KR100911613B1 - Rubber composition of tire having polybutene - Google Patents

Rubber composition of tire having polybutene Download PDF

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KR100911613B1
KR100911613B1 KR1020070107153A KR20070107153A KR100911613B1 KR 100911613 B1 KR100911613 B1 KR 100911613B1 KR 1020070107153 A KR1020070107153 A KR 1020070107153A KR 20070107153 A KR20070107153 A KR 20070107153A KR 100911613 B1 KR100911613 B1 KR 100911613B1
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rubber
polybutene
parts
weight
tire
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KR1020070107153A
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KR20090041571A (en
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조춘택
강용구
장석희
김인영
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넥센타이어 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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • B60C1/0041—Compositions of the carcass layers
    • 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

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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 점착특성, 크랙 특성, 점탄성 특성을 향상시키도록 한 폴리부텐을 함유한 타이어 고무조성물에 관한 것으로서, 원료고무 중에 폴리부텐을 함유하는 고무배합물은 원료고무 100 중량부에 대하여 폴리부텐 5~40 중량부를 배합하여 얻어지는 것을 특징으로 한다. 이와 같은 본 발명은 폴리부텐을 함유하지 않은 고무조성물에 비해서 폴리부텐을 함유한 고무조성물에서 점착 특성, 제동 특성, 내구 특성이 우수하고, 특히, 원료고무에 대비하여 폴리부텐의 중량부가 많을수록 상기의 특성들이 점차적으로 우수하다. The present invention relates to a tire rubber composition containing polybutene to improve adhesive properties, crack characteristics, and viscoelastic properties, wherein the rubber compound containing polybutene in the raw material rubber is polybutene 5 to 5 parts by weight of the raw material rubber. It is obtained by mix | blending 40 weight part. The present invention is excellent in adhesive properties, braking properties, and durability characteristics in the rubber composition containing polybutene as compared to the rubber composition containing no polybutene, and in particular, the more weight part of the polybutene relative to the raw material rubber, The properties are gradually superior.

폴리부텐, 타이어, 고무조성물 Polybutene, Tire, Rubber Composition

Description

폴리부텐을 함유한 타이어 고무조성물{RUBBER COMPOSITION OF TIRE HAVING POLYBUTENE}Tire rubber composition containing polybutene {RUBBER COMPOSITION OF TIRE HAVING POLYBUTENE}

본 발명은 폴리부텐을 함유한 타이어 고무조성물에 관한 것으로, 더욱 상세하게는, 점착 특성, 제동 특성, 내구 특성을 가진 폴리부텐을 함유한 타이어 고무조성물에 관한 것이다.The present invention relates to a tire rubber composition containing polybutene, and more particularly, to a tire rubber composition containing polybutene having adhesion characteristics, braking characteristics, and durability characteristics.

타이어와 같은 고무 제품은 성형 공정에서 우수한 점착 특성이 요구되며, 지면과 접촉하는 부위인 타이어 트레드는 우수한 제동 특성이 요구되며, 오랜 시간 동안 안전하게 주행을 하기 위해서는 우수한 내구성능이 필요하다. 그러나 이러한 특성은 서로 이율 배반적인 관계를 가지는 것으로 동시에 여러 특성을 향상시키기는 어려운 실정이다.Rubber products such as tires require excellent adhesive properties in the molding process, tire treads, which are in contact with the ground, require excellent braking properties, and require excellent durability to run safely for a long time. However, these characteristics have a mutually exclusive relationship with each other, and it is difficult to improve various characteristics at the same time.

따라서, 점착제를 사용하는 방법, 제동특성에 우수한 합성 고무의 사용, 내구성능이 우수한 천연고무의 사용 이외에 타이어에 사용되는 고무 제품의 점착 특성, 제동 특성, 내구 성능을 향상시키기 위해 여러 가지 방법이 연구되고 있는 실정이다. Therefore, in addition to the use of pressure-sensitive adhesives, the use of synthetic rubber having excellent braking characteristics, and the use of natural rubber having excellent durability, various methods have been studied to improve the adhesive properties, braking characteristics, and durability performance of rubber products used in tires. There is a situation.

