KR100347206B1 - Rubber composition containing modified silica - Google Patents

Rubber composition containing modified silica Download PDF

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KR100347206B1
KR100347206B1 KR1019940037356A KR19940037356A KR100347206B1 KR 100347206 B1 KR100347206 B1 KR 100347206B1 KR 1019940037356 A KR1019940037356 A KR 1019940037356A KR 19940037356 A KR19940037356 A KR 19940037356A KR 100347206 B1 KR100347206 B1 KR 100347206B1
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South Korea
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rubber
silica
modified silica
molecular weight
low molecular
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KR1019940037356A
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Korean (ko)
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KR960022740A (en
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장세영
박제환
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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
    • C08L21/00—Compositions of unspecified rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • 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
    • C08K3/04—Carbon
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Abstract

PURPOSE: Provided is a tire tread rubber composition containing modified silica, which improves vulcanizing-property, abrasion-resistance, rotation-resistance of tires, and low fuel-consumption and has uniform dispersibility of a filler. CONSTITUTION: The tire tread rubber composition contains: 100pts.wt. of a natural rubber, a synthetic rubber, or a mixture thereof; and 40-140pts.wt. of a reinforcing filler comprising a carbon black and 5-80pts.wt. of the modified silica. The modified silica is produced by stirring and mixing a low molecular weight isoprene rubber(L-IR) or a low molecular weight styrene butadiene rubber(L-SBR) containing a functional group with a silica in the weight ratio of 1:10-1:1000 in a solvent and performing desolvation and heat-drying, wherein the silica has a specific surface area(measured by adsorbing N2 by using a BET method) of 100-250m2/g and a dibutyl phthalate(DBP) adsorption value of 130-250ml/100g.

Description

변성 실리카가 함유된 고무 조성물Rubber composition containing modified silica

본 발명은 타이어의 회전저항 및 저연비 특성을 현저하게 향상시킬 수 있는 조성물에 관한 것으로서 특히 변성 실리카를 포함한 조성물에 관한 것이다.The present invention relates to a composition capable of significantly improving the rolling resistance and low fuel consumption characteristics of a tire, and more particularly to a composition containing modified silica.

타이어의 제반 성능 중 젖은 노면 제동력과 내마모성, 내노화성, 내충격성 등은 매우 중요하며, 특히 최근에는 환경보호 측면에서 타이어의 저연비 특성에 대한 요구수준은 더욱 높아지고 있다. 통상적으로 타이어에 실리카를 적용하면 저연비 특성이 어느 정도 개선됨이 알려져 있었으나, 다른 제반 성능의 물성 저하로 인해 이용되지 못해 왔다. 이는 실리카가 고무와 잘 섞이지 않는 성질을 가지고 있으며, 고무와의 상호결합력이 카본블랙에 못 미치기 때문이다.The wet road braking force, abrasion resistance, aging resistance, impact resistance, etc. are very important among tire performances. In particular, in recent years, the demand for low fuel consumption characteristics of tires has been increased. In general, it is known that the application of silica to tires improves the fuel economy to some extent, but it has not been used due to deterioration of physical properties of other various performances. This is because silica does not mix well with rubber and its mutual bonding strength is less than that of carbon black.

이러한 실리카의 단점을 보완하고 그 특성을 이용하기 위해 근래에는 고무와 실리카의 배합물에 유기실란 커플링제 등을 함께 첨가하여, 이들이 혼합되며 일으키는 화학반응을 이용하여 고무와 실리카가 결합되도록 만들고 있으나 이런 유기실란 커플링제들은 가격이 비싸고 원료구입의 어려움이 있어 실제 적용의 한계를 가진다. 예를 들면 유기실란화합물인 감마-메르캅토프로필트리메톡시실란(γ-mercaptopropyltrimethoxysilane)이나 비스(3-트리에톡시실일프로필)테트라설판[bis(3-triethoxylsilylpropyl)tetrasulfane](=TESPT)을 실리카와 혼합적용하고 있으나, 감마-메르캅토프로필트리메톡시실란의 경우 낮은 가류속도로 인해 적용이 거의 안되고 있으며, TESPT의 경우 가격이 비싼 단점이 있다.In order to make up for the shortcomings of the silica and to utilize its properties, recently, an organosilane coupling agent is added to the rubber and silica compound together to make the rubber and silica bond by using a chemical reaction caused by the mixing. Silane coupling agents are expensive and have difficulty in purchasing raw materials, thus limiting their practical application. For example, gamma-mercaptopropyltrimethoxysilane or bis (3-triethoxylsilylpropyl) tetrasulfane (= TESPT), which is an organosilane compound, may be mixed with silica. Although mixed application, gamma-mercaptopropyltrimethoxysilane is hardly applied due to the low vulcanization rate, and TESPT has a high price disadvantage.

