KR20020042111A - Rubber composition of tire tread for car - Google Patents

Rubber composition of tire tread for car Download PDF

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KR20020042111A
KR20020042111A KR1020000071872A KR20000071872A KR20020042111A KR 20020042111 A KR20020042111 A KR 20020042111A KR 1020000071872 A KR1020000071872 A KR 1020000071872A KR 20000071872 A KR20000071872 A KR 20000071872A KR 20020042111 A KR20020042111 A KR 20020042111A
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rubber
rubber composition
phr
tire tread
glass transition
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KR1020000071872A
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KR100375634B1 (en
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임원우
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신형인
금호산업 주식회사
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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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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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

PURPOSE: Provided is a tire tread rubber composition for a car, which is excellent in traction, rotation resistance, and abrasion-resistance and contains styrene-butadiene rubber, natural rubber, and polyurethane. CONSTITUTION: The tire tread rubber composition comprises 100phr of rubber containing 20-60phr of the styrene-butadiene rubber having a glass transition temperature of -40 to -15deg.C, 10-30phr of the natural rubber, and 20-60phr of the polyurethane having a glass transition temperature of -50 to -30deg.C, 30-60phr of a carbon black, and 20-70phr of silica, wherein the carbon black has N2SA of 7-120ml/g and DBP of 105-190ml/100g or more.

Description

승용차용 타이어 트레드 고무 조성물{Rubber composition of tire tread for car}Tire composition of tire tread for passenger cars

본 발명은 승용차용 타이어 트레드 고무 조성물에 관한 것으로서, 보다 상세하게는 유리전이온도가 높은 스티렌-부타디엔 고무, 천연고무, 내마모성이 우수한 폴리우레탄을 블렌드한 고무에 충진제로서 카본블랙과 실리카를 첨가하므로써 트랙션, 회전저항 및 내마모성이 우수하게 되는 승용차용 타이어 트레드 고무 조성물에 관한 것이다.The present invention relates to a tire tread rubber composition for passenger cars, and more particularly, traction by adding carbon black and silica as a filler to a rubber blended with styrene-butadiene rubber having high glass transition temperature, natural rubber, and polyurethane having excellent abrasion resistance. The present invention relates to a tire tread rubber composition for passenger cars which is excellent in rotational resistance and wear resistance.

최근에 타이어는 환경 친화성이 우수하면서도 저연비이고 장기 수명인 승용차용 타이어가 개발되어 왔다. 또한 동시에 트랙션 성능도 손실 없이 유지되어야 했다. 따라서 요구성능을 만족시키기 위하여 유리전이온도(Tg)가 서로 다른 고무를 블렌드하고 신소재인 실리카를 첨가하여 고무 조성물을 만들기도 했다.In recent years, tires have been developed for passenger car tires having excellent environmental friendliness, low fuel consumption, and long lifespan. At the same time, traction performance had to be maintained without loss. Therefore, in order to satisfy the required performance, rubbers having different glass transition temperatures (Tg) were blended and silica, a new material, was added to make a rubber composition.

종래에는 비교적 유리전이온도가 높은 고무를 사용하여 트랙션을 높이는 동시에 내마모성을 향상시키기 위하여 유리전이온도가 낮은 고무를 블랜드하여 사용하는 것이 보통이었다. 그리고 카본블랙 외에 실리카가 고무 보강재로서 타이어에 응용되면서 트랙션과 내마모성이 동시에 향상되었다.Conventionally, rubber having a low glass transition temperature is used as a blend in order to increase traction using rubber having a relatively high glass transition temperature. In addition to carbon black, silica has been applied to tires as a rubber reinforcement, improving traction and wear resistance at the same time.

그러나 이러한 고무 배합으로도 내마모성, 회전저항, 트랙션 등의 요구특성을 충분히 만족시키지 못하여 변성 엘라스토머를 블렌딩 하는 방법 등이 제안되기도 하였다.However, even with such a rubber formulation, a method of blending modified elastomers has been proposed because it does not sufficiently satisfy the required characteristics such as wear resistance, rotational resistance and traction.

이와 같이 종래에는 상용성이 있는 두종류 이상의 고무를 혼합하여 타이어의 요구특성을 발현하여 왔으나 이것에는 한계가 있었다.As described above, conventionally, two or more kinds of rubbers having compatibility have been mixed to express a required characteristic of a tire, but this has a limitation.

본 발명의 목적은 승용차용 타이어 트레드에 유리전이온도가 높은 스티렌-부타디엔 고무, 천연고무, 내마모성이 우수한 우레탄 고무를 사용하여 각기 특성이 우수한 두종류 이상의 비상용성 고무를 적절하게 혼합하므로써 트랙션과 내마모성을 동시에 만족시키는 승용차용 타이어 트레드 고무 조성물을 제공하는 것이다.An object of the present invention is to use styrene-butadiene rubber having high glass transition temperature, natural rubber, and urethane rubber having excellent abrasion resistance in a tire tread for a passenger car, by appropriately mixing two or more kinds of incompatible rubbers having excellent characteristics, thereby providing traction and abrasion resistance. It is at the same time to provide a tire tread rubber composition for passenger cars.

