KR100638626B1 - Tire rubber composition improved fatigue property - Google Patents

Tire rubber composition improved fatigue property Download PDF

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KR100638626B1
KR100638626B1 KR1020050044539A KR20050044539A KR100638626B1 KR 100638626 B1 KR100638626 B1 KR 100638626B1 KR 1020050044539 A KR1020050044539 A KR 1020050044539A KR 20050044539 A KR20050044539 A KR 20050044539A KR 100638626 B1 KR100638626 B1 KR 100638626B1
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rubber composition
weight
parts
carbon black
surface area
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KR1020050044539A
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Korean (ko)
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박중양
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금호타이어 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
    • 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
    • C08K3/02Elements
    • C08K3/04Carbon
    • 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
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43Compounds containing sulfur bound to nitrogen
    • C08K5/435Sulfonamides

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Provided are a rubber composition for a tire which is remarkably improved in fatigue resistance characteristics, and a tire containing the sidewall comprising the composition. The rubber composition comprises 30-35 parts by weight of the carbon black (N330) which has a N2 adsorption specific surface area of 78 m^2/g, a STSA (statistical thickness surface area) of 75 m^2/g, an iodine adsorption number of 76-84 g/kg, a DBP oil absorption of 98-106 mL/100 g, a CDBPA of 88 mL/100g, a CTAB of 82 m^2/g and a degree of coloration of 102 %; 40-50 parts by weight of the carbon black (N660) which has a N2 adsorption specific surface area of 35 m^2/g, a STSA of 34 m^2/g, an iodine adsorption number of 32-40 g/kg, a DBP oil absorption of 87-95 mL/100 g, a CDBPA of 74 mL/100g, a CTAB of 36 m^2/g and a degree of coloration of 56 %; and 0.5-1.5 parts by weight of N-dicyclohexyl-2-benzothiazole sulfonamide as a vulcanization accelerator, based on 100 parts by weight of a rubber material.

Description

내피로특성이 개선된 타이어용 고무 조성물{TIRE RUBBER COMPOSITION IMPROVED FATIGUE PROPERTY}Rubber composition for tires with improved fatigue resistance {TIRE RUBBER COMPOSITION IMPROVED FATIGUE PROPERTY}

본 발명은 내피로특성이 개선된 타이어용 고무 조성물에 관한 것으로서, 보다 상세하게는 원료고무 100중량부에 대해서, N330 카본블랙 30~35중량부, N660 카본블랙 45~50중량부, 가류촉진제 DZ가 0.5~1.5중량부 적용된 타이어용 고무 조성물에 관한 것이다. The present invention relates to a rubber composition for tires with improved fatigue resistance, and more specifically, 30 to 35 parts by weight of N330 carbon black, 45 to 50 parts by weight of N660 carbon black, and vulcanization accelerator DZ based on 100 parts by weight of raw material rubber. It relates to a rubber composition for a tire applied 0.5 to 1.5 parts by weight.

자동차 문명의 발달과 함께 개발 당시부터 지금까지 사용되면서 많은 사람들은 타이어가 단순한 차량지지 및 운반의 기능으로만 사용되고 있는 것으로 알고 있다. 그러나 최근 세계 경제와 기술력 발달에 따라 다양한 분야에서 타이어 기능에 대한 중요성이 대두되고 있고, 이에 따른 소비자의 요구 특성도 급변하고 있으며, 특히 차량의 성능향상에 따른 타이어의 성능도 비례적으로 향상되고 있어, 여기에 부응할 수 있는 새로운 성능을 갖는 타이어 개발이 시급한 실정이다. With the development of automobile civilization and being used from the time of development until now, many people know that tires are used only as a function of vehicle support and transportation. However, with the recent development of the global economy and technological prowess, the importance of tire function is emerging in various fields, and the demand characteristics of consumers are rapidly changing accordingly, and the performance of tires is also proportionally improved due to the improvement of the performance of the vehicle. Therefore, it is urgent to develop a tire having a new performance that can meet this.

