JP7414879B2 - Rubber composition, retreaded tire using the same, and method for producing the retreaded tire - Google Patents
Rubber composition, retreaded tire using the same, and method for producing the retreaded tire Download PDFInfo
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- JP7414879B2 JP7414879B2 JP2022064027A JP2022064027A JP7414879B2 JP 7414879 B2 JP7414879 B2 JP 7414879B2 JP 2022064027 A JP2022064027 A JP 2022064027A JP 2022064027 A JP2022064027 A JP 2022064027A JP 7414879 B2 JP7414879 B2 JP 7414879B2
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- rubber
- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims description 197
- 239000005060 rubber Substances 0.000 title claims description 197
- 239000000203 mixture Substances 0.000 title claims description 112
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 92
- 239000000194 fatty acid Substances 0.000 claims description 92
- 229930195729 fatty acid Natural products 0.000 claims description 92
- 150000004665 fatty acids Chemical class 0.000 claims description 91
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 87
- 239000011701 zinc Substances 0.000 claims description 45
- 229910052725 zinc Inorganic materials 0.000 claims description 45
- 235000014692 zinc oxide Nutrition 0.000 claims description 45
- 239000011787 zinc oxide Substances 0.000 claims description 45
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 29
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 17
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 16
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 15
- 244000043261 Hevea brasiliensis Species 0.000 claims description 14
- 229920003052 natural elastomer Polymers 0.000 claims description 14
- 229920001194 natural rubber Polymers 0.000 claims description 14
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 53
- 239000000377 silicon dioxide Substances 0.000 description 25
- 239000006229 carbon black Substances 0.000 description 24
- 235000019241 carbon black Nutrition 0.000 description 23
- 239000000945 filler Substances 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000003441 saturated fatty acids Nutrition 0.000 description 5
- -1 zinc fatty acid Chemical class 0.000 description 5
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 2
- 235000021322 Vaccenic acid Nutrition 0.000 description 2
- UWHZIFQPPBDJPM-FPLPWBNLSA-M Vaccenic acid Natural products CCCCCC\C=C/CCCCCCCCCC([O-])=O UWHZIFQPPBDJPM-FPLPWBNLSA-M 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UWHZIFQPPBDJPM-BQYQJAHWSA-N trans-vaccenic acid Chemical compound CCCCCC\C=C\CCCCCCCCCC(O)=O UWHZIFQPPBDJPM-BQYQJAHWSA-N 0.000 description 2
- 125000005314 unsaturated fatty acid group Chemical group 0.000 description 2
- 150000003751 zinc Chemical class 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
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-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
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/02—Replaceable treads
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C13/00—Tyre sidewalls; Protecting, decorating, marking, or the like, thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物及びそれを用いた更生タイヤ及びその更生タイヤの製造方法に関し、更に詳しくは、特定の凝集塊密度分布を有するゴム組成物及び前記ゴム組成物を用いたケースゴムを有する更生タイヤ及びその更生タイヤの製造方法に関する。 The present invention relates to a rubber composition, a retreaded tire using the same, and a method for manufacturing the retreaded tire, and more particularly, the present invention relates to a rubber composition having a specific aggregate density distribution and a case rubber using the rubber composition. The present invention relates to a retreaded tire and a method for manufacturing the retreaded tire.
経済性の観点のみならず、タイヤ製造における環境負荷低減の観点からも、更生タイヤの重要性が高まっている。
更生タイヤは、一次寿命が終了したタイヤのトレッド表面を決められた寸度に削ることにより製造した台タイヤに、新しいトレッドを再度固着、形成等することにより製造される。
空気入りタイヤにおいて更生タイヤを製造する場合、安全性を確保するためには、長期にわたって使用可能な耐久性の高い空気入りタイヤのケース部分が不可欠であり、その部材を形成するケースゴムに用いるゴム組成物には、高い耐亀裂進展性が求められる。
Retreaded tires are becoming increasingly important not only from the economic standpoint but also from the standpoint of reducing the environmental impact of tire manufacturing.
A retreaded tire is manufactured by reattaching or forming a new tread onto a base tire manufactured by scraping the tread surface of a tire whose primary life has ended to a predetermined size.
When manufacturing retreaded pneumatic tires, in order to ensure safety, it is essential to have a highly durable pneumatic tire case that can be used for a long time. The composition is required to have high crack growth resistance.
更生タイヤの耐久性を高める方法として、種々のものが知られているが、例えば、ジエン系ゴム１００重量部に対して、カーボンブラック２０～１００重量部と、変性液状ゴム５～２０重量部とを配合してなる更生タイヤ用クッションゴム組成物を用いることにより、オクルードラバーと称されるカーボンブラック凝集体中に取り込まれたゴム成分を減らし、更生タイヤの耐久性を向上することが知られている。（特許文献１） Various methods are known to improve the durability of retreaded tires. For example, 20 to 100 parts by weight of carbon black and 5 to 20 parts by weight of modified liquid rubber are added to 100 parts by weight of diene rubber. It is known that by using a cushion rubber composition for retreaded tires that contains occluded rubber, the rubber component incorporated into carbon black aggregates called occluded rubber can be reduced and the durability of retreaded tires can be improved. ing. (Patent Document 1)
しかし、特許文献１には、更生タイヤのゴム組成物中において凝集塊を減少させること、また、凝集塊自体が破壊核となり耐亀裂進展性を低下させることについては記載されず、更に、ケースゴムのゴム組成物の耐亀裂進展性を高めることによりタイヤの耐久性を高めることについても記載されていない。 However, Patent Document 1 does not mention that the agglomerates are reduced in the rubber composition of a retreaded tire, or that the agglomerates themselves become fracture nuclei and reduce crack propagation resistance. There is also no mention of increasing the durability of tires by increasing the crack growth resistance of the rubber composition.
本発明は、上記従来技術の課題及び現状に鑑み、これを解消しようとするものであり、特定の組成及び凝集塊密度を有するタイヤ用ゴム組成物を用いたケースゴムを有する更生タイヤとすることにより、ゴムの亀裂を生じる原因となり得る凝集塊をケースゴムを構成するゴム組成物中十分に減少させ、その結果、耐亀裂進展性の高いゴム組成物をケースゴムに用いた更生タイヤ、特に、ケースゴムが、航空機用を含む重荷重用更生タイヤに好適なものである更生タイヤを提供することを目的とする。 The present invention aims to solve the above-mentioned problems and current state of the prior art, and provides a retreaded tire having a case rubber using a tire rubber composition having a specific composition and agglomerate density. As a result, agglomerates that can cause rubber cracks are sufficiently reduced in the rubber composition constituting the case rubber, and as a result, a retreaded tire using a rubber composition with high crack propagation resistance as the case rubber, in particular, An object of the present invention is to provide a retreaded tire whose case rubber is suitable for retreaded tires for heavy loads including those for aircraft.
本発明者は、上記従来の課題等について、鋭意検討した結果、タイヤにおいて亀裂が発生及び進展する傾向が増大する要因のうちの一つは、タイヤ用ゴム組成物における凝集塊の発生であることを見出した。より具体的には、本発明者は、凝集塊が破壊核となり、凝集塊を起点として亀裂が生じ、加硫後のゴム組成物の耐亀裂進展性が低下することを見出した。
更に、本発明者は、ゴム組成物の耐破壊性等の特性を改良するため、酸化亜鉛（亜鉛華）に加え、脂肪酸または脂肪酸亜鉛あるいはそれらの両方を、ゴム組成物に配合しつつ、脂肪酸亜鉛等の凝集塊を抑制することにより、前記ゴム組成物の耐亀裂進展性をも向上させることが可能であることをも見出した。
そこで、本発明者は、ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下であり、ゴム１００重量部当たり２重量部以上１３重量部未満の脂肪酸亜鉛を含有するゴム組成物を用いたケースゴムを有することを特徴とする更生タイヤとすることにより、上記目的のゴム組成物及びそれを用いた空気入りタイヤが得られることを見出し、本発明を完成するに至ったのである。
As a result of intensive studies regarding the above-mentioned conventional problems, the present inventors have determined that one of the factors that increases the tendency for cracks to occur and propagate in tires is the generation of aggregates in rubber compositions for tires. I found out. More specifically, the present inventor found that the agglomerates serve as fracture nuclei, cracks occur starting from the agglomerates, and the crack propagation resistance of the rubber composition after vulcanization decreases.
