JP6473371B2 - Kneading method and method for producing rubber composition - Google Patents
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- 238000004898 kneading Methods 0.000 title claims description 77
- 229920001971 elastomer Polymers 0.000 title claims description 76
- 239000005060 rubber Substances 0.000 title claims description 76
- 239000000203 mixture Substances 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 65
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 239000006229 carbon black Substances 0.000 claims description 29
- 244000043261 Hevea brasiliensis Species 0.000 claims description 26
- 229920003052 natural elastomer Polymers 0.000 claims description 26
- 229920001194 natural rubber Polymers 0.000 claims description 26
- 238000010077 mastication Methods 0.000 claims description 22
- 230000018984 mastication Effects 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 52
- 230000008569 process Effects 0.000 description 26
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- 239000005062 Polybutadiene Substances 0.000 description 12
- 239000002174 Styrene-butadiene Substances 0.000 description 12
- 229920002857 polybutadiene Polymers 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- 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
- 239000008117 stearic acid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- UTPYTEWRMXITIN-YDWXAUTNSA-N 1-methyl-3-[(e)-[(3e)-3-(methylcarbamothioylhydrazinylidene)butan-2-ylidene]amino]thiourea Chemical compound CNC(=S)N\N=C(/C)\C(\C)=N\NC(=S)NC UTPYTEWRMXITIN-YDWXAUTNSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920005683 SIBR Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
Description
本発明は天然ゴムを含むゴム成分の素練り方法、および該素練り方法を含むゴム組成物の製造方法に関する。 The present invention relates to a method for kneading a rubber component containing natural rubber, and a method for producing a rubber composition including the kneading method.
従来タイヤトレッドには耐摩耗性が要求され、耐摩耗性を向上させるために原料ゴムとして天然ゴムを主原料とすることが知られている。しかし、天然ゴムは合成ゴムよりも分子量が大きく、加工性に劣るため、従来タイヤトレッドに配合される所定のカーボンブラックやシリカなどの補強剤を均一に分散させることが難しい。 Conventional tire treads are required to have wear resistance, and it is known that natural rubber is the main raw material as a raw rubber in order to improve wear resistance. However, since natural rubber has a higher molecular weight than synthetic rubber and is inferior in processability, it is difficult to uniformly disperse a predetermined reinforcing agent such as carbon black or silica that is blended in a conventional tire tread.
そこで、天然ゴムを少量の素練り促進剤とともに混練りし、原料ゴムの分子量を適度に下げる素練り工程を行った後に、補強剤、軟化剤などの配合剤をさらに添加して混練りする混練り工程を行う方法が知られている。しかし、タイヤトレッドに要求される十分な耐摩耗性を得るためには素練り工程後の混練り工程において配合する軟化剤の量を抑える必要があり、その結果、混練物の粘度が上昇し、混練り工程だけでなく押出し工程などの以降の工程での加工性が悪化し、生産性が低下するという問題がある。 Therefore, natural rubber is kneaded with a small amount of a peptizer, and after a mastication step for appropriately reducing the molecular weight of the raw rubber, a compounding agent such as a reinforcing agent and a softener is further added and kneaded. A method of performing a kneading process is known. However, in order to obtain sufficient wear resistance required for the tire tread, it is necessary to suppress the amount of the softening agent to be blended in the kneading step after the mastication step. As a result, the viscosity of the kneaded product increases, There is a problem that not only in the kneading process but also in the subsequent processes such as the extrusion process, the workability deteriorates and the productivity decreases.
混練物の粘度を低く抑えるため、素練り工程において素練り促進剤を多量に、例えば原料ゴム１００質量部に対して０．７〜１質量部添加する方法が知られているが、要求される耐摩耗性を確保できないため、実用化には至っていない。 In order to keep the viscosity of the kneaded product low, a method is known in which a large amount of a kneading accelerator is added in the kneading step, for example, 0.7 to 1 part by mass with respect to 100 parts by mass of the raw rubber. Since the wear resistance cannot be ensured, it has not been put to practical use.
また、特許文献１には、原料ゴムのみを３０〜４５秒混練りした後に、原料ゴム１００質量部に対して５〜１０質量部のカーボンブラックを添加して混練りする素練り方法が記載されているが、粘度低減による加工性改善効果は十分ではないという問題がある。 Patent Document 1 describes a kneading method in which only raw rubber is kneaded for 30 to 45 seconds, and then 5 to 10 parts by mass of carbon black is added to 100 parts by mass of raw rubber. However, there is a problem that the workability improvement effect due to viscosity reduction is not sufficient.
本発明は、生産性を悪化させることなく、耐摩耗性に優れるゴム組成物を得ることができる天然ゴムを含むゴム成分の素練り方法、および該素練り方法を含むゴム組成物の製造方法を提供することを目的とする。 The present invention relates to a method for kneading a rubber component containing natural rubber, which can obtain a rubber composition excellent in wear resistance without deteriorating productivity, and a method for producing a rubber composition including the mastication method. The purpose is to provide.
