KR20020048494A - A rubber composition having improved anti-cutting and anti-chipping ability - Google Patents

A rubber composition having improved anti-cutting and anti-chipping ability Download PDF

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KR20020048494A
KR20020048494A KR1020000077625A KR20000077625A KR20020048494A KR 20020048494 A KR20020048494 A KR 20020048494A KR 1020000077625 A KR1020000077625 A KR 1020000077625A KR 20000077625 A KR20000077625 A KR 20000077625A KR 20020048494 A KR20020048494 A KR 20020048494A
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South Korea
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rubber composition
cutting
weight
aramid pulp
parts
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KR1020000077625A
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Korean (ko)
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권희원
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신형인
금호산업 주식회사
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Publication of KR20020048494A publication Critical patent/KR20020048494A/en

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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
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00—Masterbatches

Abstract

PURPOSE: Provided is a rubber composition having improved abrasion resistance, anti-cutting and chipping characteristics. CONSTITUTION: The rubber composition for tire comprises 1-20 parts by weight of aramide pulp master batch based on 100 parts by weight of rubber material. The rubber composition has improved abrasion resistance, anti-cutting and chipping characteristics.

Description

내 컷팅 및 칩핑성이 향상된 고무조성물{A RUBBER COMPOSITION HAVING IMPROVED ANTI-CUTTING AND ANTI-CHIPPING ABILITY}Rubber composition with improved cutting resistance and chipping resistance {A RUBBER COMPOSITION HAVING IMPROVED ANTI-CUTTING AND ANTI-CHIPPING ABILITY}

본 발명은 내마모성 및 내 컷팅 및 칩핑성이 향상된 고무 조성물에 관한 것으로서, 더욱 상세하게는 타이어용 고무 조성물에 있어서, 아라미드 펄프 마스터 배치를 1∼20 중량부의 양으로 포함하는 내마모성 및 내 컷팅 및 칩핑성이 향상된 고무 조성물에 관한 것이다.The present invention relates to a rubber composition having improved abrasion resistance and cutting resistance and chipping resistance, and more particularly, to a rubber composition for tires, wherein the aramid pulp master batch is contained in an amount of 1 to 20 parts by weight. This improved rubber composition relates.

산업발전에 따라 도로의 포장율이 증가하고 있으나 레저용 차량(RV: recreational vehicle)의 이용이 확대되고 있어 비포장도로를 주행하고자 하는 소비자의 요구에 따라 내 컷팅 및 칩핑성이 강화된 타이어에 대한 수요가 높아지고 있다. 즉, 산악지형이나 자갈이 많은 도로를 주행할 경우 타이어 고무가 찢기거나 일부가 파손되는 경우가 흔히 발생하는 데 이러한 찢김과 파손에 대한 내성이 강한 타이어에 대한 수요가 높아지고 있는 것이다.As the development of the road increases the pavement rate of roads, but the use of recreational vehicles (RVs) is expanding, the demand for tires with improved cutting and chipping resistance is in line with the demands of consumers who want to drive on unpaved roads. It is rising. That is, when driving on mountainous terrain or gravel roads, tire rubber is often torn or partially broken, and the demand for tires that are resistant to such tearing and breakage is increasing.

종래의 고무 조성물의 이러한 단점을 폴리머 및 카본블랙을 변경하거나 그 함량을 조절하여 개선하려는 연구가 많았다. 그러나, 내 컷팅 및 칩핑성을 개선하기 위하여 입자경이 작은 카본블랙을 사용하는 경우에는 발열량이 증가하여 크랙이발생될 우려가 있는 동시에 고무배합성에 문제가 발생되었으며, 입자경이 너무 큰 카본블랙을 사용하는 경우에는 고무배합성은 양호하게 되었으나 물성이 지나치게 증가하여 내 컷팅 및 칩핑성이 오히려 약화되었다. 또한, 카본블랙의 입자경이 증가함에 따라 내마모성도 약화되었다.There have been many studies to improve this disadvantage of the conventional rubber composition by changing the polymer and carbon black or by adjusting the content thereof. However, when carbon black having a small particle size is used to improve cutting resistance and chipping resistance, there is a possibility that cracks are generated due to an increase in heat generation, and a problem occurs in rubber compounding, and carbon black having a large particle size is used. In the case of rubber compounding was good, but the physical properties were excessively increased, cutting resistance and chipping resistance was rather weakened. In addition, wear resistance was also weakened as the particle diameter of carbon black increased.