Furthermore, in order to improve the characteristics such as fracture resistance of the rubber composition, the present inventors added fatty acids and/or fatty acid zinc to the rubber composition in addition to zinc oxide (zinc white). It has also been found that by suppressing agglomerates of zinc and the like, it is possible to improve the crack growth resistance of the rubber composition.
Therefore, the present inventor determined that, in measuring the cross section of a rubber composition using a disper grader in accordance with ASTM D7723, the integrated value of the white area with a particle size of 29 μm or more is 15% or less of the integrated value of the white area with a particle size of 3 to 57 μm. By providing a retreaded tire characterized by having a case rubber using a rubber composition containing 2 parts by weight or more and less than 13 parts by weight of fatty acid zinc per 100 parts by weight of rubber, a rubber composition for the above purpose can be obtained. They have discovered that a pneumatic tire can be obtained using the same, and have completed the present invention.
すなわち、本発明は、次の（１）～（１０）に存する。
（１） ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下であり、かつ、（Ｗｈｉｔｅ Ａｒｅａ％）×（粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値）／（粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値）の値が、０．２％以下であり、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物であって、
前記ゴム組成物のゴム成分は天然ゴム及び／又はスチレン－ブタジエン共重合体（ＳＢＲ）が５０重量部以上含有され、
前記ゴム組成物はゴム成分１００重量部に対して、酸化亜鉛を０．５～１０重量部含有し、
前記ゴム組成物はさらに脂肪酸を含有し、
前記脂肪酸は、脂肪酸成分の平均分子量が２３０以下となるもの、または、脂肪酸成分のうち不飽和脂肪酸によるものの含有量が３０％以上となるものであることを特徴とするゴム組成物。
（２） 前記脂肪酸の重量部数／前記酸化亜鉛の重量部数の比が０．１５～１．５である、上記（１）に記載のゴム組成物。
（３） 充填剤を含む、上記（１）に記載のゴム組成物。
（４） 充填剤としてカーボンブラックとシリカの両方を含み、充填剤の合計量に対するシリカの量が０％以上、３０％以下である、上記（３）に記載のゴム組成物。
（５） 上記（１）～（４）のうちいずれか１つに記載のゴム組成物を用いた更生タイヤ。
（６） 重荷重用タイヤである上記（５）に記載の更生タイヤ。
（７） 上記（１）に記載のゴム組成物を用いたケースゴムを有する台タイヤのみを選択的に用い、前記ケースゴムのゴム組成物中、ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下であるゴム組成物を用いたケースゴムを有する更生タイヤを製造することを特徴とする更生タイヤの製造方法。
（８） 更生タイヤが有するケースゴムを構成するゴム組成物が、酸化亜鉛を含むウェットマスターバッチを混合することにより製造されたゴム組成物である上記（７）に記載の更生タイヤの製造方法。
（９） 台タイヤを、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物を用いたケースゴムを有する使用済みタイヤを選択的に用いて製造する上記（７）に記載の更生タイヤの製造方法。
（１０） プレキュア方式もしくはリモールド方式で更生タイヤを製造する上記（７）～（９）のいずれか１つに記載の更生タイヤの製造方法。
That is, the present invention resides in the following (1) to (10).
(1) In the measurement of the cross section of the rubber composition using a disper grader in accordance with ASTM D7723, the integrated value of the white area with a particle size of 29 μm or more is 15% or less of the integrated value of the white area with a particle size of 3 to 57 μm, and , (White Area%) x (integrated value of white area with particle size of 29 μm or more) / (integrated value of white area with particle size of 3 to 57 μm) is 0.2% or less, and zinc oxide, fatty acid and fatty acid zinc A rubber composition having a total content of 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber,
The rubber component of the rubber composition contains 50 parts by weight or more of natural rubber and/or styrene-butadiene copolymer (SBR),
The rubber composition contains 0.5 to 10 parts by weight of zinc oxide per 100 parts by weight of the rubber component,
The rubber composition further contains a fatty acid,
The rubber composition is characterized in that the fatty acid has an average molecular weight of 230 or less, or has a content of unsaturated fatty acids of 30% or more in the fatty acid component.
(2) The rubber composition according to (1) above, wherein the ratio of parts by weight of the fatty acid/parts by weight of the zinc oxide is from 0.15 to 1.5.
(3) The rubber composition according to (1) above, containing a filler.
(4) The rubber composition according to (3) above, which contains both carbon black and silica as fillers, and the amount of silica relative to the total amount of fillers is 0% or more and 30% or less.
(5) A retreaded tire using the rubber composition according to any one of (1) to (4) above.
(6) The retreaded tire according to (5) above, which is a tire for heavy loads.
(7) Selectively using only a base tire having a case rubber using the rubber composition described in (1) above, a rubber composition formed by a disper grader in accordance with ASTM D7723 in the rubber composition of the case rubber. To produce a retreaded tire having a case rubber using a rubber composition in which the integrated value of the white area with a particle size of 29 μm or more is 15% or less of the integrated value of the white area with a particle size of 3 to 57 μm. Features: A manufacturing method for retreaded tires.
(8) The method for manufacturing a retreaded tire according to (7) above, wherein the rubber composition constituting the case rubber of the retreaded tire is a rubber composition manufactured by mixing a wet masterbatch containing zinc oxide.
(9) Select a used tire with a case rubber made of a rubber composition in which the total content of zinc oxide, fatty acid, and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber. The method for producing a retreaded tire according to (7) above, which is produced by using a retreaded tire.
(10) The method for producing a retreaded tire according to any one of (7) to (9) above, wherein the retreaded tire is produced by a precure method or a remold method.
本発明によれば、耐破壊性等の特性が良好であり、耐亀裂進展性の高いゴム組成物、および前記ゴム組成物を用いた更生タイヤ及びその製造方法が提供される。
本発明の耐亀裂進展性を高めた更生タイヤ及びその製造方法により、安全性の向上、省資源による環境負荷の低減及び経済性の向上を図ることができる。
本発明の更生タイヤは、脂肪酸亜鉛を含有することにより、耐破壊性等の特性の向上がなされていることに加え、更に耐亀裂進展性が高まることにより、本発明の更生タイヤ使用時の耐久性及び安全性の向上を図ることができる。
According to the present invention, a rubber composition having good characteristics such as fracture resistance and high crack propagation resistance, a retreaded tire using the rubber composition, and a method for manufacturing the same are provided.
By using the retreaded tire with improved crack propagation resistance and the method for manufacturing the same according to the present invention, it is possible to improve safety, reduce the environmental load by saving resources, and improve economic efficiency.
By containing fatty acid zinc, the retreaded tire of the present invention not only has improved properties such as fracture resistance, but also has improved crack propagation resistance, resulting in durability when using the retreaded tire of the present invention. It is possible to improve performance and safety.
