JPH0192247A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPH0192247A JPH0192247A JP24911987A JP24911987A JPH0192247A JP H0192247 A JPH0192247 A JP H0192247A JP 24911987 A JP24911987 A JP 24911987A JP 24911987 A JP24911987 A JP 24911987A JP H0192247 A JPH0192247 A JP H0192247A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- carbon black
- formula
- weight
- parts
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 53
- 239000005060 rubber Substances 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006235 reinforcing carbon black Substances 0.000 claims abstract description 7
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 6
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 6
- 229920001194 natural rubber Polymers 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims abstract description 3
- 239000006229 carbon black Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 241000872198 Serjania polyphylla Species 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 16
- 238000010276 construction Methods 0.000 abstract description 8
- 238000005299 abrasion Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 230000006835 compression Effects 0.000 abstract 1
- 238000007906 compression Methods 0.000 abstract 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 abstract 1
- 230000020169 heat generation Effects 0.000 description 15
- 235000019241 carbon black Nutrition 0.000 description 14
- 238000005259 measurement Methods 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 102220489978 Protein LTV1 homolog_N25A_mutation Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゴム組成物に関し、更に詳しくは耐カット性、
耐摩耗性及び発熱耐久性を同時に大幅に改良し得る、建
設車両用タイヤ等のトレッド用ゴム組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rubber composition, and more specifically, its properties include cut resistance,
The present invention relates to a rubber composition for treads such as tires for construction vehicles, which can significantly improve wear resistance and heat generation durability at the same time.
（従来の技術）
タイヤトレッドに優れた耐カット性を要求されるタイヤ
には、ダンプ・トラックのように比較的悪路を走行する
機会の多い車種に装着される大型ラグパターンタイヤ及
び建設車両用タイヤがあるが、これらのタイヤのトレッ
ド用ゴム組成物にはいくつかの工夫がなされている。(Prior art) Tires that require excellent cut resistance in their tire treads include large lug pattern tires installed on vehicles that often drive on relatively rough roads, such as dump trucks, and tires for construction vehicles. There are tires, and several improvements have been made to the rubber compositions for the treads of these tires.
例えば、耐カット性を向上させるためにスチレンブタジ
ェンゴム（ＳＢＲ）とのブレンド系の使用、ロジン等の
樹脂の添加、シリカ等のポリマーゲルを多量に形成する
無機充填剤の添加等が行われている。For example, in order to improve cut resistance, a blend system with styrene butadiene rubber (SBR) is used, a resin such as rosin is added, an inorganic filler such as silica that forms a large amount of polymer gel is added, etc. ing.
（発明が解決しようとする問題点）
しかしながら、前記耐カット性を改良するために使用さ
れる種々の手法のうち、ＳＢＲとのブレンドゴムの使用
、ロジン等の樹脂の添加に関しては、ゴムの耐発熱性を
悪くし、発熱耐久性を大幅に低下させるので好ましくな
い。具体的には、長時間比較的高速で走行した場合、ト
レッドとベルトあるいはブレーカ−との面でセパレーシ
ョンが発生し易くなるという問題点がある。(Problems to be Solved by the Invention) However, among the various methods used to improve the cut resistance, the use of blended rubber with SBR and the addition of resin such as rosin do not improve the cut resistance of the rubber. This is not preferable because it worsens heat generation properties and significantly reduces heat generation durability. Specifically, when the vehicle is driven at a relatively high speed for a long period of time, there is a problem in that separation tends to occur between the tread and the belt or the breaker.
また、シリカのような無機充填剤を多量に添加する方法
では、ゴム組成物の混練り作業性が低下して分散不良を
おこし易くなり、所定のゴム物性が得られないことがあ
る。Further, in the method of adding a large amount of an inorganic filler such as silica, the kneading workability of the rubber composition decreases and poor dispersion is likely to occur, and predetermined physical properties of the rubber may not be obtained.
一方、耐摩耗性改良のためとしてＳＢＲのブレンド系を
使用する方法があるが、この方法はＳＢＲをブレンドし
ていくに従い発熱性が悪化していくので発熱耐久性が大
幅に低下すると共に、高温時の補強物性も低下してリブ
ティア−等のトラブルを発生し易くなるという好ましく
ない問題をもっている。On the other hand, there is a method of using a blend system of SBR to improve wear resistance, but in this method, as the SBR is blended, the heat generation property worsens, so the heat generation durability is significantly reduced, and the high temperature This has an undesirable problem in that the reinforcing physical properties are also deteriorated and problems such as rib tearing are more likely to occur.
