JP5458482B2 - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- JP5458482B2 JP5458482B2 JP2007227870A JP2007227870A JP5458482B2 JP 5458482 B2 JP5458482 B2 JP 5458482B2 JP 2007227870 A JP2007227870 A JP 2007227870A JP 2007227870 A JP2007227870 A JP 2007227870A JP 5458482 B2 JP5458482 B2 JP 5458482B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- rubber composition
- rubber
- parts
- silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はゴム組成物に関し、更に詳しくは疎水化澱粉を配合することにより加工性を向上させ、転がり抵抗を低減させたゴム組成物及びそれを用いた空気入りタイヤに関する。 The present invention relates to a rubber composition, and more particularly to a rubber composition having improved processability by adding hydrophobic starch and reduced rolling resistance, and a pneumatic tire using the rubber composition.
従来、タイヤ用補強性フィラーに様々な機能性を求める要求が高くなっており、ゴム組成物に従来から配合されてきたカーボンブラックの少なくとも一部に代えて、シリカを配合したシリカ配合タイヤは、従来のカーボンブラック配合タイヤよりも低燃費性とウェット性能を向上かつ両立させることができることから、近年シリカ配合タイヤが重用されている。従って、次世代タイヤにおいてもシリカは当然に使用されると予想されるが、更なる低燃費性能を有し、かつ環境対策に叶った技術を開発する必要がある。 Conventionally, there has been a high demand for various functionalities in the reinforcing filler for tires, and instead of at least a part of carbon black that has been conventionally blended in rubber compositions, silica-blended tires blended with silica are: In recent years, silica-containing tires have been heavily used because fuel efficiency and wet performance can be improved and compatible with those of conventional carbon black-containing tires. Therefore, silica is naturally expected to be used in next-generation tires, but it is necessary to develop a technology that has further low fuel consumption performance and is suitable for environmental measures.
かかる観点から、澱粉を配合した技術が開発されている。例えば特許文献１にはジエン系ゴムに澱粉、澱粉／可塑剤及び／又は変性澱粉（酸化澱粉で疎水化澱粉ではない）、シリカ並びにメチレンアクセプター及び／又はメチレンドナーを配合したゴム組成物が開示されているがこれはメチレンアクセプター及び／又はメチレンドナーとの組合せで引き裂き抵抗を改良するものである。更に特許文献２には、ジエン系ゴムに、短繊維、モース硬度が５以上の粒子及びデンプン可塑剤複合材を配合した氷雪上性能及びウェットグリップ性能を向上させたゴム組成物が開示されている。 From this point of view, a technique in which starch is blended has been developed. For example, Patent Document 1 discloses a rubber composition in which starch, starch / plasticizer and / or modified starch (oxidized starch, not hydrophobized starch), silica, and a methylene acceptor and / or a methylene donor are mixed with a diene rubber. However, this improves the tear resistance in combination with a methylene acceptor and / or a methylene donor. Further, Patent Document 2 discloses a rubber composition having improved performance on ice and snow and wet grip performance in which diene rubber is blended with short fibers, particles having a Mohs hardness of 5 or more, and a starch plasticizer composite. .
本発明の目的は、従来の澱粉が澱粉の有する水酸基により凝集してしまうため、粘弾性挙動は改善するが補強性能を低減させるという問題があることに鑑み、かかる問題を解決して、補強性能を低減させることなく、粘弾性挙動を改善したゴム組成物及びそれを用いた空気入りタイヤを提供することにある。 The purpose of the present invention is to solve the above problem by improving the viscoelastic behavior but reducing the reinforcing performance because the conventional starch aggregates due to the hydroxyl group of the starch. An object of the present invention is to provide a rubber composition with improved viscoelastic behavior and a pneumatic tire using the same without reducing the above.
本発明に従えば、ジエン系ゴム１００重量部、疎水化澱粉０．５〜３０重量部、シリカを含む補強性充填剤１０〜１２０重量部及びシリカに対して２〜１５重量％のシランカップリング剤を含んでなるゴム組成物が提供される。 According to the present invention, 100 parts by weight of diene rubber, 0.5 to 30 parts by weight of hydrophobized starch, 10 to 120 parts by weight of reinforcing filler containing silica, and 2 to 15% by weight of silane coupling to silica. A rubber composition comprising the agent is provided.
本発明に従えば、更に、前記ゴム組成物をトレッドに用いた空気入りタイヤが提供される。 According to the present invention, there is further provided a pneumatic tire using the rubber composition as a tread.
本発明によればジエン系ゴムに、シリカ及びシランカップリング剤と共に、疎水化澱粉を配合することにより、ゴムの加工性を向上させ、そして転がり抵抗を低減させることができる。 According to the present invention, by blending a diene rubber with a hydrophobic starch together with silica and a silane coupling agent, the processability of the rubber can be improved and the rolling resistance can be reduced.
