KR100227568B1 - A rubber composition for inner liner of tire - Google Patents

A rubber composition for inner liner of tire Download PDF

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KR100227568B1
KR100227568B1 KR1019970036314A KR19970036314A KR100227568B1 KR 100227568 B1 KR100227568 B1 KR 100227568B1 KR 1019970036314 A KR1019970036314 A KR 1019970036314A KR 19970036314 A KR19970036314 A KR 19970036314A KR 100227568 B1 KR100227568 B1 KR 100227568B1
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rubber
rubber composition
weight
inner liner
parts
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KR1019970036314A
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KR19990012794A (en
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이기영
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홍건희
한국타이어주식회사
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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
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/40—Thiurams, i.e. compounds containing groups
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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

Abstract

본 발명은 타이어 인너라이너용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for a tire inner liner.

본 발명은 타이어 인너라이너용 고무 조성물에 있어서, 고무기재로서 수평균 분자량이 10만 이상이고, 불포화도가 2 내지 20몰

Figure kpo00001
인 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무를 30 내지 100중량부 사용하여 이루어진 타이어 인너라이너용 고무 조성물을 제공하는 것이다.The present invention provides a rubber composition for a tire inner liner, wherein the rubber base material has a number average molecular weight of 100,000 or more and an unsaturation of 2 to 20 moles.
Figure kpo00001
It is providing the rubber composition for tire inner liner which consists of 30-100 weight part of phosphorus isobutylene-methylcyclopentadiene-cyclopentadiene rubber.

이와 같은 고무 조성물은 내공기 투과성을 향상시키고, 동시에 종래 타이어 인너라이너용 고무 조성물의 문제점 있었던 내오존 크랙성을 향상시킨다.Such a rubber composition improves air permeability and at the same time improves ozone crack resistance, which has been a problem of the conventional rubber composition for tire innerliner.

Description

타이어 인너라이너용 고무 조성물Rubber composition for tire inner liner

본 발명은 내공기 투과성 및 내오존 크랙성이 향상된 타이어 인너라이너용 고무 조성물에 관한 것이다. 더욱 상세하게는 이중결합의 위치가 고무 주쇄가 아닌 고리구조에 있는 고무 기재를 이용한 고무 조성물을 사용하여 내공기 투과성 및 내오존 크랙성을 향상시킨 타이어 인너라이너용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for tire innerliner with improved air permeability and ozone crack resistance. More particularly, the present invention relates to a rubber composition for a tire innerliner, which improves air permeability and ozone crack resistance by using a rubber composition using a rubber substrate having a ring structure in which the double bond is not a rubber main chain.

종래 사용되고 있는 튜브리스 타이어의 인너라이너용 고무로는 통상의 이소부틸렌-이소프렌 고무 대신, 염화이소부틸렌-이소프렌 고무, 브롬화이소부틸렌-이소프렌 고무 등의 할로부틸 고무가 사용되고 있다.As an inner liner rubber of a tubeless tire which is conventionally used, halobutyl rubber, such as isobutylene-isoprene rubber and isobutylene bromide-isoprene rubber, is used instead of the usual isobutylene-isoprene rubber.

이러한 할로부틸 고무들은 다른 고무에 비해 우수한 내공기 투과성을 가지고, 통상의 부틸고무에 비해 가류속도가 빨라서 인접한 카카스 고무와의 공가류도 가능하기 때문에 타이어의 인너라이너용 고무로 널리 쓰이고 있다.These halobutyl rubbers have excellent air permeability than other rubbers, and have a faster vulcanization rate than common butyl rubbers, so that they can be co-cured with adjacent carcass rubbers, and thus are widely used as rubbers for innerliners of tires.

그러나, 타이어의 인너라이너가 접하고 있는 타이어의 내부는 공기압과 온도가 높아 산화성이 강한 환경이므로 할로부틸 고무가 사용되는 경우, 고무의 주쇄내에 존재하는 1.5 내지 2.0몰

Figure kpo00002
의 이중결합이 산화에 의해 끊어져 결과적으로 인너라이너에 크랙이 발생하는 문제점을 일으키게 된다.However, when the halobutyl rubber is used because the interior of the tire, which is in contact with the inner liner of the tire, has high air pressure and temperature and is highly oxidizing, 1.5 to 2.0 mol present in the main chain of the rubber
Figure kpo00002
The double bond of is broken by oxidation, resulting in a problem of cracking in the innerliner.