上述の如く、建設車両用タイヤ等のトレッド用ゴム組成
物において、耐カット性、耐摩耗性および発熱耐久性を
同時に満足出来る改良技術は未だ見出されていないのが
現状であった。As mentioned above, in the case of rubber compositions for treads such as tires for construction vehicles, no improvement technology has yet been found that can simultaneously satisfy cut resistance, abrasion resistance, and heat generation durability.
また建設車両用タイヤ等のトレッド用ゴム組成物におけ
るＳＢＲの使用に当たっても、上記理由から制約がなさ
れていたのが実状である。Furthermore, the use of SBR in rubber compositions for treads such as tires for construction vehicles is currently subject to restrictions due to the above-mentioned reasons.
そこで本発明の目的は、耐カット性、耐摩耗性及び発熱
耐久性を同時に大幅に改善し得る建設車両用タイヤ等の
トレッド用ゴム組成物を提供することにある。Therefore, an object of the present invention is to provide a rubber composition for treads such as tires for construction vehicles, which can simultaneously significantly improve cut resistance, abrasion resistance, and heat generation durability.
（問題点を解決するための手段）
本発明者らは前記技術的問題点を解消すべ（鋭意検討を
重ねた結果、建設車両用タイヤ等のトレッド用ゴム組成
物において表面に特定量の一叶基が存在する補強性カー
ボンブラックとシランカップリング剤とを所定量当該ゴ
ム組成物に配合することによりカーボンブラック表面と
ゴムポリマーとがシランカップリング剤により強固な結
合を生じ、これらの相乗効果により発熱性と高温での補
強性としての耐摩耗性が改善され、更にシリカの存在下
で５−メチル−１，４−へキサジエンとプロピレン及び
／又はエチレンとを主成分とする樹脂を添加混合すれば
耐カット性の向上も得られることを見出し、本発明を完
成するに至った。(Means for Solving the Problems) The present inventors have solved the above-mentioned technical problems (as a result of extensive studies, it has been found that a specific amount of a compound on the surface of a rubber composition for treads such as tires for construction vehicles). By blending a predetermined amount of reinforcing carbon black in which a group exists and a silane coupling agent into the rubber composition, a strong bond is created between the carbon black surface and the rubber polymer due to the silane coupling agent, and due to the synergistic effect of these. The heat generation properties and wear resistance as reinforcing properties at high temperatures are improved, and furthermore, a resin mainly composed of 5-methyl-1,4-hexadiene and propylene and/or ethylene is added and mixed in the presence of silica. The present inventors have discovered that improved cut resistance can also be obtained, and have completed the present invention.
すなわち本発明は、天然ゴム、合成ポリイソプレンゴム
、スチレンブタジェン共重合体ゴムまたはこれらの併用
系から成る原料ゴム１００重１部に対し、窒素吸着法に
より測定した比表面積（Ｎ２ＳＡ値） カ６５〜１６に
＋２／ｇで圧縮ジブチルフタレート吸油量（ＤＢＰ値）
が７０〜１４０ ｍｌ！／１００ｇの範囲内のカーボン
ブラックであって、該カーボンブラック表面に導入され
たフェノール性水酸基の濃度が３、ＯＸ１０′２〜８．
１×１０１２（固／ ｍ ２でｐｔＬ！直が３〜５の範
囲内の補強性カーボンブランク３０〜８０重１部と、シ
リカ３〜２０重量部と、以下の一般式：％式％）
（式中のＲは水素原子またはメチル基、ｍは５〜１００
の整数を示す）で表される５−メチル−１，４−ヘキサ
ジエンとプロピレンおよび／またはエチレンとを主成分
とする樹脂１〜１０重量部と、以下の一般式（１）およ
び（２）：
Ｙ３ Ｓｔ ＣＪｂｈれＣｈＨｚｎＳＩ Ｙ３ また
はＹ３−３ＩＣＩ、Ｈ２Ｊ ・・・ （
１）（式中のＸはニトロン基、メルカプト基、アミ７基
、エポキシ基、ビニル基、塩素原子、イミド基、Ｙは炭
素数１〜４個のアルキル基またはアルコキシル基、ある
いは塩素原子、ｎおよびｍは１〜６の整数を示す）
Ｙ３ＳＩＣｆｉＨ２，Ｓ、Ｘ’ −＝ （２）
のものと同じものを示す）で表される化合物から成る群
から選択されたシランカップリング剤の少なくとも１種
を前記カーボンブラック量とシリカ量の合計機に対して
５〜２０重量％とを添加混合したことを特徴とするゴム
組成物に関するものである。That is, the present invention provides a specific surface area (N2SA value) Ka65 measured by a nitrogen adsorption method for 100 parts by weight of raw material rubber made of natural rubber, synthetic polyisoprene rubber, styrene-butadiene copolymer rubber, or a combination thereof. ~16 to +2/g compressed dibutyl phthalate oil absorption (DBP value)
is 70-140 ml! /100g, and the concentration of phenolic hydroxyl groups introduced to the surface of the carbon black is 3, OX10'2 to 8.
