KR20040042288A - Rubber composition for wiper blade - Google Patents

Rubber composition for wiper blade Download PDF

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KR20040042288A
KR20040042288A KR1020020070503A KR20020070503A KR20040042288A KR 20040042288 A KR20040042288 A KR 20040042288A KR 1020020070503 A KR1020020070503 A KR 1020020070503A KR 20020070503 A KR20020070503 A KR 20020070503A KR 20040042288 A KR20040042288 A KR 20040042288A
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South Korea
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rubber
phr
crosslinking
ethylene
wiper blade
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KR1020020070503A
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Korean (ko)
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송유창
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현대자동차주식회사
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Priority to KR1020020070503A priority Critical patent/KR20040042288A/en
Publication of KR20040042288A publication Critical patent/KR20040042288A/en

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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
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60S—SERVICING, CLEANING, REPAIRING, SUPPORTING, LIFTING, OR MANOEUVRING OF VEHICLES, NOT OTHERWISE PROVIDED FOR
    • B60S1/00—Cleaning of vehicles
    • B60S1/02—Cleaning windscreens, windows or optical devices
    • B60S1/04—Wipers or the like, e.g. scrapers
    • B60S1/32—Wipers or the like, e.g. scrapers characterised by constructional features of wiper blade arms or blades
    • B60S1/38—Wiper blades
    • B60S2001/3827—Wiper blades characterised by the squeegee or blade rubber or wiping element
    • B60S2001/3829—Wiper blades characterised by the squeegee or blade rubber or wiping element characterised by the material of the squeegee or coating thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: Provided is a rubber composition for a wiper blade, which solves the problems related with chemical surface treatments by improving ozone resistance, and has improved weather resistance and durability. CONSTITUTION: The rubber composition for a wiper blade comprises: a base rubber composed of natural rubber and ethylene-propylene rubber in a weight ratio of 85/15-65/35; 4-7.5 phr of a compatibilizer; 40-50 phr of carbon black as a reinforcing filler; 3-5 phr of a petroleum rubber softener; 3-5 phr of zinc oxide(ZnO) and 1-2 phr of stearic acid as a crosslinking activator; 2 phr or less of sulfur as a crosslinking agent; and 0.5-2.0 phr of N-t-butyl-2-benzothiazole sulfenamide and tetramethylthiuram monosulfide, as a crosslinking accelerator.

Description

와이퍼 블레이드용 고무 조성물{Rubber composition for wiper blade}Rubber composition for wiper blades

본 발명은 와이퍼 블레이드용 고무 조성물에 관한 것으로, 보다 상세하게는 와이퍼 블레이드의 성능을 향상시키기 위하여 천연고무와 에틸렌 프로필렌 디엔 고무(EPDM), 그리고 액상 에틸렌 프로필렌 디엔고무로 고무 조성물을 형성함으로써, N-이소프로필-N-페닐-파라 페닐렌디아민 또는 N-1,3-디메틸부틸-N-페닐-파라-페닐렌디아민와 같은 내오존노방제의 사용 없이도 내열성, 내오존성, 그리고 내후성이 향상되어 수명과 성능을 증대시킬 수 있는 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for wiper blades, and more particularly, to form a rubber composition with natural rubber, ethylene propylene diene rubber (EPDM), and liquid ethylene propylene diene rubber in order to improve the performance of the wiper blade. Improved heat resistance, ozone resistance and weather resistance without the use of ozone deodorants such as isopropyl-N-phenyl-paraphenylenediamine or N-1,3-dimethylbutyl-N-phenyl-para-phenylenediamine. The present invention relates to a rubber composition capable of increasing performance.

와이퍼 블레이드 고무의 성능은 초기 닦임성, 탄성, 내마모성, 기계적강도, 내후성, 내오존성, 그리고 유리와 와이퍼 블레이드 고무의 마찰로 인해 생기는 소음 등에 의해 결정된다. 와이퍼 블레이드의 재료로서 일반적으로 천연고무(NR)나 클로로프렌 고무(CR) 등의 탄성중합체가 사용되고 있다. 상기 탄성중합체는 탄성, 내마모성 및 기계적 강도 등이 우수하여 와이퍼 블레이드의 재료로서 가장 적합한 소재로 알려져 있었다. 그러나, 주쇄 내에 많은 불포화기의 이중결합을 가지고 있어, 공기 중의 오존(Ozone, O3)의 공격에 의해서 사슬결합이 끊어지면서노화가 발생하고, 제품에 크랙(crack)이 발생되는 등 문제점이 여전히 남아 있다. 상기 문제점을 해결하기 위한 방안으로, 일정량의 N-이소프로필-N-페닐-파라 페닐렌디아민 (N-isopropyl-N-phenyl-p-phenylenediamine, 이하 IPPD라 한다)이나 N-1,3-디메틸부틸-N-페닐-파라-페닐렌디아민 (N-1,3-dimethybutyl-N-phenyl-p-phenylenediamine, 이하 6PPD라 한다)와 같은 내오존노방제와 왁스류를 고무 배합시 첨가하여 NR이나 CR의 나쁜 내오존성을 개선하는 방법이 제시되었다.The performance of wiper blade rubber is determined by initial wiping, elasticity, abrasion resistance, mechanical strength, weather resistance, ozone resistance, and noise caused by friction between the glass and wiper blade rubber. In general, an elastomer such as natural rubber (NR) or chloroprene rubber (CR) is used as the material of the wiper blade. The elastomer is known to be the most suitable material for the wiper blade because of its excellent elasticity, abrasion resistance and mechanical strength. However, since there are many double bonds of unsaturated groups in the main chain, aging occurs as the chain bonds are broken by the attack of ozone (Ozone, O3) in the air, and there are still problems such as cracking in the product. have. In order to solve the problem, a certain amount of N-isopropyl-N-phenyl-paraphenylenediamine (N-isopropyl-N-phenyl-p-phenylenediamine, hereinafter referred to as IPPD) or N-1,3-dimethyl Ozone defoaming agents such as butyl-N-phenyl-para-phenylenediamine (hereinafter referred to as 6-1 PPD) and waxes are added during rubber compounding to add NR or A method for improving the bad ozone resistance of CR has been proposed.

