JP2011132471A - Rubber composition, method for producing the same, and pneumatic tire - Google Patents
Rubber composition, method for producing the same, and pneumatic tire Download PDFInfo
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- JP2011132471A JP2011132471A JP2009295192A JP2009295192A JP2011132471A JP 2011132471 A JP2011132471 A JP 2011132471A JP 2009295192 A JP2009295192 A JP 2009295192A JP 2009295192 A JP2009295192 A JP 2009295192A JP 2011132471 A JP2011132471 A JP 2011132471A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 72
- 239000005060 rubber Substances 0.000 title claims abstract description 72
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 97
- 150000001412 amines Chemical class 0.000 claims abstract description 83
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 66
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001583 allophane Inorganic materials 0.000 claims description 4
- 230000007774 longterm Effects 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002845 discoloration Methods 0.000 abstract description 11
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 230000032683 aging Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 9
- 230000003679 aging effect Effects 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- -1 amine compound Chemical class 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 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
- 239000011425 bamboo Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000002542 deteriorative effect Effects 0.000 description 3
- 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
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JYSSGQITKNFRQE-UHFFFAOYSA-N [3-(4-anilinoanilino)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical compound C1=CC(NCC(O)COC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 JYSSGQITKNFRQE-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- KEZPMZSDLBJCHH-UHFFFAOYSA-N n-(4-anilinophenyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(C=C1)=CC=C1NC1=CC=CC=C1 KEZPMZSDLBJCHH-UHFFFAOYSA-N 0.000 description 1
- DUHFYDSDYUCHGU-UHFFFAOYSA-N n-phenylaniline Chemical class C=1C=CC=CC=1NC1=CC=CC=C1.C=1C=CC=CC=1NC1=CC=CC=C1 DUHFYDSDYUCHGU-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物及びその製造方法に関するものである。また、該ゴム組成物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 and a method for producing the same. The present invention also relates to a pneumatic tire using the rubber composition.
空気入りタイヤは、長期間使用中に大気中の酸素やオゾンにより劣化されることで、サイドウォール部やトレッド部の溝底に亀裂が生じ、これが耐久性を悪化させる原因となる。そのため、耐酸化劣化や耐オゾン性を改良するために、タイヤ用ゴム組成物には、各種の老化防止剤が配合されている。その中でも、アミン系老化防止剤は、タイヤのサイドウォールゴムなどの酸化劣化やオゾン劣化を有効に防止する効果を有している。しかしながら、アミン系老化防止剤は、タイヤを茶色あるいは茶褐色に変色させていくため、その外観が悪くなり、タイヤの商品価値が低下するという問題がある。 A pneumatic tire is deteriorated by oxygen and ozone in the atmosphere during long-term use, and thus cracks are generated in the groove portions of the sidewall portions and the tread portion, which causes deterioration in durability. Therefore, various anti-aging agents are blended in the tire rubber composition in order to improve oxidation resistance and ozone resistance. Among them, the amine-based anti-aging agent has an effect of effectively preventing oxidative degradation and ozone degradation of tire sidewall rubber and the like. However, since the amine-based anti-aging agent discolors the tire to brown or brown, there is a problem that the appearance is deteriorated and the commercial value of the tire is lowered.
従来、アミン系老化防止剤による変色を防止するために、種々の提案がなされており、例えば、下記特許文献１には、アミン系老化防止剤とチオウレア系老化防止剤を特定量併用することが開示され、下記特許文献２には、アミン系老化防止剤とともに、ベンゾエート系やトリアジン系の紫外線吸収剤を併用することが開示されている。 Conventionally, various proposals have been made in order to prevent discoloration due to an amine-based anti-aging agent. For example, in Patent Document 1 below, a specific amount of an amine-based anti-aging agent and a thiourea-based anti-aging agent may be used in combination. Patent Document 2 below discloses that a benzoate-based or triazine-based ultraviolet absorber is used in combination with an amine-based antioxidant.
また、下記特許文献３には、ジエン系ゴムに対し、アミン系老化防止剤とともに比表面積の高い無機多孔質粒子を配合することにより、アミン系老化防止剤による変色を抑えて外観性を改良することが提案されており、該無機多孔質粒子として中空多孔質球状シリカが用いられることも開示されている。しかしながら、この文献では、ゴム組成物を調製する際に、アミン系老化防止剤と無機多孔質粒子をそれぞれジエン系ゴムに添加し混練している。このようなゴム組成物では、アミン系老化防止剤による変色を長期にわたって抑制する効果が不十分であり、また、耐酸化劣化性を長期間持続させる効果、即ち長期老化性も不十分であり、更なる改良が求められる。 Further, in Patent Document 3 below, by adding inorganic porous particles having a high specific surface area together with an amine-based antioxidant to diene rubber, discoloration caused by the amine-based antioxidant is suppressed and appearance is improved. It is also disclosed that hollow porous spherical silica is used as the inorganic porous particles. However, in this document, when preparing a rubber composition, an amine-based antioxidant and inorganic porous particles are added to a diene rubber and kneaded. In such a rubber composition, the effect of suppressing discoloration due to the amine-based anti-aging agent over a long period of time is insufficient, and the effect of sustaining the oxidation deterioration resistance for a long period of time, that is, the long-term aging resistance is insufficient, Further improvements are required.