본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 원료고무 중에 폴리부텐을 함유하는 고무배합물을 제조하여 고무 특성 평가를 한 결과, 점착 특성 향상, 제동 특성 향상, 내구 특성이 향상된 폴리부텐을 함유한 타이어 고무조성물을 제공하는 데 있다. The present invention is to solve the problems as described above, an object of the present invention is to prepare a rubber compound containing polybutene in the raw material rubber to evaluate the rubber properties, improved adhesion characteristics, improved braking characteristics, durability characteristics It is to provide a tire rubber composition containing an improved polybutene.

따라서, 본 발명은 상기한 바와 같은 목적을 해결하기 위하여 안출된 것으로서, 본 발명에 의한 폴리부텐을 함유한 타이어 고무조성물은, 타이어 고무조성물에 있어서, 상기 타이어에 폴리부텐을 함유하는 고무배합물이 포함된 것을 특징으로 한다. Accordingly, the present invention has been made to solve the above object, the tire rubber composition containing the polybutene according to the present invention, in the tire rubber composition, the rubber compound containing polybutene in the tire It is characterized by.

상기한 바와 같은 본 발명의 폴리부텐을 함유한 타이어 고무조성물에 의하면, 폴리부텐을 함유하지 않은 고무조성물에 비해서 폴리부텐을 함유한 고무조성물에서 점착 특성, 제동 특성, 내구 특성이 우수하고, 특히, 원료고무에 대비하여 폴리부텐의 중량부가 많을수록 상기의 특성들이 점차적으로 우수하다.According to the tire rubber composition containing the polybutene of the present invention as described above, the rubber composition containing the polybutene is superior to the rubber composition containing the polybutene in terms of adhesion characteristics, braking characteristics, and durability. As the weight part of polybutene increases in comparison with the raw material rubber, the above characteristics are gradually improved.

이하, 본 발명의 실시예를 첨부한 도면을 참조하면서 상세히 설명한다.Hereinafter, with reference to the accompanying drawings an embodiment of the present invention will be described in detail.

본 발명의 고무조성물에서 폴리부텐을 포함하는 고무배합물이 원료고무 100 중량부 중에 다양한 함량으로 적용한 바, 바람직하게는, 원료고무 100중량부 중 5~40 중량부를 사용하는 것이 좋다.When the rubber compound including polybutene in the rubber composition of the present invention is applied in various contents in 100 parts by weight of the raw rubber, it is preferable to use 5 to 40 parts by weight of 100 parts by weight of the raw rubber.

상기 고무배합물에서 원료고무는 디엔계 고무를 사용할 수 있다. 이러한 고무의 일예로서, 스티렌부타디엔고무(SBR), 니트릴부타디엔고무(NBR), 클로로프렌고무(CR), 부타디엔고무(BR), 부틸고무(IR), 천연고무(NR) 중에서 선택된 어느 하나 이상을 사용할 수 있다. Raw material rubber in the rubber compound may be a diene rubber. As an example of such rubber, any one or more selected from styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), butadiene rubber (BR), butyl rubber (IR), and natural rubber (NR) may be used. Can be.

상기 폴리부텐은 원유에서 생성되어지는 납사(NAPHTHA) 유분에서 발생되는 C4-Raffinate를 원료로 하는 보통 수평균 분자량이 300 내지 10,000 정도에 이르는 반액상 투명 점착성 물질이다. The polybutene is a semi-liquid transparent adhesive material having a number average molecular weight of about 300 to 10,000 using C 4 -Raffinate generated from naphtha (NAPHTHA) fraction produced in crude oil.

본 발명은 상기에서 언급한 원료고무, 폴리부텐을 포함하는 고무배합물 이외에 종래 타이어 고무조성물에 사용되는 보강충전제, 활성제, 노화방지제, 공정유, 가류제 및 가류촉진제와 같은 각종 첨가제를 필요에 따라 적의 선택하여 소정의 함량으로 사용할 수 있다. 그러나, 이들은 타이어 고무조성물에 사용되는 일반적인 성분으로서, 본 발명의 필수 구성 성분이 아니므로, 이하, 자세한 내용은 생략하기로 한다.The present invention is suitable for various additives such as reinforcing fillers, activators, anti-aging agents, process oils, vulcanizing agents, and vulcanization accelerators, which are used in conventional tire rubber compositions, in addition to the rubber compounds containing the above-mentioned raw rubber and polybutene. It can be selected and used in a predetermined content. However, these are general components used in the tire rubber composition, and are not essential components of the present invention, and thus detailed descriptions thereof will be omitted below.

