KR100426060B1 - Natural rubber compound with silica and polyethylene glycol - Google Patents

Natural rubber compound with silica and polyethylene glycol Download PDF

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KR100426060B1
KR100426060B1 KR10-2001-0000651A KR20010000651A KR100426060B1 KR 100426060 B1 KR100426060 B1 KR 100426060B1 KR 20010000651 A KR20010000651 A KR 20010000651A KR 100426060 B1 KR100426060 B1 KR 100426060B1
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silica
polyethylene glycol
phr
natural rubber
rubber compound
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KR10-2001-0000651A
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KR20020057556A (en
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정승기
박성수
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금호타이어 주식회사
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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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

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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

본 발명은 보강제로 실리카 및 가류보조제로 폴리에틸렌글리콜이 함유된 천연고무 배합물에 관한 것이다.The present invention relates to a natural rubber blend containing silica as a reinforcing agent and polyethylene glycol as a vulcanization aid.

본 발명의 실리카와 폴리에틸렌글리콜이 함유된 천연고무 배합물은 공지의 천연고무 배합물에 있어서, 원료고무인 천연고무 100 phr에 대하여 실리카 60∼80 phr, 실란커플링제 4.8∼6.4 phr, 가류보조제로 폴리에틸렌글리콜 2 phr 이내 포함함을 특징으로 한다.The natural rubber compound containing the silica and polyethylene glycol of the present invention is a known natural rubber compound, in which 60 to 80 phr of silica, 4.8 to 6.4 phr of silane coupling agent, and polyethylene glycol 2 are used as a vulcanization aid. It is characterized by including within the phr.

본 발명은 보강재로 카본블랙만을 사용한 종래의 기술에 대하여 카본블랙 이외에 보강재료의 일종인 실리카를 사용하여 상기의 문제점을 해결하고자 하였다. 또한 고무와 혼화성이 낮은 실리카의 단점을 해결하기 위해 실란커플링제와 폴리에틸렌글리콜을 가류보조제로 사용함으로써 역학적인 물성을 증가시키고 열안정성과 인열강도를 보강하여 회전저항 특성을 높인 천연고무 배합물을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems by using silica which is a kind of reinforcing material in addition to carbon black with respect to the conventional technology using only carbon black as the reinforcing material. In addition, the silane coupling agent and polyethylene glycol are used as vulcanization aids to solve the disadvantages of silica, which is incompatible with rubber. Therefore, natural rubber formulations with increased rotational resistance by increasing mechanical properties and strengthening thermal stability and tear strength It aims to provide.

Description

실리카와 폴리에틸렌글리콜이 함유된 천연고무 배합물{Natural rubber compound with silica and polyethylene glycol}Natural rubber compound with silica and polyethylene glycol

본 발명은 보강제로 실리카 및 가류보조제로 폴리에틸렌글리콜이 함유된 천연고무 배합물에 관한 것이다.The present invention relates to a natural rubber blend containing silica as a reinforcing agent and polyethylene glycol as a vulcanization aid.

타이어의 보강재료로 사용하는 카본블랙은 현재도 많이 사용하고 있으나 환경적인 문제와 낮은 재활용의 문제가 있다. 즉 완제품의 제동력과 회전저항이 크고 낮은 연비로 인하여 환경오염을 증가시키고 고온 점탄성 효과가 떨어지는 문제가 있다. 이러한 문제점을 해결하고자 기존의 카본블랙 사용시와 동일 또는 유사한 효과를 갖으면서도 환경친화적인 제품을 생산할 수 있는 새로운 보강재료에 대한 연구가 계속적으로 진행되고 있다.Carbon black, which is used as a reinforcing material for tires, is still used a lot but there are environmental problems and low recycling problems. That is, the braking force and rotational resistance of the finished product has a problem of increasing environmental pollution and low temperature viscoelastic effect due to low and low fuel consumption. In order to solve these problems, research on new reinforcing materials that can produce environmentally friendly products while having the same or similar effects as the existing carbon black is continuously conducted.

