KR100383245B1 - Thermoplastic Elastomer resin composition having Anti-scratch property - Google Patents

Thermoplastic Elastomer resin composition having Anti-scratch property Download PDF

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KR100383245B1
KR100383245B1 KR10-2000-0082116A KR20000082116A KR100383245B1 KR 100383245 B1 KR100383245 B1 KR 100383245B1 KR 20000082116 A KR20000082116 A KR 20000082116A KR 100383245 B1 KR100383245 B1 KR 100383245B1
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resin composition
thermoplastic elastomer
weight
elastomer resin
damage resistance
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KR20020052687A (en
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김영환
장욱진
이종대
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삼성종합화학주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

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  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

본 발명은 내손상성이 향상된 열가소성 일레스토머 수지 조성물에 관한 것으로, 보다 상세하게는The present invention relates to a thermoplastic elastomer resin composition having improved damage resistance, and more particularly.

1) 고무 성분이 완전히 또는 부분적으로 가교되어 있는 폴리올레핀계 일레스토머 100중량부;1) 100 parts by weight of a polyolefin-based elastomer in which the rubber component is completely or partially crosslinked;

2) 에틸렌-프로필렌 블록공중합체 10~40 중량부; 및2) 10 to 40 parts by weight of ethylene-propylene block copolymer; And

3) 초고분자량 실록산 수지의 마스터뱃치 3~10 중량부를 포함하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물에 관한 것이며, 본 발명에 의해 가공성, 복원성이 우수하면서도 내손상성이 향상된 일레스토머 수지 조성물을 제공할 수 있다.3) It relates to a thermoplastic elastomer resin composition having improved damage resistance including 3 to 10 parts by weight of a master batch of ultra high molecular weight siloxane resin, and according to the present invention, an elastomer resin composition having excellent workability and resilience and improved damage resistance Can provide.

Description

내손상성이 우수한 열가소성 일레스토머 수지조성물 {Thermoplastic Elastomer resin composition having Anti-scratch property}Thermoplastic Elastomer Resin Composition Having Anti-scratch Property

본 발명은 내손상성이 우수한 열가소성 일레스토머 수지조성물에 관한 것으로, 보다 상세하게는 고무성분이 완전히 또는 부분적으로 가교되어 있는 폴리올레핀계 일레스토머에 내손상성을 개선하기 위하여 실록산 수지를 처방한 열가소성 일레스토머 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic elastomer resin composition having excellent damage resistance, and more particularly, to a thermoplastic elastomer in which a siloxane resin is prescribed to improve damage resistance to a polyolefin-based elastomer in which rubber components are completely or partially crosslinked. It relates to a resin composition.

고분자 재료로서 고무나 플라스틱이 우리 일상생활에서 범용으로 광범위하게 쓰여지고 있는 가운데 제3의 재료인 열가소성 일레스토머(TPE)가 1950년대 처음 소개된 이래로 현재까지 가황고무 및 연질 PVC(Polyvinyl chloride)의 대체 재료로서 주목을 받고 있다. 이러한 열가소성 일레스토머의 특징은 고무와 같은 탄성체이면서도 플라스틱과 같이 성형가공이 가능한 물리적 특성을 갖고 있다. 가황고무와 플라스틱의 물성상의 장점을 갖고 있는 재료라고 할 수 있으며, 보다 구체적으로 설명하면 물리적 성질은 가황고무와 같이 복원력이 우수하고 연질 PVC와 같이 촉감이 부드러우며, 가공상에 있어서 열가소성이기 때문에 일반 열가소성 플라스틱 가공기기로 쉽게 가공 할 수 있으므로 부드러운 고무에서부터 단단한 플라스틱까지 광범위한 물성을 만족시켜 주는 재료로 각광을 받고 있다. 특히 열가소성 일레스토머의 최대 특징은 가황고무와 비교 할 경우 성형 가공성이 보다 뛰어나 일반적으로 사용하는 사출, 압출, 중공성형 기기로 가공이 가능하다는 것이다.As a polymer material, rubber and plastics are widely used in our daily life, and thermoplastic elastomers (TPE), a third material, have been replaced since the introduction of the first material in the 1950s, and have been replaced by vulcanized rubber and soft PVC (Polyvinyl chloride). It is attracting attention as a material. The thermoplastic elastomer has a physical property that can be molded and processed like plastic while being an elastic body such as rubber. It is a material that has the advantages of physical properties of vulcanized rubber and plastics. More specifically, the physical properties are excellent in resilience like vulcanized rubber, soft to soft like soft PVC, and thermoplastic in processing. As it can be easily processed by thermoplastic processing equipment, it has been spotlighted as a material satisfying a wide range of physical properties from soft rubber to hard plastic. In particular, the biggest feature of thermoplastic elastomers is that they can be processed with commonly used injection, extrusion and blow molding machines as they have better moldability compared to vulcanized rubber.

