JPS62263239A - Low heat-generating rubber composition - Google Patents
Low heat-generating rubber compositionInfo
- Publication number
- JPS62263239A JPS62263239A JP10676686A JP10676686A JPS62263239A JP S62263239 A JPS62263239 A JP S62263239A JP 10676686 A JP10676686 A JP 10676686A JP 10676686 A JP10676686 A JP 10676686A JP S62263239 A JPS62263239 A JP S62263239A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- parts
- weight
- rubber composition
- low heat
- 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 37
- 239000005060 rubber Substances 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- -1 tetrazole compound Chemical class 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 8
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 8
- 229920001194 natural rubber Polymers 0.000 claims abstract description 8
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 6
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 6
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 150000001993 dienes Chemical class 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- FWRCSEIJYYDVAQ-UHFFFAOYSA-N 4-(5-phenyltetrazol-2-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1N=C(C=2C=CC=CC=2)N=N1 FWRCSEIJYYDVAQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006229 carbon black Substances 0.000 abstract description 3
- 239000004902 Softening Agent Substances 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000003623 enhancer Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000020169 heat generation Effects 0.000 description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 150000002832 nitroso derivatives Chemical class 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- GJHVUNPZKRIADK-UHFFFAOYSA-N 2-nitrosoquinoline Chemical class C1=CC=CC2=NC(N=O)=CC=C21 GJHVUNPZKRIADK-UHFFFAOYSA-N 0.000 description 1
- ARIREUPIXAKDAY-UHFFFAOYSA-N 4-butylbenzaldehyde Chemical compound CCCCC1=CC=C(C=O)C=C1 ARIREUPIXAKDAY-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- KOOMFXGDLMRWSN-UHFFFAOYSA-N n-phenylnitrous amide Chemical class O=NNC1=CC=CC=C1 KOOMFXGDLMRWSN-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Chemical group 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-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、低発熱性ゴム組成物に関するものである。[Detailed description of the invention] (Industrial application field) The present invention relates to a low heat generation rubber composition.
（従来の技術）
省資源、省エネルギーの社会的要求に対応するため、ゴ
ム業界特にタイヤ業界において、ここ数年来、低燃費タ
イヤの開発か盛んに行われるようになってきた。このよ
うな低燃費タイヤの開発には低発熱性ゴム組成物が不可
決であり、例えば、特に乗用車用タイヤを目的として、
特開昭５７−５１５０３号、特開昭５７−５５２０４号
、特開昭５１１−３６７０５号に記載されているように
、結合スチレンとビニル結合の含有率をコントロールし
たスチレン−ブタジェンゴム（ＳＢＲ）を使用する方法
かあるが、これらの方法はＳＢＲ以外のゴム、特に重車
両用タイヤにもっとも広く使用されている天然ゴムには
全く応用できなかった。(Prior Art) In order to meet social demands for resource and energy conservation, the rubber industry, particularly the tire industry, has been actively developing tires with low fuel consumption over the past few years. Low heat generation rubber compositions are essential for the development of such fuel-efficient tires, and for example, especially for passenger car tires,
As described in JP-A-57-51503, JP-A-57-55204, and JP-A-511-36705, styrene-butadiene rubber (SBR) with controlled content of bound styrene and vinyl bonds is used. However, these methods could not be applied to rubbers other than SBR, especially natural rubber, which is most widely used in heavy vehicle tires.
一方、特公昭５０−３８１３１号、英国特許第１１８５
８９６号、米国特許第２３１５８５５号及び特許第２３
１５８５６号等にニトロソキノリン類、ニトロソアニリ
ン類等を添加することにより、ゴム組成物の発熱性が改
善されることか記載されている。しかしなから。On the other hand, Japanese Patent Publication No. 50-38131, British Patent No. 1185
No. 896, U.S. Patent No. 2,315,855 and Patent No. 23
No. 15856 and the like describes that the heat generation properties of rubber compositions can be improved by adding nitrosoquinolines, nitrosoanilines, etc. But because.