なお、下記特許文献４には、シリカに予め溶融した老化防止剤を吸着させたゴム用薬品マスターバッチをジエン系ゴムに配合してゴム組成物を得ることが開示されている。しかしながら、この文献は、ゴム組成物の混練時に、溶融した老化防止剤によってスリップ現象が生じ、混練効率が悪化するのを防止するために、マスターバッチ化するものであり、アミン系老化防止剤に起因する変色の抑制による外観性の向上や長期老化性の向上を目的としたものではない。 Patent Document 4 listed below discloses that a rubber chemical masterbatch obtained by adsorbing an anti-aging agent previously melted on silica is blended with a diene rubber to obtain a rubber composition. However, in this document, a master batch is used to prevent a slip phenomenon caused by the melted anti-aging agent during kneading of the rubber composition and deterioration of kneading efficiency. It is not intended to improve appearance or long-term aging by suppressing the resulting discoloration.
また、下記特許文献５には、無機多孔質粒子に特定のアミン化合物を含浸ないし充填させたマイクロカプセルをゴム組成物に配合することが開示されている。しかしながら、上記アミン化合物は加硫を促進するための促進剤であって、加硫時にマイクロカプセルから放出されることで、スコーチを悪化させることなく加硫時間を短縮させるというものであり、アミン系老化防止剤に起因する変色の抑制による外観性の向上や長期老化性の向上を目的としたものではない。 Patent Document 5 listed below discloses blending a rubber composition with microcapsules in which inorganic porous particles are impregnated or filled with a specific amine compound. However, the amine compound is an accelerator for accelerating vulcanization, and is released from the microcapsule during vulcanization, thereby shortening the vulcanization time without deteriorating the scorch. It is not intended to improve appearance or long-term aging by suppressing discoloration caused by an anti-aging agent.
本発明は、以上の点に鑑みてなされたものであり、アミン系老化防止剤による耐オゾン性の改良効果を悪化させることなく、ゴム表面の変色を抑制して外観性を向上することができ、長期老化性及び外観性に優れたゴム組成物、及びそ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 can improve the appearance by suppressing discoloration of the rubber surface without deteriorating the ozone resistance improvement effect by the amine-based anti-aging agent. An object of the present invention is to provide a rubber composition excellent in long-term aging and appearance and a method for producing the same.
本発明者は、上記課題に鑑み、鋭意検討していく中で、アミン系老化防止剤と空隙率の高い多孔質中空粒子を事前に混合させた混合物を用いることで、アミン系老化防止剤による変色を抑制し、更に耐酸化劣化性を長期間持続させることができることを見い出し、本発明を完成するに至った。 The present inventor, in the light of the above-mentioned problems, in an intensive study, by using a mixture in which an amine-based anti-aging agent and porous hollow particles having a high porosity are mixed in advance, the amine-based anti-aging agent is used. It has been found that discoloration can be suppressed and oxidation deterioration resistance can be maintained for a long time, and the present invention has been completed.
すなわち、本発明に係るゴム組成物は、空隙率５０％以上の多孔質中空粒子にアミン系老化防止剤を含浸ないし充填させた多孔質中空粒子とアミン系老化防止剤の事前混合物を、ジエン系ゴムからなるゴム成分に配合してなり、前記ゴム成分１００質量部に対して、前記アミン系老化防止剤を０．５〜８質量部、前記多孔質中空粒子を０．１〜４０質量部含有するものである。 That is, the rubber composition according to the present invention comprises a diene-based pre-mixture of porous hollow particles obtained by impregnating or filling a porous hollow particle having a porosity of 50% or more with an amine anti-aging agent and an amine anti-aging agent. It is blended in a rubber component made of rubber and contains 0.5 to 8 parts by mass of the amine-based antioxidant and 0.1 to 40 parts by mass of the porous hollow particles with respect to 100 parts by mass of the rubber component. To do.
また、本発明に係るゴム組成物の製造方法は、アミン系老化防止剤と空隙率５０％以上の多孔質中空粒子とを、前記アミン系老化防止剤を溶融させて混合し、得られた事前混合物を、ジエン系ゴムからなるゴム成分１００質量部に対して、前記アミン系老化防止剤が０．５〜８質量部、前記多孔質中空粒子が０．１〜４０質量部配合されるように、前記ゴム成分に添加し混練するものである。 In addition, the method for producing a rubber composition according to the present invention includes mixing an amine-based anti-aging agent and porous hollow particles having a porosity of 50% or more by melting the amine-based anti-aging agent and mixing the mixture. The mixture is mixed such that the amine-based antioxidant is 0.5 to 8 parts by mass and the porous hollow particles are 0.1 to 40 parts by mass with respect to 100 parts by mass of the rubber component made of diene rubber. And kneaded by adding to the rubber component.
本発明によれば、アミン系老化防止剤と上記多孔質中空粒子との事前混合物をゴム成分に配合することにより、耐オゾン性を悪化させることなく、アミン系老化防止剤によるゴム表面の変色を抑制して外観性を向上することができ、更に、長期老化性を向上することができる。 According to the present invention, by mixing a premix of an amine-based anti-aging agent and the above porous hollow particles into a rubber component, the rubber surface can be discolored by the amine-based anti-aging agent without deteriorating ozone resistance. It can suppress and can improve an external appearance property and can improve long-term aging property.
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は、ジエン系ゴムからなるゴム成分と、アミン系老化防止剤と、空隙率が５０％以上の多孔質中空粒子とを含有する。 The rubber composition according to the present invention contains a rubber component composed of a diene rubber, an amine-based antioxidant, and porous hollow particles having a porosity of 50% or more.
上記ゴム成分となるジエン系ゴムとしては、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。上記ゴム成分は、好ましくは、天然ゴム、ブタジエンゴム、スチレン−ブタジエンゴム、又はこれらの２種以上のブレンドである。 Examples of the diene rubber used as the rubber component include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber ( CR), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer, styrene-isoprene-butadiene copolymer rubber, and the like. These can be used alone or in combination of two or more. The rubber component is preferably natural rubber, butadiene rubber, styrene-butadiene rubber, or a blend of two or more thereof.
