JPH0689182B2 - Rubber composition with improved cut resistance and chipping resistance - Google Patents
Rubber composition with improved cut resistance and chipping resistanceInfo
- Publication number
- JPH0689182B2 JPH0689182B2 JP60029408A JP2940885A JPH0689182B2 JP H0689182 B2 JPH0689182 B2 JP H0689182B2 JP 60029408 A JP60029408 A JP 60029408A JP 2940885 A JP2940885 A JP 2940885A JP H0689182 B2 JPH0689182 B2 JP H0689182B2
- Authority
- JP
- Japan
- Prior art keywords
- resistance
- rubber
- weight
- rubber composition
- chipping
- 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.)
- Expired - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title claims description 28
- 239000005060 rubber Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 22
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 10
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 6
- 229920003052 natural elastomer Polymers 0.000 claims description 6
- 229920001194 natural rubber Polymers 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 4
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 239000005061 synthetic rubber Substances 0.000 claims description 4
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 3
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） この発明は、耐カツト性及び耐チツピング性を改善した
ゴム組成物、特にシクロペンタジエン及び／又はジシク
ロペンタジエンを25重量％以上の割合に共重合させた、
特定構造の石油樹脂を配合することにより耐カツト性及
び耐チツピング性を改善したゴム組成物に関する。TECHNICAL FIELD The present invention relates to a rubber composition having improved cut resistance and chipping resistance, particularly cyclopentadiene and / or dicyclopentadiene in an amount of 25% by weight or more. Polymerized,
The present invention relates to a rubber composition having improved cut resistance and chipping resistance by blending a petroleum resin having a specific structure.
（従来の技術） 舗装されていない路面、特に岩石が露出しているような
悪路を走行することが多い高荷重のトラツク・バス用大
型タイヤや、砕石現場等で使用されるオフザロード用タ
イヤ等は、それらのトレツド部やサイドウオール部にカ
ツトを受ける機会が多く、カツトの成長によるタイヤ破
壊や、雨水等がカツト部より侵入し、補強材であるスチ
ールコードを腐食させることによるタイヤ破壊に至るこ
とがある。したがつて、上記の高荷重トラツク・バス用
大型タイヤやオフザロード用タイヤの特にトレツド部
は、耐カツト性及び耐チツピング性にすぐれたゴム組成
物が必要とされている。(Prior Art) Large tires for heavy-duty trucks and buses that often travel on unpaved road surfaces, especially on rough roads with exposed rocks, and off-the-road tires used at crushed stone sites, etc. Have a lot of chances of receiving cuts on their treads and sidewalls, leading to tire damage due to growth of the cuts, and rainwater etc. invading from the cuts to corrode the steel cord that is the reinforcing material, leading to tire damage. Sometimes. Therefore, a rubber composition having excellent cut resistance and chipping resistance is required for the large tires for high-load trucks / buses and the tires for off-the-road roads, especially for the tred portion.
一般に、ゴム組成物の耐カツト性を向上させる手段とし
て、カーボンブラツクを高充填すれば、耐カツト性は向
上するが、この場合、耐カツト性を必要とするような悪
路における耐チツピング性や発熱性あるいは混練や押出
作業性が著しく劣ることが知られている。Generally, as a means for improving the cut resistance of the rubber composition, if the carbon black is highly filled, the cut resistance is improved, but in this case, the chip resistance and the resistance to chipping on a bad road that requires cut resistance and It is known that heat generation or kneading or extrusion workability is extremely poor.
このようなことから、本出願人は、特公昭48-38615号公
報に記載したように、シクロペンタジエン及び／又はジ
シクロペンタジエンを30重量％以上の割合に共重合させ
た、軟化点50〜200℃、臭素価40〜150の樹脂をスチレン
ブタジエンゴムに配合したゴム組成物を提案し、この組
成物の耐カツト性及び耐チツピング性を改善することが
できた。Therefore, the applicant of the present invention, as described in JP-B-48-38615, has a softening point of 50 to 200 obtained by copolymerizing cyclopentadiene and / or dicyclopentadiene in a proportion of 30% by weight or more. A rubber composition was proposed in which a styrene-butadiene rubber was blended with a resin having a bromine number of 40 to 150 at ℃, and the cut resistance and chipping resistance of this composition could be improved.