以下に、本発明の実施形態を詳しく説明する。
本発明の実施形態に係るゴム組成物は、ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下であり、かつ、（Ｗｈｉｔｅ Ａｒｅａ％）×（粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値）／（粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値）の値が、０．２％以下であり、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であって、
前記ゴム組成物のゴム成分は天然ゴム及び／又はスチレン－ブタジエン共重合体（ＳＢＲ）が５０重量部以上含有され、
前記ゴム組成物はゴム成分１００重量部に対して、酸化亜鉛を０．５～１０重量部含有し、
前記ゴム組成物はさらに脂肪酸を含有し、前記脂肪酸は、脂肪酸成分の平均分子量が２３０以下となるもの、または、脂肪酸成分のうち不飽和脂肪酸によるものの含有量が３０％以上となるものであることを特徴とするゴム組成物である。
本発明の実施形態に係る更生タイヤは、前記ゴム組成物を用いたことを特徴とする更生タイヤである。
また、本発明の実施形態に係る更生タイヤの製造方法は、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物を用いたケースゴムを有する台タイヤのみを選択的に用い、前記ケースゴムのゴム組成物中、ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下であるゴム組成物を用いたケースゴムを有する更生タイヤを製造することを特徴とする更生タイヤの製造方法である。
本発明の実施形態に係るゴム組成物、前記ゴム組成物を用いた更生タイヤが高い耐亀裂進展性を有する理由としては、次のものが推察される。すなわち、脂肪酸、酸化亜鉛及び脂肪酸亜鉛を含有するゴム組成物には、比較的大きい粒径２９μｍ以上の脂肪酸亜鉛凝集塊が発生し得る。前記ゴム組成物中、凝集塊の発生を防ぎ、破壊核を十分に減少させたものとすることにより、耐亀裂進展性が顕著に向上するのである。
また、脂肪酸、酸化亜鉛及び脂肪酸亜鉛を含有するゴム組成物は、耐破壊性等の特性が良好であり、本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物は、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であることで、良好な耐破壊性等の特性を有し得る。
前記更生タイヤの製造方法とすることで、上述のとおりの更生タイヤが高い耐亀裂進展性を有する理由により、良好な耐破壊性等の特性を有する更生タイヤを製造することができる。
Embodiments of the present invention will be described in detail below.
In the rubber composition according to the embodiment of the present invention, in the measurement of the cross section of the rubber composition using a disper grader in accordance with ASTM D7723, the integrated value of the white area with a particle size of 29 μm or more is higher than the integrated value of the white area with a particle size of 3 to 57 μm. 15% or less of the value, and the value of (White Area%) x (integrated value of white area with particle size of 29 μm or more) / (integrated value of white area with particle size of 3 to 57 μm) is 0.2% or less. Yes, the total content of zinc oxide, fatty acids and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber,
The rubber component of the rubber composition contains 50 parts by weight or more of natural rubber and/or styrene-butadiene copolymer (SBR),
The rubber composition contains 0.5 to 10 parts by weight of zinc oxide per 100 parts by weight of the rubber component,
The rubber composition further contains a fatty acid, and the fatty acid is such that the average molecular weight of the fatty acid component is 230 or less, or that the content of unsaturated fatty acids in the fatty acid component is 30% or more. A rubber composition characterized by:
A retreaded tire according to an embodiment of the present invention is a retreaded tire characterized by using the rubber composition.
Further, the method for manufacturing a retreaded tire according to an embodiment of the present invention uses a rubber composition in which the total content of zinc oxide, fatty acid, and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber. Selectively using only a stand tire having case rubber, in the rubber composition of the case rubber, in the measurement of the cross section of the rubber composition with a disper grader in accordance with ASTM D7723, the integrated value of White area with a particle size of 29 μm or more was determined. , a retreaded tire manufacturing method is characterized in that a retreaded tire is manufactured having a case rubber using a rubber composition having a particle size of 3 to 57 μm and a white area integrated value of 15% or less.
The following is presumed to be the reason why the rubber composition according to the embodiment of the present invention and the retreaded tire using the rubber composition have high crack growth resistance. That is, in a rubber composition containing a fatty acid, zinc oxide, and fatty acid zinc, fatty acid zinc aggregates having a relatively large particle size of 29 μm or more may occur. By preventing the generation of agglomerates and sufficiently reducing the number of fracture nuclei in the rubber composition, crack propagation resistance can be significantly improved.
Furthermore, a rubber composition containing a fatty acid, zinc oxide, and a fatty acid zinc has good properties such as fracture resistance, and the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention has a zinc oxide When the total content of fatty acids and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber, it can have properties such as good fracture resistance.
By using the method for manufacturing a retreaded tire as described above, it is possible to manufacture a retreaded tire having characteristics such as good fracture resistance due to the reason that the retreaded tire has high crack propagation resistance as described above.
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物中に存在するゴム成分としては、空気入りタイヤ等のタイヤ用のものであれば特に限定されず、主鎖に二重結合があるもの（ジエン系ゴム）であれば、例えば、天然ゴム及び／又はジエン合成系ゴムが挙げられる。前記ゴム成分は、新品タイヤ製造時に必要に応じ加硫され、硫黄架橋などがなされている。
前記ゴム成分は、具体的には、天然ゴム（ＮＲ）、合成イソプレンゴム（ＩＲ）、スチレン－ブタジエン共重合体、ポリブタジエンゴム、イソプレンゴム、エチレン－プロピレン－ジエン共重合体、クロロプレンゴム、ハロゲン化ブチルゴム、アクリロニトリル－ブタジエンゴム等の少なくとも１種から製造されたゴム成分であり得る。
破壊強力の点から、前記ゴム成分１００重量部中に、適宜加硫された天然ゴム及び／又
はスチレン－ブタジエン共重合体（ＳＢＲ）が５０重量部以上含有されることが好ましく、８０重量部以上含有されることがより好ましい。
The rubber component present in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention is not particularly limited as long as it is used for tires such as pneumatic tires, and the rubber component may include double bonds in the main chain. Examples of such rubbers include natural rubber and/or diene synthetic rubber. The rubber component is vulcanized and cross-linked with sulfur, if necessary, when manufacturing a new tire.
Specifically, the rubber components include natural rubber (NR), synthetic isoprene rubber (IR), styrene-butadiene copolymer, polybutadiene rubber, isoprene rubber, ethylene-propylene-diene copolymer, chloroprene rubber, and halogenated rubber. The rubber component may be made from at least one of butyl rubber, acrylonitrile-butadiene rubber, and the like.
From the viewpoint of breaking strength, 100 parts by weight of the rubber component preferably contains 50 parts by weight or more of appropriately vulcanized natural rubber and/or styrene-butadiene copolymer (SBR), and 80 parts by weight or more. It is more preferable that it be contained.
〔凝集塊〕
本発明において、凝集塊とは、脂肪酸亜鉛凝集塊の他、カーボンブラック、シリカ等のフィラー、加硫剤、加硫促進剤等の他の添加剤が１種又は２種以上で凝集したものを含み、ゴム組成物中に、３μｍ以上の粒子径で存在する凝集塊を意味する。
[agglomerate]
In the present invention, the term "agglomerate" refers to an agglomerate of fatty acid zinc agglomerates and one or more other additives such as fillers such as carbon black and silica, vulcanizing agents, and vulcanization accelerators. It refers to aggregates present in the rubber composition with a particle size of 3 μm or more.
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物に含有される脂肪酸亜鉛は、新品タイヤ製造時に脂肪酸亜鉛として加えられたものであっても、酸化亜鉛等の亜鉛塩又は亜鉛化合物が脂肪酸と反応して脂肪酸亜鉛となったものでもよい。 Even if the fatty acid zinc contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention is added as a fatty acid zinc at the time of manufacturing a new tire, the fatty acid zinc may be a zinc salt such as zinc oxide or a zinc salt such as zinc oxide. The compound may react with a fatty acid to form fatty acid zinc.
〔酸化亜鉛〕
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物は、酸化亜鉛（亜鉛華）を含有してもよい。
酸化亜鉛の分散性の観点から、本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物は、新品タイヤ製造時の製造工程において、酸化亜鉛を含むマスターバッチとして加えられたものであっても良い。
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物に含有される酸化亜鉛（亜鉛華）は、加硫促進助剤として用いられたものであってもよい。
この酸化亜鉛が用いられた組成では、加硫促進の点から少なくともゴム成分１００重量部に対して、酸化亜鉛を０．５～１０重量部、好ましくは、１～８重量部更に好ましくは１．５～６重量部含有していることが望ましい。
前記ゴム組成物に含有される酸化亜鉛は、微粒径酸化亜鉛が好ましい。前記微粒径酸化亜鉛の比表面積は、２ｍ２／ｇ以上であり、好ましくは１０ｍ２／ｇ以上、より好ましくは、４０ｍ２／ｇ以上、更に好ましくは５０ｍ２／ｇ以上、より更に好ましくは、６０ｍ２／ｇ以上である。また、前記酸化亜鉛の比表面積は、好ましくは、１２０ｍ２／ｇ以下である。
本発明の実施形態において、更生タイヤのケースゴムを構成するゴム組成物は、比表面積５０ｍ２／ｇ以上の微粒径酸化亜鉛をゴム１００重量部当たり０．５重量部以上８重量部以下含有することが好ましく、２重量部以上８重量部以下含有することがより好ましい。
比表面積が大きく、微粒径の酸化亜鉛を用いることで、粒径の大きい凝集塊の発生を抑制することができる。
[Zinc oxide]
The rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention may contain zinc oxide (zinc white).
