JP3175017B2 - High hardness rubber composition - Google Patents
High hardness rubber compositionInfo
- Publication number
- JP3175017B2 JP3175017B2 JP26071991A JP26071991A JP3175017B2 JP 3175017 B2 JP3175017 B2 JP 3175017B2 JP 26071991 A JP26071991 A JP 26071991A JP 26071991 A JP26071991 A JP 26071991A JP 3175017 B2 JP3175017 B2 JP 3175017B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- parts
- weight
- rubber composition
- elastic modulus
- 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 - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、加硫後の動的弾性率が
高く、破断物性 (破断伸び (％))に優れた高硬度ゴム組
成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-hardness rubber composition having a high dynamic elastic modulus after vulcanization and excellent physical properties at break (elongation at break (%)).
【０００２】[0002]
【従来の技術】従来、タイヤのビードフィラー等には硬
度の高いゴム組成物が用いられている。そして、加硫後
のゴム組成物の動的弾性率 (以下、弾性率という) を増
大させて硬度を高めるために、ゴムにカーボンブラッ
ク、硫黄、熱硬化性樹脂等の配合剤を多量に配合してい
る。たしかに、ゴムにカーボンブラックを多量配合する
ことでゴム組成物の弾性率を高めることは可能ではある
が、このゴム組成物は加工工程中におけるゴムのまとま
り、バンバリーミキサーの電力負荷の増大、ロール上で
の捲き付き状態が極めて悪く、実用に供し難いものであ
る。また、硫黄を多量に配合することでゴムの弾性率を
高めることが行なわれているが、このゴム組成物は高硫
黄配合のために押出時に硫黄のブルームが激しく、この
ためタイヤ成型作業性を困難にさせたり、製品の歩留り
を低下させる等により好ましくない。そこで、近年は、
硫黄の多量配合を避け、かつカーボンブラックの配合量
を実用に供し得る程度に抑えながら加硫後のゴム組成物
の弾性率を増大させる手段としてノボラック型フェノー
ル系樹脂やノボラック型変性フェノール系樹脂等の熱硬
化性樹脂を多量配合する例が多くなっている。2. Description of the Related Art Conventionally, rubber compositions having high hardness have been used for bead fillers and the like of tires. In order to increase the dynamic elastic modulus (hereinafter referred to as the elastic modulus) of the vulcanized rubber composition and increase its hardness, rubber is blended with a large amount of compounding agents such as carbon black, sulfur, and thermosetting resin. are doing. Certainly, it is possible to increase the elastic modulus of the rubber composition by adding a large amount of carbon black to the rubber.However, this rubber composition increases the power load of the Banbury mixer, Is extremely poor and difficult to put into practical use. In addition, it has been practiced to increase the elastic modulus of rubber by blending a large amount of sulfur.However, this rubber composition has a high sulfur bloom at the time of extrusion due to a high sulfur blending. This is not preferable because it makes it difficult or lowers the product yield. So, in recent years,
Novolak-type phenolic resins and novolak-type modified phenolic resins have been used as means for increasing the elastic modulus of a rubber composition after vulcanization while avoiding a large amount of sulfur and keeping the compounding amount of carbon black to a practically usable level. Examples of blending a large amount of the thermosetting resin are increasing.
【０００３】しかしながら、上述のような熱硬化性樹脂
とカーボンブラックを併用配合したゴム組成物は、加硫
後の弾性率についてはある程度高まるものの、破断物性
が悪く、このためタイヤのビードフィラー等に用いた場
合にはタイヤの耐久性が悪くなるという問題があった。[0003] However, the rubber composition obtained by combining the above-mentioned thermosetting resin and carbon black in combination has a somewhat high elastic modulus after vulcanization, but has a poor breaking property. When used, there is a problem that the durability of the tire is deteriorated.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
事情にかんがみなされたもので、加硫後の弾性率が高
く、破断物性に優れた高硬度ゴム組成物を提供すること
を目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and has as its object to provide a high-hardness rubber composition having a high elastic modulus after vulcanization and excellent break properties. I do.
