KR20230056260A - Dynamic cross-linking thermoplastic elastomer composition with excellent durability anf storagestability and manufacturing method of automobile weather strip using the same - Google Patents

Dynamic cross-linking thermoplastic elastomer composition with excellent durability anf storagestability and manufacturing method of automobile weather strip using the same Download PDF

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KR20230056260A
KR20230056260A KR1020210140091A KR20210140091A KR20230056260A KR 20230056260 A KR20230056260 A KR 20230056260A KR 1020210140091 A KR1020210140091 A KR 1020210140091A KR 20210140091 A KR20210140091 A KR 20210140091A KR 20230056260 A KR20230056260 A KR 20230056260A
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weather strip
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엄기용
전준하
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한국신발피혁연구원
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14Modified phenol-aldehyde condensates

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Abstract

The present invention relates to a dynamic cross-linked thermoplastic elastic body composition with excellent durability and storage stability and to an automobile weather strip manufacturing method using the same, in which a brominated alkyl phenol formaldehyde resin, where an end group is substituted with bromine by a cross-linking agent, is applied to a substrate formed of ethylene propylene diene monomer (EPDM) and polypropylene (PP) to enhance durability, while sodium gluconate is additionally input to adsorb a residual resin cross-linking agent to also enhance contamination and storage stability.

Description

내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물 및 이를 이용한 자동차 웨더스트립의 제조방법{DYNAMIC CROSS-LINKING THERMOPLASTIC ELASTOMER COMPOSITION WITH EXCELLENT DURABILITY ANF STORAGESTABILITY AND MANUFACTURING METHOD OF AUTOMOBILE WEATHER STRIP USING THE SAME}Dynamic crosslinking thermoplastic elastomer composition with excellent durability and storage stability and manufacturing method of automotive weather strip using the same

본 발명은 EPDM의 가교 효율을 높이고 미반응 가교제를 제어하여 우수한 내구성 및 저장 안정성을 가질 수 있도록 하는 동적 가교형 열가소성탄성체 조성물 및 이를 이용한 자동차 웨더스트립의 제조방법에 관한 것이다.The present invention relates to a dynamic crosslinking type thermoplastic elastomer composition capable of increasing EPDM crosslinking efficiency and controlling unreacted crosslinking agents to have excellent durability and storage stability, and a method for manufacturing an automotive weather strip using the same.

최근들어 환경오염 및 석유계 자원고갈 등으로 내연기관 자동차의 출시가 점점 줄어들고 전기차 등의 친환경차의 출시는 점점 증가하고 있으며 이에 맞추어 자동차용 부품 산업도 친환경차에 적합한 성능을 발현하기 위해 변화하고 있다.Recently, due to environmental pollution and depletion of petroleum resources, the release of internal combustion engine vehicles is gradually decreasing, and the launch of eco-friendly vehicles such as electric vehicles is increasing. .

한편, 전기차는 엔진소음이 거의 없는 장점이 있지만 풍절음, 타이어 마찰음 등의 외부 소음이 오히려 크게 들리게 느껴져 외부 소음을 차단할 수 있도록 웨더스트립 같은 씰링(sealing) 부품의 고성능화가 요구되고 있으며 친환경차의 개발 정책에 맞추어 재활용이 가능한 친환경 부품을 요구하고 있다.On the other hand, electric cars have the advantage of almost no engine noise, but external noises such as wind noise and tire friction noise are rather loud, so high-performance sealing parts such as weather strips are required to block external noise, and eco-friendly vehicle development policy Accordingly, there is a demand for eco-friendly parts that can be recycled.

보다 구체적으로 웨더 스트립은 자동차 등의 차체를 씰링하는 부품으로 외부환경으로부터 씰링 기능을 하면서 문이나 트렁크 등의 개폐시 필요한 힘 또는 유리문의 승하강시 힘을 최소화하기 위하여 웨더스트립은 균일하고 일정한 면압을 유지하여야 한다. 웨더스트립은 고무 솔리드(solid) 형태나 스폰지(sponge) 형태를 가지고 있다.More specifically, the weather strip is a component that seals the body of a car, etc., and maintains a uniform and constant surface pressure to minimize the force required when opening and closing doors or trunks or the force when raising and lowering glass doors while performing a sealing function from the external environment. shall. The weather strip has a rubber solid form or a sponge form.