1 x 1012 (solid/m2 and ptL! 1 part by weight of 30 to 80 reinforcing carbon blanks with straightness within the range of 3 to 5, 3 to 20 parts by weight of silica, and the following general formula: % formula %) ( In the formula, R is a hydrogen atom or a methyl group, m is 5 to 100
1 to 10 parts by weight of a resin whose main components are 5-methyl-1,4-hexadiene represented by (representing an integer of ) and propylene and/or ethylene, and the following general formulas (1) and (2): Y3 St CJbhreChHznSI Y3 or Y3-3ICI, H2J... (
1) (In the formula, and m represents an integer from 1 to 6) Y3SICfiH2,S,X' −= (2)
5 to 20% by weight of at least one silane coupling agent selected from the group consisting of compounds expressed by The present invention relates to a rubber composition characterized by being mixed.
本発明において使用する５−メチル−１，４−へキサジ
エンとプロピレンおよび／またはエチレンとを主成分と
する樹脂としては、例えば三菱油化側腹の市販品で下記
の第１表に示す特性をもつＲＯＰ３ＤおよびＲＯＰ３２
Ｄ（いずれも商品名）等がある。The resin containing 5-methyl-1,4-hexadiene and propylene and/or ethylene as main components used in the present invention is, for example, a commercially available product manufactured by Mitsubishi Yuka Hakko, which has the characteristics shown in Table 1 below. ROP3D and ROP32
D (both are product names), etc.
第１表
Ｈ
Ｃ（ＣＨ３）２
また、本発明において使用する、表面に一叶基の導入さ
れたカーボンブラックは、例えば特開昭６２−１８４４
６３号公報において本出願人が提示した真空低温プラズ
マ処理法等で変性処理することにより得られる。Table 1 HC(CH3)2 Furthermore, the carbon black having a single leaf group introduced onto the surface used in the present invention is disclosed in, for example, Japanese Patent Application Laid-Open No. 62-1844.
It can be obtained by a modification treatment using a vacuum low-temperature plasma treatment method proposed by the present applicant in Publication No. 63.
尚、カーボンブランクをシランカップリング剤と併用す
る際に、−ＤＨ基を導入すべく表面処理されたカーボン
ブランクをシランカップリング剤で予め変性処理しても
よい。この場合のシランカップリング剤による変性処理
方法としては、ヘンシェルミキサーを用い室温乃至８０
℃の温度雰囲気中でカーボンブラックとシランカップリ
ング剤とを５〜２０分間混合撹拌する方法がある。In addition, when using a carbon blank together with a silane coupling agent, the carbon blank surface-treated to introduce a -DH group may be modified in advance with the silane coupling agent. In this case, the modification treatment method using a silane coupling agent is performed using a Henschel mixer from room temperature to 80°C.
There is a method in which carbon black and a silane coupling agent are mixed and stirred for 5 to 20 minutes in an atmosphere at a temperature of .degree.
本発明のゴム組成物には加硫剤の硫黄、加硫促進剤、老
化防止剤、軟化剤あるいは充填剤等を適宜配合すること
ができるのは勿論のことである。It goes without saying that sulfur as a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, a softener, a filler, etc. can be appropriately blended into the rubber composition of the present invention.
本発明におけるＮ、ＳＡ値の測定はＡＳＴｌ、ｌ Ｄ
３０３７に、またＤＢＰ値の測定はＡＳＴｌＪ ［＋３
４９３に、更にティント値はＡＳＴＭ ０３２６５に準
拠して行った。Measurement of N and SA values in the present invention is performed using ASTl, l D
3037, and the DBP value was measured using ASTlJ[+3
493, and the tint value was determined in accordance with ASTM 03265.
