KR20030096775A - Tread rubber composition improved abrasion - Google Patents

Tread rubber composition improved abrasion Download PDF

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KR20030096775A
KR20030096775A KR1020020033790A KR20020033790A KR20030096775A KR 20030096775 A KR20030096775 A KR 20030096775A KR 1020020033790 A KR1020020033790 A KR 1020020033790A KR 20020033790 A KR20020033790 A KR 20020033790A KR 20030096775 A KR20030096775 A KR 20030096775A
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parts
weight
carbon black
tread rubber
rubber composition
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KR100592986B1 (en
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이영득
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금호타이어 주식회사
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F112/02—Monomers containing only one unsaturated aliphatic radical
    • C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F112/06—Hydrocarbons
    • C08F112/08—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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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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)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

PURPOSE: Provided is a tire tread rubber composition, which has improved wear resistance compared with conventional tread rubber compositions with maintaining other physical properties. CONSTITUTION: The tire tread rubber composition is characterized by comprising 110-130 parts by weight of a carbon black based on 100 parts by weight of a natural rubber. In particular, the carbon black is obtained by milling it with a styrene-butadiene rubber to form powder having a nano-scaled particle size, and has an iodine adsorption value of 115-120 mg/g and DBP adsorption value of 135-140 ml/100g. The tire tread composition optionally further comprises a conventional additive, such as a vulcanization accelerator, an anti-aging agent and zinc oxide.

Description

내마모성이 향상된 타이어 트레드 고무조성물{Tread rubber composition improved abrasion}Tread rubber composition improved abrasion

본 발명은 내마모성이 향상된 타이어 트레드 고무조성물에 관한 것으로서 보다 상세하게는 천연고무 100 중량부에 대하여 요오드 흡착가가 115∼120mg/g, DBP 흡착가가 135∼140ml/100g인 카본블랙 110∼130 중량부 포함하는 것을 특징으로 한다.The present invention relates to a tire tread rubber composition with improved abrasion resistance, and more specifically, includes 110 to 130 parts by weight of carbon black having an iodine adsorption value of 115 to 120 mg / g and a DBP adsorption value of 135 to 140 ml / 100 g based on 100 parts by weight of natural rubber. Characterized in that.

타이어 개발의 대부분은 구조적 측면과 타이어에 사용되는 재료의 응용기술개발로 집약될 수 있으며, 특히 재료부분에서는 에너지 절약 측면 및 환경 문제를 중시하는 타이어의 개발에 대부분의 연구가 이루어지고 있다.Most of the development of tires can be concentrated on the structural aspects and the development of application technology of materials used in tires. In particular, most researches have been made on the development of tires that focus on energy saving aspects and environmental problems.

일반적으로 타이어의 트레드 고무는 마모성 및 저발열성을 위해 입자 크기가 작은 카본블랙을 사용한다든지, 카본블랙의 사용량을 줄인다든지 등의 방법을 사용하였으며, 근래에는 카본블랙이 배합에서 보강 효과를 나타내는 최소단위가 어그리게이트 사이즈 수준이라는 연구결과를 응용하는 방법을 사용하였다. 그러나 이와 같은 방법으로도 내마모성은 크게 증가되지 않고 있다.In general, the tread rubber of the tire uses a method of using carbon black having a small particle size or reducing the amount of carbon black used for wear and low heat generation. We used a method of applying the results of the study that the unit is at the aggregate size level. However, even in this way, the wear resistance is not greatly increased.

본 발명은 천연고무 100 중량부에 대하여 입자의 표면적과 구조가 발달한 카본블랙을 먼저 폴리머와 배합한 후 이를 나노크기의 입자경을 가지는 분말형태로 가공한 것으로서 요오드 흡착가가 115∼120mg/g, DBP 흡착가가 135∼140ml/100g인 카본블랙 110∼130 중량부 포함하는 것을 특징으로 하는 내마모성이 향상된 트레드 고무조성물의 제공을 목적으로 한다.In the present invention, the carbon black, which has developed the surface area and structure of the particles, is first blended with a polymer, and then processed into a powder having a nano-sized particle diameter with respect to 100 parts by weight of natural rubber, and the iodine adsorption value is 115 to 120 mg / g, DBP. It is an object of the present invention to provide a tread rubber composition having improved wear resistance, comprising 110 to 130 parts by weight of carbon black having an adsorption value of 135 to 140 ml / 100 g.