이러한 웨더 스트립의 일반적인 사용 재료로는 주로 내후성(weatherbility)이 우수한 EPDM(ethylene propylene diene monomer)계 열경화성 고무가 많이 사용되고 있으나, 최근에는 EPDM 외에 열가소성 가황고무(Thermoplastic vulcanizates; TPV)가 적용되고 있는데 TPV는 EPDM에 비해 생산공정이 간편하고, 원가 절감의 효과가 있으며, 특히 자동차 부품의 경량화와 재활용을 위해 그 적용이 확대되고 있는 추세이다.As a common material for these weather strips, EPDM (ethylene propylene diene monomer)-based thermosetting rubber with excellent weatherability is mainly used, but recently, in addition to EPDM, thermoplastic vulcanizates (TPV) are being applied. Compared to EPDM, the production process is simpler and the cost is reduced, and its application is expanding, especially for the weight reduction and recycling of automobile parts.

관련 선행기술로써, 특허문헌 1에서는 EPDM 또는 컨쥬게이팅된 디엔 고무 및 이소부틸렌 고무로부터 얻어지는 열가소성 가황고무에 대한 기술을 제안하고 있지만, 상기 열가소성 가황고무는 부분적으로 가교 결합된 고무배합물을 약 10 ~ 90 중량부 함유하며 이를 통해 열가소성을 가지면서 가황 고무와 유사한 모듈러스를 발현하고자 하였으나 뛰어난 성능에도 불구하고 부분 가교 결합상의 고무 조성으로 인해 탄성 회복력이 떨어지는 문제점이 있다.As a related prior art, Patent Document 1 proposes a technology for thermoplastic vulcanized rubber obtained from EPDM or conjugated diene rubber and isobutylene rubber, but the thermoplastic vulcanized rubber partially cross-linked rubber mixture is about 10 to It contains 90 parts by weight and attempts to express a modulus similar to that of vulcanized rubber while having thermoplasticity.

즉, 웨더스트립용 TPV는 연속상을 이루는 열가소성 수지인 PP(Poly propylene)에 EPDM 가교 입자를 분산시켜 연속상의 가공성과 분산상의 고무탄성을 동시에 갖는 열가소성 탄성소재가 사용되며 EPDM의 특성이 내구성을 결정하는데, 상기와 같은 종래기술들은 EPDM의 가교효율이 미비할 뿐만 아니라 미반응 가교제에 의해 내구성 및 저장 안정성 등이 저하되는 문제점이 있었다.In other words, TPV for weather strip is a thermoplastic elastic material that has both processability of the continuous phase and rubber elasticity of the dispersed phase by dispersing EPDM cross-linked particles in PP (Poly Propylene), a thermoplastic resin that forms the continuous phase, and the characteristics of EPDM determine durability. However, the prior art as described above has problems in that the crosslinking efficiency of EPDM is insufficient and durability and storage stability are lowered due to unreacted crosslinking agents.

특허문헌 1 : 대한민국 공개특허공보 제10-1997-0027193호 "EPDM 또는 컨쥬게이팅된 디엔 고무 및 이소부틸렌 고무로부터 얻어지는 열가소성 가황고무"Patent Document 1: Korean Patent Publication No. 10-1997-0027193 "Thermoplastic vulcanized rubber obtained from EPDM or conjugated diene rubber and isobutylene rubber"

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, EPDM(Ethylene propylene diene monomer) 및 PP(Poly propylene)로 이루어지는 기재에 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지(Brominated alkyl phenolformadehyde resin)를 적용하여 그 내구성을 향상시키되, 클루코산나트륨(Sodium gluconate)을 추가 투입하여 잔류 수지 가교제를 흡착시킴으로써 오염성과 저장 안정성을 또한 개선시킬 수 있도록 함을 과제로 한다.The present invention is to solve the above problems, brominated alkyl phenolformaldehyde resin whose terminal group is substituted with bromine as a crosslinking agent on a substrate made of EPDM (Ethylene propylene diene monomer) and PP (Poly propylene) It is applied to improve its durability, but the task is to also improve contamination and storage stability by adsorbing the residual resin crosslinking agent by adding sodium gluconate.

