KR20020078245A - Tread rubber composition for snow tire - Google Patents

Tread rubber composition for snow tire Download PDF

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KR20020078245A
KR20020078245A KR1020010018301A KR20010018301A KR20020078245A KR 20020078245 A KR20020078245 A KR 20020078245A KR 1020010018301 A KR1020010018301 A KR 1020010018301A KR 20010018301 A KR20010018301 A KR 20010018301A KR 20020078245 A KR20020078245 A KR 20020078245A
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phr
rubber
srs
rubber composition
snow
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KR1020010018301A
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KR100426062B1 (en
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최희성
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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
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • 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
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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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)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Tires In General (AREA)

Abstract

PURPOSE: Provided is a tread rubber composition which comprises 3-10 phr of SRS-40VP having excellent anti-slipping property, with respect to 100 phr of rubber material, and shows excellent anti-slipping property. CONSTITUTION: The composition comprises 3-10 phr of SRS-40VP which is anti-slip, with respect to 100 phr of rubber material. The rubber material comprises 10-30 phr of natural rubber, 30-80 phr of styrene butadiene rubber(SBR), and 10-40 phr of butadiene rubber(BR). The SRS-40VP is produced by blending 90% of polynorbornene having molecular weight of 100000-400000, 5% of processing oil(aromatic oil), and 5% of others(consisting of sulfur, diphenylguanidine(DPG), N-cyclohexyl-2-bentothiazole sulfenamide(CZ) in ratio of 2:2:5), curing the blend at 180 deg.C for 30-50 minutes, and crushing the cured blend in crusher to particle size of 100 mesh or less.

Description

스노우 타이어용 트레드 고무조성물{Tread rubber composition for snow tire}Tread rubber composition for snow tires

본 발명은 스노우 타이어용 고무조성물에 관한 것으로서 보다 상세하게는 원료고무 100 phr에 대하여 미끄럼 방지제(anti-slip)로 SRS-40VP 3∼10 phr 포함하는 것을 특징으로 하는 스노우 타이어용 트레드 고무조성물에 관한 것이다.The present invention relates to a rubber composition for snow tires, and more particularly, to a tread rubber composition for snow tires, comprising SRS-40VP 3 to 10 phr as an anti-slip agent for 100 phr of raw rubber. will be.

종래 스노우 타이어에 있어서 눈 또는 빙판에서의 미끄러짐을 방지하기 위한 대책으로는 스노우 타이어의 고무조성물 중의 원료고무와 충진제에 변화를 주거나 또는 구조적으로 스노우 타이어에 스파이크를 적용한 스터드 타입(stud type)과 스파이크를 적용하지 않은 스터드레스(studless) 형태로 타이어를 설계하여 미끄러짐을 방지하고 있다.As a countermeasure to prevent slippage in snow or ice in conventional snow tires, stud types and spikes in which the raw rubber and filler in the rubber composition of the snow tire are changed or the spikes are structurally applied to the snow tire are applied. The tire is designed in studless shape to prevent slipping.

미끄러짐 방지, 수상, 빙상, 설상 제동력은 스파이크 타이어가 우수하지만 스파이크 타이어는 스파이크가 노면을 때리는 충격으로 발생하는 소음과 분진에 의한 환경오염이 심각한 문제로 지적되어 많은 나라에서 규제되고 있다.Although anti-slip, water, ice and snow braking are excellent in spike tires, spike tires are regulated in many countries because of the serious problems caused by noise and dust caused by the impact of spikes hitting the road.

스파이크 타이어에서 대두되는 문제를 개선하기 위해 개발된 스터드레스 타이어는 빙상, 설상제동력을 향상시키기 위해 실리카를 적용하거나, 발포고무를 적용한다. 하지만 실리카를 적용하는 경우 실리카 친수성기로 인해 수막파괴 현상은 우수하나 실리카가 고가여서 재료비가 크게 상승하고, 또한 정련 및 압출공정이 일반고무에 비해 매우 복잡하여 가공비를 큰 폭으로 상승시키는 문제가 지적된다.Studless tires developed to improve the problem of spike tires are made of silica or foamed rubber to improve ice and snow braking. However, when silica is applied, the hydrophilic group is excellent in water film breakage, but due to the high silica, the material cost is greatly increased, and the refining and extrusion processes are much more complicated than general rubber, which increases the processing cost significantly. .

또한 발포고무는 트레드 부위의 미세한 기포에 의해 수막을 파괴하여 빙상, 설상제동력은 향상시키나 제조상 공정이 복잡하거나 내마모 성능이 하락한다는 문제가 지적된다.In addition, the foamed rubber breaks the water film by minute bubbles in the tread area, thereby improving ice and snow braking power, but it is pointed out that the manufacturing process is complicated or the wear resistance is reduced.

