JP6215547B2 - Rubber composition for tire and pneumatic tire using the same - Google Patents
Rubber composition for tire and pneumatic tire using the same Download PDFInfo
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- JP6215547B2 JP6215547B2 JP2013060314A JP2013060314A JP6215547B2 JP 6215547 B2 JP6215547 B2 JP 6215547B2 JP 2013060314 A JP2013060314 A JP 2013060314A JP 2013060314 A JP2013060314 A JP 2013060314A JP 6215547 B2 JP6215547 B2 JP 6215547B2
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- 229920001971 elastomer Polymers 0.000 title claims description 62
- 239000005060 rubber Substances 0.000 title claims description 62
- 239000000203 mixture Substances 0.000 title claims description 48
- 229920005610 lignin Polymers 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 41
- 229920003244 diene elastomer Polymers 0.000 claims description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000004073 vulcanization Methods 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 244000043261 Hevea brasiliensis Species 0.000 description 10
- 229920003052 natural elastomer Polymers 0.000 description 10
- 229920001194 natural rubber Polymers 0.000 description 10
- 239000004636 vulcanized rubber Substances 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 8
- 235000021355 Stearic acid Nutrition 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 238000009864 tensile test Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 229920005611 kraft lignin Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- BOGPQKRGMIVEMJ-UHFFFAOYSA-N [[4,6-bis(dimethoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CON(CO)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 BOGPQKRGMIVEMJ-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IIGAELMXVLEZPM-GRVYQHKQSA-L cobalt(2+);(9z,12z)-octadeca-9,12-dienoate Chemical compound [Co+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O IIGAELMXVLEZPM-GRVYQHKQSA-L 0.000 description 2
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000010680 novolac-type phenolic resin Substances 0.000 description 2
- -1 organic acid cobalt salt Chemical class 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KFVIYKFKUYBKTP-UHFFFAOYSA-N 2-n-(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCNC1=NC(N)=NC(N)=N1 KFVIYKFKUYBKTP-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 235000019492 Cashew oil Nutrition 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- FQDIAKVSTGRSOD-UHFFFAOYSA-K [Co+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O Chemical compound [Co+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O FQDIAKVSTGRSOD-UHFFFAOYSA-K 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 1
- WCBKUQQCKNNACH-UHFFFAOYSA-N [[4,6-bis[butyl(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-butylamino]methanol Chemical compound CCCCN(CO)C1=NC(N(CO)CCCC)=NC(N(CO)CCCC)=N1 WCBKUQQCKNNACH-UHFFFAOYSA-N 0.000 description 1
- MHVFYGIQJNFWGQ-UHFFFAOYSA-N [[4,6-bis[hydroxymethyl(methyl)amino]-1,3,5-triazin-2-yl]-methylamino]methanol Chemical compound OCN(C)C1=NC(N(C)CO)=NC(N(C)CO)=N1 MHVFYGIQJNFWGQ-UHFFFAOYSA-N 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 239000010467 cashew oil Substances 0.000 description 1
- 229940059459 cashew oil Drugs 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 1
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 description 1
- SSWSYWBRGQINON-UHFFFAOYSA-L cobalt(2+);hexadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O SSWSYWBRGQINON-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、タイヤ用ゴム組成物およびそれを用いた空気入りタイヤに関するものであり、詳しくは、天然素材の配合比率を高めたタイヤ用ゴム組成物およびそれを用いた空気入りタイヤに関するものである。 The present invention relates to a rubber composition for a tire and a pneumatic tire using the same, and more particularly to a rubber composition for a tire having an increased blending ratio of natural materials and a pneumatic tire using the same. .
現在市販されているタイヤの多くは、主に石油などの化石資源由来の原材料を使用して製造されており、その製造時や廃棄時に地球温暖化の原因となるＣＯ2が発生し、大気中のＣＯ2量を増加させるという問題がある。地球温暖化が社会的問題となっている今日、主な原材料に植物由来の天然素材を用いることによって、ＣＯ2排出量の増加を抑え、環境に優しい空気入りタイヤ（エコタイヤ）を提供するという提案がなされている。 Many of the tires currently on the market are manufactured mainly using raw materials derived from fossil resources such as petroleum, and CO 2 that causes global warming is generated at the time of manufacture and disposal. There is a problem of increasing the amount of CO 2 . Today, with global warming becoming a social issue, the proposal to provide environmentally friendly pneumatic tires (eco-tyres) by suppressing the increase in CO 2 emissions by using plant-derived natural materials as the main raw materials. Has been made.
一方、空気入りタイヤは破断物性を向上させ、耐久性や操縦安定性を高めることが求められている。しかし、天然素材はその粒子サイズやゴムとの親和性によりタイヤ中で異物となり、耐久性や破断物性を悪化させるという問題点がある。 On the other hand, pneumatic tires are required to improve fracture properties and improve durability and handling stability. However, natural materials become foreign matter in the tire due to their particle size and affinity with rubber, and there is a problem that durability and fracture physical properties are deteriorated.
下記特許文献１は、ジエン系ゴム成分に対し、天然素材であるリグニンを用いて合成したリグニンスルホン酸塩またはその変性体を配合してなるゴム組成物を開示している。しかしながら特許文献１に開示されたリグニンスルホン酸塩またはその変性体は、ゴム成分中への分散性が悪く、所望の破断物性を得ることができない。 Patent Document 1 below discloses a rubber composition in which a lignin sulfonate synthesized using lignin, which is a natural material, or a modified product thereof is blended with a diene rubber component. However, the lignin sulfonate or modified product thereof disclosed in Patent Document 1 has poor dispersibility in the rubber component and cannot obtain desired fracture properties.