（発明が解決しようとする問題点） しかし、前記特公昭48-38615号公報記載のゴム組成物
は、耐カツト性及び耐チツピング性の点で改善されては
いるが、その改善の程度が時としてかなり変動すること
があり、その原因が明らかでなかつた。したがつて、こ
の組成物による前記特性の改善も実用上なお満足できる
ものでなく、これらの特性を安定して改善するゴム組成
物が必要である。(Problems to be Solved by the Invention) However, although the rubber composition described in JP-B-48-38615 is improved in terms of cut resistance and chipping resistance, the degree of improvement is sometimes However, the cause was unclear. Therefore, the improvement of the above-mentioned properties by this composition is still not practically satisfactory, and a rubber composition which stably improves these properties is required.
（問題点を解決するための手段） 本発明者らは、上記問題点を解決すべく鋭意検討した結
果、シクロペンタジエン及び／又はジシクロペンタジエ
ンを25重量％以上の割合に共重合させた樹脂中にある不
飽和結合の種類、特にノルボルネン環の二重結合（ND）
対シクロペンテン環の二重結合（CD）の比、すなわちND
/CDにより、耐カツト性及び耐チツピング性が影響され
ることを始めて確かめ、この発明を達成するに至つた。(Means for Solving Problems) The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, in a resin obtained by copolymerizing cyclopentadiene and / or dicyclopentadiene in a proportion of 25% by weight or more. Types of Unsaturated Bonds, Especially Double Bonds (ND) of Norbornene Ring
Ratio of double bonds (CD) to cyclopentene ring, ie ND
It was confirmed for the first time that the cutting resistance and chipping resistance were affected by / CD, and the present invention was achieved.
すなわち、この発明は、天然ゴム及びジエン系合成ゴム
よりなる群の中から選ばれた少なくとも１種のゴム100
重量部に対し、シクロペンタジエン及び／又はジシクロ
ペンタジエンを25重量％以上、ナフサの熱分解により副
生するシクロペンタジエン及びジシクロペンタジエン以
外のC5留分及び／又はC9留分を75重量％以下の割合で共
重合させて得た石油樹脂であり、かつ、該樹脂の構造に
含まれるノルボルネン環の二重結合（ND）対シクロペン
テン環の二重結合（CD）の比ND/CDが0.2〜0.9である石
油樹脂を１〜30重量部配合したことを特徴とする耐カツ
ト性及び耐チツピング性を改善したゴム組成物である。That is, the present invention relates to at least one rubber 100 selected from the group consisting of natural rubber and diene-based synthetic rubber.
25 parts by weight or more of cyclopentadiene and / or dicyclopentadiene, 75% by weight of C 5 fraction and / or C 9 fraction other than cyclopentadiene and dicyclopentadiene by-produced by thermal decomposition of naphtha A petroleum resin obtained by copolymerization at the following ratio, and the ratio ND / CD of the double bond (ND) of the norbornene ring to the double bond (CD) of the cyclopentene ring contained in the structure of the resin is 0.2. A rubber composition having improved cut resistance and chipping resistance, which is characterized by containing 1 to 30 parts by weight of a petroleum resin of 0.9.
この石油樹脂に共重合させたシクロペンタジエン及び／
又はジシクロペンタジエンの割合が25重量％未満の場合
は、これを配合したゴム組成物の耐チツピング性が悪く
なる。また、前記ND/CD比が0.2未満でもゴム組成物の耐
チツピング性が悪くなり、一方この比が0.9を超えると
耐カツト性が低下するので、この比が0.2〜0.9の範囲内
であることが必要であり、0.3〜0.7である場合、前記両
特性の改善上好ましい。なお、ND/CD比は1H-NMRスペク
トルにより、それぞれのピーク面積比から求められる。Cyclopentadiene and / or copolymerized with this petroleum resin
Alternatively, if the proportion of dicyclopentadiene is less than 25% by weight, the chipping resistance of the rubber composition in which it is compounded deteriorates. Further, if the ND / CD ratio is less than 0.2, the chipping resistance of the rubber composition will be poor, while if this ratio exceeds 0.9, the cut resistance will be reduced, so this ratio should be within the range of 0.2 to 0.9. Is required, and when it is 0.3 to 0.7, it is preferable in terms of improving both characteristics. The ND / CD ratio can be determined from each peak area ratio by 1 H-NMR spectrum.
この発明のゴム組成物に用いられるゴムは、天然ゴム及
びジエン系合成ゴムよりなる群の中から選ばれたゴムの
単独又はブレンドであり、中でも天然ゴム、スチレンブ
タジエンゴム及びブタジエンゴムが好ましく、特に天然
ゴム及びスチレンブタジエンゴムが好ましい。The rubber used in the rubber composition of the present invention is a rubber selected from the group consisting of natural rubber and diene-based synthetic rubber, alone or as a blend, among which natural rubber, styrene-butadiene rubber and butadiene rubber are preferable, and particularly, Natural rubber and styrene butadiene rubber are preferred.