한편, 상기와 같은 종래 기술의 문제점을 개선하기 위하여 보강성 섬유(단섬유)를 사용하는 방법이 알려졌다. 그러나, 이러한 보강성 섬유는 그 보강성에도 불구하고 분산성이 불량하기 때문에 이들 보강성 섬유의 분산을 위하여는 많은 노력이 요구되고, 만약 분산이 불량하면 이물질로서 작용하여 주행 중 타이어에 결함(defect)이 발생되는 경우가 있다는 문제점이 있었다.On the other hand, a method of using a reinforcing fiber (short fiber) in order to improve the problems of the prior art as described above is known. However, since these reinforcing fibers have poor dispersibility in spite of their reinforcing properties, much effort is required to disperse the reinforcing fibers. ), There was a problem that sometimes occurs.

본 발명은 상기와 같은 단섬유의 분산성을 개선함으로써 단섬유의 보강성을 극대화하여 내마모성 및 내 컷팅 및 칩핑성이 개선된 타이어용 고무 조성물을 제공하는 것을 그 목적으로 한다.The object of the present invention is to provide a rubber composition for tires having improved abrasion resistance, cutting resistance and chipping resistance by maximizing reinforcement of short fibers by improving the dispersibility of the short fibers as described above.

본 발명의 내마모성 및 내 컷팅 및 칩핑성이 개선된 고무 조성물은 전형적인 타이어용 고무 조성물에 아라미드 펄프 마스터 배치를 1∼20 중량부 포함하여 이루어지는 것을 특징으로 한다.The rubber composition having improved abrasion resistance, cutting resistance and chipping resistance is characterized by comprising 1 to 20 parts by weight of an aramid pulp masterbatch in a typical rubber composition for tires.

본 발명은 종래의 전형적인 타이어용 고무 조성물에 보강재로서 아라미드 펄프 마스터 배치를 첨가하여 내마모성 및 내 컷팅 및 칩팅성을 개선시킨다. 상기 종래의 전형적인 타이어용 고무 조성물은 예를 들면, 원료고무, 카본블랙, 노방제,스테아린산, 오일, 황, 촉진제로 이루어지는 조성물로서 종래 전형적으로 사용되는 함량비로 포함되어지는 조성물이 될 수 있다.The present invention adds an aramid pulp masterbatch as a reinforcement to conventional rubber compositions for tires to improve wear resistance and cut and chipping resistance. The conventional rubber composition for a typical tire may be, for example, a composition comprising a raw material rubber, carbon black, a lubricating agent, stearic acid, an oil, sulfur, and an accelerator, in a content ratio typically used in the related art.

본 발명의 조성물은 상기 종래의 전형적인 타이어용 고무 조성물에 아라미드 펄프 마스터 배치를 첨가하여 제조된다. 상기 아라미드 펄프 마스터 배치는 예를 들면, 라인 켐(Rhein Chem)사로부터 상업적으로 구입가능한 것으로서 Rhenogran P91 및 Rhenogran P95를 포함하는 두 가지 유형이 될 수 있다. 상기 두 가지 유형의 아라미드 펄프 마스터 배치는 사용된 아라미드 펄프의 종류에 따라서 구분되는 것이다. 상기 사용된 아라미드 펄프는 예를 들면, 트와론(TWARON)사로부터 구입가능한 것으로 TWARON 1091 및 TWARON 1095가 될 수 있다. 상기 TWARON 1091 및 TWARON 1095의 특성은 다음 표1에 나타낸 바와 같다.The composition of the present invention is prepared by adding an aramid pulp master batch to the conventional rubber composition for a typical tire. The aramid pulp masterbatch can be of two types, including, for example, Rhenogran P91 and Rhenogran P95 as commercially available from Rhein Chem. The two types of aramid pulp master batches are classified according to the type of aramid pulp used. The aramid pulp used can be TWARON 1091 and TWARON 1095, for example, available from TWARON. The characteristics of the TWARON 1091 and TWARON 1095 are as shown in Table 1 below.

