KR100437689B1 - Tread Rubber Composition - Google Patents
Tread Rubber Composition Download PDFInfo
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- KR100437689B1 KR100437689B1 KR10-2001-0017401A KR20010017401A KR100437689B1 KR 100437689 B1 KR100437689 B1 KR 100437689B1 KR 20010017401 A KR20010017401 A KR 20010017401A KR 100437689 B1 KR100437689 B1 KR 100437689B1
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- rubber
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- benzophenone
- rubber composition
- styrene butadiene
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 57
- 239000005060 rubber Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 27
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012965 benzophenone Substances 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical group C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000012763 reinforcing filler Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000009257 reactivity Effects 0.000 abstract description 7
- 230000006866 deterioration Effects 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000006087 Silane Coupling Agent Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- -1 Alkyl Lithium Chemical compound 0.000 description 1
- REUQOSNMSWLNPD-UHFFFAOYSA-N [2-(diethylamino)phenyl]-phenylmethanone Chemical compound CCN(CC)C1=CC=CC=C1C(=O)C1=CC=CC=C1 REUQOSNMSWLNPD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- 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
-
- 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 트레드 고무조성물에 관한 것이다.The present invention relates to a tread rubber composition.
본 발명의 트레드 고무조성물은 공지의 트레드 고무조성물에 있어서, 벤조페논계 변형제를 사용하여 말단기를 하이드록시기(-OH)로 변형시킨 스티렌 부타디엔 고무를 원료고무로 사용함으로써 트레드 고무조성물 중의 보강성 충진제인 실리카와의 반응성을 향상시켜 마모특성의 하락없이 제동력과 회전 저항성을 향상시킬 수 있는 트레드 오프(Trade off) 성능을 개선시킨 트레드 고무조성물의 제공을 목적으로 한다.In the tread rubber composition of the present invention, in the known tread rubber composition, reinforcement in the tread rubber composition is achieved by using styrene butadiene rubber in which the end group is modified with a hydroxy group (-OH) using a benzophenone-based modifier as a raw material rubber. The purpose of the present invention is to provide a tread rubber composition with improved tread off performance which can improve braking force and rotational resistance without deterioration of wear characteristics by improving reactivity with silica as a filler.
Description
본 발명은 타이어 트레드 고무조성물에 관한 것으로 보다 상세하게는 벤조페논계 변형제를 사용하여 말단기를 하이드록시기(-OH)로 변형시킨 스티렌 부타디엔 고무를 원료고무로 사용함으로써 트레드 고무조성물 중의 보강성 충진제인 실리카와의 반응성을 향상시켜 마모특성의 하락없이 제동력과 회전 저항성을 향상시킬 수 있는 트레드 오프(Trade off) 성능을 개선시킨 트레드 고무조성물에 관한 것이다.The present invention relates to a tire tread rubber composition, and more particularly, reinforcement in a tread rubber composition by using styrene butadiene rubber in which the end group is modified with a hydroxy group (-OH) using a benzophenone-based modifier as a raw material rubber. The present invention relates to a tread rubber composition having improved tread off performance which can improve braking force and rotational resistance without deterioration of wear characteristics by improving reactivity with silica as a filler.
최근 타이어 트레드 개발에 있어서 회전 저항성 감소는 필수적이며 낮은 회전 저항성은 연료소비를 감소시키는데 이는 반드시 웨트 스키드(wet skid) 성능 저하 없이 행해져야만 한다. 타이어의 회전 저항성은 트레드에서의 히스테리시스 손실(Hysterisis Loss)가 주원인으로 결과적으로 낮은 회전 저항성을 위해서는 낮은 히스테리시스(Low Hysterisis)를 가져야만 한다.In recent tire tread developments, reduced rolling resistance is essential and lower rolling resistance reduces fuel consumption, which must be done without degrading wet skid performance. The rolling resistance of the tire is mainly due to the hysteresis loss in the tread and consequently must have low hysteresis for low rolling resistance.
