KR20030094907A - Rubber composition for innerliner of tubeless type radial pneumatic tire for truck and bus - Google Patents
Rubber composition for innerliner of tubeless type radial pneumatic tire for truck and bus Download PDFInfo
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- KR20030094907A KR20030094907A KR1020020032254A KR20020032254A KR20030094907A KR 20030094907 A KR20030094907 A KR 20030094907A KR 1020020032254 A KR1020020032254 A KR 1020020032254A KR 20020032254 A KR20020032254 A KR 20020032254A KR 20030094907 A KR20030094907 A KR 20030094907A
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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
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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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
- B60C1/0008—Compositions of the inner liner
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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Abstract
Description
본 발명은 타이어 인너라이너용 고무 조성물에 관한 것으로서, 더욱 상세하게는 할로겐화 부틸고무와 함께 세팔 블록 구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 혼용하여 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시키고 인너라이너 고무의 압연과정 및 성형과정에서 치수 균일성을 개선한 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for a tire inner liner, and more particularly, to a combination of a polystyrene-polyisobutylene-polystyrene block copolymer having a cephale block structure with a halogenated butyl rubber, air permeability, fatigue resistance and crack resistance. The present invention relates to a rubber composition which improves the properties at the same time and improves the dimensional uniformity during rolling and molding of the inner liner rubber.
최근에는 트럭, 버스용 타이어의 경우에도 튜브를 사용하는 과거의 경우와는달리 튜브를 사용하지 않는 튜브리스형 타이어를 사용하는 비율이 점차로 늘어가는 추세이다.Recently, in the case of truck and bus tires, the proportion of tubeless tires that do not use tubes is gradually increasing, unlike in the past when tubes are used.
그런데, 이러한 튜브리스형 타이어의 인너라이너에는 내공기투과성의 유지를 위하여 할로겐화 부틸고무를 사용하는 것이 보통이다. 다만, 부틸고무를 사용하는 경우 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성이 잘 유지되지 못하는 단점이 있다.However, it is common to use halogenated butyl rubber in the inner liner of such a tubeless tire to maintain air permeability. However, when butyl rubber is used, dimensional uniformity is not maintained well in the rolling process and the molding process of the inner liner rubber.
한편, 최근에는 서로 혼용되지 않는 두가지 종류의 고무와 플라스틱을 함유하여 고무적인 성질과 플라스틱적인 성질을 동시에 가지는 블록공중합체를 개발하고 있는 데(일명, Thermoplastic elastomer), 이러한 열가소성 엘라스토머의 경우 개개의 플라스틱 상은 연속적인 고무상에 끼워 넣어져 물리적 가교를 형성한다. 이러한 블록공중합체는 플라스틱상의 유리전이온도 이하에서는 가교된 고무와 같은 성질을 가지며 유리전이온도 이상에서는 플라스틱과 같이 가공될 수 있으므로 고무에 비하여 재가공에 매우 유리하다.On the other hand, recently, block copolymers containing two kinds of rubbers and plastics, which are not mixed with each other, have both rubbery and plastic properties (aka, thermoplastic elastomers). In the case of such thermoplastic elastomers, individual plastics The phase is sandwiched by a continuous rubber phase to form physical crosslinks. Such block copolymers have properties such as crosslinked rubber below the glass transition temperature on plastics and can be processed like plastics above the glass transition temperature, which is very advantageous for reprocessing than rubber.
이에, 본 발명자는 상기와 같은 열가소성 엘라스토머를 인너라이너 고무 조성물에 포함시켜 통상의 할로겐화 부틸고무와 병용한 결과, 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시키고 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성을 개선할 수 있음을 알게 되어 본 발명을 완성하게 되었다.Therefore, the present inventors have included the above-mentioned thermoplastic elastomer in the inner liner rubber composition and used together with a conventional halogenated butyl rubber, thereby improving air resistance, fatigue resistance and crack resistance simultaneously, and rolling and forming the inner liner rubber. It was found that the process can improve the dimensional uniformity has been completed the present invention.
본 발명은 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시키고 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성을 개선할 수 튜브리스형 트럭,버스용 래디얼 공기입 타이어의 인너라이너 고무 조성물을 제공하는 데 그 목적이 있다.The present invention can improve the air permeability, fatigue resistance and crack resistance at the same time and improve the dimensional uniformity during the rolling and molding process of the inner liner rubber. The inner liner rubber composition of the radial pneumatic tire for tubeless trucks and buses The purpose is to provide.