上記アミン系老化防止剤としては、芳香族第２級アミンが好ましく用いられる。具体的には、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、Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、Ｎ，Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジアミン、Ｎ−（３−メタクリロイルオキシ−２−ヒドロキシプロピル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、Ｎ−シクロヘキシル−Ｎ’−フェニル−ｐ−フェニレンジアミンなどのｐ−フェニレンジアミン系老化防止剤、ｐ−（ｐ−トルエンスルホニルアミド）ジフェニルアミン、４，４’−ビス（α，α−ジメチルベンジル）ジフェニルアミン、オクチル化ジフェニルアミン、スチレン化ジフェニルアミンなどのジフェニルアミン系老化防止剤、Ｎ−フェニル−１−ナフチルアミン、Ｎ−フェニル−２−ナフチルアミン等のナフチルアミン系老化防止剤などが挙げられる。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。 As the amine-based antioxidant, an aromatic secondary amine is preferably used. Specifically, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N, N′-diphenyl-p-phenylene Diamine, N, N'-di-2-naphthyl-p-phenylenediamine, N- (3-methacryloyloxy-2-hydroxypropyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl P-Phenylenediamine-based antioxidants such as p-phenylenediamine, p- (p-toluenesulfonylamido) diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, octylated diphenylamine, styrenated diphenylamine Diphenylamine anti-aging agent such as N-phenyl-1-naphthyl Examples thereof include naphthylamine-based antioxidants such as amines and N-phenyl-2-naphthylamine. These can be used alone or in combination of two or more.
アミン系老化防止剤の配合量は、上記ゴム成分１００質量部に対して０．５〜８質量部であり、より好ましくは１〜６質量部である。アミン系老化防止剤の配合量が少なすぎると、ゴム組成物の耐オゾン性や長期老化性を確保することが難しくなる。逆に、アミン系老化防止剤の配合量が多すぎると、多孔質中空粒子を併用した場合でもゴム表面の変色を抑制することが難しくなる。 The compounding amount of the amine antioxidant is 0.5 to 8 parts by mass, more preferably 1 to 6 parts by mass with respect to 100 parts by mass of the rubber component. If the compounding amount of the amine-based anti-aging agent is too small, it becomes difficult to ensure ozone resistance and long-term aging resistance of the rubber composition. On the other hand, when the compounding amount of the amine-based antioxidant is too large, it is difficult to suppress discoloration of the rubber surface even when the porous hollow particles are used in combination.
上記多孔質中空粒子としては、空隙率が５０％以上のものが用いられる。多孔質中空粒子は、内部に中空部としての空洞を持ち、殻部が該空洞と外部を連通させる多孔質体からなるもの、即ち、中空粒子の外壁にアミン系老化防止剤等の液体が出入りできる無数の細孔を有するものである。そのため、アミン系老化防止剤を溶融混合することで、多孔質中空粒子にアミン系老化防止剤を含浸ないし充填させることができ、特には前記空洞にアミン系老化防止剤を内包することができる。多孔質中空粒子に内包されたアミン系老化防止剤は、ゴム組成物の成形後、多孔質中空粒子からマトリックスゴム中に時間の経過とともに徐々に放出されるので、アミン系老化防止剤が製品表面に過剰にブリードすることによる変色を抑え、長期にわたって外観性を保持することができる。また、アミン系老化防止剤が徐々に放出されることにより、アミン系老化防止剤による耐酸化劣化性を長期間持続させることができ、長期老化性を向上することができる。 As the porous hollow particles, those having a porosity of 50% or more are used. Porous hollow particles have a cavity as a hollow part inside, and a shell part is made of a porous body that communicates the cavity with the outside, that is, liquid such as an amine anti-aging agent enters and exits the outer wall of the hollow particle. It has innumerable pores that can be formed. Therefore, by melt-mixing the amine-based anti-aging agent, the porous hollow particles can be impregnated or filled with the amine-based anti-aging agent, and particularly, the amine-based anti-aging agent can be included in the cavity. The amine-based anti-aging agent encapsulated in the porous hollow particles is gradually released from the porous hollow particles into the matrix rubber with the passage of time after molding the rubber composition. Discoloration due to excessive bleeding can be suppressed, and appearance can be maintained over a long period of time. In addition, by gradually releasing the amine-based anti-aging agent, the oxidation deterioration resistance by the amine-based anti-aging agent can be maintained for a long time, and the long-term aging property can be improved.
ここで、多孔質中空粒子の空隙率が５０％未満では、アミン系老化防止剤を長期にわたって徐々に放出するという作用効果は期待できず、外観性や長期老化性の向上効果はほとんど得られない。空隙率は、より好ましくは７５％以上であり、更に好ましくは８５％以上である。空隙率の上限は特に限定されないが、通常は９５％以下である。 Here, when the porosity of the porous hollow particles is less than 50%, the effect of gradually releasing the amine-based anti-aging agent over a long period of time cannot be expected, and the effect of improving the appearance and long-term aging properties is hardly obtained. . The porosity is more preferably 75% or more, and still more preferably 85% or more. The upper limit of the porosity is not particularly limited, but is usually 95% or less.
多孔質中空粒子の空隙率は、一定質量の試料（即ち、多孔質中空粒子）の体積をメスシリンダーで測定し、嵩比重を求めて、下記式から求めることができる。
空隙率［％］＝（空隙体積[ml]）／（試料の嵩体積[ml]）×100
＝｛（試料の嵩体積[ml]）−（試料の実体積[ml]）｝／（試料の嵩体積[ml]）×100
＝｛１−（試料の実体積[ml]）／（試料の嵩体積[ml]）｝×100
＝｛１−（試料の嵩比重[g/ml]）／（試料の真比重[g/ml]）｝×100
The porosity of the porous hollow particles can be obtained from the following equation by measuring the volume of a sample having a constant mass (ie, porous hollow particles) with a graduated cylinder and determining the bulk specific gravity.
