JP2008184572A - Production method of modified hydrogenated natural rubber, modified hydrogenated natural rubber, rubber composition and pneumatic tire - Google Patents
Production method of modified hydrogenated natural rubber, modified hydrogenated natural rubber, rubber composition and pneumatic tire Download PDFInfo
- Publication number
- JP2008184572A JP2008184572A JP2007021080A JP2007021080A JP2008184572A JP 2008184572 A JP2008184572 A JP 2008184572A JP 2007021080 A JP2007021080 A JP 2007021080A JP 2007021080 A JP2007021080 A JP 2007021080A JP 2008184572 A JP2008184572 A JP 2008184572A
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- JP
- Japan
- Prior art keywords
- natural rubber
- group
- rubber
- modified hydrogenated
- hydrogenated natural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 244000043261 Hevea brasiliensis Species 0.000 title claims abstract description 109
- 229920003052 natural elastomer Polymers 0.000 title claims abstract description 109
- 229920001194 natural rubber Polymers 0.000 title claims abstract description 109
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- 239000005060 rubber Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 229920006173 natural rubber latex Polymers 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- 238000006011 modification reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005345 coagulation Methods 0.000 claims abstract description 6
- 230000015271 coagulation Effects 0.000 claims abstract description 6
- -1 hydrazo group Chemical group 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 239000012763 reinforcing filler Substances 0.000 claims description 12
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
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- 125000003277 amino group Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
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- 125000002560 nitrile group Chemical group 0.000 claims description 4
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
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- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
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- 230000006866 deterioration Effects 0.000 abstract description 18
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- 239000004816 latex Substances 0.000 description 22
- 235000019241 carbon black Nutrition 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 13
- 239000000945 filler Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 6
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229920003051 synthetic elastomer Polymers 0.000 description 4
- 239000005061 synthetic rubber Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
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- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
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- 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- CCDUZOUQCSPYMJ-UHFFFAOYSA-N methyl 3-(4-anilinophenyl)prop-2-enoate Chemical compound C1=CC(C=CC(=O)OC)=CC=C1NC1=CC=CC=C1 CCDUZOUQCSPYMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 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
- VCYXINNIEFYZGF-UHFFFAOYSA-N n-(1-phenylbuta-1,3-dienyl)aniline Chemical compound C=1C=CC=CC=1C(=CC=C)NC1=CC=CC=C1 VCYXINNIEFYZGF-UHFFFAOYSA-N 0.000 description 1
- GFSJJVJWCAMZEV-UHFFFAOYSA-N n-(4-anilinophenyl)-2-methylprop-2-enamide Chemical compound C1=CC(NC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 GFSJJVJWCAMZEV-UHFFFAOYSA-N 0.000 description 1
- HBTMDMMAFGLJKY-UHFFFAOYSA-N n-phenyl-4-(2-phenylethenyl)aniline Chemical compound C=1C=C(C=CC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 HBTMDMMAFGLJKY-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- RGVRXQRVWRZQRY-UHFFFAOYSA-N s-(carbamoyltrisulfanyl) carbamothioate Chemical compound NC(=O)SSSSC(N)=O RGVRXQRVWRZQRY-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、変性水添天然ゴムの製造方法、変性水添天然ゴム、ゴム組成物及びそれを用いた空気入りタイヤに関する。さらに詳しくは、本発明は、カーボンブラックまたはシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、耐劣化性、耐熱性、耐侯性等を向上させた変性水添天然ゴムの製造方法、変性水添天然ゴム、ゴム組成物及びそれを用いてなる空気入りタイヤに関するものである。 The present invention relates to a method for producing a modified hydrogenated natural rubber, a modified hydrogenated natural rubber, a rubber composition, and a pneumatic tire using the same. More specifically, the present invention is excellent in reinforcing property and affinity to carbon black or silica, improves low loss and wear resistance, and does not significantly deteriorate the high strength characteristic of natural rubber, and is resistant to deterioration. The present invention relates to a method for producing a modified hydrogenated natural rubber having improved heat resistance, weather resistance, etc., a modified hydrogenated natural rubber, a rubber composition, and a pneumatic tire using the same.
