KR100713074B1 - Rubber composition for tire tread - Google Patents

Rubber composition for tire tread Download PDF

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KR100713074B1
KR100713074B1 KR1020060052416A KR20060052416A KR100713074B1 KR 100713074 B1 KR100713074 B1 KR 100713074B1 KR 1020060052416 A KR1020060052416 A KR 1020060052416A KR 20060052416 A KR20060052416 A KR 20060052416A KR 100713074 B1 KR100713074 B1 KR 100713074B1
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rubber
coupling agent
rubber composition
composition
parts
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Korean (ko)
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임기원
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한국타이어 주식회사
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016Compositions of the tread
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

본 발명은 실리카를 보강제로 포함하는 통상의 타이어 트레드용 고무 조성물에 다음 화학식 1로 표시되는 인계 커플링제를 원료고무 100중량부에 대하여 1 내지 20중량부로 포함함으로써, 기존의 실란계 커플링제를 사용한 타이어 트레드용 조성물보다 내마모 특성 및 저연비 특성을 향상시킬 수 있다. The present invention includes a phosphorus-based coupling agent represented by the following formula (1) in 1 to 20 parts by weight based on 100 parts by weight of the raw material rubber in a rubber composition for tire treads containing silica as a reinforcing agent, thereby using an existing silane coupling agent It is possible to improve wear resistance and low fuel consumption characteristics than the composition for tire tread.

화학식 1Formula 1

Figure 112006040894432-pat00001
Figure 112006040894432-pat00001

상기 식에서, R은 탄소수 1 내지 12의 알킬기이고, n는 1 내지 10의 정수이며, R1 및 R2는 서로 같거나 다른 것으로서 수소 원자 또는 탄소수 1 내지 3의 알킬기이다. Wherein R is an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 to 10, and R 1 and R 2 are the same or different and are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.

인계커플링제*타이어*트레드*고무*조성물 Phosphorus coupling agent * tire * tread * rubber * composition

Description

타이어 트레드용 고무 조성물{Rubber composition for tire tread} Rubber composition for tire treads

본 발명은 타이어 트레드용 고무 조성물에 관한 것으로서, 더욱 상세하게는 실리카를 보강제로 포함하는 통상의 타이어 트레드용 고무조성물에 인계 커플링제를 첨가하여 내마모 특성 및 저연비 특성을 향상시킨 타이어 트레드용 고무 조성물에 관한 것이다. The present invention relates to a rubber tread rubber composition, and more particularly, to a tire tread rubber composition in which a phosphorus coupling agent is added to a general tire tread rubber composition including silica as a reinforcing agent to improve wear resistance and low fuel consumption. It is about.

타이어의 저연비 특성 및 제동성능과 같은 특성을 동시에 향상시키기 위하여 카본블랙을 대체할 수 있는 충진제가 연구되었으며 그 해결책의 하나로서 실리카의 적용이 활발히 진행되고 있다. In order to simultaneously improve properties such as low fuel efficiency and braking performance of tires, fillers that can replace carbon black have been studied. As one of the solutions, the application of silica is actively progressing.

그러나, 실리카는 대표적 친수성기인 하이드록실기(hydroxyl)를 많이 함유하고 있으므로 고무와의 상용성이 떨어져 고무와 충진제간의 이론적 결합력이 떨어지고, 이는 보강성의 제한을 가져오며 이를 해결하기 위하여 분산제 및 실란계 커플링제를 사용하고 있다. However, since silica contains a large amount of hydroxyl group (hydroxyl), which is a representative hydrophilic group, the compatibility with rubber is poor, and the theoretical bonding strength between rubber and filler is lowered, which leads to the limitation of reinforcement and to solve this problem. A ring agent is used.