Porosity [%] = (void volume [ml]) / (sample bulk volume [ml]) × 100
= {(Bulk volume [ml] of sample) − (actual volume [ml] of sample)} / (bulk volume [ml] of sample) × 100
= {1- (actual volume of sample [ml]) / (bulk volume of sample [ml])} × 100
= {1- (Sample Bulk Specific Gravity [g / ml]) / (Sample True Specific Gravity [g / ml])} × 100
多孔質中空粒子の形状は、中空部を有する限り、特に限定されず、球状でも、長球状や扁球状などの楕円体状でもよいが、好ましくは中空球状である。 The shape of the porous hollow particles is not particularly limited as long as it has a hollow portion, and may be spherical or elliptical such as oblong or oblate, but is preferably a hollow sphere.
多孔質中空粒子の大きさも、特に限定されないが、平均粒径が０．１ｎｍ〜１００μｍであることが好ましく、より好ましくは１ｎｍ〜１００μmであり、更に好ましくは２０ｎｍ〜５０μｍであり、特に好ましくは１〜２０μｍである。多孔質中空粒子の平均粒径は、透過型電子顕微鏡（ＴＥＭ）で観察して画像を得て、この画像を用いて、無作為抽出された１０個の粒子の直径を計測することにより、その相加平均として求められる。 The size of the porous hollow particles is not particularly limited, but the average particle size is preferably 0.1 nm to 100 μm, more preferably 1 nm to 100 μm, still more preferably 20 nm to 50 μm, and particularly preferably 1 ˜20 μm. The average particle diameter of the porous hollow particles is obtained by observing with a transmission electron microscope (TEM), obtaining an image, and using this image, measuring the diameter of 10 randomly extracted particles. Calculated as an arithmetic mean.
多孔質中空粒子は、無機物からなる無機多孔質中空粒子であることが好ましい。そのような無機材料としては、特に限定されず、例えば、シリカ、アルミナ、酸化チタン、ケイ酸ナトリウム、ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、カーボンなどが挙げられる。具体的には、多孔質中空シリカ、アロフェン（即ち、中空球状構造を持つアルミニウムの含水ケイ酸塩鉱物）、多孔質中空カーボンなどが挙げられ、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 porous hollow particles are preferably inorganic porous hollow particles made of an inorganic material. Such an inorganic material is not particularly limited, and examples thereof include silica, alumina, titanium oxide, sodium silicate, calcium silicate, aluminum silicate, magnesium silicate, calcium carbonate, magnesium carbonate, and carbon. Specific examples include porous hollow silica, allophane (that is, hydrated aluminum silicate mineral having a hollow spherical structure), porous hollow carbon, and the like. These may be used alone or in combination of two or more. Can do.
多孔質中空粒子の配合量は、上記ゴム成分１００質量部に対して０．１〜４０質量部であり、より好ましくは１〜２０質量部であり、更に好ましくは１〜１０質量部である。多孔質中空粒子の配合量が少なすぎると、内部に保持できるアミン系老化防止剤の量が少なくなって、外観性や長期老化性の向上効果が損なわれる。逆に、多孔質中空粒子の配合量が多すぎると、多孔質中空粒子による補強性が発揮されてゴム硬度が高くなったり、耐オゾン性が損なわれたりするおそれがある。 The compounding quantity of a porous hollow particle is 0.1-40 mass parts with respect to 100 mass parts of said rubber components, More preferably, it is 1-20 mass parts, More preferably, it is 1-10 mass parts. When the amount of the porous hollow particles is too small, the amount of the amine-based anti-aging agent that can be held inside decreases, and the effect of improving the appearance and long-term aging properties is impaired. On the other hand, if the amount of the porous hollow particles is too large, the reinforcing property by the porous hollow particles is exhibited, and the rubber hardness may be increased, or the ozone resistance may be impaired.
上記アミン系老化防止剤と多孔質中空粒子は、事前に混合し、得られた事前混合物をゴム成分に添加し混練することにより、本発明に係るゴム組成物を調製することができる。事前混合に際しては、アミン系老化防止剤を溶融させて、多孔質中空粒子と混合する。これにより、多孔質中空粒子にアミン系老化防止剤を含浸ないし充填させた複合体（即ち、アミン系老化防止剤−多孔質中空粒子複合体）からなる事前混合物が得られる。より詳細には、溶融した液状のアミン系老化防止剤は、多孔質中空粒子の殻部の細孔を通ってその内部の空洞に浸透するので、多孔質中空粒子にアミン系老化防止剤を内包した複合体が得られる。なお、アミン系老化防止剤は、多孔質中空粒子の中空部のみに充填ないし含浸されている態様には限られず、通常は中空部とともに殻部に充填ないし含浸されており、そのような態様も、当然に、上記複合体ないし事前混合物の態様として包含される。また、アミン系老化防止剤は、多孔質中空粒子の殻部のみに含浸されてもよく、また多孔質中空粒子の粒子表面に付着していてもよい。 The amine-based anti-aging agent and the porous hollow particles are mixed in advance, and the obtained pre-mixture is added to the rubber component and kneaded to prepare the rubber composition according to the present invention. In the premixing, the amine-based antioxidant is melted and mixed with the porous hollow particles. As a result, a premix composed of a composite in which porous hollow particles are impregnated or filled with an amine-based anti-aging agent (that is, an amine-based anti-aging agent-porous hollow particle composite) is obtained. More specifically, since the molten liquid amine-based anti-aging agent penetrates into the hollow space through the pores of the shell of the porous hollow particle, the amine-based anti-aging agent is included in the porous hollow particle. The resulting composite is obtained. The amine anti-aging agent is not limited to an embodiment in which only the hollow portion of the porous hollow particle is filled or impregnated, and is usually filled or impregnated in the shell portion together with the hollow portion. Of course, it is included as an embodiment of the above complex or premix. Moreover, the amine-based anti-aging agent may be impregnated only in the shell of the porous hollow particles, or may be adhered to the particle surface of the porous hollow particles.