本発明者らは前記課題を解決すべく研究を進めた結果、従来の澱粉に代えて、ゴムに、シリカ及びシランカップリング剤と共に疎水化澱粉を配合することにより、ゴム組成物の加工性を向上させ、かつ転がり抵抗を低減させることを見出した。 As a result of researches to solve the above problems, the inventors of the present invention have improved the processability of the rubber composition by blending a hydrophobic starch with silica and a silane coupling agent in place of the conventional starch. It has been found that it improves and reduces rolling resistance.
本発明に係るジエン系ゴムとしては、スチレンブタジエン共重合体（ＳＢＲ）のような芳香族ビニル共役ジエン共重合体ゴム、ポリブタジエンゴム（ＢＲ）、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）などを用いることができる。本発明によればジエン系ゴム１００重量部中に、ウェットグリップの観点から、好ましくは芳香族ビニル共役ジエン共重合体ゴム２０重量部以上、更に好ましくは３０〜１００重量部を含み、かつ耐摩耗性の観点から、好ましくはガラス転移温度（ＡＳＴＭＤＢ４１８−８２に準拠して測定）が−５０℃〜−１０℃、更に好ましくは−５０〜−２５℃である。 Examples of the diene rubber according to the present invention include aromatic vinyl conjugated diene copolymer rubber such as styrene butadiene copolymer (SBR), polybutadiene rubber (BR), natural rubber (NR), and polyisoprene rubber (IR). Can be used. According to the present invention, 100 parts by weight of diene rubber preferably contains 20 parts by weight or more of aromatic vinyl conjugated diene copolymer rubber, more preferably 30 to 100 parts by weight from the viewpoint of wet grip, and wear resistance. From the viewpoint of safety, the glass transition temperature (measured according to ASTM D418 418-82) is preferably −50 ° C. to −10 ° C., more preferably −50 to −25 ° C.
本発明に係るゴム組成物に配合される補強性充填剤は、充填剤全重量当りのシリカ含量が１０重量％以上であるのが好ましく、１５〜９０重量％であるのが、更に好ましい。他の充填剤としては主としてカーボンブラックを使用するか、その他のゴム用充填剤、例えば水酸化アルミ、クレー、炭酸カルシウムの１種又はそれ以上を配合することもできる。 シリカの配合量が少ないと、０℃より低温状態において硬くなり過ぎるおそれがあり、逆にシリカの配合量が多いと混合性が劣るようになるおそれがあるので好ましくない。 The reinforcing filler blended in the rubber composition according to the present invention preferably has a silica content of 10% by weight or more, more preferably 15 to 90% by weight, based on the total weight of the filler. As other fillers, carbon black is mainly used, or other rubber fillers such as aluminum hydroxide, clay and calcium carbonate can be blended. If the blending amount of silica is small, it may be too hard at a temperature lower than 0 ° C., and conversely if the blending amount of silica is large, the mixing property may be deteriorated.
本発明に係るゴム組成物には、前記ジエン系ゴム１００重量部に対し、補強性充填剤１０〜１２０重量部、好ましくは３０〜９０重量部配合する。 In the rubber composition according to the present invention, 10 to 120 parts by weight, preferably 30 to 90 parts by weight of the reinforcing filler is blended with 100 parts by weight of the diene rubber.
本発明において使用する疎水化澱粉は公知のものであり、Ｊ−オイルミルズ（株）よりＰＯＴ−１０などとして市販されており、本発明においてもこれらの市販品を用いることができる。疎水化の種類としては、例えばメチレンオキサイド、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどによるエーテル化（澱粉とエポキシ化合物を用いて固相反応等）などがあり、疎水化率は、０．０５〜２．０％であるのが好ましい。この疎水化率が低いと所望の効果が得られず、逆に高いと反応工程上製造不可能となるので好ましくない。 The hydrophobized starch used in the present invention is known and commercially available as POT-10 from J-Oil Mills Co., Ltd., and these commercial products can also be used in the present invention. Examples of the hydrophobization include etherification (such as solid phase reaction using starch and an epoxy compound) with methylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc., and the hydrophobization rate is 0.05-2. It is preferably 0.0%. If this hydrophobization rate is low, the desired effect cannot be obtained, and conversely if it is high, production is impossible in the reaction process, which is not preferable.