이외에, 유리와 와이퍼 블레이드의 마찰에 의한 소음을 제거하기 위해서 고무배합시 습동제를 사용하거나 또는 표면에 화학적 처리를 실시하여 마찰을 감소시키는 것이 제안되어 있다.In addition, in order to remove the noise caused by the friction between the glass and the wiper blades, it is proposed to reduce friction by using a humectant in the rubber compounding or by chemically treating the surface.

그러나 고무 배합시 첨가되는 내오존노방제인 IPPD나 6PPD, 그리고 습동제들은 고무제품의 표면으로 유출 (blooming 또는 bleeding) 되면서 그 자체의 역할을 수행한다. 하지만 앞에서 설명한 바와 같이 와이퍼 블레이드는 마찰을 감소시키기 위해서 화학적 표면처리의 공정을 거쳐야 하는데, 표면에 기어 나온 내오존노방제나 습동제는 표면의 화학적 처리시 모두 제거되거나, 또는 완전한 표면처리를 방해하게 된다. 그러므로 위와 같이 제조된 와이퍼 블레이드는 내후성이나 내오존성 등의 내구성과 소음에 문제가 발생하여 수명이 단축되는 문제점이 있다.However, the ozone antifouling agents added during rubber compounding, IPPD, 6PPD, and humectants, play a role as they flow to the surface of rubber products (blooming or bleeding). However, as described above, the wiper blade must undergo chemical surface treatment to reduce friction, and the ozone deodorant or humectant which crawls on the surface is removed during chemical treatment of the surface, or interferes with the complete surface treatment. . Therefore, the wiper blade manufactured as described above has a problem of shortening the life due to problems in durability and noise, such as weather resistance or ozone resistance.

따라서 본 발명은 상기와 같은 종래의 문제점을 해결하기 위해서 창안된 것으로, 본 발명은 천연고무나 클로로프렌의 탄성중합체가 가지는 우수한 탄성, 기계적 강도, 초기 닦임성 등은 그대로 유지하면서, IPPD나 6PPD와 같은 기존의 노화방지제를 사용을 배제하고, 내오존성과 내후성 등의 내구성을 만족시키는 목적으로, 와이퍼 블레이드용 고무 조성물을 천연고무와 에틸렌 프로필렌 디엔고무(EPDM), 그리고 액상 에틸렌 프로필렌 디엔고무로 배합물을 형성하여 내오존성을 향상시켜서, 화학적 표면처리시의 문제점을 제거하여 내후성과 내구성이 향상된 와이퍼 블레이드 고무를 개발하고자 하는데 목적이 있다.Therefore, the present invention was devised to solve the conventional problems as described above, the present invention, while maintaining the excellent elasticity, mechanical strength, initial wiping properties of natural rubber or chloroprene elastomer, such as IPPD or 6PPD For the purpose of eliminating the use of existing anti-aging agents and satisfying durability such as ozone resistance and weather resistance, the rubber composition for the wiper blade is formed of natural rubber, ethylene propylene diene rubber (EPDM), and liquid ethylene propylene diene rubber. The purpose of the present invention is to improve the ozone resistance and to eliminate the problem of chemical surface treatment, thereby developing a wiper blade rubber having improved weatherability and durability.

본 발명은 내오존성과 내후성이 우수한 에틸렌-프로필렌 디엔고무(EPDM)를 천연고무와 혼합하여 사용하는 것을 그 특징으로 한다.The present invention is characterized in that ethylene-propylene diene rubber (EPDM) having excellent ozone resistance and weather resistance is used in combination with natural rubber.