본 발명은 동적 가교형 열가소성탄성체 조성물에 있어서, EPDM 및 PP로 이루어지는 기재에 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지 및 클루코산나트륨을 포함하는 것을 특징으로 하는, 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물을 과제의 해결 수단으로 한다.The present invention is a dynamic crosslinking thermoplastic elastomer composition, characterized in that it contains an alkylphenol formaldehyde resin whose terminal group is substituted with bromine and sodium gluconate as a crosslinking agent in a base material made of EPDM and PP, and has excellent durability and storage stability. A dynamic crosslinking type thermoplastic elastomer composition is used as a solution to the problem.

또한, 본 발명은 상기와 같은 조성물을 이용한 자동차 웨더스트립의 제조방법에 있어서, EPDM 및 PP로 이루어진 기재, 경탄, 산화방지제, 가공유 및 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지를 온도 160 ~ 250℃인 이축압출기에 투입하여 혼합하는 단계(S100); 압출기의 말단에서 클루코산나트륨을 추가 투입하여 혼합하는 단계(S200); 및 상기 혼합물을 압출 또는 사출하여 자동차 웨더스트립을 제조하는 단계(S300);를 포함하는 것을 특징으로 하는, 자동차 웨더스트립의 제조방법을 과제의 다른 해결 수단으로 한다.In addition, in the present invention, in a method for manufacturing a vehicle weather strip using the composition as described above, a base material made of EPDM and PP, hard carbon, an antioxidant, a processing oil, and a crosslinking agent, an alkylphenol formaldehyde resin whose terminal group is substituted with bromine, is heated to a temperature of 160° C. Putting into a twin-screw extruder at ~ 250 ° C. and mixing (S100); Adding and mixing sodium gluconate at the end of the extruder (S200); and manufacturing a vehicle weather strip by extruding or injecting the mixture (S300).

본 발명은 EPDM 및 PP로 이루어지는 기재에 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지를 적용하여 그 내구성을 향상시키되, 클루코산나트륨을 추가 투입하여 잔류 수지 가교제를 흡착시킴으로써 오염성과 저장 안정성을 또한 개선시킬 수 있는 효과가 있다.The present invention improves the durability by applying an alkylphenol formaldehyde resin whose terminal group is substituted with bromine as a crosslinking agent to a substrate made of EPDM and PP, and improves contamination and storage stability by adsorbing the residual resin crosslinking agent by additionally adding sodium gluconate. There is also an effect that can be improved.

도 1은 본 발명에 따른 동적 가교형 열가소성탄성체 조성물을 이용한 자동차 웨더스트립의 제조방법을 나타낸 공정 흐름도1 is a process flow chart showing a method for manufacturing a vehicle weather strip using a dynamic crosslinking thermoplastic elastomer composition according to the present invention.

상기의 효과를 달성하기 위한 본 발명은 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물 및 이를 이용한 자동차 웨더스트립의 제조방법에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.In order to achieve the above effects, the present invention relates to a dynamic crosslinking thermoplastic elastomer composition having excellent durability and storage stability and a method for manufacturing a vehicle weather strip using the same, and only parts necessary for understanding the technical configuration of the present invention are described. It should be noted that descriptions of other parts will be omitted so as not to obscure the subject matter of the present invention.

이하, 본 발명에 따른 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물 및 이를 이용한 자동차 웨더스트립의 제조방법을 상세히 설명하면 다음과 같다.Hereinafter, a dynamic crosslinking type thermoplastic elastomer composition having excellent durability and storage stability and a manufacturing method of a vehicle weather strip using the same according to the present invention will be described in detail.

먼저, 본 발명에 따른 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물은, EPDM(Ethylene propylene diene monomer) 및 PP(Poly propylene)로 이루어지는 기재에 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지(Brominated alkyl phenolformadehyde resin) 및 클루코산나트륨(Sodium gluconate)을 포함하는 것을 특징으로 한다.First, the dynamic crosslinking thermoplastic elastomer composition excellent in durability and storage stability according to the present invention is an alkylphenol formaldehyde resin in which an end group is substituted with bromine as a crosslinking agent in a base material made of EPDM (Ethylene propylene diene monomer) and PP (Poly propylene). (Brominated alkyl phenolformadehyde resin) and sodium gluconate.

