JPH02296844A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPH02296844A JPH02296844A JP1117698A JP11769889A JPH02296844A JP H02296844 A JPH02296844 A JP H02296844A JP 1117698 A JP1117698 A JP 1117698A JP 11769889 A JP11769889 A JP 11769889A JP H02296844 A JPH02296844 A JP H02296844A
- Authority
- JP
- Japan
- Prior art keywords
- rubber composition
- resin
- contained
- melamine derivative
- phenolic resin
- 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 23
- 239000005060 rubber Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 150000007974 melamines Chemical class 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 7
- 239000010680 novolac-type phenolic resin Substances 0.000 claims description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 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 claims 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 claims description 2
- 239000005011 phenolic resin Substances 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920003986 novolac Polymers 0.000 abstract description 5
- 229920001568 phenolic resin Polymers 0.000 abstract description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野］
この発明はゴム組成物において特にブレーカ−を構成す
るエツジブライ、キャッププライなどの有機繊維層に好
適なゴム組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a rubber composition suitable for an organic fiber layer such as Edge Bly or cap ply constituting a breaker.
［従来の技術］
例えば空気入りラジアルタイヤは高速走行すればショル
ダ一部はせり上がりタイヤ故障に至ることから、最近で
は高速耐久性を向上させる手段として、ブレーカ−に、
タイヤ走行中のショルダー部の成長を押さえるエツジブ
ライ及びキャップブライが使用されている。[Prior Art] For example, when pneumatic radial tires are driven at high speeds, part of their shoulders swell up, leading to tire failure.
Edge bra and cap bra are used to suppress the growth of the shoulder part of the tire while the tire is running.
［発明が解決しようとする課題］
しかし従来のエツジブライ及びキャッププライに使用さ
れているゴムは、ブライ配合の転用もしくはベルト配合
に類似した配合系が用いられているが、動的弾性率はベ
ルト配合のそれ以下であり、ベルトエツジセパレーショ
ンの改善という点では決して満足で吉るものではなく、
高速耐久性能の大きな改良は期待できないのが実情であ
った。[Problems to be Solved by the Invention] However, the rubber used in conventional Edge Bly and cap plies uses a diversion from the Bry compound or a compound system similar to the belt compound; is lower than that, and is by no means satisfactory or auspicious in terms of improving belt edge separation.
The reality was that no significant improvement in high-speed durability performance could be expected.
この発明は、ベルトとの接着性を悪化させることなく、
動的弾性率の大幅な向上を図り、ベルトエツジ等の耐セ
パレーシヨン性能を改良し合わせて高速耐久性を改良し
得るゴム組成物を提供する点に目的がある。This invention does not deteriorate adhesion to the belt.
The object of the present invention is to provide a rubber composition that can significantly improve dynamic elastic modulus, improve separation resistance such as belt edge, and improve high-speed durability.
［課題を解決するための手段］
上記課題を鋭意検討の結果、ブレーカ−を構成する有機
繊維層に用いられるゴム組成物において、ノボラック型
フェノール系樹脂を、メラミン誘導体と一定の比率で配
合したゴム組成物とした場合、接着性を悪化させること
なく、動的弾性率が大幅に向上するゴム配合となること
を見出だした。[Means for Solving the Problems] As a result of intensive study of the above problems, we have developed a rubber composition in which a novolac type phenolic resin is blended with a melamine derivative at a certain ratio in the rubber composition used for the organic fiber layer constituting the breaker. It has been found that when made into a composition, a rubber compound can be obtained in which the dynamic elastic modulus is significantly improved without deteriorating adhesiveness.
すなわちこの発明は、ノボラック型フェノール系樹脂及
びメラミン誘導体を４／１〜４／３の比率で含有し、か
つ当該ノボラック型フェノール系樹脂を２〜１０ｐｈｒ
配合したことを特徴とする高硬度ゴム組成物である。That is, this invention contains a novolac type phenolic resin and a melamine derivative in a ratio of 4/1 to 4/3, and the novolac type phenolic resin is contained in a proportion of 2 to 10 phr.