본 발명은 보강재로 카본블랙만을 사용한 종래의 기술에 대하여 카본블랙 이외에 보강재료의 일종인 실리카를 사용하여 상기의 문제점을 해결하고자 하였다. 또한 고무와 혼화성이 낮은 실리카의 단점을 해결하기 위해 실란커플링제와 폴리에틸렌글리콜을 가류보조제로 사용함으로써 역학적인 물성을 증가시키고 열안정성과 인열강도를 보강하여 회전저항 특성을 높인 천연고무 배합물을 제공하는 것을 목적으로 한다.The present invention is to solve the above problems by using silica which is a kind of reinforcing material in addition to carbon black with respect to the conventional technology using only carbon black as the reinforcing material. In addition, the silane coupling agent and polyethylene glycol are used as vulcanization aids to solve the disadvantages of silica, which is incompatible with rubber. It aims to provide.

본 발명의 실리카와 폴리에틸렌글리콜이 함유된 천연고무 배합물은 공지의 천연고무 배합물에 있어서, 원료고무인 천연고무 100 phr에 대하여 실리카 60∼80 phr, 실란커플링제 4.8∼6.4 phr, 가류보조제로 폴리에틸렌글리콜 2 phr 이내 포함함을 특징으로 한다.The natural rubber compound containing the silica and polyethylene glycol of the present invention is a known natural rubber compound, in which 60 to 80 phr of silica, 4.8 to 6.4 phr of silane coupling agent, and polyethylene glycol 2 are used as a vulcanization aid. It is characterized by including within the phr.

상기에서 폴리에틸렌글리콜은 분자량이 3000∼6000인 것을 사용하는데 폴리에틸렌글리콜의 분자량에 따라 본 발명에 차이가 있지는 않으며 상기 범위의 분자량의 폴리에틸렌글리콜을 사용하는 이유는 입수가 용이하고 가격이 저렴하기 때문이다.The polyethylene glycol is used as the molecular weight of 3000 to 6000, but there is no difference in the present invention according to the molecular weight of the polyethylene glycol, the reason for using the polyethylene glycol of the above range is because it is easy to obtain and the price is low.

실리카는 BET 168∼212m2/g, CTAB 130∼159, DOP 205∼267cc/100g, 점도 7,500∼36000mPa·s, pH 6.2∼6.8, D50 2.6∼9.6㎛d인 것을 사용하는 것이 좋으며 아래의 표 1에 본 발명에 사용가능한 실리카의 종류 및 특징을 나타내었다.Silica is recommended to use BET 168 ~ 212m 2 / g, CTAB 130 ~ 159, DOP 205 ~ 267cc / 100g, viscosity 7,500 ~ 36000mPa.s, pH 6.2 ~ 6.8, D50 2.6 ~ 9.6㎛d Table 1 below The types and characteristics of silica usable in the present invention are shown.

표 1. 실리카 분류별 특성Table 1. Properties of Silica Classification

물성Properties silica-Asilica-A silica-Bsilica-B silica-Csilica-C BET(m2/g)BET (m 2 / g) 212212 175175 168168 CTAB(m2/g)CTAB (m 2 / g) 130130 159159 156156 DOP(cc/100g)DOP (cc / 100g) 205205 267267 222222 점도(mPa·s)Viscosity (mPas) -- 7,5007,500 36,00036,000 pHpH 6.26.2 6.76.7 6.86.8 D50(㎛)D50 (㎛) -- 9.29.2 2.62.6

이하 본 발명을 다음의 비교예, 실시예 및 시험예에 의하여 설명하고자 한다. 그러나 이들이 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following comparative examples, examples and test examples. However, these do not limit the technical scope of the present invention.

<비교예>Comparative Example

아래의 표 2와 같이 원료고무로 천연고무(Standard Malaysian Rubber, SMR CV) 100 phr에 대하여 카본블랙(N330) 50 phr, 분자량 4000인 폴리에틸렌글리콜(PEG) 2.0 phr, 산화아연 5.0 phr, 스테아린 산 5.0 phr, N-1-3-디메틸렌(N-1,3-Dimethylene, 6PPD) 2 phr, 왁스 2 phr, 황 1.4 phr, N-t-부틸벤조티아졸(N-t-butylbenzothiazol, TBBS) 1.8 phr, 디페닐구아니딘(Diphenylguanidine, DPG) 2.0을 160℃에서 30분간 가류하여 고무시편을 제조하였다.50 phr of carbon black (N330), polyethylene glycol (PEG) with a molecular weight of 4000 phr, zinc oxide 5.0 phr, stearic acid 5.0 with respect to 100 phr of natural rubber (Standard Malaysian Rubber, SMR CV) as raw material rubber as shown in Table 2 below. phr, N-1-3-dimethylene (N-1,3-Dimethylene, 6PPD) 2 phr, wax 2 phr, sulfur 1.4 phr, Nt-butylbenzothiazol (TBBS) 1.8 phr, diphenyl Guanidine (Diphenylguanidine, DPG) 2.0 was vulcanized at 160 ℃ for 30 minutes to prepare a rubber specimen.

