JPH01144434A - Rubber composition for tire - Google Patents
Rubber composition for tireInfo
- Publication number
- JPH01144434A JPH01144434A JP62303698A JP30369887A JPH01144434A JP H01144434 A JPH01144434 A JP H01144434A JP 62303698 A JP62303698 A JP 62303698A JP 30369887 A JP30369887 A JP 30369887A JP H01144434 A JPH01144434 A JP H01144434A
- Authority
- JP
- Japan
- Prior art keywords
- carbon black
- rubber
- rubber composition
- amount
- dst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 239000006229 carbon black Substances 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000010521 absorption reaction Methods 0.000 claims abstract description 6
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 4
- 235000019241 carbon black Nutrition 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 9
- 230000020169 heat generation Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は、自動、車用タイヤ （乗用車用タイヤ、バス
・トラック用タイヤ等）のトレッド部、サイドトレッド
部、ベーストレッド部等のゴム質として利用し得る発熱
性と耐摩耗性とを改良したタイヤ用ゴム組成物に関する
。[Detailed Description of the Invention] [Technical Field of the Invention] The present invention provides a rubber material for the tread portion, side tread portion, base tread portion, etc. of automobile tires (passenger car tires, bus/truck tires, etc.). The present invention relates to a usable rubber composition for tires with improved heat generation properties and wear resistance.
従来、タイヤ用ゴム組成物の耐摩耗性を改善する方法と
して、■粒子径の小さい、比表面積の大きいカーボンブ
ラックを使用したり、■カーボンブラック配合量を多く
したりする方法がとられている。しかしながら、用いる
カーボンブラックの粒子径が小さくなるかカーボンブラ
ック配合量を多くすると、通常、ゴム組成物中でのカー
ボンブラックの分散が悪くなったり、カーボンブラック
充填ゴム組成物の動的特性、特に発熱性を増大させ、ヒ
ステリシスロスに基づく配合ゴムの劣化促進をうながし
、性能低下をもたらす。Conventionally, the methods of improving the wear resistance of tire rubber compositions have been to use carbon black with a small particle size and large specific surface area, or to increase the amount of carbon black blended. . However, as the particle size of the carbon black used becomes smaller or the amount of carbon black added is increased, the dispersion of carbon black in the rubber composition usually deteriorates, and the dynamic properties of the carbon black-filled rubber composition, especially the exothermic properties, are affected. This increases the properties of the compounded rubber due to hysteresis loss, leading to a decline in performance.
また、カーボンブラック充填ゴム組成物の動的特性に対
して、カーボンブラックの粒子径（比表面積）以外にい
わゆる凝集体の大きさ（アグリゲートサイズ）及びその
分布が大きな影響を与えることも近年明らかになってき
た（特開昭５９−８６６３６号公報、特開昭５９−８６
６４１号公報）。In addition, it has recently become clear that, in addition to the particle size (specific surface area) of carbon black, the so-called aggregate size and its distribution have a large effect on the dynamic properties of carbon black-filled rubber compositions. (Japanese Unexamined Patent Publication No. 59-86636, Japanese Unexamined Patent Publication No. 59-86
Publication No. 641).
しかし、カーボンブラックの最多頻度モード径（Ｄｓｔ
）が大きければ発熱性の低いゴム組成物を与える一方で
耐摩耗性の低下をきたし、このため動的特性と耐摩耗性
とを兼備することはアグリゲートサイズ、分布の制御の
みでは殆んど不可能であった。However, the most frequent mode diameter (Dst) of carbon black
) is large, a rubber composition with low heat build-up can be obtained, but the abrasion resistance decreases, and for this reason, it is almost impossible to achieve both dynamic properties and abrasion resistance by controlling the aggregate size and distribution alone. It was impossible.
本発明者らは、タイヤ用ゴム組成物の耐摩耗性を向上さ
せる目的で耐摩耗性とカーボンブラックの物理的緒特性
との関連について種々研究を重ねた結果、カーボンブラ
ックの発生水素量と凝集体のストークスモード径が特定
な関係にある場合に、発熱性を低位に保持しながら飛躍
的に耐摩耗性の向上が図られることを発見し、本発明に
達するに至った。The present inventors have conducted various studies on the relationship between abrasion resistance and the physical characteristics of carbon black in order to improve the abrasion resistance of rubber compositions for tires. The present inventors have discovered that when the Stokes mode diameters of the aggregate have a specific relationship, wear resistance can be dramatically improved while heat generation is kept at a low level, leading to the present invention.