본 발명은 타이어 트레드 고무 조성물에 관한 것으로서, 좀더 상세하게는 트랙션, 회전저항 및 내마모성이 우수한 승용차용 트레드 고무 조성물에 관한 것이다.The present invention relates to a tire tread rubber composition, and more particularly, to a tread rubber composition for a passenger car excellent in traction, rolling resistance and wear resistance.

본 발명은 고무 100phr중에 스티렌-부타디엔 고무(S-SBR) 20∼60phr, 천연고무 10∼30phr, 폴리우레탄(PU) 고무 20∼60phr을 블렌드한 원료고무에 충진제로서 카본블랙 30∼60phr과 실리카 20∼70phr을 첨가하므로써 제조되는 것을 특징으로 한다.The present invention is a raw material rubber blended from 20 to 60 phr of styrene-butadiene rubber (S-SBR), 20 to 60 phr of natural rubber, and 20 to 60 phr of polyurethane (PU) rubber in 100 phr of carbon black 30 to 60 phr and silica 20 It is characterized by the fact that it is prepared by adding ~ 70phr.

본 발명에서 원료고무에는 상기한 스티렌-부타디엔 고무와 폴리우레탄 고무 외에 타이어용 고무 조성물에 사용되는 통상의 합성고무 또는 천연고무와 합성고무의 혼합고무를 더 배합할 수도 있다.In the present invention, in addition to the styrene-butadiene rubber and polyurethane rubber, the raw material rubber may further contain a conventional synthetic rubber or a mixed rubber of natural rubber and synthetic rubber used in the rubber composition for tires.

본 발명에서 사용되는 스티렌-부타디엔 고무의 유리전이온도는 -40∼-15℃이고, 폴리우레탄(PU)의 유리전이 온도는 -50∼-30℃로 양자 모두 유리전이온도가 높은 것이 바람직하다.The glass transition temperature of the styrene-butadiene rubber used in the present invention is -40 to -15 ° C, and the glass transition temperature of the polyurethane (PU) is -50 to -30 ° C, and both have high glass transition temperatures.

상기 각 성분의 함량범위와 유리전이온도 범위에서는 웨트 트랙션과 내나모성의 균형을 유지할 수 있다. 이 범위를 벗어나는 경우에는 웨트 트랙션이 좋아지면 내마모성이 나빠지고, 반대로 웨트 트랙션이 나빠지면 내마모성이 좋아지는 트레이드 오프(trade-off) 관계가 발생한다.The content range of each component and the glass transition temperature range can maintain the balance of wet traction and wear resistance. If it is out of this range, the wear resistance worsens when the wet traction improves, and on the contrary, the wear-off relationship occurs when the wet traction worsens.

또한 폴리우레탄과 그외 고무와의 사용비는 3:7∼1:9인 것이 바람직하다.Moreover, it is preferable that the usage ratio of a polyurethane and other rubber | gum is 3: 7-1: 9.

본 발명에서 충진제로서 사용되는 카본블랙은 N2SA가 70∼120ml/g이고, DBP가 105∼190ml/100g 이상인 것이 바람직하고, 카본블랙과 실리카의 총량은 원료고무 100phr에 대해서 40∼90phr을 사용하는 것이 바람직하다.Carbon black used as the filler in the present invention is preferably N 2 SA 70 ~ 120ml / g, DBP 105 ~ 190ml / 100g or more, the total amount of carbon black and silica is used 40 ~ 90phr relative to 100phr of raw rubber It is desirable to.

이하 본 발명을 하기의 실시예 및 비교예에 의하여 보다 구체적으로 설명한다. 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않으며 본 발명의 보호범위를 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following Examples and Comparative Examples. The following examples are merely examples for illustrating the present invention and do not limit the protection scope of the present invention.

실시예 및 비교예Examples and Comparative Examples

하기 표 1에 기재된 조성으로 하여 스티렌 함량과 비닐 비율을 변화시켜 S-SBR을 제조한 후, 그 물성을 측정하였다. 결과는 표 2에 나타내었다.The S-SBR was prepared by changing the styrene content and the vinyl ratio with the composition shown in Table 1, and then measured the physical properties thereof. The results are shown in Table 2.

