JP4229969B2 - Diene rubber composition - Google Patents
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- JP4229969B2 JP4229969B2 JP2007135803A JP2007135803A JP4229969B2 JP 4229969 B2 JP4229969 B2 JP 4229969B2 JP 2007135803 A JP2007135803 A JP 2007135803A JP 2007135803 A JP2007135803 A JP 2007135803A JP 4229969 B2 JP4229969 B2 JP 4229969B2
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- 239000000203 mixture Substances 0.000 title claims description 41
- 229920003244 diene elastomer Polymers 0.000 title claims description 21
- 229920001971 elastomer Polymers 0.000 claims description 47
- 239000005060 rubber Substances 0.000 claims description 47
- 239000000843 powder Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006229 carbon black Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 4
- 239000012763 reinforcing filler Substances 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ジエン系ゴム組成物に関し、更に詳しくは、ジエン系ゴム、カーボンブラック及びシルク粉末を含む、モジュラス及び貯蔵弾性率、更には高温時の弾性率に優れ、かつその弾性率の耐温度依存性に優れたシルク粉末含有ジエン系ゴム組成物並びにそれを用いた空気入りタイヤに関する。 The present invention relates to a diene rubber composition, and more specifically includes a diene rubber, carbon black, and silk powder, and has excellent modulus and storage elastic modulus, and further, an elastic modulus at high temperature, and a temperature resistance of the elastic modulus. The present invention relates to a silk powder-containing diene rubber composition excellent in dependency and a pneumatic tire using the same.
従来、ゴム工業において、補強性フィラーとしてカーボンブラックを配合しゴムを補強する手段が採られていたが、カーボンブラックを含むゴム組成物は発熱が高く、転がり抵抗が大きいという問題があった。かかる問題を解決するために、近年、カーボンブラックの一部に代わるフィラーとしてシリカを配合することが行われている。しかしながら、シリカは、シリカ表面の特性上シリカ同士で凝集し易いため、混合性が悪化することが分かっている。そのため、一般には、特許文献１に示されるように、シランカップリング剤を併用することによってシリカの分散性を高めることが行われてきたが、更なるゴム物性の改善のための新規なフィラーの探索が求められている。 Conventionally, in the rubber industry, a means for reinforcing rubber by blending carbon black as a reinforcing filler has been employed. However, a rubber composition containing carbon black has a problem of high heat generation and high rolling resistance. In order to solve such a problem, in recent years, silica has been blended as a filler to replace a part of carbon black. However, it is known that silica is easy to agglomerate with each other due to the characteristics of the silica surface, so that the mixing property is deteriorated. Therefore, in general, as shown in Patent Document 1, the dispersibility of silica has been increased by using a silane coupling agent in combination, but a novel filler for further improvement of rubber physical properties has been used. Search is sought.
特許文献２には、所定粒径のシルク粉末を樹脂やゴムに所定量配合することで、生産効率が高く、天然品に匹敵する透湿性、吸放湿性及び外観を有する成形品が得られることが開示され、また、特許文献３には、伝動用ベルトの接着ゴム層にシルク短繊維などを所定量配合することで、耐久性を高めた伝動用ベルトが得られることが開示されている。しかしながら、ジエン系ゴム組成物の物性を改善するためにシルク粉末を配合する技術は、未だ提案されていない。 In Patent Document 2, a predetermined amount of silk powder with a predetermined particle size is blended with a predetermined amount of resin or rubber to obtain a molded product having high production efficiency and moisture permeability, moisture absorption / release properties and appearance comparable to natural products. In addition, Patent Document 3 discloses that a transmission belt with improved durability can be obtained by blending a predetermined amount of silk short fibers into the adhesive rubber layer of the transmission belt. However, a technique for blending silk powder to improve the physical properties of the diene rubber composition has not yet been proposed.
従来からジエン系ゴムにカーボンブラックやシリカ以外の充填剤を配合すると弾性率やモジュラスが低下するという問題があった。従って、本発明は、ジエン系ゴム組成物に対する補強性能に優れ、モジュラス及び貯蔵弾性率、更には高温時の弾性率に優れ、かつ弾性率の温度依存性にも優れたジエン系ゴム組成物を提供することを目的とする。 Conventionally, when a filler other than carbon black or silica is blended with a diene rubber, there has been a problem that the elastic modulus and modulus are lowered. Therefore, the present invention provides a diene rubber composition that is excellent in reinforcing performance with respect to a diene rubber composition, has excellent modulus and storage elastic modulus, and further has an elastic modulus at a high temperature and also has excellent temperature dependence of the elastic modulus. The purpose is to provide.