상기 EPDM과 PP는 본 발명을 이루는 기재로써 분산상으로 ENB(Ethylidene norbornene) 함량 7 ~ 10%인 EPDM 50 ~ 80 중량% 및 연속상으로 PP 20 ~ 50 중량%로 이루어진다.The EPDM and PP are the substrates constituting the present invention, and are composed of 50 to 80% by weight of EPDM having an Ethylidene norbornene (ENB) content of 7 to 10% as a dispersed phase and 20 to 50% by weight of PP as a continuous phase.

여기서, 상기 ENB가 상기 범위를 벗어날 경우 EPDM 사용시 영구압축줄음율이 좋지 못해 소음차단 기능이 저하될 우려가 있다.Here, when the ENB is out of the above range, there is a concern that the noise blocking function may be deteriorated because the permanent compression set is not good when EPDM is used.

아울러, 상기 EDPM의 함량이 50 중량% 미만이고 PP의 함량이 50 중량%를 초과할 경우 영구압축줄음율이 좋지 못해 소음차단 기능이 저하될 우려가 있으며, EDPM의 함량이 80 중량%를 초과하고 PP의 함량이 20 중량% 미만일 경우 성형성이 좋지 못할 우려가 있다.In addition, when the content of EDPM is less than 50% by weight and the content of PP exceeds 50% by weight, there is a concern that the permanent compression set is not good and the noise blocking function is deteriorated, and the content of EDPM exceeds 80% by weight When the content of PP is less than 20% by weight, there is a concern that moldability is not good.

상기 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지는 가교제로써, EPDM을 동적가교시켜 PP에 분산시키는 기능을 하는 것으로, 기재 100 중량부에 대하여, 2 ~ 10 중량부를 사용한다.The alkylphenolformaldehyde resin whose terminal group is substituted with bromine is a crosslinking agent that dynamically crosslinks EPDM and disperses it in PP, and is used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the base material.

한편, 상기 말단기가 브롬으로 치환되지 않은 알킬페놀포름알데히드 수지의 사용시 반응이 느려 가교된 EPDM이 PP에 고르게 분산되지 못할 우려가 있다.On the other hand, when using an alkylphenol formaldehyde resin in which the terminal group is not substituted with bromine, the reaction is slow, and the crosslinked EPDM may not be evenly dispersed in PP.

아울러, 상기 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지의 함량이 2 중량부 미만일 경우 영구압축줄음율 등의 특성 개선이 어렵고 10 중량부를 초과시에는 잔류 가교제에 의한 내열성이 저하될 우려가 있다.In addition, when the content of the alkylphenol formaldehyde resin in which the terminal group is substituted with bromine is less than 2 parts by weight, it is difficult to improve properties such as compression set, and when it exceeds 10 parts by weight, heat resistance due to residual crosslinking agent may be reduced.

상기 클루코산나트륨은 잔류 수지 가교제를 흡착시켜 오염성과 저장 안정성을 개선하기 위한 것으로, 기재 100 중량부에 대하여 0.4 ~ 3 중량부를 사용한다.The sodium gluconate is used to improve contamination and storage stability by adsorbing the residual resin crosslinking agent, and is used in an amount of 0.4 to 3 parts by weight based on 100 parts by weight of the substrate.

보다 구체적으로 상기 알킬페놀포름알데히드 수지 가교제는 펄옥사이드(Peroxide) 가교제에 비해 영구압축줄음율, 내열성 등의 특성이 우수한 소재 제조가 가능하지만 잔류 수지 가교제에 의한 물성 저하, 제품 표면 오염, 흡습성에 의한 경시변화(저장 안정성) 등에 문제가 있다. 따라서 본 발명에서는 이를 해결하기 위해 클루코산나트륨 0.4 ~ 3 중량부 혼합하여 잔류 수지 가교제를 흡착시켜 오염성과 저장 안정성을 개선한다.More specifically, the alkylphenol formaldehyde resin crosslinking agent can produce materials with excellent properties such as permanent compression set and heat resistance compared to peroxide crosslinking agents, but it is possible to manufacture materials with excellent properties such as permanent compression set and heat resistance, There are problems with aging (storage stability) and the like. Therefore, in the present invention, in order to solve this problem, 0.4 to 3 parts by weight of sodium gluconate is mixed to adsorb the residual resin crosslinking agent to improve contamination and storage stability.