본 발명의 내마모성이 향상된 타이어 트레드 고무조성물은 공지의 타이어 고무조성물에 있어서, 천연고무 100 중량부에 대하여 카본블랙 110∼130 중량부 포함하는 것을 특징으로 한다.The tire tread rubber composition having improved wear resistance according to the present invention is characterized in that it comprises 110 to 130 parts by weight of carbon black with respect to 100 parts by weight of natural rubber in a known tire rubber composition.

본 발명에서 사용하는 카본블랙은 입자의 표면적과 구조가 발달한 카본블랙을 먼저 스티렌 부타디엔 고무(SBR)와 배합한 후 밀링(milling)하여 나노크기의 입자경을 가지는 분말형태로 가공한 것으로서 보다 상세하게는 요오드 흡착가가 115∼120mg/g, DBP 흡착가가 135∼140ml/100g인 카본블랙이다.The carbon black used in the present invention is a carbon black, which has developed the surface area and structure of the particles, is first blended with styrene butadiene rubber (SBR), and then milled to form a powder having a nano-sized particle diameter. Is carbon black having an iodine adsorption value of 115 to 120 mg / g and a DBP adsorption value of 135 to 140 ml / 100 g.

본 발명에서 카본블랙을 천연고무 100 중량부에 대하여 110 중량부 미만 사용할 경우 고무의 충분한 물성을 가질수 없으며, 130 중량부 초과하여 사용할 경우 가공성이 하락하여 오히려 발열이 증가하고 내마모성이 하락하는 문제가 있어 본 발명에서 카본블랙은 카본블랙을 천연고무 100 중량부에 대하여 110∼130 중량부포함하는 것이 좋다.In the present invention, when using less than 110 parts by weight of carbon black with respect to 100 parts by weight of natural rubber can not have sufficient physical properties of the rubber, when used in excess of 130 parts by weight, there is a problem that the heat workability is increased and rather the wear resistance decreases In the present invention, the carbon black may include 110 parts by weight to 130 parts by weight of carbon black based on 100 parts by weight of natural rubber.

본 발명의 트레드 고무조성물을 상기의 카본블랙 이외에도 트레드 고무조성물에 통상적으로 사용하는 유황, 가류촉진제, 노화방지제, 산화아연 등을 사용할 수 있다.Sulfur, vulcanization accelerator, anti-aging agent, zinc oxide and the like which are commonly used for the tread rubber composition of the tread rubber composition in addition to the carbon black described above can be used.

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

<비교예 1>Comparative Example 1

하기의 표 1과 같이 천연고무(SMR-CV60) 100 중량부에 대하여 카본블랙(N234) 60 중량부, 실리카(Z-157P) 30 중량부, 커플링제(SI-69) 2중량부, 공정오일 5 중량부, 스테아린산 2 중량부, 아연화 3 중량부, 가류제 2 중량부, 가황촉진제 2.0 중량부를 첨가하여 160℃에서 35분 동안 가류하여 고무시편을 제조하였다.60 parts by weight of carbon black (N234), 30 parts by weight of silica (Z-157P), 2 parts by weight of coupling agent (SI-69), process oil, based on 100 parts by weight of natural rubber (SMR-CV60), as shown in Table 1 below. Rubber parts were prepared by adding 5 parts by weight, 2 parts by weight of stearic acid, 3 parts by weight of zinc, 2 parts by weight of vulcanizing agent and 2.0 parts by weight of vulcanization accelerator, and vulcanizing at 160 ° C. for 35 minutes.

한편 상기의 카본블랙(N220)의 물성은 요오드 흡착가가 122mg/g, DBP 흡착가가 116ml/100g, 색도(Tint strength)가 114% 이다.On the other hand, the physical properties of the carbon black (N220) is iodine adsorption value of 122mg / g, DBP adsorption value of 116ml / 100g, color strength (Tint strength) 114%.

<비교예 2>Comparative Example 2

요오드 흡착가가 140mg/g, DBP 흡착가가 130ml/100g, 색도가 127%의 물성을가지는 카본블랙(N103)을 사용하는 것을 제외하고는 상기의 비교예 1과 동일한 방법으로 고무시편을 제조하였다.A rubber specimen was prepared in the same manner as in Comparative Example 1 except that carbon black (N103) having an iodine adsorption value of 140 mg / g, a DBP adsorption value of 130 ml / 100 g, and a chromaticity of 127% was used.