표1. 아라미드 펄프의 특성Table 1. Characteristics of Aramid Pulp

인자factor TWARON 1091TWARON 1091 TWARON 1095TWARON 1095 비표면적Specific surface area ∼14m2/g14 m 2 / g ∼7m2/g～ 7m 2 / g 섬유길이Fiber length 1∼2 mm1 to 2 mm 1∼2 mm1 to 2 mm 섬유코아의 직경/피브릴(fibrils)의 직경Diameter of fiber core / diameter of fibrils 10μ/100μ10μ / 100μ 10μ/100μ10μ / 100μ

Rhenogran P91 또는 Rhenogran P95의 종류는 마스터 배치용 고무에 따라, Rhenogran P91-50/BR, Rhenogran P95-50/NBR, Rhenogran P95-50/BR 등이 있다. 여기에서 Rhenogran P91-50/BR은 부타디엔 고무(BR) 100중량부에 대하여 아라미드 펄프(TWARON 1091) 50중량부를 포함하는 것을 말하고, Rhenogran P95-50/NBR은 고무(NBR) 100중량부에 대하여 아라미드 펄프(TWARON 1095) 50중량부를 포함하는 것을 말하고, Rhenogran P95-50/BR는 고무(BR) 100중량부에 대하여 아라미드 펄프(TWARON 1095) 50중량부를 포함하는 것을 말한다.Types of Rhenogran P91 or Rhenogran P95 include Rhenogran P91-50 / BR, Rhenogran P95-50 / NBR, and Rhenogran P95-50 / BR depending on the master batch rubber. Herein, Rhenogran P91-50 / BR refers to 50 parts by weight of aramid pulp (TWARON 1091) based on 100 parts by weight of butadiene rubber (BR), and Rhenogran P95-50 / NBR refers to 100 parts by weight of aramid based on 100 parts by weight of rubber (NBR). It refers to containing 50 parts by weight of pulp (TWARON 1095), Rhenogran P95-50 / BR refers to containing 50 parts by weight of aramid pulp (TWARON 1095) relative to 100 parts by weight of rubber (BR).

본 발명의 조성물에 포함되는 상기 아라미드 마스터 배치는 원료고무 100 중량부에 대하여 1∼20 중량부로 포함되어지는 것이 바람직하다. 본 발명의 조성물에 포함되는 상기 아라미드 마스터 배치의 함량이 증가함에 따라 내마모성 및 내 컷팅 및 칩핑성이 개선되나 1 중량부 미만에서는 그 개선효과가 미미하며, 20 중량부를 초과하는 경우에는 분산도가 감소하는 동시에 내마모성 및 내 컷팅 및 칩핑성의 개선효과도 적어진다.The aramid master batch contained in the composition of the present invention is preferably contained in 1 to 20 parts by weight based on 100 parts by weight of the raw material rubber. As the content of the aramid master batch included in the composition of the present invention is increased wear resistance and cutting resistance and chipping resistance is improved, but less than 1 part by weight, the improvement is insignificant, in the case of more than 20 parts by weight dispersion At the same time, the effect of improving wear resistance, cutting resistance and chipping resistance is reduced.

이하 실시예를 통하여 본 발명을 보다 구체적으로 설명한다. 그러나, 본 실시예들은 예시적인 목적일 뿐 본 발명이 이들 실시예에 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples. However, the present embodiments are for illustrative purposes only and the present invention is not limited to these embodiments.