したがって、本発明は、低発熱性を有すると共に耐摩耗
性に優れたタイヤ用ゴム組成物を提供することを目的と
する。Therefore, an object of the present invention is to provide a rubber composition for tires that has low heat build-up and excellent wear resistance.
このため、本発明は、窒素吸着比表面積（Ｎ ｚＳＡ）
１００〜２００ｍ”／ｇ 、 ２４Ｍ４ＤＢＰ吸油量
９０〜ｂ１００ｇの特性領域にあって、かつ１３００℃
でカーボンブラックＩｇ当りに発生する水素ｆｆ１（Ｈ
ｚ）が■で表わして遠心沈降法による凝集体分布の最多
頻度モード径（Ｄｓｔ ｍμ）と下記式の関係を有する
カーボンブラックを、ゴム１００重量部に対して２０〜
１００重量部配合してなることを特徴とするタイヤ用ゴ
ム組成物を要旨とするものである。For this reason, the present invention provides nitrogen adsorption specific surface area (NzSA)
100~200m''/g, 24M4DBP oil absorption is in the characteristic range of 90~b100g, and 1300℃
Hydrogen ff1 (H
z) is represented by ■ and has the relationship of the most frequent mode diameter (Dst mμ) of aggregate distribution by centrifugal sedimentation method with the following formula, at 20 to 20 parts by weight per 100 parts by weight of rubber.
The gist of the present invention is a rubber composition for tires characterized by containing 100 parts by weight of the rubber composition.
Ｈｚ≧３．７４−０．０２（Ｄｓｔ） （ｍｇ／ｇ）以
下、本発明の構成につき詳しく説明する。Hz≧3.74-0.02 (Dst) (mg/g) Hereinafter, the structure of the present invention will be explained in detail.
（１１カーボンブラック。(11 carbon black.
ここで用いるカーボンブラックは、■窒素吸着比表面積
（ＮＡＳＡ）が１００〜２０Ｏｎ＋”／ｇ ”？：！あ
り、■２４Ｍ４０ＢＰ吸油量９０〜１２０ｍ１／１００
ｇであって、０１３００℃でカーボンブラック中から発
生する水素量が、カーボンブラック１ｇ当りに換算した
量を■で表わした場合、凝集体分布の最多頻度モード径
Ｄｓｔとの関係で３．７４−０．０２（Ｄｓｔ）式によ
り算出される値以上であること。The carbon black used here has a nitrogen adsorption specific surface area (NASA) of 100 to 20 On+"/g"? :! Yes, ■24M40BP oil absorption 90-120m1/100
g, and the amount of hydrogen generated from carbon black at 0.1300°C is expressed as . The value must be greater than or equal to the value calculated by the 0.02 (Dst) formula.
カーボンブラックから発生する水素は、粒子径やストラ
フチャーとは異なる別個の特性要素で、カーボンブラッ
ク表面とゴムとの吸着を引き起こす活性点としての役割
を果たすものとみられる。カーボンブラックは、高温気
流中での原料炭化水素油の熱分解、脱水素重縮合を経て
、溶融凝集化から炭化のプロセスで生成される。Hydrogen generated from carbon black is a separate characteristic element different from particle size and stracture, and appears to play a role as an active site that causes adsorption between the carbon black surface and rubber. Carbon black is produced through thermal decomposition of raw hydrocarbon oil in a high-temperature air stream, dehydrogenation polycondensation, and a process of melt aggregation and carbonization.