실리카를 충진제로 포함하는 트레드용 타이어 조성물에 실란계 커플링제를 적용하면 상기 실리카 표면의 하이드록실기와 상기 실란계 커플링제의 알콕실기가 반응하여 알코올이 생성되어 카본블랙을 충진제로 사용한 조성물보다 많은 휘발성 물질을 발생시키며, 마모 특성이 떨어지는 문제점이 있다.When a silane coupling agent is applied to a tread tire composition containing silica as a filler, hydroxyl groups on the surface of the silica and an alkoxyl group of the silane coupling agent react to produce alcohol, which is more than the composition using carbon black as a filler. It generates a volatile material, there is a problem that the wear characteristics are poor.

이에 본 발명은 상기 서술된 실리카를 보강제로 포함하는 타이어 트레드용 고무 조성물의 보강성 향상을 위하여 실란계 커플링제 사용에 따른 종래 기술의 문제점을 해결하기 위한 것으로서, 실리카를 보강제로 포함한 타이어 트레드용 고무 조성물에서 디엔계 고무와 같이 가황될 수 있는 비닐기와 실리카와 결합할 수 있는 알콕시 또는 수산기를 지니고 있는 인계 커플링제를 사용함으로써 고무내의 실리카의 분산성을 높이고, 배합고무의 저연비 특성 및 마모 특성을 향상시킬 수 있어 본 발명에 도달하게 되었다. Accordingly, the present invention is to solve the problems of the prior art according to the use of the silane coupling agent to improve the reinforcement of the rubber tread rubber composition comprising the above-described silica as a reinforcing agent, a rubber for the tire tread containing silica as a reinforcing agent By using phosphorus coupling agent having alkoxy or hydroxyl group which can be combined with vinyl and silica which can be vulcanized like diene rubber in the composition, it improves dispersibility of silica in rubber and improves low fuel efficiency and wear characteristics of compounded rubber. The present invention has been achieved.

따라서, 본 발명의 목적은 타이어 트레드 조성물의 저연비 특성과 마모특성을 향상시킨 타이어 트레드용 고무 조성물을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a rubber composition for tire treads that has improved low fuel efficiency and wear characteristics of the tire tread composition.

이와 같은 본 발명의 목적을 달성하기 위한 본 발명은 실리카를 보강제로 포함하는 타이어 트레드용 고무 조성물에 있어서, 다음 화학식 1로 표시되는 인계 커플링제를 원료고무 100중량부에 대하여 1 내지 20중량부로 포함하는 것을 그 특징으로 한다. In order to achieve the object of the present invention, the present invention provides a rubber tread rubber composition comprising silica as a reinforcing agent, comprising 1 to 20 parts by weight of a phosphorus-based coupling agent represented by the following formula (1) based on 100 parts by weight of the raw material rubber: It is characterized by that.

Figure 112006040894432-pat00002
Figure 112006040894432-pat00002

상기 식에서, R은 탄소수 1 내지 12의 알킬기이고, n는 1 내지 10의 정수이며, R1 및 R2는 서로 같거나 다른 것으로서 수소 원자 또는 탄소수 1 내지 3의 알킬기이다.Wherein R is an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 to 10, and R 1 and R 2 are the same or different and are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.

본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention is described in more detail as follows.

본 발명은 타이어 트레드용 고무 조성물에 관한 것으로서, 원료고무는 통상의 타이어 트레드 고무 조성물에서 사용되는 디엔계 폴리머이면 어떤 것이든 가능한 바, 각별히 한정되는 것은 아니다. The present invention relates to a rubber tread rubber composition, and the raw material rubber can be any diene-based polymer used in a general tire tread rubber composition, and is not particularly limited.

또한, 본 발명의 타이어 트레드 고무 조성물은 보강제로서 실리카를 사용하는 바, 그 함량은 원료고무 100중량부에 대해 통상 20 내지 90 중량부 정도이다. In addition, the tire tread rubber composition of the present invention uses silica as a reinforcing agent, the content of which is usually about 20 to 90 parts by weight based on 100 parts by weight of the raw material rubber.