アミン系老化防止剤と多孔質中空粒子との比率は、特に限定するものではないが、アミン系老化防止剤の量をＸ質量部、多孔質中空粒子の量をＹ質量部として、Ｘ／Ｙが０．０５〜１０であることが好ましく、より好ましくは０．３〜３である。 The ratio of the amine-based anti-aging agent and the porous hollow particles is not particularly limited, but the amount of the amine-based anti-aging agent is X parts by mass, the amount of the porous hollow particles is Y parts by mass, and X / Y Is preferably 0.05 to 10, more preferably 0.3 to 3.
事前混合の方法としては、特に限定されず、アミン系老化防止剤をその融点以上の温度で多孔質中空粒子に混合するものであればよい。例えば、アミン系老化防止剤をオイルバスなどで加熱溶融させ、この加熱溶融したアミン系老化防止剤に多孔質中空粒子を添加し攪拌混合してもよく、あるいは、多孔質中空粒子を攪拌しながら、加熱溶融させたアミン系老化防止剤を添加し混合してもよく、あるいはまた、アミン系老化防止剤の粉体と多孔質中空粒子をミキサーで攪拌混合しながら、混合時のせん断による摩擦熱やヒーターによる加熱でアミン系老化防止剤を溶融させてもよい。 The premixing method is not particularly limited as long as the amine-based antioxidant is mixed with the porous hollow particles at a temperature equal to or higher than the melting point thereof. For example, an amine-based anti-aging agent may be heated and melted in an oil bath or the like, and porous hollow particles may be added to the heat-melted amine-based anti-aging agent and mixed with stirring. Alternatively, while stirring the porous hollow particles, Heat-melted amine-based anti-aging agent may be added and mixed, or friction heat due to shearing during mixing while stirring and mixing the amine-based anti-aging agent powder and porous hollow particles with a mixer Alternatively, the amine anti-aging agent may be melted by heating with a heater.
このようにして多孔質中空粒子とアミン系老化防止剤を溶融混合した後、吸引濾過を行って事前混合物を得るようにしてもよい。吸引濾過により、過剰のアミン系老化防止剤を除去しつつ、負圧によって多孔質中空粒子の内部の空洞にアミン系老化防止剤を浸透させることができるので、長期老化性と外観性を一層向上することができる。 Thus, after melt-mixing the porous hollow particles and the amine anti-aging agent, suction filtration may be performed to obtain a pre-mixture. By removing the excess amine-based anti-aging agent by suction filtration, the amine-based anti-aging agent can be infiltrated into the cavity inside the porous hollow particle by negative pressure, further improving long-term aging and appearance can do.
得られた事前混合物は、好ましくは一旦冷却してから、ゴム成分に添加される。事前混合物とゴム成分との混合は、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ニーダー等の混合機を用いて混練することにより行うことができ、本発明に係るゴム組成物を製造することができる。 The resulting premix is preferably cooled before being added to the rubber component. The mixing of the premix and the rubber component can be performed by kneading using a mixer such as a Banbury mixer or a kneader that is generally used for the preparation of a rubber composition, and the rubber composition according to the present invention is manufactured. Can do.
本発明に係るゴム組成物には、カーボンブラックやシリカなどの一般にゴム組成物において配合される補強性充填剤を配合することができる。補強性充填剤の配合量は、特に限定されないが、ゴム成分１００質量部に対して１０〜１５０質量部であることが好ましい。 In the rubber composition according to the present invention, a reinforcing filler generally blended in the rubber composition such as carbon black and silica can be blended. Although the compounding quantity of a reinforcing filler is not specifically limited, It is preferable that it is 10-150 mass parts with respect to 100 mass parts of rubber components.
本発明に係るゴム組成物には、上記した成分の他に、亜鉛華、ステアリン酸、軟化剤、硫黄、加硫促進剤など、ゴム工業において一般に使用される各種添加剤を必要に応じて配合することができる。また、本発明の効果を損なわない範囲内で、アミン系老化防止剤以外の他の老化防止剤を更に併用してもよい。該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。 In addition to the above-described components, the rubber composition according to the present invention contains various additives generally used in the rubber industry, such as zinc white, stearic acid, softener, sulfur, and vulcanization accelerator, as necessary. can do. Moreover, you may further use together other anti-aging agents other than an amine type anti-aging agent within the range which does not impair the effect of this invention. The use of the rubber composition is not particularly limited, but can be used for various rubber compositions such as tires such as treads and sidewalls, conveyor belts, and vibration-proof rubbers.
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。特には、空気入りタイヤのサイドウォール部に用いられることが好ましい。 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. In particular, it is preferably used for a sidewall portion of a pneumatic tire.
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。なお、下記の多孔質中空粒子および多孔質粒子の空隙率は、上記算出式によるものであり、真比重については、ジルコンビーズは６．０、竹炭粉砕物は１．４、多孔質中空シリカは２．１、アロフェンは２．３、多孔質中空カーボンは４．８とした。 Details of each component used in the following examples and comparative examples are as follows. In addition, the porosity of the following porous hollow particles and porous particles is based on the above calculation formula. Regarding the true specific gravity, the zircon beads are 6.0, the bamboo charcoal pulverized product is 1.4, and the porous hollow silica is 2.1, allophane was 2.3, and porous hollow carbon was 4.8.