本発明のゴム組成物に配合する補強性カーボンブラック
はＮ２５Ａ値が６５〜１６０ｍ２／ｇでＤＢＰ値が７０
〜１４Ｍ！／１００ｇの範囲内であることが要求される
が、これはこれら特性値が夫々の下限値より小さい場合
には補強効果が充分でなく、一方上限を超えるとゴムへ
の分散性が悪くなり発熱性の増大を招くことになるから
である。また、この補強性力−ボンブラックのフェノー
ル性水酸基の濃度を３．０×１０′２〜ｇ、Ｉ ＸＩＯ
”個／ｍ ２ と規定するが、これはこの下限値未満で
は高温時の引張強度が低下し、−方上限を超えると破断
伸びが低下して破壊特性が低下し、好ましくないからで
ある。好ましくは、フェノール性水酸基の濃度を３．５
ＸｌＯ１２〜５．７×１０１３個／ｍ ２の範囲内と
する。更に、この補強性カーボンブラックの一叶基導入
によるｐＨ値を３〜５の範囲内と規定するが、これはｐ
Ｈ値が３未満では加硫が遅れ好ましくなく、一方５を超
えると一叶基が減少して本発明の目的を達成することが
出来なくなるからである。The reinforcing carbon black blended into the rubber composition of the present invention has an N25A value of 65 to 160 m2/g and a DBP value of 70.
~14M! /100g, but this is because if these characteristic values are smaller than their respective lower limits, the reinforcing effect will not be sufficient, while if they exceed the upper limit, dispersibility into rubber will deteriorate and heat generation will occur. This is because it will lead to an increase in sexuality. In addition, this reinforcing force - the concentration of phenolic hydroxyl groups in the bomb black was 3.0 x 10'2~g, IXIO
This is because if the lower limit is less than this, the tensile strength at high temperature will decrease, and if it exceeds the upper limit, the elongation at break will decrease and the fracture properties will deteriorate, which is not preferable. Preferably, the concentration of phenolic hydroxyl groups is 3.5
It is within the range of 12 to 5.7×10 13 XlO/m 2 . Furthermore, the pH value due to the introduction of a single leaf group in this reinforcing carbon black is specified to be within the range of 3 to 5;
If the H value is less than 3, vulcanization will be delayed, which is undesirable, while if it exceeds 5, the number of monolobal groups will decrease, making it impossible to achieve the object of the present invention.
本発明においては上記特性を有する補強性カーボンブラ
ックをゴム成分１００重量部に対して３０〜８０重量部
配合するが、これは３０部重量部未満ではゴム組成物に
対して補強効果が充分で（、まなく、−方２０重量部を
超えるとゴムに対する分散性が悪くなり好ましくないか
らである。In the present invention, 30 to 80 parts by weight of reinforcing carbon black having the above-mentioned characteristics is blended with respect to 100 parts by weight of the rubber component, but if it is less than 30 parts by weight, the reinforcing effect is sufficient for the rubber composition ( This is because if the amount exceeds 20 parts by weight, the dispersibility in rubber deteriorates, which is not preferable.
次に、本発明のゴム組成物に配合するシリカについては
耐カット性と発熱性との関係から３〜２０重量部の範囲
が適正である。すなわち、３重量部未満ではかかる目的
に対する効果が充分でなく、一方２０重量部を超えると
耐摩耗性および高温破壊特性の低下を招くことになるか
らである。Next, the appropriate amount of silica to be blended into the rubber composition of the present invention is in the range of 3 to 20 parts by weight in view of the relationship between cut resistance and heat generation properties. That is, if it is less than 3 parts by weight, the effect for this purpose will not be sufficient, while if it exceeds 20 parts by weight, it will lead to a decrease in wear resistance and high temperature fracture properties.