본 발명은 상기와 같은 문제점을 해결하기 위하여 공지의 스노우 타이어에 있어서 미끄럼 방지 특성이 우수한 SRS-40VP을 원료고무 100 phr에 대하여 3∼10 phr 포함하도록 하여 미끄럼 방지 특성이 우수한 트레드 고무조성물의 제공을 목적으로 한다.The present invention is to provide a tread rubber composition with excellent anti-slip properties by including 3 to 10 phr with respect to 100 phr of the raw material rubber SRS-40VP excellent in anti-slip properties in the known snow tire to solve the above problems. The purpose.

본 발명의 스노우 타이어용 트레드 고무조성물은 공지의 스노우 타이어용 트레드 고무조성물에 있어서, 원료고무 100 phr에 대하여 미끄럼 방지제(anti-slip)로 SRS-40VP 3∼10 phr 포함하는 것을 특징으로 한다.The tread rubber composition for snow tires of the present invention is a known tread rubber composition for snow tires, characterized in that it comprises SRS-40VP 3 to 10 phr as an anti-slip to 100 phr of raw rubber.

본 발명에서 사용하는 원료고무는 천연고무 10∼30 phr, 스티렌 부타디엔 고무(SBR) 30∼80 phr, 부타디엔 고무(BR) 10∼40 phr 포함한다.The raw material rubber used in the present invention includes 10 to 30 phr of natural rubber, 30 to 80 phr of styrene butadiene rubber (SBR) and 10 to 40 phr of butadiene rubber (BR).

천연고무를 10 phr 미만 사용시 발열특성이 하락하는 문제가 있어 좋지 않고, 30 phr 초과 사용하면 뚜렷한 물성의 향상없이 사용량만 증가하여 원료 비용이 증가하는 문제가 있어 천연고무의 사용량은 10∼30 phr을 유지하는 것이 좋으며, 스티렌 부타디엔 고무를 30 phr 미만 사용시 물성이 하락하는 문제가 있어 좋지 않고, 80 phr 초과 사용하면 가류속도가 지연되는 문제가 있어 스티렌 부타디엔 고무의 사용량은 30∼80 phr을 유지하는 것이 좋다.When using less than 10 phr of natural rubber, there is a problem of deterioration of heat generation characteristics, and when using more than 30 phr, there is a problem of increasing raw material cost without obvious improvement of physical properties. It is good to maintain, and it is not good that there is a problem of deterioration of physical properties when using less than 30 phr of styrene butadiene rubber, and there is a problem of delayed vulcanization speed when using more than 80 phr. good.

또한, 부타디엔 고무를 10 phr 미만 사용시 동적특성이 저하되는 문제가 있어 좋지 않고, 40 phr 초과 사용하면 물성이 하락하는 문제가 있어 부타디엔 고무의 사용량은 10∼40 phr을 유지하는 것이 좋다.In addition, when the butadiene rubber is used less than 10 phr, there is a problem that the dynamic properties are deteriorated, and if the use of more than 40 phr there is a problem that the physical properties are deteriorated, so the amount of butadiene rubber is preferably used 10 to 40 phr.

한편 본 발명에서 미끄럼 방지제로 사용하는 SRS-40VP는 분자량이 100000∼400000인 폴리노르보넨(polynorbornene)이 90%, 공정유(아모마틱 오일)가 5%, 기타물질 5%(유황, 디페닐구아니딘(DPG), N-시클로헥실-2-벤토티아졸 설펜아미드(CZ)가 2:2:5의 비율)로 구성된 것을 배합 후 180℃로 30∼50분 동안 가류후에 분쇄기에서 100 메쉬(mesh) 이내로 분쇄한 것을 사용한다.Meanwhile, SRS-40VP used as an anti-slip agent in the present invention is 90% polynorbornene (polynorbornene) having a molecular weight of 100000-400000, 5% process oil (amomatic oil), 5% other substances (sulfur, diphenylguanidine (DPG), consisting of N-cyclohexyl-2-bentothiazole sulfenamide (CZ) in a ratio of 2: 2: 5) and then 100 mesh in the mill after vulcanization at 180 ° C. for 30-50 minutes. Use crushed to within.

본 발명에서 SRS-40VP를 원료고무 100 phr에 대하여 3 phr 미만 사용시 젖은노면 및 빙판에서의 제동력 성능이 저하되는 문제가 있어 좋지 않고, 10 phr 초과 사용하면 물성이 하락하는 문제가 있어 SRS-40VP의 사용량은 3∼10 phr 유지하는 것이 좋다.In the present invention, when using less than 3 phr SRS-40VP with respect to 100 phr of the raw material rubber, there is a problem that the braking force performance on wet roads and ice is not good, and when using more than 10 phr of the SRS-40VP It is recommended to keep the amount of 3 to 10 phr.