충진제로서는 카본블랙 N330과 실리카 Z-175를 혼용하여 고무 100phr에 대해서 최대 90phr까지 사용하였다. 또한 실리카의 분산성을 향상시키기 위하여 실란커플링제인 Si-69를 3∼8phr 사용하였다.As a filler, carbon black N330 and silica Z-175 were mixed and used up to 90 phr for 100 phr of rubber. In addition, in order to improve the dispersibility of silica, 3 to 8 phr of Si-69 was used.

배합된 고무 조성물의 웨트 트랙션과 회전저항 특성은 각각 tanδ(0℃), tanδ(70℃)로 측정하였고, 각각 그 값이 클수록 웨트 트랙션이 우수하고 회전저항 특성이 열세하다.The wet traction and rotation resistance characteristics of the blended rubber composition were measured by tan δ (0 ° C.) and tan δ (70 ° C.), respectively. The higher the value, the better the wet traction and the poor rolling resistance properties.

내마모성은 독일공업규격 DIN53516에 준하여 DIN 마모시험으로 평가하였으며, DIN 마모량의 숫자가 작을수록 내마모성이 우수하다.Abrasion resistance was evaluated by DIN abrasion test in accordance with German Industrial Standard DIN53516. The smaller the number of DIN abrasions, the better the abrasion resistance.

종류Kinds 스티렌(중량%)Styrene (% by weight) 비닐(%)vinyl(%) 무늬점도Viscosity 유리전이온도Tg(℃)Glass Transition Temperature Tg (℃) S-SBR 1S-SBR 1 3939 3838 4343 -25-25 S-SBR 2S-SBR 2 3030 3939 9999 -43-43 S-SBR 3S-SBR 3 2121 6262 5050 -32-32 S-SBR 4S-SBR 4 1515 7676 8585 -29-29

(배합 : phr)(Compound: phr) 성분ingredient 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 S-SBR 1S-SBR 2S-SBR 3S-SBR 4폴리우레탄RSS#3N330Z-175Si-696PPDZnO스테아르산방향족오일SCZDPGS-SBR 1S-SBR 2S-SBR 3S-SBR 4 PolyurethaneRSS # 3N330Z-175Si-696PPDZnO Stearic Acid Aromatic Oil SCZDPG -100----503052323821.52-100 ---- 503052323821.52 -50-50--503052323821.52-50-50--503052323821.52 60---2020503052323821.5260 --- 2020503052323821.52 -60--2020503052323821.52-60--2020503052323821.52 --60-2020503052323821.52--60-2020503052323821.52 ---602020503052323821.52--- 602020503052323821.52 tanδ(0℃)tanδ(70℃)DIN 마모인장강도300%모듈러스tanδ (0 ℃) tanδ (70 ℃) DIN wear tensile strength 300% modulus 100100100100100100100100100100 10210110297981021011029798 1031009910210110310099102101 10095931041021009593104102 10397951041031039795104103 10598981051041059898105104

RSS#3 : 천연고무RSS # 3: Natural Rubber

PU : Uniroyal Chemical, 비중 1.06, MS 1+10(100℃)=30∼60PU: Uniroyal Chemical, Specific Gravity 1.06, MS 1 + 10 (100 ℃) = 30 ~ 60

N330 : CCK, N2SA=80㎡/g, DBP=102ml/100gN330: CCK, N 2 SA = 80㎡ / g, DBP = 102ml / 100g

Z-175 : KofraneZ-175: Kofrane

Si-69 : DegussaSi-69: Degussa

6PPD : Flexsis6PPD: Flexsis

CZ : FlexsisCZ: Flexsis

DPG : AkrochemDPG: Akrochem

단일한 S-SBR 고무 조성물(비교예 1)과 비교하여 Tg가 낮은 고무 조성물(S-SBR 2)과 비닐함량과 Tg가 높은 고무 조성물(S-SBR 4)을 블렌딩한 고무 조성물(비교예 2)은 웨트 트랙션이 우수한 반면, 내마모성은 다소 열세였다.Compared to a single S-SBR rubber composition (Comparative Example 1), a rubber composition blended with a low Tg rubber composition (S-SBR 2) and a vinyl content and high Tg rubber composition (S-SBR 4) (Comparative Example 2) ) Had good wet traction, while the wear resistance was somewhat poor.

그러나 Tg가 높은 S-SBR(S-SBR 1, 3, 4)와 내마모성이 우수한 우레탄 고무를 사용하므로써 웨트 트랙션과 내마모성을 동시에 만족시키는 고무 조성물을 제공할 수 있는데 이러한 사실은 실시예 1∼4를 통해서 알 수 있었다.However, by using S-SBR (S-SBR 1, 3, 4) having high Tg and urethane rubber having excellent wear resistance, it is possible to provide a rubber composition satisfying both wet traction and wear resistance. I could see through.