This is a high hardness rubber composition characterized by having been blended with
ノボラック型フェノール系樹脂が２ｐｈｒより少ない場
合は動的弾性率が２０ ｐｈｒ未満となりベルトエツジ
のセパレーション、高速耐久性の点で改良効果は乏しく
、１０ｐｈｒを越えると加硫速度が遅く、メラミン誘導
体が組合わされると、さらにこの傾向が促進され生産性
が低下する。また、ノボラック型フェノール系樹脂がメ
ラミン誘導体の４／１を越える比率では樹脂化が不完全
で改良効果が乏しく、４／３より少ない比率では加硫速
度が遅（生産性の点で問題があり、さらに動的弾性率も
これ以上向上せずコスト面から好ましくない。If the amount of novolac type phenolic resin is less than 2 phr, the dynamic modulus will be less than 20 phr, and there will be little improvement effect in terms of belt edge separation and high-speed durability.If it exceeds 10 phr, the vulcanization rate will be slow and melamine derivatives will be As a result, this tendency is further accelerated and productivity decreases. In addition, if the ratio of novolac type phenolic resin exceeds 4/1 of the melamine derivative, the resinization will be incomplete and the improvement effect will be poor, and if the ratio is less than 4/3, the vulcanization rate will be slow (problems in terms of productivity). Furthermore, the dynamic elastic modulus does not improve any further, which is not preferable from a cost standpoint.
従ってノボラック型フェノール系樹脂を、２〜１０ｐｈ
ｒ配合し、かつメラミン誘導体との配合比率で４／１〜
４／３の範囲で含有することが好ましい。Therefore, the novolak type phenolic resin should be used at 2 to 10 ph.
r blended, and the blending ratio with melamine derivatives is 4/1 ~
The content is preferably 4/3.
ノボラック型フェノール系樹脂としては、ノボラック型
フェノール樹脂、ノボラック型クレゾール樹脂、ノボラ
ック型レゾルシン樹脂など用いることができるが、特に
ノボラック型クレゾール樹脂等に比して臭気及び加工性
の点で好ましいノボラック型フェノール樹脂が好適であ
る。またさらにノボラック型フェノール系樹脂をロジン
油、トール油、カシュー油、リノール油、オレイン酸、
リルイン酸などのオイルで変性したものが弾性率向上の
点で好ましい。As the novolak-type phenolic resin, novolak-type phenol resin, novolak-type cresol resin, novolak-type resorcinol resin, etc. can be used, but novolak-type phenol is particularly preferable in terms of odor and processability compared to novolak-type cresol resin etc. Resins are preferred. In addition, novolak type phenolic resins are added to rosin oil, tall oil, cashew oil, linole oil, oleic acid,
Those modified with oil such as lyluic acid are preferred in terms of improving the elastic modulus.
メラミン誘導体としては特に限定されないが、下式で示
される化合物が好ましい。The melamine derivative is not particularly limited, but compounds represented by the following formula are preferred.
式中、Ｒ１、Ｒ２、Ｒ４、Ｒ９は、−ＣＨ２０Ｈ，−Ｃ
Ｈ２０ＣＨ３、−ＣＨ２０Ｃ２Ｈ，、Ｒ３は一０ＣＨ３
、ＯＣ２Ｒ５、Ｒ６はＣＨ２０ＣＨ３、ＣＨ２０Ｃ２Ｒ
５の各群から適宜選定される基であり、ｎは１〜５の範
囲のものである。特にＲ３が一０ＣＨ３、その他の基が
−ＣＨ２０Ｈ，−ＣＨ２０ＣＨ３であるメチロールメラ
ミン誘導体が好適である。これらのメラミン誘導体は、
たとえば、メラミンにホルムアルデヒドを作用させてメ
チル化し、さらに、メチルアルコールでメトキシ化させ
て水あめ状の部分メトキシ化メチロールメラミンとして
得られる。In the formula, R1, R2, R4, R9 are -CH20H, -C
H20CH3, -CH20C2H,, R3 is -CH3
, OC2R5, R6 are CH20CH3, CH20C2R
5, and n is in the range of 1 to 5. Particularly preferred are methylolmelamine derivatives in which R3 is 10CH3 and other groups are -CH20H and -CH20CH3. These melamine derivatives are
For example, melamine is methylated by the action of formaldehyde, and then methoxylated with methyl alcohol to obtain partially methoxylated methylolmelamine in the form of starch syrup.