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 1과 같이 천연고무 15 phr, 스티렌 부타디엔 고무 45 phr 및 부타디엔 고무 40 phr로 구성된 원료고무 100 phr에 대하여 통상적으로 스노우용 타이어의 조성물 중 충진제로 카본블랙 70 phr, 활성제로 산화아연(ZnO) 4 phr, 프로세스 오일 15 phr, 유황 3 phr, 가황촉진제 1 phr을 첨가한 후 160℃에서 35분 동안 가류하여 고무시편을 제조하였다.100 phr of raw rubber consisting of 15 phr of natural rubber, 45 phr of styrene butadiene rubber and 40 phr of butadiene rubber, as shown in Table 1 below, is typically 70 phr of carbon black as a filler in a snow tire composition, and zinc oxide (ZnO) as an activator. 4 phr, 15 phr of process oil, 3 phr of sulfur, 1 phr of a vulcanization accelerator were added, and then vulcanized at 160 ° C. for 35 minutes to prepare a rubber specimen.

<실시예 1><Example 1>

아래의 표 1과 같이 천연고무 15 phr, 스티렌 부타디엔 고무 45 phr 및 부타디엔 고무 40 phr로 구성된 원료고무 100 phr에 대하여 통상적으로 스노우용 타이어의 조성물 중 충진제로 카본블랙 70 phr, 활성제로 산화아연(ZnO) 4 phr, 프로세스 오일 15 phr, 유황 3 phr, 가황촉진제 1 phr 및 미끄럼 방지제로 SRS-40VP 3 phr을 첨가한 후 160℃에서 35분 동안 가류하여 고무시편을 제조하였다.100 phr of raw rubber consisting of 15 phr of natural rubber, 45 phr of styrene butadiene rubber and 40 phr of butadiene rubber, as shown in Table 1 below, is typically 70 phr of carbon black as a filler in a snow tire composition, and zinc oxide (ZnO) as an activator. ) 4 phr, 15 phr of process oil, 3 phr of sulfur, 1 phr of a vulcanization accelerator and 3 phr of an anti-slip agent were added, followed by vulcanization at 160 ° C. for 35 minutes to prepare a rubber specimen.

상기에서 미끄럼 방지제로 사용한 SRS-40VP은 분자량이 400000인 폴리노르보넨이 90%, 공정유(아모마틱 오일)가 5%, 기타물질 5%(유황, 디페닐구아니딘(DPG), N-시클로헥실-2-벤토티아졸 설펜아미드(CZ)가 2:2:5의 비율)로 구성된 것을 배합 후 180℃로 50분 동안 가류후에 분쇄기에서 100 메쉬(mesh)로 분쇄한 것을 사용하였다.SRS-40VP used as an anti-slip agent is 90% polynorbornene having a molecular weight of 400000, 5% process oil (amomatic oil), 5% other substances (sulfur, diphenylguanidine (DPG), N-cyclohexyl 2-bentothiazole sulfenamide (CZ) in a ratio of 2: 2: 5) was used after pulverization at 180 ° C. for 50 minutes after blending to grind to 100 mesh in a grinder.

<실시예 2><Example 2>

SRS-40VP 5 phr 사용하는 것을 제외하고는 상기 실시예 1과 같은 조성물, 조성비 및 방법에 의하여 고무시편을 제조하였다.A rubber specimen was prepared by the same composition, composition ratio, and method as in Example 1, except that 5 phr of SRS-40VP was used.

<실시예 3><Example 3>

SRS-40VP 10 phr 사용하는 것을 제외하고는 상기 실시예 1과 같은 조성물, 조성비 및 방법에 의하여 고무시편을 제조하였다.A rubber specimen was prepared by the same composition, composition ratio, and method as in Example 1, except that 10 phr of SRS-40VP was used.

표 1. 비교예 및 실시예의 고무조성물(단위 : phr)Table 1. Rubber Compositions of Comparative Examples and Examples (Unit: phr)

항목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 천연고무Natural rubber 1515 1515 1515 1515 합성고무(SBR/BR)Synthetic Rubber (SBR / BR) 45/4045/40 45/4045/40 45/4045/40 45/4045/40 충진제Filler 7070 7070 7070 7070 활성제Active agent 44 44 44 44 프로세스 오일Process oil 1515 1616 1616 1616 유황brimstone 33 33 33 33 가황촉진제Vulcanization accelerator 1One 1One 1One 1One SRS-40VPSRS-40VP -- 33 55 1010

<시험예><Test Example>

상기 비교예 및 실시예의 고무시편을 스노우 타이어의 트레드로 사용한 후 ASTM 관련 규정에 의하여 젖은노면(Wet) 및 빙판(Ice)에서의 미끄러짐 저항과 동적특성을 측정하여 그 결과를 아래의 표 2에 정리하여 나타내었다.After using the rubber specimens of Comparative Examples and Examples as a tread of the snow tire, the slip resistance and dynamic characteristics of the wet and ice sheets were measured by ASTM-related regulations, and the results are summarized in Table 2 below. It is shown.