本発明によれば、ジエン系ゴム１００重量部、シルク粉末０．１〜３０重量部及びカーボンブラック１０〜１００重量部を含んでなり、前記シルク粉末が１８０〜３００℃で３０〜４８０分間乾熱処理したものである、ゴム組成物（但し、ジエン系ゴム１００重量部に対して、密閉乾燥機中でシルク原料を１８０〜３００℃の温度条件下に３０〜４８０分間熱処理して得られる乾熱処理シルク粉末０．１〜３０重量部、シリカを含む補強性充填剤４０〜１００重量部、及びシリカに対して３〜２０重量％のシランカップリング剤を配合してなるゴム組成物を除く。）並びにそれを用いた空気入りタイヤが提供される。 According to the present invention, 100 parts by weight of a diene rubber, 0.1 to 30 parts by weight of silk powder and 10 to 100 parts by weight of carbon black are included, and the silk powder is dry heat treated at 180 to 300 ° C. for 30 to 480 minutes. A dry heat-treated silk obtained by heat-treating a silk raw material for 30 to 480 minutes at a temperature of 180 to 300 ° C. in a hermetic dryer with respect to 100 parts by weight of a diene rubber. Excluding rubber compositions formed by blending 0.1 to 30 parts by weight of powder, 40 to 100 parts by weight of reinforcing filler containing silica, and 3 to 20% by weight of silane coupling agent based on silica. A pneumatic tire using the same is provided.
本発明者等は、ジエン系ゴム組成物に、カーボンブラックと共に、シルク粉末を配合することにより、モジュラス及び貯蔵弾性率、更には高温時の弾性率に優れ、かつ弾性率の温度依存性にも優れたゴム組成物が得られることを見出した。 The present inventors have blended silk powder together with carbon black into the diene rubber composition, so that the modulus and storage elastic modulus are excellent in elastic modulus at high temperature, and the elastic modulus is also temperature dependent. It has been found that an excellent rubber composition can be obtained.
本発明のゴム組成物に用いられるジエン系ゴムとしては、例えば、天然ゴム（ＮＲ）、各種ブタジエンゴム（ＢＲ）、各種スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、ポリイソプレンゴム（ＩＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、クロロプレンゴム、エチレン−プロピレン−ジエン共重合体ゴム、スチレン−イソプレン共重合体ゴム、スチレン−イソプレン−ブタジエン共重合体ゴム、イソプレン−ブタジエン共重合体ゴムなどが挙げられる。また、前記ジエン系ゴムは、それぞれがエポキシ基、アルコキシシラン基、水酸基含有基などで変性されたものであってもよい。これらのジエン系ゴムは、単独で又は二種以上のブレンドゴムとして、使用することができる。 Examples of the diene rubber used in the rubber composition of the present invention include natural rubber (NR), various butadiene rubbers (BR), various styrene-butadiene copolymer rubbers (SBR), polyisoprene rubber (IR), acrylonitrile. -Butadiene copolymer rubber (NBR), chloroprene rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber, etc. Can be mentioned. The diene rubber may be modified with an epoxy group, an alkoxysilane group, a hydroxyl group-containing group, or the like. These diene rubbers can be used alone or as a blend rubber of two or more.
本発明のゴム組成物に用いるシルク粉末は、所定量のカーボンブラックと共にジエン系ゴム１００重量部に対して、０．１〜３０重量部、好ましくは１〜１５重量部の量で配合する。この配合量が０．１重量部未満であると所期の効果がなく、逆に３０重量部を超えるとゴム組成物の耐摩耗性能が著しく低下するので好ましくない。 The silk powder used in the rubber composition of the present invention is blended in an amount of 0.1 to 30 parts by weight, preferably 1 to 15 parts by weight with respect to 100 parts by weight of the diene rubber together with a predetermined amount of carbon black. If the blending amount is less than 0.1 parts by weight, the desired effect is not obtained. Conversely, if it exceeds 30 parts by weight, the wear resistance of the rubber composition is remarkably lowered.