したがって本発明の目的は、天然素材の配合比率を高め、破断物性等のタイヤ用途に重要な各種物性を向上させたタイヤ用ゴム組成物およびそれを用いた空気入りタイヤを提供することにある。 Accordingly, an object of the present invention is to provide a rubber composition for tires and a pneumatic tire using the same, in which the blending ratio of natural materials is increased and various physical properties important for tire use such as fracture properties are improved.
本発明者らは鋭意研究を重ねた結果、ジエン系ゴムに酢酸リグニンを特定量配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。
すなわち本発明は以下のとおりである。
As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of lignin acetate with diene rubber, and the present invention has been completed.
That is, the present invention is as follows.
１．ジエン系ゴム１００質量部に対し、酢酸リグニンを０．０５〜２０質量部配合してなることを特徴とするタイヤ用ゴム組成物。
２．前記１に記載のタイヤ用ゴム組成物を使用した空気入りタイヤ。
1. A tire rubber composition comprising 0.05 to 20 parts by mass of lignin acetate per 100 parts by mass of a diene rubber.
2. A pneumatic tire using the tire rubber composition described in 1 above.
本発明は、ジエン系ゴムに酢酸リグニンを特定量配合することを特徴としている。酢酸リグニンは、針葉樹、広葉樹などの木本系植物、麦藁などの草本系植物といった天然素材としての植物を原料として調製することができるので、ＣＯ2排出量の増加を抑え、環境に優しい空気入りタイヤ（エコタイヤ）を提供することができる。また、酢酸リグニンは、ゴム成分中への分散性に優れ、破断物性を大幅に向上させることができる。したがって、操縦安定性に優れたゴム組成物およびそれを用いた空気入りタイヤを提供することができる。 The present invention is characterized by blending a specific amount of lignin acetate with a diene rubber. Lignin acetate can be prepared from natural plants such as conifers and broad-leaved trees, and herbaceous plants such as wheat straw, so it suppresses the increase in CO 2 emissions and is environmentally friendly. A tire (eco-tire) can be provided. In addition, lignin acetate has excellent dispersibility in the rubber component and can greatly improve the physical properties at break. Therefore, it is possible to provide a rubber composition excellent in handling stability and a pneumatic tire using the rubber composition.
以下、本発明をさらに詳細に説明する。
（ジエン系ゴム）
本発明で使用されるジエン系ゴムは、ゴム組成物に配合することができる任意のジエン系ゴムを用いることができ、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で末端変性されていても、エポキシ化されていてもよい。
Hereinafter, the present invention will be described in more detail.
(Diene rubber)
As the diene rubber used in the present invention, any diene rubber that can be blended in the rubber composition can be used, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR). Styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), and the like. These may be used alone or in combination of two or more. The molecular weight and microstructure are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
（酢酸リグニン）
本発明には、リグニンとして酢酸リグニンが用いられる。
酢酸リグニンは、針葉樹、広葉樹などの木本系植物、麦藁などの草本系植物といった植物を原料とし、当該植物の細胞壁から、いわゆる酢酸蒸解法によって抽出することにより得られる。酢酸蒸解法の詳細については特に限定されるものではなく、例えば、原料としての植物を、数％の水と極微量の塩酸とを含む酢酸溶液中に浸漬した後、加熱するといった、公知の各種の方法を採用することができる。
(Lignin acetate)
In the present invention, lignin acetate is used as the lignin.
Lignin acetate can be obtained by extracting from a cell wall of a plant such as a coniferous tree or a broad-leaved tree plant or a herbaceous plant such as wheat straw by the so-called acetic acid cooking method. The details of the acetic acid cooking method are not particularly limited. For example, the plant as a raw material is immersed in an acetic acid solution containing several percent of water and a very small amount of hydrochloric acid and then heated. This method can be adopted.
また、本発明に用いる酢酸リグニンの軟化点は、好ましくは５０〜２５０℃であり、より好ましくは１００〜２２０℃、特に好ましくは１５０〜２００℃である。酢酸リグニンの軟化点は、酢酸蒸解法における加熱温度、加熱時間などの抽出条件によって適宜調整できる。
酢酸リグニンは、タイヤ用ゴム組成物を調製する際、すなわちジエン系ゴムに配合する際には固体である。このため、配合時の作業性および取り扱い性に優れる。配合時の作業性および取扱い性は、固体の酢酸リグニンを粉砕し、粉末状に加工することでより向上させることができる。
また、ゴム組成物を調製するための混練時には、一般的に、ゴム成分の温度が酢酸リグニンの軟化点を超えるか、または軟化点に近い温度となる。これにより、酢酸リグニンはゴム成分中で流動性を発現するか、または相溶性に優れた状態になると考えられ、その結果、酢酸リグニンがゴム成分中に均一に分散する。
ゴム成分中でのリグニン類の流動状態または相溶状態については、後述する実施例１〜３と比較例１〜２との対比により明示している。すなわち、酢酸リグニンは、加硫時の流動性が良好であるか、または加硫時にゴム成分との相溶性が良好であると考えられ、ゴム成分への分散性が良好となる。これに対し、クラフトリグニンやリグニンスルホン酸カルシウムは、加硫時の流動性や加硫時のゴム成分との相溶性が十分でないと考えられ、ゴム成分への分散性が低くなる。
なお、酢酸リグニンの軟化点は、示差走査型熱量計（ＤＳＣ）を用いて測定した。具体的には、まず測定試料を、一旦２５０℃まで昇温して、５分間保持した後、直ちに室温まで冷却した。この試料約１０ｍｇを秤取し、−２０℃から２５０℃程度までの温度範囲で、毎分１０℃の条件で昇温しながら測定した。測定結果から得られたカーブの吸熱ピークの値を軟化点とした。
Moreover, the softening point of the lignin acetate used for this invention becomes like this. Preferably it is 50-250 degreeC, More preferably, it is 100-220 degreeC, Most preferably, it is 150-200 degreeC. The softening point of acetic acid lignin can be appropriately adjusted according to extraction conditions such as heating temperature and heating time in acetic acid cooking method.
