KR20020019832A - Tread rubber composition improved reinforcement - Google Patents

Tread rubber composition improved reinforcement Download PDF

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KR20020019832A
KR20020019832A KR1020000053190A KR20000053190A KR20020019832A KR 20020019832 A KR20020019832 A KR 20020019832A KR 1020000053190 A KR1020000053190 A KR 1020000053190A KR 20000053190 A KR20000053190 A KR 20000053190A KR 20020019832 A KR20020019832 A KR 20020019832A
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rubber
silica
phr
rubber composition
pdms
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KR1020000053190A
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Korean (ko)
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한승철
이현화
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신형인
금호산업 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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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 tread rubber composition having improved reinforcing property, which contains polydimethyl siloxane(PDMS) to disperse silica, as a reinforcing agent, uniformly in the rubber composition and to improve the interaction between the silica and a raw rubber. CONSTITUTION: The tread rubber composition comprises 100phr of the raw rubber comprising a natural rubber or a synthetic rubber such as styrene-butadiene rubber and butadiene rubber, 40-80phr of the settled silica having a BET value of 130-200m¬2/g, and 10-50phr of the polydimethyl siloxane(PDMS) having a molecular weight of 30000-50000.

Description

보강성이 향상된 트레드 고무조성물{Tread rubber composition improved reinforcement}Tread rubber composition improved reinforcement

본 발명은 보강성이 향상된 트레드 고무조성물에 관한 것으로서 보다 상세하게는 보강제로 실리카를 사용하는 공지의 트레드 고무조성물에 있어서, 폴리디메틸실록산(polydimethylsiloxane, PDMS)을 고무조성물에 첨가하여 원료고무와 보강제인 실리카와의 친화성을 향상시켜 고무내에서 실리카를 고루 분산되도록 하여 고무조성물의 분산성을 향상시킬 수 있는 트레드 고무조성물에 관한 것이다.The present invention relates to a tread rubber composition with improved reinforcement, and more particularly, in a known tread rubber composition using silica as a reinforcing agent, polydimethylsiloxane (PDMS) is added to the rubber composition to provide a raw rubber and reinforcing agent. The present invention relates to a tread rubber composition capable of improving the dispersibility of the rubber composition by improving the affinity with silica to disperse the silica evenly in the rubber.

자동차 고연비화의 일환으로 타이어의 회전저항 감소를 목적으로 타이어 트레드 고무조성물에서 보강제로 사용하고 있으며 큰 비율을 차지하고 있는 카본블랙 대신 실리카를 사용하는 기술들이 지속적으로 개발되어 왔다. 그러나 실리카는 표면이 극성 실라놀 그룹(silanol group)으로 구성되어 있어 비극성의 성질을 나타나는 천연고무, 스티렌-부타디엔 고무, 부타디엔 고무와 같은 타이어 트레드에 주로 사용되는 고분자와의 상호작용(interaction)이 약하다. 또한 실리카의 표면에 분포하고 있는 실라놀 그룹들이 수소결합으로 강하게 결합되어 있어 고무조성물 내부로쉽게 분산되지 않는 단점을 가지고 있다.As part of high fuel efficiency in automobiles, tire tread rubber composition is used as a reinforcing agent to reduce tire rolling resistance, and technologies using silica instead of carbon black, which occupy a large proportion, have been continuously developed. However, silica has a weak interaction with polymers that are mainly used for tire treads such as natural rubber, styrene-butadiene rubber, butadiene rubber, which are composed of polar silanol groups. . In addition, silanol groups distributed on the surface of silica are strongly bonded by hydrogen bonds, and thus have a disadvantage in that they are not easily dispersed into the rubber composition.

이러한 단점들을 해결하기 위해 실란 커플링제(silane coupling agent)가 개발되었다. 실란 커플링제는 보강제로 사용하는 실리카 표면의 실라놀 그룹과 고무조성물의 원료고무를 연결하는 가교(bridge) 역할을 하지만, 가격이 비싸고 공정과정에서 에탄올 등이 휘발되는 단점이 있으며, 고무조성물의 배합과정에서 실리카 구조(structure)가 쉽게 분산되지 않기 때문에 더 강한 전단력(shear force)을 가해주거나, 실리카의 고른 분산을 위해서 배합공정을 추가해야 하는 문제점이 있다.To solve these shortcomings, silane coupling agents have been developed. The silane coupling agent acts as a bridge that connects the silanol group on the silica surface used as a reinforcing agent with the rubber of the raw material of the rubber composition. However, the silane coupling agent is expensive and has the disadvantage of volatilizing ethanol during the process. Since the silica structure is not easily dispersed in the process, there is a problem in that a stronger shear force is applied or a compounding process needs to be added for even dispersion of the silica.