一方、同様に本発明のゴム組成物に併用配合するシラン
カップリング剤の配合量は上記カーボンブラック量とシ
リカ量の合計量に対して規定するが、これはカーボンブ
ラックおよびシリカの表面とゴムポリマーとがかかるシ
ランカップリング剤を介して強固な結合を生じ、これら
の相乗効果により発熱性と補強性の改善がなされること
から、上述の如くカーボンブラック量とシリカ量の合計
量に対して規定した方がゴム成分に対して規定するより
も良いという知見に基づくためである。この知見に基づ
き本発明においてはシランカップリング剤の配合量を上
記合計量に対し５〜２０重量％と規定するが、これは５
重量％未満では所望効果を発揮し得ず、一方２０重量％
を超えるとゴム物性等に悪影響を及ぼすことになるから
である。On the other hand, the amount of the silane coupling agent to be mixed in the rubber composition of the present invention is determined based on the total amount of the above carbon black and silica, and this is based on the surface of the carbon black and silica and the rubber polymer. A strong bond is formed through the silane coupling agent, and the synergistic effect of these improves heat generation and reinforcing properties. This is based on the knowledge that it is better to do so than to specify for rubber components. Based on this knowledge, in the present invention, the blending amount of the silane coupling agent is defined as 5 to 20% by weight based on the above total amount;
If it is less than 20% by weight, the desired effect cannot be achieved;
This is because if it exceeds this, it will have an adverse effect on the physical properties of the rubber.
更に本発明のゴム組成物に同時併用添加するものとして
５−メチル−１，４−へキサジエンとプロピレンおよび
／またはエチレンとを主成分とする樹脂があり、これを
ゴム成分に対し１〜１０重量部の範囲内で添加するが、
この添加量をかかる範囲内に規定したのは、１重量部未
満では耐カット性が充分でなく、一方１０重量部を超え
るとゴム組成物の硬度が高くなり過ぎるばかりでなく耐
亀裂成長性が低下し、好ましくないからである。Furthermore, there is a resin whose main components are 5-methyl-1,4-hexadiene and propylene and/or ethylene, which can be added simultaneously to the rubber composition of the present invention in an amount of 1 to 10% by weight based on the rubber component. Although it is added within the range of
The reason for specifying this addition amount within this range is that if it is less than 1 part by weight, the cut resistance will not be sufficient, whereas if it exceeds 10 parts by weight, not only will the hardness of the rubber composition become too high, but also the crack growth resistance will deteriorate. This is because it is undesirable.
以上説明してきたように本発明の構成とすることで補強
性と発熱性の大幅な改良効果が見られるのは、前述のよ
うに−ＯＨ基導入処理が施され分散性が改良さだ活性カ
ーボンブラックとシランカップリング剤との間に化学的
に強固な一次結合が形成され、更にこのシランカップリ
ング剤がゴムポリマーとの間で相互作用して、カーボン
ブラック−シランカップリング剤−ゴムポリマー同志が
全体的に高温に強い結合を形成するからである。尚、シ
リカの場合にも同様な効果が期待できるのは勿論のこと
である。As explained above, the structure of the present invention can significantly improve reinforcing properties and heat generation properties because activated carbon black is treated with -OH group introduction and has improved dispersibility as described above. A chemically strong primary bond is formed between the carbon black, the silane coupling agent, and the rubber polymer, and the silane coupling agent interacts with the rubber polymer to form a bond between the carbon black, the silane coupling agent, and the rubber polymer. This is because a bond that is strong against high temperatures is formed overall. It goes without saying that similar effects can be expected in the case of silica.
一方、耐カツト性向上を図るために前記所定の樹脂を配
合する場合、置襖基（Ｒ）の３０％以上、好ましくは６
０％以上がメチル基であることが好ましい。これは、プ
ロピレン単位がこの程度ないと耐カツト性効果が充分に
発揮されないからである。On the other hand, when the predetermined resin is blended in order to improve cut resistance, 30% or more of the fusuma group (R), preferably 6
It is preferable that 0% or more is a methyl group. This is because without this amount of propylene units, the cut resistance effect cannot be sufficiently exhibited.
また、前記樹脂を使用した場合、カーボンブラックが未
処理の場合には該樹脂中のポリプロピレンが選択的にゴ
ムのイソプレン鎖と高温で積極的に反応してゲル層を形
成するが、本発明のように−ＯＨ基で変性したカーボン
系ではスチレンブタジェンゴム（ＳＢＲ）等の合成ゴム
系に対してもゲル層を形成することが確認されている。Furthermore, when the above resin is used and the carbon black is untreated, the polypropylene in the resin selectively reacts actively with the isoprene chains of the rubber at high temperatures to form a gel layer. It has been confirmed that carbon-based rubbers modified with -OH groups form gel layers even on synthetic rubbers such as styrene-butadiene rubber (SBR).
