JP4137966B2 - Rubber composition - Google Patents
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- JP4137966B2 JP4137966B2 JP2006301507A JP2006301507A JP4137966B2 JP 4137966 B2 JP4137966 B2 JP 4137966B2 JP 2006301507 A JP2006301507 A JP 2006301507A JP 2006301507 A JP2006301507 A JP 2006301507A JP 4137966 B2 JP4137966 B2 JP 4137966B2
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- 229920001971 elastomer Polymers 0.000 title claims description 46
- 239000005060 rubber Substances 0.000 title claims description 46
- 239000000203 mixture Substances 0.000 title claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 11
- 229920003244 diene elastomer Polymers 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 13
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003921 oil Substances 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- -1 triethoxysilylpropyl Chemical group 0.000 description 1
- 238000005406 washing 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、ゴム組成物に関し、更に詳細には、アルカリ処理したシルク粉末を所定量配合した、フィラーの分散性に優れ、かつ高温時の弾性率に優れたゴム組成物に関する。 The present invention relates to a rubber composition, and more particularly, to a rubber composition excellent in filler dispersibility and excellent in elastic modulus at high temperature, which is formulated with a predetermined amount of alkali-treated silk powder.
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、ゴムの発熱が高く、転がり抵抗が大きいという問題があった。そこで、近年、カーボンブラックに代わるフィラーとしてシリカを配合することで上記問題を解決している。しかしながら、シリカには、その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、以下の特許文献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, means for reinforcing rubber by blending carbon black as a reinforcing filler has been employed, but there has been a problem that the heat generated by rubber is high and the rolling resistance is large. Therefore, in recent years, the above problem has been solved by blending silica as a filler instead of carbon black. However, it is known that the silica is easily agglomerated with each other due to the characteristics of the silica surface, so that the mixing property is deteriorated. Therefore, in general, as shown in the following Patent Document 1, the dispersibility of silica has been increased by using a silane coupling agent in combination, but this is a novel method for further improving the physical properties of rubber. Search for fillers is required.
以下の特許文献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、以下の特許文献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、シリカ含有ゴム組成物の混合・加工性を高め、かつ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 below, a predetermined amount of silk powder having 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, hygroscopicity and appearance comparable to natural products. In addition, Patent Document 3 below 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. ing. However, no technology has been proposed for blending silk powder in order to improve the mixing and processability of the silica-containing rubber composition and improve the physical properties.
本発明では、シリカ配合系ゴム組成物に、所定量のアルカリ処理したシルク粉末を配合することで、当該ゴム組成物の混合・加工性を高め、かつ良好な物性を達成することができるゴム組成物を提供することを目的とする。 In the present invention, a rubber composition that can improve mixing and processability of the rubber composition and achieve good physical properties by blending a predetermined amount of alkali-treated silk powder with the silica-blended rubber composition. The purpose is to provide goods.
本発明によれば、ジエン系ゴム１００重量部に対して、アルカリ処理したシルク粉末０．１〜３０重量部、シリカ１０〜１００重量部、カーボンブラック５〜５０重量部、及びシリカに対して５〜２０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が提供される。 According to the present invention, 0.1 to 30 parts by weight of alkali-treated silk powder, 10 to 100 parts by weight of silica, 5 to 50 parts by weight of carbon black, and 5 to 5 parts by weight of silica with respect to 100 parts by weight of diene rubber. A rubber composition comprising -20% by weight of a silane coupling agent is provided.
本発明では、シリカ配合系ゴム組成物において、従来のシランカップリング剤と共に、所定量のアルカリ処理したシルク粉末を配合すると、混合・加工性を高め、かつ弾性率及び転がり抵抗の物性向上が図れることを見出したものである。 In the present invention, when a predetermined amount of an alkali-treated silk powder is blended with a conventional silane coupling agent in a silica-blended rubber composition, mixing / workability can be improved and physical properties of elastic modulus and rolling resistance can be improved. This is what we found.
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。 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.
本発明のゴム組成物に用いられるアルカリ処理した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、好ましくは５０μｍ以下、更に好ましくは３５μｍ以下のものが有効に使用される。当該アルカリ処理した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 alkali-treated silk powder used in the rubber composition of the present invention, for example, using a 250 mesh sieve based on the Tyler sieve standard, the maximum particle size is less than 63 μm, preferably 50 μm or less, more preferably 35 μm or less. Are effectively used. As the alkali-treated silk powder, the smaller the particle size, the better the reinforcing performance.