本発明のゴム組成物に用いるシルク粉末としては、例えば、タイラー篩基準による２５０メッシュの篩を用いて、最大粒径が６３μｍより小さいものが好ましく、５０μｍ以下であるのが更に好ましく、３５μｍ以下のものが特に好ましく、有効に使用される。シルク粉末としては、粒度の小さいものほど、補強性能が向上するので好ましい。 As the silk powder used in the rubber composition of the present invention, for example, a 250 mesh sieve based on the Tyler sieve standard is preferably used, and the maximum particle size is preferably less than 63 μm, more preferably 50 μm or less, and 35 μm or less. Are particularly preferred and are used effectively. As the silk powder, the smaller the particle size, the better the reinforcing performance, so that it is preferable.
本発明の好ましい第一の態様で用いる乾熱処理されたシルク粉末は、例えば、熱風乾燥機の各段に２００ｇずつ、計６段にシルク原料を敷き並べ、２１０℃、６０分間熱風乾燥を行うことで脆化が可能になる。粉砕は、ボールミル粉砕法で３時間粉砕することで粉末状にすることができる。なお、前記乾熱処理条件は温度が１８０℃以下では時間効率の面で好ましくなく、温度が３００℃を超えるとシルクが燃えてしまう可能性が高くなる。よって、温度は、１８０〜３００℃であることが好ましく、より好ましくは２００〜２２０℃である。また乾熱処理時間は３０〜４８０分間であるのが好ましく、より好ましくは３０〜３００分間である。 The dry-heat treated silk powder used in the first preferred embodiment of the present invention is, for example, 200 g in each stage of a hot air dryer, with silk raw materials arranged in a total of 6 stages, and hot air drying at 210 ° C. for 60 minutes. Embrittlement is possible. The pulverization can be made into powder by pulverizing for 3 hours by a ball mill pulverization method. The dry heat treatment condition is not preferable in terms of time efficiency when the temperature is 180 ° C. or lower, and when the temperature exceeds 300 ° C., there is a high possibility that the silk will burn. Therefore, it is preferable that temperature is 180-300 degreeC, More preferably, it is 200-220 degreeC. The dry heat treatment time is preferably 30 to 480 minutes, more preferably 30 to 300 minutes.
本発明の好ましい第二の態様で用いるアルカリ処理したシルク粉末としては、例えば、シルクを水酸化ナトリウムなどのアルカリで脆化処理後、塩酸で中和し、次いで、洗浄、乾燥を行い、ボールミルにて粉砕し、５０μｍの篩を通すことによって、容易に得ることができる。 As the alkali-treated silk powder used in the second preferred embodiment of the present invention, for example, the silk is embrittled with an alkali such as sodium hydroxide, neutralized with hydrochloric acid, then washed and dried. And can be easily obtained by passing through a 50 μm sieve.
本発明のゴム組成物には、前記シルク粉末に加えて、補強充填剤としてカーボンブラックを使用することができる。かかるカーボンブラックとしては、ゴム組成物、特に空気入りタイヤ用ゴム組成物として使用することができる任意のカーボンブラックを用いることができ、その配合量としては、前記ジエン系ゴム１００重量部に対して、１０〜１００重量部、好ましくは２０〜７０重量部配合する。この配合量が１０重量部未満では補強効果が十分でなく、逆に１００重量部を超えると、加工成形性に劣るようになるので好ましくない。 In the rubber composition of the present invention, carbon black can be used as a reinforcing filler in addition to the silk powder. As such carbon black, any carbon black that can be used as a rubber composition, particularly a rubber composition for a pneumatic tire, can be used, and the blending amount thereof is 100 parts by weight of the diene rubber. 10 to 100 parts by weight, preferably 20 to 70 parts by weight. If the blending amount is less than 10 parts by weight, the reinforcing effect is not sufficient. Conversely, if the blending amount exceeds 100 parts by weight, the processability becomes inferior.
本発明に係るゴム組成物には、更に、加硫又は架橋剤、加硫又は架橋促進剤、各種ワックス、オイル、老化防止剤、充填材、可塑剤などのタイヤ用、その他のゴム組成物用に配合されている各種配合剤を配合することができ、かかる配合剤は、一般的な方法で混練してゴム組成物とし、加硫または架橋することができる。これら配合剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 The rubber composition according to the present invention further includes a vulcanization or crosslinking agent, a vulcanization or crosslinking accelerator, various waxes, oils, anti-aging agents, fillers, plasticizers and other tires, and other rubber compositions. Various compounding agents blended in the above can be blended, and these blending agents can be kneaded by a general method to obtain a rubber composition, which can be vulcanized or crosslinked. The compounding amounts of these compounding agents can be set to conventional general compounding amounts as long as the object of the present invention is not adversely affected.