このようなニトロソ化合物は、確かに５１．＠性を改善
するか、特にポリイソプレンゴムに適用した場合、ポリ
マーのしやっ解作用か大きくゴム組成物の＃庁耗性を著
しく低下させるといった欠点を有していた。また上記ニ
トロソ化合物はポリイソプレンゴムに適用した場合には
、発熱性を著しく改善するか１合成ゴム、例えばスチレ
ン−ブタジェン共重合ゴムやポリブタジェンゴム等に適
用した場合、発熱性改良効果は余り期待できなかった。Such nitroso compounds are certainly 51. In particular, when it is applied to polyisoprene rubber, it has the disadvantage that it significantly reduces the wear resistance of the rubber composition due to the large softening effect of the polymer. Furthermore, when the above-mentioned nitroso compound is applied to polyisoprene rubber, it significantly improves the heat generation property, but when applied to synthetic rubber, such as styrene-butadiene copolymer rubber or polybutadiene rubber, the heat generation property improvement effect is not so great. I couldn't expect it.
（発明か解決しようとする問題点）
本発明は、前記のような天然ゴムに応用することかてき
なかったり、ポリイソプレンゴムに適用した場合、しゃ
っ解作用か大きかったり、更には、スチレン−ブタジェ
ン共重合体ゴムやポリブタジェンゴムに適用した場合、
余り発熱改良効果がＮ′ｆｔ出来なかったりする問題を
解決して、このような欠点のない低発熱性ゴム組成物を
提供しようとするものである。(Problems to be Solved by the Invention) The present invention cannot be applied to natural rubber as described above, and when applied to polyisoprene rubber, it has a large sagging effect, and furthermore, it has problems with styrene rubber. When applied to butadiene copolymer rubber or polybutadiene rubber,
The present invention aims to solve the problem that the heat generation improvement effect N'ft is not so great and to provide a low heat generation rubber composition that does not have such drawbacks.
（問題点を解決するための手段）
木発明者らは、上記欠点を改善することを目的として、
ニトロソ化合物以外の発熱改良剤について鋭意検討した
結果、本発明に到達したものである。(Means for solving the problem) In order to improve the above-mentioned drawbacks, the inventors of the tree
The present invention was arrived at as a result of intensive studies on heat generation improvers other than nitroso compounds.
すなわち、本発明は、天然ゴム及び／又−はジニン系合
成ゴムからなるゴム１００ 重量部に、補強性充填材２
０〜１５０重量部、
一般式
式中Ｒ１及び／又はＲ２は水素原子、炭素数１から４の
アルキル基、ヒドロキシル基、ハロゲン、アルコキシ基
を、ｍ及び／又はｎは１ないし２を示す
で表わされるテトラゾール化合物０．１〜１０重量部配
合したことを特徴とする低発熱性ゴム組成物に関するも
のである。That is, in the present invention, 2 parts by weight of a reinforcing filler is added to 100 parts by weight of rubber made of natural rubber and/or dinin-based synthetic rubber.
0 to 150 parts by weight, in the general formula, R1 and/or R2 represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, an alkoxy group, and m and/or n represent 1 to 2. The present invention relates to a low heat build-up rubber composition characterized by containing 0.1 to 10 parts by weight of a tetrazole compound.
本発明において使用するゴムとしては、天然ゴム、合成
ポリイソプレンゴム、スチレン−ブタジェンゴム共重合
ゴム、ポリブタジェンゴム、ブチルゴム等てあり、これ
らのゴムを単独もしくは２種以上併所することができる
。Rubbers used in the present invention include natural rubber, synthetic polyisoprene rubber, styrene-butadiene rubber copolymer rubber, polybutadiene rubber, butyl rubber, and these rubbers may be used alone or in combination of two or more.