From the viewpoint of the dispersibility of zinc oxide, the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention is one that is added as a masterbatch containing zinc oxide in the manufacturing process when manufacturing a new tire. It's okay.
The zinc oxide (zinc white) contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention may be used as a vulcanization accelerator.
In the composition using this zinc oxide, from the viewpoint of accelerating vulcanization, the amount of zinc oxide is 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 1. It is desirable to contain 5 to 6 parts by weight.
The zinc oxide contained in the rubber composition preferably has a fine particle size. The specific surface area of the fine particle size zinc oxide is 2 m 2 /g or more, preferably 10 m 2 /g or more, more preferably 40 m 2 /g or more, still more preferably 50 m 2 /g or more, even more preferably , 60 m 2 /g or more. Further, the specific surface area of the zinc oxide is preferably 120 m 2 /g or less.
In an embodiment of the present invention, the rubber composition constituting the case rubber of the retreaded tire contains 0.5 parts by weight or more and 8 parts by weight or less of fine particle size zinc oxide with a specific surface area of 50 m 2 /g or more per 100 parts by weight of rubber. The content is preferably 2 parts by weight or more and 8 parts by weight or less.
By using zinc oxide having a large specific surface area and a fine particle size, it is possible to suppress the generation of agglomerates with a large particle size.
〔脂肪酸〕
本発明の実施形態において、脂肪酸は、単体で加えられる他、脂肪酸亜鉛の脂肪酸成分として加えられる。
本明細書中、脂肪酸成分とは、単体として存在する脂肪酸だけでなく、解離した脂肪酸又は亜鉛等金属イオンの対イオンとして存在する脂肪酸部分を含む。
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物に含有される脂肪酸としては、前記ゴム組成物中に含まれる脂肪酸成分（脂肪酸亜鉛となっている脂肪酸も含む）の平均分子量が２３０以下となるもの、または、脂肪酸成分のうち不飽和脂肪酸によるもの含有量が３０％以上となるものが挙げられる。
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物に含有される脂肪酸としては、本発明の効果を損なわないものであれば制限されないが、炭素数８以上の脂肪酸が好ましく、炭素数８～１８の直鎖脂肪酸がより好ましい。また、前記脂肪酸は、飽和脂肪酸であっても不飽和脂肪酸であっても良く、不飽和脂肪酸である場合には、不飽和脂肪酸中の二重結合が１個または２個であるものが好ましい。
前記脂肪酸は、例えば、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸などの飽和脂肪酸や、オレイン酸、リノール酸、バクセン酸などの不飽和脂肪酸の少なくとも１種（各単独又はこれらの２種以上の混合物）が挙げられる。
〔fatty acid〕
In an embodiment of the present invention, the fatty acid is added alone or as a fatty acid component of zinc fatty acid.
In this specification, the fatty acid component includes not only a fatty acid present as a simple substance but also a fatty acid moiety present as a dissociated fatty acid or a counter ion of a metal ion such as zinc.
The fatty acid contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention has an average molecular weight of the fatty acid component (including the fatty acid that is zinc fatty acid) contained in the rubber composition. 230 or less, or those in which the content of unsaturated fatty acids among the fatty acid components is 30% or more.
The fatty acid contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention is not limited as long as it does not impair the effects of the present invention, but fatty acids having 8 or more carbon atoms are preferred; Straight chain fatty acids having 8 to 18 carbon atoms are more preferred. Further, the fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and when it is an unsaturated fatty acid, it is preferable that the unsaturated fatty acid has one or two double bonds.
The fatty acid is, for example, at least one of saturated fatty acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, and myristic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and vaccenic acid (each alone or two of these). mixtures of more than one species).
〔脂肪酸亜鉛〕
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物に含有される脂肪酸亜鉛としては、本発明の効果を損なわないものであれば制限されないが、炭素数８以上の脂肪酸を脂肪酸成分とするものが好ましく、炭素数８～１８の直鎖脂肪酸を脂肪酸成分とするものがより好ましい。また、前記脂肪酸亜鉛における脂肪酸は、飽和脂肪酸であっても不飽和脂肪酸であっても良く、不飽和脂肪酸である場合には、不飽和脂肪酸中の二重結合が１個または２個であるものが好ましい。
前記脂肪酸亜鉛の脂肪酸成分となる脂肪酸として、具体的には、ミリスチリン酸（平均分子量２２８．３７）、オレイン酸（二重結合数１、平均分子量２８２．４６）、カプリル酸（平均分子量１４４．２１）、ペラルゴン酸（平均分子量１５８．２３）、カプリン酸（平均分子量１７２．２６）、ラウリン酸（平均分子量２００．３２）、リノール酸（二重結合数２、平均分子量２８０．４５）、バクセン酸（二重結合数１、平均分子量２８２．４６）等が挙げられる。
本発明において、本発明の実施形態に係る更生タイヤのケースゴム中に含まれる脂肪酸亜鉛中の脂肪酸成分の平均分子量が２３０以下であるか又は脂肪酸亜鉛の脂肪酸成分のうち、不飽和脂肪酸によるものの含有量が３０％以上であることが好ましいが、１）用いられている脂肪酸及び脂肪酸亜鉛中の脂肪酸成分の中で、飽和脂肪酸（及び飽和脂肪酸亜鉛）である場合は、飽和脂肪酸（脂肪酸亜鉛の形態で存在するものを含む）の平均分子量が２３０以下、例えばミリスチン酸、ラウリン酸、カプリン酸、カプリル酸等であること、２）不飽和脂肪酸（及び不飽和脂肪酸亜鉛）であることが好ましく、３）飽和脂肪酸（及び飽和脂肪酸亜鉛）と不飽和脂肪酸（及び不飽和脂肪酸亜鉛）を併存する場合には、分子量２３０以下の飽和脂肪酸と、不飽和結合含有の脂肪酸の合計が３０％以上となることが好ましい。
[Fatty acid zinc]
The fatty acid zinc contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention is not limited as long as it does not impair the effects of the present invention. Preferably, those containing a straight chain fatty acid having 8 to 18 carbon atoms as a fatty acid component are preferable. Further, the fatty acid in the fatty acid zinc may be a saturated fatty acid or an unsaturated fatty acid, and when it is an unsaturated fatty acid, the unsaturated fatty acid has one or two double bonds. is preferred.
Specifically, the fatty acids serving as fatty acid components of the fatty acid zinc include myristic acid (average molecular weight 228.37), oleic acid (number of double bonds 1, average molecular weight 282.46), and caprylic acid (average molecular weight 144.21). ), pelargonic acid (average molecular weight 158.23), capric acid (average molecular weight 172.26), lauric acid (average molecular weight 200.32), linoleic acid (number of double bonds 2, average molecular weight 280.45), vaccenic acid (number of double bonds: 1, average molecular weight: 282.46), etc.
In the present invention, the average molecular weight of the fatty acid component in the fatty acid zinc contained in the case rubber of the retreaded tire according to the embodiment of the present invention is 230 or less, or the fatty acid component of the fatty acid zinc contains unsaturated fatty acids. The amount is preferably 30% or more, but 1) If the fatty acids and fatty acid zinc used are saturated fatty acids (and saturated fatty acid zinc), the saturated fatty acids (in the form of fatty acid zinc) 2) unsaturated fatty acids (and unsaturated fatty acid zinc), preferably 3) unsaturated fatty acids (including those present in ) When saturated fatty acids (and saturated fatty acid zinc) and unsaturated fatty acids (and unsaturated fatty acid zinc) coexist, the total of saturated fatty acids with a molecular weight of 230 or less and fatty acids containing unsaturated bonds must be 30% or more. is preferred.