<실시예 1><Example 1>

카본블랙(N330) 대신에 실리카(B grade) 60 phr, 실란커플링제(Si-69) 4.8 phr 사용하는 것을 제외하고는 상기 비교예와 같은 조성물 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Comparative Example except that 60 phr silica (B grade) and 4.8 phr silane coupling agent (Si-69) were used instead of carbon black (N330).

<실시예 2><Example 2>

카본블랙(N330) 대신에 실리카(B grade) 70 phr, 실란커플링제(Si-69) 5.6 phr 사용하는 것을 제외하고는 상기 비교예와 같은 조성물 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Comparative Example except that 70 phr silica (B grade) and 5.6 phr silane coupling agent (Si-69) were used instead of carbon black (N330).

<실시예 3><Example 3>

카본블랙(N330) 대신에 실리카(B grade) 80 phr, 실란커플링제(Si-69) 6.4 phr 사용하는 것을 제외하고는 상기 비교예와 같은 조성물 및 방법을 이용하여 고무시편을 제조하였다.A rubber specimen was prepared using the same composition and method as in Comparative Example except that 80 phr silica (B grade) and 6.4 phr silane coupling agent (Si-69) were used instead of carbon black (N330).

표 2. 비교예 및 실시예의 고무 조성물Table 2. Rubber Compositions of Comparative Examples and Examples

항 목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 천연고무Natural rubber 100100 100100 100100 100100 카본블랙(N330)Carbon black (N330) 5050 00 00 00 실리카(B grade)Silica (B grade) 00 6060 7070 8080 실란커플링제(Si-69)Silane Coupling Agent (Si-69) 00 4.84.8 5.65.6 6.46.4 폴리에틸렌글리콜Polyethylene glycol 2.02.0 2.02.0 2.02.0 2.02.0 산화아연Zinc oxide 5.05.0 5.05.0 5.05.0 5.05.0 스테아린산Stearic acid 3.03.0 3.03.0 3.03.0 3.03.0 6PPD6PPD 2.02.0 2.02.0 2.02.0 2.02.0 왁스Wax 2.02.0 2.02.0 2.02.0 2.02.0 황sulfur 1.41.4 1.41.4 1.41.4 1.41.4 TBBSTBBS 1.81.8 1.81.8 1.81.8 1.81.8 디페닐구아니딘(DPG)Diphenylguanidine (DPG) 2.02.0 2.02.0 2.02.0 2.02.0

<시험예><Test Example>

상기 비교예 및 실시예 1∼3에 의해 제조한 고무시편을 ASTM 관련규정에 의하여 경도, 300% 모듈러스(Modulus), 인장강도, 신율, 찢어짐 저항 및 마모손실을 측정하여 그 결과를 아래의 표 3에 정리하여 나타내었다.The rubber specimens prepared according to Comparative Examples and Examples 1 to 3 were measured for hardness, 300% modulus, tensile strength, elongation, tear resistance, and abrasion loss according to ASTM-related regulations. In summary, it is shown.

표 3. 비교예 및 실시예 시편의 물성Table 3. Properties of Comparative Examples and Examples Specimen

항 목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 경도Hardness 6969 7676 7979 8484 300% 모듈러스(kg/cm2)300% modulus (kg / cm 2 ) 160160 181181 197197 223223 인장강도(kgf/cm2)Tensile strength (kgf / cm 2 ) 310310 300300 270270 282282 신율(%)% Elongation 520520 500500 420420 410410 찢어짐 저항(kg/cm)Tear resistance (kg / cm) 9292 125125 9393 9393 마모손실(mg)Wear loss (mg) 28.528.5 26.526.5 26.026.0 24.524.5

상기 표 3의 결과에서처럼 원료고무인 천연고무 100 phr에 대하여 실리카 60∼80 phr, 실란커플링제 4.8∼6.4 phr, 가류보조제로 폴리에틸렌글리콜 2 phr 이내 포함함을 특징으로 하는 본 발명의 천연고무 배합물은 카본블랙만을 사용한 종래 고무배합물에 비하여 300% 모듈러스, 내마모성이 증가함을 알 수 있다.As shown in the results of Table 3, the natural rubber compound of the present invention is characterized in that the raw rubber includes 60 to 80 phr of silica, 4.8 to 6.4 phr of a silane coupling agent, and 2 phr of polyethylene glycol as a vulcanization aid. It can be seen that 300% modulus and wear resistance are increased compared to the conventional rubber compound using only black.