그러나 이러한 열가소성 일레스토머는 경도가 낮기 때문에 내손상성이 약한 단점이 있다.However, such thermoplastic elastomers have a disadvantage of poor damage resistance because of their low hardness.

본 발명은 상기와 같은 종래 기술의 문제점을 개선한 것으로, 복원력이 높고 촉감이 부드러우면서도 내손상성이 우수한 열가소성 일레스토머 수지 중합체를 제공하여 냉장고 가스켓 및 자동차 창문의 가스켓에 사용하도록 함을 목적으로 한다.The present invention improves the problems of the prior art as described above, and provides a thermoplastic elastomer resin polymer having high resilience and soft touch and excellent damage resistance to be used in a gasket of a refrigerator gasket and a car window. do.

즉 본 발명은That is, the present invention

1) 고무 성분이 완전히 또는 부분적으로 가교되어 있는 폴리올레핀계 일레스토머 100중량부;1) 100 parts by weight of a polyolefin-based elastomer in which the rubber component is completely or partially crosslinked;

2) 에틸렌-프로필렌 블록공중합체 10~40 중량부; 및2) 10 to 40 parts by weight of ethylene-propylene block copolymer; And

3) 초고분자량 실록산 수지의 마스터뱃치 3~10 중량부를 포함하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물에 관한 것이다.3) A thermoplastic elastomer resin composition having improved damage resistance including 3 to 10 parts by weight of a master batch of ultra high molecular weight siloxane resin.

이하에서 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 1)성분의 폴리올레핀계 일레스토머는 고무 성분이 완전히 또는 부분적으로 가교된 것으로, 상기 폴리올레핀계 일레스토머 중에 가교된 고무성분의 함량은 10~40 중량%가 적당하다. 가교된 고무의 함량이 10 중량% 미만인 경우 복원력이 없고, 40 중량%를 초과하면 압출 특성이 나쁘다. 이러한 고무 성분이 부분적으로 가교되어 있는 폴리올레핀계 일레스토머를 사용함으로 인해 탄성 및 가공성이 우수한 효과를 나타낸다.In the polyolefin elastomer of component 1) of the present invention, the rubber component is completely or partially crosslinked, and the content of the crosslinked rubber component in the polyolefin elastomer is preferably 10 to 40% by weight. When the content of the crosslinked rubber is less than 10% by weight, there is no restoring force, and when the content of the crosslinked rubber is more than 40% by weight, the extrusion property is poor. The use of polyolefin-based elastomers in which such rubber components are partially crosslinked results in excellent elasticity and processability.

상기 2)성분의 에틸렌-프로필렌 블록공중합체는 에틸렌 함량은 25∼40 중량%인 것이 바람직하다. 보다 구체적으로는 내충격성이 요구되는 경우 에틸렌 함량이 높은 것을 사용하고 굴곡강성이 요구되는 경우 에틸렌 함량이 낮은 제품을 사용한다. 상기 에틸렌-프로필렌 블록공중합체의 함량은 폴리올레핀계 일레스토머 100 중량부 대비 10∼40 중량부가 바람직하다.It is preferable that the ethylene-propylene block copolymer of the said 2) component is 25-40 weight%. More specifically, when impact resistance is required, a high ethylene content is used, and when flexural rigidity is required, a product having a low ethylene content is used. The content of the ethylene-propylene block copolymer is preferably 10 to 40 parts by weight based on 100 parts by weight of the polyolefin-based elastomer.