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物において、脂肪酸、酸化亜鉛及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であることが好ましく、より好ましくは４重量部以上１３重量部未満であり、更に好ましくは７重量部以上１３重量部未満である。
前記ゴム組成物において、この脂肪酸、酸化亜鉛及び脂肪酸亜鉛の合計含有量が１３重量部以上の含有量では、耐亀裂進展性、耐破壊性等の特性の向上が見られないものとなり、好ましくない。
In the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention, the total content of fatty acids, zinc oxide, and fatty acid zinc may be 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber. It is preferably 4 parts by weight or more and less than 13 parts by weight, and even more preferably 7 parts by weight or more and less than 13 parts by weight.
In the rubber composition, if the total content of the fatty acid, zinc oxide, and fatty acid zinc is 13 parts by weight or more, no improvement in properties such as crack growth resistance and fracture resistance is observed, which is undesirable. .
前記ゴム組成物において、上記ゴム成分、酸化亜鉛、脂肪酸及び／又は脂肪酸亜鉛の他に、タイヤトレッド用などのゴム組成物で通常使用される充填材が含有されていてもよく、例えば、カーボンブラック、シリカ等ケイ酸化合物系フィラー等の無機充填材を含有することができる。 In addition to the rubber components, zinc oxide, fatty acid and/or fatty acid zinc, the rubber composition may contain fillers commonly used in rubber compositions for tire treads, such as carbon black. , an inorganic filler such as a silicic acid compound filler such as silica.
〔充填剤〕
〔カーボンブラック〕
含有されるカーボンブラックとしては、特に制限はなく、従来ゴムの補強用充填材として慣用されているものの中から任意のものが選択して用いられていてもよい。カーボンブラックとしては、例えば、ＧＰＦ（Ｎ６６０）、ＦＥＦ（Ｎ５５０）、ＳＲＦ（Ｎ７７４）、ＨＡＦ（Ｎ３３０）、ＩＳＡＦ（Ｎ２２０）、ＩＳＡＦ－ＨＳ（Ｎ２３４）、ＳＡＦ（Ｎ１１０）等が挙げられる。好ましくは、窒素吸着比表面積（Ｎ２ＳＡ）が３０～１５０ｍ２／ｇ、かつジブチルフタレート（ＤＢＰ）吸油量が６０～１４０ｃｍ３／１００ｇのカーボンブラック（例えば、Ｎ２３４、Ｎ１１０、Ｎ２２０、Ｎ５５０、Ｎ３２６、Ｎ３３０）である。さらにより好ましくは、Ｎ５５０、Ｎ３２６、Ｎ３３０である。これら
のカーボンブラックが用いられていることにより、諸物性の改良効果は大きくなる。
これらのカーボンブラックの含有量は、発熱性、耐亀裂進展性の点から、ゴム成分１００重量部に対して、２０～６０重量部含有せしめることが望ましい。
〔filler〕
〔Carbon black〕
The carbon black to be contained is not particularly limited, and any carbon black that is conventionally used as a reinforcing filler for rubber may be selected and used. Examples of carbon black include GPF (N660), FEF (N550), SRF (N774), HAF (N330), ISAF (N220), ISAF-HS (N234), and SAF (N110). Preferably, carbon black (for example, N234 , N110, N220, N550, N326, N330 ). Even more preferred are N550, N326, and N330. By using these carbon blacks, the effect of improving various physical properties becomes greater.
The content of carbon black is preferably 20 to 60 parts by weight based on 100 parts by weight of the rubber component from the viewpoint of heat generation property and crack growth resistance.
〔シリカ及びシランカップリング剤〕
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物が含有することができるシリカ等ケイ酸化合物系フィラーにおいても特に制限はなく、例えば、湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、ケイ酸カルシウム、ケイ酸アルミニウム等が挙げられるが、中でも破壊特性が優れる湿式シリカが好ましい。また、上記カーボンブラックと併用されたものであってもよい。シリカは、ＣＴＡＢ（セチルトリメチルアンモニウムブロミド）比表面積が好ましくは５０ｍ２／ｇ以上、更に好ましくは９０ｍ２ｇ以上であり、また、好ましくは３５０ｍ２／ｇ以下、より好ましくは３００ｍ２／ｇ以下である。
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物が含有することができるシリカの量は、ゴム１００重量部当たり０重量部であっても良く、また、ゴム１００重量部当たり０重量部より多くても良く、例えば、５重量部以上であっても良い。前記シリカの量は、ゴム１００重量部当たり３０重量部以下であることが好ましく、より好ましくは２０重量部以下であり、さらに好ましくは１５重量部以下である。
充填剤の合計量に対するシリカの量は、特に制限はないが、好ましくは、１０％以上、より好ましくは１５％以上である。また、前記シリカの量は、好ましくは、３０％以下、より好ましくは、２５％以下である。
[Silica and silane coupling agent]
There are no particular limitations on the silicic acid compound filler such as silica that can be contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention. For example, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, etc. Among them, wet silica is preferred because of its excellent fracture properties. Further, it may be used in combination with the above carbon black. The silica has a CTAB (cetyltrimethylammonium bromide) specific surface area of preferably 50 m 2 /g or more, more preferably 90 m 2 / g or more, and preferably 350 m 2 /g or less, more preferably 300 m 2 /g or less. be.
The amount of silica that can be contained in the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention may be 0 parts by weight per 100 parts by weight of rubber, or per 100 parts by weight of rubber. The amount may be more than 0 parts by weight, for example, 5 parts by weight or more. The amount of silica is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less per 100 parts by weight of rubber.
The amount of silica relative to the total amount of fillers is not particularly limited, but is preferably 10% or more, more preferably 15% or more. Further, the amount of silica is preferably 30% or less, more preferably 25% or less.
充填材としてシリカが用いられた場合は、シランカップリング剤が用いられたものであってもよい。このシランカップリング剤としては、特に制限はなく、従来ゴム組成物に使用されている公知のもの、例えば、ビス（３－トリエトキシシリルプロピル）ポリスルフィド、γ－メルカプトプロピルトリエトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシランなどで有り得る。所望により用いられるシランカップリング剤の含有量は、シリカに対して、通常１～２０質量％の範囲で選定される。シランカップリング剤の量を上記範囲にすることによってカップリング剤としての効果が充分に発揮され、ゴム成分のゲル化を引き起こすことがない。カップリング剤としての効果及びゲル化防止などの点から、このシランカップリング剤の好ましい含有量は、シリカに対して５～１５質量％の範囲である。 When silica is used as the filler, a silane coupling agent may also be used. The silane coupling agent is not particularly limited, and includes known ones conventionally used in rubber compositions, such as bis(3-triethoxysilylpropyl) polysulfide, γ-mercaptopropyltriethoxysilane, γ-amino Examples include propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane. The content of the silane coupling agent used if desired is usually selected in the range of 1 to 20% by mass based on the silica. By setting the amount of the silane coupling agent within the above range, the effect as a coupling agent is fully exhibited and gelling of the rubber component is not caused. From the viewpoint of effectiveness as a coupling agent and prevention of gelation, the preferred content of this silane coupling agent is in the range of 5 to 15% by mass based on silica.