（実施例） 以下に本発明を実施例により説明する。(Example) The present invention will be explained below using examples.
真空低温プラズマ処理
５００ｄのパイレックス製フラスコ型プラズマチャンバ
ー内にカーボンブラック５０ｇを入れ、処理を均一にし
て灰化を抑制するために少なくとも５ｒｐｍ以上でフラ
スコを回転させながら真空低温プラズマ処理を行った。Vacuum low-temperature plasma treatment 50 g of carbon black was placed in a 500 d Pyrex flask-shaped plasma chamber, and vacuum low-temperature plasma treatment was performed while rotating the flask at at least 5 rpm to make the treatment uniform and suppress ashing.
この真空低温プラズマ処理は、高周波出力（１３，５６
ＭＨｚ）２５Ｗ 、真空度０．３Ｔｏｒｒおよび処理ガ
ス流量５０ｍ７ｍ１ｎの条件下、下記の第２表に示す処
理ガスおよび処理時間にて行った。This vacuum low temperature plasma treatment uses high frequency output (13,56
MHz) 25W, a vacuum degree of 0.3 Torr, and a processing gas flow rate of 50 m7 m1n, using the processing gases and processing times shown in Table 2 below.
かかる処理により各カーボンブラックの表面に導入され
た一ＯＨ基の濃度およびｐＨ値は以下のようにして測定
した。The concentration and pH value of 1OH groups introduced onto the surface of each carbon black by such treatment were measured as follows.
−ＯＨ基の濃度測定 カーボンブラック表面の−ＤＨ基の濃度はＨ，Ｐ。-OH group concentration measurement The concentrations of -DH groups on the carbon black surface are H and P.
Ｂｏｅｈｍの方法（Ａｎｇｅｗ、 Ｃｈｅｎ、１ｎｔｅ
ｒｎａｔ、 Ｅｄｉｔ、。Boehm's method (Angew, Chen, 1nte
rnat, Edit,.
５、５３３（１９６６）および同、３．６６９（１９６
４）） に従い、表面−〇Ｈ基を炭酸水素ナトリウム
、水酸化ナトリウムにより中和することにより求めた。5, 533 (1966) and Ibid., 3.669 (1966)
4)), it was determined by neutralizing the -○H groups on the surface with sodium hydrogen carbonate and sodium hydroxide.
ｐＨ値の測定
試料１ｇをイオン交換水１００ ｍｌ中に添加して１５
分間煮沸し、４８時間放置した後、スターテでかき混ぜ
乍ら懸濁液のｐＨ値をｐＨメーターで測定した。Add 1 g of the pH value measurement sample to 100 ml of ion-exchanged water.
After boiling for 48 hours and stirring with a starter, the pH value of the suspension was measured with a pH meter.
表面−ＤＨ基の濃度およびｐＨ値の測定結果を第２表に
併記する。The measurement results of the surface -DH group concentration and pH value are also listed in Table 2.
上述の如く処理した第２表に示す各種カーボンブラック
を、下記の第３表に示すシランカップリング剤と共に以
下の第４表に示す配合割合（重量部）でゴム成分等と配
合して、各種試験ゴム組成物を作成した。The various carbon blacks shown in Table 2 that have been treated as described above are mixed with rubber components, etc. in the proportions (parts by weight) shown in Table 4 below, along with the silane coupling agents shown in Table 3 below. A test rubber composition was created.
これら試験ゴム組成物につき、以下に示す引張強度、モ
ジュラスおよび発熱製としてｔａｎ δを測定した。For these test rubber compositions, the tensile strength, modulus, and tan δ as shown below were measured.
引張強度
ＪＩＳ Ｋ６３０１に準じて１００℃にて３００％伸長
時の引張応力を測定した。Tensile stress The tensile stress at 300% elongation at 100° C. was measured according to JIS K6301.
ｔａｎ δ
レオメトリックス社製メカニカルスペクトロメーターを
用いて、動的剪断歪振幅１．０％、振動１．０Ｈｚおよ
び測定温度３０℃にて測定した。値が小さい程分散性は
良好である。Measurement was performed using a mechanical spectrometer manufactured by Tan δ Rheometrics at a dynamic shear strain amplitude of 1.0%, vibration of 1.0 Hz, and measurement temperature of 30°C. The smaller the value, the better the dispersibility.