本発明のゴム組成物には、ジエン系ゴム１００重量部に対し、疎水化澱粉０．５〜３０重量部、好ましくは３〜１５重量部配合する。この疎水化澱粉の配合量が少ないと所望の効果が得られず、逆に多いとゴム組成物中での分散不良がおこるので好ましくない。 In the rubber composition of the present invention, 0.5 to 30 parts by weight, preferably 3 to 15 parts by weight of hydrophobic starch is added to 100 parts by weight of the diene rubber. If the blended amount of the hydrophobized starch is small, the desired effect cannot be obtained. Conversely, if the blended amount is large, poor dispersion in the rubber composition occurs, which is not preferable.
本発明に係るゴム組成物には、前記した成分に加えて、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量は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。 In addition to the components described above, the rubber composition according to the present invention is used for tires such as vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plasticizers, and other rubber compositions. Various additives that are generally blended in can be blended, and such additives can be kneaded by a general method to form a composition, which can be used for vulcanization or crosslinking. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜３及び比較例１〜２
サンプルの調製
表Ｉに示す配合（重量部）において、加硫促進剤と硫黄を除く成分を１．８リットルの密閉型ミキサーで６分間混練し、１５５℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物を用いて以下に示す試験法で未加硫物性（ムーニー粘度及びムーニースコーチ）を評価した。
Examples 1-3 and Comparative Examples 1-2
Sample preparation In the formulation (parts by weight) shown in Table I, the ingredients other than the vulcanization accelerator and sulfur were kneaded for 6 minutes in a 1.8 liter closed mixer and released when the temperature reached 155 ° C. Got. A vulcanization accelerator and sulfur were kneaded with this master batch with an open roll to obtain a rubber composition. Using this rubber composition, unvulcanized physical properties (Mooney viscosity and Mooney scorch) were evaluated by the following test methods.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で２０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性（引張弾性率及び貯蔵弾性率Ｅ’）を測定した。 Next, the obtained rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 20 minutes to prepare a vulcanized rubber sheet, and the physical properties of the vulcanized rubber ( Tensile modulus and storage modulus E ′) were measured.
ゴム物性評価試験法
ムーニー粘度：ＪＩＳ Ｋ−６３００に準拠して１００℃にて測定し、比較例１を１００として指数表示した。この値が小さい程加工性に優れることを示す。
ムーニースコーチ：ＪＩＳ Ｋ−６３００に準拠して１２０℃にて測定し、比較例１を１００として指数表示した。この値が大きい程、加工性に優れることを示す。
Rubber physical property evaluation test method Mooney viscosity: Measured at 100 ° C. according to JIS K-6300. It shows that it is excellent in workability, so that this value is small.
Mooney scorch: Measured at 120 ° C. according to JIS K-6300, and indexed with Comparative Example 1 as 100. It shows that it is excellent in workability, so that this value is large.
引張弾性率（Ｍ１００及びＭ３００）：ＪＩＳ Ｋ−６２５１に準拠して１００％モジュラス（Ｍ１００）及び３００％モジュラス（Ｍ３００）を測定し、比較例１を１００として指数表示した。この値が大きい程補強性能に優れることを示す。
貯蔵弾性率Ｅ’（６０℃）：粘弾性スペクトロメータ（東洋精機製作所製）を用い周波数２０Hz、初期歪み１０％、動歪み±２％、温度６０℃の条件で測定し、比較例１を１００として指数表示した。この値が大きい程、高温時の補強性能が高いことを示す。
Tensile modulus (M100 and M300): 100% modulus (M100) and 300% modulus (M300) were measured according to JIS K-6251, and indexed with Comparative Example 1 as 100. The larger this value, the better the reinforcing performance.
Storage modulus E ′ (60 ° C.): Measured using a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho) under the conditions of frequency 20 Hz, initial strain 10%, dynamic strain ± 2%, temperature 60 ° C. As an index. The larger this value, the higher the reinforcement performance at high temperatures.
表Ｉ脚注
＊１：バイエル製ＶＳＬ５０２５（芳香族ビニル含量２５重量％、共役ジエンポリマーの１，２結合６７％、Ｔｇ−２６℃）
＊２：バイエル製ＢＵＮＡ ＣＢ２０
＊３：ローディア製Ｚｅｏｓｉｌ１１６５ＭＰ
＊４：（株）Ｊオイルミルズ製コーンスターチ
＊５：（株）Ｊオイルミルズ製ＰＯＴ−１０
＊６：東海カーボン（株）製Ｎ２３４
＊７：正同化学工業（株）製「酸化亜鉛３種」
＊８：日本油脂（株）製ビーズステアリン酸
＊９：フレキシス製６ＰＰＤ
＊１０：デクサ製Ｓｉ６９
＊１１：富士興産（株）製アロマックス３号
＊１２：大内新興化学工業（株）製ノクセラーＣＺ−Ｇ
＊１３：大内新興化学工業（株）製ノクセラーＤ
＊１４：鶴見化学工業（株）製約５％油処理硫黄
Table I footnote * 1: Bayer VSL 5025 (aromatic vinyl content 25% by weight, conjugated diene polymer 1,2 bond 67%, Tg-26 ° C.)