またゴム組成物の動的弾性率は２０Ｍ、、以上であるこ
とが好ましい。Further, the dynamic elastic modulus of the rubber composition is preferably 20 M or more.
［作用］
この発明はノボラック型フェノール系樹脂をメラミン誘
導体と一定の比率で配合したゴム組成物であるので、動
的弾性率が大幅に向上し、しかも接着性を悪化させるこ
ともないことから、ベルトエツジプライ、キャッププラ
イ等のブレーカ−を構成する有機繊維層に使用すると、
ベルトエ・ソジセパレーション性能が改良され、高速耐
久性能が大幅に改善される。[Function] Since this invention is a rubber composition in which a novolac type phenolic resin is blended with a melamine derivative at a certain ratio, the dynamic elastic modulus is greatly improved, and the adhesiveness is not deteriorated. When used in organic fiber layers that make up breakers such as belt edge ply and cap ply,
The belt-e-soji separation performance has been improved, and high-speed durability performance has been greatly improved.
［実施例］
第１表に示すゴムをベルトエツジゴム及びキャップゴム
に使用したタイヤサイズ１９５／６０Ｒ１４のラジアル
タイヤを試作し、タイヤの耐久性能を試験した。[Example] A radial tire with a tire size of 195/60R14 was produced using the rubber shown in Table 1 for the belt edge rubber and cap rubber, and the durability performance of the tire was tested.
第１表にその試験結果を併記する。The test results are also listed in Table 1.
なおノボラック型フェノール樹脂はオイル変性された樹
脂である。メラミン誘導体は前記式において、Ｒ１が−
ＣＨ２０ＨＳＲ３が−ｏＣＨ３、Ｒ２、Ｒ４、Ｒ１、Ｒ
６が−ＣＨ２０ＣＨ３であって、ｎ＝１〜３のものの混
合物を使用した。Note that the novolac type phenol resin is an oil-modified resin. In the above formula, R1 is -
CH20HSR3 is -oCH3, R2, R4, R1, R
A mixture where 6 is -CH20CH3 and n=1 to 3 was used.
実走エツジセパ性能は、試作された本タイヤを実走評価
したもので、ベルト間セパレーションの長さを比較例１
を１００として指数表示した。数値の小さい程セパレー
ションが小さいことを示している。The actual running edge separation performance is an evaluation of the prototype tire, and the length of the separation between the belts was compared to Comparative Example 1.
is expressed as an index with 100. The smaller the numerical value, the smaller the separation.
加硫速度は東洋精機社製オツシレーティングディスクレ
オテスターを使用し、１６０℃で加硫し、最小トルクよ
り最大トルクの５０％に上昇するまでに要する時間（分
）を表示した。The vulcanization speed was determined by vulcanizing at 160° C. using an oscillating disc rheotester manufactured by Toyo Seiki Co., Ltd., and the time (minutes) required for the torque to increase from the minimum torque to 50% of the maximum torque was indicated.
高速耐久性はＥＴＲＴＯ規準のＥＣ３０の条件でドラム
評価を行い、比較例１をコントロールとして同一ステッ
プ内の走行時間を指数表示した。For high-speed durability, the drum was evaluated under the conditions of EC30 according to the ETRTO standard, and the running time within the same step was expressed as an index using Comparative Example 1 as a control.
数値が大きいほど良好である。The larger the value, the better.
動的弾性率の測定は、若木製作所製の動的粘弾性スペク
トロメータを用い、６０℃で周波数５０Ｈｚ、動歪１％
で測定した値である。The dynamic elastic modulus was measured using a dynamic viscoelasticity spectrometer manufactured by Wakagi Seisakusho at 60°C, a frequency of 50 Hz, and a dynamic strain of 1%.
This is the value measured at
第１表から、オイル変性のノボラック型フェノール樹脂
を、メラミン誘導体と一定の比率で配合したゴム組成物
とした場合、接着性を低下させずに弾性率が向上し、結
果として高速耐久性の顕著な改善が認められる。Table 1 shows that when a rubber composition is prepared by blending oil-modified novolak-type phenolic resin with a melamine derivative at a certain ratio, the elastic modulus improves without reducing adhesion, resulting in remarkable high-speed durability. Significant improvements were observed.