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로 말단에 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)로 변성시킨 실리카를 고무조성물에 적용함으로써 가류특성이 개선되고 충진제의 분산성이 좋아져서 타이어의 성능 중 특히 회전저항과 내마모 특성이 개선된 고무 조성물을 제공한다.The present invention is to solve the above problems, the vulcanization characteristics by applying to the rubber composition silica modified with low molecular weight isoprene rubber (L-IR) or low molecular weight styrene butadiene rubber (L-SBR) containing a functional group at the end This improved and improved dispersibility of the filler provides a rubber composition with improved tire performance, in particular rolling resistance and wear resistance.

본 발명은 변성 실리카를 적용한 타이어 트레드용 고무에 관한 것으로 (A) 체인의 한쪽 말단에 관능기를 가진 저분자량의 용액중합 이소프렌(또는 스티렌부타딘엔) 고무를 10∼1,000배 무게비의 실리카와 용매 중에서 혼합한 다음, 탈용매 및 열러리하여 얻은 변성 실리카를 (B) 천연고무, 합성고무 또는 이들의 혼용고무로 이루어진 트레드용 고무 100중량부에 대해 단독으로 또는 카본블랙과 함께 총 40∼140중량부 적용하고, 통상의 타이어 제조에 쓰는 보강제, 가류제, 가류활성제, 가류촉진제 및 기타 첨가제를 배합하여 이루어진 변성 실리카가 함유된 트레드용 고무 조성물로써 종래의 타이어 고무 조성물보다 내마모성과 보강제의 분산성 그리고 특히 주행성능이 개선되는 효과가 있는 것으로 이를 구체적으로 설명하면 다음과 같다.The present invention relates to a rubber for tire treads to which modified silica is applied. (A) A low molecular weight solution-polymerized isoprene (or styrene-butadiene) rubber having a functional group at one end of a chain in silica and a solvent having a weight ratio of 10 to 1,000 times. After mixing, denatured silica obtained by desolvation and heat treatment is totally 40 to 140 parts by weight based on 100 parts by weight of the rubber for tread composed of (B) natural rubber, synthetic rubber or mixed rubber thereof. Rubber composition for treads containing modified silica, which is applied and blended with reinforcing agents, vulcanizing agents, vulcanizing agents, vulcanizing accelerators and other additives used in the manufacture of conventional tires. The driving performance is improved and described in detail as follows.

본 발명의 고무 조성물은 천연고무, 합성고무 또는 이들이 혼용고무 100중량부에, 보장성 충진제 40∼140중량부와 아연화(ZnO) 등의 가류활성제, 황 또는 유황공여형 가류제 및 가류촉진제 그리고 기타 첨가제를 혼합하여 이루어진다.The rubber composition of the present invention is a natural rubber, synthetic rubber or mixed rubber of 100 parts by weight, 40 to 140 parts by weight of a guarantee filler and a vulcanizing agent such as zinc (ZnO), sulfur or sulfur donor type vulcanizing agent and vulcanization accelerator and other additives It is made by mixing.