상기와 같은 목적을 달성하기 위한 본 발명의 튜브리스형 트럭,버스용 래디얼 공기입 타이어의 인너라이너 고무 조성물은 원료고무로서 할로겐화 부틸고무 80∼90중량%와; 중량평균분자량이 40,000∼80,000이고, 분자량 분포(Mw/Mn)가 1.1∼1.2이며, 폴리스티렌 함량이 25∼45중량%이며 세팔 블록의 구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체 10∼20중량%를 포함하는 것임을 그 특징으로 한다.The inner liner rubber composition of the radial pneumatic tire for tubeless truck and bus of the present invention for achieving the above object is 80 to 90% by weight of halogenated butyl rubber as raw material rubber; Polystyrene-polyisobutylene-polystyrene block copolymer having a weight average molecular weight of 40,000 to 80,000, a molecular weight distribution (Mw / Mn) of 1.1 to 1.2, a polystyrene content of 25 to 45% by weight, and having a structure of cephale block It is characterized by containing 20% by weight.
도 1은 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체에 있어서 선형블록구조와 세팔 블록 구조의 모식도를 나타낸 것으로서, 좌측이 선형블록구조이고 우측이 세팔블록 구조이다.Figure 1 shows a schematic diagram of the linear block structure and the cephale block structure in the polystyrene-polyisobutylene-polystyrene block copolymer, the left side is a linear block structure and the right side is a cephaloc block structure.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 인너라이너의 요구 물성인 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시키고 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성을 개선하고자 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 할로겐화 부틸고무와 혼용한 인너라이너 고무조성물에 관한 것이다.The present invention provides a polystyrene-polyisobutylene-polystyrene block copolymer to improve the air permeability, fatigue resistance and crack resistance, which are required properties of the inner liner, and to improve the dimensional uniformity during rolling and molding of the inner liner rubber. The present invention relates to an inner liner rubber composition mixed with halogenated butyl rubber.
본 발명에서 할로겐화 부틸고무와 혼용되는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체는 중량평균분자량이 40,000∼80,000이고, 분자량 분포(Mw/Mn)가 1.1∼1.2이며, 폴리스티렌 함량이 25∼45중량%이며 세팔 블록의 구조를 갖는 것이다. 이를 일반적인 블록공중합체와 비교하여 나타내면 다음 표 1과 같다.In the present invention, the polystyrene-polyisobutylene-polystyrene block copolymer mixed with halogenated butyl rubber has a weight average molecular weight of 40,000 to 80,000, a molecular weight distribution (Mw / Mn) of 1.1 to 1.2, and a polystyrene content of 25 to 45 weight % And has the structure of a cefal block. This is shown in Table 1 when compared with the general block copolymer.
상기 표 1 기재에 있어서, 선형 블록구조와 세팔블록 구조의 모식도를 도 1에 나타내었다. 도 1에 있어서 좌측이 선형의 디블록 및 트리블록 공중합체를 나타낸 모식도이고, 우측이 본 발명에 따른 세팔 블록구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체의 모식도이다.In the description of Table 1, a schematic diagram of the linear block structure and the cephaloc block structure is shown in FIG. 1. In FIG. 1, the left side is a schematic diagram which shows linear diblock and a triblock copolymer, and the right side is a schematic diagram of the polystyrene-polyisobutylene-polystyrene block copolymer which has a cephale block structure which concerns on this invention.
본 발명에서는 세팔 블록 구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 할로겐화 부틸고무에 10∼20중량% 정도로 포함한다.In the present invention, the polystyrene-polyisobutylene-polystyrene block copolymer having a cephale block structure is included in the halogenated butyl rubber at about 10 to 20% by weight.
세팔 블록 구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체는 플라스틱과 고무의 특성을 동시에 가지므로 할로겐화 부틸고무와 함께 사용되어 인너라이너 고무의 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시킬 수 있고, 또한 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성을 개선할 수 있게 한다.Polystyrene-polyisobutylene-polystyrene block copolymer having a cephale block structure has the characteristics of plastic and rubber at the same time, so it can be used together with halogenated butyl rubber to improve the air permeability, fatigue resistance and crack resistance of the inner liner rubber. It is also possible to improve the dimensional uniformity in the rolling process and the molding process of the inner liner rubber.
그리고, 할로겐화 부틸고무라 함은 통상 인너라이너 고무 조성물에서 원료고무로 사용하는데 부틸기의 화학구조 때문에 내공기투과성이 매우 뛰어나다.In addition, halogenated butyl rubber is generally used as a raw material rubber in the inner liner rubber composition, and has excellent air permeability due to the chemical structure of the butyl group.