ゴム成分として天然ゴムを用いた場合には、作業性、発熱性の点から、上記カーボンブラック及び／又は上記シリカと、天然ゴムとのマスターバッチ、好ましくは、カーボンブラックと天然ゴムとのマスターバッチから構成されたものが用いられていることが好ましい。
天然ゴムマスターバッチとしては、乾式マスターバッチ及びウェットマスターバッチのいずれを用いたものであってもよい。
ここで、乾式マスターバッチとは、天然ゴムと、カーボンブラックとをバンバリーミキサー、インターナルミキサー、ロール等の混練機にて混練してマスターバッチとするものである。
また、ウェットマスターバッチとは、天然ゴムラテックスと、カーボンブラックとを混合してマスターバッチとするものであり、カーボンブラックを予め水中に分散させたスラリー溶液とした後に混合したものであることが好ましい。カーボンブラックの分散性をよくするためには、ローター・ステータータイプのハイシアーミキサー、高圧ホモジナイザー、超音波ホモジナイザー、コロイドミル等を用い、均一に混合したものであることが望ましい。
また、カーボンブラックの分散性を高めるためには、連続混練り機を用いてウェットマ
スターバッチを乾燥したものであることが好ましく、連続混練り機として２軸混練押出機を用いたものであることが更に好ましい。分散度をより向上させるためには、ウェットマスターバッチがより好ましい。
上記の天然ゴムカーボンブラックマスターバッチを用いたものであることにより、天然ゴムとジエン系などの合成ゴムとの併用の場合であっても、カーボンブラックが合成ゴムに偏在していることを防ぐことができるものとなる。
When natural rubber is used as the rubber component, from the viewpoint of workability and heat generation, a masterbatch of the above carbon black and/or the above silica and natural rubber, preferably a masterbatch of carbon black and natural rubber. It is preferable to use one composed of the following.
The natural rubber masterbatch may be either a dry masterbatch or a wet masterbatch.
Here, the dry masterbatch is a masterbatch obtained by kneading natural rubber and carbon black using a kneading machine such as a Banbury mixer, an internal mixer, or a roll.
In addition, a wet masterbatch is a masterbatch made by mixing natural rubber latex and carbon black, and it is preferable that carbon black is dispersed in water in advance to form a slurry solution and then mixed. . In order to improve the dispersibility of carbon black, it is desirable to mix it uniformly using a rotor-stator type high shear mixer, high pressure homogenizer, ultrasonic homogenizer, colloid mill, etc.
In addition, in order to improve the dispersibility of carbon black, it is preferable that the wet masterbatch be dried using a continuous kneader, and a twin-screw kneading extruder should be used as the continuous kneader. is even more preferable. In order to further improve the degree of dispersion, a wet masterbatch is more preferred.
By using the above natural rubber carbon black masterbatch, even when natural rubber and synthetic rubber such as diene type rubber are used together, carbon black can be prevented from being unevenly distributed in the synthetic rubber. become something that can be done.
更に、本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物には、上記ゴム成分、酸化亜鉛、脂肪酸及び／又は脂肪酸亜鉛、充填材、加硫剤となる硫黄の他、加硫促進剤（チアゾール系、スルフェンアミド系、ジチオ酸塩系）、老化防止剤、作業性改良剤等のゴム業界で通常使用される配合剤を本発明の効果を損なわない範囲で用いられたものであってもよい。 Furthermore, the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention contains, in addition to the above-mentioned rubber components, zinc oxide, fatty acid and/or fatty acid zinc, filler, and sulfur as a vulcanizing agent. Compounding agents commonly used in the rubber industry, such as sulfur accelerators (thiazole-based, sulfenamide-based, dithioate-based), anti-aging agents, and workability improvers, were used to the extent that they did not impair the effects of the present invention. It may be something.
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物では、粒径２９μｍ以上の脂肪酸亜鉛凝集塊密度が低いものとなり、ゴム強度の弱い部分及び破壊核が生じにくく、耐亀裂進展性を大幅に向上させることができる。 In the rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention, the density of fatty acid zinc agglomerates with a particle size of 29 μm or more is low, making it difficult to form parts with weak rubber strength and fracture nuclei, and preventing crack development. performance can be significantly improved.
本発明の実施形態に係る更生タイヤのケースゴムを構成するゴム組成物は、上記ゴム成分、酸化亜鉛、上記特性の脂肪酸及び／又は脂肪酸亜鉛、充填材、加硫剤、加硫促進剤、老化防止剤等を混練り、熱入れ、押出等することにより製造されたものであってよい。 The rubber composition constituting the case rubber of the retreaded tire according to the embodiment of the present invention includes the above rubber component, zinc oxide, fatty acid and/or fatty acid zinc having the above characteristics, filler, vulcanizing agent, vulcanization accelerator, aging It may be manufactured by kneading an inhibitor or the like, heating, extruding, or the like.
〔ケースゴム〕
本明細書中、ケースゴムとは、空気入りタイヤのサイドウォール部と、リムホイルに当接するビード部等、タイヤ内部のカーカス層等を保護する部分を構用いたるゴム部材をいう。
[Case rubber]
In this specification, the case rubber refers to a rubber member that covers the sidewall portion of a pneumatic tire, the bead portion that contacts the rim foil, and other portions that protect the carcass layer inside the tire.
〔更生タイヤ〕
本発明の実施形態に係る更生タイヤは、ＡＳＴＭ Ｄ７７２３に準拠した、ディスパーグレーダーによるゴム組成物の断面の測定において、粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値が、粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値の１５％以下、より好ましくは１２％以下、更に好ましくは１０％以下であり、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物を用いたケースゴムを有することを特徴とする更生タイヤである。
また、本発明の実施形態に係る更生タイヤは、上記ディスパーグレーダーによるゴム組成物の断面の測定において、（Ｗｈｉｔｅ Ａｒｅａ％）×（粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値）／（粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値）の値が、０．２％以下である、好ましくは０．１８％以下、より好ましくは０．１６５％以下である。
本発明の実施形態に係る更生タイヤは、例えば、トレッド部と、クラウン部と、タイヤ側面を構成するサイドウォール部と、リムホイルに当接するビード部とを有する。また、本発明の実施形態に係る更生タイヤは、例えば、ビードコアと、カーカス層とを有する。カーカス層のタイヤ径方向内側には、チューブに相当する気密性の高いゴム層であるインナーライナーが設けられている。
本発明の実施形態に係る更生タイヤは、台タイヤから、例えば、プレキュア方式、リ・モールド方式等の方法で製造される。
[Retreaded tires]
In the retreaded tire according to the embodiment of the present invention, in the measurement of the cross section of the rubber composition using a disper grader in accordance with ASTM D7723, the integrated value of the white area with a particle size of 29 μm or more is the integrated value of the white area with a particle size of 3 to 57 μm. 15% or less, more preferably 12% or less, still more preferably 10% or less, and the total content of zinc oxide, fatty acid and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber. A retreaded tire characterized by having a case rubber using a composition.
Further, in the retreaded tire according to the embodiment of the present invention, in the measurement of the cross section of the rubber composition using the disper grader, (White Area%) x (integrated value of white area with particle size of 29 μm or more) / (particle size of 3 to 57 μm) White area integrated value) is 0.2% or less, preferably 0.18% or less, more preferably 0.165% or less.
A retreaded tire according to an embodiment of the present invention includes, for example, a tread portion, a crown portion, a sidewall portion forming a side surface of the tire, and a bead portion that contacts a rim foil. Further, the retreaded tire according to the embodiment of the present invention includes, for example, a bead core and a carcass layer. An inner liner, which is a rubber layer with high airtightness and corresponds to a tube, is provided inside the carcass layer in the tire radial direction.
The retreaded tire according to the embodiment of the present invention is manufactured from a stand tire by, for example, a precure method, a re-molding method, or the like.
