JP2011162627A - Method for manufacturing rubber composition - Google Patents
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- JP2011162627A JP2011162627A JP2010025438A JP2010025438A JP2011162627A JP 2011162627 A JP2011162627 A JP 2011162627A JP 2010025438 A JP2010025438 A JP 2010025438A JP 2010025438 A JP2010025438 A JP 2010025438A JP 2011162627 A JP2011162627 A JP 2011162627A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title abstract description 14
- 239000011425 bamboo Substances 0.000 claims abstract description 46
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 45
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 45
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 45
- 241001330002 Bambuseae Species 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 38
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 26
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 26
- 229920001194 natural rubber Polymers 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000013329 compounding Methods 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 10
- 241000196324 Embryophyta Species 0.000 claims abstract description 9
- 239000003610 charcoal Substances 0.000 claims description 40
- 229920003244 diene elastomer Polymers 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 abstract description 10
- 230000002787 reinforcement Effects 0.000 abstract description 6
- 239000003245 coal Substances 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 abstract 1
- 235000019645 odor Nutrition 0.000 description 47
- 238000010077 mastication Methods 0.000 description 34
- 230000018984 mastication Effects 0.000 description 34
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000004898 kneading Methods 0.000 description 9
- 239000004636 vulcanized rubber Substances 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- -1 softener Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010092 rubber production Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 241000209128 Bambusa Species 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
- 240000001080 Grifola frondosa Species 0.000 description 1
- 235000007710 Grifola frondosa Nutrition 0.000 description 1
- RSHFXVVRRRVVNQ-YOJQQDEFSA-N Phleixanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC=C(/C)C=CC(O)C(C)(C)OC2OC(CO)C(O)C(O)C2O RSHFXVVRRRVVNQ-YOJQQDEFSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物の製造方法に関するものである。 The present invention relates to a method for producing a rubber composition.
天然ゴムは、合成ゴムに比べて分子量が大きいため、各種配合剤を直接添加して均一に混練りすることは困難である。このため、天然ゴムを極少量のしゃく解剤（素練り促進剤）とともに混練りし、ゴム分子量を適度な大きさに下げる素練り工程が必要となる。 Since natural rubber has a higher molecular weight than synthetic rubber, it is difficult to add various compounding agents directly and knead them uniformly. For this reason, a kneading process is required in which natural rubber is kneaded with a very small amount of a peptizer (peptizer) and the rubber molecular weight is reduced to an appropriate level.
しかしながら、素練り工程では、天然ゴム中に含まれている臭気成分が温度上昇によって揮発し、また、非ゴム成分が更に酸化、分解して新たな臭気も発生するため、作業場の環境が悪化するという問題がある。 However, in the mastication process, the odor component contained in the natural rubber is volatilized by the temperature rise, and the non-rubber component is further oxidized and decomposed to generate a new odor. There is a problem.
そこで、素練り工程において、天然ゴムに亜鉛華を添加したり、カーボンブラックを添加したり、低温で排出するようにしたり、香料を配合したりすることにより、素練り時の臭気を低減する手法が提案されている（下記特許文献１〜３参照）。これらの従来手法では、天然ゴムの素練り時等、ゴム組成物の製造段階での作業環境を改善することについては開示されているものの、加硫後のゴム製品時における臭気を低減する効果については言及されていない。 Therefore, in the mastication process, a method of reducing odor during mastication by adding zinc white to natural rubber, adding carbon black, discharging at low temperature, or blending fragrances. Has been proposed (see Patent Documents 1 to 3 below). Although these conventional methods have been disclosed to improve the working environment at the manufacturing stage of the rubber composition, such as when masticating natural rubber, the effect of reducing odor at the time of rubber products after vulcanization Is not mentioned.
下記特許文献４には、竹炭又は木炭をゴムに混入するゴム臭脱臭製造工法が開示されている。しかしながら、この文献は、ゴム製造時に接着剤を混合する場合の脱臭を目的として、ゴムと接着剤に竹炭又は木炭を混合するものであり、天然ゴムの臭気を低減するために、天然ゴムの素練り時に竹炭や木炭を配合する点は開示されておらず、また、素練り時に混合することによる有利な効果も開示されていない。 Patent Document 4 below discloses a rubber odor deodorization manufacturing method in which bamboo charcoal or charcoal is mixed into rubber. However, this document is for mixing bamboo and charcoal into rubber and adhesive for the purpose of deodorization when the adhesive is mixed at the time of rubber production, and in order to reduce the odor of natural rubber, The point of blending bamboo charcoal or charcoal at the time of kneading is not disclosed, and the advantageous effect of mixing at the time of kneading is not disclosed.