상기 3)성분인 초고분자량 실록산 수지의 마스터뱃치는 내손상성을 향상시키기 위해 사용된 초고분자량 실록산 수지의 액상 점도가 높은 특성을 나타내기 때문에 이를 마스터뱃치화하여 사용한 것이다. 마스터뱃치의 제조에 사용되는 수지는 폴리프로필렌, 폴리에틸렌, 폴리아세탈, 나이론 등 각 용도에 맞게 선정하여 사용 할수 있으나, 바람직하게는 에틸렌초산중합체를 사용하는 것이 좋다. 상기 초고분자량 실록산 수지는 점도가 60,000 이상, 더욱 바람직하게는 10,000,000 ~ 30,000,000 ㎟/sec인 것을 20∼60 중량% 사용한다.The masterbatch of the ultra-high molecular weight siloxane resin, which is the component 3), has a high liquid phase viscosity property of the ultra-high molecular weight siloxane resin used to improve damage resistance, and thus, it is used as a masterbatch. Resin used in the production of the master batch can be selected and used according to each application, such as polypropylene, polyethylene, polyacetal, nylon, preferably ethylene acetate polymer is used. The ultra high molecular weight siloxane resin has a viscosity of 60,000 or more, more preferably 20 to 60% by weight of 10,000,000 to 30,000,000 mm 2 / sec.

본 발명의 조성물은 본 발명의 목적을 벗어나지 않는 범위 내에서 가교제, 가공 오일, 무기 충진제 및 기타 첨가제 등을 추가로 포함할 수 있다.The composition of the present invention may further include a crosslinking agent, a processing oil, an inorganic filler and other additives and the like without departing from the object of the present invention.

이하 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 하기의 실시예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것을 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are for the purpose of explanation and are not intended to limit the present invention.

실시예 1~8 및 비교예 1~7Examples 1-8 and Comparative Examples 1-7

표 1 및 표 2에 나타난 비율에 따라 폴리올레핀계 열가소성 일레스토머(삼성종합화학(주), STE65)에 블록공중합체(삼성종합화학(주), BI530)과 실록산의 함량이 40중량%이고 에틸렌초산중합체를 사용한 실록산 수지 마스터뱃치(삼성종합화학(주), EV6040)를 혼합하여 이축압출기로 용융혼련하여 각 조성물을 펠렛상으로 제조하고, 각 조성물을 사출기를 이용하여 시편을 제조한 다음 아래 실험방법에 따라 평가를 실시하였다.According to the ratio shown in Table 1 and Table 2, the content of the block copolymer (Samsung Synthetic Co., Ltd., BI530) and siloxane is 40% by weight in the polyolefin-based thermoplastic elastomer (Samsung General Chemical Co., Ltd., STE65). The siloxane resin masterbatch (Samsung General Chemical Co., Ltd., EV6040) using an acetate polymer was mixed and melt-kneaded with a twin screw extruder to prepare each composition in pellet form, and each composition was prepared by using an injection machine. Evaluation was performed in accordance with the method.

물성시험 방법Property test method

1. 내손상성 판정방법1. Determination of damage resistance

평판식 내마모시험기를 이용하여 각 조성물의 시편을 시험한 후 긁힘의 정도를 육안으로 판정하였다.After the specimens of each composition were tested using a flat wear resistance tester, the degree of scratching was visually determined.