비교예 1의 고무 조성물과 유사한 S-SBR 2 60phr에 우레탄 고무 20phr을 블렌딩한 고무 조성물(실시예 2)은 웨트 트랙션은 비교예 1과 유사하면서도 내마모성은 우수한 것을 알 수 있었다.The rubber composition (Example 2) blended with 20 phr of urethane rubber to 60 phr of S-SBR 2 similar to the rubber composition of Comparative Example 1 was found that the wet traction is similar to Comparative Example 1 but excellent in wear resistance.

그리고 비닐함량이 많고 Tg가 높은 S-SBR과 우레탄 고무를 사용한 고무 조성물(실시예 3, 4)은 딱딱한 S-SBR이 차지하는 고무상에 의하여 높은 웨트 트랙션을 발현하고, 통상적으로 높은 웨트 트랙션으로 손실되기 쉬운 내마모성을 내마모성이 우수한 우레탄 고무를 일정량 첨가함으로써 크게 개선할 수 있었다.And rubber compositions (Examples 3 and 4) using S-SBR and urethane rubber with high vinyl content and high Tg express high wet traction by the rubber phase occupied by hard S-SBR, and are usually lost by high wet traction. Abrasion resistance tends to be greatly improved by adding a certain amount of urethane rubber having excellent abrasion resistance.

이상에서 알 수 있는 바와 같이, 본 발명에 의한 고무 조성물은 트랙션, 회전저항 및 내마모성을 동시에 만족시키는 효과가 있다.As can be seen from the above, the rubber composition according to the present invention has the effect of satisfying traction, rotational resistance and wear resistance at the same time.

Claims (5)

유리전이온도가 -40∼-15℃인 스티렌-부타디엔 고무 20∼60phr, 천연고무 10∼30phr, 유리전이 온도가 -50∼-30℃인 폴리우레탄 20∼60phr을 포함하는 고무 100phr에 대하여 카본블랙 30∼60phr과 실리카 20∼70phr을 배합하여 이루어진 것을 특징으로 하는 승용차용 타이어 트레드 고무 조성물.Carbon black for 100 phr rubber containing 20 to 60 phr of styrene-butadiene rubber having a glass transition temperature of -40 to 15 ° C, 10 to 30 phr of natural rubber and 20 to 60 phr of polyurethane having a glass transition temperature of -50 to -30 ° C. A tire tread rubber composition for passenger cars comprising 30 to 60 phr and 20 to 70 phr of silica. 제 1항에 있어서, 상기 카본블랙은 N2SA가 7∼120ml/g이고, DBP가 105∼190ml/100g 이상인 것을 특징으로 하는 승용차용 타이어 트레드 고무 조성물.The tire tread rubber composition for a passenger car according to claim 1, wherein the carbon black has a N 2 SA of 7 to 120 ml / g and a DBP of 105 to 190 ml / 100 g or more. 제 1항에 있어서, 카본블랙과 실리카의 총량이 고무 100phr에 대해서 50∼90phr의 범위인 것을 특징으로 하는 승용차용 타이어 트레드 고무 조성물.The tire tread rubber composition for a passenger car according to claim 1, wherein the total amount of carbon black and silica is in the range of 50 to 90 phr with respect to 100 phr of rubber. 제 1항에 있어서, 폴리우레탄과 그외 고무와의 사용비는 3:7∼1:9인 것을 특징으로 하는 승용차용 타이어 트레드 고무 조성물.The tire tread rubber composition for a passenger car according to claim 1, wherein the use ratio of polyurethane and other rubber is 3: 7 to 1: 9. 제 1항 내지 제 5항중 어느 한항의 고무 조성물을 트레드에 적용한 것을 특징으로 하는 승용차용 타이어.A tire for a passenger car, wherein the rubber composition according to any one of claims 1 to 5 is applied to a tread.
KR10-2000-0071872A 2000-11-30 2000-11-30 Rubber composition of tire tread for car KR100375634B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923360A (en) * 2014-05-10 2014-07-16 任新年 Abrasion-resistant rubber for tire and preparing method of abrasion-resistant rubber
CN104961931A (en) * 2015-07-14 2015-10-07 常州市盈顺电子有限公司 Polyvinylidene fluoride tire having adsorption and dust removal capacity and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60139729A (en) * 1983-12-27 1985-07-24 Ube Ind Ltd Production of reinforced rubber composition
KR100256422B1 (en) * 1997-11-29 2000-05-15 신형인 A rubber composition of urethane-tire
JP2000302923A (en) * 1998-10-08 2000-10-31 Sumitomo Wiring Syst Ltd Elastomer composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923360A (en) * 2014-05-10 2014-07-16 任新年 Abrasion-resistant rubber for tire and preparing method of abrasion-resistant rubber
CN104961931A (en) * 2015-07-14 2015-10-07 常州市盈顺电子有限公司 Polyvinylidene fluoride tire having adsorption and dust removal capacity and preparation method thereof

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