대부분의 트레드 고무화합물 중에서 원료고무는 스티렌 부타디엔 고무(E-SBR)/천연고무(NR)/부타디엔 고무(BR)의 혼합물로 이루어져 있다. E-SBR은 웨트 스키드 저항성에는 유리하나 회전 저항성에 불리하고 NR 및 BR은 회전 저항성에는 유리하나 웨트 스키드 저항성에는 불리하다. 따라서 이러한 일반적인 폴리머 시스템(Polymer System)에서는 웨트 스키드 특성을 희생시키지 않고 회전 저항성을 개선시키는 것은 불가능하다.Among most tread rubber compounds, raw rubber consists of a mixture of styrene butadiene rubber (E-SBR) / natural rubber (NR) / butadiene rubber (BR). E-SBR is advantageous for wet skid resistance but disadvantageous to rotational resistance. NR and BR are advantageous for rotational resistance but disadvantageous to wet skid resistance. Therefore, in such a general polymer system, it is impossible to improve rotational resistance without sacrificing wet skid characteristics.
이러한 단점을 해결하고자 알킬 리튬 개시제(Alkyl Lithium Intiator)를 사용한 E-SBR은 다양한 분자 설계(Molecular Design)를 가능하게 하여 스티렌 함량, 분자량 분포 등의 마이크로 구조를 조절하고 있으며, 또한 최근 보강성 충진제인 실리카와의 반응성을 향상시키기 위해 다양한 기능기를 도입하는 방법이 지속적으로 개발되고 있는 실정이나 아직까지 뚜렷한 결과를 얻지 못하고 있는 실정이다.In order to solve this drawback, E-SBR using Alkyl Lithium Intiator enables various molecular designs to control microstructures such as styrene content and molecular weight distribution. Methods for introducing various functional groups to improve the reactivity with silica is being developed continuously, but the situation has not yet obtained a clear result.
본 발명은 공지의 트레드 고무조성물에 있어서, 폴리머 1 molecular 당 0.3∼1 mol의 벤조페논계 변형제를 사용하여 말단기를 하이드록시기(-OH)로 변형시킨 스티렌 부타디엔 고무를 원료고무로 사용함으로써 트레드 고무조성물 중의 보강성 충진제인 실리카와의 반응성을 향상시켜 마모특성의 하락없이 제동력과 회전 저항성을 향상시킬 수 있는 트레드 오프(Trade off) 성능을 개선시킨 트레드 고무조성물을 제공하는 것을 목적으로 한다.In the known tread rubber composition, a styrene butadiene rubber obtained by modifying a terminal group to a hydroxyl group (-OH) using 0.3 to 1 mol of a benzophenone-based modifier per molecular weight of a polymer is used as a raw material rubber. An object of the present invention is to provide a tread rubber composition having improved tread off performance, which can improve braking force and rotational resistance without deterioration of wear characteristics by improving reactivity with silica as a reinforcing filler in the tread rubber composition.
본 발명의 트레드 고무조성물은 공지의 트레드 고무조성물에 있어서, 폴리머 1 molecular 당 0.3∼1 mol의 벤조페논계 변형제를 사용하여 말단기를 하이드록시기(-OH)로 변형시킨 스티렌 부타디엔 고무를 트레드 고무조성물의 원료고무로 사용한다.The tread rubber composition of the present invention is a tread of styrene butadiene rubber in which a terminal group is modified with a hydroxyl group (-OH) by using 0.3 to 1 mol of a benzophenone-based modifier per molecule of a known tread rubber composition. Used as raw material rubber of rubber composition.
상기에서 벤조페논계 변형제는 4,4'-비스-(디에틸아미노)벤조페논(4,4'-bis-(diethylamino)benzophenone, EAB) 또는 하기 구조식 (1)의 3.3',4.4'-벤조페논테트라카르복실릭 디안하드라이드(3.3',4.4'-Benzophenonetetracarboxylic dianhydride)을 사용한다.The benzophenone-based modifying agent is 4,4'-bis- (diethylamino) benzophenone (4,4'-bis- (diethylamino) benzophenone, EAB) or 3.3 ', 4.4'- of Structural Formula (1) Benzophenonetetracarboxylic dianhydride (3.3 ', 4.4'-Benzophenonetetracarboxylic dianhydride) is used.