일반적인 승용차용 타이어보다 트럭/버스용 타이어의 대표적인 경향이 장기사용 특성 부분이다. 특히 트럭/버스용 타이어는 비교적 고가의 제품이면서 타이어 성능에 따른 사용기간의 편차가 많아, 일정한 성능을 유지하면서 장기사용 가능한 제품 개발이 필수적이다. 또한 소비자들은 장기 사용에 따른 추가적인 리싸이클 사용을 필수적으로 요구하고 있어, 타이어의 장기 사용에 따른 내피로 특성 유지가 매우 중요한 부분이고, 내피로 특성을 장기간 유지할 수 있는 고무 조성물의 개발이 필요하다. The typical trend of truck / bus tires is that of long-term use characteristics rather than general passenger tires. In particular, tires for trucks / buses are relatively expensive products and have a large variation in the service life due to tire performance. In addition, since consumers are required to use additional recycling according to long-term use, it is very important to maintain fatigue resistance according to long-term use of tires, and it is necessary to develop a rubber composition that can maintain fatigue resistance for a long time.

타이어를 장기간 사용하고, 또한 재생 후에도 신생 타이어와 유사하거나 그 이상의 성능을 유지하기 위해서는 카카스부의 보강이 필수적인 것으로 알려져 있다. 카카스부는 차량으로부터의 과도한 하중과 부담을 공기압과 맞대어 지지하고 있으므로 카카스층의 안정화가 장기 내구력 확보를 위한 필수 조건으로 알려져 있다. 이러한 카카스부를 공기압과 직접적으로 접촉하는 인너라이너부와 구별하기 위하여 백업층을 사용하고 있으며, 백업층은 인너라이너층으로부터 침투되는 수분 등을 억제하고, 보강성 코드와 고무간의 접착을 추가적으로 보완해 주는 기능을 한다. It is known that reinforcement of the carcass is essential in order to use the tire for a long time and to maintain the performance similar to or higher than that of the new tire even after regeneration. Since the carcass unit supports excessive loads and burdens from the vehicle against the air pressure, stabilization of the carcass layer is known as an essential condition for securing long-term durability. The backing layer is used to distinguish the carcass part from the inner liner part which is in direct contact with the air pressure. Giving functions.

통상적으로 장기주행 타이어의 경우 우선적으로 백업층이 파괴된 후 점진적으로 카카스층이 파괴되는 진행 양상을 띄고 있으므로, 본 발명에서는 백업층의 내피로 특성을 향상시켜 카카스부를 보호함과 동시에 장기 내구성을 향상시키는 고무조성물을 발명코자 한다. In general, in the case of long-run tires, since the carcass layer is gradually destroyed after the backup layer is first destroyed, the present invention improves the fatigue resistance of the backup layer to protect the carcass and at the same time long-term durability. It is intended to invent a rubber composition that improves.

이러한 문제점을 해결하기 위하여 미국특허 US-6519925호에서는 Multi-filamentary yarn을 사용하여 내피로 특성을 개선하였으며, 또한 미국특허 US-6427736호에서는 셀룰로오스 섬유를 사용하여 공기압 타이어의 내피로특성 개선에 관한 발명을 하였다. In order to solve this problem, US Pat. No. 6,519,925 improves fatigue resistance by using multi-filamentary yarns, and US Pat. No. 6,6427736 uses invention to improve fatigue resistance of pneumatic tires using cellulose fibers. Was done.

본 발명은 상기와 같은 문제점을 개선하기 위한 것으로서, 본 발명의 목적은 타이어의 내구성에 중요한 영향을 미치는 카카스층을 보호할 수 있는 고무조성물을 백업층에 사용하므로써 장기 내구성을 향상시켜 내피로특성이 개선된 타이어용 고무 조성물을 제공하는 것이다.The present invention is to improve the above problems, an object of the present invention is to improve the long-term durability by using a rubber composition that can protect the carcass layer which has an important effect on the durability of the tire in the backup layer fatigue resistance characteristics The improved rubber composition for a tire is provided.

본 발명은 내피로특성이 개선된 타이어용 고무 조성물에 관한 것으로서, 보다 상세하게는 원료고무 100중량부에 대해서, N330 카본블랙 30~35중량부, N660 카본블랙 45~50중량부, 가류촉진제 DZ가 0.5~1.5중량부 적용된 타이어용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for tires with improved fatigue resistance, and more specifically, 30 to 35 parts by weight of N330 carbon black, 45 to 50 parts by weight of N660 carbon black, and vulcanization accelerator DZ based on 100 parts by weight of raw material rubber. It relates to a rubber composition for a tire applied 0.5 to 1.5 parts by weight.