・アミン系老化防止剤：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、６ＰＰＤ、大内新興化学工業株式会社製「ノクラック６Ｃ」、
・多孔質中空粒子１：多孔質中空シリカ、鈴木油脂工業（株）製「ゴッドボールＢ−６Ｃ」（空隙率＝９１％、平均粒径＝２．０〜２．５μｍ、細孔の平均径＝５〜１５ｎｍ）、
・多孔質中空粒子２：アロフェン、品川化成（株）製「セカードＫＷ」（空隙率＝８０％、平均粒径＝３．５〜５ｎｍ、細孔の平均径＝０．３〜０．５ｎｍ）、
・多孔質中空粒子３：多孔質中空カーボン、（株）ニューメタルエンドケミカルス製「ナノポーラスカーボン」（空隙率＝９３％、平均粒径＝２０〜５０ｎｍ、細孔の平均径＝２ｎｍ）、
・多孔質粒子ａ：ジルコンビーズ、東レ株式会社製「トレセラムジルコンビーズ」（空隙率＝４％、平均粒径＝４００μｍ）、
・多孔質粒子ｂ：孟宗竹の竹炭（宮崎土晃株式会社製「１号炭」）をハンマーミルで粉砕し、ふるいにより分級した竹炭粉砕物（空隙率＝４６％、平均粒径＝１００μｍ）、
・シリカ：東ソー・シリカ株式会社製「ニップシールＡＱ」、
・カーボンブラック：ＨＡＦ、東海カーボン株式会社製「シースト３」。
Amine-based anti-aging agent: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, 6PPD, “NOCRACK 6C” manufactured by Ouchi Shinsei Chemical Co., Ltd.,
Porous hollow particles 1: Porous hollow silica, “God Ball B-6C” manufactured by Suzuki Oil & Fats Co., Ltd. (porosity = 91%, average particle size = 2.0 to 2.5 μm, average diameter of pores) = 5-15 nm),
-Porous hollow particles 2: Allophane, “Secard KW” manufactured by Shinagawa Kasei Co., Ltd. (porosity = 80%, average particle size = 3.5-5 nm, average pore diameter = 0.3-0.5 nm) ,
-Porous hollow particle 3: Porous hollow carbon, "Nanoporous carbon" manufactured by New Metal End Chemicals Co., Ltd. (porosity = 93%, average particle size = 20-50 nm, average pore diameter = 2 nm),
-Porous particles a: zircon beads, “Traceram zircon beads” manufactured by Toray Industries, Inc. (porosity = 4%, average particle size = 400 μm),
-Porous particles b: Bamboo charcoal from Bunso bamboo (“No. 1 charcoal” manufactured by Miyazaki Dogo Co., Ltd.) was pulverized with a hammer mill and classified by sieving (porosity = 46%, average particle size = 100 μm),
・ Silica: “Nip Seal AQ” manufactured by Tosoh Silica Corporation,
Carbon black: HAF, “Seast 3” manufactured by Tokai Carbon Co., Ltd.
・天然ゴム：ＲＳＳ＃３、
・ブタジエンゴム：宇部興産（株）製「ＢＲ１５０」、
・亜鉛華：三井金属鉱業（株）製「１号亜鉛華」、
・ステアリン酸：花王（株）製「工業用ステアリン酸」、
・硫黄：鶴見化学工業（株）製「５％油処理粉末硫黄」、
・加硫促進剤：ＮＳ、大内新興化学工業株式会社製「ノクセラーＮＳ−Ｐ」。
・ Natural rubber: RSS # 3,
・ Butadiene rubber: “BR150” manufactured by Ube Industries, Ltd.
・ Zinc flower: “No. 1 zinc flower” manufactured by Mitsui Mining & Smelting Co., Ltd.
・ Stearic acid: “Industrial stearic acid” manufactured by Kao Corporation
・ Sulfur: “5% oil-treated powder sulfur” manufactured by Tsurumi Chemical Co., Ltd.
Vulcanization accelerator: NS, “Noxeller NS-P” manufactured by Ouchi Shinsei Chemical Co., Ltd.
評価方法は以下の通りである。
・長期老化性：加硫ゴム片をギヤーオーブンにて６０℃で１ヶ月、２ヶ月及び３か月の老化後に、ＪＩＳ Ｋ６２５１に準拠した引張試験（ダンベル３号）を実施して破断伸びを測定し、下記式により破断伸びの保持率（破壊特性保持率）を求めた。
破断伸びの保持率（％）＝１００×（老化後破断伸び）／（老化前破断伸び）
保持率が高いほど、耐酸化劣化性に優れ、老化２ヶ月後、３か月後にも高い保持率を示すことで長期老化性（即ち、耐酸化劣化性の持続効果）に優れることを意味する。
The evaluation method is as follows.
・ Long-term aging: After vulcanized rubber pieces are aged for 1 month, 2 months and 3 months at 60 ° C in a gear oven, a tensile test (dumbbell No. 3) according to JIS K6251 is performed to measure the elongation at break. Then, the retention of elongation at break (fracture property retention) was determined by the following formula.
Retention rate of breaking elongation (%) = 100 × (breaking elongation after aging) / (breaking elongation before aging)
The higher the retention rate, the better the oxidation resistance, and the higher the retention rate after 2 months and 3 months, the better the long-term aging (that is, the sustained effect of oxidation resistance). .