以下、実施例及び比較例によって本発明を更に説明するが、本発明の技術的範囲をこれらの実施例に限定するものでないことは言うまでもない。 EXAMPLES Hereinafter, although this invention is further demonstrated by an Example and a comparative example, it cannot be overemphasized that the technical scope of this invention is not limited to these Examples.
実施例１〜３及び比較例１
試験サンプルの調製
表Ｉに示す配合（重量部）に従って、硫黄及び加硫促進剤を除くゴム、シリカ、乾熱処理されたシルク粉末などの各配合成分を１.７Ｌの密閉式バンバリーミキサーに装填して５分間混合し、混合機外に放出して室温まで冷却したマスターバッチを、再度同バンバリーミキサーに投入し、これに硫黄と加硫促進剤を配合、混合してゴム組成物を得た。次いで、このゴム組成物を１５ｃｍ×１５ｃｍ×０.２ｃｍの金型中で、１６０℃、２０分間プレス加硫して試験サンプル（ゴムシート）を作製し、以下の方法で１００％モジュラス（Ｍ１００）及び貯蔵弾性率を評価した。結果は表Ｉに示す。
Examples 1 to 3 and Comparative Example 1
Preparation of test samples According to the formulation (parts by weight) shown in Table I, each compounding component such as rubber, silica, and dry heat-treated silk powder excluding sulfur and vulcanization accelerator was loaded into a 1.7 L closed banbury mixer. The master batch which was mixed for 5 minutes, discharged to the outside of the mixer and cooled to room temperature was charged into the Banbury mixer again, and sulfur and a vulcanization accelerator were blended and mixed with it to obtain a rubber composition. Next, this rubber composition was press vulcanized in a 15 cm × 15 cm × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a test sample (rubber sheet), and 100% modulus (M100) was produced by the following method. And the storage modulus was evaluated. The results are shown in Table I.
試験方法
Ｍ１００：ＪＩＳ Ｋ ６２５１によって、１００％伸長時のモジュラスを測定した。
貯蔵弾性率：東洋精機製作所製粘弾性スペクトロメータを用い、静的歪み１０％、動的歪み±２％、周波数２０Ｈｚの条件下で測定した。測定温度は２０℃である。
Test method M100: The modulus at 100% elongation was measured according to JIS K 6251.
Storage elastic modulus: Measured using a viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of static strain 10%, dynamic strain ± 2%, and frequency 20 Hz. The measurement temperature is 20 ° C.
表Ｉ脚注
天然ゴム：ＲＳＳ＃３
カーボンブラック：東海カーボン（株）製 シーストＭ
ＳＰ−１：シナノケンシ（株）製 乾熱処理シルクパウダー
ＳＰ−２：シナノケンシ（株）製 乾熱処理シルクパウダー
ＳＰ−３：シナノケンシ（株）製 乾熱処理シルクパウダー
ステアリン酸：日本油脂（株）製ビーズステアリン酸
亜鉛華：正同化学（株）製 酸化亜鉛３種
オイル：（株）ジャパンエナジー製 プロセスＸ−１４０
加硫促進剤：大内新興化学（株）製 ノクセラーＮＳ−Ｐ
硫黄：細井化学工業（株）製 油処理イオウ
Table I Footnote natural rubber: RSS # 3
Carbon black: Seast M manufactured by Tokai Carbon Co., Ltd.
SP-1: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. SP-2: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. SP-3: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. Stearic acid: Bead stearin manufactured by Nippon Oil & Fats Acid Zinc Hana: Zinc Oxide, Inc. 3 types of zinc oxide Oil: Japan Energy Co., Ltd. Process X-140
Vulcanization accelerator: Nouchira NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Oil treatment sulfur manufactured by Hosoi Chemical Co., Ltd.
表Ｉに示した通り、カーボンブラック配合系の比較例１（この値を１００として指数表示した）に比較してカーボンブラック配合系ジエン系ゴム組成物に所定量の乾熱処理されたシルク粉末を配合した実施例１〜３では、１００％モジュラス（Ｍ１００）及び／又は貯蔵弾性率に優れたゴム組成物が得られる。 As shown in Table I, a predetermined amount of dry-heat treated silk powder was blended with the carbon black blended diene rubber composition in comparison with the carbon black blended comparative example 1 (this value was expressed as 100). In Examples 1 to 3, rubber compositions excellent in 100% modulus (M100) and / or storage elastic modulus can be obtained.