◎ :긁힘에 의한 백화가 전혀 없음◎: No whitening due to scratching

○:긁힘에 의한 백화가 거의 없음○: Almost no whitening due to scratching

△ :긁힘에 의한 백화가 보이나 심하지 없음(Triangle | delta): Whitening by a scratch is seen, but is not severe

X :긁힘에 의한 백화가 심하게 없음X: No whitening due to scratches

2. 경도측정 : ASTM D2240에 의거하여 측정(단위:SHORE A)2. Hardness measurement: Measured according to ASTM D2240 (Unit: SHORE A)

3. 영구압축줄음율 : ASTM D395에 의거하여 측정(단위:%)3. Permanent compression rate: measured according to ASTM D395 (unit:%)

실시예 1Example 1 실시에 22 to implementation 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 열가소성 일레스토머Thermoplastic elastomer 100100 100100 100100 100100 100100 100100 블록공중합체Block copolymer 2020 2020 2020 3030 4040 3030 실록산 마스터뱃치Siloxane masterbatch 33 55 1010 55 55 33 경도Hardness 6565 6565 6565 8585 9595 8585 영구압출줄음율Permanent Extrusion 2828 2828 2929 4242 5252 4343 내손상성Damage resistance ○○ ◎◎ ◎◎ ◎◎ ◎◎ ○○

비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 비교예 5Comparative Example 5 비교예 6Comparative Example 6 열가소성 일레스토머Thermoplastic elastomer 100100 100100 100100 100100 100100 100100 블록공중합체Block copolymer 2020 2020 2020 5050 6060 8080 실록산 마스터뱃치Siloxane masterbatch -- 1One 22 55 55 1010 경도Hardness 6565 6565 6565 40D40D 42D42D 50D50D 영구압축줄음율Permanent compression 2828 2828 2828 6060 6565 7575 내손상성Damage resistance ×× △△ △△ ◎◎ ◎◎ ◎◎

본 발명에 의하면 복원력이 높고 촉감이 부드러우면서도 내손상성이 우수한 열가소성 일레스토머 수지 중합체를 제공하여 자동차 창문 및 냉장고 도어의 가스켓류의 소재로서 유용하게 사용될 수 있도록 한다.According to the present invention, a thermoplastic elastomer resin polymer having high resilience, soft touch, and excellent damage resistance can be usefully used as a gasket material for automobile windows and refrigerator doors.

Claims (5)

1) 고무 성분이 완전히 또는 부분적으로 가교되어 있는 폴리올레핀계 일레스토머 100중량부;1) 100 parts by weight of a polyolefin-based elastomer in which the rubber component is completely or partially crosslinked; 2) 에틸렌-프로필렌 블록공중합체 10~40 중량부; 및2) 10 to 40 parts by weight of ethylene-propylene block copolymer; And 3) 초고분자량 실록산수지의 마스터뱃치 3~10 중량부를 포함하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물.3) A thermoplastic elastomer resin composition having improved damage resistance including 3 to 10 parts by weight of a master batch of ultra high molecular weight siloxane resin. 제 1항에 있어서, 상기 폴리올레핀계 일레스토머에 가교된 고무성분의 함량이 10~40 중량%인 것을 특징으로 하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물.The thermoplastic elastomer resin composition having improved damage resistance according to claim 1, wherein the content of the rubber component crosslinked to the polyolefin elastomer is 10 to 40% by weight. 제 1항에 있어서, 상기 에틸렌-프로필렌 블록공중합체 중 포함된 에틸렌 함량이 25∼40 중량%인 것을 특징으로 하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물.The thermoplastic elastomer resin composition having improved damage resistance according to claim 1, wherein the ethylene content of the ethylene-propylene block copolymer is 25 to 40 wt%. 제 1항에 있어서, 상기 초고분자량 실록산수지의 마스터뱃치가 점도가 60,000 ㎟/sec 이상인 실록산 수지를 20∼60 중량% 포함하는 것을 특징으로 하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물.2. The thermoplastic elastomer resin composition of claim 1, wherein the master batch of the ultra high molecular weight siloxane resin contains 20 to 60 wt% of a siloxane resin having a viscosity of 60,000 mm2 / sec or more. 제 1항에 있어서, 상기 초고분자량 실록산 수지의 마스터뱃치 제조에 에틸렌초산공중합체를 사용하는 것을 특징으로 하는 내손상성이 향상된 열가소성 일레스토머 수지 조성물.The thermoplastic elastomer resin composition of claim 1, wherein an ethylene acetate copolymer is used to prepare the master batch of the ultra high molecular weight siloxane resin.
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