......(1) ......(One)
본 발명의 트레드 고무조성물에 있어서, 원료고무는 상기 벤조페논계 변형제에 의해 말단기가 하이드록시기(-OH)로 변형된 스티렌 부타디엔 고무를 단독으로 사용하거나 또는 말단기가 하이드록시기(-OH)로 변형된 스티렌 부타디엔 고무 10∼70 phr과 천연고무 30∼90 phr의 혼합고무 또는 말단기가 하이드록시기(-OH)로 변형된 스티렌 부타디엔 고무 10∼70 phr과 부타디엔 고무 30∼90 phr의 혼합고무를 사용한다.In the tread rubber composition of the present invention, the raw material rubber is a styrene butadiene rubber in which the terminal group is modified to a hydroxyl group (-OH) by the benzophenone-based modifier alone, or the terminal group is a hydroxyl group (-OH). Mixed rubber of 10 to 70 phr of styrene butadiene rubber and 30 to 90 phr of natural rubber or 30 to 90 phr of butadiene rubber of which butadiene is modified to hydroxyl group (-OH) Use
상기의 벤조페논계 변형제를 이용하여 원료고무 중 스티렌 부타디엔 고무의 말단기에 하이드록시기(-OH)를 제공함으로써 원료고무에 극성을 제공하고 이러한 고무의 극성은 보강성 충진제로서 그 사용량이 지속적으로 증가하고 있으며 특히 극성과의 반응성이 좋은 실리카와의 반응성을 증가시켜 최종적으로 제동력과 회전 저항성을 개선시킬 수 있는 트레드 고무조성물을 제공할 수 있게 된다.By using the benzophenone-based modifiers to provide a hydroxyl group (-OH) at the end of the styrene butadiene rubber in the raw material rubber to provide a polarity to the raw material rubber, the polarity of the rubber as a reinforcing filler, its amount of use is continuously In particular, it is possible to provide a tread rubber composition that can improve the braking force and the rolling resistance by increasing the reactivity with silica having good polar reactivity.
결과적으로 벤조페논계 변형제에 의해 원료고무 중 부타디엔 고무의 말단기를 하이드록시기의 극성기로 변형시킴으로써 원료고무와 실리카와의 상호작용을 증가시켜 고가의 실란 커플링제의 사용량을 줄여 기존의 부타디엔 고무를 원료고무로 사용하는 고무조성물에 비해 원가절감도 가능하게 된다.As a result, the benzophenone-based modifier transforms the end group of butadiene rubber in the raw rubber into a polar group of the hydroxyl group, thereby increasing the interaction of the raw rubber with silica, thereby reducing the amount of expensive silane coupling agents and reducing the amount of conventional butadiene rubber. Cost reduction is also possible compared to rubber compositions that use rubber as raw material rubber.
상기에서 스티렌 부타디엔 고무의 말단기를 하이드록시기의 극성기로 변형시키는 벤조페논계 변형제를 폴리머 1 molecular 당 0.3 mol 미만 사용하면 충분한 하이드록시기의 변형이 일어나지 않는 문제점이 있으며, 폴리머 1 molecular 당 1 mol 초과 사용하면 스티렌 부타디엔 고무 말단기의 하이드록시기의 변형율에 대한 차이가 없어 원료비 절감차원에서 벤조페논계 변형제는 폴리머 1 molecular 당 0.3∼1 mol을 유지하는 것이 좋다.When the benzophenone-based modifying agent that transforms the end group of the styrene butadiene rubber into the polar group of the hydroxy group is less than 0.3 mol per polymer, sufficient hydroxyl group deformation does not occur. If it is used more than mol, there is no difference in the deformation rate of the hydroxy group of the styrene butadiene rubber end group, so in order to reduce the raw material cost, it is preferable to maintain 0.3 to 1 mol per polymer per molecule.
벤조페논계 변형제에 의한 스티렌 부타디엔의 고무의 말단기를 하이드록시기를 변화시키는 변형비율은 60∼90%로 하도록 하여 실리카와의 반응성을 향상시킬 수 있도록 한다.The modification ratio of changing the hydroxy group to the end group of the rubber of styrene butadiene by the benzophenone-based modifier is 60 to 90% to improve the reactivity with silica.
특히 본 발명에서 스티렌 부타디엔 고무를 단독으로 원료고무로 사용하는 경우 일반적인 비변형 스티렌 부타디엔 고무 및 말단기의 하이드록시기 변형비율이 30∼40%인 스티렌 부타디엔 고무와 말단기의 하이드록시기 변형비율이 60∼90%인 스티렌 부타디엔 고무를 함께 적용시 특히 제동력에서 우수함을 실험적으로 알게 되었다.In particular, in the present invention, when styrene butadiene rubber alone is used as a raw material rubber, the hydroxy group modification ratio of styrene butadiene rubber and terminal group having a hydroxy group modification ratio of 30 to 40% of general unmodified styrene butadiene rubber and terminal group is Experimental results have shown that the application of styrene butadiene rubber (60-90%) together is particularly good in braking power.
