KR100234482B1 - A rubber composition improved ozone resistance and adherence - Google Patents

A rubber composition improved ozone resistance and adherence Download PDF

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KR100234482B1
KR100234482B1 KR1019970040148A KR19970040148A KR100234482B1 KR 100234482 B1 KR100234482 B1 KR 100234482B1 KR 1019970040148 A KR1019970040148 A KR 1019970040148A KR 19970040148 A KR19970040148 A KR 19970040148A KR 100234482 B1 KR100234482 B1 KR 100234482B1
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rubber
phr
rubber composition
epdm
maleic
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KR1019970040148A
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KR19990017267A (en
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고진환
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신형인
금호산업주식회사
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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
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • 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 원료 고무에 대하여 이피디엠 고무와 생 고무 블렌드의 적용으로 내오존성과 내산화성 및 타고무와의 계면 접착력을 향상시키는 사이드월 고무 조성물에 관한 것이다.The present invention relates to a sidewall rubber composition which improves interfacial adhesion between ozone resistance and oxidation resistance and rideability by applying EPDM rubber and raw rubber blend to raw rubber.

본 발명에 있어 원료 고무 100 중량부에 대하여 사용 되는 이피디엠 고무(EPDM Rubber)는 이중결합과 분자량이 큰 고무를 생고무와 블렌드(40/60)하고 타고무와 계면 접차력을 보완 하기 위하여 점착제 말레익 모디파이드 로진 에스터(maleic modified rosin ester : pentaerythitol ester of maleic modified resin)의 적용으로 타 고무와 코큐어(co-cure) 특성의 개선으로 계면접착력을 향상 시키는 고무 조성물을 얻을 수 있다.EPDM rubber used in the present invention based on 100 parts by weight of the raw material rubber is a double bond and a large molecular weight rubber (40/60) blended with raw rubber and to improve the rubber and interfacial contact pressure adhesive maleic By applying a modified rosin ester (maleic modified rosin ester) of maleic modified resin (rubber), it is possible to obtain a rubber composition that improves interfacial adhesion by improving other rubber and co-cure properties.

Description

내 오존 및 계면 접착력이 향상된 고무 조성물Rubber composition with improved ozone and interfacial adhesion

본 발명은 TBR 또는 PCR 승용차 타이어에 있어서, 사이드월 부위의 오존이나 내열에 의한 크랙을 개선하고 노방제가 외부로 이동(migration)에 의한 사이드월 부위 변색을 방지하여 외관 품질을 향상 시키는 고무조성물에 관한 것이다.The present invention relates to a rubber composition for improving the appearance quality of a TBR or PCR passenger car tire by improving cracks caused by ozone or heat in the sidewall and preventing discoloration of the sidewall due to migration of the road agent to the outside. will be.

종래에는 사이드월(side wall) 부위에 내오존성을 개선하기 위하여 사용한 폴리머는 NR/SBR/BR 블렌드나, NR/BR 블렌드한 고무에 노방제, 6PPD (N-(1,3-Dimety1 Buty1), N!PH-P-Pheny1 Diamine), TMDQ(2,2,4-Trimety1-1,2-Dihydro Quinolin), SPN(Styrenated Phenol), BLE-N(Diphey1 Amine)과 아세톤의 반응물) 등을 사용하고, 미세결정 왁스(microcrystalline wax)도 고무 표면에 피막을 형성하여 정적인 상태에서 오존공격에 의한 크랙을 감소키 위하여 2-5phr 정도 사용한다. 그러나 이들 방법에 있어 가장 문제가 되는 것은 노화방지제가 주행중 열이나, 오존이 존재하는 대기중에서 소멸하여 노방효과가 감소하거나, 오존 크랙을 발생하여 타이어 수명 단축이나, 심한 경우네는 타이어 사고로 이어질수 있다는 것이다.Conventionally, polymers used to improve ozone resistance in the side wall area are NR / SBR / BR blends, lubricating agents for NR / BR blended rubbers, 6PPD (N- (1,3-Dimety1 Buty1), N! PH-P-Pheny1 Diamine), TMDQ (2,2,4-Trimety1-1,2-Dihydro Quinolin), SPN (Styrenated Phenol), BLE-N (Diphey1 Amine) and acetone In addition, microcrystalline wax is also used to form a film on the surface of the rubber to use 2-5phr to reduce the cracks caused by ozone attack in the static state. However, the most problematic in these methods is that the anti-aging agent may be dissipated in the atmosphere where heat or ozone is present, reducing the road effect, or causing ozone cracks, resulting in reduced tire life or, in extreme cases, tire accidents. will be.