상기 고무 조성물에 총 40∼140중량부 적용하는 보강성 충진제는 카본블랙과 상기 (A)항의 변성 실리카를 혼합 조성한 것으로써 변성 실리카의 함량은 5∼80중량부의 범위에서 사용하되 적정량은 10∼60중량부이다.A total of 40 to 140 parts by weight of the reinforcing filler to be applied to the rubber composition is a mixture of carbon black and the modified silica of (A). The content of the modified silica is used in the range of 5 to 80 parts by weight, but an appropriate amount is 10 to 60. Parts by weight.

본 발명에 사용되는 고무의 예로는 천연 고무, 폴리부타디엔 고무, 스티렌부타디엔 고무, 부틸고무, 할로겐화부틸 고무 또는 이들의 혼합물이고 변성 실리카는 아래에 나타낸 바와 같이 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)과 실리카를 용매 중에서 교반 혼합한 다음, 탈용매 및 열처리 건조시켜 제조하며, 여기에 사용하는 실리카는 BET법을 사용하여 N2를 흡착시켜 측정한 표면적이 100∼250㎡/g이고, 디부틸프탈레이트(DBP) 흡착가가 130∼250ml/100g의 범위인 것이 바람직하고, 상기 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)와 실리카의 혼합 중량비는 1:10∼1:1000 정도가 적당하다.Examples of the rubber used in the present invention are natural rubber, polybutadiene rubber, styrenebutadiene rubber, butyl rubber, butyl halide rubber or mixtures thereof and the modified silica is a low molecular weight isoprene rubber containing a functional group as shown below (L- IR) or low molecular weight styrene-butadiene rubber (L-SBR) and silica are prepared by stirring and mixing in a solvent, followed by desolvation and heat treatment drying, and the silica used is measured by adsorbing N 2 using BET method. It is preferable that the surface area is 100-250 m <2> / g, and the dibutyl phthalate (DBP) adsorption value is 130-250 ml / 100 g, and the low molecular weight isoprene rubber (L-IR) or the low molecular weight styrene butadiene rubber containing the said functional group As for the mixed weight ratio of (L-SBR) and silica, about 1: 10-1: 1000 are suitable.

여기서, R은 분자량 1,000∼5,000인 이소프렌 또는 스티렌부타디엔 고무 체인이고, X는 실리카 등의 보강 충진제와 화학결합 또는 수소결합을 할 수 있는 관능기를 최소한 1개 이상 가진 것으로 카르복실기(CO2H), 술핀산기(SO2H), 술폰산기(SO2H), 포스핀산기(H2PO3) 등이다.Here, R is an isoprene or styrenebutadiene rubber chain having a molecular weight of 1,000 to 5,000, X is a carboxyl group (CO 2 H), sulfene having at least one functional group capable of chemical or hydrogen bonding with a reinforcing filler such as silica. Acid groups (SO 2 H), sulfonic acid groups (SO 2 H), phosphinic acid groups (H 2 PO 3 ), and the like.

상기의 제조 과정에서 (1) 용매 중 혼합은 메탄올, 에탄올, THF 등의 일반적 용매나 이들의 혼합용매에 상기 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)(X-R)와 실리카를 혼합 중량비 1:10∼1:1,000으로 실리카를 섞고 충분히 교반하여 준다. 다음으로, (2) 탈용매 및 열처리 과정은 진공증발건조(vacuum evaporation)하여 용매를 제거하고, 진공건조오븐(vacuum oven)에서 100∼140℃의 온도로 6∼15시간 건조시킨다.In the above production process, (1) mixing in the solvent is a low molecular weight isoprene rubber (L-IR) or a low molecular weight styrene butadiene rubber (L-) containing the functional group in a general solvent such as methanol, ethanol, THF, or a mixed solvent thereof. SBR) (XR) and silica are mixed in a weight ratio of 1:10 to 1: 1,000 and mixed with silica. Next, (2) desolvation and heat treatment process to remove the solvent by vacuum evaporation (vacuum evaporation), it is dried for 6 to 15 hours at a temperature of 100 ~ 140 ℃ in a vacuum oven (vacuum oven).