この場合、脱水素重縮合後の残存水素量を多くすること
により発生水素量を増加させることができることから、
発生水素量の多いカーボンブラックは炭素微結晶構造の
形成が不十分な状態にあり、構成する粒子表面が化学的
活性ラジラルに富む状態を示している。したがって、カ
ーボンブラックから発生する水素量の多少はカーボンブ
ラックの生成過程における反応時間、反応温度と密接に
関係している。その結果、カーボンブラック凝集体の最
多頻度モード径（Ｄｓ ｔ）と相関する関係にある。本
発明では、カーボンブラックからの発生水素量を３．７
４−０．０２（Ｄｓｔ）式により算出される値以上に設
定することにより、表面活性度が高い独特の表面性状の
付与が可能となる。ここで、最多頻度モード径（Ｄｓｔ
）とは、第１図に示されるように、凝集体分布のピーク
における凝集体モード径をいう。In this case, since the amount of hydrogen generated can be increased by increasing the amount of hydrogen remaining after dehydrogenation polycondensation,
Carbon black that generates a large amount of hydrogen has a carbon microcrystalline structure that is insufficiently formed, and the particle surfaces thereof are rich in chemically active radicals. Therefore, the amount of hydrogen generated from carbon black is closely related to the reaction time and reaction temperature in the carbon black production process. As a result, there is a correlation with the most frequent mode diameter (Dst) of carbon black aggregates. In the present invention, the amount of hydrogen generated from carbon black is 3.7
By setting the value to be greater than or equal to the value calculated by the formula 4-0.02 (Dst), it is possible to provide a unique surface texture with high surface activity. Here, the most frequent mode diameter (Dst
) refers to the aggregate mode diameter at the peak of the aggregate distribution, as shown in FIG.
上記のようにカーボンブラックの発生水素量を特定する
ことによりポリマー成分との界面反応が十分に進行し、
発熱の増加を伴わずに耐摩耗性の飛躍的向上がはかられ
る。つまり、カーボンブラック凝集体の最多頻度モード
径（Ｄｓｔ）が同一の場合は、相対的に高い耐摩耗性を
付与することが可能となる。これらの効果は、タイヤの
キャップトレッド用等の優れた耐摩耗性の要求されるゴ
ム組成物において著しく、特に窒素吸着比表面積が１０
０〜２０抛”／ｇのカーボンブラックに適用した場合に
実用的効果が大きい。As mentioned above, by specifying the amount of hydrogen generated by carbon black, the interfacial reaction with the polymer component will proceed sufficiently.
A dramatic improvement in wear resistance can be achieved without an increase in heat generation. In other words, when the most frequent mode diameters (Dst) of carbon black aggregates are the same, relatively high wear resistance can be imparted. These effects are remarkable in rubber compositions that require excellent wear resistance, such as those for tire cap treads, and are especially noticeable in rubber compositions that require excellent wear resistance, such as those used in tire cap treads.
The practical effect is great when applied to carbon black of 0 to 20"/g.
本発明のカーボンブラックにおいて、窒素吸着比表面積
が１００ｍ”７ｇ未満の場合には耐摩耗性が低くなり、
２００＋ｍ”／ｇを越すと耐発熱性、加工性の大幅な低
下が起って実用的でない。In the carbon black of the present invention, when the nitrogen adsorption specific surface area is less than 100 m''7g, the wear resistance becomes low.
If it exceeds 200+m''/g, heat resistance and processability will be significantly reduced, making it impractical.
また、２４Ｍ４０ＢＰ吸油量を９０〜１２０ｍ１／１０
０ｇとする理由は、９０ｍ１／１００ｇ未満では耐摩耗
性が十分でなく、一方、１２０ｍ１／１００ｇ超では配
合ゴムの弾性率が上昇し、例えば、トレンド部などに用
いた場合には耐チッピング性が低下するからである。し
たがって、耐発熱性の低下を招かないで耐摩耗性の向上
をもたらすゴム組成物を得るには、上記■〜■を同時に
満足するカーボンブラック特性が必要であり、いずれか
１つでも満たされない場合には両特性を兼備することは
できない。In addition, 24M40BP oil absorption amount is 90~120m1/10
The reason why it is set at 0g is that if it is less than 90m1/100g, the abrasion resistance will not be sufficient, whereas if it exceeds 120m1/100g, the elastic modulus of the compounded rubber will increase, and for example, if it is used in trend parts, the chipping resistance will be poor. This is because it decreases. Therefore, in order to obtain a rubber composition that improves abrasion resistance without causing a decrease in heat resistance, it is necessary to have carbon black properties that simultaneously satisfy the above ■~■, and if any one of them is not satisfied, cannot have both characteristics.
（２） ゴム。(2) Rubber.
ゴムとしては、例えば、天然ゴム、スチレン−ブタジェ
ン共重合体ゴム、ポリブタジェンゴム、合成ポリブタジ
ェンゴム、ブチルゴムなどのタイヤ用ゴムとして通常用
いられる各種のゴムを単独あるいはブレンドして用いる
ことができる。As the rubber, for example, various rubbers commonly used as tire rubber such as natural rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, synthetic polybutadiene rubber, and butyl rubber can be used alone or in a blend. can.