なお、竹炭粉末はスタッドレスタイヤに用いることで、路面の水を吸着し氷上性能を向上することが知られている（下記特許文献５参照）。しかしながら、竹炭粉末を配合すると、一般には破断強度が低下するため、スタッドレスタイヤ以外には用いられていないのが実情である。従って、竹炭粉末を配合する場合、かかる補強性の低下を抑制することが求められる。 Incidentally, it is known that bamboo charcoal powder adsorbs water on the road surface and improves the performance on ice by using it in a studless tire (see Patent Document 5 below). However, when bamboo charcoal powder is blended, the breaking strength is generally lowered, so that it is actually not used except for studless tires. Therefore, when mix | blending bamboo charcoal powder, it is calculated | required to suppress the fall of this reinforcement.
本発明は、以上の点に鑑みてなされたものであり、天然ゴムに起因する臭気を低減してゴム組成物の製造時における作業環境を改善するとともに、加硫後のゴム製品の臭気も低減し、更にはゴム製品の補強性の低下も抑えることができる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 has been made in view of the above points, and reduces the odor caused by natural rubber to improve the working environment during production of the rubber composition, and also reduces the odor of the rubber product after vulcanization. Furthermore, it aims at providing the manufacturing method of the rubber composition which can also suppress the fall of the reinforcement of rubber products.
本発明者は、上記課題に鑑み、鋭意検討していく中で、竹炭粉末などの植物の多孔質性炭化物の粉末を天然ゴムの素練り時に配合することにより、ゴム製造の作業環境を改善できるだけでなく、製品後の臭気も低減でき、更には、このような粉末を素練り時に配合することで、臭気の低減効果が大きく、またかかる粉末を配合した際の一般的なデメリットである補強性の低下も抑制できることを見い出し、本発明を完成するに至った。 In view of the above problems, the present inventor can improve the working environment for rubber production by blending plant porous carbide powder such as bamboo charcoal powder during mastication of natural rubber in the course of diligent study. In addition, the odor after the product can be reduced, and by adding such powders during mastication, the effect of reducing odors is great, and reinforcement is a general demerit when such powders are added. As a result, it was found that the decrease in the thickness could be suppressed, and the present invention was completed.
すなわち、本発明に係るゴム組成物の製造方法は、天然ゴムを５０質量部以上含むジエン系ゴム１００質量部に対し、植物の多孔質性炭化物からなる平均粒径５００μｍ以下の粉末を０．０５〜５質量部配合して第１段階の混合操作を行うことにより素練りゴムを作製し、得られた素練りゴムに、フィラーを含む配合剤を配合して第２段階の混合操作を行うものである。 That is, in the method for producing a rubber composition according to the present invention, 0.05 parts of powder having an average particle diameter of 500 μm or less made of a plant porous carbide is added to 100 parts by weight of a diene rubber containing 50 parts by weight or more of natural rubber. Mixing up to 5 parts by mass to produce a kneaded rubber by performing the first stage mixing operation, and blending the resulting kneaded rubber with a compounding agent containing a filler to perform the second stage mixing operation It is.
本発明によれば、植物の多孔質性炭化物粉末を素練り時に混合することにより、天然ゴムから揮発する臭気を吸着させ、作業場の臭気を低減することができる。また、かかる粉末を素練り時に混合することにより、その分散性が改善されると考えられ、加硫後のゴム製品を暴露したときに発生する臭気の低減効果も向上し、またその補強性の低下も抑えることができる。 ADVANTAGE OF THE INVENTION According to this invention, the odor which volatilizes from natural rubber can be adsorb | sucked by mixing the porous carbide powder of a plant at the time of mastication, and the odor of a workplace can be reduced. In addition, it is considered that the dispersibility is improved by mixing such powder during mastication, and the effect of reducing odor generated when the rubber product after vulcanization is exposed is improved. The decrease can also be suppressed.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本発明に係るゴム組成物の製造方法では、第１段階の混合操作として、天然ゴムを含むジエン系ゴムの素練りを行い、次いで、第２段階の混合操作として、得られた素練りゴムにフィラーを含む通常の配合剤を混合する混練りを行う。 In the method for producing a rubber composition according to the present invention, the diene rubber containing natural rubber is masticated as the first stage mixing operation, and then the resulting masticated rubber is mixed as the second stage mixing operation. Kneading is performed by mixing a normal compounding agent containing a filler.
第１段階の素練り工程において混合を行うゴム、すなわち素練りを行うゴムは、天然ゴムを主成分とするものであり、天然ゴムを５０質量％（ジエン系ゴム全体を１００質量部として天然ゴムを５０質量部）以上含有するものであれば、天然ゴム単独であってもよく、天然ゴムと他のジエン系ゴムとの併用であってもよい。好ましくは、天然ゴムを７０質量％以上含むことである。 The rubber to be mixed in the first mastication process, that is, the rubber to be masticated is mainly composed of natural rubber, and is 50% by mass of natural rubber (100% by mass of the whole diene rubber). Natural rubber alone or a combination of natural rubber and another diene rubber may be used. Preferably, it contains 70% by mass or more of natural rubber.