引張強度、モジュラスおよびｔａｎ δの測定結果を第
３表に併記する。The measurement results of tensile strength, modulus, and tan δ are also listed in Table 3.
次いで、これらゴム組成物をタイヤトレッドに用いて、
供試タイヤとしてタイヤサイズＯＲＲ１４００Ｒ２５で
ラグ溝の各種タイヤを試作し、各々実車装着して耐カッ
ト性および耐摩耗性を評価し、またドラム走行により発
熱耐久性を評価した。これらタイヤ性能の評価法は下記
の通りである。Next, these rubber compositions are used for tire treads,
Various tires with lug grooves of tire size ORR1400R25 were manufactured as test tires, and each was mounted on an actual vehicle to evaluate cut resistance and abrasion resistance, and heat generation durability was evaluated by running on a drum. The evaluation method for these tire performances is as follows.
尚、天然ゴム（ＮＲ）単独系、ＳＢＲ単独系およびＮＲ
／ＳＢＲ併用系の各ゴムポリマー系毎にコントロールヲ
トって、これらコントロールの各タイヤ性能を１００と
して評価結果を指数で表示した。結果は数値が大きい程
良好である。In addition, natural rubber (NR) single system, SBR single system, and NR
A control was set for each rubber/polymer system of the /SBR combination system, and the evaluation results were expressed as an index, with each tire performance of these controls set as 100. The higher the numerical value, the better the result.
耐カット性
悪路走行が全体の６０％程度である使用条件下で１．５
万ｋｍ実車走行させ、その際のトレッド表面のカット深
さの状態から評価した。Cut resistance: 1.5 under usage conditions where driving on rough roads accounts for approximately 60% of the total.
The vehicle was driven for 10,000 km and evaluated based on the cut depth of the tread surface.
耐摩耗性 ２．０万ｋｍ走行後の溝深さ（ｍｍ）から評価した。Abrasion resistance Evaluation was made from the groove depth (mm) after traveling 20,000 km.
発熱耐久性
ＪＩＳ規格（Ｄ−４２３０＋耐久性ドラムテスト）に従
って評価し、その際の走行距離で評価した。The heat generation durability was evaluated according to the JIS standard (D-4230+durability drum test), and the running distance was evaluated.
得られた結果を第４表に併記する。The obtained results are also listed in Table 4.
（発明の効果）
上記第４表に示す測定結果からも分かるように、本発明
の所定の要件を満足するゴム組成物では、いずれのゴム
成分系においても比較例のゴム組成物に比し耐カット性
、耐摩耗性および発熱耐久性が良好に改良されている。(Effects of the Invention) As can be seen from the measurement results shown in Table 4 above, the rubber compositions that satisfy the predetermined requirements of the present invention have greater durability than the rubber compositions of the comparative examples in all rubber component systems. Cutting performance, abrasion resistance, and heat generation durability are improved.
従って、本発明のゴム組成物は建設車両用タイヤ等のト
レッド用として極めて有用である。Therefore, the rubber composition of the present invention is extremely useful for treads such as tires for construction vehicles.