표 2. 비교예 및 실시예 시편의 물성측정Table 2. Measurement of Properties of Comparative Examples and Examples

항목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 미끄러짐저항*Slip resistance * Wet(Index)Wet (Index) 100100 105105 109109 116116 Ice(Index)Ice (Index) 100100 109109 110110 112112 동적특성Dynamic characteristics Tan δ(℃)Tan δ (℃) 0.190.19 0.250.25 0.260.26 0.280.28 E'(Npa, ℃)E '(Npa, ° C) 25.925.9 23.423.4 21.921.9 19.819.8 물성Properties 인장강도(kg/cm2)Tensile Strength (kg / cm 2 ) 197197 193193 189189 185185 경도Hardness 7474 7373 7272 7171

* 실시예의 미끄러짐 저항은 비교예 수치를 100으로 기준시 작성한 것임* The slip resistance of the example is prepared based on the comparative example value of 100.

상기 표 2에서처럼 본 발명의 스노우 타이어용 트레드 고무조성물에 의한 고무시편을 스노우 타이어의 트레드로 적용시 젖은노면 및 빙판에서의 미끄럼짐 저항 및 동적특성 향상됨을 알 수 있다.As shown in Table 2, when the rubber specimen of the tread rubber composition of the present invention is applied to the tread of the snow tire, the slip resistance and the dynamic characteristics of the wet road surface and the ice sheet are improved.

Claims (3)

공지의 스노우 타이어용 트레드 고무조성물에 있어서, 원료고무 100 phr에 대하여 미끄럼 방지제(anti-slip)로 SRS-40VP 3∼10 phr 포함하는 것을 특징으로 하는 스노우 타이어용 트레드 고무조성물In the known tread rubber composition for snow tires, a tread rubber composition for snow tires comprising SRS-40VP 3 to 10 phr as an anti-slip with respect to 100 phr of raw rubber. 제 1항에 있어서, 원료고무는 천연고무 10∼30 phr, 스티렌 부타디엔 고무(SBR) 30∼80 phr, 부타디엔 고무(BR) 10∼40 phr 포함하는 것을 특징으로 하는 스노우 타이어용 트레드 고무조성물The tread rubber composition according to claim 1, wherein the raw rubber comprises 10 to 30 phr of natural rubber, 30 to 80 phr of styrene butadiene rubber (SBR) and 10 to 40 phr of butadiene rubber (BR). 제 1항에 있어서, SRS-40VP는 분자량이 100000∼400000인 폴리노르보넨이 90%, 공정유(아모마틱 오일)가 5%, 기타물질 5%(유황, 디페닐구아니딘(DPG), N-시클로헥실-2-벤토티아졸 설펜아미드(CZ)가 2:2:5의 비율)로 구성된 것을 배합 후 180℃로 30∼50분 동안 가류후에 분쇄기에서 100 메쉬(mesh) 이내로 분쇄한 것임을 특징으로 하는 스노우 타이어용 트레드 고무조성물According to claim 1, SRS-40VP is 90% polynorbornene having a molecular weight of 100000-400000, process oil (amomatic oil) 5%, other substances 5% (sulfur, diphenylguanidine (DPG), N- Cyclohexyl-2-bentothiazole sulfenamide (CZ) is a 2: 2: 5 ratio), and after vulcanization at 180 ° C. for 30 to 50 minutes after blending, is pulverized within 100 mesh in a grinder. Tread rubber composition for snow tire
KR10-2001-0018301A 2001-04-06 2001-04-06 Tread rubber composition for snow tire KR100426062B1 (en)

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Publication number Priority date Publication date Assignee Title
JPS6035938B2 (en) * 1977-04-27 1985-08-17 日本ゼオン株式会社 Rubber material with excellent friction resistance on ice
KR950014196A (en) * 1993-11-18 1995-06-15 윤양중 Rubber composition for steedless snow tires with spike effect
KR100356585B1 (en) * 1995-02-22 2003-03-19 금호산업 주식회사 Tread rubber composition for four seasons, improving traction performance and fuel consumption simultaneously
KR980001004A (en) * 1996-06-07 1998-03-30 남일 Snow tires having treads composed of different rubber compositions for treads

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