本発明者は、鋭意検討の結果、所定量の素練り促進剤および充填剤を添加する天然ゴムを含むゴム成分の素練り方法とし、素練り促進剤の添加量および充填剤を添加する際の温度を管理することで、前記課題を解決できることを見出し、さらに検討を重ねて本発明を完成することに成功した。 As a result of diligent study, the present inventor made a method of kneading a rubber component containing natural rubber to which a predetermined amount of a peptizer and a filler are added. The inventors have found that the above-mentioned problems can be solved by controlling the temperature, and have succeeded in completing the present invention through further studies.
すなわち本発明は、天然ゴムを含むゴム成分の素練り方法であって、ゴム成分１００質量部に対して０．０３〜０．７５質量部の素練り促進剤を含有するゴム成分の素練りを開始する素練り開始工程、ならびに素練り温度が１００〜１６０℃に達した際に、ゴム成分１００質量部に対して１２〜４０質量部のカーボンブラックおよび／またはシリカを添加する添加工程を含む素練り方法に関する。 That is, the present invention is a method for kneading a rubber component containing natural rubber, which comprises kneading a rubber component containing 0.03 to 0.75 parts by mass of a kneading accelerator with respect to 100 parts by mass of the rubber component. Elemental process including starting process, and adding process of adding 12 to 40 parts by mass of carbon black and / or silica with respect to 100 parts by mass of rubber component when mastication temperature reaches 100 to 160 ° C It relates to the kneading method.
前記カーボンブラックの平均粒子径が１０〜３５ｎｍであり、前記シリカの窒素吸着比表面積が４０〜２４０ｍ2／ｇであることが好ましい。 The carbon black preferably has an average particle diameter of 10 to 35 nm, and the silica has a nitrogen adsorption specific surface area of 40 to 240 m 2 / g.
また本発明は、前記素練り方法を含むゴム組成物の製造方法に関する。 Moreover, this invention relates to the manufacturing method of the rubber composition containing the said mastication method.
本発明によれば、生産性を悪化させることなく、耐摩耗性に優れたゴム組成物を得ることができるゴム成分の素練り方法、および該素練り方法を含むゴム組成物の製造方法を提供することができる。 According to the present invention, there is provided a rubber component mastication method capable of obtaining a rubber composition excellent in wear resistance without deteriorating productivity, and a method for producing a rubber composition including the mastication method. can do.
＜素練り方法＞
本発明の素練り方法は、天然ゴムを含むゴム成分の素練り方法であって、所定量の素練り促進剤を含有するゴム成分の素練りを開始する素練り開始工程、ならびに所定の素練り温度に達した際に、所定量のカーボンブラックおよび／またはシリカを添加する添加工程を含む素練り方法である。
<Powdering method>
The kneading method of the present invention is a kneading method of a rubber component containing natural rubber, a kneading start step for starting mastication of a rubber component containing a predetermined amount of a kneading accelerator, and a predetermined kneading This is a mastication method including an addition step of adding a predetermined amount of carbon black and / or silica when the temperature is reached.
素練り開始工程
素練り開始工程は、天然ゴムを含むゴム成分に所定量の素練り促進剤を添加し、バンバリーミキサーやニーダーなどの密閉式ミキサー、オープンロールなどの公知の混練機を用いて素練りを開始する工程である。
The kneading start process The kneading start process is performed by adding a predetermined amount of a kneading accelerator to a rubber component containing natural rubber, and using a kneading machine such as a closed mixer such as a Banbury mixer or a kneader or an open roll. This is a process of starting kneading.
天然ゴムとしては、天然ゴム（ＮＲ）や、エポキシ化天然ゴム（ＥＮＲ）、水素化天然ゴム（ＨＮＲ）、脱タンパク質天然ゴム（ＤＰＮＲ）、高純度天然ゴム（ＨＰＮＲ）などの改質天然ゴムなども含まれる。 Natural rubber (NR), modified natural rubber such as epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), deproteinized natural rubber (DPNR), high purity natural rubber (HPNR), etc. Is also included.
前記ＮＲとしては特に限定されず、ＳＩＲ２０、ＲＳＳ＃３、ＴＳＲ２０など、ゴム工業において一般的なものを使用することができる。 The NR is not particularly limited, and those generally used in the rubber industry such as SIR20, RSS # 3, TSR20, and the like can be used.
素練り開始工程では、天然ゴムとともに天然ゴム以外のゴム成分を添加することもできるが、本発明の素練り方法による効果がより得られるという理由から、素練り開始工程で添加するゴム成分は、天然ゴム単独とすることが好ましい。 In the mastication start process, rubber components other than natural rubber can be added together with natural rubber, but because the effect of the mastication method of the present invention is more obtained, the rubber component added in the mastication start process is It is preferable to use natural rubber alone.