구체적으로 본 발명은Specifically, the present invention

천연고무 및 에틸렌-프로필렌 고무가 85/15 ∼ 65/35 중량%비로 혼합되어 있는 고무 혼합물에 대하여,For rubber mixtures in which natural rubber and ethylene-propylene rubber are mixed at a ratio of 85/15 to 65/35% by weight,

상용화제 4 ∼ 7.5 phr;Compatibilizers 4 to 7.5 phr;

보강 충진제인 카본블랙 40 ∼ 50 phr;Carbon black 40 to 50 phr as reinforcing filler;

석유계 고무 연화제 3 ∼ 5 phr;Petroleum rubber softener 3-5 phr;

가교 활성제로 산화아연 (ZnO) 3 ∼ 5phr 및 스테아린산 1 ∼ 2 phr;Zinc oxide (ZnO) 3-5 phr and stearic acid 1-2 phr as crosslinking activators;

가교제로 유황 2 phr 이하;Sulfur up to 2 phr as crosslinker;

가교 촉진제로 N-t-부틸-2-벤조티아졸 설펜아마이드 (N-t-butyl-2-benxothiazole sulfenamide)와, 테트라메틸티우람 모노설파이드(Tetramethylthiuram monosulfide) 0.5 ∼ 2.0 phr; 를 포함하는 와이퍼 블레이드용 고무 조성물을 그 특징으로 한다.N-t-butyl-2-benxothiazole sulfenamide and tetramethylthiuram monosulfide 0.5 to 2.0 phr as a crosslinking accelerator; Characterized in that the rubber composition for the wiper blade comprising a.

이하 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 와이퍼 블레이트 고무 조성물은 천연고무와 에틸렌-프로필렌 디엔 고무를 혼합하여 사용한다.The wiper blade rubber composition of the present invention uses a mixture of natural rubber and ethylene-propylene diene rubber.

에틸렌-프로필렌 디엔고무 (ethylene-propylene-diene rubber)는 구조적으로 주쇄 내에 이중결합을 거의 가지고 있지 않기 때문에 오존 (Oznoe)이나 산소에 의한 노화에 상당히 강하다. 그러나, 탄성이나 내마모성 등의 기계적 강도는 천연고무에 비해 상대적으로 떨어져서 에틸렌-프로필렌 디엔고무를 단독으로 사용하기에는 부족함이 있다. 이에, 본 발명에서는 천연고무를 혼합하여 탄성 및 내마모성을 높일 수 있다. 상기 천연고무는 주쇄 내에 많은 불포화기의 이중결합을 가지고 있어, 공기 중의 오존의 공격에 의해서 사슬결합이 끊어지면서 노화 및 크랙이 발생할 우려가 있으므로, 그 함량을 제한한다. 바람직하기로는 천연고무와 에틸렌-프로필렌 디엔고무를 85/15 ∼ 65/35 중량% 비율로 사용한다.Ethylene-propylene-diene rubber is very resistant to aging by ozone or oxygen because it has few double bonds in its backbone. However, mechanical strength such as elasticity and abrasion resistance is relatively inferior to that of natural rubber, and thus it is insufficient to use ethylene-propylene diene rubber alone. Thus, in the present invention, it is possible to increase elasticity and wear resistance by mixing natural rubber. The natural rubber has a large number of double bonds of unsaturated groups in the main chain, the chain bond is broken by the attack of ozone in the air, so aging and cracks may occur, thereby limiting its content. Preferably, natural rubber and ethylene-propylene diene rubber are used in a ratio of 85/15 to 65/35% by weight.

최종적으로 얻어진 와이퍼 블레이드 조성물은 천연고무를 연속상으로 하고 에틸렌-프로필렌 디엔고무가 분산상으로 균일하게 분포되어 있는 매트릭스 구조를 가진다. 이렇게 제조된 고무 조성물은 탄성이나 내마모성 등의 기계적 물성은 천연고무의 물성수준에 근접하게 유지하면서 내오존성과 내열성, 내약품성 그리고 내후성 등이 목표수준을 만족하는 결과를 얻을 수 있다.The finally obtained wiper blade composition has a matrix structure in which natural rubber is a continuous phase and ethylene-propylene diene rubber is uniformly distributed in a dispersed phase. In the rubber composition thus prepared, mechanical properties such as elasticity and abrasion resistance may be maintained close to those of natural rubber, and ozone, heat resistance, chemical resistance, and weather resistance may achieve a target level.

상기 조성에 더하여 본 발명에서는 제3성분으로서 유기 및 무기 첨가제를 첨가한다.In addition to the above composition, in the present invention, organic and inorganic additives are added as third components.

천연고무 및 에틸렌-프로필렌 디엔 고무는 혼합 사용시 물성이 우수하나, 서로간의 구조적인 차이로 인하여 사용성이 좋지 못하다. 이처럼, 특정한 고무들을 블렌드 할 때는 화학적으로나 물리적으로 상용성이 상이한 경우에는 제 3성분으로서 적당한 상용화제를 사용하여 서로의 상용성을 최대한 크게 만드는 것이 바람직하다. 2가지 이상의 고무들을 혼합할 때 적당한 상용화제를 첨가하게 되면, 분산상의 입자 직경이 연속상에 미세하게 분산되므로 양쪽 성분의 특성을 보다 효과적으로 발현되게 한다.Natural rubber and ethylene-propylene diene rubber have excellent physical properties when mixed and used, but due to structural differences between them, their usability is poor. As such, when blending certain rubbers, the chemically and physically different compatibility, it is desirable to make the compatibility with each other as much as possible using a suitable compatibilizer as the third component. When a suitable compatibilizer is added when mixing two or more rubbers, the particle diameter of the dispersed phase is finely dispersed so that the characteristics of both components can be expressed more effectively.

