10분(190℃, 2.16kg) 수준의 용융지수를 가지는 것을 특징으로 하는 복합수지 펠릿.
The method of claim 7,
The waste separator is a scrap or defective product generated during the process of ceramic coating on one side or both sides using a separator fabric made of ultrahigh molecular weight polyethylene (UHMWPE), and 0.001 to 10 g/10 minutes (190°C, 2.16) The composite resin pellet, characterized in that it has a melt index of kg) level.
삭제delete 삭제delete 삭제delete 청구항 제7항에 있어서,
상기 복합수지 펠릿은 용융지수가 0.05 ~ 100g/10분(190℃, 2.16kg) 수준인 것을 특징으로 하는 복합수지 펠릿.
The method of claim 7,
The composite resin pellets, characterized in that the melt index is 0.05 ~ 100g / 10 minutes (190 ℃, 2.16kg) level of the composite resin pellets.
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