실시예Example

본 발명의 아라미드 펄프 마스터 배치가 포함된 고무 조성물, 아라미드 펄프 마스터 배치는 포함하지 않고 아라미드 펄프만을 포함하는 조성물 및 아라미드 펄프 및 아라미드 펄프 마스터 배치 모두 포함하지 않는 조성물의 물성을 알아보기 위하여 하기의 표2에 나타낸 바와 같이 조성물 V-1, V-2, V-3, V-4, V-5, V-6을 제조하였다.In order to examine the physical properties of the rubber composition containing the aramid pulp master batch of the present invention, the composition containing no aramid pulp master batch, but only aramid pulp and a composition not containing both aramid pulp and aramid pulp master batch Compositions V-1, V-2, V-3, V-4, V-5, V-6 were prepared as shown.

표2. 실시예에 사용된 조성물(단위: 중량부)Table 2. Compositions Used in Examples (unit: parts by weight)

구분division V-1V-1 V-2V-2 V-3V-3 V-4V-4 V-5V-5 V-6V-6 천연고무Natural rubber 100100 100100 100100 100100 100100 100100 아라미드펄프Aramid Pulp -- 3030 -- -- -- -- 아라미드펄프 마스터배치Aramid Pulp Masterbatch -- -- 55 1010 2020 3030 스테아린산Stearic acid 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 오일oil 1010 1010 1010 1010 1010 1010 노방제Labor 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 촉진제accelerant 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 0.50.5 황sulfur 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0

본 실시예서 사용된 아라미드 펄프 마스터 배치는 라인 켐(Rhein Chem)사로부터 상업적으로 구입한 Rhenogran P91-50/BR이었다. 상기 Rhenogran P91-50/BR은 상용화된 부타디엔 고무(BR)와 아라미드 펄프(TWARON 1091)를 혼합하여 만든 타이어 원재료 고무이다. 사용된 아리미드 펄프(TWARON 1091)의 특성은 상기 상세한 설명란의 표1에 나타낸 바와 같다. 혼합된 함량비는 고무 100 중량부에 대하여 아라미드 펄프 50중량부이었다.The aramid pulp master batch used in this example was Rhenogran P91-50 / BR, commercially available from Rhein Chem. Rhenogran P91-50 / BR is a tire raw material rubber made by mixing a commercially available butadiene rubber (BR) and aramid pulp (TWARON 1091). The properties of the arimid pulp (TWARON 1091) used are as shown in Table 1 of the above detailed description. The mixed content ratio was 50 parts by weight of aramid pulp based on 100 parts by weight of rubber.

본 실시예에 의한 고무의 물성 측정 결과는 하기의 표3에 나타내었다. 표3에 나타낸 바와 같이, 아라미드 펄프 마스터 배치의 함량이 증가함에 따라 모듈러스는 증가하며 이에 따라 내마모성 및 내 컷팅 및 칩핑성도 강화되었다. 그러나, 20중량부를 초과하는 함량으로 포함되었을 때(V-6)는 분산도가 낮아지며 물성을 더 개선시키는 효과도 없었다. 즉, 20 중량부를 기준으로 변곡점을 나타냄을 알 수 있었다. 또한, 아라미드 펄프 마스터 배치를 사용한 V-3, V-4, V-5, V-6의 경우가 아라미드 펄프 마스터 배치 대신에 아라미드 펄프를 사용한 V-2에 비하여 분산성 및 기타 물성에 있어 우수함을 알 수 있었다. 또한, 아라미드 펄프를 사용한 V-2의 경우가 아라미드 펄프 마스터 배치를 사용한 경우에 비하여 분산성을 올려주기 위하여 최대 2배 이상의 밀(mill) 작업이 필요하였다.The physical property measurement results of the rubber according to the present embodiment are shown in Table 3 below. As shown in Table 3, as the content of the aramid pulp masterbatch increased, the modulus increased, thereby enhancing the wear resistance and the cutting and chipping resistance. However, when included in an amount exceeding 20 parts by weight (V-6) the dispersion degree was lowered and there was no effect of further improving the physical properties. That is, it was found that the inflection point was expressed based on 20 parts by weight. In addition, V-3, V-4, V-5, and V-6 using aramid pulp master batches were superior in dispersibility and other physical properties compared to V-2 using aramid pulp instead of aramid pulp master batches. Could know. In addition, in the case of V-2 using aramid pulp, a milling operation of up to two times or more was required in order to increase dispersibility compared with the case of using aramid pulp master batch.