본 발명의 변성 실리카 배합량이 고무 100중량부에 대해 5중량부 미만이면 충분한 효과를 기대할 수 없으며, 인장강도, 동적 모듈러스, 반발 탄성, 경도 등이 80중량부까지는 증가하나 그 이상에서는 가소화 현상이 일어나므로 80중량부 이상 적용은 바람직하지 않다.If the modified silica compounding amount of the present invention is less than 5 parts by weight with respect to 100 parts by weight of rubber, sufficient effect cannot be expected. The tensile strength, dynamic modulus, resilience, hardness, etc. increase to 80 parts by weight, but the plasticization phenomenon is higher than that. Therefore, application of more than 80 parts by weight is undesirable.

본 발명에서는 보강성 충진제로 변성 실리카 및 카본블랙을 사용하고 가류 활성제로서는 산화아연(ZnO), 가류제로서는 분말 유황, 불용성 유황 등을 사용하며, 유황공여형 가류제로서는 데트라메틸치우람설파이드, 테트라부틸치우람디설파이드를, 가류촉진제로서는 티아졸, 설펜아미드계 촉진제를 포함한다.In the present invention, modified silica and carbon black are used as reinforcing fillers, zinc oxide (ZnO) as a vulcanization activator, powder sulfur, insoluble sulfur, etc. are used as vulcanizing agents, and detramethylchiuram sulfide, Tetrabutyl chiuram disulfide includes a thiazole and a sulfenamide type accelerator as a vulcanization accelerator.

이들 첨가제를 적용함에 있어 산화아연은 0∼10중량부를 사용하되 0∼7중량부가 적당하며, 가류제는 0.5∼7중량부, 가류 촉진제는 0.3∼6중량부가 바람직하다. 이들 성분들은 혼용 및 분리하여 혹은 다른 고무 조성물과 배합하여 사용할 수 있다.In applying these additives, zinc oxide is preferably 0 to 10 parts by weight, preferably 0 to 7 parts by weight, 0.5 to 7 parts by weight of vulcanizing agent and 0.3 to 6 parts by weight of vulcanization accelerator. These components may be used in combination and separately or in combination with other rubber compositions.

이하에서는 실시예 및 비교예를 통하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail through Examples and Comparative Examples.

실시예(1, 2, 3) 및 비교예(1, 2, 3)Examples (1, 2, 3) and Comparative Examples (1, 2, 3)

표 1의 조성에 따라 고무 조성물을 제조한 후 각 샘플의 물성을 측정하여 그 결과를 표 2에 나타냈으며, 이때 물성 측정에 사용한 시험방법은 다음과 같다.After the rubber composition was prepared according to the composition of Table 1, the physical properties of each sample were measured, and the results are shown in Table 2, wherein the test method used for the physical property measurement was as follows.

반발탄성 시험Resilience test

HEALEY Rebound Tester(B. F. Goodrich사)기를 사용했으며, 스틸 볼이 시편에 떨어질 때 반발되는 정도를 측정하였다.A HEALEY Rebound Tester (B. F. Goodrich) was used to measure the rebound of steel balls when they fell on the specimen.

발열 시험Fever test

Flexometer 시험기(B. F. Goodrich사)를 이용하여 측정했다.It measured using the Flexometer tester (B. F. Goodrich).

동적 점탄성 시험Dynamic viscoelastic test

GABO(EFLEXON-13) 시험기를 이용했으며, 시험조건은 Tension Mode에서 주파수 11Hz, 변형 진폭 0.123%, Pretension 10%로 하여 시험했다.A GABO (EFLEXON-13) tester was used and the test conditions were tested at a frequency of 11 Hz, strain amplitude of 0.123%, and pretension of 10% in tension mode.

상기 표 1, 2에서 볼 수 있듯이 변성 실리카를 적용하면 0℃ tanδ에는 큰 영향을 주지 않으면서 60℃ tanδ값의 감소 및 반발탄성 특성이 현저히 좋아짐을 확인할 수 있으며, 내마모 특성도 카본블랙 적용화합물과 대차를 보이지 않는다. 또한 고무 조성물에서 변성 실리카 배합량의 증가에 따른 가류속도에서 큰 차이가 없다.As shown in Tables 1 and 2, it can be seen that when the modified silica is applied, the reduction of the 60 ° C tanδ value and the rebound elastic properties are remarkably improved without significantly affecting 0 ° C tanδ, and the wear resistance is also a carbon black applied compound. And does not show the balance. In addition, there is no significant difference in the vulcanization rate due to the increase in the amount of modified silica in the rubber composition.