【０００５】[0005]
【課題を解決するための手段】本発明の高硬度ゴム組成
物は、天然ゴム、ポリイソプレンゴム、ポリブタジエン
ゴム、スチレン−ブタジエン共重合体ゴム、ブチルゴム
の１種又は２種以上からなるゴム分１00重量部に対し、
70〜90重量部の平均粒子径が40ｍμ以下のカーボンブラ
ックと５〜20重量部のノボラック型変性フェノール系樹
脂と１〜10重量部のヘキサあるいはペンタメトキシヘキ
サメチロールメラミンの単体もしくは部分縮合物と20〜
35重量部の粘度 20000〜50000cpsの重合カーダノールを
配合してなることを特徴とする。The high-hardness rubber composition of the present invention comprises a rubber composition comprising one or more of natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber and butyl rubber. For parts by weight,
70 to 90 parts by weight of carbon black having an average particle diameter of 40 mμ or less, 5 to 20 parts by weight of a novolak-type modified phenolic resin and 1 to 10 parts by weight of a simple substance or a partial condensate of hexa or pentamethoxyhexamethylol melamine. ~
It is characterized by comprising 35 parts by weight of polymerized cardanol having a viscosity of 20000 to 50000 cps.
【０００６】以下、本発明の構成につき詳しく説明す
る。 (１) ゴム分。 天然ゴム (ＮＲ) 、ポリイソプレンゴム (ＩＲ) 、ブチ
ルゴム、ポリブタジエンゴム (ＢＲ) 、スチレン−ブタ
ジエン共重合体ゴム (ＳＢＲ) の１種又は２種以上から
なる。これらのゴムは、公知のものでよい。Hereinafter, the configuration of the present invention will be described in detail. (1) Rubber content. It is composed of one or more of natural rubber (NR), polyisoprene rubber (IR), butyl rubber, polybutadiene rubber (BR), and styrene-butadiene copolymer rubber (SBR). These rubbers may be known ones.
【０００７】(２) カーボンブラック。 平均粒子径が40ｍμ以下のものであって、例えば、ＳＡ
Ｆ, ＩＳＡＦ, Ｉ−ＩＳＡＦ, ＣＦ, ＳＣＦ, ＨＡＦな
どのいわゆるハードカーボンである。また、カーボンブ
ラックの粒子径については、粒子径40ｍμを超えるもの
を前記のカーボンブラックに混合して使用してもよく、
使用するカーボンブラックの総平均粒子径が40ｍμ以下
になるように配合すれば本発明の目的は達せられる。平
均粒子径が40ｍμ超の場合には、ゴム組成物の動的弾性
率が不十分となる。(2) Carbon black. Having an average particle size of 40 mμ or less, for example, SA
So-called hard carbon such as F, ISAF, I-ISAF, CF, SCF, and HAF. Further, regarding the particle diameter of carbon black, those having a particle diameter of more than 40 mμ may be used as a mixture with the carbon black,
The object of the present invention can be achieved by blending the carbon black to be used so that the total average particle diameter of the carbon black used is 40 mμ or less. When the average particle diameter is more than 40 mμ, the dynamic elastic modulus of the rubber composition becomes insufficient.
【０００８】カーボンブラックは、上記ゴム分１00重量
部に対して70〜90重量部配合することを要する。70重量
部未満ではゴム組成物の動的弾性率が十分に出ず、一
方、90重量部を超えるとカーボンブラックの分散性およ
びゴム組成物の加工性が悪くなり、実用に供し得なくな
る。 (３) ノボラック型変性フェノール系樹脂。[0008] It is necessary to add 70 to 90 parts by weight of carbon black to 100 parts by weight of the rubber component. When the amount is less than 70 parts by weight, the dynamic elastic modulus of the rubber composition is not sufficiently obtained. On the other hand, when the amount exceeds 90 parts by weight, the dispersibility of carbon black and the processability of the rubber composition are deteriorated, and the rubber composition is not practically usable. (3) Novolak-type modified phenolic resin.