Lignin acetate is a solid when preparing a rubber composition for a tire, that is, when blended with a diene rubber. For this reason, it is excellent in workability and handling at the time of blending. Workability and handling at the time of blending can be further improved by pulverizing solid lignin acetate and processing it into a powder form.
Further, at the time of kneading for preparing the rubber composition, the temperature of the rubber component generally exceeds the softening point of the lignin acetate or is close to the softening point. Thereby, it is considered that lignin acetate exhibits fluidity in the rubber component or is in a state of excellent compatibility, and as a result, lignin acetate is uniformly dispersed in the rubber component.
The flow state or compatibility state of lignins in the rubber component is clearly shown by comparison between Examples 1 to 3 and Comparative Examples 1 and 2 described later. That is, the lignin acetate is considered to have good fluidity during vulcanization or good compatibility with the rubber component during vulcanization, resulting in good dispersibility in the rubber component. On the other hand, kraft lignin and calcium lignin sulfonate are considered to have insufficient fluidity during vulcanization and compatibility with the rubber component during vulcanization, resulting in low dispersibility in the rubber component.
The softening point of lignin acetate was measured using a differential scanning calorimeter (DSC). Specifically, the measurement sample was first heated to 250 ° C. and held for 5 minutes, and then immediately cooled to room temperature. About 10 mg of this sample was weighed and measured in the temperature range from -20 ° C to about 250 ° C while raising the temperature at 10 ° C per minute. The endothermic peak value of the curve obtained from the measurement results was taken as the softening point.
（充填剤）
本発明のタイヤ用ゴム組成物は、各種充填剤を配合することができる。充填剤としてはとくに制限されず、用途により適宜選択すればよいが、例えばシリカ、カーボンブラック、無機充填剤等が挙げられる。無機充填剤としては、例えばクレー、タルク、炭酸カルシウム等を挙げることができる。中でもカーボンブラックが好ましい。
(filler)
The tire rubber composition of the present invention may contain various fillers. The filler is not particularly limited and may be appropriately selected depending on the application. Examples thereof include silica, carbon black, and inorganic filler. Examples of the inorganic filler include clay, talc, and calcium carbonate. Of these, carbon black is preferred.
（タイヤ用ゴム組成物の配合割合）
本発明のタイヤ用ゴム組成物は、ジエン系ゴム１００質量部に対し、酢酸リグニンを０．０５〜２０質量部配合してなることを特徴とする。
酢酸リグニンの配合量が０．０５質量部未満であると、配合量が少な過ぎて本発明の効果を奏することができない。逆に２０質量部を超えると、破断物性が悪化する。
(Combination ratio of tire rubber composition)
The tire rubber composition of the present invention is characterized in that 0.05 to 20 parts by mass of lignin acetate is blended with 100 parts by mass of the diene rubber.
When the blending amount of lignin acetate is less than 0.05 parts by mass, the blending amount is too small to achieve the effects of the present invention. Conversely, if it exceeds 20 parts by mass, the fracture properties deteriorate.
酢酸リグニンのさらに好ましい配合量は、ジエン系ゴム１００質量部に対し、１〜１５質量部である。 A more preferable blending amount of lignin acetate is 1 to 15 parts by mass with respect to 100 parts by mass of the diene rubber.
本発明のタイヤ用ゴム組成物には、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、充填剤、老化防止剤、可塑剤などのゴム組成物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も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。 In addition to the above-described components, the tire rubber composition of the present invention generally contains a rubber composition such as a vulcanization or cross-linking agent, a vulcanization or cross-linking accelerator, a filler, an antioxidant, and a plasticizer. Various additives that have been used 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. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated.
また本発明のタイヤ用ゴム組成物は従来の空気入りタイヤの製造方法に従って空気入りタイヤを製造するのに適しており、とくにトレッド、好ましくはキャップトレッドに適用するのがよい。 Moreover, the rubber composition for tires of the present invention is suitable for producing a pneumatic tire according to a conventional method for producing a pneumatic tire, and is particularly preferably applied to a tread, preferably a cap tread.
これとは別に、本発明のタイヤ用ゴム組成物は、ビードフィラー、サイドウォール、リムクッション、ガムフィニッシング、競技用タイヤのトレッド、ベルトコートのタイヤの各パーツに適用することも好適である。 Apart from this, the rubber composition for tires of the present invention is also preferably applied to each part of bead fillers, sidewalls, rim cushions, gum finishing, competition tire treads, and belt coat tires.