上記カーボンブラックの配合割合は、ゴム１００重量部
に対して２０重量部未満では目的とする高補強性のゴム
組成物が得られず、一方、１００重量部超では耐発熱性
の大幅な低下が起って配合ゴムの劣化促進をうながし性
能低下を引き起こす。If the blending ratio of carbon black is less than 20 parts by weight based on 100 parts by weight of rubber, the desired highly reinforcing rubber composition cannot be obtained, whereas if it exceeds 100 parts by weight, the heat resistance will be significantly reduced. This accelerates the deterioration of compounded rubber and causes a decline in performance.
本発明のゴム組成物は、カーボンブラックの他に必要に
応じて、例えば、硫黄等の加硫剤、加硫促進剤、加硫促
進助剤、老化防止剤、粘着付与剤、軟化剤、充填剤等を
含有してもよい。In addition to carbon black, the rubber composition of the present invention may contain, if necessary, a vulcanizing agent such as sulfur, a vulcanization accelerator, a vulcanization accelerating aid, an anti-aging agent, a tackifier, a softener, a filler, etc. It may also contain agents etc.
以下に実施例および比較例を示す。Examples and comparative examples are shown below.
実施例、比較例
第１表に示される配合内容（重量部、カーボンブラック
以外の成分は全て（共通）で種々のゴム組成物（実施例
１〜４、比較例１〜６）を作製した。Examples and Comparative Examples Various rubber compositions (Examples 1 to 4 and Comparative Examples 1 to 6) were prepared using the formulation contents (parts by weight, all components other than carbon black were common) shown in Table 1.
この場合に用いるそれぞれのカーボンブラック特性を第
１表に示す。なお、その特性値は下記の測定方法（１）
〜（４）によるものである。Table 1 shows the properties of each carbon black used in this case. The characteristic values are measured using the following method (1).
This is based on (4).
（１） 窒素吸着比表面積（Ｎ、ＳＡ）。(1) Nitrogen adsorption specific surface area (N, SA).
ＡＳＴＭ−０３０３７（１９８４年）“５ｔａｎｄａｒ
ｄ Ｍｅｔｈｏｄｓ ｏｆＴｅｓｔｉｎｇ Ｃａｒｂｏ
ｎ Ｂｌａｃｋ−５ｕｒｆａｃｅ Ａｒｅａｂｙ Ｎ１
ｔｒｏｑｅｎ Ａｄｓｏｒｐｔｉｏｎ ”Ｍｏｔｈｏｄ
、 Ｃによる。ASTM-03037 (1984) “5tandar
dMethods ofTesting Carbo
n Black-5surface Area N1
troquen Adsorption ”Mothod
, by C.
（２１２４Ｍ ４０ Ｂ Ｐ吸油量。(2124M 40B P oil absorption.
ＡＳＴＭ−０３４９３（１９８４年）による。According to ASTM-03493 (1984).
（３）発生水素量。(3) Amount of hydrogen generated.
カーボンブラックを次に示す条件で、１３００℃で発生
する水素量をカーボンブラック１ｇあたりに、換算した
■数で表わしたものである。測定は、まず、カーボンブ
ラックのｌθ■を高温熱分解装置（ソリッド・パイロラ
イザー）を用いて１３００℃で１２０秒（２０秒×６回
）熱分解させ、接続したガスクロマトグラフィー（品性
ＧＣ−９Ａ）に発生ガスを導入する。この際、キャリア
ガスとして窒素ガスを一定流量（３０ｍｌ／分）で流入
させる。The amount of hydrogen generated at 1300° C. for carbon black under the following conditions is expressed as a number of square meters per gram of carbon black. In the measurement, carbon black lθ■ was first thermally decomposed at 1300°C for 120 seconds (20 seconds x 6 times) using a high-temperature pyrolyzer (solid pyrolyzer), and then subjected to gas chromatography (quality GC- Introduce generated gas to 9A). At this time, nitrogen gas is introduced as a carrier gas at a constant flow rate (30 ml/min).
ガスクロマトグラフィーの分析方法はＴＣＤ方式を用い
、条件は次の通りである。The gas chromatography analysis method used the TCD method, and the conditions were as follows.