前記アルカリ処理したシルク粉末は、例えば、シルクを水酸化ナトリウムで脆化処理後、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。 The alkali-treated silk powder can be easily obtained, for example, by emulsifying silk with sodium hydroxide, neutralizing with hydrochloric acid, washing, drying, pulverizing with a ball mill, and passing through a 50 μm sieve. Can get to.
本発明のゴム組成物に用いられるアルカリ処理したシルク粉末は、前記ジエン系ゴム１００重量部に対して、０．１〜３０重量部、より好ましくは１〜１５重量部の量で配合される。この配合量が０．１重量部未満であると所望の効果がなく、逆に３０重量部を超えると当該ゴム組成物の破断伸び及び強度が著しく低下するので好ましくない。 The alkali-treated silk powder used in the rubber composition of the present invention is blended in an amount of 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the diene rubber. If the amount is less than 0.1 parts by weight, the desired effect is not obtained. Conversely, if it exceeds 30 parts by weight, the elongation at break and strength of the rubber composition are remarkably lowered.
本発明のゴム組成物に用いられるシリカの配合量としては、前記ジエン系ゴム１００重量部に対して、１０〜１００重量部、より好ましくは４０〜８０重量部の量で配合される。このシリカ配合量が１０重量部未満では、シリカ特有の効果が得られないので好ましくなく、逆に１００重量部を超えると、当該ゴム組成物の混合・加工性が悪化し、また硬さが高くなり過ぎて成形しにくくなるので好ましくない。 The amount of silica used in the rubber composition of the present invention is 10 to 100 parts by weight, more preferably 40 to 80 parts by weight, based on 100 parts by weight of the diene rubber. If the amount of silica is less than 10 parts by weight, the silica-specific effects cannot be obtained, which is not preferable. On the other hand, if it exceeds 100 parts by weight, the mixing / workability of the rubber composition is deteriorated and the hardness is high. It is not preferable because it becomes too difficult to mold.
本発明のゴム組成物におけるフィラーとしてシリカと併用して用いられるカーボンブラックの配合量は、前記ジエン系ゴム１００重量部に対して、５〜５０重量部、好ましくは５〜４０重量部の配合量とすることができる。この配合量が５０重量部を超えると、当該ゴム組成物の発熱が高くなり、転がり抵抗性が大きくなるので好ましくない。 The compounding amount of carbon black used in combination with silica as a filler in the rubber composition of the present invention is 5 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the diene rubber. It can be. If the blending amount exceeds 50 parts by weight, the heat generation of the rubber composition increases, and the rolling resistance increases, which is not preferable.
更に本発明のゴム組成物には、配合シリカに対して、５〜２０重量％、好ましくは５〜１２重量％のシランカップリング剤が配合される。かかる所定量のシランカップリング剤を配合すると、シリカ−カップリング剤−ゴム間の反応効率がよく、ゴム補強性に優れるので好ましい。当該シランカップリング剤としては、含硫黄シランカップリング剤の使用が好ましく、例えば、特に、３,３´−ビス(トリメトキシ又はトリエトキシシリルプロピル)ジスルフィドが好ましく、３,３´−ビス(トリエトキシシリルプロピル)テトラスルフィドが最も好ましい。 Furthermore, the rubber composition of the present invention contains 5 to 20% by weight, preferably 5 to 12% by weight, of a silane coupling agent based on the compounded silica. It is preferable to blend such a predetermined amount of the silane coupling agent because the reaction efficiency between the silica-coupling agent-rubber is good and the rubber reinforcing property is excellent. As the silane coupling agent, a sulfur-containing silane coupling agent is preferably used. For example, 3,3′-bis (trimethoxy or triethoxysilylpropyl) disulfide is particularly preferable, and 3,3′-bis (triethoxy Silylpropyl) tetrasulfide is most preferred.
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 violated.
以下、実施例およ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.