<실시예><Example>

하기의 표 1과 같이 천연고무(SMR-CV60) 100 중량부에 대하여 카본블랙 60 중량부, 실리카(Z-157P) 30 중량부, 커플링제(SI-69) 2 중량부, 공정오일 5 중량부, 스테아린산 2 중량부, 아연화 3 중량부, 가류제 2 중량부, 가황촉진제 2.0 중량부를 첨가하여 160℃에서 35분 동안 가류하여 고무시편을 제조하였다.60 parts by weight of carbon black, 30 parts by weight of silica (Z-157P), 2 parts by weight of coupling agent (SI-69), and 5 parts by weight of process oil, based on 100 parts by weight of natural rubber (SMR-CV60), as shown in Table 1 below. 2 parts by weight of stearic acid, 3 parts by weight of zinc, 2 parts by weight of vulcanizing agent, and 2.0 parts by weight of vulcanization accelerator were added and vulcanized at 160 ° C. for 35 minutes to prepare a rubber specimen.

한편 상기의 카본블랙은 스티렌 부타디엔 고무(SBR 1500)와 밴부리믹서(banbury)에서 밀링(milling)하여 나노크기의 입자경을 가지는 분말형태로 가공한 것으로서 물성은 요오드 흡착가가 115mg/g, DBP 흡착가가 135ml/100g, 색도가 120% 이다.On the other hand, the carbon black is milled in styrene butadiene rubber (SBR 1500) and banbury (banbury) and processed into a powder having a nano-sized particle diameter, the physical properties of the iodine adsorption value is 115mg / g, DBP adsorption value 135 ml / 100 g, chromaticity 120%.

표 1. 비교예 및 실시예 고무시편의 고무조성물Table 1. Comparative Examples and Examples Rubber Compositions of Rubber Specimens

항목Item 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예Example 천연고무Natural rubber 100100 100100 100100 카본블랙Carbon black 6060 6060 6060 실리카Silica 3030 3030 3030 커플링제Coupling agent 33 33 33 공정오일Process oil 55 55 55 스테아린산Stearic acid 22 22 22 아연화Zincification 33 33 33 가류제(유황)Vulcanizing (sulfur) 22 22 22 가황촉진제Vulcanization accelerator 2.02.0 2.02.0 2.02.0

<시험예><Test Example>

비교예 및 실시예의 고무시편에 대하여 ASTM 관련 규정으로 물성을 측정하여 그 결과를 아래의 표 2 내지 표 3에 정리하여 나타내었다.Physical properties of the rubber specimens of Comparative Examples and Examples were measured by ASTM-related regulations, and the results are summarized in Tables 2 to 3 below.

표 2. 고무시편의 물성측정 결과(Ⅰ)Table 2. Measurement results of rubber specimens (Ⅰ)

항목Item 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예Example DSR*DSR * test temp(℃)test temp (℃) 100100 100100 100100 T01T01 9898 106106 114114 T02T02 15891589 19301930 23952395 maxmax 337337 341341 346346 RheoRheo test temp(℃)test temp (℃) 160160 12601260 160160 Torque(max)Torque (max) 52.152.1 53.653.6 56.656.6 Torque(min)Torque (min) 16.316.3 18.118.1 19.519.5 T40T40 32.1532.15 26.826.8 23.7423.74 T90T90 47.4847.48 44.8144.81 4242 End CureEnd cure 52.2352.23 42.2942.29 46.246.2 MooneyviscosityMooneyviscosity 점도(125℃)Viscosity (125 ℃) 80.5880.58 92.3892.38 94.1294.12 T05T05 61.261.2 48.848.8 38.1338.13 T03T03 78.2778.27 60.6760.67 51.0751.07 점도(100℃)Viscosity (100 ° C) 107.4107.4 119.8119.8 123.5123.5

*DSR : Dynamic stress relaxationDSR: Dynamic stress relaxation

표 3. 고무시편의 물성측정 결과(Ⅱ)Table 3. Measurement Results of Rubber Specimen (Ⅱ)