이하 본 발명을 다음의 비교예 및 실시예에 의하여 설명하고자 한다. 그러나 이들이 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following comparative examples and examples. However, these do not limit the technical scope of the present invention.
<비교예>Comparative Example
아래의 표 1과 같은 특성을 갖는 스티렌 부타디엔 고무(S-SBR-1) 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 9.3 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.For 100 phr of styrene butadiene rubber (S-SBR-1) having the characteristics shown in Table 1 below, 59.2 phr of silica used in a known tread rubber composition, 9.3 phr of silane coupling agent, 1.1 phr of vulcanizing agent, and 1.2 phr of accelerator were used. Rubber samples were prepared by vulcanization at 160 ° C. for 30 minutes. Table 2 below shows the amount of the composition used together.
<실시예 1><Example 1>
아래의 표 1과 같은 특성을 갖는 스티렌 부타디엔 고무(S-SBR-2)를 벤조페논계 변형제로 폴리머 1 molecular 당 4,4'-비스-(디에틸아미노)벤조페논(4,4'-bis-(diethylamino)benzophenone, EAB) 0.5 mol을 사용하여 스티렌 부타디엔 고무(S-SBR-2)의 하이드록시기 변형비율을 60% 유지시켰다.4,4'-bis- (diethylamino) benzophenone (4,4'-bis) per molecule of the styrene butadiene rubber (S-SBR-2) having the characteristics shown in Table 1 as a benzophenone-based modifier The hydroxyl group modification ratio of styrene butadiene rubber (S-SBR-2) was maintained at 60% using 0.5 mol of-(diethylamino) benzophenone (EAB).
상기와 같이 하이드록시기 변형비율을 60% 유지한 스티렌 부타디엔 고무(S-SBR-2) 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 9.3 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.100 phr of styrene butadiene rubber (S-SBR-2) having a hydroxyl group modification ratio of 60% as described above, 59.2 phr of silica used in known tread rubber compositions, 9.3 phr of silane coupling agent, 1.1 phr of vulcanizing agent, A rubber specimen was prepared by vulcanizing 1.2 phr of accelerator at 160 ° C. for 30 minutes. Table 2 below shows the amount of the composition used together.
<실시예 2><Example 2>
상기 비교예의 스티렌 부타디엔 고무(S-SBR-1) 70 phr 및 실시예 1의 스티렌부타디엔 고무(S-SBR-2) 30 phr로 구성된 원료고무 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 9.3 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.Silica used in a known tread rubber composition for a raw material rubber composed of 70 phr of styrene butadiene rubber (S-SBR-1) of the comparative example and 30 phr of styrene butadiene rubber (S-SBR-2) of Example 1 59.2 phr, 9.3 phr of silane coupling agent, 1.1 phr of vulcanizing agent, and 1.2 phr of accelerator were vulcanized at 160 ° C. for 30 minutes to prepare a rubber specimen. Table 2 below shows the amount of the composition used together.
<실시예 3><Example 3>
아래의 표 1과 같은 특성을 갖는 스티렌 부타디엔 고무(S-SBR-3)를 벤조페논계 변형제로 폴리머 1 molecular 당 4,4'-비스-(디에틸아미노)벤조페논(4,4'-bis-(diethylamino)benzophenone, EAB) 0.7 mol을 사용하여 스티렌 부타디엔 고무(S-SBR-3)의 하이드록시기 변형비율을 70% 유지시켰다.4,4'-bis- (diethylamino) benzophenone (4,4'-bis) per molecule of the styrene butadiene rubber (S-SBR-3) having the characteristics shown in Table 1 as a benzophenone-based modifier The hydroxyl group ratio of styrene butadiene rubber (S-SBR-3) was maintained at 70% using 0.7 mol of-(diethylamino) benzophenone (EAB).