カラム：モレキュラシーブ、５Ａ、 ３ｍφ×３１ｍ試
料注入部温度：１００℃
カラム温度：４０℃
キャリアーガス：窒素ガス、３０ｎ＋１／分発生水素量
の定量はあらかじめ所定量（ｉｃｅの水素ガスに空気を
混合して１１とし、そのうちのｌ ｃｃを使用）の水素
量の面積−重量（ｍｇ）を求めておき、面積法によって
求めた。Column: Molecular sieve, 5A, 3 mφ x 31 m Sample injection part temperature: 100°C Column temperature: 40°C Carrier gas: Nitrogen gas, 30n+1/min To determine the amount of hydrogen generated, mix a predetermined amount (ice hydrogen gas with air). 11, of which 1 cc was used), the area-weight (mg) of the hydrogen amount was determined by the area method.
（４）カーボンブラック凝集体の最多頻度モード径（Ｄ
ｓ ｔ）。(4) Most frequent mode diameter (D
s t).
ジョイス・レーブル社製ディスク・セントリフヱージを
使用し、遠心沈降法により次の方法で測定を行った。The measurement was carried out by the centrifugal sedimentation method using a disk centrifage manufactured by Joyce Lable in the following manner.
すなわち、ＪＩＳ Ｋ ６２２１ （１９８２） ５法
により乾燥して精秤したカーボンブラックを、エタノー
ル２０％水溶液に加え、カーボンブラック濃度を０．０
０５重量％にした後、超音波で十分に分散させて試料と
した。一方、ディスク・セントフリュージの回転速度を
８００Ｏｒｐｍに設定し、スピン液（蒸溜水）１０＋ｓ
ｌをこのディスク・セントリフユージに加えたのちに０
．５＋＋１のバッファー液（２０容量％エタノール水溶
液）を注入した。ついで、これを試料溶液０．５〜１．
Ｏｓｌを注射器で加え、遠心沈降を開始させ、光電沈降
法により第１図に示すような凝集体分布曲線を作成した
。この曲線から口ｓｔを求めた。That is, carbon black that had been dried and accurately weighed according to JIS K 6221 (1982) 5 method was added to a 20% aqueous ethanol solution to bring the carbon black concentration to 0.0.
After adjusting the concentration to 0.5% by weight, the sample was sufficiently dispersed using ultrasonic waves. On the other hand, set the rotation speed of the disk centrifuge to 800 rpm, and use the spin liquid (distilled water) for 10 + s.
After adding l to this disk centrifuge, 0
．． 5++1 buffer solution (20 volume % ethanol aqueous solution) was injected. Then, add this sample solution to 0.5 to 1.
Osl was added with a syringe, centrifugal sedimentation was started, and an aggregate distribution curve as shown in FIG. 1 was created by photoelectroprecipitation. The mouth st was determined from this curve.
第１表にゴム組成物の加硫物性を示す。この加硫物性は
、各種カーボンブラックを配合したゴム組成物を混練し
、１４８℃で３０分間プレス加硫して得られた加硫物に
ついて、粘弾性特性、ランボーン摩耗を評価した結果を
記したものである。Table 1 shows the vulcanized physical properties of the rubber composition. The physical properties of this vulcanization are the results of evaluating the viscoelastic properties and Lambourne wear of the vulcanizate obtained by kneading a rubber composition blended with various carbon blacks and press vulcanizing it at 148°C for 30 minutes. It is something.
発熱性の代替指標であるｔａｎδについては、粘弾性ス
ペクトロメーター（岩本製作所■製）を用いて温度１０
０℃、歪率ｌＯ±２％、周波数２０１１ｚで測定した値
を用いた。配合ｌを１００として指数で示した。値が小
さい程良好である。Regarding tanδ, which is an alternative index of exothermicity, a viscoelastic spectrometer (manufactured by Iwamoto Seisakusho ■) was used at a temperature of 10
The values measured at 0° C., strain rate lO±2%, and frequency 2011z were used. It is expressed as an index with the formulation l being 100. The smaller the value, the better.
ランボーン摩耗については、ランボーン式摩耗試験機に
より試験片円板と研磨円板とを角度をつけずに接触回転
させ、このとき試験片との間にスリップを生じさせ、単
位時間当りの試験片の摩耗量を測定する。（配合ｌの摩
耗量）×１００÷（試料の摩耗量）で表示。値が大きい
ほど良好。Regarding Lambourn wear, a test piece disk and a polishing disk are rotated in contact with each other without making an angle using a Lambourn type abrasion tester, and at this time slip is generated between the test piece and the test piece per unit time. Measure the amount of wear. Displayed as (amount of wear of mixture 1) x 100 ÷ (amount of wear of sample). The higher the value, the better.