이에 본 발명은 이와 같은 문제점을 해결하여 이중결합 함량의 증가로 가류속도가 빠르고, 동시에 고무의 주쇄가 아닌 고리구조에 이중결합이 있기 때문에 이중결합의 증가에 따른 내공기 투과성 및 내오존 크랙성능의 저하를 방지할 수 있는 고무 조성물을 제공하는 것을 목적으로 하고 있다.Accordingly, the present invention solves this problem, and the vulcanization rate is fast due to the increase of the double bond content, and at the same time, since there are double bonds in the ring structure instead of the main chain of rubber, the air permeability and ozone crack performance of the double bond increases. It aims at providing the rubber composition which can prevent a fall.

본 발명은 타이어 인너라이너용 고무 조성물에 있어서, 고무 기재로서 수평균 분자량이 10만 이상이고, 불포화도가 2 내지 20몰

Figure kpo00003
인 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무를 30 내지 100중량부 사용하여 이루어진 타이어 인너라이너용 고무 조성물이다.In the rubber composition for tire inner liner, the present invention provides a rubber-based base material having a number average molecular weight of 100,000 or more and an unsaturation of 2 to 20 mol.
Figure kpo00003
It is the rubber composition for tire innerliners which consists of 30-100 weight part of phosphorus isobutylene- methylcyclopentadiene-cyclopentadiene rubber.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 타이어 인너라이너용 고무 조성물에 있어서, 고무 기재로서 수평균 분자량이 10만 이상이고, 불포화도가 2 내지 20몰

Figure kpo00004
인 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무를 30 내지 100중량부 사용하여 이루어진 튜브용 고무 조성물로서, 이와 같은 고무 조성물은 가류속도가 빠르고, 내공기 투과성 및 내오존 크랙성을 향상시킨다.In the rubber composition for tire inner liner, the present invention provides a rubber-based base material having a number average molecular weight of 100,000 or more and an unsaturation of 2 to 20 mol.
Figure kpo00004
30 to 100 parts by weight of phosphorus isobutylene-methylcyclopentadiene-cyclopentadiene rubber, wherein the rubber composition has a high vulcanization rate and improves air permeability and ozone crack resistance. .

상기에서, 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무는 이소부틸렌-이소프렌 고무 조성물보다 이중 결합이 증가하여 가류속도를 증가시킬 수 있으며, 또한 이중결합의 위치가 고무 주쇄가 아닌 고리구조에 있기 때문에 열이나 산소에 의해 이중결합이 분해되어도 고리 구조만 절단되고 주쇄는 남아 있게 된다. 이러한 이유로 인너라이너의 크랙생성과 크랙성장이 늦어지게 되어 내공기 투과성이 양호한 상태로 유지되게 된다.In the above, isobutylene-methylcyclopentadiene-cyclopentadiene rubber has a double bond is increased than the isobutylene-isoprene rubber composition can increase the vulcanization rate, and also the position of the double bond is not a rubber backbone ring structure Since the double bond is decomposed by heat or oxygen, only the ring structure is cut and the main chain remains. For this reason, crack generation and crack growth of the inner liner are delayed, so that the air permeability is maintained in a good state.

또한, 할로부틸 고무를 사용하는 경우 가류속도를 증가시키기 위해 이소프렌 함량을 증가시키면 내공기 투과성이 저하되지만, 본 발명에서 사용되는 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무는 시클로펜타디엔이나 메틸시클로펜타디엔 함량이 증가할수록 내공기 투과성이 오히려 향상되어 이중결합 함량의 증가에 따른 내공기 투과성 저하를 막을 수 있다.In addition, in the case of using halobutyl rubber, if the isoprene content is increased to increase the vulcanization rate, the air permeability decreases, but the isobutylene-methylcyclopentadiene-cyclopentadiene rubber used in the present invention is cyclopentadiene. As the methylcyclopentadiene content is increased, the air permeability is rather improved to prevent the decrease in the air permeability due to the increase in the double bond content.