이하, 본 발명을 다음의 비교예, 실시예에 의하여 상세히 설명한다. Hereinafter, the present invention will be described in detail by the following comparative examples and examples.

<비교예>Comparative Example

원료고무로서, 천연고무(NR) 100중량부의 원료고무 100중량부에 대하여 카본블랙(N330) 35중량부, 아연화 5.0중량부, 스테아린산 2.0중량부, 가류제로서 황 2.25중량부, 가류촉진제로서 N-t-부틸 벤조티아졸 설펜아미드(N-t- butylbenzothiazole sulfenamide, NS) 0.7중량부를 밀폐식 반바리 믹서에서 혼합하 여 마스터 배치를 제조한 후, 개방형 2축 롤밀에서 혼합 고무를 제조하여 165℃에서 10분간 가류하여 고무를 제조하였다.As a raw material rubber, 35 parts by weight of carbon black (N330), 5.0 parts by weight of zinc, 5.0 parts by weight of stearic acid, 2.25 parts of sulfur as a vulcanizing agent, and Nt as a vulcanization accelerator based on 100 parts by weight of natural rubber (NR) 100 parts by weight of raw rubber. 0.7 parts by weight of -butyl benzothiazole sulfenamide (NS) were mixed in a closed half-barrier mixer to prepare a master batch, and then mixed rubber was prepared in an open twin screw mill and vulcanized at 165 ° C for 10 minutes. To prepare a rubber.

하기의 표1에 상기에서 언급한 조성을 다시 나타내었다.Table 1 below shows the above-mentioned composition again.

<실시예 1><Example 1>

원료고무로서, 천연고무(NR) 100중량부의 원료고무 100중량부에 대하여 카본블랙(N330) 35중량부, 아연화 5.0중량부, 스테아린산 2.0중량부, 가류제로서 황 2.25중량부, 가류촉진제로서, N-t-부틸벤조티아졸 설펜아미드(N-t-butylbenzothiazole sulfenamide, NS) 0.7중량부, 폴리부텐(Polybutene) 5.0중량부를 밀폐식 반바리 믹서에서 혼합하여 마스터 배치를 제조한 후, 개방형 2축 롤밀에서 혼합 고무를 제조하여 165℃에서 10분간 가류하여 고무를 제조하였다.As raw material rubber, 35 parts by weight of carbon black (N330), 5.0 parts by weight of zinc, 5.0 parts by weight of stearic acid, 2.25 parts of sulfur as a vulcanizing agent, and a vulcanization accelerator, based on 100 parts by weight of natural rubber (NR) 100 parts by weight of raw rubber. 0.7 parts by weight of Nt-butylbenzothiazole sulfenamide (NS) and 5.0 parts by weight of polybutene were mixed in a closed half-barrier mixer to prepare a masterbatch, followed by mixing rubber in an open twin screw mill. To prepare a rubber by quenching for 10 minutes at 165 ℃.

하기의 표1에 상기에서 언급한 조성을 다시 나타내었다.Table 1 below shows the above-mentioned composition again.

<실시예 2><Example 2>

원료고무로서 천연고무(NR) 100중량부의 원료고무 100중량부에 대하여 카본블랙(N330) 35중량부, 아연화 5.0중량부, 스테아린산 2.0중량부, 가류제로서 황 2.25중량부, 가류촉진제로서 N-t-부틸벤조티아졸 설펜아미드(N-t-butylbenzothiazole sulfenamide, NS) 0.7중량부, 폴리부텐 (Polybutene) 10.0중량부를 밀폐식 반바리 믹서에서 혼합하여 마스터 배치를 제조한 후, 개방형 2축 롤밀에서 혼합 고무를 제조하여 165℃에서 10분간 가류하여 고무를 제조하였다.35 parts by weight of carbon black (N330), 5.0 parts by weight of zinc, 5.0 parts by weight of stearic acid, 2.25 parts of sulfur as a vulcanizing agent, and Nt- as a vulcanization accelerator based on 100 parts by weight of natural rubber (NR) as 100 parts by weight of raw rubber. 0.7 parts by weight of butylbenzothiazole sulfenamide (NS) and 10.0 parts by weight of polybutene (Polybutene) were mixed in an airtight half-barrier mixer to prepare a master batch, followed by mixing rubber in an open twin screw mill. And vulcanized at 165 ° C. for 10 minutes to produce a rubber.

하기의 표1에 상기에서 언급한 조성을 다시 나타내었다.Table 1 below shows the above-mentioned composition again.