本発明において発熱改良剤として使用するテトラゾール
化合物の具体的なものは、２−ｐ−カルボキシルフェニ
ル−５−フェニルテトラゾール（ＣＰＰＴ）、 ２−ｐ
−カルボキシルフェニル−５−ｐ−トリルテトラゾール
（ＣＰＴＴ）、 ２−Ｐ−カルボキシルフェニル−５−
Ｐ−ｎ−ブチルフェニルテトラゾール（ＣＰＢＰＴ）
、 ２− ｐ−カルボキシルフェニル−５−ｐ−クロロ
フェニルテトラゾール（ＣＰＣＰＴ） 、 ２− ｐ−
カルボキシルフェニル−５−ｐ−メトキシフェニルテト
ラゾール（ＣＰＭＰＴ） 、 ２−ｐ−カルボキシル
フェニル−５−（３’ 、５’ −シーｔ−ブチル−４
′−ヒドロキシフェニル）テトラゾール（ＣＰＢＨＰＴ
）等であり、これらは単独であっても２種以上併用して
もよい、テトラゾール化合物の配合量は０．１〜１０重
景部である。０．１重量部てはゴム組成物の発熱改良効
果がほとんど期待できず、１０重量部を越えると、もは
や増量効果がなくなるばかりか、ゴム組成物の機械的性
質か低下するため好ましくない。Specific examples of the tetrazole compounds used as the heat generation improver in the present invention include 2-p-carboxylphenyl-5-phenyltetrazole (CPPT), 2-p
-Carboxylphenyl-5-p-tolyltetrazole (CPTT), 2-P-carboxylphenyl-5-
P-n-butylphenyltetrazole (CPBPT)
, 2-p-carboxylphenyl-5-p-chlorophenyltetrazole (CPCPT), 2-p-
Carboxylphenyl-5-p-methoxyphenyltetrazole (CPMPT), 2-p-carboxylphenyl-5-(3',5'-t-butyl-4
'-Hydroxyphenyl)tetrazole (CPBHPT
), which may be used alone or in combination of two or more, and the amount of the tetrazole compound to be blended is 0.1 to 10 parts. If the amount is 0.1 part by weight, hardly any effect of improving the heat generation of the rubber composition can be expected, and if it exceeds 10 parts by weight, not only will the effect of increasing the amount be lost, but also the mechanical properties of the rubber composition will deteriorate, which is not preferable.
本発明に３いて補強性充填剤（カーボンブラックなど）
の配合量は、２０〜１５０重量部てあり ２０重量部未
満てはゴム組成物の補強性か劣り、１５０重量部を越え
ると発熱性が著しく悪化するばかってなく、耐摩耗性等
の物性か著しく悪化する。In the present invention, reinforcing filler (such as carbon black)
The blending amount is 20 to 150 parts by weight.If it is less than 20 parts by weight, the reinforcing properties of the rubber composition will be poor, and if it exceeds 150 parts by weight, not only will the heat generation property deteriorate significantly, but the physical properties such as abrasion resistance will deteriorate. Significantly worsens.
本発明においては、上記の補強性充填剤と発熱改良剤以
外に、必要に応じて軟化剤、老化防止剤、加硫促進剤、
加硫促進助剤、加硫剤等の通常ゴム工業て使用される配
合剤を適宜配合することができる。In the present invention, in addition to the above-mentioned reinforcing fillers and heat generation improvers, softeners, anti-aging agents, vulcanization accelerators,
Compounding agents commonly used in the rubber industry, such as vulcanization accelerators and vulcanizing agents, can be appropriately blended.
また１本発明のゴムｍ成物は、タイヤ、コンベアベルト
、ホース等のあらゆるゴム製品に適用てきる。Furthermore, the rubber composition of the present invention can be applied to all kinds of rubber products such as tires, conveyor belts, hoses, etc.
（実施例）
以下１本発明を、合成例、実施例及び比較例により詳細
に説明する。(Example) The present invention will be explained in detail below using a synthesis example, an example, and a comparative example.