前記素練り促進剤（しゃく解剤）としては、従来ゴム工業において使用されている、大内新興化学工業（株）製のノクタイザーＳＤ、川口化学工業（株）製のペプター３Ｓなどのチオフェノールやジスルフィドが挙げられる。 Examples of the peptizer (peptizer) include thiophenols such as Nouchitizer SD manufactured by Ouchi Shinsei Chemical Co., Ltd. and Pepter 3S manufactured by Kawaguchi Chemical Co., Ltd., which are conventionally used in the rubber industry. A disulfide is mentioned.
素練り促進剤の全ゴム成分１００質量部に対する含有量は、０．０３質量部以上であり、０．０５質量部以上が好ましく、０．１０質量部以上がより好ましい。素練り促進剤の含有量が０．０３質量部未満の場合は、素練り促進剤の添加による粘度低減の効果が得られず、加工性が悪化し、生産性が低下する傾向がある。また、素練り促進剤の含有量は、０．７５質量部以下であり、０．５０質量部以下が好ましく、０．３０質量部以下がより好ましい。素練り促進剤の含有量が０．７５質量部を超える場合は、ゴム組成物の耐摩耗性が悪化する傾向がある。なお、本明細書における「全ゴム成分」とは、本発明の素練り方法を含む製造方法で製造されるゴム組成物中のゴム成分全てを示し、例えば後述のベース練り工程などで添加するゴム成分なども含むものである。 Content with respect to 100 mass parts of all rubber components of a peptizer is 0.03 mass part or more, 0.05 mass part or more is preferable and 0.10 mass part or more is more preferable. When the content of the kneading accelerator is less than 0.03 parts by mass, the effect of reducing the viscosity due to the addition of the kneading accelerator cannot be obtained, and the workability tends to deteriorate and the productivity tends to decrease. Moreover, content of a peptizer is 0.75 mass part or less, 0.50 mass part or less is preferable and 0.30 mass part or less is more preferable. When the content of the kneading accelerator exceeds 0.75 parts by mass, the wear resistance of the rubber composition tends to deteriorate. The “total rubber component” in the present specification refers to all rubber components in the rubber composition produced by the production method including the kneading method of the present invention, for example, rubber added in the base kneading step described later. Including ingredients and the like.
素練り開始工程で開始された素練りは、素練り物の温度が後述の素練り温度に達するまで行う。 The kneading started in the kneading start process is performed until the temperature of the kneaded product reaches a kneading temperature described later.
添加工程
添加工程は、素練り物温度が所定の素練り温度に達した際に、所定量のカーボンブラックおよび／またはシリカを添加する工程である。所定量のカーボンブラックおよび／またはシリカを素練り温度が所定の温度に達した際に添加することで、素練り物の粘度が適度であり加工性に優れ、添加するカーボンブラックおよび／またはシリカの分散性が向上し耐摩耗性に優れる傾向がある。
Addition Step The addition step is a step of adding a predetermined amount of carbon black and / or silica when the temperature of the kneaded product reaches a predetermined temperature of kneading. By adding a predetermined amount of carbon black and / or silica when the kneading temperature reaches a predetermined temperature, the viscosity of the kneaded product is moderate and excellent in workability, and dispersion of the added carbon black and / or silica There is a tendency to improve the wear resistance.
カーボンブラックおよび／またはシリカを添加する素練り温度は、１００℃以上であり、１１０℃以上が好ましく、１２０℃以上がさらに好ましい。添加時の素練り温度が１００℃未満の場合は、素練り物の粘度が高いため加工性が悪く、添加したカーボンブラックおよび／またはシリカの分散性が悪化する傾向がある。また、添加時の素練り温度は、１６０℃以下であり、１５０℃以下が好ましく、１４０℃以下がより好ましい。添加時の素練り温度が１６０℃を超える場合は、素練り促進剤によるしゃく解効果が過剰となり、天然ゴム分子量が低下しゴム組成物の耐摩耗性が悪化する傾向、および温度上昇により火災が発生する恐れがある。 The kneading temperature for adding carbon black and / or silica is 100 ° C. or higher, preferably 110 ° C. or higher, and more preferably 120 ° C. or higher. When the kneading temperature at the time of addition is less than 100 ° C., the viscosity of the kneaded product is high, so that the processability is poor and the dispersibility of the added carbon black and / or silica tends to deteriorate. Moreover, the kneading temperature at the time of addition is 160 degrees C or less, 150 degrees C or less is preferable and 140 degrees C or less is more preferable. If the kneading temperature at the time of addition exceeds 160 ° C., the peptization effect by the kneading accelerator becomes excessive, the natural rubber molecular weight tends to decrease, the wear resistance of the rubber composition tends to deteriorate, and the temperature rise causes a fire. May occur.
添加工程で添加するカーボンブラックとしては特に限定されず、ＧＰＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦなど、ゴム工業において一般的なものを使用でき、単独で用いても、２種以上を併用してもよい。 Carbon black to be added in the addition step is not particularly limited, and those generally used in the rubber industry such as GPF, FEF, HAF, ISAF, and SAF can be used, either alone or in combination of two or more. Good.
