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KR100227445B1 - The rubber composition for tire bladder - Google Patents

The rubber composition for tire bladder Download PDF

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Publication number
KR100227445B1
KR100227445B1 KR1019970047019A KR19970047019A KR100227445B1 KR 100227445 B1 KR100227445 B1 KR 100227445B1 KR 1019970047019 A KR1019970047019 A KR 1019970047019A KR 19970047019 A KR19970047019 A KR 19970047019A KR 100227445 B1 KR100227445 B1 KR 100227445B1
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weight
parts
rubber composition
rubber
sulfur
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KR1019970047019A
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KR19990025412A (en
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문찬식
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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
    • B60C1/0025—Compositions of the sidewalls
    • 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
    • C08K3/06—Sulfur
    • 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
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

본 발명은 타이어 가류용 브라더 고무 조성물에 있어서, 기본재료 고무로 이소부틸렌과 파라-메틸스티렌의 브롬화된 코폴리머를 사용하고 통상의 배합 첨가제를 사용하고, 상기 기재 고무 100중량부당 유황(중량부)과 디벤조치아질 디설파이드(가류촉진제)(중량부)를 각각 0.2 내지 1.0중량부를 사용하되 유황/디벤조치아질디설파이드의 중량비를 0.4 내지 1.8로 하는 것을 특징으로 하는 타이어 가류용 브라더 고무 조성물이다.The present invention relates to a rubber composition for tire vulcanization, in which a brominated copolymer of isobutylene and para-methylstyrene is used as the base rubber, and a conventional compounding additive is used, and sulfur per 100 parts by weight of the base rubber is used. ) And dibenzothiazyl disulfide (vulcanization accelerator) (parts by weight) of 0.2 to 1.0 parts by weight, respectively, wherein the weight ratio of sulfur / dibenzochiazil disulfide is 0.4 to 1.8. .

Description

타이어 가류용 브라더 고무조성물Brother rubber composition for tire vulcanization

본 발명은 타이어 가류시에 사용되는 브라더 고무 조성물에 관한 것이다.The present invention relates to a brother rubber composition for use in tire vulcanization.

일반적으로 타이어는 고무, 카본블랙, 유황 및 기타 고무용 약품을 혼합한 배합고무를 압출하거나, 이 배합고무를 코드, 비드 와이어 등에 토핑(Topping)하는 압연공정을 거쳐 재단된 여러 가지 반제품을 조합하는 성형공정을 거쳐 그린케이스라고 하는 생타이어가 제조된다.Generally, tires are extruded compounded rubber containing rubber, carbon black, sulfur, and other rubber chemicals, or a combination of various semi-finished products cut through a rolling process of topping the compounded rubber to cords and bead wires. Through the molding process, a green tire called a green case is manufactured.

생타이어는 몰드에 넣고 열과 압력을 가하여 일정 시간동안 가류하여 타이어로 완성되는데 이 가류 공정에서 사용되는 기계를 가류기라 한다.The raw tire is put into a mold and quenched for a certain time by applying heat and pressure to complete the tire. The machine used in this vulcanization process is called a vulcanizer.

가류기에서는 그린 케이스 내부에서 몰드 측에 압력을 가함으로써 그린 케이스가 타이어 형상을 갖추게 되며, 이때 가압 매체의 누출을 막고 가압 매체가 그린 케이스와 직접 접촉되지 않도록 하기 위하여 브라더를 통하여 가압 및 가열하게 된다.In the vulcanizer, the green case has a tire shape by applying pressure to the mold side in the green case. At this time, the green case is pressurized and heated through a brother to prevent leakage of the pressurized medium and prevent the pressurized medium from directly contacting the green case. .