본 발명은 상기와 같은 문제점을 해결하기 위해 보강제로 실리카를 사용하는 공지의 트레드 고무조성물에 있어서, 폴리디메틸실록산(polydimethylsiloxane, PDMS)을 고무조성물에 첨가하여 원료고무와 보강제인 실리카와의 친화성을 향상시켜 고무내에서 실리카를 고루 분산되도록 하여 실리카의 분산 개선 및 실리카와 원료고무와의 상호작용을 향상시킴과 동시에 실란 커플링제의 사용량을 감소시켜 원가절감, 환경문제 개선, 고무조성물의 배합공정 단순화 및 이에 따른 에너지 절약을 목적으로 한다.The present invention is a known tread rubber composition using silica as a reinforcing agent to solve the above problems, by adding polydimethylsiloxane (polydimethylsiloxane, PDMS) to the rubber composition, the affinity between the raw material rubber and silica as a reinforcing agent. Improves dispersion of silica and improves the interaction between silica and raw rubber, and reduces the amount of silane coupling agent used to reduce costs, improve environmental problems, and simplify the formulation of rubber compositions. And thus energy saving.

본 발명은 보강제로 실리카를 사용하는 공지의 트레드 고무조성물에 있어서, 천연고무 또는 스티렌-부타디엔 고무, 부타디엔 고무와 같은 합성고무를 단독 또는 혼합한 원료고무 100 phr에 대하여 실리카 40∼80 phr, 폴리디메틸실록산(polydim ethylsiloxane, PDMS) 10∼50 phr 사용함을 특징으로 하는 트레드 고무조성물이다.In the known tread rubber composition using silica as a reinforcing agent, silica 40 to 80 phr, polydimethyl based on 100 phr of natural rubber or synthetic rubber such as styrene-butadiene rubber and butadiene rubber alone or mixed A tread rubber composition characterized by using 10-50 phr of siloxane (polydim ethylsiloxane, PDMS).

상기에서 실리카는 BET 값이 130∼200 m2/g인 침강 실리카이며, 폴리디메틸실록산(PDMS)은 실리카와 친화성이 강한 고분자로서 분자량은 30000∼50000인 것을 사용한다.In the above, silica is precipitated silica having a BET value of 130 to 200 m 2 / g, and polydimethylsiloxane (PDMS) is a polymer having a high affinity with silica and having a molecular weight of 30000 to 50000.

본 발명에서 실리카를 40∼80 phr 사용시 폴리디메틸실록산을 10 phr 미만으로 사용하면 실리카 표면의 실라놀 그룹과 반응할 수 있는 폴리디메틸실록산의 양이 부족하여 실리카와 원료고무와의 가교역할을 하기 어려우며, 50 phr 초과하여 사용하면 실리카의 실라놀 그룹과 반응 후 남은 폴리디메틸실록산이 실리카와 원료고무의 가교역할을 방해하여 좋지 않다.In the present invention, when 40 to 80 phr of silica is used, less than 10 phr of polydimethylsiloxane is insufficient in the amount of polydimethylsiloxane that can react with silanol groups on the surface of silica, making it difficult to crosslink the silica and the raw material rubber. When used in excess of 50 phr, the polydimethylsiloxane remaining after the reaction with the silanol group of silica will not interfere with the crosslinking role of the silica and the raw material rubber.

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

<비교예>Comparative Example

스티렌-부타디엔 고무 80 phr 및 부타디엔 고무 20 phr로 구성된 원료고무 100 phr에 대하여 실리카 80 phr, 실란 커플링제 6.4 phr, 산화아연 3 phr, 스테아린산 2 phr, 황 1.5 phr, N-cyclehexyl-2-Benzothiazol sulfenamide(CZ) 1.5 phr, N,N-Diphenyl Guanidine(DPG) 1.5 phr의 고무조성물을 160℃에서 30분간 가류하여 고무시편을 제조하였다. 아래의 표 1에 이의 조성물을 나타내었다.80 phr of raw rubber consisting of 80 phr of styrene-butadiene rubber and 20 phr of butadiene rubber, 80 phr of silica, 6.4 phr of silane coupling agent, 3 phr of zinc oxide, 2 phr of stearic acid, 1.5 phr of sulfur, N-cyclehexyl-2-Benzothiazol sulfenamide (CZ) 1.5 phr, N, N-Diphenyl Guanidine (DPG) A rubber composition of 1.5 phr was vulcanized at 160 ℃ for 30 minutes to prepare a rubber specimen. Table 1 below shows its composition.