カーボンブラックの平均粒子径は、カーボンブラックの補強効果の観点から１０ｎｍ以上が好ましく、１３ｎｍ以上がより好ましい。また、カーボンブラックの平均粒子径は、カーボンブラックの分散性およびゴム組成物の発熱性の観点から３５ｎｍ以下が好ましく、３０ｎｍ以下がより好ましい。なお、本明細書におけるカーボンブラックの平均粒子径は数平均粒子径であり、透過型電子顕微鏡により測定される。 The average particle size of carbon black is preferably 10 nm or more, and more preferably 13 nm or more from the viewpoint of the reinforcing effect of carbon black. In addition, the average particle size of carbon black is preferably 35 nm or less, and more preferably 30 nm or less, from the viewpoint of dispersibility of carbon black and heat generation of the rubber composition. In addition, the average particle diameter of carbon black in this specification is a number average particle diameter, and is measured with a transmission electron microscope.
また、添加工程で添加するシリカとしては、乾式法シリカ（無水ケイ酸）、湿式法シリカ（含水ケイ酸）などを用いることができる。なかでも、表面のシラノール基が多く、シランカップリング剤との反応点が多いという理由から、湿式法により調製されたシリカを用いることが好ましい。 Moreover, as a silica added at an addition process, a dry process silica (anhydrous silicic acid), a wet process silica (hydrous silicic acid), etc. can be used. Especially, it is preferable to use the silica prepared by the wet method from the reason that there are many silanol groups on the surface and there are many reaction points with a silane coupling agent.
シリカの窒素吸着比表面積（Ｎ2ＳＡ）は、シリカの補強効果の観点から４０ｍ2／ｇ以上が好ましく、６０ｍ2／ｇ以上がより好ましく、８０ｍ2／ｇ以上がさらに好ましく、１００ｍ2／ｇ以上が特に好ましい。また、シリカのＮ2ＳＡは、シリカの分散性およびゴム組成物の発熱性の観点から２４０ｍ2／ｇ以下が好ましく、２００ｍ2／ｇ以下がより好ましく、１８０ｍ2／ｇ以下がさらに好ましく、１６０ｍ2／ｇ以下が特に好ましい。なお、本明細書におけるシリカのＮ2ＳＡは、ＡＴＳＭ Ｄ３０３７−８１に準じてＢＥＴ法で測定される値である。 The nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 40 m 2 / g or more, more preferably 60 m 2 / g or more, still more preferably 80 m 2 / g or more, and 100 m 2 / g from the viewpoint of the reinforcing effect of silica. The above is particularly preferable. The N 2 SA of the silica is preferably 240 m 2 / g or less in view of exothermic dispersibility and the rubber composition of the silica, more preferably not more than 200 meters 2 / g, more preferably 180 m 2 / g or less, 160 m 2 / g or less is particularly preferable. Incidentally, N 2 SA of the silica herein is a value determined by the BET method in accordance with ATSM D3037-81.
添加工程におけるカーボンブラックおよび／またはシリカの全ゴム成分１００質量部に対する合計添加量は、１２質量部以上であり、１５質量部以上が好ましく、２０質量部以上がより好ましい。合計添加量が１２質量部未満の場合は、本発明の素練り方法による効果が十分に得られず、生産性が悪化する傾向がある。また、カーボンブラックおよび／またはシリカの合計添加量は、４０質量部以下であり、３０質量部以下が好ましく、２５質量部以下がより好ましい。合計添加量が４０質量部を超える場合は、カーボンブラックやシリカが凝集してゲル状となるため、ゴム成分への分散性が悪化し、耐摩耗性が低下する傾向がある。 The total amount of carbon black and / or silica added to 100 parts by mass of the rubber component in the addition step is 12 parts by mass or more, preferably 15 parts by mass or more, and more preferably 20 parts by mass or more. When the total addition amount is less than 12 parts by mass, the effect of the kneading method of the present invention cannot be sufficiently obtained, and the productivity tends to deteriorate. The total amount of carbon black and / or silica added is 40 parts by mass or less, preferably 30 parts by mass or less, and more preferably 25 parts by mass or less. When the total addition amount exceeds 40 parts by mass, carbon black and silica aggregate to form a gel, so that dispersibility in the rubber component is deteriorated and wear resistance tends to be reduced.
添加工程でカーボンブラックおよび／またはシリカを添加した素練り物を、公知の方法などでさらに素練りすることで、最終素練り物を得ることができる。 The final kneaded product can be obtained by further kneading the kneaded product to which carbon black and / or silica is added in the adding step by a known method or the like.