試験サンプルの調製
表１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、当該ゴムを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。この未加硫ゴム組成物の一部を以下のムーニー粘度試験のサンプルに供した。次いで、この残部のゴム組成物を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、以下の引張試験及び粘弾性試験に供した。
Preparation of test sample According to the composition (parts by weight) shown in Table 1, each compounding 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 put into the Banbury mixer again, and sulfur and a vulcanization accelerator were blended and mixed therewith to obtain a rubber composition. It was. A portion of this unvulcanized rubber composition was subjected to the following Mooney viscosity test samples. Then, the remaining rubber composition was press vulcanized at 160 ° C. for 20 minutes in a 15 cm × 15 cm × 0.2 cm mold to prepare a test sample (rubber sheet). The following tensile test and viscoelasticity test were performed. It was used for.
試験方法
１）ムーニー粘度： ＪＩＳ Ｋ６３００−１に準拠して、ムーニー粘度計にてＬ型ロータ（３８.１ｍｍ径、５.５ｍｍ厚）を使用し、予熱時間１分、ロータの回転時間４分、１００℃、２ｒｐｍの条件で測定した。結果は、比較例１を１００として指数で示した。指数が小さい程、加工性が優れていることを示す。
２）Ｍ３００： ＪＩＳ Ｋ６２５１に準拠して、３号ダンベルにて２ｍｍのゴムシートを打ち抜き、５００ｍｍ／分の引張速度にてＭ３００（３００％モジュラス）を測定した。結果は、比較例１を１００として指数で示した。指数が大きい程、補強性能に優れていることを示す。
３）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１を１００として指数で示した。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。
Test Method 1) Mooney Viscosity: In accordance with JIS K6300-1, using a Mooney viscometer with an L-shaped rotor (38.1 mm diameter, 5.5 mm thickness), preheating time 1 minute, rotor rotation time 4 minutes , Measured at 100 ° C. and 2 rpm. The results are shown as an index with Comparative Example 1 as 100. The smaller the index, the better the workability.
2) M300: In accordance with JIS K6251, a 2 mm rubber sheet was punched with a No. 3 dumbbell, and M300 (300% modulus) was measured at a tensile speed of 500 mm / min. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the better the reinforcing performance.
3) E ′ (60 ° C.): In accordance with JIS K6394, using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho Co., Ltd., static strain = 10%, dynamic strain = ± 2%, frequency = 20 Hz E ′ (60 ° C.) was measured under the following conditions. The results are shown as an index with Comparative Example 1 as 100. The larger the index, the higher the elastic modulus at high temperature, which is superior.
実施例１〜５及び比較例１〜４
結果を、以下の表１に示す。
The results are shown in Table 1 below.
表１の結果から、シリカ配合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１〜５では、加工性能が向上し、補強性能も向上し、更に粘弾性を改善していることが分かる。 From the results of Table 1, in Examples 1 to 5 in which a predetermined blending amount of an alkali-treated silk powder was blended with a silica-blended rubber composition, processing performance was improved, reinforcing performance was improved, and viscoelasticity was further improved. I understand that
よって、本発明のゴム組成物は、特に、タイヤのトレッド部やカーカスコート、ビードフィラー部及びリムクッション部などとして、空気入りタイヤに利用すれば極めて有用である。 Therefore, the rubber composition of the present invention is extremely useful when used in a pneumatic tire, particularly as a tread portion, a carcass coat, a bead filler portion, a rim cushion portion, or the like of a tire.
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006301507A JP4137966B2 (en) | 2006-11-07 | 2006-11-07 | Rubber composition |
| PCT/JP2007/071852 WO2008056797A1 (en) | 2006-11-07 | 2007-11-05 | Rubber composition and pneumatic tire using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006301507A JP4137966B2 (en) | 2006-11-07 | 2006-11-07 | Rubber composition |
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| Publication Number | Publication Date |
|---|---|
| JP2008115316A JP2008115316A (en) | 2008-05-22 |
| JP4137966B2 true JP4137966B2 (en) | 2008-08-20 |
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| JP2006301507A Expired - Fee Related JP4137966B2 (en) | 2006-11-07 | 2006-11-07 | Rubber composition |
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| JP6121280B2 (en) * | 2013-08-02 | 2017-04-26 | 東洋ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP6141158B2 (en) | 2013-09-18 | 2017-06-07 | 東洋ゴム工業株式会社 | Rubber composition for tire tread and pneumatic tire |
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2006
- 2006-11-07 JP JP2006301507A patent/JP4137966B2/en not_active Expired - Fee Related
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| JP2008115316A (en) | 2008-05-22 |
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