여기서, 상기 클루코산나트륨의 함량이 0.4 중량부 미만일 경우 오염성과 저장 안정성 개선 효율이 미비해질 우려가 있으며, 3 중량부를 초과할 경우 오히려 물성을 저하시킬 우려가 있다.Here, when the content of sodium glucosan is less than 0.4 parts by weight, there is a concern that contamination and storage stability improvement efficiency may be insufficient, and when it exceeds 3 parts by weight, there is a fear of deteriorating physical properties.

한편, 본 발명에서는 첨가제로써 물성향상을 위한 경탄, 열가소성탄성체와의 반응성 및 내열성 개선 효과를 위한 산화방지제, 연질화를 위한 가공유 등의 첨가가 가능하며, 일 예로 경탄 5 ~ 10 중량부, 산화방지제(아민(amin)계 또는 아인산염계) 0.1 ~ 0.2 중량부, 가공유 20 ~ 25 중량부를 사용할 수 있지만, 반드시 여기에 한정되는 것은 아니고, 제품의 사용환경이나 달성하고자 하는 물성 등을 고려하여 이미 공지된 다양한 첨가제 및 함량의 적용이 가능하다.On the other hand, in the present invention, as additives, hard coal for improving physical properties, antioxidants for improving reactivity with thermoplastic elastomers and heat resistance, and processing oil for softening can be added. For example, 5 to 10 parts by weight of hard coal, antioxidants (Amin-based or phosphite-based) 0.1 to 0.2 parts by weight and 20 to 25 parts by weight of processing oil can be used, but it is not necessarily limited thereto, and has already been known in consideration of the use environment of the product or the physical properties to be achieved. Various additives and contents can be applied.

다음으로 본 발명에 따른 자동차 웨더스트립의 제조방법은 도 1에 도시된 바와 같이, EPDM 및 PP로 이루어진 기재, 경탄, 산화방지제, 가공유 및 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지를 온도 160 ~ 250℃인 이축압출기에 투입하여 혼합하는 단계(S100)와, 압출기의 말단에서 클루코산나트륨을 추가 투입하여 혼합하는 단계(S200) 및, 상기 혼합물을 압출 또는 사출하여 자동차 웨더스트립을 제조하는 단계(S300)를 포함한다.Next, as shown in FIG. 1, in the manufacturing method of the automobile weather strip according to the present invention, a substrate made of EPDM and PP, hard carbon, antioxidant, processing oil, and a crosslinking agent are used to heat an alkylphenol formaldehyde resin whose terminal group is substituted with bromine. Adding and mixing in a twin-screw extruder at 160 to 250 ° C (S100), adding and mixing sodium gluconate at the end of the extruder (S200), and extruding or injecting the mixture to manufacture a vehicle weather strip Step S300 is included.

즉, 본 발명에 따른 자동차 웨더스트립의 제조방법은 상기와 같이 클루코산나트륨을 압출기 말단에서 투입하여 가교 반응에 방해를 주지 않고 가교 반응이 끝나고 남은 잔류 수지 가교제에 흡착되도록 하며, 이로 인해 오염성과 저장 안정성을 개선할 수 있다.That is, in the manufacturing method of the automobile weather strip according to the present invention, sodium gluconate is introduced from the end of the extruder as described above so that the crosslinking reaction is not disturbed and adsorbed to the remaining resin crosslinking agent after the crosslinking reaction, which causes contamination and storage. Stability can be improved.

한편, 상기 단계별 각 조성의 함량은 이미 상술하였으므로 여기서는 생략하며, 압출 또는 사출 조건이나 방법 역시 특정 조건에 한정하지 않고 자동차 웨더스트립의 종류나 사용환경 등에 따라 이미 공지된 다양한 조건 및 방법의 적용이 가능하다.On the other hand, since the content of each composition for each step has already been described above, it is omitted here, and extrusion or injection conditions or methods are not limited to specific conditions, and various conditions and methods that are already known can be applied depending on the type of automotive weather strip or use environment. do.

이하, 본 발명을 아래 실시예에 의거하여 더욱 상세히 설명하지만, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the examples below, but the present invention is not limited by the examples.

1. 자동차 웨더스트립의 제조1. Manufacture of automotive weather strips

(실시예 1)(Example 1)

ENB 함량 8.9%인 EPDM 75 중량% 및 PP 25 중량%로 이루어진 기재 100 중량부에 대하여, 경탄 5 중량부, 산화방지제(아민) 0.2 중량부, 가공유 20 중량부, 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지 6 중량부를 온도 200℃인 이축압출기에 투입하여 혼합(S100)하면서, 압출기의 말단에서 클루코산나트륨 1.2 중량부를 추가 투입하여 혼합하였다(S200). 그리고 상기 혼합물을 자동차 웨더스트립 형태로 사출하여 제조하였다(S300).Based on 100 parts by weight of a substrate composed of 75% by weight of EPDM with an ENB content of 8.9% and 25% by weight of PP, 5 parts by weight of hard coal, 0.2 parts by weight of an antioxidant (amine), 20 parts by weight of processing oil, and a crosslinking agent in which the terminal group is substituted with bromine. 6 parts by weight of an alkylphenol formaldehyde resin was added to a twin-screw extruder at a temperature of 200 ° C. and mixed (S100), while 1.2 parts by weight of sodium gluconate was additionally added at the end of the extruder and mixed (S200). Then, the mixture was prepared by injection in the form of an automobile weather strip (S300).

(실시예 2)(Example 2)

ENB 함량 7%인 EPDM 50 중량% 및 PP 50 중량%로 이루어진 기재 100 중량부에 대하여, 경탄 5 중량부, 산화방지제(아민) 0.1 중량부, 가공유 20 중량부, 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지 2 중량부를 온도 160℃인 이축압출기에 투입하여 혼합(S100)하면서, 압출기의 말단에서 클루코산나트륨 0.4 중량부를 추가 투입하여 혼합하였다(S200). 그리고 상기 혼합물을 자동차 웨더스트립 형태로 압출하여 제조하였다(S300).Based on 100 parts by weight of a substrate composed of 50% by weight of EPDM and 50% by weight of PP having an ENB content of 7%, 5 parts by weight of hard coal, 0.1 part by weight of an antioxidant (amine), 20 parts by weight of processing oil, and a crosslinking agent in which the terminal group is substituted with bromine. 2 parts by weight of an alkylphenol formaldehyde resin was added to a twin-screw extruder at a temperature of 160 ° C. and mixed (S100), while 0.4 parts by weight of sodium gluconate was additionally added at the end of the extruder and mixed (S200). And the mixture was prepared by extruding in the form of a car weather strip (S300).

(실시예 3)(Example 3)

ENB 함량 10%인 EPDM 80 중량% 및 PP 20 중량%로 이루어진 기재 100 중량부에 대하여, 경탄 10 중량부, 산화방지제(아민) 0.2 중량부, 가공유 25 중량부, 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지 10 중량부를 온도 250℃인 이축압출기에 투입하여 혼합(S100)하면서, 압출기의 말단에서 클루코산나트륨 3 중량부를 추가 투입하여 혼합하였다(S200). 그리고 상기 혼합물을 자동차 웨더스트립 형태로 사출하여 제조하였다(S300).Based on 100 parts by weight of a substrate composed of 80% by weight of EPDM with an ENB content of 10% and 20% by weight of PP, 10 parts by weight of hard coal, 0.2 parts by weight of an antioxidant (amine), 25 parts by weight of processing oil, and a crosslinking agent in which the terminal group is substituted with bromine. 10 parts by weight of an alkylphenol formaldehyde resin was added to a twin-screw extruder at a temperature of 250 ° C. and mixed (S100), while 3 parts by weight of sodium gluconate was additionally added at the end of the extruder and mixed (S200). Then, the mixture was prepared by injection in the form of an automobile weather strip (S300).

(비교예 1)(Comparative Example 1)

실시예 1과 동일하게 제조하되, 클루코산나트륨을 첨가하지 않았다.It was prepared in the same way as in Example 1, but sodium gluconate was not added.

(비교예 2)(Comparative Example 2)

실시예 2와 동일하게 제조하되, 클루코산나트륨을 첨가하지 않았다.It was prepared in the same way as in Example 2, but sodium glucosanate was not added.

(비교예 3)(Comparative Example 3)

실시예 1과 동일하게 제조하되, 클루코산나트륨을 첨가하지 않았고, 가교제로 디큐밀퍼옥사이드(Dicumyl peroxide) 1.0 중량부를 혼합하였다.It was prepared in the same manner as in Example 1, but sodium gluconate was not added, and 1.0 parts by weight of dicumyl peroxide was mixed as a crosslinking agent.

2. 자동차 웨더스트립의 평가2. Evaluation of automotive weather strips

(1) 내구성(1) durability

상기 실시예 및 비교예에 대한 물성과 내열성 등의 내구성을 평가하였으며, 그 시험기준 및 결과는 아래 [표 1]에 나타내었다.Durability, such as physical properties and heat resistance, was evaluated for the examples and comparative examples, and the test criteria and results are shown in [Table 1] below.

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 시험
기준
test
standard
경도 (A type)Hardness (A type) 7878 7878 7878 7878 8080 8080 ASTM D-224ASTM D-224 비중importance 0.920.92 0.920.92 0.920.92 0.920.92 0.920.92 0.920.92 ASTM D-792ASTM D-792 영구압축줄음율
(70℃×22시간, %)
permanent compression set
(70℃×22 hours, %)
2525 2424 2424 2525 2626 3636 KS M6660KS-M6660
인장강도 (kgf/cm2)Tensile strength (kgf/cm 2 ) 8080 8080 8080 7575 7575 8282 ASTM D-412ASTM D-412 내열성
[150℃×168시간]
heat resistance
[150℃×168 hours]
인장강도 (kgf/cm2)Tensile strength (kgf/cm 2 ) 7474 7474 7474 6464 6464 4545 ASTM D-412ASTM D-412
변화율 (%)Change rate (%) -7.5-7.5 -7.5-7.5 -7.5-7.5 -14.7-14.7 -14.7-14.7 -45.1-45.1 --

(2) 저장 안정성(2) storage stability

상기 실시예 및 비교예에 대한 저장 안정성을 평가하였으며, 그 시험기준 및 결과는 아래 [표 2] 및 [표 3]에 나타내었다.Storage stability was evaluated for the above examples and comparative examples, and the test criteria and results are shown in [Table 2] and [Table 3] below.

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 영구압축줄음율
(70℃*?*시간, %)
KS M6660
permanent compression set
(70℃*?*time, %)
KS-M6660
2525 2424 2525 2626 2525 2424 2424 2525 2525 2626 2525 2424 2525 2626 2525
인장강도 (kgf/cm2)
ASTM D-412
Tensile strength (kgf/cm 2 )
ASTM D-412
8080 8282 8181 8282 8181 8080 8181 8282 8181 8080 8080 8181 8181 8181 8282

구분division 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 당일day 1주후1 week later 2주후2 weeks later 3주후3 weeks later 4주후4 weeks later 영구압축줄음율
(70℃*?*시간, %)
KS M6660
permanent compression set
(70℃*?*time, %)
KS-M6660
2525 2828 3131 3636 4545 2626 2929 3030 3434 4444 3636 3939 4141 4444 5151
인장강도 (kgf/cm2)
ASTM D-412
Tensile strength (kgf/cm 2 )
ASTM D-412
7575 7272 6868 6262 5454 7575 7474 6969 6767 6060 8282 7878 6868 6666 5959

상기 [표 1] 및 [표 2]에서와 같이, 본 발명의 실시예에 따른 자동차 웨더스트립은 비교예에 비하여 그 내구성이 우수하면서도 저장 안정성 또한 개선되었음을 알 수 있다. As shown in [Table 1] and [Table 2], it can be seen that the automobile weather strip according to the embodiment of the present invention has excellent durability and improved storage stability compared to the comparative example.

상술한 바와 같은, 본 발명의 바람직한 실시예에 따른 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물 및 이를 이용한 자동차 웨더스트립의 제조방법을 상기한 설명 및 도면에 따라 설명하였지만 이는 예를 들어 설명한 것에 불과하며 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 변화 및 변경이 가능하다는 것을 이 분야의 통상적인 기술자들은 잘 이해할 수 있을 것이다.As described above, the dynamic crosslinking type thermoplastic elastomer composition excellent in durability and storage stability according to a preferred embodiment of the present invention and the manufacturing method of a vehicle weather strip using the same have been described according to the above description and drawings, but this is for example Those skilled in the art will be able to understand that various changes and modifications are possible without departing from the technical spirit of the present invention.