〔更生タイヤの製造方法〕
本発明の実施形態に係る更生タイヤは、例えばプレキュア方式である次の方法により製造される。
本発明は、脂肪酸又は脂肪酸亜鉛の凝集塊が溶解して凝集することを抑制すること、破
壊核の増加を抑えるものであり、プレキュア方式、リモールド方式の更生タイヤ製造方式に関わらず、効果を発揮する。
本発明の実施形態に係る更生タイヤの製造方法は、例えば、台タイヤを製造する工程と、台タイヤにあらかじめ加硫したトレッドパターンを固着して形成し、クッションゴムを介して接着すること等によりトレッドを形成する工程とを有する。
本発明の実施形態に係る更生タイヤを製造するために、脂肪酸、酸化亜鉛及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物を用いたケースゴムを有する台タイヤのみを選択的に用いて製造しても良い。
本発明の実施形態に係る更生タイヤの酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量を上記のものとすることにより、更生タイヤの耐破壊性等の特性を向上させるとともに、本発明の実施形態に係る更生タイヤのケースゴムの成分を上記値に近いものとすることができ、効率的に本発明の実施形態に係る更生タイヤを製造することができる。
更生タイヤが有するケースゴムを構成するゴム組成物を、酸化亜鉛を含むウェットマスターバッチを混合することにより製造されたゴム組成物としてもよい。このことにより、酸化亜鉛の分散性が高まり、酸化亜鉛の凝集を抑制することができる。
台タイヤを、酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であるゴム組成物を用いたケースゴムを有する使用済みタイヤを選択的に用いて製造してもよい。本発明の実施形態に係る更生タイヤを製造することに適した使用済みタイヤのみを選択的に用いることにより、本発明の実施形態に係る更生タイヤの製造を効率的に行うことができる。
[Manufacturing method for retreaded tires]
The retreaded tire according to the embodiment of the present invention is manufactured by the following method, which is, for example, a precure method.
The present invention suppresses the dissolution and agglomeration of agglomerates of fatty acids or fatty acid zinc, and suppresses the increase in fracture nuclei, and is effective regardless of whether the retread tire manufacturing method is a precure method or a remold method. do.
The method for manufacturing a retreaded tire according to an embodiment of the present invention includes, for example, a step of manufacturing a base tire, and forming a pre-vulcanized tread pattern on the base tire by adhering it with a cushion rubber. and forming a tread.
A case using a rubber composition in which the total content of fatty acid, zinc oxide, and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber, in order to manufacture a retreaded tire according to an embodiment of the present invention. It is also possible to manufacture the tire by selectively using only the base tire having rubber.
By setting the total content of zinc oxide, fatty acid, and fatty acid zinc in the retreaded tire according to the embodiment of the present invention to the above-mentioned values, characteristics such as fracture resistance of the retreaded tire can be improved, and The components of the case rubber of such a retreaded tire can be made close to the above values, and the retreaded tire according to the embodiment of the present invention can be efficiently manufactured.
The rubber composition constituting the case rubber of the retreaded tire may be a rubber composition manufactured by mixing a wet masterbatch containing zinc oxide. This increases the dispersibility of zinc oxide and suppresses aggregation of zinc oxide.
Selectively use a used tire having a case rubber made of a rubber composition in which the total content of zinc oxide, fatty acid, and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber. It may be manufactured by By selectively using only used tires suitable for manufacturing the retreaded tire according to the embodiment of the present invention, the retreaded tire according to the embodiment of the present invention can be efficiently manufactured.
回収した使用済みタイヤを更生可能か否か検査する工程と、使用済みタイヤからトレッド部を削り取る工程などが実行される。使用済みタイヤからトレッド部が削り取られた台タイヤに、加硫されたトレッドを固着し、形成することにより更生タイヤを作製する。 A process of inspecting whether the collected used tires can be retreaded, a process of scraping off the tread from the used tires, etc. are executed. A retreaded tire is produced by fixing and forming a vulcanized tread onto a base tire whose tread portion has been scraped off from a used tire.
最終検査工程において、加硫後の更生タイヤの傷などの不良の有無、耐圧性などが検査される。最終検査工程において、一定基準を満たした更生タイヤが製品になる。 In the final inspection process, the retreaded tire after vulcanization is inspected for defects such as scratches, pressure resistance, etc. In the final inspection process, retreaded tires that meet certain standards become products.
本発明の実施形態に係る台タイヤは、本発明の実施形態に係る台タイヤのケースゴムを構成するゴム組成物が上記規定した成分となるようゴム組成物を配合して通常の方法によって製造されたものであってもよい。
本発明の実施形態に係る台タイヤ及び更生タイヤは、重荷重用でも、更に好ましい適用としては、航空機用又はＯＲ（オフ・ザ・ロード）用として、クラウン部の厚みが２５ｍｍ以上となるものが特に好適である。
The stand tire according to the embodiment of the present invention is manufactured by a normal method by blending a rubber composition such that the rubber composition constituting the case rubber of the stand tire according to the embodiment of the present invention has the above-specified components. It may be something like that.
The stand tires and retreaded tires according to the embodiments of the present invention can be used for heavy loads, and more preferably for aircraft or OR (off-the-road) use, and those with a crown thickness of 25 mm or more are particularly suitable. suitable.
次に、実施例及び比較例により本発明を更に詳細に説明するが、本発明は下記実施例等に限定されるものではない。
また、脂肪酸亜鉛凝集塊の密度及び耐亀裂進展性は、次のように測定した。
＜凝集塊密度の測定・積算方法＞
加硫済みのゴム組成物を用い、ＡＳＴＭ Ｄ７７２３に準拠して凝集塊量、凝集塊粒径分布を評価した。
ディスパーグレーダーによるゴム組成物の断面の測定において、解像度以上の大きさの凝集塊が存在する部分は、凝集塊の大きさに応じた面積を有するＷｈｉｔｅ Ａｒｅａとして観測される。単位面積中、Ｗｈｉｔｅ Ａｒｅａの占める面積の百分率による割合を、Ｗｈｉｔｅ Ａｒｅａ％とする。
ディスパーグレーダーの解像度は、３μｍを選択した。
本明細書中、２９μｍ以上の凝集塊の占める面積とは、（Ｗｈｉｔｅ Ａｒｅａ％）×（粒径２９μｍ以上のＷｈｉｔｅ ａｒｅａ積算値）／（粒径３～５７μｍのＷｈｉｔｅ ａｒｅａ積算値）をいう。
Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
Further, the density and crack growth resistance of fatty acid zinc aggregates were measured as follows.
<Measurement and integration method of aggregate density>
Using the vulcanized rubber composition, the amount of agglomerates and the particle size distribution of agglomerates were evaluated in accordance with ASTM D7723.
When measuring the cross section of a rubber composition using a disper grader, a portion where an aggregate larger than the resolution exists is observed as a white area having an area corresponding to the size of the aggregate. The percentage of the area occupied by White Area in a unit area is defined as White Area%.
The resolution of the disper radar was selected to be 3 μm.
In this specification, the area occupied by aggregates of 29 μm or more refers to (White Area%)×(integrated value of white area with particle size of 29 μm or more)/(integrated value of white area with particle size of 3 to 57 μm).
＜耐亀裂進展性の評価＞
アメリカ合衆国のＦＡＡ（Ｆｅｄｅｒａｌ Ａｖｉａｔｉｏｎ Ａｄｍｉｎｉｓｔｒａｔｉｏｎ：連邦航空局）の“ＴＳＯ（Ｔｅｃｈｎｉｃａｌ Ｓｔａｎｄａｒｄ Ｏｒｄｅｒ）”のＴＳＯ－ｃ６２ｅに規定の動力計（Ｄｙｎａｍｏｍｅｔｅｒ）試験実施後、タイヤを裁断し、ベルトコード間の亀裂程度を確認した。
試験実施後のタイヤを６０°刻みで裁断し、断面６か所のベルトコード間亀裂の合計数を指標化した（値が小さいほど良好である）。
<Evaluation of crack growth resistance>
After conducting a dynamometer test as specified in TSO-c62e of the FAA (Federal Aviation Administration) "TSO (Technical Standard Order)" of the United States, the tire was cut and the extent of cracks between the belt cords was checked. did.
The tire after the test was cut into pieces at 60° intervals, and the total number of cracks between the belt cords at six locations in the cross section was used as an index (the smaller the value, the better).