본 발명은 특별히 실리카 분산도를 향상시키고 실란계 커플링제를 사용함으로서 발생하는 문제점을 해결하는 방안으로서, 종래의 실란계 커플링제 대신에 상기 화학식 1로 표시되는 인계 커플링제를 사용하여 저연비 특성 및 마모 특성을 향상시킬 수 있다.The present invention is to solve the problems caused by improving the silica dispersion degree and using a silane coupling agent in particular, low fuel consumption characteristics and wear by using the phosphorus coupling agent represented by the formula (1) instead of the conventional silane coupling agent Properties can be improved.

이같은 역할을 하는 인계 커플링제를 원료고무 100중량부에 대해 1 내지 30 중량부를 포함하는 바, 만일 그 함량이 원료고무 100중량부에 대해 1중량부 미만이면 그 첨가의 효과가 미미하며, 30중량부 초과면 스코치 위험 및 고무의 기계적 물 성을 저하시키는 문제가 있을 수 있다.It contains 1 to 30 parts by weight with respect to 100 parts by weight of the raw material rubber containing a phosphorus-based coupling agent that plays such a role, if the content is less than 1 part by weight based on 100 parts by weight of raw rubber, the effect of the addition is insignificant, 30 parts by weight Negative excess may present problems with scorch hazards and reduce the mechanical properties of the rubber.

본 발명에서는 상기와 같은 구성 성분 이외에도, 통상의 타이어 트레드용 고무 조성물에 포함되는 가황제인 유황; 가류활성제인 산화아연, 스테아린산; 연화제로서 아로마틱 오일; 가황촉진제로서 CBS와 DPG; 및 노화방지제로서 6C 등을 포함할 수 있는 것은 물론이다.In the present invention, in addition to the above components, sulfur which is a vulcanizing agent contained in a rubber composition for a tire tread; Zinc oxide and stearic acid as vulcanizing agents; Aromatic oils as softeners; CBS and DPG as vulcanization accelerators; And 6C, etc., as an anti-aging agent, of course.

이하, 실시예에 의거하여 보다 상세하게 설명하면 다음과 같은 바, 본 발명의 보호범위가 다음의 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the protection scope of the present invention is not limited to the following Examples.

실시예 1 내지 3 및 비교예Examples 1 to 3 and Comparative Examples

다음 표 1과 같은 조성으로 배합제를 반바리 믹서에서 배합하여 150℃에서 방출하여 타이어 트레드용 고무 조성물을 제조하였으며, 미가류 물성 및 얻어진 고무시편을 160℃에서 가류하여 물성시험을 하였다.Next, the compounding agent was blended in a half-barrier mixer to prepare a rubber composition for tire treads by releasing the mixture at a temperature of 150 ° C. The unvulcanized physical properties and the obtained rubber specimens were vulcanized at 160 ° C. for physical property tests.

(표 1)Table 1

Figure 112006040894432-pat00003
Figure 112006040894432-pat00003

상기 표 1에서 인계 커플링제는 황을 함유하고 있지 않으므로 실시예에서 약간의 황을 보정해 주었다. Since the phosphorus-based coupling agent in Table 1 does not contain sulfur, some sulfur was corrected in Examples.

비교예와 실시예에 따라 얻어진 고무시편의 물성을 다음 표 2에 나타내었으며, 여기서 300% 모듈러스는 상기 각각의 고무 조성물로부터 아령 모양의 시편을 제작한 다음, 인장강도 시험기(Instron)를 이용하여 시편을 300% 신장시켰을 때의 모듈러스를 측정한 것이고, 마모도는 람본 마모도로서 상온에서 미끄럼비 25%, 하 중 1.5kg에서 회전시켜 마모된 고무의 손실량을 의미하며 수치가 작을수록 우수한 마모성능을 나타낸다. 60℃ Tanδ 는 60℃에서의 회전저항을 나타내는 척도로서, 그 수치가 낮을수록 우수한 저연비 특성을 나타낸다. The physical properties of the rubber specimens obtained according to the comparative examples and examples are shown in Table 2, where 300% modulus was made of the dumbbell-shaped specimens from the respective rubber compositions, and then the tensile strength tester (Instron) The modulus at 300% elongation is measured, and the wear degree is the rambon wear degree, which means the loss of worn rubber by rotating at a sliding ratio of 25% and a load of 1.5 kg at room temperature. The smaller the value, the better the wear performance. 60 ° C Tan δ is a measure of rotational resistance at 60 ° C. The lower the value, the better the low fuel consumption characteristics.