タイヤビードフィラー用ゴム組成物としては、破断物性のほかに、硬度、耐クラック性等の向上が求められる。これを満たすために、タイヤビードフィラー用ゴム組成物は、ＮＲ３０質量部以上を含むジエン系ゴム１００質量部に対し、酢酸リグニンを０．０５〜２０質量部、窒素吸着比表面積(Ｎ２ＳＡ)が２５〜１００ｍ２／ｇ、好ましくは４０〜９３ｍ２／ｇのカーボンブラックを３０〜１００質量部、ノボラック型フェノール樹脂およびメチレン供与体をその合計として１〜５０質量部配合するのが好ましい。メチレン供与体は、ノボラック型フェノール樹脂に対し、５〜１５質量％添加するのがよい。
ノボラック型フェノール樹脂は、フェノール樹脂、レゾルシン樹脂およびクレゾール樹脂から選択される少なくとも１種の樹脂であり、これらはいずれも公知の樹脂である。ノボラック型フェノール系樹脂は、オイルまたは脂肪酸で変性していてもよく、例えば、ロジン油、トール油、カシュー油、リノール酸、オレイン酸、リノレイン酸などのオイルで変性した樹脂を挙げることができる。
メチレン供与体は、ヘキサメチレンテトラミンやメラミン誘導体等が挙げられる。メラミン誘導体は、例えば、ヘキサメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチロールメラミン、ヘキサエトキシメチルメラミン、ヘキサキス−（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ’’−トリメチル−Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミン、Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミン、Ｎ−メチロールメラミン、Ｎ，Ｎ’−（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ’’−トリブチル−Ｎ，Ｎ’，Ｎ’’−トリメチロールメラミン等が挙げられる。
As a rubber composition for a tire bead filler, improvement of hardness, crack resistance and the like is required in addition to fracture properties. In order to satisfy this, the tire bead filler rubber composition has 0.05 to 20 parts by mass of lignin acetate and nitrogen adsorption specific surface area (N 2 SA) with respect to 100 parts by mass of diene rubber containing 30 parts by mass or more of NR. There 25~100m 2 / g, preferably 30 to 100 parts by weight of carbon black 40~93m 2 / g, preferably incorporated 1 to 50 parts by weight of a novolak type phenolic resin and methylene donor as a total. The methylene donor is preferably added in an amount of 5 to 15% by mass relative to the novolac type phenol resin.
The novolac type phenol resin is at least one resin selected from a phenol resin, a resorcin resin, and a cresol resin, all of which are known resins. The novolac-type phenolic resin may be modified with oil or fatty acid, and examples thereof include resins modified with oils such as rosin oil, tall oil, cashew oil, linoleic acid, oleic acid, and linolenic acid.
Examples of the methylene donor include hexamethylenetetramine and melamine derivatives. Melamine derivatives include, for example, hexamethylol melamine, hexamethoxymethyl melamine, pentamethoxymethylol melamine, hexaethoxymethyl melamine, hexakis- (methoxymethyl) melamine, N, N ′, N ″ -trimethyl-N, N ′, N '' -Trimethylol melamine, N, N ', N''-trimethylol melamine, N-methylol melamine, N, N'-(methoxymethyl) melamine, N, N ', N''-tributyl-N, N ', N ″ -trimethylolmelamine and the like.
タイヤサイドウォール、リムクッションおよびガムフィニッシング用ゴム組成物としては、破断物性のほかに、弾性率、耐セット性等の向上が求められる。これを満たすために、タイヤサイドウォール、リムクッションおよびガムフィニッシング用ゴム組成物は、ＮＲ３０〜７０質量部およびＢＲ７０〜３０質量部を含むジエン系ゴム１００質量部に対し、酢酸リグニンを０．０５〜２０質量部、窒素吸着比表面積(Ｎ２ＳＡ)が３０〜１３０ｍ２／ｇ、好ましくは９９〜１２０ｍ２／ｇのカーボンブラックを３０〜９０質量部配合するのが好ましい。 Rubber compositions for tire sidewalls, rim cushions, and gum finishing are required to have improved elastic modulus, set resistance, etc. in addition to fracture properties. In order to satisfy this, the tire sidewall, the rim cushion, and the rubber composition for gum finishing have 0.05 to 70 parts by mass of lignin acetate to 100 parts by mass of diene rubber including 30 to 70 parts by mass of NR and 70 to 30 parts by mass of BR. It is preferable to blend 30 to 90 parts by mass of carbon black having 20 parts by mass and a nitrogen adsorption specific surface area (N 2 SA) of 30 to 130 m 2 / g, preferably 99 to 120 m 2 / g.
競技用タイヤのトレッド用ゴム組成物としては、破断物性のほかに、モジュラス、耐摩耗性等の向上が求められる。これを満たすために、競技用タイヤのトレッド用ゴム組成物は、ガラス転移温度（Ｔｇ）−２０℃以上のＳＢＲ４０質量部以上を含むジエン系ゴム１００質量部に対し、酢酸リグニンを０．０５〜２０質量部、窒素吸着比表面積(Ｎ２ＳＡ)が１３０〜３００ｍ２／ｇ、好ましくは１４０〜２８０ｍ２／ｇのカーボンブラック６０〜１５０質量部配合するのが好ましい。 A rubber composition for a tread for a competition tire is required to have improved modulus, abrasion resistance, etc. in addition to fracture properties. In order to satisfy this, the rubber composition for a tread for a racing tire has a lignin acetate content of 0.05 to 100 parts by mass of a diene rubber containing 40 parts by mass or more of SBR having a glass transition temperature (Tg) of −20 ° C. or more. It is preferable to mix 20 parts by mass and 60 to 150 parts by mass of carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 130 to 300 m 2 / g, preferably 140 to 280 m 2 / g.
タイヤベルトコート用ゴム組成物としては、破断物性のほかに、モジュラス、耐セパレーション性等の向上が求められる。これを満たすために、タイヤベルトコート用ゴム組成物は、ＮＲ１００質量部に対し、酢酸リグニンを０．０５〜２０質量部、
有機酸コバルト塩をコバルト量として０．１〜０．５質量部配合するのが好ましい。有機酸コバルト塩としては、ナフテン酸コバルト、ステアリン酸コバルト、オレイン酸コバルト、リノール酸コバルト、リノレイン酸コバルト、パルミチン酸コバルト、ネオデカン酸コバルト、ロジン酸コバルト、トール油酸コバルト、ホウ酸三ネオデカン酸コバルト等が挙げられる。また、ノボラック型フェノール樹脂をＮＲ１００質量部に対し、０．１〜５質量部配合するのがさらに好ましい。ノボラック型フェノール樹脂は、上記で例示したとおりである。
As a rubber composition for a tire belt coat, in addition to fracture properties, improvements in modulus, separation resistance, and the like are required. In order to satisfy this, the rubber composition for a tire belt coat is 0.05 to 20 parts by mass of lignin acetate with respect to 100 parts by mass of NR.