上記他のジエン系ゴムとしては、特に限定されず、例えば、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）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、スチレン−イソプレン共重合体ゴム、ブタジエン−イソプレン共重合体、スチレン−イソプレン−ブタジエン共重合体ゴム、ブチルゴム等が挙げられる。これらはそれぞれ単独で又は２種以上組み合わせて用いることができる。 The other diene rubber is not particularly limited. For example, isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), Examples thereof include styrene-isoprene copolymer rubber, butadiene-isoprene copolymer, styrene-isoprene-butadiene copolymer rubber, and butyl rubber. These can be used alone or in combination of two or more.
素練り工程では、上記ジエン系ゴム１００質量部に対して、植物の多孔質性炭化物からなる粉末を０．０５〜５質量部配合して混合操作を行うことにより素練りゴムを作製する。植物の多孔質性炭化物は、木や竹などの植物を材料として炭化して得られる炭素を主成分となる固体生成物からなる多孔質性物質であり、本発明ではこのような炭化物を粉砕して得られる粉末状のものが用いられる。かかる多孔質性炭化物の粉末を配合することにより、素練り時に天然ゴムから揮発する臭気を吸着して臭気を低減できるとともに、加硫時及び加硫後のゴム製品暴露により生じる臭いも吸着することができ、よって、作業環境の改善とともに、ゴム製品での臭気も低減することができる。 In the mastication step, 0.05 to 5 parts by mass of a powder composed of a plant porous carbide is blended with 100 parts by mass of the diene rubber to prepare a mastication rubber. A porous carbide of a plant is a porous substance made of a solid product mainly composed of carbon obtained by carbonizing a plant such as wood or bamboo. In the present invention, such a carbide is pulverized. A powdery product obtained in this way is used. By blending such porous carbide powder, it is possible to reduce the odor by adsorbing the odor volatilized from natural rubber during mastication, and also to absorb the odor caused by the rubber product exposure during and after vulcanization. Therefore, the odor in the rubber product can be reduced with improvement of the working environment.
該粉末の平均粒径は５００μｍ以下であることが好ましく、より好ましくは１０〜５００μｍであり、更に好ましくは１０〜２００μｍである。平均粒径が５００μｍを超えると、臭気の吸着効果が不十分となり、また、素練り時に添加することによる補強性の低下抑制効果が不十分となる。ここで、平均粒径は、レーザ回折式粒度分布測定装置にて測定される値である。 It is preferable that the average particle diameter of this powder is 500 micrometers or less, More preferably, it is 10-500 micrometers, More preferably, it is 10-200 micrometers. When the average particle size exceeds 500 μm, the effect of adsorbing odors becomes insufficient, and the effect of suppressing the reduction in reinforcement by adding during mastication becomes insufficient. Here, the average particle diameter is a value measured by a laser diffraction particle size distribution measuring apparatus.
該粉末の比表面積は特に限定されないが、ＢＥＴ法（ＪＩＳ Ｋ６２１７−７（多点法））による比表面積が１００ｍ２／ｇ以上であることが好ましく、より好ましくは１５０ｍ２／ｇ以上、更に好ましくは２５０ｍ２／ｇ以上である。この比表面積が大きいほど多孔質であり臭気成分の吸着性に優れるので、上限は特に限定されないが、通常は３５０ｍ２／ｇ以下である。 The specific surface area of the powder is not particularly limited, but the specific surface area according to the BET method (JIS K6217-7 (multipoint method)) is preferably 100 m 2 / g or more, more preferably 150 m 2 / g or more, and still more preferably. Is 250 m 2 / g or more. The larger the specific surface area, the more porous and the better the adsorption of odor components, so the upper limit is not particularly limited, but it is usually 350 m 2 / g or less.
上記多孔質性炭化物としては、竹炭、木炭が好ましく、特に好ましくは、竹を材料として炭化して得られる竹炭である。ここでいう竹は、孟宗竹、苦竹、淡竹、紋竹などの各種の竹のほか、千鳥笹、仙台笹などの笹も含む概念である。竹炭粉末は、その特有の多孔質性により、天然ゴムから揮発する臭気の吸着性能に優れる。 As the porous carbide, bamboo charcoal and charcoal are preferable, and bamboo charcoal obtained by carbonizing bamboo as a material is particularly preferable. Bamboo here is a concept that includes various bamboos such as 孟 mong bamboo, maitake bamboo, pale bamboo, and crested bamboo, as well as bamboo such as chidori bamboo and Sendai bamboo. Bamboo charcoal powder is excellent in adsorption performance of odors volatilized from natural rubber due to its unique porosity.
竹炭の製法は、備長炭と同様に竹材を炭化するもので、例えば、竹材を窯を用いて蒸し焼きにして炭化することにより得られる。得られた竹炭を公知の粉砕機（例えば、ボールミル）を用いて粉末状に粉砕し、例えばＪＩＳ Ｚ８８０１に記載の標準ふるいによって所定の粒径にふるい分けした粒状体を用いることができる。竹炭粉末の形状は、特に限定されるものではなく、例えば略球状、略立方体状、略柱状や略繊維状などの各種形状のもの、またそれらの混合物を用いることができる。 Bamboo charcoal is produced by carbonizing bamboo material in the same manner as Bincho charcoal. For example, bamboo charcoal is obtained by steaming and baking bamboo material using a kiln. The obtained bamboo charcoal can be pulverized into a powder using a known pulverizer (for example, a ball mill), and a granular material obtained by sieving to a predetermined particle size using a standard sieve described in JIS Z8801 can be used. The shape of the bamboo charcoal powder is not particularly limited, and various shapes such as a substantially spherical shape, a substantially cubic shape, a substantially columnar shape and a substantially fibrous shape, or a mixture thereof can be used.