N330 카본블랙의 함량은 30~35중량부가 바람직하고, 32~34중량부가 더욱 바람직하다.30-35 weight part is preferable and, as for content of N330 carbon black, 32-34 weight part is more preferable.

N660 카본블랙의 함량은 45~50중량부가 바람직하고, 46~48중량부가 더욱 바람직하다.As for content of N660 carbon black, 45-50 weight part is preferable, and 46-48 weight part is more preferable.

본 발명의 타이어용 고무 조성물은 카본블랙으로서 N330과 N660을 상기와 같은 함량 범위로 혼합하여 사용하므로써, 고무조성물의 내피로특성 향상과 완제품 타이어 장기 내구성을 향상시킬 수 있다.The rubber composition for a tire of the present invention is used by mixing N330 and N660 as the carbon black in the content range as described above, thereby improving fatigue resistance of the rubber composition and long-term durability of the finished tire.

본 발명에서 사용된 카본블랙들(상품명 ; N330, N660)의 주요성질과 주요특징은 다음과 같다.The main properties and main features of the carbon blacks (trade names; N330, N660) used in the present invention are as follows.

제조사 : COLUMBIAN CHEMICALS COMPANY CO., LTDManufacturer: COLUMBIAN CHEMICALS COMPANY CO., LTD

조성물Composition N330N330 N660 N660 질소흡착 비표면적 값 ; NSA(㎡/g)Nitrogen adsorption specific surface area value; NSA (㎡ / g) 7878 3535 STSA(㎡/g)STSA (㎡ / g) 7575 3434 요오드 흡착가 ; IODINE(g/kg)Iodine adsorption value; IODINE (g / kg) 76~8476-84 32~4032-40 DBP 흡유량 ; DBPA(mL/100g)DBP oil absorption; DBPA (mL / 100 g) 98~10698-106 87~9587-95 CDBPA(mL/100g)CDBPA (mL / 100 g) 8888 7474 CTAB(㎡/g)CTAB (㎡ / g) 8282 3636 착색도 ; TINT(%IRTB)Degree of coloring; TINT (% IRTB) 102102 5656

주)week)

ㆍSTSA(Statistical Thickness Surface Area) : 카본블랙의 외부 비표면적.ㆍ STSA (Statistical Thickness Surface Area): External specific surface area of carbon black.

ㆍCDBPA : 구조를 나타내는 척도로, 24Mpa 압력으로 4회 전단 압축을 가하여 파괴한 후 흡유량을 측정함.ㆍ CDBPA: It is a measure of the structure, and the oil absorption is measured after breaking by applying 4 times of shear compression at 24Mpa pressure.

ㆍCTAB : 요오드흡착가 및 질소흡착가와 마찬가지로 비표면적 즉, 카본입자 크기를 측정하는 방법으로 세틸트리메틸암모늄 브로마이드를 사용하여 측정함.CTAB: It is measured using cetyltrimethylammonium bromide as a method of measuring specific surface area, that is, carbon particle size, similarly to iodine adsorption value and nitrogen adsorption value.

본 발명에서 사용되는 가류촉진제 DZ는 N-디시클로헥실-2-벤조티아졸설폰아미드로서, BAYER사 제품으로, 0.5~1.5중량부 사용되는 것이 바람직하다. 상기 DZ의 사용량이 1.5중량부를 초과하는 경우에는 가류속도가 너무 빨라서 고무 조성물들간에 원만한 결합을 하기 전에 가교반응이 일어나 원하는 고무 조성물을 얻을 수 없고, 제조공정상에서도 일부 가류가 진행되어 불량 제조의 원인이 되며, 사용량이 0.5중량부 미만인 경우에는 가류시간이 길어져서 공정 불안정과 제조비용의 상승의 원인이 된다. The vulcanization accelerator DZ used in the present invention is N-dicyclohexyl-2-benzothiazolesulfonamide, and 0.5 to 1.5 parts by weight of a BAYER company is preferably used. If the amount of the DZ exceeds 1.5 parts by weight, the vulcanization rate is so fast that a crosslinking reaction occurs before the smooth bonding between the rubber compositions, so that the desired rubber composition cannot be obtained. If the amount is less than 0.5 parts by weight, the vulcanization time becomes long, which causes process instability and an increase in manufacturing cost.