본 발명에서 사용되는 천연고무와 에틸렌-프로필렌 디엔 고무는 주쇄내의 불포화도의 차이와 보강제인 카본블랙과의 친화성, 그리고 가황 속도 등의 구조적인 차이로 인해서 서로 상용성이 좋지 못하여, 블렌드시 균일한 혼합상태의 고무 조성물을 얻기가 어려운 문제점이 있다. 이러한 문제점을 해결하기 위하여, 본 발명에서는 액상 에틸렌-프로필렌 디엔 고무를 상용화제로써 4 ∼ 7.5 phr까지 상기 혼합 고무 조성물 (천연고무 + 에틸렌-프로필렌 디엔 고무)에 첨가함으로써 균일한 (homogeneous) 조성물을 얻을 수 있다. 사용 가능한 상용화제는 이 분야에서 통상적으로 사용되고 있는 것이면 어느 것이든 가능하고, 본 발명에서 특별히 한정하지는 않는다The natural rubber and ethylene-propylene diene rubber used in the present invention are not compatible with each other due to structural differences such as differences in unsaturation in the main chain, affinity with carbon black as a reinforcing agent, and vulcanization rate. There is a problem that it is difficult to obtain a rubber composition in a mixed state. In order to solve this problem, in the present invention, a homogeneous composition is obtained by adding liquid ethylene-propylene diene rubber to the mixed rubber composition (natural rubber + ethylene-propylene diene rubber) up to 4 to 7.5 phr as a compatibilizer. Can be. The usable compatibilizer can be any one as long as it is commonly used in this field, and is not particularly limited in the present invention.

상기 상용화제 외에 최종 고무 조성물의 물성을 높이기 위하여 여러가지 첨가제를 사용할 수 있다. 이러한 첨가제의 선택은 이 분야의 통상적인 지식을 가진 자에 의하여 선택되어 지며 그 함량 또한 적절히 조절된다.Various additives may be used in addition to the compatibilizer to increase the physical properties of the final rubber composition. The choice of such additives is chosen by one of ordinary skill in the art and the content thereof is also appropriately controlled.

본 발명에서는 고무의 보강재로 고무와의 친화성이 우수하고 분산이 용이한 카본블랙을 사용한다. 그 함량은 상기 혼합 고무 조성물 100 중량부에 대해 40 ∼ 50 phr(parts per hundred rubber)를 사용함으로써 장기간 사용 되더라도 내구성이 우수한 고무 조성물을 얻을 수 있다. 만약 그 사용량이 50 중량부를 초과하면 강도 측면에선 유리하나, 외부의 충격시 카본블랙이 크랙의 발생점이 될 가능성이 크고 또한 고무의 주 기능인 탄성력이 떨어지는 문제점이 있어 바람직하지 못하다. 상기 카본블랙의 종류는 본 발명에서 특별히 한정하지는 않으며 이 분야에서 널리 사용되는 것이면 사용가능하며, 일예로 SAF(입경; 11 ∼ 19nm), ISAF(입경; 20 ∼ 25nm), HAF(입경; 26 ∼ 30nm), FF(입경; 31 ∼ 39nm), FEF(입경; 40 ∼ 48nm), GPF(입경; 49 ∼ 60nm), SRF(입경; 61 ∼ 100nm), FT(입경; 101 ∼ 200nm), MT(입경; 201 ∼ 500nm) 등의 카본블랙을 더욱 함유할 수 있다.In the present invention, carbon black having excellent affinity with rubber and easily dispersing is used as a rubber reinforcing material. The content is 40 to 50 phr (parts per hundred rubber) with respect to 100 parts by weight of the mixed rubber composition can be obtained a rubber composition excellent in durability even if used for a long time. If the amount of use exceeds 50 parts by weight, it is advantageous in terms of strength, but it is not preferable because carbon black is likely to be a point of occurrence of cracks when impacted from the outside and the elastic force, which is a main function of rubber, is lowered. The kind of the carbon black is not particularly limited in the present invention and may be used as long as it is widely used in this field. For example, SAF (particle diameter; 11 to 19 nm), ISAF (particle diameter; 20 to 25 nm), and HAF (particle diameter; 26 to 30 nm), FF (particle diameter; 31 to 39 nm), FEF (particle diameter; 40 to 48 nm), GPF (particle diameter; 49 to 60 nm), SRF (particle diameter; 61 to 100 nm), FT (particle diameter; 101 to 200 nm), MT ( Particle diameters; 201 to 500 nm) and the like.

또다른 첨가제로 카본블랙의 분산을 돕고, 고무제품의 연성도 (flexibility)를 개선하기 위하여 고무 연화제를 고무 혼합 조성물에 대하여 3 ∼ 5 phr 첨가한다.Another additive is to add 3 to 5 phr of a rubber softener to the rubber blend composition to help disperse the carbon black and to improve the ductility of the rubber product.