It is preferable to add 0.1 to 0.5 parts by mass of the organic acid cobalt salt as the amount of cobalt. Examples of organic acid cobalt salts include cobalt naphthenate, cobalt stearate, cobalt oleate, cobalt linoleate, cobalt linoleate, cobalt palmitate, cobalt neodecanoate, cobalt rosinate, cobalt tall oil, cobalt trineodecanoate. Etc. Moreover, it is more preferable to mix 0.1-5 mass parts of novolac type phenol resin with respect to 100 mass parts of NR. The novolac type phenol resin is as exemplified above.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
標準例１、実施例１〜３および比較例１〜３
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、約１５０℃でミキサー外に放出させて室温冷却した。続いて、該組成物に加硫促進剤および硫黄を加えてオープンロールにて混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１６０℃、２０分間プレス加硫して加硫ゴム試験片を得、以下に示す試験法で加硫ゴム試験片の物性を測定した。
Standard Example 1, Examples 1-3 and Comparative Examples 1-3
Sample Preparation In the formulation (parts by mass) shown in Table 1, the components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes in a 1.7 liter closed Banbury mixer, and then released outside the mixer at about 150 ° C. Cooled to room temperature. Subsequently, a vulcanization accelerator and sulfur were added to the composition and kneaded with an open roll to obtain a rubber composition. Next, the obtained rubber composition was press vulcanized at 160 ° C. for 20 minutes in a predetermined mold to obtain a vulcanized rubber test piece, and the physical properties of the vulcanized rubber test piece were measured by the following test method.
１００％モジュラス（Ｍ１００）および破断強度（ＴＢ）：ＪＩＳ Ｋ６２５１に準拠して引張試験にて評価した。結果は標準例１の値を１００として指数表示した。この指数が高いほどモジュラスまたは破断強度が高く、また、ゴム成分中への酢酸リグニンの分散性も良好であると判断できる。
耐摩耗性：ＪＩＳ Ｋ６２６４に準拠し、ランボーン摩耗試験機を用い、荷重４．０ｋｇ（３９Ｎ）、スリップ率３０％の条件にて測定した。結果は標準例の値を１００として指数表示した。この指数が高いほど耐摩耗性に優れることを意味する。
結果を表１に併せて示す。
100% modulus (M100) and breaking strength (TB): evaluated by a tensile test according to JIS K6251. The results were expressed as an index with the value of standard example 1 being 100. It can be judged that the higher the index, the higher the modulus or breaking strength, and the better the dispersibility of lignin acetate in the rubber component.
Abrasion resistance: Measured in accordance with JIS K6264 using a Lambourn abrasion tester under the conditions of a load of 4.0 kg (39 N) and a slip ratio of 30%. The results are shown as an index with the value of the standard example being 100. Higher index means better wear resistance.
The results are also shown in Table 1.
＊１：ＮＲ（ＳＴＲ２０）
＊２：カーボンブラック（キャボットジャパン（株）製ショウブラックＮ２３４）
＊３：酢酸リグニン（軟化点：５０〜２００℃）
＊４：クラフトリグニン（木本系植物からクラフト法によってパルプを抽出した際に副生成物として得られたリグニン）
＊５：リグニンスルホン酸塩（日本製紙ケミカル（株）製サンエキスｓｃｐ、リグニンスルホン酸カルシウム）
＊６：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊７：ステアリン酸（日油(株)製ビーズステアリン酸）
＊８：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊９：加硫促進剤（大内新興化学工業（株）製ノクセラーＮＳ−Ｐ）
* 1: NR (STR20)
* 2: Carbon black (Show Black N234 from Cabot Japan Co., Ltd.)
* 3: Lignin acetate (softening point: 50-200 ° C)
* 4: Kraft lignin (lignin obtained as a by-product when pulp is extracted from woody plants by the Kraft method)
* 5: Lignin sulfonate (San extract scp manufactured by Nippon Paper Chemicals Co., Ltd., calcium lignin sulfonate)
* 6: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 7: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 8: Sulfur (Tsurumi Chemical Industry Co., Ltd. Jinhua Indian Oil Fine Powdered Sulfur)
* 9: Vulcanization accelerator (Noxeller NS-P, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
上記の表１から明らかなように、実施例１〜３で調製されたゴム組成物は、ジエン系ゴムに酢酸リグニンを特定量配合したので、従来の代表的な標準例１に比べて、ゴム成分中への酢酸リグニンの分散性が高まり、モジュラス、破断強度および耐摩耗性が同時に向上している。
これに対し、比較例１は、クラフトリグニンを配合した例であるので、破断強度および耐摩耗性が悪化した。
比較例２は、酢酸リグニンの配合量が本発明で規定する上限を超えているので、破断強度および耐摩耗性が悪化した。
比較例３は、リグニンスルホン酸カルシウムを配合した例であるので、モジュラス、破断強度および耐摩耗性がいずれも悪化した。
As is clear from Table 1 above, the rubber compositions prepared in Examples 1 to 3 were blended with a specific amount of lignin acetate in a diene rubber, so that the rubber composition compared to the conventional representative standard example 1 The dispersibility of lignin acetate in the ingredients is increased, and the modulus, breaking strength and wear resistance are improved simultaneously.
On the other hand, since Comparative Example 1 is an example in which kraft lignin was blended, the breaking strength and the wear resistance were deteriorated.
Since the compounding quantity of the lignin acetate exceeded the upper limit prescribed | regulated by this invention in the comparative example 2, breaking strength and abrasion resistance deteriorated.
Since Comparative Example 3 was an example in which calcium lignin sulfonate was blended, the modulus, breaking strength, and wear resistance were all deteriorated.