Claims (1)
ジエン共重合体ゴムまたはこれらの併用系から成る原料
ゴム１００重量部に対し、窒素吸着法により測定した比
表面積（Ｎ＿２ＳＡ値）が６５〜１６０ｍ＾２／ｇで圧
縮ジブチルフタレート吸油量（ＤＢＰ値）が７０〜１４
０ｍｌ／１００ｇの範囲内のカーボンブラックであって
、該カーボンブラック表面に導入されたフェノール性水
酸基の濃度が３．０×１０＾１＾２〜８．１×１０＾１
＾４個／ｍ＾２でｐＨ値が３〜５の範囲内の補強性カー
ボンブラック３０〜８０重量部と、シリカ３〜２０重量
部と、以下の一般式： ▲数式、化学式、表等があります▼ （式中のＲは水素原子またはメチル基、ｍは５〜１００
の整数を示す）で表される５−メチル−１，４−ヘキサ
ジエンとプロピレンおよび／またはエチレンとを主成分
とする樹脂１〜１０重量部と、以下の一般式（１）およ
び（２）： Ｙ＿３−Ｓｉ−Ｃ＿ｎＨ＿２＿ｎＳ＿ｍＣ＿ｎＨ＿２＿
ｎＳｉ−Ｙ＿３またはＹ＿３−ＳｉＣ＿ｎＨ＿２＿ｎＸ
・・・（１） （式中のＸはニトロソ基、メルカプト基、アミノ基、エ
ポキシ基、ビニル基、塩素原子、イミド基、Ｙは炭素数
１〜４個のアルキル基またはアルコキシル基、あるいは
塩素原子、ｎおよびｍは１〜６の整数を示す） Ｙ＿３ＳｉＣ＿ｎＨ＿２＿ｎＳ＿ｍＸ′・・・（２） （式中のＸ′は▲数式、化学式、表等があります▼ または▲数式、化学式、表等があります▼、Ｙ、ｍおよ
びｎは夫々前記のものと同じものを示す）で表される化
合物から成る群から選択されたシランカップリング剤の
少なくとも１種を前記カーボンブラック量とシリカ量の
合計量に対して５〜２０重量％とを添加混合したことを
特徴とするゴム組成物。[Claims] 1. The specific surface area (N_2SA value) measured by nitrogen adsorption method with respect to 100 parts by weight of raw rubber made of natural rubber, synthetic polyisoprene rubber, styrene-butadiene copolymer rubber, or a combination thereof: Compressed dibutyl phthalate oil absorption (DBP value) is 70 to 14 at 65 to 160 m^2/g
Carbon black within the range of 0ml/100g, and the concentration of phenolic hydroxyl groups introduced on the surface of the carbon black is 3.0 x 10^1^2 to 8.1 x 10^1
30 to 80 parts by weight of reinforcing carbon black with a pH value of 3 to 5 at ^4 pieces/m^2, 3 to 20 parts by weight of silica, and the following general formula: ▲ Numerical formula, chemical formula, table, etc. Yes▼ (R in the formula is a hydrogen atom or a methyl group, m is 5-100
1 to 10 parts by weight of a resin whose main components are 5-methyl-1,4-hexadiene represented by (representing an integer of ) and propylene and/or ethylene, and the following general formulas (1) and (2): Y_3-Si-C_nH_2_nS_mC_nH_2_
nSi-Y_3 or Y_3-SiC_nH_2_nX
...(1) (in the formula, Atom, n and m are integers from 1 to 6) Y_3SiC_nH_2_nS_mX'...(2) (X' in the formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , Y, m and n are the same as those mentioned above), based on the total amount of carbon black and silica. A rubber composition characterized in that 5 to 20% by weight of the above ingredients are added and mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24911987A JPH0192247A (en) | 1987-10-03 | 1987-10-03 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24911987A JPH0192247A (en) | 1987-10-03 | 1987-10-03 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0192247A true JPH0192247A (en) | 1989-04-11 |
Family
ID=17188225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24911987A Pending JPH0192247A (en) | 1987-10-03 | 1987-10-03 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0192247A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005523924A (en) * | 2002-04-23 | 2005-08-11 | ゼネラル・エレクトリック・カンパニイ | Blocked mercaptosilane hydrolysates as coupling agents for inorganic-containing elastomer compositions |
| KR20110128811A (en) * | 2009-03-11 | 2011-11-30 | 술저 믹스팩 아게 | Device for dispensing a filling mass |
| WO2014103876A1 (en) * | 2012-12-28 | 2014-07-03 | 横浜ゴム株式会社 | Rubber composition for pneumatic tires for construction vehicles |
-
1987
- 1987-10-03 JP JP24911987A patent/JPH0192247A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005523924A (en) * | 2002-04-23 | 2005-08-11 | ゼネラル・エレクトリック・カンパニイ | Blocked mercaptosilane hydrolysates as coupling agents for inorganic-containing elastomer compositions |
| KR20110128811A (en) * | 2009-03-11 | 2011-11-30 | 술저 믹스팩 아게 | Device for dispensing a filling mass |
| WO2014103876A1 (en) * | 2012-12-28 | 2014-07-03 | 横浜ゴム株式会社 | Rubber composition for pneumatic tires for construction vehicles |
| JP2014129436A (en) * | 2012-12-28 | 2014-07-10 | Yokohama Rubber Co Ltd:The | Rubber composition for pneumatic tire for construction vehicle |
| US9878580B2 (en) | 2012-12-28 | 2018-01-30 | The Yokohama Rubber Co., Ltd. | Rubber composition for pneumatic tires for construction vehicles |
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