이외에, 고무 조성물의 황에 의한 가교화를 수행하기 위하여 황 및 가교제 등을 첨가한다. 이러한 가교 시스템은 고무의 내열성, 내구성 등의 물성에 중요한 역할을 하게 되므로 가교제, 촉진제 및 가교 활성제의 배합비율이 적절히 조절되어야만 한다. 본 발명에서는 상기 가교시스템으로서 천연고무와 에틸렌-프로필렌 디엔고무의 공가교를 가능토록 하기 위하여 유황과 과산화물을 같이 사용하는 가교시스템을 적용하였다. 구체적으로, 열 가교를 증가시키기 위한 가교 활성제로 산화아연(ZnO) 3 ∼ 5phr, 스테아린산을 1 ∼ 2 phr 첨가하고, 가교제로 유황을 고무 중량비로 2 phr 이하, 촉진제로 N-t-부틸-2-벤조티아졸 설펜아마이드 (N-t-butyl-2-benxothiazole sulfenamide)와, 테트라메틸티우람 모노설파이드 (Tetramethylthiuram monosulfide)를 0.5 ∼ 2.0 phr 적용하였다. 이러한 가교시스템으로 인해서 압축영구 줄음률을 개선할 수 있게 되었다.In addition, sulfur, a crosslinking agent, and the like are added to effect crosslinking with sulfur of the rubber composition. Since such a crosslinking system plays an important role in physical properties such as heat resistance and durability of the rubber, the blending ratio of the crosslinking agent, the accelerator and the crosslinking activator must be properly adjusted. In the present invention, in order to enable co-crosslinking of natural rubber and ethylene-propylene diene rubber as the crosslinking system, a crosslinking system using both sulfur and a peroxide was applied. Specifically, 3 to 5 phr of zinc oxide (ZnO) and 1 to 2 phr of stearic acid are added as a crosslinking activator to increase thermal crosslinking, and sulfur is contained in a rubber weight ratio of 2 phr or less as a crosslinking agent, and Nt-butyl-2-benzo as an accelerator. Thiazole sulfenamide (Nt-butyl-2-benxothiazole sulfenamide) and tetramethylthiuram monosulfide were applied at 0.5 to 2.0 phr. Due to this crosslinking system it is possible to improve the compression set.

이외에 산화방지제(ANTI-OXIDANT), 노화 물성 저하를 방지하기 위해 결합화제 (COUPLING AGENT)를 등으로 이루어지는 통상의 고무 조성물에 사용되는 첨가제가 필요에 따라 사용될 수 있다.In addition to the additives used in conventional rubber compositions consisting of antioxidant (ANTI-OXIDANT), COUPLING AGENT, etc. in order to prevent deterioration of aging properties can be used as necessary.

또한, 상기 본 발명의 와이퍼 블레이드용 고무 조성물의 제조방법은 본 명세서에서 별도로 설명하지 않겠는 바, 그 제조방법은 이 분야에서 통상적으로 사용되는 제조방법에 따라 제조가 가능하다. 일예로 통상의 기계적 혼련법에 의하여 제조하는 것이 가능하다. 구체적으로 예를들면, 반바리 믹서, 싱글스크류 압출기, 트윈스크류 압출기, 다륜스크류 압출기 등의 일반적인 용융 혼련기를 이용하는 방법을 채용할 수 있다. 또한, 본 발명의 조성물에 대한 성형 가공법의 경우 압출성형, 중공성형, 사출성형, 시트성형 등으로 특히 한정되는 것은 없으나 사출성형이 가장 적합하다.In addition, the manufacturing method of the rubber composition for the wiper blade of the present invention will not be described separately herein, the manufacturing method may be prepared according to a manufacturing method commonly used in this field. For example, it is possible to manufacture by a conventional mechanical kneading method. Specifically, for example, a method using a general melt kneading machine such as a short-barrier mixer, a single screw extruder, a twin screw extruder, or a multi-screw screw extruder can be adopted. In addition, the molding process for the composition of the present invention is not particularly limited to extrusion molding, blow molding, injection molding, sheet molding, etc., but injection molding is most suitable.

본 발명의 바람직한 실시예에 따르면 상기 조성으로 제조된 조성물의 물성을 측정한 결과, 우수한 기계적 강도 및 내오존성을 갖는 탄성 중합체가 얻어짐을 확인할 수 있었다. 또한 내열노화시험, 내알콜성 노화시험 및 내오존성 노화시험에서도 만족스러운 결과를 얻었다. 이에 따라 종래 천연고무나 클로로프렌 고무 단독으로 와이퍼 블레이드의 생산시 내오존성을 개선하기 위해서 첨가한 IPPD나 6PPD와 같은 내오존노방제의 사용으로 화학적 표면 처리시 야기되는 문제점을 개선할 수 있게 되었다.According to a preferred embodiment of the present invention, it was confirmed that the elastic polymer having excellent mechanical strength and ozone resistance was obtained as a result of measuring the physical properties of the composition prepared with the composition. In addition, satisfactory results were obtained in the heat aging test, the alcohol resistance aging test, and the ozone resistance aging test. Accordingly, it is possible to improve the problems caused by chemical surface treatment by using ozone-resistant agents such as IPPD or 6PPD added to improve ozone resistance in the production of wiper blades using conventional natural rubber or chloroprene alone.