상기와 같이 하이드록시기 변형비율을 70% 유지한 스티렌 부타디엔 고무(S-SBR-3) 30 phr 및 상기 비교예의 스티렌 부타디엔 고무(S-SBR-1) 70 phr로 구성된 원료고무 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 9.3 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.30 phr of styrene butadiene rubber (S-SBR-3) having a hydroxy group modification ratio of 70% and 70 phr of styrene butadiene rubber of the comparative example (S-SBR-1) as described above is known about 100 phr 59.2 phr of silica, 9.3 phr of silane coupling agent, 1.1 phr of vulcanizing agent, and 1.2 phr of accelerator were used for 30 minutes at 160 ° C. to prepare a rubber specimen. Table 2 below shows the amount of the composition used together.
<실시예 4><Example 4>
아래의 표 1과 같은 특성을 스티렌 부타디엔 고무(S-SBR-4)를 벤조페논계 변형제로 폴리머 1 molecular 당 4,4'-비스-(디에틸아미노)벤조페논(4,4'-bis-(diethylamino)benzophenone, EAB) 0.8 mol을 사용하여 스티렌 부타디엔 고무(S-SBR-4)의 하이드록시기 변형비율을 80% 유지시켰다.4,4'-bis- (diethylamino) benzophenone (4,4'-bis-) per styrene polymer of styrene butadiene rubber (S-SBR-4) as a benzophenone-based modifier The hydroxy group modification ratio of styrene butadiene rubber (S-SBR-4) was maintained at 80% using 0.8 mol of (diethylamino) benzophenone (EAB).
상기와 같이 하이드록시기 변형비율을 80% 유지한 스티렌 부타디엔 고무(S-SBR-4) 30 phr 및 상기 비교예의 스티렌 부타디엔 고무(S-SBR-1) 70 phr로 구성된 원료고무 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 9.3 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.30 phr of styrene butadiene rubber (S-SBR-4) having a hydroxy group modification ratio of 80% and 70 phr of styrene butadiene rubber of the comparative example (S-SBR-1) as described above is known about 100 phr 59.2 phr of silica, 9.3 phr of silane coupling agent, 1.1 phr of vulcanizing agent, and 1.2 phr of accelerator were used for 30 minutes at 160 ° C. to prepare a rubber specimen. Table 2 below shows the amount of the composition used together.
<실시예 5>Example 5
아래의 표 1과 같은 특성을 갖는 스티렌 부타디엔 고무(S-SBR-4)를 벤조페논계 변형제로 폴리머 1 molecular 당 4,4'-비스-(디에틸아미노)벤조페논(4,4'-bis-(diethylamino)benzophenone, EAB) 0.8 mol을 사용하여 스티렌 부타디엔 고무(S-SBR-4)의 하이드록시기 변형비율을 80% 유지시켰다.4,4'-bis- (diethylamino) benzophenone (4,4'-bis) per molecule of the styrene butadiene rubber (S-SBR-4) having the characteristics shown in Table 1 as a benzophenone-based modifier The hydroxyl group ratio of styrene butadiene rubber (S-SBR-4) was maintained at 80% using 0.8 mol of-(diethylamino) benzophenone (EAB).
상기와 같이 하이드록시기 변형비율을 80% 유지한 스티렌 부타디엔 고무(S-SBR-4) 30 phr 및 상기 비교예의 스티렌 부타디엔 고무(S-SBR-1) 70 phr로 구성된 원료고무 100 phr에 대하여 공지의 트레드 고무조성물에 사용하는 실리카 59.2 phr, 실란 커플링제 4.65 phr, 가류제 1.1 phr, 촉진제 1.2 phr을 160℃에서 30분 동안 가류하여 고무시편을 제조하였다. 아래의 표 2에 상기 조성물의 사용량을 정리하여 나타내었다.30 phr of styrene butadiene rubber (S-SBR-4) having a hydroxy group modification ratio of 80% and 70 phr of styrene butadiene rubber of the comparative example (S-SBR-1) as described above is known about 100 phr A rubber specimen was prepared by vulcanizing silica 59.2 phr, silane coupling agent 4.65 phr, vulcanizing agent 1.1 phr, and accelerator 1.2 phr for 30 minutes at 160 ° C. Table 2 below shows the amount of the composition used together.
표 1. S-SBR-1 내지 S-SBR-4의 특성Table 1. Characteristics of S-SBR-1 to S-SBR-4
표 2. 비교예 및 실시예의 고무조성물(단위 : phr)Table 2. Rubber Compositions of Comparative Examples and Examples (Unit: phr)
<시험예><Test Example>
상기 비교예 및 실시예 1∼5에 의해 제조한 고무시편을 ASTM 관련규정에 의하여 인장물성, 피코마모, 피로특성, 발열특성 및 동적특성을 측정하여 그 결과를 아래의 표 3에 정리하여 나타내었다.The rubber specimens prepared in Comparative Examples and Examples 1 to 5 were measured for tensile properties, picowear, fatigue properties, exothermic properties, and dynamic properties according to ASTM-related regulations, and the results are summarized in Table 3 below. .