(표 2)Table 2

  비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 300% 모듈러스300% modulus 97 97 98 98 93 93 91 91 마모도(g)Wear (g) 0.41 0.41 0.38 0.38 0.34 0.34 0.31 0.31 60℃ tan δ60 ℃ tan δ 0.148 0.148 0.142 0.142 0.135 0.135 0.132 0.132

상기 표 3에서 확인할 수 있는 바와 같이, 본 발명의 타이어 트레드용 고무 조성물은 300% 모듈러스를 유지하면서, 마모도 및 60℃ tanδ가 비교예에 비하여 월등함을 알 수 있다. 또한 본 발명의 인계 커플링제를 사용하면 실란계 커플링제를 사용한 비교예 대비 내마모특성 및 저연비 특성이 향상됨을 알 수 있다. As can be seen in Table 3, the rubber composition for tire tread of the present invention can be seen that the wear degree and 60 ℃ tan δ is superior to the comparative example, while maintaining 300% modulus. In addition, it can be seen that the use of the phosphorus-based coupling agent of the present invention improves abrasion resistance and low fuel consumption compared to the comparative example using the silane-based coupling agent.

이상에서 상세하게 설명한 바와 같이, 본 발명에 따라 실리카를 보강제로 사용하면서 커플링제로서 인계 커플링제를 도입하면 기존의 실란계 커플링제를 사용한 트레드 조성물보다 내마모 특성 및 저연비 특성을 향상시킬 수 있으므로 타이어 트레드 조성물에 유용하다. As described in detail above, if the phosphorus-based coupling agent is introduced as a coupling agent while using silica as a reinforcing agent according to the present invention, it is possible to improve wear resistance and low fuel consumption characteristics compared to a tread composition using a conventional silane coupling agent. Useful for tread compositions.

Claims (1)

실리카를 보강제로 포함하는 타이어 트레드용 고무 조성물에 있어서,In the rubber composition for tire tread comprising silica as a reinforcing agent, 다음 화학식 1로 표시되는 인계 커플링제를 원료고무 100중량부에 대하여 1 내지 20중량부로 포함하는 타이어 트레드용 고무 조성물.The rubber composition for tire treads comprising a phosphorus-based coupling agent represented by the following formula (1) in an amount of 1 to 20 parts by weight based on 100 parts by weight of the raw material rubber. 화학식 1Formula 1
Figure 112006040894432-pat00004
Figure 112006040894432-pat00004
상기 식에서, R은 탄소수 1 내지 12의 알킬기이고, n는 1 내지 10의 정수이며, R1 및 R2는 서로 같거나 다른 것으로서 수소 원자 또는 탄소수 1 내지 3의 알킬기이다.Wherein R is an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 to 10, and R 1 and R 2 are the same or different and are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3462503B2 (en) 1994-10-11 2003-11-05 株式会社ブリヂストン Rubber composition with improved chargeability and pneumatic tire using the same
KR20040091123A (en) * 2002-03-15 2004-10-27 제온 코포레이션 Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers
KR100548149B1 (en) 2004-11-04 2006-01-31 한국타이어 주식회사 Rubber composition for tire tread

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3462503B2 (en) 1994-10-11 2003-11-05 株式会社ブリヂストン Rubber composition with improved chargeability and pneumatic tire using the same
KR20040091123A (en) * 2002-03-15 2004-10-27 제온 코포레이션 Diene rubber, process for production thereof, rubber compositions, process for producing the same, and crosslinked rubbers
KR100548149B1 (en) 2004-11-04 2006-01-31 한국타이어 주식회사 Rubber composition for tire tread

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