Claims (2)

공지의 천연고무 배합물에 있어서,In known natural rubber formulations, 원료고무인 천연고무 100 phr에 대하여 BET 168∼212m2/g, CTAB 130∼159, DOP 205∼267cc/100g, 점도 7,500∼36000mPa·s, pH 6.2∼6.8, D50 2.6∼9.6㎛d인실리카 60∼80 phr, 실란커플링제 4.8∼6.4 phr, 가류보조제로 폴리에틸렌글리콜 2 phr 포함함을 특징으로 하는 실리카와 폴리에틸렌글리콜이 함유된 천연고무 배합물.BET 168 to 212 m 2 / g, CTAB 130 to 159, DOP 205 to 267 cc / 100 g, viscosity 7,500 to 36000 mPa · s, pH 6.2 to 6.8, D50 2.6 to 9.6 μm d A natural rubber blend containing silica and polyethylene glycol, characterized in that it contains 80 phr, a silane coupling agent of 4.8 to 6.4 phr, and a vulcanization aid comprising 2 phr of polyethylene glycol. 삭제delete
KR10-2001-0000651A 2001-01-05 2001-01-05 Natural rubber compound with silica and polyethylene glycol KR100426060B1 (en)

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KR20030024955A (en) * 2001-09-19 2003-03-28 금호산업 주식회사 The silica rubber composition of improved processing and dispersibility
US11453763B2 (en) 2018-03-16 2022-09-27 The North Face Apparel Corp. Rubber terpene footwear

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US5403570A (en) * 1991-06-26 1995-04-04 Rhone-Poulenc Chimie Dispersible silica particulates
JPH093245A (en) * 1995-04-17 1997-01-07 Sumitomo Chem Co Ltd Rubber composition, its production and tire tread
US5703151A (en) * 1995-04-17 1997-12-30 Sumitomo Chemical Company, Limited Rubber composition
KR19980070789A (en) * 1997-01-24 1998-10-26 제임스 더블유. 궤드리 Compositions and Methods for Improving Dispersibility and Adhesion of Silica in Elastomeric Materials
KR19990009413A (en) * 1997-07-09 1999-02-05 남일 Tread Rubber Composition
JPH11181160A (en) * 1997-12-25 1999-07-06 Sumitomo Rubber Ind Ltd Rubber composition for tire tread
JPH11343366A (en) * 1998-06-01 1999-12-14 Sumitomo Rubber Ind Ltd Rubber composition for tire tread
KR100321858B1 (en) * 1999-07-07 2002-02-01 신형인 Low Hardness Snow Tread Compound for Ice Road Enhanced Wear Resistant

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5403570A (en) * 1991-06-26 1995-04-04 Rhone-Poulenc Chimie Dispersible silica particulates
US5587416A (en) * 1991-06-26 1996-12-24 Rhone-Poulenc Chimie Dispersible silica particulates and reinforcement of elastomer/rubber matrices therewith
JPH093245A (en) * 1995-04-17 1997-01-07 Sumitomo Chem Co Ltd Rubber composition, its production and tire tread
US5703151A (en) * 1995-04-17 1997-12-30 Sumitomo Chemical Company, Limited Rubber composition
KR19980070789A (en) * 1997-01-24 1998-10-26 제임스 더블유. 궤드리 Compositions and Methods for Improving Dispersibility and Adhesion of Silica in Elastomeric Materials
KR19990009413A (en) * 1997-07-09 1999-02-05 남일 Tread Rubber Composition
JPH11181160A (en) * 1997-12-25 1999-07-06 Sumitomo Rubber Ind Ltd Rubber composition for tire tread
JPH11343366A (en) * 1998-06-01 1999-12-14 Sumitomo Rubber Ind Ltd Rubber composition for tire tread
KR100321858B1 (en) * 1999-07-07 2002-02-01 신형인 Low Hardness Snow Tread Compound for Ice Road Enhanced Wear Resistant

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