표 3. 비교예 및 실시예 1∼5 시편의 물성측정 결과Table 3. Results of Measurement of Physical Properties of Comparative Examples and Examples 1 to 5 Specimens
상기 표 3의 결과에서처럼 벤조페논계 변형제를 반응시켜 원료고무 중의 스티렌 부타디엔 고무 말단기를 하이드록시기(-OH)로 변형시킨 것을 원료고무로 사용한 실시예의 고무조성물에 의한 고무시편이 기존의 스티렌 부타디엔 고무를 원료고무로 사용한 비교예의 고무시편과 비교해볼 때 마모특성 및 회전 저항성은 동등 수준을 유지하면서 노면에서의 제동력(Tanδ0℃)이 2∼3배 정도 향상됨을 알 수 있다.As shown in the results of Table 3, the rubber specimens of the rubber composition of the embodiment using the benzophenone-based modifier reacted with the styrene butadiene rubber end group in the raw material rubber to the hydroxyl group (-OH) as the raw material rubber are styrene Compared with the rubber sample of the comparative example using butadiene rubber as the raw material rubber, it can be seen that the braking force (Tanδ0 ° C) on the road surface is improved by 2-3 times while maintaining the same level of abrasion characteristics and rotational resistance.
한편 실시예 5의 경우 실란 커플링제의 양을 50% 감량했음에도 전반적인 물성이 하락되지 않고 동적 특성의 경우 제동력과 회전 저항성이 비교예 대비 향상됨을 보였다. 이러한 특성을 감안하면 실라 커플링제를 감량함으로써 원가절감도 가능하게 된다.On the other hand, in the case of Example 5, even though the amount of the silane coupling agent was reduced by 50%, the overall physical properties did not decrease, and in the case of the dynamic characteristics, the braking force and the rotational resistance were improved compared to the comparative example. In view of these characteristics, cost reduction is also possible by reducing the sila coupling agent.
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| US20100190885A1 (en) * | 2009-01-29 | 2010-07-29 | Kuo-Chih Hua | Tire with rubber component containing silica and use of combination of blocked and unblocked alkoxyorganomercaptosilane coupling agents |
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| US4762870A (en) * | 1987-04-13 | 1988-08-09 | The Firestone Tire & Rubber Company | Rubber compositions modified with hydroxy-benz-imidazole oxides |
| US4822844A (en) * | 1987-02-24 | 1989-04-18 | The Yokohama Rubber Co., Ltd. | Rubber compositions |
| US5194513A (en) * | 1990-08-28 | 1993-03-16 | The Goodyear Tire & Rubber Company | Rubber compositions containing a hydroxy aryl substituted maleamic acid |
| JPH06270603A (en) * | 1993-03-18 | 1994-09-27 | Bridgestone Corp | Pneumatic tyre |
| KR960022742A (en) * | 1994-12-29 | 1996-07-18 | 남일 | Rubber composition for tire tread |
| US6057397A (en) * | 1995-01-23 | 2000-05-02 | Nippon Zeon Co., Ltd. | Rubber composition and process for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4822844A (en) * | 1987-02-24 | 1989-04-18 | The Yokohama Rubber Co., Ltd. | Rubber compositions |
| US4762870A (en) * | 1987-04-13 | 1988-08-09 | The Firestone Tire & Rubber Company | Rubber compositions modified with hydroxy-benz-imidazole oxides |
| US5194513A (en) * | 1990-08-28 | 1993-03-16 | The Goodyear Tire & Rubber Company | Rubber compositions containing a hydroxy aryl substituted maleamic acid |
| JPH06270603A (en) * | 1993-03-18 | 1994-09-27 | Bridgestone Corp | Pneumatic tyre |
| KR960022742A (en) * | 1994-12-29 | 1996-07-18 | 남일 | Rubber composition for tire tread |
| US6057397A (en) * | 1995-01-23 | 2000-05-02 | Nippon Zeon Co., Ltd. | Rubber composition and process for preparing the same |
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