또한 천연고무와 에틸렌-프로필렌 디엔고무 블렌드의 가교시스템을 유황과 과산화물로 동시에 유도할 수 있는 공가교시스템을 실시하여 압축영구줄음률을 개선하는 효과가 있어 와이퍼 블레이드의 품질향상에 기여 할 수 있다.In addition, the cross-linking system of natural rubber and ethylene-propylene diene rubber blend can be simultaneously introduced into sulfur and peroxide to improve compressive permanent shrinkage, thereby contributing to the improvement of wiper blade quality.

이와 같은 본 발명을 실시예에 의거하여 설명하겠는 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Although this invention is demonstrated based on an Example, this invention is not limited by an Example.

와이퍼 블레이드용 고무 조성물을 제조하기 위해 하기 표 1에 나타낸 바대로 고무 배합을 실시하여 시편을 제조하였으며, 그 결과를 비교 평가하였다.In order to prepare a rubber composition for the wiper blade, a rubber compounding was carried out as shown in Table 1 to prepare a specimen, and the results were compared and evaluated.

실시예 1 ∼ 5 및 비교예 1Examples 1-5 and Comparative Example 1

천연고무, 에틸렌-프로필렌 디엔 고무 및 상용화제를 반바리 믹서 (BANBURY MIXER, KOBE STEEL. CO)를 이용하여 2분간 소련 후 카본블랙을 투입하고 2분간 혼련하였다. 그 후 기타 첨가제를 혼합하여 2분간 혼련하여 카본 바스터 배치(Carbon Master Batch CMB)를 제조하였다. 상기 제조된 CMB에 가황제를 롤 믹서(Roll Mixer)를 이용하여 분산 혼합하였다.Natural rubber, ethylene-propylene diene rubber, and a compatibilizer were kneaded for 2 minutes and then mixed with carbon black for 2 minutes using a BANBURY MIXER (KOBE STEEL.CO). Thereafter, other additives were mixed and kneaded for 2 minutes to prepare a carbon master batch (MB). The vulcanizing agent was dispersed and mixed in the prepared CMB using a roll mixer.

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 비교예 1Comparative Example 1 천연고무 (중량%)Natural rubber (wt%) 8585 7070 6565 6565 6565 100100 EDPM (중량%)EDPM (% by weight) 7.57.5 3030 3535 3535 3535 -- 1)액상 EDPM (중량부*) 1) Liquid EDPM (parts by weight * ) 7.57.5 44 44 -- -- -- 산화아연 (중량부)Zinc Oxide (parts by weight) 55 55 33 55 55 33 스테아린산 (중량부)Stearic Acid (parts by weight) 1One 1One 1One 1One 1One 22 2)산화방지제 1 (중량부) 2) antioxidant 1 (by weight) 33 -- -- -- -- -- 3)산화방지제 2 (중량부) 3) antioxidant 2 (parts by weight) -- -- -- 1One 1One -- 내오존방지제 (중량부)Ozone resistant agent (parts by weight) -- -- -- -- -- 33 Wax (중량부)Wax (parts by weight) -- -- -- -- -- 22 카본블랙 (중량부)Carbon Black (parts by weight) 5050 4545 5050 4040 4040 4545 석유계 연화제 (중량부)Petroleum Softener (parts by weight) 33 33 1010 33 33 55 유황 (중량부)Sulfur (parts by weight) 2.02.0 1.751.75 1.251.25 2.02.0 0.60.6 2.02.0 촉진제 (중량부)Accelerator (parts by weight) 1.51.5 1.51.5 0.950.95 1.751.75 1.71.7 1.251.25 DCP 40% (중량부)DCP 40% (by weight) -- -- -- -- 2.52.5 -- 1)액상 EPDM : Uniroyal Trilene 67 or Trilene 772)산화방지제 1 : Polymerized 1,2-dihydro-2,2,4-trimethylquinoline, Uniroyal Naugard Q3)산화방지제 2 : 4,4-Bis(alpha, alpha-dimethylbenzyl)diphenylamine, UniroyalNaugard 445중량부*: 천연고무, EPDM 을 100 중량부 기준으로 한 중량부 1) Liquid EPDM: Uniroyal Trilene 67 or Trilene 77 2) Antioxidant 1: Polymerized 1,2-dihydro-2,2,4-trimethylquinoline, Uniroyal Naugard Q 3) Antioxidant 2: 4,4-Bis (alpha, alpha -dimethylbenzyl) diphenylamine, UniroyalNaugard 445 parts by weight * : parts by weight based on 100 parts by weight of natural rubber, EPDM

시험예Test Example

상기 실시예 1 ∼ 5 및 비교예에서 얻어진 고무 조성물의 물성을 알아보기 위하여 국내 KS 관련규격에 의해 각종 물성을 측정하였고, 얻어진 결과를 하기 표 2에 나타내었다.In order to find out the physical properties of the rubber composition obtained in Examples 1 to 5 and Comparative Examples, various physical properties were measured by domestic KS-related standards, and the obtained results are shown in Table 2 below.