항목Item 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예Example RheovibronRheovibron TgTg -31-31 -31-31 -31-31 Tand(0℃)Tand (0 ℃) 0.1680.168 0.1610.161 0.1750.175 Tand(70℃)Tand (70 degrees Celsius) 0.1320.132 0.130.13 0.130.13 H.B.U(heat built up)H.B.U (heat built up) temp. risetemp. rise 33.133.1 35.735.7 3535 temp. settemp. set 9898 9898 98.498.4 ReboundRebound indexindex 33.0333.03 32.6532.65 34.434.4 DMFC*DMFC * 가로(mm)Width (mm) 7.57.5 88 8.18.1 세로(mm)Length (mm) 15.215.2 2525 2525 AbrasionAbrasion picopico 0.0190.019 0.01650.0165 0.01450.0145 TensileTensile 초기Early 경도Hardness 7070 7272 7272 100% 모듈러스100% modulus 31.931.9 29.829.8 38.638.6 300% 모듈러스300% modulus 162.6162.6 171.2171.2 206.3206.3 인장강도The tensile strength 281.9281.9 312312 294.2294.2 신장율Elongation 468.2468.2 458.8458.8 397.4397.4 노화(24hr, 185℃)Aging (24hr, 185 ℃) 경도Hardness 7575 7777 7777 100% 모듈러스100% modulus 56.956.9 53.253.2 69.469.4 300% 모듈러스300% modulus -**-** 294.4294.4 -- 인장강도The tensile strength 236.2236.2 297297 289.6289.6 신장율Elongation 270.6270.6 298.5298.5 263.3263.3

*DMFC : Dimattia Flex CrackingDMFC: Dimattia Flex Cracking

** - : 시편파괴**-: Specimen Destruction

상기 시험예의 결과로부터 본 발명의 트레드 고무조성물은 종래의 트레드 고무조성물에 의한 고무와 비교시 여러 가지 물성에 있어서 동등 수준을 유지하면서 보다 내마모성이 향상됨을 알 수 있다.From the results of the test example, it can be seen that the tread rubber composition of the present invention is more abrasion resistant while maintaining the same level in various physical properties as compared with the rubber of the conventional tread rubber composition.

Claims (2)

공지의 타이어 트레드 고무조성물에 있어서,In known tire tread rubber compositions, 천연고무 100 중량부에 대하여 카본블랙 110∼130 중량부 포함하는 것을 특징으로 하는 내마모성이 향상된 타이어 트레드 고무조성물.A tire tread rubber composition having improved wear resistance, comprising 110 to 130 parts by weight of carbon black based on 100 parts by weight of natural rubber. 제 1 항에 있어서, 카본블랙은 스티렌 부타디엔 고무와 밀링하여 나노크기의 입자경을 가지는 분말형태로 가공한 것으로서 요오드 흡착가가 115∼120mg/g, DBP 흡착가가 135∼140ml/100g 임을 특징으로 하는 내마모성이 향상된 타이어 트레드 고무조성물.The method of claim 1, wherein the carbon black is milled with styrene butadiene rubber and processed into a powder having a nano-sized particle diameter, wear resistance of iodine adsorption is 115 ~ 120mg / g, DBP adsorption is 135 ~ 140ml / 100g Improved tire tread rubber composition.
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KR100803318B1 (en) * 2007-02-23 2008-02-13 금호타이어 주식회사 Rubber composition for tire comprising chain type carbon black

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JPH0662807B2 (en) * 1986-05-26 1994-08-17 株式会社ブリヂストン Improved rubber composition
JPH06287356A (en) * 1993-04-06 1994-10-11 Bridgestone Corp Pneumatic tire
JP2000080302A (en) * 1998-09-07 2000-03-21 Tokai Carbon Co Ltd Hard-based high structure carbon black and rubber composition blended with carbon black
JP2001040139A (en) * 1999-05-21 2001-02-13 Yokohama Rubber Co Ltd:The Rubber composition for tire tread and preparation thereof
KR100387295B1 (en) * 2000-11-15 2003-06-12 한국타이어 주식회사 Tire tread rubber composition
KR20020082016A (en) * 2001-04-23 2002-10-30 금호산업 주식회사 Tread rubber composition for truck and bus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100803318B1 (en) * 2007-02-23 2008-02-13 금호타이어 주식회사 Rubber composition for tire comprising chain type carbon black

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