현재 가장 널리 사용되어 지고 있는 브라더의 고무 조성물은 부틸고무 기본에 일킬 페놀 포름알데히드 수지를 사용하여 수지 경화시킨 것을 주로 사용하여 왔다. 이러한 고무 조성물을 사용하여 제조한 타이어 가류용 브라더는 사용 중에 내부에 심한 라미네이션(lamination) 현상(내부 갈라짐 현상)이 발생하여 라미네이션 현상이 발생한 부분이 발생치 않은 부분에 비하여 얇아짐이 발생하므로 인하여 그 부분의 과대팽창 내지는 접힘 현상이 일어나 타이어 제조 불량을 다수 발생 시킬 뿐 아니라 브라더의 수명을 현저히 저하시키는 원인으로 인식되어 왔다.Brother's rubber composition, which is the most widely used at present, has mainly used resin cured using butyl rubber-based ilky phenol formaldehyde resin. Tire vulcanizing brother manufactured using such a rubber composition has a severe lamination phenomenon (internal cracking phenomenon) inside during use, resulting in thinner than the portion where no lamination phenomenon occurs. Overexpansion or folding of the part has been recognized as a cause of not only causing a large number of tire manufacturing defects but also significantly reducing the life of the brother.

이러한 라미네이션 현상의 발생원인은 타이어 가류용 브라더 고무 내부에 존재하는 작은 공극(porosity) 및 휘발성 물질에 의한 기체 발생이 원인으로 판명되어 왔다.The cause of the lamination phenomenon has been found to be due to the generation of gas by the small porosity and volatile substances present in the tire rubber brother rubber.

따라서, 본 발명은 타이어의 가류시 사용되는 브라더 고무조성물의 내부에 라미네이션 현상이 발행하지 않도록 고무 내부에 존재하는 작은 공극 및 휘발성 물질에 의한 기체발생을 억제하여 가류용 브라더 고무의 사용수명을 향상시키는 것을 과제로 한다.Accordingly, the present invention is to suppress the generation of gas by the small voids and volatiles present in the rubber so that the lamination phenomenon does not occur in the rubber rubber composition used during the vulcanization of the tire to improve the service life of the vulcanizing brother rubber Let's make it a task.

도 1은 본 발명의 실시예 1의 고무조성물을 사용후(타이어 약 500개 제조후)의 가류 브라더의 내부 표면의 사진(5배 확대)이다.1 is a photograph (5 times magnification) of the inner surface of a vulcanizing brother after using the rubber composition of Example 1 of the present invention (after production of about 500 tires).

도 2는 종래기술의 비교예 1의 고무조성물을 사용후(타이어 약 500개 제조후)의 가류 브라더의 내부 표면의 사진(5배 확대)이다.2 is a photograph (5 times magnification) of the inner surface of the vulcanizing brother after using the rubber composition of Comparative Example 1 of the prior art (after production of about 500 tires).

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 타이어 가류용 브라더 고무조성물에 있어서, 기본재료 고무로 이소부틸렌과 파라-메틸스티렌의 브롬화된 코폴리머를 사용하고 통상의 배합 첨가제를 사용하고, 상기 기재 고무 100중량부당 유황(중량부)과 디벤조치아질 디설파이드(가류촉진제)(중량부)를 각각 0.2 내지 1.0중량부를 사용하되 유황/디벤조치아질디설파이드의 중량비를 0.4 내지 1.8로 하는 것을 특징으로 하는 타이어 가류용 브라더 고무조성물이다.The present invention relates to a rubber composition for tire vulcanization, in which a brominated copolymer of isobutylene and para-methylstyrene is used as the base rubber, and a conventional compounding additive is used, and sulfur per 100 parts by weight of the base rubber is used. ) And dibenzothiazyl disulfide (vulcanization accelerator) (parts by weight), each of which is 0.2 to 1.0 parts by weight, and a sulfur rubber compound for tire vulcanization, characterized in that the weight ratio of sulfur / dibenzochiazil disulfide is 0.4 to 1.8. .

이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

본 발명은 타이어 가류용 브라더 고무조성물에 있어서, 기체발생을 줄이고 수명을 향상시키기 위하여 이소부틸렌과 p-메틸스티렌의 브롬화된 코폴리머 100중량부를 기본으로 사용하고 카본블랙, 산화아연(ZnO), 스테아린산 등과 같이 통상의 가류브라더용 알킬 페놀 포름알데히드 수지를 5 내지 10중량부를 사용하여 혼합한 고무조성물을 수지 경화를 시키되 상기 기재 고무 100중량부당 유황(중량부)과 디벤조치아질 디설파이드(가류촉진제)(중량부)를 각각 0.2 내지 1.0중량부를 사용하되 유황/디벤조치아질디설파이드의 중량비를 0.4 내지 1.8로 하여 같이 혼합하여 가류시키는 것으로 이루어진다.In the present invention, in the rubber composition for tire vulcanization, 100 parts by weight of brominated copolymers of isobutylene and p-methylstyrene are used as the basis, and carbon black, zinc oxide (ZnO), The resin composition is cured by mixing a rubber composition containing 5-10 parts by weight of an alkyl phenol formaldehyde resin for conventional vulcanizing broth, such as stearic acid, but sulfur (parts by weight) and dibenzochizyl disulfide (vulcanization accelerator) per 100 parts by weight of the base rubber. ) (Parts by weight) and 0.2 to 1.0 parts by weight, respectively, and the sulfur / dibenzochiazil disulfide by weight ratio of 0.4 to 1.8, and mixed together to vulcanize.

상기 에서 유황/디벤조치아질 디설파이드의 중량비가 0.4 이하인 경우와 1.8 이상인 경우에는 타이어 가류용 고무 조성물의 제조과정에서 기포가 발생하게되어 바람직하지 못하다.In the case where the weight ratio of sulfur / dibenzothiazyl disulfide is 0.4 or less and 1.8 or more, bubbles are generated in the manufacturing process of the rubber composition for tire vulcanization, which is not preferable.

이하, 실시예로 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to Examples.

실시예 1 내지 6Examples 1-6

이소부틸렌과 p-메틸스티렌의 브롬화된 코폴리머 100중량부를 기본으로 사용하고 카본블랙, 산화아연(ZnO), 스테아린산 등과 같이 통상의 가류브라더용 알킬 페놀 포름알데히드 수지, 유황/디벤조치아질 디설파이드를 표 1의 조건으로 하고, , 가류시간을 다음 표 1에 나타난 바와 같이 하여 통상의 제조방법으로 가류용 브라더 고무조성물을 제조하였다. 상기 실시예로 제조된 고무 조성물의 물성을 측정하여 표 1에 병기하였다.100 parts by weight of brominated copolymers of isobutylene and p-methylstyrene are used as bases, and alkyl phenol formaldehyde resins for sulfur vulcanizing broths such as carbon black, zinc oxide (ZnO) and stearic acid, sulfur / dibenzothiazyl disulfide To the conditions of Table 1, and, as shown in Table 1, the vulcanization time was prepared a rubber rubber composition for vulcanization in a conventional manufacturing method. The physical properties of the rubber composition prepared in the above Example was measured and described in Table 1.

또한, 본 발명의 실시예 1의 고무조성물을 사용후(타이어 약 500개 제조후)의 가류 브라더의 내부 표면의 사진(5배 확대)을 도 1에 나타냈다.In addition, the photograph (5 times magnification) of the inner surface of the vulcanizing brother after using the rubber composition of Example 1 of the present invention (after manufacturing about 500 tires) is shown in FIG.

비교예1Comparative Example 1

유황과 디벤조치아질 디설파이드를 사용하지 않는 것을 제외 하고는 표 1에 나타난 조건으로 하여 실시예와 유사하게 고무 조성물을 제조하였다.A rubber composition was prepared in a similar manner to the example under the conditions shown in Table 1 except that sulfur and dibenzothiazyl disulfide were not used.

상기 비교예로 제조된 고무 조성물의 물성을 측정하여 표 1에 병기 하였다.The physical properties of the rubber composition prepared in Comparative Example was measured and described in Table 1.

또한, 비교예 1의 고무조성물을고 사용후(타이어 약 500개 제조후)의 가류 브라더의 내부 표면의 사진(5배 확대)을 도 2에 나타냈다.Moreover, the photograph (5 times magnification) of the inner surface of the vulcanizing brother after using the rubber composition of the comparative example 1 (after manufacturing about 500 tires) is shown in FIG.