植物の多孔質性炭化物からなる粉末は、上記ジエン系ゴム１００質量部に対して、０．０５〜５質量部の範囲内で配合される。該粉末の配合量が０．０５質量部未満では、臭気の低減効果が不十分である。逆に配合量が５質量部を超えると、未加硫ゴムのムーニー粘度が高くなって加工性が悪化するとともに、破断強度が低下して補強性が悪化してしまう。 The powder which consists of a plant porous carbide | carbonized_material is mix | blended within the range of 0.05-5 mass parts with respect to 100 mass parts of said diene rubbers. When the blending amount of the powder is less than 0.05 parts by mass, the effect of reducing odor is insufficient. On the other hand, when the blending amount exceeds 5 parts by mass, the Mooney viscosity of the unvulcanized rubber is increased, the workability is deteriorated, the breaking strength is lowered, and the reinforcement property is deteriorated.
第１段階の素練り工程では、上記多孔質性炭化物の粉末とともに、しゃく解剤（素練り促進剤）を配合することが好ましい。しゃく解剤を配合することにより、天然ゴムの可塑化を早め、上記多孔質性炭化物の粉末の分散性を向上することができるものと考えられ、最終的なゴム組成物において補強性の低下をより効果的に抑制することができる。しゃく解剤としては、例えば、芳香族メルカプタン系、芳香族ジスルフィド系、芳香族メルカプタン金属系、またはこれらの混合系を用いることができ、特に限定されない。 In the first mastication step, it is preferable to blend a peptizer (peptizer) together with the porous carbide powder. It is considered that by adding a peptizer, the plasticization of natural rubber can be accelerated, and the dispersibility of the porous carbide powder can be improved. It can suppress more effectively. As the peptizer, for example, an aromatic mercaptan system, an aromatic disulfide system, an aromatic mercaptan metal system, or a mixed system thereof can be used, and it is not particularly limited.
しゃく解剤の配合量としては、特に限定されるものではないが、上記ジエン系ゴム１００質量部に対して、０．０５〜２質量部であることが好ましく、より好ましくは０．１〜１質量部である。 The blending amount of the peptizer is not particularly limited, but is preferably 0.05 to 2 parts by mass, more preferably 0.1 to 1 part per 100 parts by mass of the diene rubber. Part by mass.
第１段階の素練り工程における混合操作は、一般にゴム組成物の調製に用いられるバンバリーミキサーやロール、ニーダー等の混合機を用いて行うことができ、混合機の種類は特に限定されない。混合温度も特に限定されるものではなく、例えば１１０〜１８０℃で行うことができ、より好ましくは１３０〜１７０℃、特に好ましくは１４０〜１７０℃である。 The mixing operation in the first mastication step can be performed using a Banbury mixer, a roll, a kneader or the like that is generally used for preparing a rubber composition, and the type of the mixer is not particularly limited. The mixing temperature is not particularly limited, and can be carried out, for example, at 110 to 180 ° C., more preferably 130 to 170 ° C., particularly preferably 140 to 170 ° C.
第２段階の混合操作では、上記で得られた素練りゴムに、フィラーを含む配合剤を配合して混練りを行う。この混練り工程では、通常、加硫系配合剤を除く配合剤が配合される。具体的には、フィラー（充填剤）、亜鉛華、ステアリン酸、老化防止剤、軟化剤、可塑剤、ワックスなど、ゴム組成物に通常配合される各種添加剤を配合することができる。また、この混練り工程において、天然ゴム以外のジエン系ゴムを追加的に配合し、混練してもよい。なお、上記フィラーとしては、例えば、カーボンブラック、シリカの他、クレーやタルクなどの各種無機充填剤が挙げられ、特に限定されない。 In the mixing operation in the second stage, the compounded rubber containing the filler is mixed with the kneaded rubber obtained above and kneaded. In this kneading step, a compounding agent other than the vulcanizing compounding agent is usually compounded. Specifically, various additives usually blended in the rubber composition, such as filler (filler), zinc white, stearic acid, anti-aging agent, softener, plasticizer, and wax, can be blended. In this kneading step, a diene rubber other than natural rubber may be additionally blended and kneaded. In addition, as said filler, various inorganic fillers, such as clay and a talc other than carbon black and a silica, are mentioned, for example, It does not specifically limit.