또한, 본 발명에서는 다른 기타 배합제들을 통상적인 배합량으로 첨가할 수 있음을 물론인 바, 구체적으로는 카본블랙 60중량부, 방향족 오일 6중량부, 가공조제 8중량부, 수지 5중량부, 스테아린산 0.5중량부, 가류촉진제 2중량부, 가류제로서 산화아연 2중량부, 그리고 유황 1중량부 되도록 첨가할 수 있다.In addition, of course, the present invention may add other compounding agents in a conventional compounding amount, specifically, 60 parts by weight of carbon black, 6 parts by weight of aromatic oil, 8 parts by weight of processing aid, 5 parts by weight of resin, stearic acid 0.5 parts by weight, 2 parts by weight of vulcanization accelerator, 2 parts by weight of zinc oxide as vulcanizing agent, and 1 part by weight of sulfur may be added.
본 발명에 따른 인너라이너 고무 조성물은 가공중의 치수균일성, 내공기투과성, 내피로성 및 내크랙성을 동시에 향상시킬 수 있는 최적배합이다.The inner liner rubber composition according to the present invention is an optimal combination that can simultaneously improve the dimensional uniformity, air permeability, fatigue resistance and crack resistance during processing.
이하, 본 발명을 실시함으로써 얻어지는 효과를 실시예 및 비교예로 제조된 고무조성물의 특성을 시험비교하여 효과를 설명하였다.Hereinafter, the effect was demonstrated by carrying out the test comparison of the characteristic of the rubber composition manufactured by the Example and the comparative example with the effect obtained by implementing this invention.
실시예 1∼2 및 비교예 1∼4Examples 1-2 and Comparative Examples 1-4
다음 표 2와 같이 배합제를 반바리 믹서를 이용하여 배합하여 고무시트를 제조하였다. 이 고무시트를 170℃의 가류프레스에서 15분간 가류하여 시험시편을 준비한 뒤, 모듈러스, 내공기투과성, 내크랙성장성, 내피로성을 측정하였으며, 무니점도는 가류하지 않은 고무시트를 몬산토(Monsanto)에서 제작한 MV2000으로 측정하였다. 그 결과는 다음 표 3과 같다.As shown in Table 2, a rubber sheet was prepared by blending the blending agent using a half-barrier mixer. The rubber sheet was quenched in a vulcanization press at 170 ° C. for 15 minutes to prepare test specimens, and then modulus, air permeability, crack growth resistance, and fatigue resistance were measured, and the Mooney viscosity was measured at Monsanto. It measured by the produced MV2000. The results are shown in Table 3 below.
상기 표 3의 결과로부터, 첫째, 가공중의 치수균일성을 나타내는 Die swell에 있어서 본 발명의 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록 공중합체를 사용하는 경우에는 공히 이를 사용하지 않은 비교예들에 비하여 Die swell값이 나쁘다.From the results in Table 3, first, in the case of using the polystyrene-polyisobutylene-polystyrene block copolymer of the present invention in the die swell showing the dimensional uniformity during processing, The die swell value is bad.
이는 본 발명에 따른 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 사용하는 경우 가공중의 치수균일성이 높다고 할 수 있다. 특히, 선형블록이 아닌 세팔블록 구조를 갖는 DN-77을 사용하는 실시예 1 및 실시예 2가 가공중의 치수균일성이 가장 뛰어남을 알 수 있다.This can be said to be a high dimensional uniformity during processing when using the polystyrene-polyisobutylene-polystyrene block copolymer according to the present invention. In particular, it can be seen that Example 1 and Example 2 using DN-77 having a cephaloc block structure rather than a linear block has the best dimensional uniformity during processing.
둘째, 내공기 투과성의 경우 블록 공중합체 내에 폴리부타디엔을 환원한 부위가 있는 비교예 4의 경우에는 비교예 1에 대비하여서도 내공기투과성이 나쁘다. 다만, 이소부틸렌기가 들어있는 블록공중합체를 응용하는 경우에는 비교예 1에 비하여 공통적으로 내공기투과성이 향상된다. 특히, 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 20중량%로 포함하는 본 발명 실시예 2의 경우에는 내공기투과성이 약 78% 정도 향상됨을 알 수 있다.Second, in the case of air permeability, Comparative Example 4 having a site where polybutadiene is reduced in the block copolymer has poor air permeability even in comparison with Comparative Example 1. However, when the block copolymer containing isobutylene group is applied, air permeability is improved in common compared with the comparative example 1. In particular, in the case of Example 2 of the present invention containing 20% by weight of polystyrene-polyisobutylene-polystyrene block copolymer it can be seen that the air permeability is improved by about 78%.