실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예Comparative example RECIPE1) RECIPE 1) 유황(중량부)Sulfur (parts by weight) 0.850.85 0.750.75 0.600.60 0.250.25 0.750.75 0.500.50 -- 디벤조치아질디설파이드(중량부)Dibenzochiazil disulfide (parts by weight) 0.500.50 0.500.50 0.600.60 0.600.60 0.600.60 0.600.60 -- 알킬페놀포름알데히드 수지(중량부)Alkylphenol formaldehyde resin (weight part) 5.05.0 5.05.0 5.05.0 5.05.0 5.05.0 5.05.0 1010 RHEO2) RHEO 2) 30%가류시간30% Curfew 05:0905:09 06:2706:27 04:5604:56 05:0705:07 05:5405:54 07:4607:46 05:3605:36 90%가류시간90% Curfew 08:5808:58 11:2611:26 08:2108:21 08:2808:28 10:1410:14 13:3613:36 23:4323:43 M.V.3) MV 3) 무늬점도Viscosity 82.882.8 73.973.9 81.981.9 82.082.0 81.481.4 82.882.8 7979 스코치타임Scotch time 41:4841:48 38:2538:25 27:3727:37 26:0526:05 37:3037:30 27:5027:50 55:0055:00 인장물성4) Tensile Properties 4) 경도300%모듈러스파단강도파단시 신율Elongation at Break at Hardness 300% Modulus 64541247266454124726 65471258316547125831 64601276826460127682 71711356587171135658 66631256566663125656 68731356526873135652 63641366906364136690 연구신장늘음율(%)5) Research elongation rate (%) 5) (150%×48시간)(150% x 48 hours) 123123 117117 111111 107107 112112 108108 135135

1)이소부틸렌과 파라-메틸스티렌의 브롬화된 코폴리 100중량부당 주요조성물의 중량(단 비교예는 부틸고무 100중량부당 조성비)1) Weight of main composition per 100 parts by weight of brominated copoly of isobutylene and para-methylstyrene (comparative example is composition ratio per 100 parts by weight of butyl rubber)

2)Rheometer 시험은 몬산토제 R-100을 사용하여 186℃에서 측정함.2) Rheometer test was measured at 186 ℃ using Monsanto R-100.

3)무니 점도 시험은 몬산토제를 사용하여 125℃에서 측정함.3) Mooney viscosity test is measured at 125 ℃ using Monsanto.

4)인장물성은 KS 표준의 아령형 3호를 사용하여 측정함.4) Tensile properties are measured using the dumbbell type No. 3 of KS standard.

5)영구 신장 늘음율은 낮을수록 유리함.5) The lower the permanent elongation, the better.

본 발명의 고무 조성물을 사용하는 경우 종래 기술에서 발생하는 라미네이트현상이 발생하지 않으며, 상기 표 1에 나타난 바와 같이 본 발명에 의한 고무 조성물은 영구 신장 늘음율이 20%이상 향상되어 타이어 가류용 고무 조성물의 사용 수명을 약 50%이상 늘리는 효과를 나타냈다.When using the rubber composition of the present invention does not occur in the laminate phenomenon occurs in the prior art, as shown in Table 1, the rubber composition according to the present invention is 20% or more permanent elongation is improved rubber composition for tire vulcanization It has the effect of increasing the service life of about 50% or more.

Claims (1)

타이어 가류용 브라더 고무조성물에 있어서, 기본재료 고무로 이소부틸렌과 파라-메틸스티렌의 브롬화된 코폴리머를 사용하고 통상의 배합 첨가제를 사용하고, 상기 기재 고무 100중량부당 유황(중량부)과 디벤조치아질 디설파이드(가류촉진제)(중량부)를 각각 0.2 내지 1.0중량부를 사용하되 유황/디벤조치아질디설파이드의 중량비를 0.4 내지 1.8로 하는 것을 특징으로 하는 타이어 가류용 브라더 고무 조성물.In a rubber composition for tire vulcanization, sulfur (parts by weight) and di per 100 parts by weight of the base rubber are used by using a brominated copolymer of isobutylene and para-methylstyrene as a base material rubber and using a conventional compounding additive. A vulcanized tire rubber composition for vulcanizing tires, wherein 0.2 to 1.0 parts by weight of benzothiazyl disulfide (vulcanization accelerator) (parts by weight) is used, and the weight ratio of sulfur / dibenzochiazil disulfide is 0.4 to 1.8.
KR1019970047019A 1997-09-12 1997-09-12 The rubber composition for tire bladder KR100227445B1 (en)

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