第２段階の混合操作の後、得られた混練りマスターバッチに、加硫系配合剤を配合して第３の混合操作を行うことができ、これによりゴム組成物が得られる。加硫系配合剤としては、硫黄などの加硫剤、加硫促進剤が挙げられる。これらの加硫系配合剤は、フィラーとともに第２段階の混練り工程で配合すると、せん断発熱による温度上昇でフィラーが均一に分散しない状態で加硫が進むおそれがあるため、フィラー分散後の第３工程で配合することが好ましい。 After the second stage mixing operation, the resulting kneading master batch can be mixed with a vulcanizing compounding agent to perform a third mixing operation, whereby a rubber composition is obtained. Examples of the vulcanizing compounding agent include vulcanizing agents such as sulfur and vulcanization accelerators. When these vulcanizing compounding agents are blended together with the filler in the second kneading step, vulcanization may proceed in a state where the filler is not uniformly dispersed due to a temperature rise due to shear heat generation. It is preferable to mix | blend in 3 processes.
これらの第２及び第３段階の混合操作も、一般にゴム組成物の調製に用いられるバンバリーミキサーやロール、ニーダー等の混合機を用いて行うことができ、混合操作自体は特に限定されるものではない。 These second and third stage mixing operations can also be performed using a Banbury mixer, a roll, a kneader or the like that is generally used for preparing a rubber composition, and the mixing operation itself is not particularly limited. Absent.
本発明に係るゴム組成物の用途は、特に限定されないが、トレッドやサイドウォール等のタイヤ、コンベアベルト、防振ゴムなどの各種ゴム組成物に用いることができる。該ゴム組成物をタイヤに用いる場合、常法に従い、例えば１４０〜１８０℃で加硫成形することにより、各種空気入りタイヤのゴム部分（トレッドゴムやサイドウォールゴムなど）を構成することができる。 Although the use of the rubber composition according to the present invention is not particularly limited, it can be used for various rubber compositions such as tires such as treads and sidewalls, conveyor belts, and vibration-proof rubbers. When the rubber composition is used for a tire, rubber portions (tread rubber, sidewall rubber, etc.) of various pneumatic tires can be formed by vulcanization molding at, for example, 140 to 180 ° C. according to a conventional method.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
下記実施例及び比較例で使用した各成分の詳細は以下の通りである。
・天然ゴム：ＴＳＲ２０
・しゃく解剤：大内新興化学工業（株）製「ノクタイザーＳＫ」
・竹炭粉末１：孟宗竹の竹炭（宮崎土晃（株）製「１号炭」）をハンマーミルで粉砕し、得られた粉砕物をＪＩＳ Ｚ８８０１記載の標準ふるいにより分級した平均粒径２０μｍの竹炭粉末（ＢＥＴ比表面積＝３１５ｍ２／ｇ）。平均粒径の測定は島津製作所製の粒度分布測定装置「ＳＡＬＤ−２０００Ａ」による（以下同じ）。
Details of each component used in the following examples and comparative examples are as follows.
・ Natural rubber: TSR20
・ Scrubbing agent: “Nokutizer SK” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
-Bamboo charcoal powder 1: Bamboo charcoal from Somune bamboo ("No. 1 charcoal" manufactured by Miyazaki Dogo Co., Ltd.) was pulverized with a hammer mill, and the resulting pulverized product was classified with a standard sieve described in JIS Z8801. Powder (BET specific surface area = 315 m 2 / g). The average particle size is measured by a particle size distribution measuring device “SALD-2000A” manufactured by Shimadzu Corporation (the same applies hereinafter).
・竹炭粉末２：孟宗竹の竹炭（宮崎土晃（株）製「１号炭」）をハンマーミルで粉砕し、得られた粉砕物をＪＩＳ Ｚ８８０１記載の標準ふるいにより分級した平均粒径２００μｍの竹炭粉末（ＢＥＴ比表面積＝２４５ｍ２／ｇ）。 ・ Bamboo charcoal powder 2: Bamboo charcoal with an average particle size of 200 μm obtained by crushing bamboo charcoal from Somune bamboo (“No. 1 charcoal” manufactured by Miyazaki Dogo Co., Ltd.) with a hammer mill and classifying the obtained pulverized product with a standard sieve described in JIS Z8801 Powder (BET specific surface area = 245 m 2 / g).
・竹炭粉末３：孟宗竹の竹炭（宮崎土晃（株）製「１号炭」）をハンマーミルで粉砕し、得られた粉砕物をＪＩＳ Ｚ８８０１記載の標準ふるいにより分級した平均粒径８００μｍの竹炭粉末（ＢＥＴ比表面積＝１５ｍ２／ｇ）。 -Bamboo charcoal powder 3: Bamboo charcoal with an average particle size of 800 μm obtained by crushing bamboo charcoal from Somune bamboo (“No. 1 charcoal” manufactured by Miyazaki Dogo Co., Ltd.) with a hammer mill and classifying the resulting pulverized product with a standard sieve described in JIS Z8801 Powder (BET specific surface area = 15 m 2 / g).