標準例２、実施例４〜５
本発明のタイヤ用ゴム組成物のビードフィラーへの適合性を評価した。
表２に示す配合（質量部）において、実施例１と同様に加硫ゴム試験片を作成し、以下に示す試験法で加硫ゴム試験片の物性を測定した。
耐クラック性：ＪＩＳ Ｋ６２６０に準拠して屈曲亀裂成長試験を行った。結果は標準例２の値を１００として指数表示した。この指数が高いほど耐クラック性が良好であることを意味する。
破断強度（ＴＢ）：ＪＩＳ Ｋ６２５１に準拠して引張試験にて評価した。結果は標準例２の値を１００として指数表示した。この指数が高いほど破断強度が高く、また、ゴム成分中への酢酸リグニンの分散性も良好であると判断できる。
硬度：ＪＩＳ Ｋ６３０１に準拠して測定した。結果は標準例２の値を１００として指数表示した。この指数が高いほど硬度が高く良好であることを意味する。
結果を表２に併せて示す。
Standard Example 2, Examples 4-5
The suitability of the rubber composition for tires of the present invention to bead fillers was evaluated.
In the composition (parts by mass) shown in Table 2, a vulcanized rubber test piece was prepared in the same manner as in Example 1, and the physical properties of the vulcanized rubber test piece were measured by the following test method.
Crack resistance: A flex crack growth test was conducted according to JIS K6260. The result was expressed as an index with the value of Standard Example 2 being 100. Higher index means better crack resistance.
Breaking strength (TB): Evaluated by a tensile test in accordance with JIS K6251. The result was expressed as an index with the value of Standard Example 2 being 100. It can be judged that the higher the index, the higher the breaking strength and the better the dispersibility of the lignin acetate in the rubber component.
Hardness: Measured according to JIS K6301. The result was expressed as an index with the value of Standard Example 2 being 100. Higher index means higher hardness and better.
The results are also shown in Table 2.
＊１：ＮＲ（ＲＳＳ＃３）
＊２：ＳＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ １５０２）
＊３：カーボンブラック（東海カーボン（株）製シーストＳＯ、Ｎ２ＳＡ＝４２ｍ２／ｇ）
＊４：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊５：ステアリン酸（日油(株)製ビーズステアリン酸）
＊６：プロセスオイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊７：酢酸リグニン（実施例１で使用したもの）
＊８：ノボラック型フェノール樹脂（住友ベークライト（株）製カシュー変性フェノール樹脂）
＊９：メチレン供与体（大内新興化学工業（株）製ヘキサメチレンテトラミン）
＊１０：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊１１：加硫促進剤（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
* 1: NR (RSS # 3)
* 2: SBR (Nipol 1502 manufactured by Zeon Corporation)
* 3: Carbon black (Shiest SO manufactured by Tokai Carbon Co., Ltd., N 2 SA = 42 m 2 / g)
* 4: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 5: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 6: Process oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 7: Lignin acetate (used in Example 1)
* 8: Novolac-type phenolic resin (cashew modified phenolic resin manufactured by Sumitomo Bakelite Co., Ltd.)
* 9: Methylene donor (Hexamethylenetetramine manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.)
* 10: Sulfur (Tsurumi Chemical Industry Co., Ltd. Kinka Ink Fine Powdered Sulfur)
* 11: Vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller CZ-G)
上記の表２から明らかなように、実施例４〜５で調製されたゴム組成物は、ジエン系ゴムに酢酸リグニンを特定量配合したので、従来の代表的な標準例２に比べて、硬度を維持しながら、耐クラック性および破断強度が改善され、ビードフィラー用として好適であることが示された。 As is clear from Table 2 above, the rubber compositions prepared in Examples 4 to 5 were blended with a specific amount of lignin acetate in a diene rubber, so that the hardness was higher than that of the conventional representative standard example 2. While maintaining the above, the crack resistance and breaking strength were improved, indicating that it is suitable for bead fillers.
標準例３、実施例６〜８
本発明のタイヤ用ゴム組成物のタイヤサイドウォール、リムクッションおよびガムフィニッシングへの適合性を評価した。
表３に示す配合（質量部）において、実施例１と同様に加硫ゴム試験片を作成し、以下に示す試験法で加硫ゴム試験片の物性を測定した。
耐セット性：ＪＩＳ Ｋ６３０１に準拠して測定した。結果は標準例３の値を１００として指数表示した。この指数が高いほど耐熱セット性が良好であることを意味する。
破断強度（ＴＢ）：ＪＩＳ Ｋ６２５１に準拠して引張試験にて評価した。結果は標準例３の値を１００として指数表示した。この指数が高いほど破断強度が高く、また、ゴム成分中への酢酸リグニンの分散性も良好であると判断できる。
硬度：ＪＩＳ Ｋ６３０１に準拠して測定した。結果は標準例３の値を１００として指数表示した。この指数が高いほど硬度が高く良好であることを意味する。
結果を表３に併せて示す。
Standard Example 3, Examples 6-8
The suitability of the rubber composition for tires of the present invention to tire sidewalls, rim cushions and gum finishing was evaluated.
In the composition (parts by mass) shown in Table 3, vulcanized rubber test pieces were prepared in the same manner as in Example 1, and the physical properties of the vulcanized rubber test pieces were measured by the test methods shown below.
Set resistance: Measured according to JIS K6301. The results are shown as an index with the value of standard example 3 as 100. Higher index means better heat resistance set property.
Breaking strength (TB): Evaluated by a tensile test in accordance with JIS K6251. The results are shown as an index with the value of standard example 3 as 100. It can be judged that the higher the index, the higher the breaking strength and the better the dispersibility of the lignin acetate in the rubber component.