본 발명은 하기 실시예와 비교예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예는 본 발명을 예시하기 위한 것에 지나지 않으며, 본 발명의 보호범 위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples and comparative examples, the following examples are only for illustrating the present invention, and are not intended to limit the protection scope of the present invention.

실시예 및 비교예Examples and Comparative Examples

표 1에 나타낸 조성에 따라 고무 조성물을 제조하고, 기본물성 및 내피로특성을 측정하여 그 결과를 각각 하기 표 2 및 표 3에 나타내었다.A rubber composition was prepared according to the composition shown in Table 1, the basic physical properties and fatigue resistance were measured, and the results are shown in Tables 2 and 3, respectively.

하기 표 1에 나타난 배합비율로 반바리 챔버온도 90℃ 이하, 회전수 60RPM으로 4분 30초간 혼련후 100℃로 유지되는 밀에서 시팅(sheeting)하였다. 시팅된 고무 배합물은 반바리 챔버온도 80℃ 이하에서 가황제를 첨가하여 2분간 배합후 145℃에서 30분간 가류하여 내피로특성 시험을 실시하였다.The mixing ratios shown in Table 1 were sheeted in a mill maintained at 100 ° C. after kneading at a chamber temperature of 90 ° C. for less than 4 minutes and 30 seconds at a rotational speed of 60 RPM. The seated rubber compound was added to a vulcanizing agent at a half-barrier chamber temperature of 80 ° C. or less, and then mixed for 2 minutes and quenched at 145 ° C. for 30 minutes to carry out fatigue resistance test.

Figure 112005027837411-pat00001
Figure 112005027837411-pat00001

ㆍ고무 : STR-10K를 소련하여 사용ㆍ Rubber: used STR-10K by Soviet Union

ㆍMANOBOND : COBALT BORONEODECANOATE(접착증진제), 태광정밀화학제. ㆍ MANOBOND: COBALT BORONEODECANOATE (Adhesive Promoter), Taekwang Fine Chemical.

ㆍB-18-S : 레졸시놀 포름알데하이드 수지(접착제), INDSPEC(PITSUBURG, USA)제.B-18-S: Resorcinol formaldehyde resin (adhesive), INDSPEC (PITSUBURG, USA).

ㆍMOR : N-옥시디에틸렌-2-벤조티아졸-설펜아미드(가류촉진제), 동양제철화학(주)제.MOR: N-oxydiethylene-2-benzothiazole-sulfenamide (a vulcanization accelerator), the Tong Yang Steel Chemical Co., Ltd. product.

ㆍSULFASAN : 4,4-디티오디몰포린(가류촉진제), 상해경해화공창(중국)제.ㆍ SULFASAN: 4,4-Dithiodimorpholine (vulcanization accelerator), Shanghai Kyunghwa Chemical (China).

ㆍPVI : N-시클로헥실티오프탈이미드(가류지연제), 용진유화제.PVI: N-cyclohexylthioptalimide (vulcanization delaying agent), a lysing emulsifier.

ㆍ황 : 80%-CrystexSulfur: 80% -Crystex

ㆍCYREZ964 : 헥사-메톡시-메틸-멜라민(HMMM)(65%) + HISIL 233(35%)(접착제), 금호석유화학(주)제.CYREZ964: Hexa-methoxy-methyl-melamine (HMMM) (65%) + HISIL 233 (35%) (adhesive), manufactured by Kumho Petrochemical Co., Ltd.

Figure 112005027837411-pat00002
Figure 112005027837411-pat00002

Figure 112005027837411-pat00003
Figure 112005027837411-pat00003

- 내피로 특성은 DIMATIA시험기를 이용하여 30,000회 반복굴절 후 크랙의 성장량을 기록한 것으로서, 크랙 성장이 적은 것이 내피로특성 효과가 큰 고무 조성물임을 나타내는 것이다.-Fatigue resistance was recorded as the amount of crack growth after 30,000 repeated refractions using a DIMATIA tester, indicating that the less crack growth is a rubber composition with greater fatigue resistance effect.