【０００９】本発明において用いるノボラック型変性フ
ェノール系樹脂としては、ロジンオイル、トールオイ
ル、カシューオイル、リノール酸、オレイン酸、リノレ
イン酸等のオイルで変性したノボラック型フェノール系
樹脂、またはキシレン、メシチレン等の芳香族炭化水素
で変性したノボラック型フェノール系樹脂、およびニト
リルゴム等のゴムで変性したノボラック型フェノール系
樹脂が挙げられる。The novolak-type modified phenolic resin used in the present invention includes a novolak-type phenolic resin modified with an oil such as rosin oil, tall oil, cashew oil, linoleic acid, oleic acid and linoleic acid, or xylene and mesitylene. And a novolak-type phenolic resin modified with a rubber such as a nitrile rubber.
【００１０】この樹脂の配合量は上記ゴム分１00重量部
に対して５〜20重量部であることが必要である。５重量
部未満では動的弾性率が低くなり、一方、20重量部を超
えると混合加工性がわるくなる。 (４) ヘキサあるいはペンタメトキシヘキサメチロール
メラミンの単体もしくは部分縮合物。It is necessary that the amount of the resin is 5 to 20 parts by weight based on 100 parts by weight of the rubber component. If the amount is less than 5 parts by weight, the dynamic elastic modulus is low, while if it exceeds 20 parts by weight, the mixing processability becomes poor. (4) A simple substance or partial condensate of hexa or pentamethoxyhexamethylol melamine.
【００１１】ここで、ヘキサあるいはペンタメトキシヘ
キサメチロールメラミンとは、ヘキサメトキシヘキサメ
チロールメラミン又はペンタメトキシヘキサメチロール
メラミンをいう。"部分縮合物" とは、ヘキサあるいは
ペンタメトキシヘキサメチロールメラミンの部分縮合物
をいう。Here, the term “hexa or pentamethoxyhexamethylolmelamine” refers to hexamethoxyhexamethylolmelamine or pentamethoxyhexamethylolmelamine. “Partial condensate” refers to a partial condensate of hexa or pentamethoxyhexamethylol melamine.
【００１２】配合量は、上記ゴム分１00重量部に対し、
１〜10重量部である。１重量部未満ではゴム組成物の動
的弾性率が十分でなく、一方、10重量部を超えると破断
物性が低下するからである。 (５) 重合カーダノール。 下記式に示されるようにカシューナット殻液 (カシュー
オイル) を加熱重合させて得られる公知のものである。The compounding amount is based on 100 parts by weight of the rubber component.
It is 1 to 10 parts by weight. If the amount is less than 1 part by weight, the dynamic elastic modulus of the rubber composition is not sufficient, while if it exceeds 10 parts by weight, the physical properties of breakage deteriorate. (5) Polymerized cardanol. As shown in the following formula, it is a known product obtained by heating and polymerizing cashew nut shell liquid (cashew oil).
【００１３】 [0013]
【００１４】本発明においては、粘度20000 〜50000cps
の重合カーダノ−ルを使用する。粘度が20000cps未満で
は加硫後の弾性率の向上が十分には期待できない。粘度
が50000cps超では未加硫時のゴム組成物の粘度が高くな
りすぎて加工性を低下させてしまう。尚、本発明におい
て重合カーダノ−ルの粘度とは、JIS Z 8803に準拠した
方法で測定した粘度を意味する。本発明で用いる重合カ
ーダノ−ルの配合量は、ゴム分100 重量部に対して20〜
35重量部である。20重量部未満では未加硫時の軟化効果
が低く、35重量部を超えると動的弾性率が低くなる。In the present invention, the viscosity is 20,000 to 50,000 cps.