この発明のゴム組成物において、前記石油樹脂のゴム10
0重量部に対する配合量が１重量部未満の場合は、ゴム
組成物の耐カツト性及び耐チツピング性の改善が得られ
ず、30重量部を超える場合は、耐発熱性や耐磨耗性が悪
化するので、１〜30重量部配合することが必要であり、
３〜15重量部の配合が好ましい。In the rubber composition of the present invention, the petroleum resin rubber 10
If the compounding amount is less than 1 part by weight with respect to 0 part by weight, the cut resistance and chipping resistance of the rubber composition cannot be improved, and if it exceeds 30 parts by weight, heat resistance and abrasion resistance are poor. As it will worsen, it is necessary to mix 1 to 30 parts by weight,
A blending amount of 3 to 15 parts by weight is preferable.
この発明においては、前記石油樹脂の他に、カーボンブ
ラツク、シリカ、炭酸カルシウム等の補強材や充填剤、
老化防止剤、加硫促進剤、オイル等の軟化剤等の通常ゴ
ム工業において用いられる配合剤を必要に応じて適宜配
合することができる。In the present invention, in addition to the petroleum resin, carbon black, silica, reinforcing materials and fillers such as calcium carbonate,
Compounding agents that are usually used in the rubber industry, such as anti-aging agents, vulcanization accelerators, and softening agents such as oils, can be appropriately compounded as necessary.
（実施例） 次に実施例及び比較例によつてこの発明をさらに詳細に
説明する。(Example) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例 １〜８ 比較例 １〜５ 表１に示す成分組成及びND/CD比を有する10種類の石油
樹脂サンプルをゴム100重量部に対し各10重量部用い、
その他は表２に示す割合を用い、バンバリーミキサーで
混練り後、加硫し、耐カツト性及びトレツド外観につい
て検討した。結果を表２に示す。Examples 1 to 8 Comparative Examples 1 to 5 Ten kinds of petroleum resin samples having the composition and ND / CD ratio shown in Table 1 were used for each 100 parts by weight of rubber, and 10 parts by weight were used.
Other than the above, the ratios shown in Table 2 were used, and after kneading with a Banbury mixer, vulcanization was performed and the cut resistance and the appearance of the tread were examined. The results are shown in Table 2.
尚、各種の試験法は下記の通りである。The various test methods are as follows.
（Ａ）耐カツト性 振子式衝撃カツト試験機にて、一定の高さから鋼鉄性の
刃を打ちつけて傷をつけ、そのカツトの深さを測定し、
比較例１の値を100として指数で表示した。値が大なる
程耐カツト性が良好なことを示す。(A) Cut resistance With a pendulum impact cut tester, a steel blade is struck from a certain height to scratch it, and the depth of the cut is measured.
The value of Comparative Example 1 was set to 100 and displayed as an index. The larger the value, the better the cut resistance.
（Ｂ）トレツド外観試験 トレツドを４分割して表２のゴム組成物により1000-20
のトラツク・バス用タイヤを作成し、砕石場等の突出岩
石の多い悪路でひんぱんに急ブレーキをかけながら3000
km走行後、トレツド表面100cm2当りの大カツト（深さ5m
m以上の傷）数、小カツト（深さ１〜5mm未満の傷）数及
びチツピング（25mm2以上のゴムの小片がそぎとられた
現象）数を評価し比較例１を100として指数で表示し
た。値が大なる程良好なことを示す。(B) Appearance test of the treads The treads were divided into four parts, and 1000-20
Create truck tires for trucks and buses of 3000, while applying sudden braking frequently on rough roads with many protruding rocks such as quarries.
After driving for km, a large cut per 100 cm 2 of surface of the tread (5 m depth)
The number of scratches (m or more), the number of small cuts (scratches with a depth of 1 to less than 5 mm) and the number of chippings (a phenomenon in which a small piece of rubber of 25 mm 2 or more was scraped off) were evaluated and displayed as an index with Comparative Example 1 as 100. did. The larger the value, the better.