<실시예 1><Example 1>

스티렌-부타디엔 고무 80 phr 및 부타디엔 고무 20 phr로 구성된 원료고무 100 phr에 대하여 실리카 80 phr, 실란 커플링제 4.8 phr, 폴리디메틸실록산(PDMS) 20 phr, 산화아연 3 phr, 스테아린산 2 phr, 황 1.5 phr, CZ 1.5 phr, DPG 1.5 phr의 고무조성물을 160℃에서 30분간 가류하여 고무시편을 제조하였다. 아래의 표 1에 이의 조성물을 나타내었다.80 phr of silica, 100 phr of styrene-butadiene rubber and 20 phr of butadiene rubber, 4.8 phr of silane coupling agent, 20 phr of polydimethylsiloxane (PDMS), 3 phr of zinc oxide, 2 phr of stearic acid, 1.5 phr of sulfur Rubber compositions of CZ 1.5 phr and DPG 1.5 phr were vulcanized at 160 ° C. for 30 minutes to prepare rubber specimens. Table 1 below shows its composition.

<실시예 2><Example 2>

실란 커플링제 6.4 phr 사용하는 것을 제외하고는 상기 실시예 1과 같은 조성물 및 방법으로 고무시편을 제조하였으며 아래의 표 1에 이의 조성물을 나타내었다.Except for using the silane coupling agent 6.4 phr rubber specimens were prepared by the same composition and method as in Example 1, and their compositions are shown in Table 1 below.

표 1. 비교예 및 실시예의 고무조성물(단위: phr)Table 1. Rubber compositions of comparative examples and examples (unit: phr)

항 목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 스티렌-부타디엔 고무*Styrene-butadiene rubber * 8080 8080 8080 부타디엔 고무Butadiene rubber 2020 2020 2020 실리카Silica 8080 8080 8080 실란 커플링제**Silane Coupling Agent ** 6.46.4 4.84.8 6.46.4 PDMSPDMS -- 2020 2020 산화아연Zinc oxide 33 33 33 스테아린산Stearic acid 22 22 22 황sulfur 1.51.5 1.51.5 1.51.5 CZCZ 1.51.5 1.51.5 1.51.5 DPGDPG 1.51.5 1.51.5 1.51.5

* 스티렌-부티디엔 고무: 스티렌(styrene) 25%, 비닐(vinyl) 50%, Tg= -30℃* Styrene-Butidiene rubber: 25% styrene, 50% vinyl, Tg = -30 ℃

** 실란 커플링제: Tetraethoxysilylpropyltetrasulfide(TESPT)** Silane Coupling Agent: Tetraethoxysilylpropyltetrasulfide (TESPT)

<시험예><Test Example>

상기 비교예 및 실시예의 고무시편 ASTM 관련규정에 의하여 무니시험, 레오미터시험, 인장시험, 동적시험, 피코시험 등을 측정하여 그 결과를 아래의 표 2에 정리하여 나타내었다.In accordance with the ASTM-related regulations of the rubber specimens of Comparative Examples and Examples, the Mooney test, rheometer test, tensile test, dynamic test, pico test and the like were measured and the results are shown in Table 2 below.