・木炭粉末：平均粒径３００μｍの備長炭（ウバメ樫）の粉末（ＢＥＴ比表面積＝１２５ｍ２／ｇ）
・カーボンブラック：Ｎ３３９、東海カーボン（株）製「シーストＫＨ」（ＢＥＴ＝９０ｍ２／ｇ、ＤＢＰ吸油量＝１１９ｃｍ３／１００ｇ）
・亜鉛華：三井金属鉱業（株）製「亜鉛華１種」
・ステアリン酸：花王（株）製「ルナックＳ−２０」
・老化防止剤：大内新興化学工業（株）製「ノクラック６Ｃ」
・ワックス：日本精蝋（株）製「ＯＺＯＡＣＥ０３５５」
・加硫促進剤１：三新化学工業（株）製「サンセラーＤＭ−Ｇ」
・加硫促進剤２：住友化学（株）製「ソクシノールＣＺ」
・硫黄：鶴見化学工業（株）製「粉末硫黄」。
Charcoal powder: powder of Bincho charcoal with a mean particle size of 300 μm (BET specific surface area = 125 m 2 / g)
Carbon black: N339, Tokai Carbon Co., Ltd. "Seast KH" (BET = 90m 2 / g, DBP oil absorption = 119cm 3 / 100g)
・ Zinc flower: “Zinc flower 1” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Lunac S-20” manufactured by Kao Corporation
Anti-aging agent: “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
・ Wax: Nippon Seiwa Co., Ltd. “OZOACE0355”
・ Vulcanization accelerator 1: Sanshin Chemical Co., Ltd. “Sunseller DM-G”
・ Vulcanization accelerator 2: “Soccinol CZ” manufactured by Sumitomo Chemical Co., Ltd.
・ Sulfur: “Powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
評価方法は以下の通りである。
・ムーニー粘度：ＪＩＳ Ｋ６３００に準拠して、東洋精機（株）製ロータレスムーニー粘度測定機を用い、未加硫のゴム組成物を１００℃で１分間予熱後、４分後のトルク値を測定し、比較例１の値を１００とした指数で示した。数値が大きいほど、粘度が高いことを示す。
The evaluation method is as follows.
Mooney viscosity: according to JIS K6300, using a rotorless Mooney viscosity measuring machine manufactured by Toyo Seiki Co., Ltd., preheat the unvulcanized rubber composition at 100 ° C for 1 minute and measure the torque value after 4 minutes. In addition, the index is shown with the value of Comparative Example 1 as 100. It shows that a viscosity is so high that a numerical value is large.
・臭い強度：「素練り時の臭い」については、素練りゴムをバンバリーミキサーから排出後、速やかに臭気をポリエチレン袋に回収し、臭い強度を評価した。「加硫ゴムの臭い」については、ゴム組成物を１６０℃×３０分間で加硫した加硫サンプル（厚さ２ｍｍ、縦横１５０ｍｍ）を、ポリエチレン袋に入れて、屋外で２週間暴露後、臭い強度を評価した。評価は、臭いの強度を６段階臭気強度表示法に基づき、下記６段階（０〜６）でランク付けし、モニター３名の平均値を採用した。
強度０：無臭 強度１：やっと感知できる臭い 強度２：弱い臭い
強度３：楽に感知できる臭い 強度４：強い臭い 強度５：強烈な臭い。
・ Odor strength: For “odor during mastication”, the masticated rubber was discharged from the Banbury mixer, and then the odor was quickly collected in a polyethylene bag to evaluate the odor intensity. Regarding the “odor of vulcanized rubber”, a vulcanized sample (thickness 2 mm, length and width 150 mm) obtained by vulcanizing the rubber composition at 160 ° C. for 30 minutes is placed in a polyethylene bag and exposed to the outdoors for 2 weeks. The strength was evaluated. Evaluation was based on the 6-level odor intensity display method based on the 6-level odor intensity display method, and the average value of 3 monitors was adopted.
Intensity 0: No odor Intensity 1: Finally a perceived odor Intensity 2: A weak odor Intensity 3: Easily perceived odor Intensity 4: Strong odor Intensity 5: Strong odor
・破断強度：ゴム組成物を１６０℃×３０分間で加硫した加硫サンプルについて、ＪＩＳ Ｋ６２５１に準じて３号ダンベル型試験片を用いて、島津製作所製引張り試験機にて引張試験を実施し、比較例１の破断強度の値を１００とした指数で示した。 ・ Breaking strength: A vulcanized sample obtained by vulcanizing a rubber composition at 160 ° C. for 30 minutes was subjected to a tensile test using a No. 3 dumbbell-type test piece according to JIS K6251 with a tensile tester manufactured by Shimadzu Corporation. The results are shown as an index with the value of the breaking strength of Comparative Example 1 as 100.