表１から、本発明に係るゴム組成物（実施例１〜４）は
、同水準の窒素吸着比表面積（ＮｔＳＡ）レヘルテハ、
従来品種（７）ＳＡＦ（ＮＩＩＯ１Ｎ１２１） 、ｌ５
ＡＦ （Ｎ２２０）級ハードカーボンブラックを配合し
たゴム組成物（比較例１〜３）以上の耐摩耗性を有しな
がら、発熱性の代替指標であるｔａｎδを低いレベルに
保有することがわかる。From Table 1, the rubber compositions according to the present invention (Examples 1 to 4) have the same level of nitrogen adsorption specific surface area (NtSA),
Conventional type (7) SAF (NIIO1N121), l5
It can be seen that the rubber compositions containing AF (N220) grade hard carbon black have abrasion resistance higher than that of the rubber compositions (Comparative Examples 1 to 3), while maintaining tan δ, which is an alternative index of heat generation, at a low level.
比較例５は、２４Ｍ４０ＢＰが本発明カーボンブラック
の範囲外のものであり、ｔａｎδが本発明カーボンブラ
ックに比べて高く、発熱性が劣ることがわかる。比較例
６は発生水素量が本発明カーボンブラックの範囲外であ
り、実施例１への本発明カーポジブラックに比べて、発
熱性、耐摩耗性がいずれも劣っていることがわかる。It can be seen that in Comparative Example 5, 24M40BP is outside the range of the carbon black of the present invention, has a higher tan δ than the carbon black of the present invention, and is inferior in heat generation property. It can be seen that in Comparative Example 6, the amount of hydrogen generated was outside the range of the carbon black of the present invention, and compared to the carbon black of the present invention in Example 1, both heat generation property and abrasion resistance were inferior.
表１の（）内の数値は、はぼ同じ窒素吸着比表面積であ
る比較例２、実施例３，４を比較するため、比較例２の
ｊａｎδ指数、耐摩耗性指数を１００としたときの実施
例３，４それぞれの指数をあられしたものである。実施
例３．４は、比較例２に比べて発熱性、耐摩耗性が優れ
ていることがわかる。In order to compare Comparative Example 2 and Examples 3 and 4, which have almost the same nitrogen adsorption specific surface area, the values in parentheses in Table 1 are based on the janδ index and wear resistance index of Comparative Example 2 being 100. This figure shows the respective indexes of Examples 3 and 4. It can be seen that Examples 3 and 4 are superior in heat generation properties and wear resistance compared to Comparative Example 2.
第２図にカーボンブラックの発生水素量０１□）と最多
頻度モード径（Ｄｓｔ）との関係を示す。第２図中の番
号は、表１における配合番号を示す。FIG. 2 shows the relationship between the amount of hydrogen generated in carbon black (01□) and the most frequent mode diameter (Dst). The numbers in FIG. 2 indicate the formulation numbers in Table 1.
第２図から、本発明に係るカーボンブラックは、１Ｌ２
＝３．７４ ０．０２ｘＤｓｔの線よりも上に位置する
ことがわかる（配合７．６．８，３、すなわち実施例１
〜４）。From FIG. 2, the carbon black according to the present invention is 1L2
= 3.74 It can be seen that it is located above the line of 0.02xDst (Formulation 7.6.8, 3, that is, Example 1
~4).
以上、説明したように本発明によれば、特定のカーボン
ブラックをゴムに特定量配合することにより、発熱性を
低位に保持しながら、耐摩耗性の優れたゴム組成物を得
ることができる。As described above, according to the present invention, by blending a specific amount of specific carbon black into rubber, it is possible to obtain a rubber composition with excellent wear resistance while keeping heat generation at a low level.
このゴム組成物は、特に大型車両用タイヤ、乗用車用タ
イヤのトレッドとして用いて効果が極−めて大である。This rubber composition is particularly effective when used as a tread for tires for large vehicles and tires for passenger cars.