<실시예 3><Example 3>

원료고무로서 천연고무(NR) 100중량부의 원료고무 100중량부에 대하여 카본블랙(N330) 35중량부, 아연화 5.0중량부, 스테아린산 2.0중량부, 가류제로서 황 2.25중량부, 가류촉진제로서 N-t-부틸벤조티아졸 설펜아미드(N-t-butylbenzothiazole sulfenamide, NS) 0.7중량부, 폴리부텐 (Polybutene) 20.0중량부를 밀폐식 반바리 믹서에서 혼합하여 마스터 배치를 제조한 후, 개방형 2축 롤밀에서 혼합 고무를 제조하여 165℃에서 10분간 가류하여 고무를 제조하였다.35 parts by weight of carbon black (N330), 5.0 parts by weight of zinc, 5.0 parts by weight of stearic acid, 2.25 parts of sulfur as a vulcanizing agent, and Nt- as a vulcanization accelerator based on 100 parts by weight of natural rubber (NR) as 100 parts by weight of raw rubber. 0.7 parts by weight of butylbenzothiazole sulfenamide (NS) and 20.0 parts by weight of polybutene (Polybutene) were mixed in a closed half-barrier mixer to prepare a master batch, followed by mixing rubber in an open twin screw mill. And vulcanized at 165 ° C. for 10 minutes to produce a rubber.

하기의 표 1에 상기에서 언급한 조성을 다시 나타내었다.Table 1 below shows the above-mentioned composition again.

<실시예 4><Example 4>

원료고무로서 천연고무(NR) 100중량부의 원료고무 100중량부에 대하여 카본블랙(N330) 35중량부, 아연화 5.0중량부, 스테아린산 2.0중량부, 가류제로서 황 2.25중량부, 가류촉진제로서 N-t-부틸벤조티아졸 설펜아미드(N-t-butylbenzothiazole sulfenamide, NS) 0.7중량부, 폴리부텐 (Polybutene) 40.0중량부를 밀폐식 반바리 믹서에서 혼합하여 마스터 배치를 제조한 후, 개방형 2축 롤밀에서 혼합 고무를 제조하여 165℃에서 10분간 가류하여 고무를 제조하였다.35 parts by weight of carbon black (N330), 5.0 parts by weight of zinc, 5.0 parts by weight of stearic acid, 2.25 parts of sulfur as a vulcanizing agent, and Nt- as a vulcanization accelerator based on 100 parts by weight of natural rubber (NR) as 100 parts by weight of raw rubber. 0.7 parts by weight of butylbenzothiazole sulfenamide (NS) and 40.0 parts by weight of polybutene (Polybutene) were mixed in an airtight half-barrier mixer to prepare a master batch, followed by mixing rubber in an open twin screw mill. And vulcanized at 165 ° C. for 10 minutes to produce a rubber.

하기의 표1에 상기에서 언급한 조성을 다시 나타내었다.Table 1 below shows the above-mentioned composition again.

표1 : 비교예 및 실시예의 조성 Table 1: Composition of Comparative Examples and Examples

항목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 NRNR 100100 100100 100100 100100 100100 카본블랙Carbon black 3535 3535 3535 3535 3535 아연화Zincification 5.05.0 5.05.0 5.05.0 5.05.0 5.05.0 스테아린산Stearic acid 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 황sulfur 2.252.25 2.252.25 2.252.25 2.252.25 2.252.25 NSNS 0.70.7 0.70.7 0.70.7 0.70.7 0.70.7 폴리부텐Polybutene 00 55 1010 2020 4040

<시험예 1> <Test Example 1>

상기 비교예 및 실시예 1~4에서 제조한 고무 시편을 ASTM 관련 규정에 의하여 점착력, 탄젠트 델타(Tanδ(0℃)), 크랙 특성 같은 물성을 측정하고 그 결과를 아래의 표2에 나타내었다.The rubber samples prepared in Comparative Examples and Examples 1 to 4 measured physical properties such as adhesive strength, tan delta (Tan δ (0 ° C.)), and crack properties according to ASTM-related regulations, and the results are shown in Table 2 below.