항목Item 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 비교예 1Comparative Example 1 경도 (shore A)Hardness (shore A) 6161 6969 6060 7070 6464 6262 모듈러스 (㎏f/㎠) 100%Modulus (㎏f / ㎠) 100% 3030 3838 2626 3535 2727 3333 신율 (%)Elongation (%) 450450 431431 490490 490490 560560 443443 인장강도 (㎏f/㎠)Tensile Strength (㎏f / ㎠) 192192 185185 176176 220220 241241 240240 압축영구줄음률(%)(80 ℃ ×22 hrs)Compressive permanent shrinkage (%) (80 ° C × 22 hrs) 2626 3333 3434 3434 2020 3333 * 내열노화시험 (80 ℃ ×72 hrs)* Heat aging test (80 ℃ × 72 hrs) 경도변화율 (pts)Hardness change rate (pts) +7+7 00 +2+2 +1+1 00 +3+3 신율변화율 (%)Elongation rate of change (%) -29-29 -12-12 -10-10 -13-13 -2-2 -11-11 인장강도변화율 (%)Tensile Strength Change Rate (%) -14-14 -13-13 -15-15 -1-One +2+2 -4-4 * 내알콜성 노화시험 (실온 ×24 hrs)* Alcohol resistance aging test (room temperature × 24 hrs) 무게변화율 (%)Weight change rate (%) 1One 1One -0.5-0.5 00 00 1One 부피변화율 (%)Volume change rate (%) 1One 1One -0.5-0.5 -0.5-0.5 +0.5+0.5 1One * 내오존성 노화시험 (40 ℃ ×50 pphm ×72 hrs ×20 % 신장)* Ozone resistance aging test (40 ℃ × 50 pphm × 72 hrs × 20% elongation) 크랙발생Crack 크랙발생없음No crack 크랙발생없음No crack 크랙발생없음No crack 크랙발생없음No crack 크랙발생Crack

상기 표 2에 따르면, 에틸렌-프로필렌 디엔고무를 사용하지 않고 천연고무에 내오존노방제와 왁스류를 사용하여 배합한 비교예와 에틸렌-프로필렌 디엔 고무와 액상 에틸렌-프로필렌 디엔 고무를 사용한 실시예를 비교한 결과, 본 발명에 따른 실시예 1 ∼ 3의 고무 조성물은 전반적으로 기계적 물성이 약간 낮아진 반면, 실시예 4 ∼ 5의 고무 조성물은 에틸렌 프로필렌 디엔고무의 함량이 높음에도 불구하고 비교예와 유사한 물성을 나타내었다. 이러한 결과는 천연고무와 에틸렌-프로필렌 디엔고무를 혼합하면 천연고무 단독의 경우에 비해서 기계적 물성이 떨어진다는 사실이 인정되지만, 실시예 4 ∼ 5에 따른 결과에 의해 이런 점을 극복 할 수 있는 것으로 나타났다.According to Table 2 above, Comparative Examples in which ozone antifouling agents and waxes are combined with natural rubber without using ethylene-propylene diene rubber and Examples using ethylene-propylene diene rubber and liquid ethylene-propylene diene rubber are shown. As a result, the rubber compositions of Examples 1 to 3 according to the present invention had slightly lower overall mechanical properties, while the rubber compositions of Examples 4 to 5 were similar to the comparative examples despite the high content of ethylene propylene diene rubber. Physical properties were shown. These results indicate that the mixing of natural rubber and ethylene-propylene diene rubber is inferior to the physical properties of natural rubber alone, but the results according to Examples 4 to 5 show that this can be overcome. .

더욱이, 비교예 1의 조성물은 화학적 표면처리시 고무 표면에 스며나온 내오존방지제와 왁스류가 씻겨나가면서 문제가 발생하지만, 실시예 1 ∼ 5의 그것은 화학적 표면처리시 아무런 문제가 발생되지 않을 것이 기대된다. 따라서, 본 발명에 의해 얻어진 고무 조성물은 전반적으로 와이퍼 블레이드의 고무의 성능이 향상되는 것으로 판단된다.Moreover, the composition of Comparative Example 1 has a problem in that the ozone inhibitor and waxes that have leaked out to the rubber surface during chemical surface treatment are washed away, but in Examples 1 to 5, it does not cause any problem during chemical surface treatment. It is expected. Therefore, it is judged that the rubber composition obtained by the present invention generally improves the performance of the rubber of the wiper blade.