第１図はカーボンブラックの凝集体分布と最多頻度モー
ド径（Ｄｓ ｔ）の関係図である。
第２図は本発明に係るカーボンブラックのトレッドを示
すために図示した発生水素量（Ｈｔ）と最多頻度モード
径（Ｄｓ ｔ）との関係図である。
代理人 弁理士 小 川 信 −FIG. 1 is a diagram showing the relationship between the aggregate distribution of carbon black and the most frequent mode diameter (Dst). FIG. 2 is a diagram showing the relationship between the amount of hydrogen generated (Ht) and the most frequent mode diameter (Ds t), which is illustrated to illustrate the carbon black tread according to the present invention. Agent Patent Attorney Nobuo Ogawa −
Claims (1)
／ｇ、２４Ｍ４ＤＢＰ吸油量９０〜１２０ｍｌ／１００
ｇの特性領域にあって、かつ１３００℃でカーボンブラ
ック１ｇ当りに発生する水素量（Ｈ＿２）がｍｇで表わ
して、遠心沈降法による凝集体分布の最多頻度モード径
（Ｄｓｔｍμ）と下記式の関係を有するカーボンブラッ
クを、ゴム１００重量部に対して２０〜１００重量部配
合してなることを特徴とするタイヤ用ゴム組成物。 Ｈ＿２≧３．７４−０．０２（Ｄｓｔ）（ｍｇ／ｇ）[Claims] Nitrogen adsorption specific surface area (N_2SA) 100 to 200 m^2
/g, 24M4DBP oil absorption 90-120ml/100
The relationship between the most frequent mode diameter (Dstmμ) of aggregate distribution by centrifugal sedimentation method and the following formula, where the amount of hydrogen (H_2) generated per gram of carbon black at 1300°C is expressed in mg in the characteristic region of 1. A rubber composition for a tire, comprising 20 to 100 parts by weight of carbon black having the following properties per 100 parts by weight of rubber. H_2≧3.74-0.02 (Dst) (mg/g)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62303698A JP2562338B2 (en) | 1987-12-01 | 1987-12-01 | Rubber composition for tires |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62303698A JP2562338B2 (en) | 1987-12-01 | 1987-12-01 | Rubber composition for tires |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01144434A true JPH01144434A (en) | 1989-06-06 |
| JP2562338B2 JP2562338B2 (en) | 1996-12-11 |
Family
ID=17924167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62303698A Expired - Lifetime JP2562338B2 (en) | 1987-12-01 | 1987-12-01 | Rubber composition for tires |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2562338B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220150A (en) * | 2004-02-03 | 2005-08-18 | Showa Cabot Kk | Carbon black excellent in abrasion resistance |
| JP2005350496A (en) * | 2004-06-08 | 2005-12-22 | Showa Cabot Kk | Semiconductor composition |
| WO2016024397A1 (en) * | 2014-08-11 | 2016-02-18 | 株式会社ブリヂストン | Rubber composition, crosslinked rubber composition, and tire |
| JP2017114981A (en) * | 2015-12-22 | 2017-06-29 | 株式会社ブリヂストン | Rubber composition and tire |
| JP2018158996A (en) * | 2017-03-23 | 2018-10-11 | 横浜ゴム株式会社 | Heavy duty pneumatic tire |
-
1987
- 1987-12-01 JP JP62303698A patent/JP2562338B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005220150A (en) * | 2004-02-03 | 2005-08-18 | Showa Cabot Kk | Carbon black excellent in abrasion resistance |
| JP2005350496A (en) * | 2004-06-08 | 2005-12-22 | Showa Cabot Kk | Semiconductor composition |
| JP4673005B2 (en) * | 2004-06-08 | 2011-04-20 | キャボットジャパン株式会社 | Semiconductive composition |
| WO2016024397A1 (en) * | 2014-08-11 | 2016-02-18 | 株式会社ブリヂストン | Rubber composition, crosslinked rubber composition, and tire |
| JP2016037591A (en) * | 2014-08-11 | 2016-03-22 | 株式会社ブリヂストン | Rubber composition, crosslinked rubber composition and tire |
| US10167375B2 (en) | 2014-08-11 | 2019-01-01 | Bridgestone Corporation | Rubber composition, crosslinked rubber composition, and tire |
| JP2017114981A (en) * | 2015-12-22 | 2017-06-29 | 株式会社ブリヂストン | Rubber composition and tire |
| JP2018158996A (en) * | 2017-03-23 | 2018-10-11 | 横浜ゴム株式会社 | Heavy duty pneumatic tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2562338B2 (en) | 1996-12-11 |
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