＜ゴム組成物の製造方法＞
本発明のゴム組成物の製造方法は、前記素練り方法を含むこと以外は、従来のゴム組成物の製造方法とすることができ、例えば、前記素練り方法で得られた素練り物、他のゴム成分、加硫系薬剤以外の従来ゴム工業で用いられている配合剤などを混練りするベース練り工程（Ｘ工程）、および加硫系薬剤を混練りする仕上げ練り工程（Ｆ工程）を行い、その後加硫する方法（加硫工程）などによりゴム組成物を製造する方法とすることができる。
<Method for producing rubber composition>
The method for producing a rubber composition of the present invention can be a conventional method for producing a rubber composition, except that it includes the mastication method. For example, a kneaded product obtained by the mastication method, Perform base kneading process (X process) for kneading compounding ingredients used in the rubber industry other than rubber components and vulcanizing chemicals, and finishing kneading process (F process) for kneading vulcanizing chemicals Then, it can be set as the method of manufacturing a rubber composition by the method of vulcanizing (vulcanization process) etc. after that.
ベース練り工程
ベース練り工程は、前記素練り方法で得られた素練り物に、さらなるゴム成分や加硫系薬剤以外の配合剤などを適宜添加し、バンバリーミキサーやニーダーなどの密閉式ミキサー、オープンロールなどの公知の混練機を用いて混練りする工程である。
Base kneading step In the base kneading step, additional ingredients other than rubber components and vulcanizing chemicals are appropriately added to the kneaded product obtained by the kneading method, and a closed mixer such as a Banbury mixer or a kneader, an open roll This is a step of kneading using a known kneader.
ベース練り工程で添加できるゴム成分としては、従来ゴム工業で用いられているゴム成分であれば特に限定されず、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、スチレンイソプレンブタジエンゴム、（ＳＩＢＲ）、エチレンプロピレンジエンゴム（ＥＰＤＭ）、クロロプレンゴム（ＣＲ）、アクリロニトリルブタジエンゴム（ＮＢＲ）などが挙げられる。なかでも、ＳＢＲ、ＢＲが好ましい。なお、ベース練り工程で天然ゴムを添加することもできるが、ゴム組成物に配合される天然ゴムは全て素練り開始工程で添加し、素練りすることが加工性の観点から好ましい。 The rubber component that can be added in the base kneading step is not particularly limited as long as it is a rubber component conventionally used in the rubber industry, and isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene. Examples include butadiene rubber, (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). Of these, SBR and BR are preferable. Although natural rubber can be added in the base kneading step, it is preferable from the viewpoint of workability that all the natural rubber blended in the rubber composition is added in the kneading start step and kneaded.
前記ＳＢＲとしては、未変性の溶液重合ＳＢＲ（Ｓ−ＳＢＲ）、未変性の乳化重合ＳＢＲ（Ｅ−ＳＢＲ）、およびこれらの変性ＳＢＲ（変性Ｓ−ＳＢＲ、変性Ｅ−ＳＢＲ）などが挙げられ、なかでも、カーボンブラックやシリカとの結合に優れるという理由から、末端が変性された変性ＳＢＲが好ましい。変性ＳＢＲとしては、特開２００１−１１４９３８号公報に記載されているアルコキシ基を含有する有機ケイ素化合物で変性したシリカ用変性ＳＢＲなどが挙げられる。 Examples of the SBR include unmodified solution polymerization SBR (S-SBR), unmodified emulsion polymerization SBR (E-SBR), and modified SBR thereof (modified S-SBR, modified E-SBR), and the like. Among these, a modified SBR having a modified terminal is preferable because of excellent bonding with carbon black or silica. Examples of the modified SBR include modified SBR for silica modified with an organosilicon compound containing an alkoxy group described in JP-A No. 2001-114938.
ＳＢＲのスチレン含有量は、ウェットグリップ性能の観点から５質量％以上が好ましく、１０質量％以上がより好ましい。また、ＳＢＲのスチレン含有量は、低温特性の観点から４５質量％以下が好ましく、４０質量％以下がより好ましい。なお、本明細書におけるＳＢＲのスチレン含有量は、1Ｈ−ＮＭＲ測定により算出される値である。 The styrene content of SBR is preferably 5% by mass or more from the viewpoint of wet grip performance, and more preferably 10% by mass or more. The styrene content of SBR is preferably 45% by mass or less, more preferably 40% by mass or less from the viewpoint of low temperature characteristics. In addition, the styrene content of SBR in the present specification is a value calculated by 1 H-NMR measurement.
前記ＢＲとしては特に限定されず、例えば、日本ゼオン（株）製のＢＲ１２２０、宇部興産（株）製のＢＲ１３０Ｂ、ＢＲ１５０Ｂなどの高シス含有量のＢＲ（ハイシスＢＲ）、宇部興産（株）製のＶＣＲ４１２、ＶＣＲ６１７などのシンジオタクチックポリブタジエン結晶を含有するＢＲ（ＳＰＢ含有ＢＲ）などを使用できる。 The BR is not particularly limited. For example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR130B manufactured by Ube Industries, Ltd., BR150B, and the like with high cis content BR (Hisys BR), manufactured by Ube Industries, Ltd. BR (SPB-containing BR) containing syndiotactic polybutadiene crystals such as VCR 412 and VCR 617 can be used.