実施例４〜７及び比較例２〜３
試験サンプルの調製
表IIに示す配合（重量部）に従って、硫黄及び加硫促進剤を除くゴム、シリカ、乾熱処理されたシルク粉末などの各配合成分を１.７Ｌの密閉式バンバリーミキサーに装填して５分間混合し、混合機外に放出して室温まで冷却したマスターバッチを、再度同バンバリーミキサーに投入し、これに硫黄と加硫促進剤を配合、混合してゴム組成物を得た。次いで、このゴム組成物を１５ｃｍ×１５ｃｍ×０.２ｃｍの金型中で、１６０℃、２０分間プレス加硫して試験サンプル（ゴムシート）を作製し、以下のＥ´（高温貯蔵弾性率）及びその温度依存性を評価した。結果は表Ｉに示す。
Examples 4-7 and Comparative Examples 2-3
Preparation of test sample According to the formulation (parts by weight) shown in Table II, each compounding component such as rubber excluding sulfur and vulcanization accelerator, silica, dry-heat treated silk powder, etc. was loaded into a 1.7 L closed banbury mixer. The master batch which was mixed for 5 minutes, discharged to the outside of the mixer and cooled to room temperature was charged into the Banbury mixer again, and sulfur and a vulcanization accelerator were blended and mixed with it to obtain a rubber composition. Next, this rubber composition was press vulcanized in a 15 cm × 15 cm × 0.2 cm mold at 160 ° C. for 20 minutes to produce a test sample (rubber sheet). The following E ′ (high temperature storage elastic modulus) And its temperature dependence was evaluated. The results are shown in Table I.
試験方法
１）高温貯蔵弾性率Ｅ´（６０℃）： ＪＩＳ Ｋ６３９４に準拠して、（株）東洋精機製作所製の粘弾性スペクトロメーターを用いて、静的歪＝１０％、動的歪＝±２％、周波数＝２０Ｈｚの条件下でＥ´（６０℃）を測定した。結果は比較例２の値を１００として指数で示した。この指数が大きい程、高温時の弾性率が高く、優れていることを示す。
２）弾性率の温度依存性：Ｅ´の測定法を用いて、［（２０℃の時のＥ´）−（１００℃の時のＥ´）］を計算した。結果は比較例２の値を１００として指数で表示した。この指数が小さい程、温度依存性に優れることを示す。
Test Method 1) High-temperature storage elastic modulus E ′ (60 ° C.): Static strain = 10%, dynamic strain = ± using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho in accordance with JIS K6394 E ′ (60 ° C.) was measured under the conditions of 2% and frequency = 20 Hz. The results are shown as an index with the value of Comparative Example 2 as 100. The larger this index is, the higher the elastic modulus at high temperature is.
2) Temperature dependence of elastic modulus: [(E ′ at 20 ° C.) − (E ′ at 100 ° C.)]] was calculated using the measurement method of E ′. The result was expressed as an index with the value of Comparative Example 2 as 100. It shows that it is excellent in temperature dependence, so that this index | exponent is small.
表II脚注
天然ゴム：ＲＳＳ＃３
カーボンブラック：東海カーボン（株）製 シーストＭ
ＳＰ−４：シナノケンシ（株）製 乾熱処理シルクパウダー
ＳＰ−５：シナノケンシ（株）製 乾熱処理シルクパウダー
ＳＰ−６：シナノケンシ（株）製 乾熱処理シルクパウダー
ステアリン酸：日本油脂（株）製ビーズステアリン酸
亜鉛華：正同化学（株）製 酸化亜鉛３種
オイル：（株）ジャパンエナジー製 プロセスＸ−１４０
加硫促進剤：大内新興化学（株）製 ノクセラーＮＳ−Ｐ
硫黄：細井化学工業（株）製 油処理イオウ
Table II Footnote natural rubber: RSS # 3
Carbon black: Seast M manufactured by Tokai Carbon Co., Ltd.
SP-4: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. SP-5: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. SP-6: Dry heat treated silk powder manufactured by Shinano Kenshi Co., Ltd. Acid Zinc Hana: Zinc Oxide, Inc. 3 types of zinc oxide Oil: Japan Energy Co., Ltd. Process X-140
Vulcanization accelerator: Nouchira NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Oil treatment sulfur manufactured by Hosoi Chemical Co., Ltd.