Is used. If the viscosity is less than 20000 cps, it is not possible to sufficiently improve the elastic modulus after vulcanization. If the viscosity is more than 50000 cps, the viscosity of the rubber composition before vulcanization becomes too high, thereby lowering processability. In the present invention,
The viscosity of the polymerization cardanol is based on JIS Z 8803.
It means the viscosity measured by the method. The amount of the polymerization cardanol used in the present invention is from 20 to 100 parts by weight of the rubber component.
35 parts by weight. If the amount is less than 20 parts by weight, the softening effect at the time of unvulcanization is low.
【００１５】(６) このようにしてなる本発明のゴム組
成物には、必要に応じて、加硫剤、加硫促進剤等の他の
配合剤を適宜配合してもよい。(6) The rubber composition of the present invention thus obtained may optionally contain other compounding agents such as a vulcanizing agent and a vulcanization accelerator.
【００１６】[0016]
【実施例】下記表１に示される配合内容 (重量部) で各
成分を混合した。この混合は、Ｂ型バンバリーミキサー
(容量1.7L) で通常どおり混練りを実施することにより
行ない、得られた各種ゴム組成物を160℃で15分間プレ
ス加硫して厚さ２mmの加硫ゴムシートを作成した。EXAMPLES Each component was mixed according to the formulation (parts by weight) shown in Table 1 below. This mixing is a B-type Banbury mixer
The mixture was kneaded as usual (at a capacity of 1.7 L), and the obtained rubber compositions were press-vulcanized at 160 ° C. for 15 minutes to prepare a vulcanized rubber sheet having a thickness of 2 mm.
【００１７】このゴムシートを用いて、動的弾性率につ
いては岩本製作所製粘弾性スペクトロメータで、長さ20
mm、幅５mmの短冊状サンプルに初期歪５％伸長させた状
態で周波数20Hz、動歪２％の条件下 (室温) で測定し
た。破断伸びについては、JIS-K-6301に準じて測定し
た。これらの結果を表１に示す。また、タイヤ耐久性の
評価は、表１に示す本発明ゴム組成物および比較ゴム組
成物をタイヤ (165SR13)のビードフィラーに用い、JATM
A 規格に従い、空気圧は最大許容空気圧とし、速度81km
/hで低荷重より荷重を増加させて行き、タイヤビード部
破壊が生じるまでの走行距離を測定することによった。
この結果を指数で表１に示す。数値が大きい方がよい。Using this rubber sheet, the dynamic elastic modulus was measured with a viscoelastic spectrometer manufactured by Iwamoto Seisakusho, having a length of 20 mm.
The measurement was performed under the condition (room temperature) of a frequency of 20 Hz and a dynamic strain of 2% in a state where a rectangular sample having a width of 5 mm and an initial strain of 5 mm were stretched by 5%. The elongation at break was measured according to JIS-K-6301. Table 1 shows the results. Tire durability was evaluated using the rubber composition of the present invention and the comparative rubber composition shown in Table 1 as bead fillers for tires (165SR13).
According to the A standard, the air pressure is the maximum allowable air pressure, speed 81 km
The load was increased from a low load at / h, and the running distance until the tire bead portion was broken was measured.
The results are shown in Table 1 as indices. Larger numbers are better.
【００１８】 [0018]
【００１９】表１から明らかなように、本発明ゴム組成
物は、破断伸び、JIS硬度、および動的弾性率のいずれ
においても優れており、本発明ゴム組成物をビードフィ
ラーに用いたタイヤは耐久性において優れていることが
判る。As is clear from Table 1, the rubber composition of the present invention is excellent in all of elongation at break, JIS hardness and dynamic elastic modulus. It turns out that it is excellent in durability.