［素練りゴムの調製］
下記表１に示す配合に従って、第１段階混合として素練りを行った。素練り工程では、１．７Ｌのバンバリーミキサーを用い、ローター回転数１００ｒｐｍの条件で、３分間素練りした。素練り時の排出温度は表１に示す通りである。なお、比較例４については、混合温度が１３０℃となった段階で排出した（低温排出の例）。各素練りゴムについて、臭い強度を評価した。結果は表１に示す通りである。
[Preparation of kneaded rubber]
According to the formulation shown in Table 1 below, mastication was performed as the first stage mixing. In the mastication step, a 1.7 L Banbury mixer was used and mastication was performed for 3 minutes under the condition of a rotor rotation speed of 100 rpm. The discharge temperature during mastication is as shown in Table 1. In addition, about the comparative example 4, it discharged | emitted when the mixing temperature became 130 degreeC (example of low temperature discharge | emission). Each masticated rubber was evaluated for odor strength. The results are as shown in Table 1.
［ゴム組成物の調製］
１．７Ｌのバンバリーミキサーを用い、上記で得られた素練りゴムに、表１の第２段階混合の欄に示した成分を配合して、混練りマスターバッチを得た（排出温度：１５０℃）。次いで、得られた混練りマスターバッチに、第３段階混合の欄に示した成分を混合して、ゴム組成物を製造した（排出温度：１１０℃）。得られた各ゴム組成物について、ムーニー粘度を測定するとともに、加硫サンプルについて、破断強度と臭い強度を測定評価した。結果は表１に示す通りである。
[Preparation of rubber composition]
Using a 1.7 L Banbury mixer, the components shown in the second stage mixing column of Table 1 were blended into the kneaded rubber obtained above to obtain a kneaded master batch (discharge temperature: 150 ° C. ). Next, the obtained kneading master batch was mixed with the components shown in the third stage mixing column to produce a rubber composition (discharge temperature: 110 ° C.). About each obtained rubber composition, while measuring Mooney viscosity, the rupture strength and odor strength were measured and evaluated about the vulcanized sample. The results are as shown in Table 1.
表１に示すように、通常の素練りを行った比較例１では、素練り時の臭いが強烈であり、加硫ゴムについても屋外暴露後に強い臭いを感じるものであった。これに対し、従来の作業環境改善手法として素練り時にカーボンブラックを配合した比較例２では、素練り時の臭いについては改善効果が見られたものの、加硫ゴムの暴露後の臭いについては比較例１と同等で改善効果は得られなかった。素練り時に亜鉛華を配合した比較例３でも、比較例２と同様、加硫ゴムの暴露後の臭いについては改善効果は得られなかった。比較例４では、素練り時に低温排出することで、素練り時の臭いについては改善効果に優れていたものの、加硫ゴムの暴露後の臭いについては改善効果は見られず、一方でゴム組成物のムーニー粘度が高くなって加工性が損なわれていた。 As shown in Table 1, in Comparative Example 1 in which normal mastication was performed, the odor during mastication was intense, and the vulcanized rubber also felt a strong odor after outdoor exposure. On the other hand, in Comparative Example 2 in which carbon black was blended during mastication as a conventional work environment improvement method, although an improvement effect was seen with respect to the odor during mastication, the odor after exposure to vulcanized rubber was compared. The improvement effect was not obtained as in Example 1. In Comparative Example 3 in which zinc white was blended at the time of mastication, as in Comparative Example 2, the effect of improving the odor after exposure to the vulcanized rubber was not obtained. In Comparative Example 4, by discharging at a low temperature during mastication, although the odor during mastication was excellent in the improvement effect, the odor after exposure to the vulcanized rubber was not improved, while the rubber composition The Mooney viscosity of the product increased and the processability was impaired.
比較例５は、素練り工程無しで、竹炭粉末を他の配合剤とともに直接天然ゴムに混合したものであり、この場合、破断強度が低下していた。一方、比較例６では、素練り工程で竹炭粉末を配合したものの、竹炭粉末の粒径が大きすぎて、素練り時及び加硫ゴムの状態でも臭気の低減効果が得られなった。比較例７では、素練り工程で配合した竹炭粉末の量が多すぎて、ゴム組成物のムーニー粘度が高く加工性が悪化するとともに、破断強度が大幅に悪化していた。比較例８では、通常の素練りを行った天然ゴムに、竹炭粉末を他の配合剤とともに第２段階で混合しており、この場合、素練り時に竹炭粉末を混合していないため、素練り時の臭気の低減効果が得られないことはもちろんのこと、加硫ゴムの破断強度の抑制効果にも劣っていた。 In Comparative Example 5, bamboo charcoal powder was directly mixed with natural rubber together with other compounding agents without a mastication step, and in this case, the breaking strength was reduced. On the other hand, in the comparative example 6, although bamboo charcoal powder was mix | blended at the mastication process, the particle size of the bamboo charcoal powder was too large, and the odor reduction effect was not acquired at the time of mastication and the state of vulcanized rubber. In Comparative Example 7, the amount of bamboo charcoal powder blended in the mastication process was too large, the Mooney viscosity of the rubber composition was high and processability was deteriorated, and the breaking strength was greatly deteriorated. In Comparative Example 8, bamboo charcoal powder was mixed in the second stage together with other compounding agents in natural rubber that had been subjected to normal mastication. In this case, bamboo charcoal powder was not mixed during mastication. Of course, the effect of reducing the odor at the time was not obtained, and the effect of suppressing the breaking strength of the vulcanized rubber was inferior.