상기에서, 고무기재로 사용한 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무는 수평균 분자량이 10만 이상이고, 불포화도가 2 내지 20몰

Figure kpo00005
인 것이 바람직하다. 수평균 분자량이 10만 미만인 경우 요구되어지는 물성이 얻어지는 것이 어렵다. 또한, 불포화도가 2몰
Figure kpo00006
미만인 경우 가류속도가 너무 느려 바람직하지 않고, 20몰
Figure kpo00007
초과하는 경우 가류속도는 빨라지지만 유리전이온도가 상승하여 저온에서의 탄성이 낮아지는 문제가 있다.In the above description, the isobutylene-methylcyclopentadiene-cyclopentadiene rubber used as the rubber substrate has a number average molecular weight of 100,000 or more and an unsaturation of 2 to 20 mol.
Figure kpo00005
Is preferably. If the number average molecular weight is less than 100,000, it is difficult to obtain the required physical properties. In addition, unsaturation is 2 mol
Figure kpo00006
Less than 20 mol
Figure kpo00007
If exceeded, the vulcanization speed is increased, but there is a problem that the glass transition temperature is increased to lower the elasticity at low temperature.

이하, 실시예를 통해 발명을 더욱 상세히 설명한다.Hereinafter, the invention will be described in more detail with reference to Examples.

[실시예 1]Example 1

고무기재로 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무(이하, IMCR이라 함) 100중량부를 사용하고, 카본 블랙 50중량부, 오일 17중량부, 점착제 1중량부, 스테아린산 0.3중량부, 칼슘 스테아레이트 0.7중량부, 산화아연 3중량부, 테트라메틸티우람디설파이드 2중량부, 황 1중량부를 상기 고무 기재와 혼합한 후, 170℃에서 가류하였다. 얻어진 인너라이너용 고무 조성물로 제조된 시편에 대하여 공기 투과율, 동적피로특성을 노화 전후에 측정하여 그 결과를 표 1에 기재하였다.100 parts by weight of isobutylene-methylcyclopentadiene-cyclopentadiene rubber (hereinafter referred to as IMCR) as a rubber base material, 50 parts by weight of carbon black, 17 parts by weight of oil, 1 part by weight of adhesive, 0.3 parts by weight of stearic acid, 0.7 parts by weight of calcium stearate, 3 parts by weight of zinc oxide, 2 parts by weight of tetramethylthiuram disulfide, and 1 part by weight of sulfur were mixed with the rubber substrate, followed by vulcanization at 170 ° C. The air permeability and the dynamic fatigue characteristics of the specimens made of the obtained inner liner rubber composition were measured before and after aging, and the results are shown in Table 1.

[비교예 1]Comparative Example 1

고무기재로 브롬화이소부틸렌-이소프렌 고무(이하, Br-IIR이라 함) 및 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무(이하, IMCR이라 함)를 각각 50중량부를 사용하고, 카본 블랙 50중량부, 오일 17중량부, 점착제 1중량부, 스테아린산 0.3중량부, 산화아연 3중량부, 테트라메틸티우람디설파이드 2중량부, 및 가류제로서 황을 0.5중량부, 디벤조티아질디설파이드를 1중량부를 고무 기재와 혼합한 후, 170℃에서 가류하였다. 얻어진 인너라이너용 고무 조성물로 제조된 시편에 대하여 공기 투과율, 동적피로특성을 노화 전후에 측정하여 그 결과를 표 1에 기재하였다.50 parts by weight of isobutylene bromide-isoprene rubber (hereinafter referred to as Br-IIR) and isobutylene-methylcyclopentadiene-cyclopentadiene rubber (hereinafter referred to as IMCR) were used as the rubber substrate, and carbon black 50 parts by weight, 17 parts by weight of oil, 1 part by weight of adhesive, 0.3 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 2 parts by weight of tetramethylthiuram disulfide, and 0.5 parts by weight of sulfur as divulcanizing agent, dibenzothiazyl disulfide 1 part by weight of the rubber substrate was mixed and then vulcanized at 170 ° C. The air permeability and the dynamic fatigue characteristics of the specimens made of the obtained inner liner rubber composition were measured before and after aging, and the results are shown in Table 1.