（発明の効果） 表２から明らかなように、シクロペンタジエン及び／又
はジシクロペンタジエンを25重量％以上の割合に共重合
させ、かつND/CDが0.2〜0.9である石油樹脂を天然ゴム
及びジエン系合成ゴムよりなる群の中から選ばれた少な
くとも１種のゴム100重量部に対し１〜30重量部配合し
たゴム組成物は、耐カツト性及び耐チツピング性が著し
く改善されていることがわかる。 (Effects of the invention) As is apparent from Table 2, petroleum resin having a cyclopentadiene and / or dicyclopentadiene copolymerized in a proportion of 25% by weight or more and having ND / CD of 0.2 to 0.9 is used as a natural rubber and a diene. It can be seen that the rubber composition containing 1 to 30 parts by weight with respect to 100 parts by weight of at least one rubber selected from the group consisting of synthetic rubbers has remarkably improved cut resistance and chipping resistance. .
この発明のゴム組成物は、耐カツト性及び耐チツピング
性が顕著に改善されるため、特にタイヤトレツド用とし
て好適であるが、タイヤのサイドウオールや他のゴム製
品に適用することもできる。The rubber composition of the present invention is remarkably improved in cut resistance and chipping resistance, and thus is particularly suitable for tire treads, but can also be applied to tire sidewalls and other rubber products.
Claims (2)
の中から選ばれた少なくとも１種のゴム100重量部に対
し、シクロペンタジエン及び／又はジシクロペンタジエ
ンを25重量％以上、ナフサの熱分解により副生するシク
ロペンタジエン及びジシクロペンタジエン以外のC5留分
及び／又はC9留分を75重量％以下の割合で共重合させて
得た石油樹脂であり、かつ、該樹脂の構造に含まれるノ
ルボルネン環の二重結合（ND）対シクロペンテン環の二
重結合（CD）の比ND/CDが0.2〜0.9である石油樹脂を１
〜30重量部配合したことを特徴とする耐カット性及び耐
チッピング性を改善したゴム組成物。1. Pyrolysis of naphtha in an amount of 25% by weight or more of cyclopentadiene and / or dicyclopentadiene based on 100 parts by weight of at least one rubber selected from the group consisting of natural rubber and diene-based synthetic rubber. Is a petroleum resin obtained by copolymerizing a C 5 fraction and / or a C 9 fraction other than cyclopentadiene and dicyclopentadiene, which are by-products, at a ratio of 75% by weight or less, and is included in the structure of the resin. A petroleum resin having a ratio of double bond (ND) of norbornene ring to double bond (CD) of cyclopentene ring of ND / CD of 0.2 to 0.9
A rubber composition having improved cut resistance and chipping resistance, characterized by being mixed in an amount of up to 30 parts by weight.
１項記載のゴム組成物。2. The rubber composition according to claim 1, which has an ND / CD of 0.3 to 0.7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60029408A JPH0689182B2 (en) | 1985-02-19 | 1985-02-19 | Rubber composition with improved cut resistance and chipping resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60029408A JPH0689182B2 (en) | 1985-02-19 | 1985-02-19 | Rubber composition with improved cut resistance and chipping resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61190538A JPS61190538A (en) | 1986-08-25 |
| JPH0689182B2 true JPH0689182B2 (en) | 1994-11-09 |
Family
ID=12275304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60029408A Expired - Lifetime JPH0689182B2 (en) | 1985-02-19 | 1985-02-19 | Rubber composition with improved cut resistance and chipping resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689182B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0699600B2 (en) * | 1987-07-08 | 1994-12-07 | 丸善石油化学株式会社 | Rubber composition |
| WO2005090463A1 (en) * | 2004-03-18 | 2005-09-29 | Bridgestone Corporation | Pneumatic tire |
| JP4602716B2 (en) * | 2004-08-24 | 2010-12-22 | 住友ゴム工業株式会社 | Rubber composition for tread |
| FR2910905B1 (en) | 2006-12-27 | 2010-08-20 | Michelin Soc Tech | PLASTICATING SYSTEM AND RUBBER COMPOSITION FOR PNEUMATIC INCORPORATING SAID SYSTEM |
| JP5926880B2 (en) * | 2009-05-28 | 2016-05-25 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4838615A (en) * | 1971-09-17 | 1973-06-07 | ||
| JPS5638335A (en) * | 1979-09-05 | 1981-04-13 | Japan Synthetic Rubber Co Ltd | Rubber composition |
| JPS61148249A (en) * | 1984-12-21 | 1986-07-05 | Maruzen Sekiyu Kagaku Kk | Rubber composition and additive therefor |
| JPH0371464A (en) * | 1989-08-11 | 1991-03-27 | Sanyo Electric Co Ltd | Loading device for cassette tape |
-
1985
- 1985-02-19 JP JP60029408A patent/JPH0689182B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61190538A (en) | 1986-08-25 |
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