・外観性：加硫ゴム片を日光に照射させ、照射前（屋外曝露０日）、２０日後（屋外曝露２０日）、４０日後（屋外曝露４０日）、及び１２０日後（屋外曝露１２０日）における加硫ゴム片の表面を目視により観察して、下記の基準で外観性を評価した。 Appearance: Irradiated vulcanized rubber pieces with sunlight, before irradiation (0 days outdoors), 20 days after (20 days outdoors), 40 days (40 days outdoors), 120 days after (120 days outdoors) The surface of the vulcanized rubber piece was visually observed, and the appearance was evaluated according to the following criteria.
◎：表面が黒く、ほとんど変色なし、
○：わずかに茶色または白色に変色している、
△：やや茶色または白色に変色している、
×：茶褐色または白色に変色している。
A: Black surface, almost no discoloration,
○: Slightly brown or white
Δ: Discolored slightly brown or white,
X: Discolored to brown or white.
・耐オゾン性：加硫ゴム片を２５％伸長した条件下でオゾンウェザーメーター装置中に設置し、オゾン濃度１００ｐｐｈｍ、温度５０℃の環境下で２４時間放置し、その後、クラックの発生状態を目視により観察し、下記の基準で耐オゾン性を評価した。 ・ Ozone resistance: Placed in an ozone weather meter under 25% elongation of the vulcanized rubber piece, left in an environment with an ozone concentration of 100 pphm and a temperature of 50 ° C. for 24 hours, and then visually observed the occurrence of cracks The ozone resistance was evaluated according to the following criteria.
◎：クラック発生なし、
○：肉眼では確認できないが１０倍の拡大鏡では確認できるクラックが発生している、
△：１ｍｍ以下のクラックが発生している、
×：１ｍｍを超えるクラックが発生している。
◎: No cracking,
○: Cracks that cannot be confirmed with the naked eye but can be confirmed with a 10x magnifier have occurred.
Δ: Cracks of 1 mm or less have occurred,
X: Cracks exceeding 1 mm are generated.
［実施例１］
アミン系老化防止剤１００ｇをオイルバスにて１５０℃で溶融させ、これに多孔質中空粒子１を２０ｇ添加して攪拌混合した。得られた混合物を、ブフナー漏斗、吸引瓶及びアスピレータを用いて吸引濾過して過剰のアミン系老化防止剤を除去し、その後、室温で冷却することにより、多孔質中空粒子１にアミン系老化防止剤を内包させた事前混合物４０ｇを得た。該事前混合物は、アミン系老化防止剤（Ｘ）と多孔質中空粒子（Ｙ）を質量比でＸ：Ｙ＝３：３にて含有する。バンバリーミキサーを使用し、下記表１に示す配合に従って、上記事前混合物をジエン系ゴムに添加するとともに、他の配合剤も常法に従って添加し混練することにより、ゴム組成物を調製した。
[Example 1]
100 g of an amine anti-aging agent was melted at 150 ° C. in an oil bath, and 20 g of porous hollow particles 1 were added thereto and mixed with stirring. The resulting mixture was suction filtered using a Buchner funnel, suction bottle and aspirator to remove excess amine-based anti-aging agent, and then cooled at room temperature to prevent amine-based anti-aging on porous hollow particles 1. 40 g of a premix containing the agent was obtained. The premix contains the amine-based antioxidant (X) and the porous hollow particles (Y) at a mass ratio of X: Y = 3: 3. Using a Banbury mixer, according to the formulation shown in Table 1 below, the above premix was added to the diene rubber, and other compounding agents were added and kneaded in accordance with a conventional method to prepare a rubber composition.
［実施例２］
多孔質中空粒子１に代えて、多孔質中空粒子２を２０ｇ添加し、その他は実施例１と同様にして、４０ｇの事前混合物（Ｘ：Ｙ＝３：３）を得て、該事前混合物をジエン系ゴムに添加し混練することで、ゴム組成物を調製した。
[Example 2]
Instead of the porous hollow particles 1, 20 g of the porous hollow particles 2 were added, and in the same manner as in Example 1, 40 g of a premix (X: Y = 3: 3) was obtained. A rubber composition was prepared by adding to a diene rubber and kneading.
［実施例３］
多孔質中空粒子１に代えて、多孔質中空粒子３を２０ｇ添加し、その他は実施例１と同様にして、４０ｇの事前混合物（Ｘ：Ｙ＝３：３）を得て、該事前混合物をジエン系ゴムに添加し混練することで、コム組成物を調製した。
[Example 3]
In place of the porous hollow particles 1, 20 g of the porous hollow particles 3 were added, and in the same manner as in Example 1, 40 g of a premix (X: Y = 3: 3) was obtained. A comb composition was prepared by adding to a diene rubber and kneading.
［実施例４〜７］
実施例１において、多孔質中空粒子１の添加量を変更することで、アミン系老化防止剤と多孔質中空粒子の質量比が異なる事前混合物を得て、その他は実施例と同様にして、ゴム組成物を調製した。アミン系老化防止剤（Ｘ）と多孔質中空粒子（Ｙ）の質量比は、実施例４がＸ：Ｙ＝３：０．５、実施例５がＸ：Ｙ＝３：３５、実施例６がＸ：Ｙ＝１：３、実施例７がＸ：Ｙ＝６：３である。
[Examples 4 to 7]
In Example 1, by changing the addition amount of the porous hollow particles 1, a pre-mixture having a different mass ratio of the amine-based anti-aging agent and the porous hollow particles was obtained. A composition was prepared. The mass ratio of the amine-based antioxidant (X) to the porous hollow particles (Y) is as follows: Example 4 is X: Y = 3: 0.5, Example 5 is X: Y = 3: 35, Example 6 Is X: Y = 1: 3, and Example 7 is X: Y = 6: 3.