Hardness: Measured according to JIS K6301. The results are shown as an index with the value of standard example 3 as 100. Higher index means higher hardness and better.
The results are also shown in Table 3.
＊１：ＮＲ（ＲＳＳ＃３）
＊２：ＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ ＢＲ１２２０）
＊３：カーボンブラック−１（東海カーボン（株）製シースト６、Ｎ２ＳＡ＝１１９ｍ２／ｇ）
＊４：カーボンブラック−２（東海カーボン（株）製シーストＳＯ、Ｎ２ＳＡ＝４２ｍ２／ｇ）
＊５：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊６：ステアリン酸（日油(株)製ビーズステアリン酸）
＊７：プロセスオイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊８：酢酸リグニン（実施例１で使用したもの）
＊９：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊１０：加硫促進剤（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
* 1: NR (RSS # 3)
* 2: BR (Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.)
* 3: Carbon black-1 (Tokai Carbon Co., Ltd. Seest 6, N 2 SA = 119 m 2 / g)
* 4: Carbon black-2 (Toast Carbon Co., Ltd. Seest SO, N 2 SA = 42 m 2 / g)
* 5: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 6: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 7: Process oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 8: Lignin acetate (used in Example 1)
* 9: Sulfur (fine powdered sulfur with Jinhua seal oil from Tsurumi Chemical Co., Ltd.)
* 10: Vulcanization accelerator (Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.)
上記の表３から明らかなように、実施例６〜８で調製されたゴム組成物は、ジエン系ゴムに酢酸リグニンを特定量配合したので、従来の代表的な標準例３に比べて、硬度を維持しながら（硬度は指数９７まで許容できる）、耐セット性および破断強度が改善され、タイヤサイドウォール、リムクッションおよびガムフィニッシング用として好適であることが示された。 As is apparent from Table 3 above, the rubber compositions prepared in Examples 6 to 8 were blended with a specific amount of lignin acetate in a diene rubber, so that the hardness was higher than that of the conventional representative standard example 3. (Hardness is acceptable up to an index of 97) while improving set resistance and breaking strength, it has been shown to be suitable for tire sidewalls, rim cushions and gum finishing.
標準例４、実施例９〜１０
本発明のタイヤ用ゴム組成物の競技用タイヤのトレッドへの適合性を評価した。
表４に示す配合（質量部）において、実施例１と同様に加硫ゴム試験片を作成し、以下に示す試験法で加硫ゴム試験片の物性を測定した。
３００％モジュラス（Ｍ３００）：ＪＩＳ Ｋ６２５１に準拠し、１００℃にて引張試験を行い、３００％変形モジュラスを測定した。結果は標準例４の値を１００として指数表示した。この指数が高いほどモジュラスが高いことを意味する。
破断強度（ＴＢ）：ＪＩＳ Ｋ６２５１に準拠し、１００℃にて引張試験を行い、破断時の強度を求めた。結果は標準例４の値を１００として指数表示した。この指数が高いほど破断強度が高く、また、ゴム成分中への酢酸リグニンの分散性も良好であると判断できる。
耐摩耗性：ランボーン摩耗試験機を用い、ＪＩＳ Ｋ６２６４に準拠し、荷重４．０ｋｇ（３９Ｎ）、スリップ率３０％の条件にて測定した。結果は標準例４の値を１００として指数表示した。この指数が高いほど耐摩耗性が高く良好であることを意味する。
結果を表４に併せて示す。
Standard Example 4, Examples 9-10
The suitability of the rubber composition for tires of the present invention to the tread of a racing tire was evaluated.
In the formulation (parts by mass) shown in Table 4, vulcanized rubber test pieces were prepared in the same manner as in Example 1, and the physical properties of the vulcanized rubber test pieces were measured by the test methods shown below.
300% modulus (M300): Based on JIS K6251, a tensile test was performed at 100 ° C. to measure a 300% deformation modulus. The results were expressed as an index with the value of standard example 4 being 100. Higher index means higher modulus.
Breaking strength (TB): Based on JIS K6251, a tensile test was performed at 100 ° C. to determine the strength at break. The results were expressed as an index with the value of standard example 4 being 100. It can be judged that the higher the index, the higher the breaking strength and the better the dispersibility of the lignin acetate in the rubber component.
Abrasion resistance: Measured under the conditions of a load of 4.0 kg (39 N) and a slip rate of 30% using a Lambourn abrasion tester in accordance with JIS K6264. The results were expressed as an index with the value of standard example 4 being 100. Higher index means higher wear resistance and better.
The results are also shown in Table 4.
＊１：ＳＢＲ（日本ゼオン（株)製Ｎｉｐｏｌ ＮＳ４１２、ゴム成分のＴｇ＝−６℃、油展量＝ＳＢＲ１００質量部に対し５０質量部）
＊２：カーボンブラック（三菱化学（株）製ダイアブラックＡ、Ｎ２ＳＡ＝１４２ｍ２／ｇ）
＊３：アロマオイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊４：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊５：ステアリン酸（日油(株)製ビーズステアリン酸）
＊６：老化防止剤（フレキシス社製６ＰＰＤ）
＊７：酢酸リグニン（実施例１で使用したもの）
＊８：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊９：加硫促進剤（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
* 1: SBR (Nipol NS412 manufactured by Nippon Zeon Co., Ltd., Tg of rubber component = −6 ° C., oil extended amount = 50 parts by mass with respect to 100 parts by mass of SBR)
* 2: Carbon black (Mitsubishi Chemical Corporation Dia Black A, N 2 SA = 142 m 2 / g)
* 3: Aroma oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 4: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 5: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 6: Anti-aging agent (6PPD manufactured by Flexis)
* 7: Lignin acetate (used in Example 1)
* 8: Sulfur (Tsurumi Chemical Industry Co., Ltd. Jinhua Indian Oil Fine Powdered Sulfur)
* 9: Vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. Noxeller CZ-G)
上記の表４から明らかなように、実施例９〜１０で調製されたゴム組成物は、ジエン系ゴムに酢酸リグニンを特定量配合したので、従来の代表的な標準例４に比べて、モジュラス、破断強度および耐摩耗性が改善され、競技用タイヤのトレッド用として好適であることが示された。 As is apparent from Table 4 above, the rubber compositions prepared in Examples 9 to 10 were blended with a specific amount of lignin acetate in the diene rubber, so that the modulus was higher than that of the conventional representative standard example 4. It has been shown that the breaking strength and wear resistance are improved and it is suitable for use in treads for competition tires.