［発明の効果］
以上の如くこの発明は、ノボラック型フェノール系樹脂
をメラミン誘導体と一定の比率で配合したゴム組成物で
あるので、従来の接着重点志向の配合ゴムに比べ、接着
性の低下することなく弾性率が大幅に向上し、高速耐久
性能に極めて優れたブレーカ−の有機繊維層と成し得る
ゴム組成物を提供できた。[Effects of the Invention] As described above, the present invention is a rubber composition in which a novolac type phenolic resin is blended with a melamine derivative at a certain ratio, so the adhesiveness is lower than that of conventional compounded rubbers that are oriented to focus on adhesion. We were able to provide a rubber composition that can be used as an organic fiber layer of a breaker, which has a significantly improved modulus of elasticity and excellent high-speed durability performance.
Claims (2)
ム組成物において、ノボラック型フェノール系樹脂及び
メラミン誘導体を４／１〜４／３の比率で含有し、かつ
当該ノボラック型フェノール系樹脂を２〜１０ｐｈｒ配
合したことを特徴とするゴム組成物。(1) In the rubber composition used for the organic fiber layer constituting the breaker, the novolac type phenolic resin and the melamine derivative are contained in a ratio of 4/1 to 4/3, and the novolac type phenolic resin is contained in the ratio of 2 to 4/3. A rubber composition characterized by containing 10 phr.
イル変性された請求項１記載のゴム組成物。(2) The rubber composition according to claim 1, wherein the novolac type phenolic resin is oil-modified with rosin oil or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1117698A JPH02296844A (en) | 1989-05-10 | 1989-05-10 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1117698A JPH02296844A (en) | 1989-05-10 | 1989-05-10 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02296844A true JPH02296844A (en) | 1990-12-07 |
Family
ID=14718089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1117698A Pending JPH02296844A (en) | 1989-05-10 | 1989-05-10 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02296844A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283274A (en) * | 1992-06-19 | 1994-02-01 | Uniroyal Chemical Company, Inc. | Substituted pyrimidines and substituted triazines as rubber-to-metal adhesion promoters |
| JP2003002006A (en) * | 2001-06-27 | 2003-01-08 | Toyo Tire & Rubber Co Ltd | Pneumatic tire |
| EP1323776A2 (en) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Use of plastified novolak resins as additive for rubber mixtures |
| JP2009046576A (en) * | 2007-08-20 | 2009-03-05 | Sumitomo Rubber Ind Ltd | Rubber composition for breaker edge-covering, and tire having breaker edge-covering by using the same |
| JP2015221901A (en) * | 2011-01-19 | 2015-12-10 | ブリヂストン アメリカズ タイヤ オペレイションズ エルエルシー | Rubber composition suitable for use as cap ply in tire |
-
1989
- 1989-05-10 JP JP1117698A patent/JPH02296844A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5283274A (en) * | 1992-06-19 | 1994-02-01 | Uniroyal Chemical Company, Inc. | Substituted pyrimidines and substituted triazines as rubber-to-metal adhesion promoters |
| JP2003002006A (en) * | 2001-06-27 | 2003-01-08 | Toyo Tire & Rubber Co Ltd | Pneumatic tire |
| EP1323776A2 (en) * | 2001-12-20 | 2003-07-02 | Surface Specialties Germany GmbH & Co. KG | Use of plastified novolak resins as additive for rubber mixtures |
| EP1323776A3 (en) * | 2001-12-20 | 2004-01-14 | Surface Specialties Germany GmbH & Co. KG | Use of plastified novolak resins as additive for rubber mixtures |
| JP2009046576A (en) * | 2007-08-20 | 2009-03-05 | Sumitomo Rubber Ind Ltd | Rubber composition for breaker edge-covering, and tire having breaker edge-covering by using the same |
| JP2015221901A (en) * | 2011-01-19 | 2015-12-10 | ブリヂストン アメリカズ タイヤ オペレイションズ エルエルシー | Rubber composition suitable for use as cap ply in tire |
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