이상과 같이 본 발명에 따른 고무 조성물은 변성 실리카를 충진제 및 결합제로 포함함으로써 저연비 특성과 내마모 특성이 우수할 뿐 아니라 종래의 실리카를 첨가한 고무 조성물에서 야기되었던 가류속도 및 분산성의 문제까지도 해결한 것이다.As described above, the rubber composition according to the present invention includes a modified silica as a filler and a binder, which is excellent in low fuel efficiency and abrasion resistance, and also solves problems of vulcanization rate and dispersibility caused by rubber compositions containing silica. will be.

Claims (1)

천연고무, 합성고무 또는 이들의 혼용고무 100중량부 및 보강성 충진제 40∼140중량부를 포함하고, 상기 보강성 충진제는 카본블랙과 변성 실리카의 혼합물이고, 이중 상기 변성 실리카의 함량이 5∼80중량부이며, 상기 변성 실리카는 BET법에 사용하여 N2를 흡착시켜 측정한 비표면적 값이 100∼250㎡/g이고, 디부틸프탈레이트(DBP) 흡착가가 130∼250ml/100g인 실리카((SiO2)nN2O)를, 중량 기준으로 한쪽 말단에 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)(하기 식의 X-R): 실리카=1:10∼1:1,000의 비로 한쪽 말단에 관능기를 함유한 저분자량 이소프렌 고무(L-IR) 또는 저분자량 스티렌부타디엔 고무(L-SBR)와 용매 중에서 교반하면서 혼합한 다음, 탈용매 및 열처리 건조시켜 제조되는 것임을 특징으로 하는 변성 실리카가 함유된 타이어 트레드용 고무 조성물.100 parts by weight of natural rubber, synthetic rubber or mixed rubber thereof and 40 to 140 parts by weight of reinforcing filler, wherein the reinforcing filler is a mixture of carbon black and modified silica, and the content of the modified silica is 5 to 80 weight The modified silica is a silica ((SiO 2 ) having a specific surface area value of 100 to 250 m 2 / g and a dibutyl phthalate (DBP) adsorption value of 130 to 250 ml / 100 g as measured by adsorption of N 2 using the BET method. ) n N 2 O) by weight based on low molecular weight isoprene rubber (L-IR) or low molecular weight styrenebutadiene rubber (L-SBR) containing functional groups at one end (XR of the following formula): silica = 1: 10 A low molecular weight isoprene rubber (L-IR) or a low molecular weight styrenebutadiene rubber (L-SBR) containing a functional group at one end in a ratio of ˜1: 1,000 is mixed with stirring in a solvent, followed by desolvation and heat treatment drying. Characterized in that the modified silica The tire tread rubber composition. X-RX-R (단, R은 분자량이 1,000∼5,000인 이소프렌 또는 스티렌부타디엔 고무 체인이고, X는 카르복실기(COOH), 술핀산기(SO2H), 술폰산기(SO3H) 및 포스핀산기(H2PO3)로 이루어지는 군으로부터 선택된 1 이상의 관능기).(Where R is an isoprene or styrenebutadiene rubber chain having a molecular weight of 1,000 to 5,000, and X is a carboxyl group (COOH), a sulfinic acid group (SO 2 H), a sulfonic acid group (SO 3 H) and a phosphinic acid group (H 2 PO 3)). At least one functional group selected from the group consisting of
KR1019940037356A 1994-12-27 1994-12-27 Rubber composition containing modified silica KR100347206B1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR860002545A (en) * 1984-09-21 1986-04-26 디.에이.토마스 Method for preparing filler reinforcing rubber vulcanizate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR860002545A (en) * 1984-09-21 1986-04-26 디.에이.토마스 Method for preparing filler reinforcing rubber vulcanizate

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