標準例５、実施例１１〜１３
本発明のタイヤ用ゴム組成物のベルトコートへの適合性を評価した。
表５に示す配合（質量部）において、実施例１と同様に加硫ゴム試験片を作成し、以下に示す試験法で加硫ゴム試験片の物性を測定した。
１００％モジュラス（Ｍ１００）：ＪＩＳ Ｋ６２５１に準拠し、１００℃にて引張試験を行い、１００％変形モジュラスを測定した。結果は標準例５の値を１００として指数表示した。この指数が高いほどモジュラスが高いことを意味する。
破断強度（ＴＢ）：ＪＩＳ Ｋ６２５１に準拠し、１００℃にて引張試験を行い、破断時の強度を求めた。結果は標準例５の値を１００として指数表示した。この指数が高いほど破断強度が高く、また、ゴム成分中への酢酸リグニンの分散性も良好であると判断できる。
耐水接着性：ＡＳＴＭ Ｄ１８７１に準拠し、ブラスメッキワイヤーを用いて測定した。結果は、標準例５の値を１００として指数で表示した。この指数が高いほど、ゴム付着力が大きく、ゴムとワイヤの接着性が良好であり、耐水接着性に優れることを意味する。
結果を表５に併せて示す。
Standard Example 5, Examples 11-13
The suitability of the rubber composition for tires of the present invention to a belt coat was evaluated.
In the composition (parts by mass) shown in Table 5, a vulcanized rubber test piece was prepared in the same manner as in Example 1, and the physical properties of the vulcanized rubber test piece were measured by the following test method.
100% modulus (M100): Based on JIS K6251, a tensile test was performed at 100 ° C., and a 100% deformation modulus was measured. The results were expressed as an index with the value of standard example 5 being 100. Higher index means higher modulus.
Breaking strength (TB): Based on JIS K6251, a tensile test was performed at 100 ° C. to determine the strength at break. The results were expressed as an index with the value of standard example 5 being 100. It can be judged that the higher the index, the higher the breaking strength and the better the dispersibility of the lignin acetate in the rubber component.
Water-resistant adhesion: Measured using a brass-plated wire in accordance with ASTM D1871. The result was expressed as an index with the value of standard example 5 being 100. The higher the index, the greater the rubber adhesion, the better the adhesion between the rubber and the wire, and the better the water-resistant adhesion.
The results are also shown in Table 5.
＊１：ＮＲ（ＳＴＲ２０）
＊２：カーボンブラック（キャボットジャパン（株）製ショウブラックＮ２３４）
＊３：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊４：老化防止剤（フレキシス社製６ＰＰＤ）
＊５：ステアリン酸コバルト（ＤＩＣ（株）製）
＊６：酢酸リグニン（実施例１で使用したもの）
＊７：クレゾール樹脂（田岡化学工業(株)製スミカノール６１０）
＊８：ＰＭＭＭ（バラケミカル製スミカノール５０７Ａ、ペンタメトキシメチロールメラミン、メラミン誘導体６５％）
＊９：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊１０：加硫促進剤（大内新興化学工業（株）製ノクセラーＮＳ−Ｐ）
* 1: NR (STR20)
* 2: Carbon black (Show Black N234 from Cabot Japan Co., Ltd.)
* 3: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 4: Anti-aging agent (6PPD manufactured by Flexis)
* 5: Cobalt stearate (manufactured by DIC Corporation)
* 6: Lignin acetate (used in Example 1)
* 7: Cresol resin (Sumikanol 610, manufactured by Taoka Chemical Co., Ltd.)
* 8: PMMM (Sumikanol 507A from Bara Chemical, pentamethoxymethylol melamine, 65% melamine derivative)
* 9: Sulfur (fine powdered sulfur with Jinhua seal oil from Tsurumi Chemical Co., Ltd.)
* 10: Vulcanization accelerator (Nouchira NS-P manufactured by Ouchi Shinsei Chemical Co., Ltd.)
上記の表５から明らかなように、実施例１１〜１３で調製されたゴム組成物は、ジエン系ゴムに酢酸リグニンを特定量配合したので、従来の代表的な標準例５に比べて、耐水接着性を維持しながら、モジュラスおよび破断強度が改善され、ベルトコート用として好適であることが示された。 As is clear from Table 5 above, the rubber compositions prepared in Examples 11 to 13 were blended with a specific amount of lignin acetate in a diene rubber, so that the water resistance was higher than that of the conventional representative standard example 5. The modulus and breaking strength were improved while maintaining adhesion, indicating that it is suitable for belt coating.
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| US20160230008A1 (en) * | 2013-10-16 | 2016-08-11 | Sumitomo Bakelite Co., Ltd. | Resin composition, rubber composition, and cured article |
| WO2016185351A1 (en) * | 2015-05-15 | 2016-11-24 | Bridgestone Corporation | Tyre sealant layer |
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| US8664305B2 (en) * | 2009-02-10 | 2014-03-04 | The Goodyear Tire & Rubber Company | Functionalized lignin, rubber containing functionalized lignin and products containing such rubber composition |
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