ｐ−アミノ安息香酸４５．２ｇ （０，３ｆｆモル）、
５０ｖｏ１％エタノール水溶液−１８０ｍＭ、３５％１
ｌｃｊ１８ｔａｎの溶液に、ＮａＮ０ｚ（９７％）２：
１．Ｓｇ（０，３３モル）を水１２０ Ｉｌｌに溶解し
た溶液な０〜ｌＯ°Ｃて１時間かけて滴下する事により
、原料のジアゾニウム塩の溶液を得た。p-aminobenzoic acid 45.2 g (0.3 ff mol),
50vol 1% ethanol aqueous solution - 180mM, 35%1
In a solution of lcj18tan, NaN0z (97%) 2:
1. A solution of Sg (0.33 mol) dissolved in 120 Ill of water was added dropwise at 0 to 10°C over 1 hour to obtain a solution of the raw material diazonium salt.
次にベンズアルデヒドのｐ−トルエンスルホニルヒドラ
ゾン８２．２ｇ （０，：１モル）のピリジン１．２文
の溶液に、上記のジアゾニウム塩の溶液を一１０〜Ｏ℃
で４時間かけて滴下した後、更に一１０〜０℃で３時間
、０〜１０”Ｃて８時間攪拌を行って反応を終でさせな
、生成した結晶を濾過し、濾紙上をよく水洗した後、５
０°Ｃで４８時間、８ＩＬ乾燥して目的とする２−ｐ−
カルボキシルフェニル−５−フェニルテトラゾール（ｍ
、ｐ、＞３００℃） ４３．７ｇ（収率５４．８％）を
得た。Next, a solution of the above diazonium salt was added to a solution of 82.2 g (0.:1 mole) of p-toluenesulfonylhydrazone of benzaldehyde in 1.2 g of pyridine at -10 to 0°C.
After adding dropwise over 4 hours, stir at -10 to 0℃ for 3 hours and at 0 to 10''C for 8 hours to complete the reaction.Filter the formed crystals and thoroughly wash the filter paper with water. After that, 5
Dry 8IL at 0°C for 48 hours to obtain the desired 2-p-
Carboxylphenyl-5-phenyltetrazole (m
, p, >300° C.) 43.7 g (yield 54.8%) were obtained.
ベンズアルデヒドのＰ−）−ルエンスルホニルヒドラゾ
ンの代りにｐ−メチルベンズアルデドのｐ−トルエンス
ルホニルヒドラゾン８［ｉ、４ｇ （０，：１モル）を
用いた他は合成例１に５８１１シて行い目的とする２−
ｐ−カルボキシフェニル−５−ｐ−トリルテトラゾール
５１．２ｇ （収率６１．０％）を得た。The procedure of Synthesis Example 1 was repeated except that p-toluenesulfonylhydrazone 8[i, 4g (0,:1 mol) of p-methylbenzaldede was used instead of P-)-luenesulfonylhydrazone of benzaldehyde. 2-
51.2 g (yield 61.0%) of p-carboxyphenyl-5-p-tolyltetrazole was obtained.
（ＣＰＢＰＴ）
ベンズアルデヒドのｐ−トルエンスルホニルヒドラゾン
の代りにｐ−ｎ−ブチルベンズアルデヒドのＰ−トルエ
ンスルホニルヒドラゾン９！１．Ｏｇ（０，３モル）を
用いた他は合成例１に準拠して行い目的とする２−Ｐ−
カルボキシフェニル−ｐ−ｎ−ブチルフェニルテトラゾ
ール４９．２ｇ （収率５０．ｇ％）を得た。(CPBPT) P-toluenesulfonylhydrazone of p-n-butylbenzaldehyde instead of p-toluenesulfonylhydrazone of benzaldehyde 9!1. The desired 2-P-
49.2 g (yield 50.g%) of carboxyphenyl-pn-butylphenyltetrazole was obtained.
ベンズアルデヒドのＰ−）−ルエンスルホニルヒトラゾ
ンの代りにｐ−クロロベンズアルデヒドのｐ−トルエン
スルホニルヒドラゾン９２．６ｇ （０．３モル）を用
いた他は、合成例１に準拠して行ない目的とする２−Ｐ
−カルボキシルフェニル−５−ｐ−クロロフェニルテト
ラゾール５７−２１ （収率６３、４％）を得た。Synthesis Example 1 was followed except that 92.6 g (0.3 mol) of p-toluenesulfonylhydrazone of p-chlorobenzaldehyde was used instead of P-)-luenesulfonylhydrazone of benzaldehyde. -P
-Carboxylphenyl-5-p-chlorophenyltetrazole 57-21 (yield 63, 4%) was obtained.