〔実施例１～１0及び比較例１～８〕
下記表１に示す組成及び凝集塊密度分布を有するゴム組成物、及び前記ゴム組成物を用いたケースゴムを有する更生タイヤを製造し、それを用いて耐亀裂進展性の評価を行った。その結果を表１に示す。
実施例１～１0及び比較例１～８は、カーボンブラックを含むゴム組成物である。
実施例１～5は、シリカを含まないゴム組成物である。
実施例6～１0は、シリカを含むゴム組成物である。また、実施例１0は、更にシランカップリング剤を含むゴム組成物である。
比較例１～７は、シリカを含まないゴム組成物であり、比較例８は、シリカを含むゴム組成物である。
[Examples 1 to 10 and Comparative Examples 1 to 8]
A retreaded tire having a rubber composition having the composition and agglomerate density distribution shown in Table 1 below, and a case rubber using the rubber composition was manufactured, and the crack growth resistance was evaluated using the same. The results are shown in Table 1.
Examples 1 to 10 and Comparative Examples 1 to 8 are rubber compositions containing carbon black.
Examples 1-5 are silica-free rubber compositions.
Examples 6-10 are rubber compositions containing silica. Moreover, Example 10 is a rubber composition that further contains a silane coupling agent.
Comparative Examples 1 to 7 are rubber compositions that do not contain silica, and Comparative Example 8 is a rubber composition that contains silica.
＊１：カーボンブラック：旭カーボン社製、ＨＡＦ、Ｎ３３０
＊２：シリカ１：東ソーシリカ社製、ＮＩＰＳＩＬ ＫＱ
＊３：シリカ２：ＳＯＬＶＡＹ社製、Ｚｅｏｓｉｌ Ｐｒｅｍｉｕｍ ２００ＭＰ
＊４：シリカ３：東ソーシリカ社製、ＮＩＰＳＩＬ ＡＱ
＊５：シリカ４：Ｅｖｏｎｉｋ社製、Ｕｌｔｒａｓｉｌ ５５００ＧＲ
＊６：シランカップリング剤：信越化学工業社製、ビストリエトキシシリルプロピルポリスルフィド
＊７：老化防止剤：大内新興化学工業社製、ノクラック６Ｃ
＊８：加硫促進剤：大内新興化学工業社製、Ｎ－シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド（ノクセラーＣＺ）
*1: Carbon black: manufactured by Asahi Carbon Co., Ltd., HAF, N330
*2: Silica 1: Manufactured by Tosoh Silica Co., Ltd., NIPSIL KQ
*3: Silica 2: Zeosil Premium 200MP manufactured by SOLVAY
*4: Silica 3: Manufactured by Tosoh Silica Co., Ltd., NIPSIL AQ
*5: Silica 4: Made by Evonik, Ultrasil 5500GR
*6: Silane coupling agent: Shin-Etsu Chemical Co., Ltd., bistriethoxysilylpropyl polysulfide *7: Anti-aging agent: Ouchi Shinko Chemical Co., Ltd., Nocrack 6C
*8: Vulcanization accelerator: Ouchi Shinko Chemical Industry Co., Ltd., N-cyclohexyl-2-benzothiazolylsulfenamide (Noxela CZ)
耐亀裂進展性は、比較例６を１００として指標化した。
表１に示す通り、本発明の実施形態に係る更生タイヤを成すケースゴムの組成及び物性範囲内である実施例１～１0のケースゴムは、本発明の実施形態に係る更生タイヤを成すケースゴムの組成及び物性範囲外となる比較例１～８のケースゴムと比較して耐亀裂進展性が良好である。
実施例１～１0及び比較例１～８の結果より、本発明の実施形態に係るゴム組成物の耐亀裂進展性が向上していることが示された。
The crack growth resistance was indexed with Comparative Example 6 as 100.
As shown in Table 1, the case rubbers of Examples 1 to 10 whose compositions and physical properties are within the range of the case rubbers constituting the retreaded tires according to the embodiments of the present invention are the case rubbers constituting the retreaded tires according to the embodiments of the present invention. The crack growth resistance is better than that of the case rubbers of Comparative Examples 1 to 8, which are outside the composition and physical property range.
The results of Examples 1 to 10 and Comparative Examples 1 to 8 showed that the crack growth resistance of the rubber compositions according to the embodiments of the present invention was improved.
本発明では、耐亀裂進展性を有する更生タイヤ及びその製造方法が得られるので、特に航空機、トラック、バス、建設車両等の重荷重用空気入りタイヤにおける更生タイヤ及びその製造に好適に適用することができる。 The present invention provides a retreaded tire with crack propagation resistance and a method for manufacturing the same, so it can be applied particularly to retreaded tires for heavy-duty pneumatic tires such as aircraft, trucks, buses, construction vehicles, etc., and the manufacturing thereof. can.
Claims (3)
前記ゴム組成物のゴム成分は天然ゴム及び／又はスチレン－ブタジエン共重合体（ＳＢＲ）が５０重量部以上含有され、
前記ゴム組成物はゴム成分１００重量部に対して、酸化亜鉛を０．５～１０重量部含有し、
前記酸化亜鉛は、比表面積が１０ｍ ２ ／ｇ以上であって、
前記ゴム組成物は脂肪酸を含有し、
酸化亜鉛、脂肪酸及び脂肪酸亜鉛の合計含有量が、ゴム１００重量部当たり２重量部以上１３重量部未満であり、
前記脂肪酸は、炭素数８～１８の飽和脂肪酸であって、脂肪酸成分の平均分子量が２３０以下となるもの、または、炭素数８～１８の不飽和脂肪酸であって、不飽和脂肪酸中の二重結合が１個又は２個であるものであることを特徴とするゴム組成物を用いたケースゴムを有する台タイヤのみを選択的に用い、前記ゴム組成物を用いたケースゴムを有する更生タイヤを製造することを特徴とする更生タイヤの製造方法。 In measuring the cross section of the rubber composition using a disper grader in accordance with ASTM D7723, the integrated value of the white area with a particle size of 29 μm or more is 15% or less of the integrated value of the white area with a particle size of 3 to 57 μm, and (White A rubber composition in which the value of (Area%) x (integrated value of white area with a particle size of 29 μm or more) / (integrated value of white area with a particle size of 3 to 57 μm) is 0.2% or less,
The rubber component of the rubber composition contains 50 parts by weight or more of natural rubber and/or styrene-butadiene copolymer (SBR),
The rubber composition contains 0.5 to 10 parts by weight of zinc oxide per 100 parts by weight of the rubber component,
The zinc oxide has a specific surface area of 10 m 2 /g or more,
The rubber composition contains a fatty acid,
The total content of zinc oxide, fatty acids and fatty acid zinc is 2 parts by weight or more and less than 13 parts by weight per 100 parts by weight of rubber,
The fatty acid is a saturated fatty acid with a carbon number of 8 to 18 and the average molecular weight of the fatty acid component is 230 or less, or an unsaturated fatty acid with a carbon number of 8 to 18 and a double Selectively use only base tires having a case rubber made of a rubber composition characterized by one or two bonds , and retread tires having a case rubber made of the rubber composition. A method for manufacturing a retreaded tire.
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| JP2000219778A (en) | 1999-02-02 | 2000-08-08 | Yokohama Rubber Co Ltd:The | Tread rubber composition for heavy load tire or its retreaded tire |
| JP2003055505A (en) | 2001-08-20 | 2003-02-26 | Sumitomo Rubber Ind Ltd | Rubber composition and tire using the same |
| JP2010270266A (en) | 2009-05-25 | 2010-12-02 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
| WO2011096235A1 (en) | 2010-02-04 | 2011-08-11 | 株式会社ブリヂストン | Retreaded tire |
| JP2012031287A (en) | 2010-07-30 | 2012-02-16 | Toyo Tire & Rubber Co Ltd | Rubber composition and pneumatic tire |
| JP2013133190A (en) | 2011-12-26 | 2013-07-08 | Bridgestone Corp | Rubber composition for conveyor belt, and conveyor belt using the same |
| JP2013185012A (en) | 2012-03-06 | 2013-09-19 | Bridgestone Corp | Natural rubber, rubber composition, and tire |
| JP2014227532A (en) | 2013-05-27 | 2014-12-08 | 電気化学工業株式会社 | Chloroprene rubber composition, vulcanized molding, and vibration-proof rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022089897A (en) | 2022-06-16 |
| WO2018021538A1 (en) | 2018-02-01 |
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