Claims (3)

동적 가교형 열가소성탄성체 조성물에 있어서,
EPDM(Ethylene propylene diene monomer) 및 PP(Poly propylene)로 이루어지는 기재에 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지(Brominated alkyl phenolformadehyde resin) 및 클루코산나트륨(Sodium gluconate)을 포함하는 것을 특징으로 하는, 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물.
In the dynamic crosslinking thermoplastic elastomer composition,
It is characterized in that it contains brominated alkyl phenolformaldehyde resin and sodium gluconate in which the end group is substituted with bromine as a crosslinking agent on a base material made of EPDM (Ethylene propylene diene monomer) and PP (Poly propylene) A dynamic crosslinking thermoplastic elastomer composition with excellent durability and storage stability.
제 1항에 있어서,
상기 동적 가교형 열가소성탄성체 조성물은,
ENB(Ethylidene norbornene) 함량 7 ~ 10%인 EPDM 50 ~ 80 중량% 및 PP 20 ~ 50 중량%로 이루어진 기재 100 중량부에 대하여, 경탄 5 ~ 10 중량부, 산화방지제 0.1 ~ 0.2 중량부, 가공유 20 ~ 25 중량부, 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지 2 ~ 10 중량부 및 클루코산나트륨 0.4 ~ 3 중량부를 혼합하여 이루어지는 것을 특징으로 하는, 내구성과 저장 안정성이 우수한 동적 가교형 열가소성탄성체 조성물.
According to claim 1,
The dynamic crosslinking thermoplastic elastomer composition,
5 to 10 parts by weight of hard coal, 0.1 to 0.2 parts by weight of antioxidants, 20 parts by weight of processing oil, based on 100 parts by weight of a substrate composed of 50 to 80% by weight of EPDM with 7 to 10% of Ethylidene norbornene (ENB) and 20 to 50% by weight of PP. ~ 25 parts by weight, 2 to 10 parts by weight of an alkylphenol formaldehyde resin whose terminal group is substituted with bromine as a crosslinking agent, and 0.4 to 3 parts by weight of sodium gluconate, a dynamic crosslinking type thermoplastic with excellent durability and storage stability. elastomer composition.
제 1항에 따른 조성물을 이용한 자동차 웨더스트립의 제조방법에 있어서,
EPDM 및 PP로 이루어진 기재, 경탄, 산화방지제, 가공유 및 가교제로 말단기가 브롬으로 치환된 알킬페놀포름알데히드 수지를 온도 160 ~ 250℃인 이축압출기에 투입하여 혼합하는 단계(S100);
압출기의 말단에서 클루코산나트륨을 추가 투입하여 혼합하는 단계(S200); 및
상기 혼합물을 압출 또는 사출하여 자동차 웨더스트립을 제조하는 단계(S300);를 포함하는 것을 특징으로 하는, 자동차 웨더스트립의 제조방법.
In the method for manufacturing a vehicle weather strip using the composition according to claim 1,
A base material made of EPDM and PP, hard carbon, antioxidant, processing oil, and an alkylphenol formaldehyde resin whose terminal group is substituted with bromine as a crosslinking agent are put into a twin-screw extruder at a temperature of 160 to 250 ° C. and mixed (S100);
Adding and mixing sodium gluconate at the end of the extruder (S200); and
A method for manufacturing a vehicle weather strip, characterized in that it comprises: extruding or injecting the mixture to manufacture a vehicle weather strip (S300).
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KR970027193A (en) 1995-11-13 1997-06-24 칼루자 마이클 이. Thermoplastic Vulcanized Rubber Obtained from EPDM or Conjugated Diene Rubber and Isobutylene Rubber
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* Cited by examiner, † Cited by third party
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KR970027193A (en) 1995-11-13 1997-06-24 칼루자 마이클 이. Thermoplastic Vulcanized Rubber Obtained from EPDM or Conjugated Diene Rubber and Isobutylene Rubber
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