（ ＣＰＭＰＴ）
ベンズアルデヒドのｐ−トルエンスルホニルヒドラゾン
の代りにｐ−メトキシベンズアルデヒドのｐ−トルエン
スルホニルヒドラゾンｑｔ．ｚｇ（０．３モル）を用い
た他は，合成例１に準拠して行ない目的とする２゛−Ｐ
−カルボキシフェニル−５−Ｐ−メトキシフェニルテト
ラゾール５８．１ｇ（収率６５．４％）を得た。(CPMPT) p-toluenesulfonylhydrazone qt. of p-methoxybenzaldehyde instead of p-toluenesulfonylhydrazone of benzaldehyde. The desired 2゛-P was prepared according to Synthesis Example 1 except that zg (0.3 mol) was used.
-Carboxyphenyl-5-P-methoxyphenyltetrazole 58.1 g (yield 65.4%) was obtained.
（ＣＰＢＩＩＰＴ）
ベンズアルデヒドのＰ−）−ルエンスルホニルヒトラゾ
ンの代りに３．５−ジ−ｔ−フチルー４−ヒドロキシベ
ンズアルデヒドのＰ−トルエンスルホニルヒドラゾン１
２０．６ ｇ （Ｏｊモル）を用いた他は、合成例１に
準拠して行ない目的とする２−Ｐ−カルボキシルフェニ
ル−５− （ ３’ 、５’−ジ−ｔ−ブチル−４′−
ヒドロキシフェニル）テトラゾール６９．２ｇ （収−
１５８．５％）を得た。(CPBIIPT) P-toluenesulfonylhydrazone 1 of 3,5-di-t-phthyl-4-hydroxybenzaldehyde instead of P-)-luenesulfonylhydrazone of benzaldehyde
The desired 2-P-carboxylphenyl-5-(3',5'-di-t-butyl-4'-
69.2g (yield) of hydroxyphenyl)tetrazole
158.5%).
実施例１〜６．比較例１〜３
天然ゴム１００亜量部にＩＳＡＦカーボンブラック５０
重量部，ステアリン酸３重量部、Ｎ−（ｔ，］−ジメチ
ルブチル）−Ｎ′−フェニル−ｐ−フェニレンジアミン
ｌｉＭ部、亜鉛華５重量部、Ｎ−オキシジエチレン−２
−ベンゾチアゾールスルフェンアミド０．５重量部、″
ｉＩＬ黄２．５重量部に第１表に示した各種テトラゾー
ル化合物を５．７５ｘ ｔｏ−”モル相当量を配合した
各種ゴムＭｉｆＯＩｔ．物をバンバリーミキサ−を用い
て混練りして作成し、反発弾性，ゾル分子量について評
価した．比較のためニトロソ化合物についても同様に評
価した．結果を第１表に示した．尚，評価方法は以下の
通りである。Examples 1-6. Comparative Examples 1 to 3 100 parts of natural rubber and 50 parts of ISAF carbon black
parts by weight, 3 parts by weight of stearic acid, N-(t,]-dimethylbutyl)-N'-phenyl-p-phenylenediamine liM parts, 5 parts by weight of zinc white, N-oxydiethylene-2
- 0.5 parts by weight of benzothiazole sulfenamide, ″
Various rubber MifOIt. products were prepared by blending 2.5 parts by weight of iIL yellow with 5.75 x molar equivalent of various tetrazole compounds shown in Table 1 using a Banbury mixer to create repulsion. Elasticity and sol molecular weight were evaluated. For comparison, a nitroso compound was also evaluated in the same way. The results are shown in Table 1. The evaluation method is as follows.
反発弾性二，月Ｓに６３旧に従って測定した。Repulsion elasticity was measured in accordance with the 63rd edition.
ゾル分子量：未加硫ゴム組成物をテトラヒトロフランに
浸漬し４８ＩＩｊｆ間後、カーボンゲルを除去した残液
にて、東洋
曹達製 Ｈｉｇｈ ５ｐｅｅｄ ＬｉｑｕｉｄＣｈｒ
ｏｍａｔｏｇｒａｐｈ ＨＬＣ−８０２Ａ を使用し
てゾル分の分子ｆｆｉ（ＭＷ）を測定した。Sol molecular weight: The unvulcanized rubber composition was immersed in tetrahydrofuran for 48IIjf, and the remaining liquid after removing the carbon gel was immersed in High 5peed Liquid Chr manufactured by Toyo Soda.
The molecular ffi (MW) of the sol fraction was measured using an omatograph HLC-802A.
第１表より、本発明のゴム組成物はポリマーのしゃワ解
作用がなく１発熱性が著しく改善されていることか明ら
かである。From Table 1, it is clear that the rubber composition of the present invention has no shower decomposition effect of the polymer and has significantly improved heat generation properties.
実施例７〜．比較例４〜
スチレン・ブタジェン共重合ゴム（５ＢＲ１７１２）１
３７．５重量部に、 ｌ５ＡＦ力−ボンブラツク６５重
量部、ステアリン醜１重量部、亜鉛華３重量部。Example 7~. Comparative Example 4 ~ Styrene-butadiene copolymer rubber (5BR1712) 1
37.5 parts by weight, 65 parts by weight of l5AF force-bon black, 1 part by weight of stearin, and 3 parts by weight of zinc white.
１．３−ジフェニルグアニジン０．５重量部、ジベンゾ
チアジルジスルフィド１．０重量部、ＩＩＩＬ黄１．５
重量部に第２表に示した各種テトラゾール化合物を５．
７ＳＸ １０−’モル相当量を配合した各種ゴム組成物
をバンバリーミキサ−を用いて混練りして作成し１反発
弾性について評価した。比較のためニトロソ化合物につ
いても同様に評価した。結果を第２表に示した。1.3-diphenylguanidine 0.5 parts by weight, dibenzothiazyl disulfide 1.0 parts by weight, IIIL yellow 1.5 parts by weight
5. Various tetrazole compounds shown in Table 2 in parts by weight.
Various rubber compositions containing an amount equivalent to 10-' mol of 7SX were kneaded using a Banbury mixer and evaluated for impact resilience. For comparison, nitroso compounds were also evaluated in the same way. The results are shown in Table 2.
第２表よりテトラゾール化合物を配合した本発明のスチ
レン−ブタジェン共重合ゴム組成物はニトロソ化合物を
配合した比較例対比１発熱改良効果か著しいことがわか
る。From Table 2, it can be seen that the styrene-butadiene copolymer rubber composition of the present invention containing a tetrazole compound has a remarkable heat generation improvement effect of 1 compared to the comparative example containing a nitroso compound.
Claims (1)
１００重量部に、補強性充填材２０〜１５０重量部、 一般式 ▲数式、化学式、表等があります▼ 式中Ｒ＾１及び／又はＲ＾２は水素原子、炭素数１から
４のアルキル基、ヒドロキシル基、 ハロゲン、アルコキシ基を、ｍ及び／又は ｎは１ないし２を示す で表わされるテトラゾール化合物０．１〜１０重量部配
合したことを特徴とする低発熱性ゴム組成物。[Claims] 1. 100 parts by weight of rubber made of natural rubber and/or diene-based synthetic rubber, 20 to 150 parts by weight of reinforcing filler, general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula R ^1 and/or R^2 are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a halogen, an alkoxy group, and m and/or n are 1 to 2, and the tetrazole compound is 0.1 to 2. A low heat build-up rubber composition characterized by containing 10 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10676686A JPS62263239A (en) | 1986-05-12 | 1986-05-12 | Low heat-generating rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10676686A JPS62263239A (en) | 1986-05-12 | 1986-05-12 | Low heat-generating rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62263239A true JPS62263239A (en) | 1987-11-16 |
Family
ID=14442026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10676686A Pending JPS62263239A (en) | 1986-05-12 | 1986-05-12 | Low heat-generating rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62263239A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069241A (en) * | 2000-08-28 | 2002-03-08 | Bridgestone Corp | Rubber composition for belt, and belt |
| JP2009007511A (en) * | 2007-06-29 | 2009-01-15 | Yokohama Rubber Co Ltd:The | Diene-based rubber composition |
| IT201900025804A1 (en) * | 2019-12-30 | 2021-06-30 | Pirelli | COMPOSITIONS FOR ELASTOMERIC COMPOUNDS INCLUDING POLYTETRAZOLIC AND PNEUMATIC CROSS LINKERS THAT INCLUDE THEM |
| WO2021260635A1 (en) * | 2020-06-26 | 2021-12-30 | Pirelli Tyre S.P.A. | Compositions for elastomeric compounds comprising tetrazole compatibilizing agents and tyres comprising the same |
-
1986
- 1986-05-12 JP JP10676686A patent/JPS62263239A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069241A (en) * | 2000-08-28 | 2002-03-08 | Bridgestone Corp | Rubber composition for belt, and belt |
| JP2009007511A (en) * | 2007-06-29 | 2009-01-15 | Yokohama Rubber Co Ltd:The | Diene-based rubber composition |
| IT201900025804A1 (en) * | 2019-12-30 | 2021-06-30 | Pirelli | COMPOSITIONS FOR ELASTOMERIC COMPOUNDS INCLUDING POLYTETRAZOLIC AND PNEUMATIC CROSS LINKERS THAT INCLUDE THEM |
| WO2021137143A1 (en) * | 2019-12-30 | 2021-07-08 | Pirelli Tyre S.P.A. | Compositions for elastomeric compounds including polytetrazole cross-linking agents and tyres comprising the same |
| WO2021260635A1 (en) * | 2020-06-26 | 2021-12-30 | Pirelli Tyre S.P.A. | Compositions for elastomeric compounds comprising tetrazole compatibilizing agents and tyres comprising the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Heideman et al. | Activators in accelerated sulfur vulcanization | |
| JP3647963B2 (en) | Silica reinforced rubber compound and tire having tread thereof | |
| JP4157608B2 (en) | Rubber composition | |
| KR20170019354A (en) | Alkylidene aminoganidine and salt thereof, modifier composition, modified rubber for tire, rubber composition for tire, and tire | |
| JP2001146532A (en) | Rubber containing short-fiber reinforcing material having adhesion promotor, and product including tire having member made of composite material with the rubber | |
| JP5173312B2 (en) | Additive for rubber composition, rubber composition and tire using the same | |
| EP0723991A1 (en) | Silica reinforced rubber composition and use in tires | |
| EP2202266A1 (en) | Silica-rich rubber compositions and methods of making same | |
| JPH10101847A (en) | Silica-reinforced rubber composition and its use in tire | |
| JP2000063570A (en) | Rubber composition containing anti-reversing matter and tire containing the same | |
| JP2001233997A (en) | Rubber composition and process for preparation thereof | |
| DE112016001707T5 (en) | Rubber compound and mature | |
| JP2014024912A (en) | Tread rubber composition for high-performance tire, and high-performance tire | |
| JP3690890B2 (en) | Low exothermic rubber composition | |
| JPS62263239A (en) | Low heat-generating rubber composition | |
| JPH11263882A (en) | Rubber composition | |
| JP6026320B2 (en) | Rubber composition and pneumatic tire | |
| JPH10324776A (en) | Rubber composition | |
| JP2000136269A (en) | Rubber composition | |
| JP5239485B2 (en) | Rubber composition and pneumatic tire using the same | |
| JP2016196575A (en) | Rubber composition for tire | |
| US6476115B1 (en) | Silica reinforced rubber composition which contains oleylammonium bromide and/or mercaptoimidazolium bromide coupling agents to enhance electrical conductivity and article of manufacture, including a tire, having at least one component comprised of such rubber composition | |
| JPH11255964A (en) | Rubber composition | |
| JP2003041059A (en) | Rubber composition for tire tread | |
| JPS6395240A (en) | Low heat-generation rubber composition |