따라서, 본 발명은 종래의 천연고무나 클로로프렌 고무 단독으로 와이퍼 블레이드의 생산시 내오존성을 개선하기 위해서 첨가한 IPPD나 6PPD와 같은 내오존노방제의 사용으로 화학적 표면 처리시 야기되는 문제점을 개선하는 효과가 있고, 또한 천연고무와 에틸렌-프로필렌 디엔고무의 혼합시 소량의 액상 에틸렌-프로필렌 디엔고무를 첨가함으로써 균일한 조성물을 얻을 수 있어 우수한 기계적 강도와 내오존성을 갖는 탄성중합체를 얻을 수 있는 장점이 있다.Accordingly, the present invention is effective in improving the problems caused by chemical surface treatment by using ozone antifouling agents such as IPPD or 6PPD added to improve ozone resistance in the production of wiper blades with conventional natural rubber or chloroprene rubber alone. In addition, a uniform composition can be obtained by adding a small amount of liquid ethylene-propylene diene rubber when mixing natural rubber and ethylene-propylene diene rubber, thereby obtaining an elastomer having excellent mechanical strength and ozone resistance. .

그리고 천연고무와 에틸렌-프로필렌 디엔고무 블렌드의 가교시스템을 유황과 과산화물로 동시에 유도할 수 있는 공가교시스템을 실시하여 압축영구줄음률을 개선하는 효과가 있어 와이퍼 블레이드의 품질향상에 기여 할 수 있다.In addition, the cross-linking system of natural rubber and ethylene-propylene diene rubber blend can be induced simultaneously with sulfur and peroxide to improve compressive permanent shrinkage, thereby contributing to the improvement of wiper blade quality.

Claims (2)

와이퍼 블레이드용 고무 조성물에 있어서,In the rubber composition for wiper blades, 천연고무 및 에틸렌-프로필렌 고무가 85/15 ∼ 65/35 중량%비로 혼합되어 있는 고무 혼합물에 대하여,For rubber mixtures in which natural rubber and ethylene-propylene rubber are mixed at a ratio of 85/15 to 65/35% by weight, 상용화제 4 ∼ 7.5 phr;Compatibilizers 4 to 7.5 phr; 보강 충진제인 카본블랙 40 ∼ 50 phr;Carbon black 40 to 50 phr as reinforcing filler; 석유계 고무 연화제 3 ∼ 5 phr;Petroleum rubber softener 3-5 phr; 가교 활성제로 산화아연 (ZnO) 3 ∼ 5phr 및 스테아린산 1 ∼ 2 phr;Zinc oxide (ZnO) 3-5 phr and stearic acid 1-2 phr as crosslinking activators; 가교제로 유황 2 phr 이하;Sulfur up to 2 phr as crosslinker; 가교 촉진제로 N-t-부틸-2-벤조티아졸 설펜아마이드 (N-t-butyl-2-benxothiazole sulfenamide)와, 테트라메틸티우람 모노설파이드 (Tetramethylthiuram monosulfide) 0.5 ∼ 2.0 phr; 를 포함하는 것을 특징으로 하는 와이퍼 블레이드용 고무 조성물.N-t-butyl-2-benxothiazole sulfenamide and tetramethylthiuram monosulfide 0.5 to 2.0 phr as crosslinking accelerator; Rubber composition for wiper blades comprising a. 제 1항에 있어서, 상기 가교활성제, 가교제 및 가교 촉진제를 포함하는 가교시스템은 천연고무와 에틸렌-프로필렌 디엔고무 블렌드의 가교를 동시에 유도하는 공가교시스템인 것을 특징으로 하는 조성물.The composition of claim 1, wherein the crosslinking system comprising a crosslinking agent, a crosslinking agent and a crosslinking accelerator is a co-crosslinking system which induces crosslinking of a natural rubber and an ethylene-propylene diene rubber blend simultaneously.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100687692B1 (en) * 2006-05-16 2007-02-27 (주) 세흥 Rubber alloy and manufacturing method the same
KR101427678B1 (en) * 2012-11-23 2014-08-07 조선대학교산학협력단 Rubber compound of automobile accessories to improve aging physical properties

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008190A (en) * 1973-01-02 1977-02-15 The B. F. Goodrich Company Vulcanizates of EPDM and diene rubber blends
US4861819A (en) * 1987-11-02 1989-08-29 Ford Motor Company Wiper blade compositions
JPH11335566A (en) * 1998-05-22 1999-12-07 Yokohama Rubber Co Ltd:The Wiper blade
KR20010027458A (en) * 1999-09-14 2001-04-06 하기와라 세이지 Wiper blade
JP2001219821A (en) * 1999-11-29 2001-08-14 Yokohama Rubber Co Ltd:The Wiper blade

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008190A (en) * 1973-01-02 1977-02-15 The B. F. Goodrich Company Vulcanizates of EPDM and diene rubber blends
US4861819A (en) * 1987-11-02 1989-08-29 Ford Motor Company Wiper blade compositions
JPH11335566A (en) * 1998-05-22 1999-12-07 Yokohama Rubber Co Ltd:The Wiper blade
KR20010027458A (en) * 1999-09-14 2001-04-06 하기와라 세이지 Wiper blade
JP2001219821A (en) * 1999-11-29 2001-08-14 Yokohama Rubber Co Ltd:The Wiper blade

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100687692B1 (en) * 2006-05-16 2007-02-27 (주) 세흥 Rubber alloy and manufacturing method the same
KR101427678B1 (en) * 2012-11-23 2014-08-07 조선대학교산학협력단 Rubber compound of automobile accessories to improve aging physical properties

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