ＢＲを含有する場合の全ゴム成分中の含有量は、耐摩耗性の観点から５質量％以上が好ましく、１０質量％以上がより好ましい。また、ＢＲの含有量は、ゴム強度、トレッドのチップカット発生抑制の観点から８０質量％以下が好ましく、７０質量％以下がより好ましい。 The content of all rubber components when BR is contained is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of wear resistance. Further, the BR content is preferably 80% by mass or less, and more preferably 70% by mass or less from the viewpoint of rubber strength and suppression of occurrence of tread chip cut.
ベース練り工程で添加できる配合剤としては、例えば、カーボンブラックやシリカなどの補強用充填剤、カップリング剤、オイルなどの軟化剤、ステアリン酸、酸化亜鉛、各種老化防止剤、オゾン劣化防止剤、ワックスなどが挙げられる。なお、ベース練り工程で補強用充填剤としてカーボンブラックおよび／またはシリカを添加する場合は、前記添加工程で添加するカーボンブラックまたはシリカと同一のものとすることもできるが、含有量の観点からは明確に区分けされる。 Examples of compounding agents that can be added in the base kneading step include reinforcing fillers such as carbon black and silica, coupling agents, softening agents such as oil, stearic acid, zinc oxide, various anti-aging agents, ozone deterioration preventing agents, Wax etc. are mentioned. In addition, when adding carbon black and / or silica as a reinforcing filler in the base kneading step, it can be the same as the carbon black or silica added in the addition step, but from the viewpoint of content Clearly divided.
またベース練り工程（Ｘ工程）は、配合剤の分散性向上などを目的とし、素練り物、ゴム成分および配合剤の一部を混練りするＸ１工程、さらに残りの配合剤を添加し混練りするＸ２工程などに分けて混練りする工程とすることもできる。 The base kneading step (step X) is for the purpose of improving the dispersibility of the compounding agent, for example, the X1 step of kneading part of the kneaded product, the rubber component and the compounding agent, and further adding the remaining compounding agent and kneading. It can also be set as the process of kneading | mixing by dividing into X2 processes.
仕上げ練り工程
仕上げ練り工程は、前記ベース練り工程で得られた混練物に、従来ゴム工業で用いられている加硫系薬剤などを添加、混練りし、未加硫ゴム組成物を得る工程である。
Finishing and kneading process The finishing and kneading process is a process in which vulcanized chemicals and the like conventionally used in the rubber industry are added to the kneaded product obtained in the base kneading process and kneaded to obtain an unvulcanized rubber composition. is there.
仕上げ練り工程は、ベース練り工程で得られた混練物を通常１００℃以下、好ましくは２０〜８０℃となるまで冷却した後に行うことが好ましい。 The finishing kneading step is preferably performed after cooling the kneaded product obtained in the base kneading step to 100 ° C or lower, preferably 20 to 80 ° C.
仕上げ練り工程で添加する加硫系薬剤としては、硫黄、硫黄化合物などの加硫剤、スルフェンアミド系、チアゾール系、グアニジン系加硫促進剤などの加硫促進剤などが挙げられる。 Examples of the vulcanizing agent added in the finishing kneading step include vulcanizing agents such as sulfur and sulfur compounds, and vulcanizing accelerators such as sulfenamide-based, thiazole-based and guanidine-based vulcanizing agents.
仕上げ練り工程で得られた未加硫ゴム組成物を、公知の方法などで加硫することで加硫ゴム組成物を得ることができる。 A vulcanized rubber composition can be obtained by vulcanizing the unvulcanized rubber composition obtained in the final kneading step by a known method or the like.
＜ゴム組成物＞
本発明のゴム組成物の製造方法によって得られるゴム組成物における全ゴム成分中の天然ゴムの含有量は、本発明の素練り方法とすることの効果がより得られるという理由から１００質量％であることが好ましい。
<Rubber composition>
The content of natural rubber in all rubber components in the rubber composition obtained by the method for producing a rubber composition of the present invention is 100% by mass because the effect of the mastication method of the present invention can be obtained more. Preferably there is.
本発明のゴム組成物の製造方法により製造されたゴム組成物は、タイヤの各部材に好適に用いることができ、耐摩耗性に優れるという理由から、特にトレッドに好適に用いることができる。さらにトレッドがキャップトレッドとベーストレッドからなる２層構造のトレッドである場合はキャップトレッドに好適に用いることができる。 The rubber composition produced by the method for producing a rubber composition of the present invention can be suitably used for each member of a tire and can be particularly suitably used for a tread because it has excellent wear resistance. Furthermore, when the tread is a tread having a two-layer structure including a cap tread and a base tread, it can be suitably used for a cap tread.