표2 : 각 배합 고무의 물리적 특성 측정Table 2: Measurement of physical properties of each compounded rubber

항목Item 비교예Comparative example 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 * 점착력 (kgf/cm2)* Adhesion (kg f / cm 2 ) 0.210.21 0.310.31 0.520.52 0.630.63 1.351.35 ** Tanδ (0℃)** Tanδ (0 ℃) 0.1550.155 0.1650.165 0.2030.203 0.2480.248 0.3780.378 *** Demattia Test (발생법, 회)*** Demattia Test 5천5,000 1만 5천15,000 2만20,000 3만30,000 9만90,000 **** Demattia Test (성장법, mm)**** Demattia Test (Growth Method, mm) 10.110.1 7.27.2 6.76.7 5.65.6 5.15.1

* 점착력(kgf/cm2) : 점착 특성을 나타낸 것으로, 수치가 높을수록 우수함을 의미한다.* Adhesion (kg f / cm 2 ): shows the adhesive properties, the higher the value means better.

** Tanδ(0℃) : 타이어의 성능 중 젖은 길에서의 제동 특성을 예측할 수 있는 값으로, 수치가 높을수록 우수함을 의미한다.** Tanδ (0 ℃): It is a value that can predict the braking characteristics on wet road among tire performance. The higher the value, the better.

*** Demattia Test (발생법, 회) : Demattia Tester 이용하여 Crack이 최초 발생 했을 때의 횟수를 표시한 것으로 수치가 높을수록 내구 특성이 우수함을 의미한다.*** Demattia Test (Occurrence Method, Time): Depicia Tester indicates the number of times the first occurrence of a crack. The higher the value, the better the durability.

**** Demattia Test (성장법, mm) : Demattia Tester 이용하여 Crack의 성장 길이를 표시한 것으로 수치가 작을수록 내구 특성이 우수함을 의미한다.**** Demattia Test (Growth Method, mm): It shows the growth length of crack by using Demattia Tester. The smaller the value, the better durability.

본 발명에서 폴리부텐을 함유한 고무조성물은 점착 특성, 제동 특성, 내구 특성이 동시에 향상된다. In the present invention, the rubber composition containing polybutene is improved at the same time adhesive properties, braking properties, and durability characteristics.

이상에서 설명한 본 발명에 따른 폴리부텐을 함유한 타이어 고무조성물은, 하나의 바람직한 실시예에 불과한 것으로서, 본 발명은 상기한 실시예에 한정되지 않는 것이므로, 이하의 특허청구범위에서 청구하는 바와 같이 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변경 실시가 가능한 범위까지 본 발명의 기술적 정신이 있다고 할 것이다.The tire rubber composition containing the polybutene according to the present invention described above is just one preferred embodiment, and the present invention is not limited to the above-described embodiment, and thus, as claimed in the following claims. Without departing from the gist of the invention, anyone of ordinary skill in the art to which the present invention will have the technical spirit of the present invention to the extent that various modifications can be made.

Claims (5)

원료고무 100중량부 중, 10 ∼ 30 중량부인 폴리부텐을 함유하는 타이어 고무조성물에 있어서,In the tire rubber composition containing polybutene which is 10-30 parts by weight in 100 parts by weight of the raw material rubber, 폴리부텐을 함유하는 고무배합물이 타이어의 사이드 월, 카카스 중 적어도 하나 이상에 사용되고, 상기 폴리부텐의 수평균 분자량이 300 ~ 399이며, 상기 원료고무는 부타디엔고무(BR)로 구성된 것을 특징으로 하는 폴리부텐을 함유한 타이어 고무조성물.A rubber compound containing polybutene is used in at least one of sidewalls and carcasses of a tire, and the number average molecular weight of the polybutene is 300 to 399, and the raw material rubber is composed of butadiene rubber (BR). Tire rubber composition containing polybutene. 삭제delete 삭제delete 삭제delete 삭제delete
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KR101276654B1 (en) * 2010-11-26 2013-06-19 한국타이어 주식회사 Master batch and tire manufactured by using the same
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Publication number Priority date Publication date Assignee Title
JPH115874A (en) * 1997-06-17 1999-01-12 Yokohama Rubber Co Ltd:The Rubber composition
KR20030045120A (en) * 2000-10-18 2003-06-09 엑손모빌 케미칼 패턴츠 인코포레이티드 Elastomeric composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH115874A (en) * 1997-06-17 1999-01-12 Yokohama Rubber Co Ltd:The Rubber composition
KR20030045120A (en) * 2000-10-18 2003-06-09 엑손모빌 케미칼 패턴츠 인코포레이티드 Elastomeric composition

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