이상과 같은 결과로부터 아라미드 펄프 마스터 배치를 사용함으로써 내마모성 및 내 컷팅 및 칩핑성이 향상됨을 확인 할 수 있었다.From the above results, it was confirmed that the wear resistance, the cutting resistance and the chipping resistance were improved by using the aramid pulp master batch.

표3. 실시예에 따른 조성물의 물성Table 3. Physical Properties of Compositions According to Examples

구분division V-1V-1 V-2V-2 V-3V-3 V-4V-4 V-5V-5 V-6V-6 분산도(%)% Dispersion 100100 8080 100100 100100 100100 9898 인장강도(kg/㎠)Tensile Strength (kg / ㎠) 100100 100100 100100 9999 100100 100100 모듈러스(kgf/㎠)Modulus (kgf / ㎠) 100100 105105 110110 115115 120120 110110 내마모성Wear resistance 100100 9090 105105 110110 120120 109109 내컷팅 및칩핑성Cutting and chipping resistance 100100 9595 9999 105105 100100 100100

본 발명에 따르면, 고무 조성물에 아라미드 펄프 마스터 배치를 적정량 포함시키므로써 내마모성 및 내 컷팅 및 칩핑성이 향상된 타이어용 고무 조성물을 얻을 수 있다.According to the present invention, a rubber composition for a tire having improved abrasion resistance, cutting resistance and chipping resistance can be obtained by including an appropriate amount of aramid pulp master batch in the rubber composition.

Claims (1)

타이어용 고무 조성물에 있어서, 원료고무 100 중량부에 대하여 아라미드 펄프 마스터 배치를 1∼20 중량부 포함하여 이루어지는 것을 특징으로 하는 내마모성 및 내 컷팅 및 칩핑성이 향상된 고무 조성물.The rubber composition for a tire comprising 1 to 20 parts by weight of an aramid pulp masterbatch based on 100 parts by weight of raw material rubber, wherein the rubber composition has improved wear resistance, cutting resistance and chipping resistance.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100477432B1 (en) * 2002-05-31 2005-03-23 금호타이어 주식회사 Tire under tread rubber composition involving the function of the cap ply
KR100696288B1 (en) * 2005-06-03 2007-03-19 금호타이어 주식회사 Rim flange rubber composition for truck and bus tire with improved abrasion resistance
KR100823897B1 (en) * 2007-03-28 2008-04-21 금호타이어 주식회사 Rubber compound for snow tire

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63256639A (en) * 1987-04-14 1988-10-24 Yokohama Rubber Co Ltd:The Tire rubber composition
KR910002439A (en) * 1989-07-14 1991-02-25 베. 마이 Water soluble metallocene complex pharmaceutical composition
WO1999007770A1 (en) * 1997-08-12 1999-02-18 E.I. Du Pont De Nemours And Company Process for making a uniform dispersion of aramid fibers and polymer
JP2001164052A (en) * 1999-12-14 2001-06-19 Sumitomo Rubber Ind Ltd Rubber composition and pneumatic tire using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63256639A (en) * 1987-04-14 1988-10-24 Yokohama Rubber Co Ltd:The Tire rubber composition
KR910002439A (en) * 1989-07-14 1991-02-25 베. 마이 Water soluble metallocene complex pharmaceutical composition
WO1999007770A1 (en) * 1997-08-12 1999-02-18 E.I. Du Pont De Nemours And Company Process for making a uniform dispersion of aramid fibers and polymer
JP2001164052A (en) * 1999-12-14 2001-06-19 Sumitomo Rubber Ind Ltd Rubber composition and pneumatic tire using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100477432B1 (en) * 2002-05-31 2005-03-23 금호타이어 주식회사 Tire under tread rubber composition involving the function of the cap ply
KR100696288B1 (en) * 2005-06-03 2007-03-19 금호타이어 주식회사 Rim flange rubber composition for truck and bus tire with improved abrasion resistance
KR100823897B1 (en) * 2007-03-28 2008-04-21 금호타이어 주식회사 Rubber compound for snow tire

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