前記ゴム組成物を用いたタイヤは、本発明の素練り方法を含むこと以外は通常の方法によって製造される。すなわち、本発明の素練り方法を含む製造方法で製造されたゴム組成物を未加硫の段階でトレッドなどのタイヤ部材の形状にあわせて押出し加工し、タイヤ成形機上で、通常の方法により、他のタイヤ部材とともに貼り合わせて未加硫タイヤを成形する。該未加硫タイヤを加硫機中で加熱・加圧し、本発明に係るタイヤを得ることができる。 A tire using the rubber composition is manufactured by a usual method except that the mastication method of the present invention is included. That is, the rubber composition produced by the production method including the mastication method of the present invention is extruded in accordance with the shape of a tire member such as a tread at an unvulcanized stage, and is subjected to a normal method on a tire molding machine. The unvulcanized tire is formed by bonding together with other tire members. The unvulcanized tire can be heated and pressurized in a vulcanizer to obtain the tire according to the present invention.
前記タイヤは、乗用車用タイヤ、トラック・バス用タイヤ、二輪車用タイヤなどとして好適に用いることができる。 The tire can be suitably used as a tire for passenger cars, a tire for trucks and buses, a tire for motorcycles, and the like.
本発明を実施例に基づいて説明するが、本発明は実施例のみに限定されるものではない。 The present invention will be described based on examples, but the present invention is not limited to the examples.
実施例および比較例で使用した各種薬品について説明する。
ＮＲ：ＳＩＲ２０
素練り促進剤：大内新興化学工業（株）製のノクタイザーＳＤ
カーボンブラック：キャボットジャパン（株）製のショウブラックＮ２２０（平均粒子径：２２ｎｍ）
シリカ：東ソー・シリカ（株）製のニップシールＡＱ（Ｎ2ＳＡ：２００ｍ2／ｇ）
ＳＢＲ：日本ゼオン（株）製のＮｉｐｏｌ １５０２（Ｅ−ＳＢＲ、スチレン含量：２３．５質量％）
オイル：Ｈ＆Ｒ社製のＶＩＶＡＴＥＣ５００（ＴＤＡＥオイル）
シランカップリング剤：エボニックデグッサ社製のＳｉ２６６（ビス（３−トリエトキシシリルプロピル）ジスルフィド）
老化防止剤：大内新興化学工業（株）製のノクラック６Ｃ（Ｎ−１，３−ジメチルブチル−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ステアリン酸：日油（株）製のステアリン酸「椿」
酸化亜鉛：三井金属鉱業（株）製の酸化亜鉛２種
ワックス：大内新興化学工業（株）製のサンノックＮ
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤ＣＢＳ：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド）
加硫促進剤ＤＰＧ：大内新興化学工業（株）製のノクセラーＤ（１，３−ジフェニルグアニジン）
Various chemicals used in Examples and Comparative Examples will be described.
NR: SIR20
Kneading accelerator: Nouchitizer SD manufactured by Ouchi Shinsei Chemical Co., Ltd.
Carbon black: Show Black N220 (average particle size: 22 nm) manufactured by Cabot Japan
Silica: NIPSEAL AQ (N 2 SA: 200 m 2 / g) manufactured by Tosoh Silica Co., Ltd.
SBR: Nipol 1502 (E-SBR, styrene content: 23.5% by mass) manufactured by Nippon Zeon Co., Ltd.
Oil: VIVETEC500 (TDAE oil) manufactured by H & R
Silane coupling agent: Si266 (bis (3-triethoxysilylpropyl) disulfide) manufactured by Evonik Degussa
Anti-aging agent: NOCRACK 6C (N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) manufactured by Ouchi Shinsei Chemical Co., Ltd.
Stearic acid: Stearic acid “椿” manufactured by NOF Corporation
Zinc oxide: 2 types of zinc oxide manufactured by Mitsui Kinzoku Mining Co., Ltd .: Sunnock N manufactured by Ouchi Shinsei Chemical
Sulfur: powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. CBS: Noxeller CZ (N-cyclohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Vulcanization accelerator DPG: Noxeller D (1,3-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
実施例および比較例
密閉式ミキサー（（株）神戸製鋼所製のＢＢ２７０型）にて、表１のＩに示す薬品（質量部）を、表１に示す「投入温度」に達するまで素練りした。その後、表１のＩＩに示すカーボンブラックおよび／またはシリカ（質量部）を添加し、排出温度１１５℃まで素練りを行い、最終素練り物を得た（素練り工程）。得られた素練り物に、表１のＸ工程に示す各種薬品（質量部）を添加し、３分間、排出温度１６０℃で混練りした（ベース練り工程）。その後、表１のＦ工程に示す硫黄および加硫促進剤（質量部）を添加し、２分間、排出温度１００℃で混練りすることで、未加硫ゴム組成物を得た（仕上げ練り工程）。得られた未加硫ゴム組成物を、１７０℃で２０分間加硫し、加硫ゴム組成物を作製した。
Examples and Comparative Examples In a closed mixer (BB270 type manufactured by Kobe Steel, Ltd.), chemicals (parts by mass) shown in I of Table 1 were kneaded until the “input temperature” shown in Table 1 was reached. . Thereafter, carbon black and / or silica (parts by mass) shown in II of Table 1 was added and masticated to a discharge temperature of 115 ° C. to obtain a final masticated product (mastication process). Various chemicals (parts by mass) shown in Step X of Table 1 were added to the obtained kneaded product, and kneaded at a discharge temperature of 160 ° C. for 3 minutes (base kneading step). Thereafter, sulfur and a vulcanization accelerator (part by mass) shown in Step F of Table 1 were added and kneaded at a discharge temperature of 100 ° C. for 2 minutes to obtain an unvulcanized rubber composition (finish kneading step). ). The obtained unvulcanized rubber composition was vulcanized at 170 ° C. for 20 minutes to produce a vulcanized rubber composition.