* 2: Bayer BUNA CB20
* 3: Rhodia Zeosil 1165MP
* 4: Cornstarch manufactured by J Oil Mills Co., Ltd. * 5: POT-10 manufactured by J Oil Mills Co., Ltd.
* 6: N234 made by Tokai Carbon Co., Ltd.
* 7: “Zinc oxide 3 types” manufactured by Shodo Chemical Industry Co., Ltd.
* 8: Bead stearic acid manufactured by Nippon Oil & Fats Co., Ltd. * 9: 6PPD manufactured by Flexis
* 10: Dexa Si69
* 11: Aromax 3 manufactured by Fuji Kosan Co., Ltd. * 12: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 13: Noxeller D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 14: Approximately 5% oil-treated sulfur manufactured by Tsurumi Chemical Co., Ltd.
以上の通り、本発明に係るゴム組成物は、加工性が良く（粘度が低い）、高モジュラスなゴムを得ることができるので、剛性の高いことが必要なタイヤトレッド用ゴム組成物として使用することができる。 As described above, since the rubber composition according to the present invention has good processability (low viscosity) and can obtain a high modulus rubber, it is used as a rubber composition for a tire tread that requires high rigidity. be able to.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007227870A JP5458482B2 (en) | 2007-09-03 | 2007-09-03 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007227870A JP5458482B2 (en) | 2007-09-03 | 2007-09-03 | Rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009057514A JP2009057514A (en) | 2009-03-19 |
| JP5458482B2 true JP5458482B2 (en) | 2014-04-02 |
Family
ID=40553557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007227870A Expired - Fee Related JP5458482B2 (en) | 2007-09-03 | 2007-09-03 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5458482B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115627084B (en) * | 2022-11-11 | 2024-02-27 | 郑州圣莱特空心微珠新材料有限公司 | Surface treatment method of glass beads and silicone rubber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005133025A (en) * | 2003-10-31 | 2005-05-26 | Sumitomo Rubber Ind Ltd | Rubber composition |
| JP2005154586A (en) * | 2003-11-26 | 2005-06-16 | Sumitomo Rubber Ind Ltd | Rubber composition |
| JP4762561B2 (en) * | 2005-01-31 | 2011-08-31 | 東洋ゴム工業株式会社 | Rubber composition for tire tread |
| JP4796327B2 (en) * | 2005-04-27 | 2011-10-19 | 住友ゴム工業株式会社 | Composite of starch and rubber composition containing the same |
-
2007
- 2007-09-03 JP JP2007227870A patent/JP5458482B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009057514A (en) | 2009-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5376008B2 (en) | Rubber composition for tire | |
| JP5234203B2 (en) | Rubber composition for tire | |
| JP5737324B2 (en) | Rubber composition for tire | |
| JP4788843B1 (en) | Rubber composition for tire | |
| JP4294070B2 (en) | Rubber composition for tire | |
| JP5381332B2 (en) | Rubber composition for tire tread | |
| JP4796327B2 (en) | Composite of starch and rubber composition containing the same | |
| JP2008308615A (en) | Rubber composition for tire | |
| JP5194546B2 (en) | Rubber composition | |
| JP6481255B2 (en) | Rubber composition for tire | |
| JP5321751B2 (en) | Rubber composition for tire, pneumatic tire, and method for producing rubber composition for tire | |
| KR100775886B1 (en) | Rubber composition and process for preparing the same | |
| JP2015209540A (en) | Rubber composition for tire tread | |
| JP2008138086A (en) | Rubber composition for tire tread | |
| JP5582921B2 (en) | Rubber composition for studless tire and studless tire | |
| EP3567076A1 (en) | Vulcanized rubber composition and pneumatic tire | |
| JP4902166B2 (en) | Rubber composition for sidewall, method for producing the same, and pneumatic tire using the rubber composition | |
| JP5920544B2 (en) | Rubber composition for tire | |
| JP2006188571A (en) | Rubber composition and tire formed out of the same | |
| JP5463734B2 (en) | Rubber composition for tire | |
| JP5458482B2 (en) | Rubber composition | |
| JP2018172639A (en) | Rubber composition, and tire | |
| JP2009007422A (en) | Rubber composition and tire | |
| JP5019745B2 (en) | Rubber composition | |
| JP2007217465A (en) | Rubber composition for tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100713 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111116 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130115 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130314 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130604 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130820 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130927 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131217 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131230 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5458482 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |