• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention is a tread rubber composition for tires to which silica is applied as a reinforcing filler, and includes a tread rubber composition containing 1 to 5 parts by weight of pipepiridinylsilane based on 100 parts by weight of the raw material rubber. According to the above configuration, it is possible to minimize defects caused by alcohol and water generated during the reaction of the silica and the silane coupling agent, and to simultaneously improve the strength, wear resistance, and low fuel consumption characteristics, which are mechanical properties.
    公开号:KR20040000829A
    申请号:KR1020020035794
    申请日:2002-06-25
    公开日:2004-01-07
    发明作者:박병호
    申请人:금호타이어 주식회사；
    IPC主号:
    专利说明:

    Compound Recipes of Silica Reinforced Rubber for Tread}
    [1] The present invention relates to a tread rubber composition comprising 1 to 5 parts by weight of tripiperidinylsilane with respect to 100 parts by weight of raw rubber as a tread rubber composition for applying silica as a reinforcing filler.
    [2] In the automotive industry, regulations on resource conservation and environmental pollution are tightening. In the tire industry, improving wear resistance while having low fuel consumption while reducing vibration resistance is one of the most important tasks. As a solution to this problem, it is widely known that the rolling resistance of a tire can be reduced by using silica instead of carbon black, which is a conventional reinforcing filler, in a tire tread formulation. Recently, an alkyl silane system (Japanese Patent Application Laid-Open No. Hei 1-88501) or an amino group substituent (Japanese Patent Application Laid-Open Publication No. 5-23286) has been introduced as a rubber material for tires, which has affinity with silica and diene rubber. Rubber compounds for tire treads have been introduced to improve heat generation and low fuel consumption while maintaining.
    [3] Precipitated silica is a low-cost reinforcing filler that replaces carbon black used as a reinforcing agent in the tire industry, and its use has been increasing recently, and high temperature viscoelastic properties, which exhibit low fuel efficiency compared to carbon black using silane coupling agents, have been used. It is widely used to lower the characteristic value of the tangent delta. However, silica has a problem in that its affinity with rubber, known as a nonpolar system, is poor due to the polarity and hydrophilic property of the surface, and the silica particles are cohesive and the viscosity is increased so that workability is difficult.
    [4] In order to improve the reinforcement by the reinforcing agent, a silane coupling agent is used to improve the bonding force between the rubber and the reinforcing agent. Coupling agents commonly used in the tire industry include γ-mercaptopropyltrimethoxysilane and bis (3-triethoxysilyl) propyltetrasulfide and γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide. However, as a result of the reaction with silica in the compounding process of these coupling agents, alcohol or water is generated. These are the main factors that significantly reduce the dimensional stability of the extrudate due to the generation of pores by preliminary vulcanization and foaming during the process, especially in the extrusion process. Bubbles in the post-crosslinked product act as a major factor of the drop in properties.
    [5] Accordingly, the present invention is caused by ethanol or water generated as a by-product when reacting with a silane coupling agent, which is a crosslinking agent, by applying tripiperidinylsilane (TPS) to a rubber composition containing silica as a tread rubber compound for tires. It is an object of the present invention to provide a rubber composition which minimizes defects and simultaneously improves mechanical strength, tensile strength and wear resistance and low fuel consumption.
    [6] The present invention is a tread rubber composition for applying a silica as a reinforcing filler, and includes a tread rubber composition containing 1 to 5 parts by weight of tripiperidinylsilane with respect to 100 parts by weight of raw material rubber.
    [7] Tripiperidinylsilane is a substance that can be obtained by reacting an excess of piperidine (C 5 H 11 N) with trichlorosilane (SiHCl 3 ).
    [8] SiHCl 3 + C 5 H 11 N (excess) → (C 5 H 10 N) 3 -SiH
    [9] The tripiperidinylsilane reacts with alcohol or water generated during the reaction of the silica with the silane coupling agent in the rubber compound to react with piperidine and trihydroxysilane (Si (OH) 3 ) or triethoxysilane (Si (OCH 2 CH 3 ) 3 ).
    [10] When described in more detail with reference to the following structural formula.
    [11] (C 5 H 10 N) 3 -SiH + H 2 O → 3C 5 H 11 N + Si (OH) 3
    [12] (C 5 H 10 N) 3 -SiH + CH 3 CH 2 OH → 3C 5 H 11 N + Si (OCH 2 CH 3 ) 3
    [13] As can be seen from the above scheme, tripiperidinylsilane serves to remove by-product alcohol and water. Accordingly, defects or bubbles in the extrudate and post-vulcanized rubber compound can be significantly reduced to ensure dimensional stability of the extrudate. In addition, piperidine produced as a by-product acts as a reactive activator, and trihydroxysilane and triethoxysilane act as coupling agents, contributing to remarkably improving vulcanization properties.
    [14] The tread rubber composition of the present invention comprises a known composition. The raw material rubber is not particularly limited as the natural rubber or the synthetic rubber alone or as a mixed rubber of natural rubber and synthetic rubber.
    [15] The reinforcing filler may generally be added in an amount of 10 to 80 parts by weight and a silane coupling agent in an amount of 0.8 to 10 parts by weight based on 100 parts by weight of the raw material rubber. Preferably, the composition ratio of the tripiperidinyl silane to the silane coupling agent is 0.5 to 1.
    [16] The tripiperidinyl silane is added in an amount of 1 to 5 parts by weight, preferably 1 to 4.5 parts by weight, based on 100 parts by weight of the raw material rubber. If the amount is less than 1 part by weight, it is not preferable in view of the blendability and uniformity of the blend, and if it is more than 5 parts by weight, it may act as a softener to lower the physical properties.
    [17] The blending process of the tread rubber composition prepared with the composition comprises first preparing a primary master batch containing silica by mixing silica or silica / carbon black mixture and silane coupling agent as a reinforcing agent to the raw rubber; A second master batch manufacturing step of adding tripiperidinylsilane together with known additives such as zinc oxide, preservative, and activator to the first master batch composition; And adding a vulcanizing agent, accelerator in the process of final mixing.
    [18] When carbon black is added during the blending process, the carbon black is not particularly limited, but is preferably selected from 60 to 150 mg / g of iodine adsorption and 80 to 150 cm 3/100 g of DBP oil absorption. An example of satisfying the above conditions is N220, it is preferable to add 30 to 60 parts by weight based on 100 parts by weight of the raw material rubber.
    [19] The silica is preferably selected from BET 100 to 180 m 2 / g, CTAB 100 to 200 m 2 / g, DBP 150 to 250 cm 3/100 g, and more preferably, the adsorption average area is about 8500 nm 2 before blending and 7000 to about blended. 8400nm 2 is good.
    [20] Hereinafter, the content of the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention, and the scope of the present invention should not be construed as being limited to these embodiments.
    [21] Example 1 Preparation of Rubber Composition
    [22] By combining the composition shown in Table 1 to prepare a tread rubber composition according to a known example, the measurement results of the physical properties are shown in Table 2.
    [23] <Table 1> Rubber composition (unit: parts by weight)
    [24] FurtheranceR-1R-2R-3R-4R-5 SBR100100100100100 Silica3030303030 N2203030303030 Si-692.42.42.42.42.4 TPS01.53.04.56.0 Other * 1010101010 CZ1.01.01.01.01.0 S1.81.81.81.81.8 DPG0.50.50.50.50.5
    [25] * 3 parts by weight of zinc, 1 part by weight of stearic acid, a defoaming agent (RD / 6C / wax) = 2/2/2 parts by weight
    [26] <Table 2> Property Measurement Results
    [27] FurtheranceR-1R-2R-3R-4R-5 Pattern test (125 degrees Celsius)Scorch time (minutes)10.110.411.011.211.4 Rheometer Test (180 ° C) End Cure (min)8.38.28.18.07.9 Torque (lbs.in)11.410.810.210.09.8 Torque (lbs.in)36.637.140.139.237.5 Tension (kgf / cm 2 )256260261260267 Elongation (%)520522521533549 Tan Delta ** (60 ℃)0.1010.9410.9320.9010.9109 Cut and Chip (g)2.6642.5472.3572.3592.621 Wear resistant ♩ 0.4230.4160.3890.3130.417 Dimensional stability ♪ 118110106105109
    [28] ** Tan delta (60 ℃): It is a value that can predict the low fuel efficiency characteristics of tire performance, measured by Elastomerics (Model 1332) (frequency: 11Hz, average level: 10%, amplitude: 5%).
    [29] ♩ Wear-resistance: The wear resistance was evaluated by using PICO test equipment. It shows the amount lost after 80 rotations.
    [30] Dimensional Stability: Expressed as the swelling ratio of the extrudate to the die diameter ratio, the larger the value, the lower the dimensional stability.
    [31] As can be seen from the experimental results, it is shown that the application of tripiperidinyl silane accelerates the vulcanization rate of rubber without significantly affecting the scorch properties. This is believed to be because piperidine activates the vulcanization reaction. Compared with R-1 without using tripiperidinyl silane, R-2 and R-3 with 1.5 parts by weight and 3 parts by weight of tripiperidinyl silane had 60 ° C. tandelta values of 0.941 and 0.931 as R-1. It is significantly lower than. More interesting results were found to be excellent in low fuel efficiency, wear resistance, tensile strength and dimensional stability.
    [32] Compared with R-5 with 6 parts by weight of tripiperidinyl silane and the appropriate amount of R-3, the low fuel consumption characteristics are excellent, but the wear resistance and tensile strength are decreased. These phenomena show that the excess amount acts as a plasticizer when applying more than an appropriate amount of pipepiridinyl silane, the physical property improvement effect is no longer seen.
    [33] According to the present invention, it is possible to minimize defects caused by alcohol and water generated during the reaction of the silica and the silane coupling agent, and to simultaneously improve the strength, wear resistance, and low fuel consumption characteristics, which are mechanical properties.
    权利要求:
    Claims (3)
    [1" claim-type="Currently amended] In a tread rubber composition for a tire containing silica and a silane coupling agent,
    A tread rubber composition comprising 1 to 5 parts by weight of tripiperidinylsilane based on 100 parts by weight of raw rubber
    [2" claim-type="Currently amended] The tread rubber composition according to claim 1, comprising 10 to 80 parts by weight of silica and 0.8 to 10 parts by weight of a silane coupling agent with respect to 100 parts by weight of the raw material rubber.
    [3" claim-type="Currently amended] The tread rubber composition according to claim 1, wherein the composition ratio of the pipepidinedinsilane to the silane coupling agent is 0.5 to 1.
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    同族专利:
    公开号 | 公开日
    KR100476013B1|2005-03-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-06-25|Application filed by 금호타이어 주식회사
    2002-06-25|Priority to KR10-2002-0035794A
    2004-01-07|Publication of KR20040000829A
    2005-03-10|Application granted
    2005-03-10|Publication of KR100476013B1
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2002-0035794A|KR100476013B1|2002-06-25|2002-06-25|Compound Recipes of Silica Reinforced Rubber for Tread|
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