これに対し、実施例１〜５であると、素練り時に竹炭粉末や木炭粉末を配合したことにより、素練り時の臭気を低減することができた。また、最終的なゴム組成物についても、ムーニー粘度の上昇を伴うことなく、即ち加工性の悪化を抑えながら、加硫ゴムの暴露後の臭気を低減することができ、また、竹炭や木炭の粉末を配合する場合のデメリットである破断強度の低下も抑制することができた。 On the other hand, in Examples 1-5, the odor at the time of mastication was able to be reduced by mix | blending bamboo charcoal powder and charcoal powder at the time of mastication. In addition, the final rubber composition can reduce the odor after exposure to vulcanized rubber without increasing Mooney viscosity, that is, while suppressing deterioration of processability. It was also possible to suppress the decrease in breaking strength, which is a disadvantage when blending powder.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014094988A (en) * | 2012-11-07 | 2014-05-22 | Toyo Tire & Rubber Co Ltd | Tire member and its manufacturing method |
| JP2015017209A (en) * | 2013-07-12 | 2015-01-29 | 東洋ゴム工業株式会社 | Method for producing rubber masterbatch |
| JP2016199723A (en) * | 2015-04-14 | 2016-12-01 | 住友ゴム工業株式会社 | Mastication method and manufacturing method of rubber composition |
| CN112250952A (en) * | 2020-09-11 | 2021-01-22 | 浙江仙通橡塑股份有限公司 | Odorless automobile sealing strip and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128798A (en) * | 2001-10-29 | 2003-05-08 | Fuji Photo Film Co Ltd | Biodegradable resin molded product |
| JP2005162865A (en) * | 2003-12-02 | 2005-06-23 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
| JP2006501315A (en) * | 2001-12-12 | 2006-01-12 | ミリケン・アンド・カンパニー | Antibacterial colored vulcanized rubber article |
| JP2006298215A (en) * | 2005-04-21 | 2006-11-02 | Toyo Tire & Rubber Co Ltd | Pneumatic tire |
| JP2007070581A (en) * | 2005-09-09 | 2007-03-22 | Tokai Rubber Ind Ltd | Method for manufacturing rubber composition and rubber product obtained by the same |
| JP2007126524A (en) * | 2005-11-01 | 2007-05-24 | Toyo Tire & Rubber Co Ltd | Method for producing rubber composition for tire |
| JP2009051942A (en) * | 2007-08-27 | 2009-03-12 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
| JP2009167294A (en) * | 2008-01-16 | 2009-07-30 | Yokohama Rubber Co Ltd:The | Method for manufacturing rubber composition for use in tire |
| JP2011162626A (en) * | 2010-02-08 | 2011-08-25 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
-
2010
- 2010-02-08 JP JP2010025438A patent/JP5461217B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003128798A (en) * | 2001-10-29 | 2003-05-08 | Fuji Photo Film Co Ltd | Biodegradable resin molded product |
| JP2006501315A (en) * | 2001-12-12 | 2006-01-12 | ミリケン・アンド・カンパニー | Antibacterial colored vulcanized rubber article |
| JP2005162865A (en) * | 2003-12-02 | 2005-06-23 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
| JP2006298215A (en) * | 2005-04-21 | 2006-11-02 | Toyo Tire & Rubber Co Ltd | Pneumatic tire |
| JP2007070581A (en) * | 2005-09-09 | 2007-03-22 | Tokai Rubber Ind Ltd | Method for manufacturing rubber composition and rubber product obtained by the same |
| JP2007126524A (en) * | 2005-11-01 | 2007-05-24 | Toyo Tire & Rubber Co Ltd | Method for producing rubber composition for tire |
| JP2009051942A (en) * | 2007-08-27 | 2009-03-12 | Toyo Tire & Rubber Co Ltd | Rubber composition for tire tread and pneumatic tire |
| JP2009167294A (en) * | 2008-01-16 | 2009-07-30 | Yokohama Rubber Co Ltd:The | Method for manufacturing rubber composition for use in tire |
| JP2011162626A (en) * | 2010-02-08 | 2011-08-25 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014094988A (en) * | 2012-11-07 | 2014-05-22 | Toyo Tire & Rubber Co Ltd | Tire member and its manufacturing method |
| JP2015017209A (en) * | 2013-07-12 | 2015-01-29 | 東洋ゴム工業株式会社 | Method for producing rubber masterbatch |
| JP2016199723A (en) * | 2015-04-14 | 2016-12-01 | 住友ゴム工業株式会社 | Mastication method and manufacturing method of rubber composition |
| CN112250952A (en) * | 2020-09-11 | 2021-01-22 | 浙江仙通橡塑股份有限公司 | Odorless automobile sealing strip and preparation method thereof |
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