표 2. 비교예 및 실시예의 고무시편의 특성Table 2. Properties of Rubber Specimens of Comparative Examples and Examples

항 목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 무니(@125℃)점도T5Mooney (@ 125 ℃) viscosity T5 89638963 83608360 82558255 레오미터 시험(@160℃)T40T90MAXE.C.*Rheometer Test (@ 160 ° C) T40T90MAXE.C. * 1014.23815.61014.23815.6 10.115.73817.310.115.73817.3 7.511.34112.57.511.34112.5 인장시험경도300%모듈러스(kg/cm2)인장강도(kg/cm2)신율(%)Tensile Test Hardness 300% Modulus (kg / cm 2 ) Tensile Strength (kg / cm 2 ) Elongation (%) 66892205806689220580 6610025060066100250600 6811025056068110250560 동적시험Tg(℃)Tan D 0℃Tan D 70℃Dynamic test Tg (℃) Tan D 0 ℃ Tan D 70 ℃ -290.2330.102-290.2330.102 -320.2210.095-320.2210.095 -320.2230.088-320.2230.088 피코(Pico)(g)Pico (g) 0.0310.031 0.0280.028 0.0250.025

* E.C.: 경화 후(End Cure)를 의미함* E.C .: means end cure

상기 표 2의 결과에서처럼 실리카를 보강제로 사용하는 고무조성물에 있어서, 본 발명과 같이 폴리디메틸실록산을 사용한 실시예의 고무시편은 폴리디메틸실록사산을 사용하지 않은 비교예의 고무시편에 비해 배합물의 점도는 감소하면서 가류물성이 향상되었다. 이는 폴리디메틸실록산을 사용하면 보강제로 사용된 실리카가 고무조성물 내에서 분산이 고루 되었으며, 실리카와 원료고무와의 상호작용이 향상되었음을 의미한다.In the rubber composition using silica as a reinforcing agent, as shown in the results of Table 2, the rubber sample of the example using polydimethylsiloxane as in the present invention has a reduced viscosity compared to the rubber sample of the comparative example without using polydimethylsiloxane. While vulcanization properties were improved This means that the use of the polydimethylsiloxane was uniformly dispersed in the rubber composition of the silica used as a reinforcing agent, and the interaction between the silica and the raw material rubber was improved.

Claims (3)

보강제로 실리카를 사용하는 공지의 트레드 고무조성물에 있어서, 천연고무 또는 스티렌-부타디엔 고무, 부타디엔 고무와 같은 합성고무를 단독 또는 혼합한 원료고무 100 phr에 대하여 실리카 40-80 phr, 폴리디메틸실록산(polydimethylsil oxane, PDMS) 10∼50 phr 사용함을 특징으로 하는 보강성이 향상된 고무조성물In a known tread rubber composition using silica as a reinforcing agent, silica 40-80 phr, polydimethylsil (polydimethylsil) with respect to 100 phr of natural rubber or synthetic rubber such as styrene-butadiene rubber and butadiene rubber alone or mixed oxane, PDMS) Rubber composition with improved reinforcement, characterized by using 10-50 phr 제 1항에 있어서, 실리카는 BET 값이 130∼200 m2/g인 침강 실리카인 것을 특징으로 하는 보강성이 향상된 고무조성물The rubber composition according to claim 1, wherein the silica is precipitated silica having a BET value of 130 to 200 m 2 / g. 제 1항에 있어서, 폴리디메틸실록산의 분자량은 30000∼50000인 것을 특징으로 하는 보강성이 향상된 고무조성물The rubber composition with improved reinforcement according to claim 1, wherein the polydimethylsiloxane has a molecular weight of 30000 to 50000.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490314A (en) * 1980-11-28 1984-12-25 High Voltage Engineering Corporation Radiation cured silicone rubber articles
EP0366558A1 (en) * 1988-10-27 1990-05-02 Nissin Chemical Industry Co., Ltd. Rubber composition
JPH07179666A (en) * 1993-09-07 1995-07-18 Goodyear Tire & Rubber Co:The Tire with silica-reinforced tread
JPH08302070A (en) * 1995-03-09 1996-11-19 Sumitomo Chem Co Ltd Rubber composition
KR19990044192A (en) * 1996-06-26 1999-06-25 가이자끼 요이찌로 Rubber composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490314A (en) * 1980-11-28 1984-12-25 High Voltage Engineering Corporation Radiation cured silicone rubber articles
EP0366558A1 (en) * 1988-10-27 1990-05-02 Nissin Chemical Industry Co., Ltd. Rubber composition
JPH07179666A (en) * 1993-09-07 1995-07-18 Goodyear Tire & Rubber Co:The Tire with silica-reinforced tread
JPH08302070A (en) * 1995-03-09 1996-11-19 Sumitomo Chem Co Ltd Rubber composition
KR19990044192A (en) * 1996-06-26 1999-06-25 가이자끼 요이찌로 Rubber composition

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