【００２０】[0020]
【発明の効果】以上説明したように本発明ゴム組成物
は、加硫後の動的弾性率が高く、かつ破断物性にも優れ
ている。したがって、このゴム組成物からなるビードフ
ィラーを有するタイヤは、前記表１から明らかなよう
に、耐久性に優れるものである。As described above, the rubber composition of the present invention has a high dynamic modulus of elasticity after vulcanization and also has excellent fracture properties. Therefore, a tire having a bead filler made of the rubber composition has excellent durability, as is clear from Table 1.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 61:28 93:00） (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 21/00 C08K 3/04 C08L 23/22 C08L 61/06 C08L 61/28 C08L 93/00 Continuation of the front page (51) Int.Cl. 7 identification code FI C08L 61:28 93:00) (58) Field surveyed (Int.Cl. 7 , DB name) C08L 21/00 C08K 3/04 C08L 23 / 22 C08L 61/06 C08L 61/28 C08L 93/00
Claims (1)
タジエンゴム、スチレン−ブタジエン共重合体ゴム、ブ
チルゴムの１種又は２種以上からなるゴム分１00重量部
に対し、70〜90重量部の平均粒子径が40ｍμ以下のカー
ボンブラックと５〜20重量部のノボラック型変性フェノ
ール系樹脂と１〜10重量部のヘキサあるいはペンタメト
キシヘキサメチロールメラミンの単体もしくは部分縮合
物と20〜35重量部の粘度 20000〜50000cpsの重合カーダ
ノールを配合してなる高硬度ゴム組成物。1. An average particle diameter of 70 to 90 parts by weight based on 100 parts by weight of a rubber component composed of one or more of natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, and butyl rubber. Is 40 mμ or less, 5 to 20 parts by weight of a novolak-type modified phenolic resin and 1 to 10 parts by weight of a simple substance or a partial condensate of hexa or pentamethoxyhexamethylol melamine and 20 to 35 parts by weight having a viscosity of 20000 to 50000 cps A high hardness rubber composition comprising a polymerized cardanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26071991A JP3175017B2 (en) | 1991-10-08 | 1991-10-08 | High hardness rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26071991A JP3175017B2 (en) | 1991-10-08 | 1991-10-08 | High hardness rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0598081A JPH0598081A (en) | 1993-04-20 |
| JP3175017B2 true JP3175017B2 (en) | 2001-06-11 |
Family
ID=17351810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26071991A Expired - Fee Related JP3175017B2 (en) | 1991-10-08 | 1991-10-08 | High hardness rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3175017B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372859A (en) * | 2010-08-09 | 2012-03-14 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174464A3 (en) * | 2000-07-14 | 2004-01-07 | Surface Specialties Germany GmbH & Co. KG | Rubber article with low development of heat |
| DE10162771A1 (en) * | 2001-12-20 | 2003-07-10 | Solutia Germany Gmbh & Co Kg | Use of plasticized novolaks as an additive to rubber compounds |
| KR20030062174A (en) * | 2002-01-16 | 2003-07-23 | 엘지전선 주식회사 | Highly durable rubber compounds |
| US7132481B2 (en) * | 2002-05-17 | 2006-11-07 | The Goodyear Tire & Rubber Company | Composite of melamine derivative and carbon black, rubber composition and article having a component thereof |
| JP5592351B2 (en) | 2009-03-30 | 2014-09-17 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| JP2010254166A (en) * | 2009-04-27 | 2010-11-11 | Bridgestone Corp | Rubber composition for rubber crawlers, and rubber crawler |
| JP5471826B2 (en) * | 2010-05-21 | 2014-04-16 | 横浜ゴム株式会社 | Rubber composition for tire tread and pneumatic tire using the same |
| JP5731771B2 (en) | 2010-08-27 | 2015-06-10 | 株式会社ブリヂストン | Manufacturing method of rubber composition, rubber composition and tire using the same |
-
1991
- 1991-10-08 JP JP26071991A patent/JP3175017B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372859A (en) * | 2010-08-09 | 2012-03-14 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
| CN102372859B (en) * | 2010-08-09 | 2013-05-15 | 韩国轮胎株式会社 | Rubber composition for tire and tire manufactured by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0598081A (en) | 1993-04-20 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| LAPS | Cancellation because of no payment of annual fees |