［比較例１，９］
バンバリーミキサーを使用し、下記表１に示す配合に従って、事前混合することなく、各成分を添加し混練することにより、ゴム組成物を調製した。
[Comparative Examples 1 and 9]
Using a Banbury mixer, a rubber composition was prepared by adding and kneading each component according to the formulation shown in Table 1 below without premixing.
［比較例２〜５］
多孔質中空粒子１に代えて、表１に記載の各粒子を用いて、その他は実施例１と同様にして、事前混合物を得て、該事前混合物をジエン系ゴムに添加し混練することで、ゴム組成物を調製した。
[Comparative Examples 2 to 5]
In place of the porous hollow particles 1, using the respective particles shown in Table 1, except that in the same manner as in Example 1, a premix was obtained, and the premix was added to the diene rubber and kneaded. A rubber composition was prepared.
［比較例６〜８］
実施例１において、多孔質中空粒子１の添加量を変更することで、アミン系老化防止剤と多孔質中空粒子の質量比が異なる事前混合物を得て、その他は実施例と同様にして、コム組成物を調製した。アミン系老化防止剤（Ｘ）と多孔質中空粒子（Ｙ）の質量比は、比較例６がＸ：Ｙ＝３：０．０５、比較例７がＸ：Ｙ＝３：４５、比較例８がＸ：Ｙ＝１０：３である。
[Comparative Examples 6-8]
In Example 1, by changing the addition amount of the porous hollow particles 1, a pre-mixture having different mass ratios of the amine-based antioxidant and the porous hollow particles was obtained. A composition was prepared. The mass ratio between the amine-based antioxidant (X) and the porous hollow particles (Y) is as follows: Comparative Example 6 is X: Y = 3: 0.05, Comparative Example 7 is X: Y = 3: 45, Comparative Example 8 Is X: Y = 10: 3.
このようにして得られた各ゴム組成物について、１６０℃×３０分で加硫して厚さ２ｍｍの加硫ゴム片を作製し、得られた加硫ゴム片を用いて、長期老化性、外観性及び耐オゾン性を評価した。結果を表１に示す。 For each rubber composition thus obtained, vulcanized at 160 ° C. for 30 minutes to produce a vulcanized rubber piece having a thickness of 2 mm, and using the obtained vulcanized rubber piece, long-term aging, Appearance and ozone resistance were evaluated. The results are shown in Table 1.
表１に示すように、本発明に係る実施例１〜７であると、アミン系老化防止剤の単独使用である比較例１に対し、耐オゾン性を損なうことなく、外観性を大幅に向上することができた。また、長期老化性も顕著に改善されており、よって、外観性と長期老化性の双方に優れた改善効果が認められた。 As shown in Table 1, when it is Examples 1-7 which concern on this invention, with respect to the comparative example 1 which is single use of an amine type anti-aging agent, an external appearance property is improved significantly, without impairing ozone resistance. We were able to. Moreover, the long-term aging property was also remarkably improved, and thus an improvement effect excellent in both appearance and long-term aging property was recognized.
これに対し、アミン系老化防止剤とシリカを事前混合した比較例２や、アミン系老化防止剤とカーボンブラックを事前混合した比較例３では、長期老化性に若干の改善が認められたものの、その効果は不十分であり、また外観性については殆ど改善効果は得られなかった。また、アミン系老化防止剤と多孔質粒子を事前混合したものの、多孔質粒子の空隙率が低く、中空構造でもない比較例４，５では、外観性及び長期老化性の改善効果が不十分であり、実施例１〜７に見られたような顕著な向上効果は得られなかった。 On the other hand, in Comparative Example 2 in which amine-based anti-aging agent and silica were pre-mixed and in Comparative Example 3 in which amine-based anti-aging agent and carbon black were pre-mixed, although a slight improvement in long-term aging was observed, The effect was insufficient, and almost no improvement effect was obtained with respect to appearance. In addition, although the amine-based anti-aging agent and the porous particles are premixed, in Comparative Examples 4 and 5 in which the porosity of the porous particles is low and the structure is not hollow, the effect of improving the appearance and long-term aging is insufficient. There was no remarkable improvement effect as seen in Examples 1-7.
比較例６では、多孔質中空粒子の含有量が少ないため、外観性及び長期老化性の改善効果は得られなかった。また、比較例７では、多孔質中空粒子の含有量が多すぎたため、実施例に比べて、外観性と耐オゾン性が損なわれていた。比較例８では、アミン系老化防止剤の含有量が多すぎて、外観性が損なわれていた。 In Comparative Example 6, since the content of the porous hollow particles was small, the effect of improving the appearance and long-term aging properties could not be obtained. Moreover, in comparative example 7, since there was too much content of the porous hollow particle, the external appearance property and ozone resistance were impaired compared with the Example. In Comparative Example 8, the content of the amine anti-aging agent was too much, and the appearance was impaired.
比較例９では、アミン系老化防止剤と多孔質中空粒子を併用するものの、これらを事前溶融せずにそれぞれゴム成分に添加混合したため、長期老化性の改善効果が小さく、また外観性の向上効果が実施例のものに比べて明らかに劣っていた。 In Comparative Example 9, although the amine-based anti-aging agent and the porous hollow particles are used in combination, the effects of improving long-term aging are small and the appearance is improved because they are added and mixed with the rubber components without being previously melted. Was clearly inferior to that of the example.
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| US9969221B2 (en) | 2013-07-05 | 2018-05-15 | Sumitomo Rubber Industries, Ltd. | Pneumatic tire |
| JP2018100342A (en) * | 2016-12-20 | 2018-06-28 | 東洋ゴム工業株式会社 | Tire rubber composition, tire and method for producing the same |
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