본 발명은 이런 기존의 문제점을 해결하기 위하여 종래의 NR/SBR 블렌드나, NR/SBR/BR 블렌드 고무에서 노방제, 6PPD나 TMDQ 노방제를 1 - 4 phr 적용하며, 미세결정 왁스(Microcrystalline wax)를 1 - 2 phr 적용한 경우에, 노방제는 105 ℃에서 6일간 방치시 소멸로 인하여 노방제 잔류양이 2 - 3 % 만 남아 있으며, 미세결정 왁스는 C25-C27 카본 분포에서는 잔류양이 85% 존재 하였다. 이로 인해 타이어는 주행시 타이어 내부는 120-140 ℃, 외부는 55 - 75 ℃정도의 열이 발생되므로 노방제 소멸로 인해 오존에 의한 크랙 발생을 방지하기에는 거의 불가능한 실정이다.The present invention is applied to the conventional NR / SBR blend, or NR / SBR / BR blend rubber in the conventional NR / SBR / BR blend rubber, 1-4 phr, 6PPD or TMDQ lubricating agent, and microcrystalline wax When 1-2 phr is applied, the preservative remains only 2-3% of the preservative due to the disappearance when left at 105 ° C for 6 days, and the microcrystalline wax has a residual amount of 85% in the C25-C27 carbon distribution. Existed. Due to this, the tire generates heat of about 120-140 ° C. inside the tire and 55-75 ° C. outside the tire, so it is almost impossible to prevent cracks caused by ozone due to the disappearance of the preservative.

더구나, 여름철이나, 오존이 많이 발생하는 지역에서는 매우 심각한 실정이다. 실험실에서 NR/BR 블렌드나, NR/SBR/BR 블렌드에 노방제나 왁스를 적용하여 오존 시험을 하면 40 ℃, 50 ppm 오존 농도 에서도 오존 크랙이 정적인 조건에서는 24시간 정도만 방치해도 발생한다. 노방제의 소멸양이 많이 이를 충당키 위하여 노방제 양을 많이 적용해도 효과는 그리 크지 않으므로 본 발명은 종래의 문제점을 해결하기 위하여 타이어의 첨가 되는 고무와 약품을 달리함으서 타이어의 오존 크랙을 감소하는 고무조성물을 제공하였다.Moreover, it is very serious in the summer and in areas with high ozone. In the laboratory, ozone testing of NR / BR blends or NR / SBR / BR blends with preservatives or waxes can occur at 40 ° C and 50 ppm ozone concentrations for 24 hours under static conditions. In order to solve this problem, the present invention reduces ozone cracks of tires by varying rubber and chemicals added to tires to solve the conventional problems. To provide a rubber composition.

본 발명은 상기와 같은 목적을 달성하기 위하여 고무 조성물은 기존 사용한 고무인 NR, BR, SBR 고무가 이중 결합이 많아 오존이 고무의 이중결합을 공격하여 고무 분자쇄 절단을 가져오므로 이를 방지키 위하여 이중결합이 적고 공정가공성이 좋은 오일첨가 이엔비(Oil extended ENB) 타입의 EPDM을 NR 고무와 블렌드하여 적용한다. 그러나 EPDM/NR 블렌드의 사이드월 고무는 근접부위 고무인 NR/SBR, NR/SBR/BR 고무와 코큐어(Co-cure) 특성이 저조하여, 계면접착력이 떨어지는 문제점이 있다.In order to achieve the above object, the rubber composition has a large number of double bonds of NR, BR, and SBR rubbers, which are conventionally used rubbers, and ozone attacks the double bonds of the rubber, resulting in cutting of the molecular chain of the rubber. Oil-bonded ENB type EPDM with low bonding and good processability is blended with NR rubber. However, the sidewall rubber of the EPDM / NR blend has poor co-cure characteristics with the NR / SBR, NR / SBR / BR rubber, which is a proximal rubber, and thus has a problem of poor interfacial adhesion.

본 발명의 목적은 EPDM/NR 블렌드 고무에서 계면 접착력을 향상하기 위한 방안을 제시한 것이다.An object of the present invention is to propose a method for improving interfacial adhesion in EPDM / NR blend rubber.

이하 실시예 및 비교예를 통하여 본 발명을 상세하게 설명한다. 그러나, 본 발명이 이들 실시예에 국한되는 것은 아니다.Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the present invention is not limited to these examples.

[실시예 1]Example 1

표 1 은 고무의 중량을 100으로 하여 무게를 나타냈으며 고무의 가공성과 화학적인 반응 특성을 고려 하여 배합 조성을 설정 하였다. 배합순서는 반바리믹서에서 고무의 분산 개선에 의한 물성을 향상 시키기 위하여 1차에서는 NR에 카본블랙의 1/2를 투입 배합 하고, 2차 배합에서 EPDM과 혼합하며 3차 배합에서 남은 카본블랙과 약품을 투입하여 배합 하고 F/M 배합에서 유황과 촉진제를 첨가하여 표 1과 같이 배합하였다.Table 1 shows the weight of the rubber to 100, and set the formulation in consideration of the processability and chemical reaction characteristics of the rubber. In order to improve the physical properties by improving the dispersion of rubber in the half-barrier mixer, in the first step, 1/2 of carbon black is added to NR, and it is mixed with EPDM in the second compounding, The chemicals were added and blended, and the sulfur and accelerators were added in the F / M formulation, and the formulation was performed as shown in Table 1.

[실시예 2]Example 2

실시예 1과 동일하게 하고 점착제로 산가 13.91인 말레익 모디파이드 로진 에스터 5 phr을 첨가하여 고무조성물 배합하였다.In the same manner as in Example 1, 5 phr of a maleic modified rosin ester having an acid value of 13.91 was added as an adhesive to mix a rubber composition.

[비교예][Comparative Example]

천연고무 50 phr, SBR 30 phr, BR 20 phr, 가류활성제 7 phr, 카본블랙 50 phr, 노화방지제 4 phr, 왁스 2 phr, 공정오일 6 phr, 유황 1.8 phr 및 가류촉진제 0.85 phr 첨가하여 고무 조성물을 얻었다.Natural rubber 50 phr, SBR 30 phr, BR 20 phr, vulcanizing agent 7 phr, carbon black 50 phr, antioxidant 4 phr, wax 2 phr, process oil 6 phr, sulfur 1.8 phr and vulcanization accelerator 0.85 phr Got it.

Figure kpo00001
Figure kpo00001

1) EDPM : 100% Oil extended ENB 타입의 EPDM1) EDPM: EPDM of 100% Oil extended ENB type

2) 노방제 : 6PPD (N-(1,3-Dimethy1 Buty1), N! PH - P - Pheny1 Diamine), TMDQ (2,2,4-Trimety1-1,2-Dihydro Quinolin)2) Preservatives: 6PPD (N- (1,3-Dimethy1 Buty1), N! PH-P-Pheny1 Diamine), TMDQ (2,2,4-Trimety1-1,2-Dihydro Quinolin)

3) 왁스 : Microcrystalline wax (M.p : 63℃)3) Wax: Microcrystalline wax (M.p: 63 ℃)

4) 접착제 : Msleic Modified Rosin Ester (Pentaerythitol ester of maleic modified rosin (acid value : 13.91)4) Adhesive: Msleic Modified Rosin Ester (Pentaerythitol ester of maleic modified rosin (acid value: 13.91)

표 1의 시험 고무의 준비를 통하여 배합 고무의 가황 조건 및 시험은 ASTM 규격에 준하여 시험 하였고, 가황 특성 및 물성 측정의 결과는 표 2와 같다.The vulcanization conditions and tests of the compound rubber through the preparation of the test rubber of Table 1 were tested in accordance with ASTM standards, and the results of vulcanization characteristics and physical properties are shown in Table 2.

하기 표 2에서 나타난 결과에서 보듯이, NR, BR, SBR고무를 사용한 경우에는 노방제 6PPD, TMDQ와 미세 결정 왁스를 적용해도 고무의 특성상 오존시험 결과 정적 오존 시험에서도 24시간 만에 오존 크랙을 발생하였다.As shown in the results shown in Table 2, when NR, BR, and SBR rubber were used, ozone cracks were generated in 24 hours even in the static ozone test as a result of the ozone test even if the preservative 6PPD, TMDQ and the microcrystalline wax were applied. It was.

그러나, 이중 결합이 적은 EPDM을 40 중량부 적용한 경우에는 정적 오존시험에서 336간 방치해도 전혀 오존 크랙의 발생이 없었다. 또한 EPDM/NR 블렌드 고무에서 계면 접착력을 향상하기 위햐여 말레익 모디파이드 로진 에스터 (Maleic Modified Rosin Ester : Pentaerythitol ester of maleic modified rosin)를 적용한 결과, 코큐어 특성의 향상으로 접착력이 향상 되는 결과를 얻었다.However, when 40 parts by weight of EPDM with less double bonds were applied, no ozone crack was generated even when left for 336 in the static ozone test. Maleic Modified Rosin Ester (Pentaerythitol ester of maleic modified rosin) was applied to improve interfacial adhesion in EPDM / NR blend rubber, resulting in improved cohesive properties. .

Figure kpo00002
Figure kpo00002

본 발명은 TBR 또는 PCR 승용차 타이어에 있어서 노화방지제를 적용하여 사이드월 부위의 오존이나 내열에 의한 크랙을 개선하는데 있어 사용된 노화방지제가 외부로 이동하여 사이드 월 부위 변색을 가져오는 현상을 감소하여 타이어의 외관 품질을 향상시키고, 코 큐어 특성향상으로 접착력이 향상된 고무조성물을 얻었다.The present invention is applied to the anti-aging agent in TBR or PCR passenger car tires to reduce the phenomenon that the anti-aging agent used to improve the cracks due to ozone or heat in the side wall area to the outside to cause discoloration of the side wall area tire The rubber composition was improved by improving the appearance quality and improving the adhesive strength by improving the curing properties.

Claims (2)

타이어의 내오존 및 계면접착력을 향상시키기 위한 사이드월 고무조성물에 있어서, 원료고무 100 phr에 대하여 프리블렌딩(Pre-blending)한 천연고무 60 phr, EPDM 40 phr과 점착제로 산가가 13.91인 말레익 모디파이드 로진 에스터(말레익 모디파이드 로진의 펜타이리시톨 에스터) 3~10 phr을 혼합하는 것을 특징으로 하는 타이어용 고무조성물.In the sidewall rubber composition for improving the ozone resistance and interfacial adhesion of tires, 60 phr of natural rubber pre-blended with 100 phr of raw rubber, and 40 phr of EPDM and maleic modifier having an acid value of 13.91 with adhesive A rubber composition for tires, characterized by mixing 3 to 10 phr of a fed rosin ester (maleic modified rosin pentyrithitol ester). 제1항에 있어서, 프리블렌딩은 1차 배합에서 천연고무에 카본블랙의 1/2를 배합하고, 2차 배합에서 EPDM과 혼합하며, 3차 배합에서 남은 카본블랙과 약품을 투입하여 배합하는 것을 특징으로 하는 타이어용 고무조성물.The method of claim 1, wherein the pre-blending comprises mixing 1/2 of carbon black with natural rubber in the first blending, mixing with EPDM in the second blending, and blending the chemicals with the carbon black remaining in the third blending. A rubber composition for tires, characterized by the above-mentioned.
KR1019970040148A 1997-08-22 1997-08-22 A rubber composition improved ozone resistance and adherence KR100234482B1 (en)

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KR20040017551A (en) * 2002-08-22 2004-02-27 금호타이어 주식회사 Tire rubber composition with improved interfacial properties
KR101427678B1 (en) * 2012-11-23 2014-08-07 조선대학교산학협력단 Rubber compound of automobile accessories to improve aging physical properties

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