得られた未加硫ゴム組成物および加硫ゴム組成物について、以下の評価を行った。結果を表１に示す。 The following evaluation was performed about the obtained unvulcanized rubber composition and vulcanized rubber composition. The results are shown in Table 1.
＜混練生産性＞
未加硫ゴム組成物の質量（ｔ）を、素練り工程、ベース練り工程ならびに仕上げ練り工程の合計練り時間（ｈ）で除した値を算出し、表１に示す。該値が大きいほど、混練生産性に優れることを示す。
<Kneading productivity>
A value obtained by dividing the mass (t) of the unvulcanized rubber composition by the total kneading time (h) of the kneading step, the base kneading step and the finishing kneading step is calculated and shown in Table 1. It shows that it is excellent in kneading | mixing productivity, so that this value is large.
＜ムーニー粘度＞
仕上げ練り工程終了後、得られた未加硫ゴム組成物を２５℃まで冷却し、２４時間後にＪＩＳ Ｋ６３００に準拠したムーニー粘度の測定方法に従い、１３０℃でムーニー粘度（ＭＬ1+4）を測定した。ムーニー粘度が低いほど、加工性に優れることを示す。なお、本発明において、ムーニー粘度の性能目標値は７０以下であり、６７以下が好ましい。
<Mooney viscosity>
After the finishing kneading step, the obtained unvulcanized rubber composition is cooled to 25 ° C., and after 24 hours, the Mooney viscosity (ML 1 + 4 ) is measured at 130 ° C. according to the Mooney viscosity measuring method according to JIS K6300. did. It shows that it is excellent in workability, so that Mooney viscosity is low. In the present invention, the performance target value of Mooney viscosity is 70 or less, preferably 67 or less.
＜耐摩耗性試験＞
各加硫ゴム組成物について、ＪＩＳ Ｋ６２６４−２のピコ摩耗試験に準拠して、摩耗前後の試験片の質量を測定した。摩耗前後の試験片の質量変化を比較例１の値を１００として指数表示した。耐摩耗性指数が小さいほど、耐摩耗性に優れていることを示す。なお、本発明において、耐摩耗性指数の性能目標値は９７以下であり、９５以下が好ましい。
<Abrasion resistance test>
About each vulcanized rubber composition, the mass of the test piece before and behind abrasion was measured based on the pico abrasion test of JISK6264-2. The change in mass of the test piece before and after abrasion was displayed as an index with the value of Comparative Example 1 being 100. It shows that it is excellent in abrasion resistance, so that an abrasion resistance index is small. In the present invention, the performance target value of the wear resistance index is 97 or less, preferably 95 or less.
表１に示す結果より、所定の素練り方法を行うことにより未加硫ゴム組成物の粘度を低く抑えることができ、生産性を悪化させることなく耐摩耗性に優れるゴム組成物を製造できることが分かる。 From the results shown in Table 1, the viscosity of the unvulcanized rubber composition can be kept low by performing a predetermined mastication method, and a rubber composition having excellent wear resistance can be produced without deteriorating productivity. I understand.
Claims (4)
前記素練り工程で得られた素練り物に、カーボンブラックおよび／またはシリカを添加するベース練り工程
を含むタイヤ用ゴム組成物の製造方法。 A rubber component containing a peptizer of 0.03 to 0.75 parts by weight of natural rubber with respect to 100 parts by mass including rubber component masticated, when mastication temperature reaches 100 to 160 ° C. A mastication step of adding 12 to 40 parts by mass of carbon black and / or silica to 100 parts by mass of the rubber component , and
A method for producing a tire rubber composition , comprising: a base kneading step of adding carbon black and / or silica to the kneaded product obtained in the mastication step .
前記シリカの窒素吸着比表面積が４０〜２４０ｍ2／ｇである請求項１または２記載の製造方法。 The carbon black has an average particle size of 10 to 35 nm,
The production method according to claim 1 or 2, wherein the silica has a nitrogen adsorption specific surface area of 40 to 240 m 2 / g.
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