表IIに示した通り、比較例２及び３のカーボンブラック配合系ジエン系ゴム組成物に、所定量の乾熱処理されたシルク粉末を配合した実施例４〜７では、高温時での弾性率に優れ、その温度依存性にも優れたゴム組成物が得られる。 As shown in Table II, in Examples 4 to 7 in which a predetermined amount of dry-heat treated silk powder was blended with the carbon black blended diene rubber compositions of Comparative Examples 2 and 3, the elastic modulus at high temperatures was increased. A rubber composition excellent in temperature dependency is obtained.
実施例８〜１０及び比較例４
試験サンプルの調製
表IIIに示す配合（重量部）に従って、硫黄及び加硫促進剤を除くゴム、シリカ、アルカリ処理したシルク粉末などの各配合成分を１.７Ｌの密閉式バンバリーミキサーに装填して５分間混合し、混合機外に放出して室温まで冷却したマスターバッチを、再度同バンバリーミキサーに投入し、これに硫黄と加硫促進剤を配合、混合してゴム組成物を得た。このゴム組成物を１５ｃｍ×１５ｃｍ×０.２ｃｍの金型中で、１６０℃、２０分間プレス加硫して試験サンプル（ゴムシート）を作製し、得られた加硫物の高温貯蔵弾性率及びその温度依存性を前述の方法で評価し、結果を表IIIに示した。
Examples 8 to 10 and Comparative Example 4
Preparation of test sample According to the formulation (parts by weight) shown in Table III, each component such as rubber, silica, and alkali-treated silk powder excluding sulfur and vulcanization accelerator was loaded into a 1.7 liter closed Banbury mixer. The master batch which was mixed for 5 minutes, discharged to the outside of the mixer and cooled to room temperature was again put into the Banbury mixer, and sulfur and a vulcanization accelerator were blended and mixed therewith to obtain a rubber composition. This rubber composition was press vulcanized at 160 ° C. for 20 minutes in a 15 cm × 15 cm × 0.2 cm mold to produce a test sample (rubber sheet). The temperature dependence was evaluated by the method described above, and the results are shown in Table III.
表III脚注
天然ゴム：ＲＳＳ＃３
カーボンブラック：東海カーボン（株）製 シーストＭ
ＳＰ−７：シナノケンシ（株）製 アルカリ処理シルクパウダー
ＳＰ−８：シナノケンシ（株）製 アルカリ処理シルクパウダー
ステアリン酸：日本油脂（株）製ビーズステアリン酸
亜鉛華：正同化学（株）製 酸化亜鉛３種
オイル：（株）ジャパンエナジー製 プロセスＸ−１４０
促進剤：大内新興化学（株）製 ノクセラーＮＳ−Ｐ
硫黄：細井化学工業（株）製 油処理イオウ
Table III Footnote natural rubber: RSS # 3
Carbon black: Seast M manufactured by Tokai Carbon Co., Ltd.
SP-7: Alkaline-treated silk powder manufactured by Shinano Kenshi Co., Ltd. SP-8: Alkaline-treated silk powder manufactured by Shinano Kenshi Co., Ltd. Stearic acid: Bead stearic acid manufactured by Nippon Oil & Fats Co., Ltd. Three types of oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Accelerator: Nouchira NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.
Sulfur: Oil treatment sulfur manufactured by Hosoi Chemical Co., Ltd.
表IIIの結果から、比較例４のカーボンブラック配合ジエン系ゴム組成物に、所定配合量のアルカリ処理したシルク粉末を配合した実施例８〜１０では、高温貯蔵弾性率に優れ、その温度依存性にも優れたゴム組成物が得られることは明らかである。 From the results of Table III, in Examples 8 to 10 in which the carbon black-blended diene rubber composition of Comparative Example 4 was blended with a predetermined blending amount of alkali-treated silk powder, it was excellent in high-temperature storage elastic modulus and its temperature dependence. It is clear that an excellent rubber composition can be obtained.
以上の通り、本発明のゴム組成物は、前述の如く、高温弾性率及びその温度依存性に優れるので、空気入りタイヤ、特にそのアンダートレッド、ビードフィラー、ベルトコートゴム、サイドトレッド、リムクッションなどに利用すれば極めて有用である。 As described above, the rubber composition of the present invention is excellent in the high-temperature elastic modulus and its temperature dependency as described above, so that it is a pneumatic tire, particularly its under tread, bead filler, belt coat rubber, side tread, rim cushion, etc. It is extremely useful if it is used.
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