상기의 실시예의 결과로부터 알 수 있는 바와 같이, N330 카본블랙과 N660 카본블랙을 변량적용 사용하여 적절한 모듈러스를 유지하면서 장기 반복에 의한 내피로 특성을 개선할 수 있다.As can be seen from the results of the above examples, fatigue resistance by long-term repetition can be improved by using variably applying N330 carbon black and N660 carbon black.

이상의 비교예 및 실시예에서 알 수 있는 바와 같이, 본 발명에 의하여 제조된 내피로특성이 개선된 타이어용 고무 조성물은 내피로특성이 현저히 개선되는 효과를 갖는다.As can be seen from the above comparative examples and examples, the rubber composition for tires with improved fatigue resistance produced by the present invention has an effect of significantly improving fatigue resistance.

Claims (2)

원료고무 100중량부에 대해서, 질소흡착 비표면적 값이 78㎡/g이고, STSA가 75㎡/g이고, 요오드 흡착가가 76~84g/kg이고, DBP흡유량이 98~106mL/100g이고, CDBPA가 88mL/100g이고, CTAB가 82㎡/g이고, 착색도가 102%인 카본블랙 30~35중량부, 질소흡착 비표면적 값이 35㎡/g이고, STSA가 34㎡/g이고, 요오드 흡착가가 32~40g/kg이고, DBP흡유량이 87~95mL/100g이고, CDBPA가 74mL/100g이고, CTAB가 36㎡/g이고, 착색도가 56%인 카본블랙 45~50중량부, 가류촉진제로서 N-디시클로헥실-2-벤조티아졸설폰아미드 0.5~1.5중량부를 포함하여 이루어지는 것을 특징으로 하는 내피로 특성이 개선된 타이어용 고무 조성물.Nitrogen adsorption specific surface area value is 78 m2 / g, STSA is 75 m2 / g, iodine adsorption value is 76-84 g / kg, DBP oil absorption is 98-106 mL / 100 g, and CDBPA 30 to 35 parts by weight of carbon black having 88 mL / 100 g, CTAB of 82 m 2 / g, 102% coloration, nitrogen adsorption specific surface area of 35 m 2 / g, STSA of 34 m 2 / g, and iodine adsorption value of 32 45-50 parts by weight of carbon black with ~ 40 g / kg, DBP oil absorption of 87-95 mL / 100 g, CDBPA of 74 mL / 100 g, CTAB of 36 m2 / g, coloration of 56%, and as a vulcanization accelerator. Rubber composition for tires with improved fatigue resistance characterized in that it comprises 0.5 to 1.5 parts by weight of clohexyl-2-benzothiazolesulfonamide. 제 1항의 타이어용 고무 조성물로 제조된 타이어.A tire made of the rubber composition for tires of claim 1.
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KR20150121522A (en) * 2014-04-21 2015-10-29 한국타이어 주식회사 Rubber composition for tire tread and tire manufactured by using the same

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KR100443460B1 (en) 2002-05-24 2004-08-09 한국타이어 주식회사 Rubber composition for tire curing air-bag
KR100451966B1 (en) 2001-10-11 2004-10-08 금호타이어 주식회사 Building bladder rubber composition for improved fatigue failure properties

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KR100451966B1 (en) 2001-10-11 2004-10-08 금호타이어 주식회사 Building bladder rubber composition for improved fatigue failure properties
KR100443460B1 (en) 2002-05-24 2004-08-09 한국타이어 주식회사 Rubber composition for tire curing air-bag

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150121522A (en) * 2014-04-21 2015-10-29 한국타이어 주식회사 Rubber composition for tire tread and tire manufactured by using the same
JP2015206029A (en) * 2014-04-21 2015-11-19 ハンコック タイヤ カンパニー リミテッド Rubber composition for tire tread, and tire manufactured using the same
KR101582253B1 (en) 2014-04-21 2016-01-04 한국타이어 주식회사 Rubber composition for tire tread and tire manufactured by using the same

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