셋째, 내피로성의 경우 공통적으로 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 10중량% 정도로 포함하면 이를 사용하지 않는 비교예 1에 비하여 약 30% 정도 개선된다. 다만 블록공중합체 비율을 10중량%에서 20중량%로 올리면 내피로성은 약간 저하됨을 알 수 있다.Third, in the case of fatigue resistance, when the polystyrene-polyisobutylene-polystyrene block copolymer is included in about 10% by weight, it is improved by about 30% compared to Comparative Example 1, which does not use it. However, when the block copolymer ratio is increased from 10% by weight to 20% by weight, fatigue fatigue may be found to decrease slightly.
넷째, 내크랙성의 경우 블록 공중합체 내에 폴리부타디엔을 환원한 부위가 있는 비교예 4의 경우에는 블록공중합체를 사용하지 않는 비교예 1에 대비하여서 거의 동등수준이나, 이소부틸렌기가 들어있는 블록공중합체를 응용하는 경우에는 공통적으로 비교예 1에 비하여 내크랙성이 향상된다.Fourth, in the case of crack resistance, Comparative Example 4 having the site where the polybutadiene was reduced in the block copolymer was substantially equivalent to Comparative Example 1 in which the block copolymer was not used, but in the block air containing isobutylene groups. When coalescing is applied, crack resistance improves compared with the comparative example 1 in common.
결론적으로는 80% 할로겐화 부틸 고무-20% DN-77 블록공중합체를 100중량부로 사용하는 실시예 2가 내공기투과성 및 가공중의 치수균일성적인 측면에서 가장 최적의 물성을 나타낸다.In conclusion, Example 2 using 100% by weight of 80% halogenated butyl rubber-20% DN-77 block copolymer shows the most optimum physical properties in terms of air permeability and dimensional uniformity during processing.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 세팔블록 구조를 갖는 폴리스티렌-폴리이소부틸렌-폴리스티렌 블록공중합체를 할로겐화 부틸고무와 혼용한 인너라이너 고무 조성물은 내공기 투과성, 내피로성 및 내크랙성을 동시에 향상시킬 수 있으면서 인너라이너 고무의 압연과정 및 성형과정에서 치수균일성을 개선할 수 있다.As described in detail above, the inner liner rubber composition in which a polystyrene-polyisobutylene-polystyrene block copolymer having a cephaloc block structure according to the present invention is mixed with a halogenated butyl rubber has air resistance, fatigue resistance and crack resistance. At the same time, it is possible to improve the dimensional uniformity in the rolling process and the molding process of the inner liner rubber.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100746335B1 (en) * | 2006-03-28 | 2007-08-03 | 금호타이어 주식회사 | Tire inner liner rubber composition |
US20150202923A1 (en) * | 2012-08-01 | 2015-07-23 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire including inner liner |
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US5276094A (en) * | 1992-11-12 | 1994-01-04 | Polysar Rubber Corp. | Compositions of butyl elastomers and block copolymers of polyisobutylene |
US5631316A (en) * | 1993-09-30 | 1997-05-20 | Exxon Chemical Patents Inc. | Tire innerliner comprising ester-functionalized elastomeric interpolymers of C4-C7 isomonoolefin and para-alkylstyrene |
US5705549A (en) * | 1995-04-17 | 1998-01-06 | Bridgestone Corporation | Rubber compositions |
KR20030090283A (en) * | 2002-05-22 | 2003-11-28 | 한국타이어 주식회사 | Tire bladder rubber composition |
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2002
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US5276094A (en) * | 1992-11-12 | 1994-01-04 | Polysar Rubber Corp. | Compositions of butyl elastomers and block copolymers of polyisobutylene |
US5631316A (en) * | 1993-09-30 | 1997-05-20 | Exxon Chemical Patents Inc. | Tire innerliner comprising ester-functionalized elastomeric interpolymers of C4-C7 isomonoolefin and para-alkylstyrene |
US5705549A (en) * | 1995-04-17 | 1998-01-06 | Bridgestone Corporation | Rubber compositions |
KR20030090283A (en) * | 2002-05-22 | 2003-11-28 | 한국타이어 주식회사 | Tire bladder rubber composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100746335B1 (en) * | 2006-03-28 | 2007-08-03 | 금호타이어 주식회사 | Tire inner liner rubber composition |
US20150202923A1 (en) * | 2012-08-01 | 2015-07-23 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire including inner liner |
US10272721B2 (en) * | 2012-08-01 | 2019-04-30 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire including inner liner |
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