[비교예 2]Comparative Example 2

고무기재로 Br-IIR를 100중량부를 사용하고, 카본 블랙 50중량부, 오일 17중량부, 점착제 1중량부, 스테아린산 0.3중량부, 산화아연 3중량부, 테트라메틸티우람디설파이드 2중량부 및 가류제로서 황 0.5중량부와 디벤조티아질디설파이드 1중량부를 상기 고무 기재와 혼합한 후, 170℃에서 가류하였다. 얻어진 인너라이너용 고무 조성물로 제조된 시편에 대하여 공기 투과율, 동적피로특성을 노화 전후에 측정하여 그 결과를 표 1에 기재하였다.Using 100 parts by weight of Br-IIR as a rubber base, 50 parts by weight of carbon black, 17 parts by weight of oil, 1 part by weight of adhesive, 0.3 part by weight of stearic acid, 3 parts by weight of zinc oxide, 2 parts by weight of tetramethylthiuram disulfide and vulcanizate 0.5 parts by weight of sulfur and 1 part by weight of dibenzothiazyl disulfide were mixed with the rubber substrate as a zeolite, followed by vulcanization at 170 ° C. The air permeability and the dynamic fatigue characteristics of the specimens made of the obtained inner liner rubber composition were measured before and after aging, and the results are shown in Table 1.

Figure kpo00008
Figure kpo00008

1) ML1+8＠125℃ : 무니 점도계(Mooney Viscometer)에서 대형 로토(large rotor)를 사용하여 125℃에서 1분간 예열후 8분후 측정한 무니 점도값을 나타낸다.1) ML1 + 8 ＠ 125 ° C: The Mooney viscosity value measured after 8 minutes of preheating at 125 ° C using a large rotor in a Mooney Viscometer.

2) Fatigue-to-Failure : 동적피로특성을 나타내는 항목으로 Fatigue-to-Failure 시험기를 사용하여 측정한 결과로서 상온에서 100

Figure kpo00009
반복적인 신장하에서 절단시까지의 회수를 의미한다.2) Fatigue-to-Failure: This item shows the dynamic fatigue characteristics. It is measured using a Fatigue-to-Failure tester.
Figure kpo00009
The number of times from cutting under repeated stretching to cutting.

표 1에 나타난 바와 같이, 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무를 사용한 고무 조성물(실시예 1)은 브롬화이소부틸렌-이소프렌 고무를 사용한 고무 조성물(비교예 1 및 비교예 2)과 비교하여, 노화 전후 모두에서 동적피로특성 및 공기 투과도가 우수함을 알 수 있다.As shown in Table 1, the rubber composition using the isobutylene-methylcyclopentadiene-cyclopentadiene rubber (Example 1) is a rubber composition using the isobutylene bromide-isoprene rubber (Comparative Example 1 and Comparative Example 2) Compared with the above, it can be seen that the dynamic fatigue characteristics and the air permeability are excellent both before and after aging.

이와 같이, 본 발명의 타이어 인너라이너용 고무 조성물은 이중결합이 고무의 주쇄가 아닌 고리구조에 존재하기 때문에, 이중결합의 증가에 따라 가류속도가 증가하고, 또한 주쇄내에 이중결합이 공기압과 열에 의해 끊어져 크랙이 발생할 수 있는 가능성이 감소되고, 이에 따라 내공기 투과성 및 내오존 크랙성이 향상된다.As described above, in the rubber composition for a tire inner liner of the present invention, since the double bond is present in the ring structure rather than the main chain of the rubber, the vulcanization rate increases with the increase of the double bond, and the double bond in the main chain is caused by air pressure and heat. The possibility of breaking and cracking is reduced, thereby improving air resistance and ozone crack resistance.

Claims (1)

고무기재, 카본블랙, 오일, 점착제, 스테아린산, 칼슘 스테아레이트, 산화아연, 테트라메틸티우람디설파이드, 황 및 통상의 첨가제로 이루어진 타이어 인너라이너용 고무 조성물에 있어서, 상기 고무기재로 수평균 분자량이 10만 이상이고, 불포화도가 2 내지 20몰
Figure kpo00010
인 이소부틸렌-메틸시클로펜타디엔-시클로펜타디엔 고무를 50중량부 초과 100중량부 이하로 사용하는 것을 특징으로 하는 타이어 인너라이너용 고무 조성물.In a rubber composition for a tire inner liner composed of rubber base, carbon black, oil, pressure-sensitive adhesive, stearic acid, calcium stearate, zinc oxide, tetramethylthiuram disulfide, sulfur, and usual additives, the rubber base has a number average molecular weight of 10 More than 10,000, and unsaturation 2 to 20 mol
Figure kpo00010
A phosphorus isobutylene-methylcyclopentadiene-cyclopentadiene rubber is used in excess of 50 parts by weight and 100 parts by weight or less, a rubber composition for a tire inner liner.
KR1019970036314A 1997-07-31 1997-07-31 A rubber composition for inner liner of tire KR100227568B1 (en)

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