天然ゴムは、合成ゴムと比較して、優れた生ゴム強度（グリーンストレングス）を有し加工性に優れている上、加硫ゴムとしても機械的強度が高く、耐摩耗性に優れていることから、トラック／バス用タイヤ等の大型タイヤの全部材や、小型タイヤのケース部材に多く用いられている。
しかしながら、天然ゴムを含むゴム成分を用いたゴム組成物においては、天然ゴムの分子構造（不飽和結合等）に起因して、耐劣化性、耐熱性、耐侯性等が劣るという問題がある。このような問題に対処するために、例えばエチレン−プロピレン−ジエン三元共重合体（ＥＰＤＭ）のような不飽和結合が少ないポリマーをブレンドする手法が知られているが、この場合、該ポリマーは、天然ゴムとの相溶性が悪く、得られるゴム組成物の強度が低下するのを免れないという問題が生じる。
Natural rubber has superior raw rubber strength (green strength) and excellent processability compared to synthetic rubber, and also has high mechanical strength and excellent wear resistance as vulcanized rubber. It is often used for all members of large tires such as truck / bus tires and case members of small tires.
However, in a rubber composition using a rubber component containing natural rubber, there is a problem that deterioration resistance, heat resistance, weather resistance, etc. are inferior due to the molecular structure (unsaturated bond, etc.) of natural rubber. In order to cope with such a problem, a technique of blending a polymer having a low unsaturated bond such as ethylene-propylene-diene terpolymer (EPDM) is known. There is a problem that compatibility with natural rubber is poor and the strength of the resulting rubber composition is inevitably lowered.
このように、従来の技術では、天然ゴムの特徴である高強度を損なうことなく、耐劣化性、耐熱性、耐候性等を向上させることは困難であるのが実状であった。
一方、天然ゴムを水素添加する技術は、以前より知られているが、タイヤ用途として用いた例は、これまで知られていない。例えば部分水添ゴムに関しては、低発熱性、グリップ特性、耐久性等を改善する目的で、スチレン−ブタジエン共重合ゴム（ＳＢＲ）における、ブタジエン部の二重結合を部分水素添加してなるものを含むタイヤトレッド用ゴム組成物が開示されている（例えば、特許文献１及び２参照）。
本出願人は、天然ゴムの不飽和結合を部分的に水素添加した水添天然ゴムに関する技術を出願した（特願２００６−１０３２７４）。この水添天然ゴムは、従来の天然ゴムに比べ、分子鎖切断やゲル化が抑制されているため、耐劣化性、耐熱性及び耐候性が改善されている。
しかし、水素添加により天然ゴム主鎖の規則性は落ちるため、高水素添加率では天然ゴムの特性である伸長結晶性、強度（耐破壊性）は低下する懸念は残されている。
As described above, in the prior art, it is actually difficult to improve the deterioration resistance, heat resistance, weather resistance, etc. without impairing the high strength characteristic of natural rubber.
On the other hand, the technology of hydrogenating natural rubber has been known for some time, but no example used for tires has been known so far. For example, with regard to partially hydrogenated rubber, for the purpose of improving low heat build-up, grip characteristics, durability, etc., styrene-butadiene copolymer rubber (SBR) is obtained by partially hydrogenating the double bond of the butadiene part. A rubber composition for a tire tread is disclosed (see, for example, Patent Documents 1 and 2).
The present applicant has applied for a technology relating to hydrogenated natural rubber in which unsaturated bonds of natural rubber are partially hydrogenated (Japanese Patent Application No. 2006-103274). This hydrogenated natural rubber has improved degradation resistance, heat resistance and weather resistance since molecular chain scission and gelation are suppressed as compared with conventional natural rubber.
However, since the regularity of the main chain of the natural rubber is lowered by hydrogenation, there is a concern that the elongation crystallinity and strength (destructive resistance), which are the characteristics of the natural rubber, are lowered at a high hydrogenation rate.
また、年々タイヤに対する低燃費化の要求は高まってきている。カーボンブラックやシリカなどの充填剤に対してポリマーの補強性、親和性を向上させる技術として、合成ゴムでは末端変性、官能基含有モノマーの共重合などの技術が開発されている。
一方、天然ゴムは、その優れた物理特性を生かして多量に使用されており、天然ゴム自身の改良によって充填剤に対する補強性、親和性を改良する技術として、天然ゴム分子に極性基含有単量体をグラフト重合することによって、補強性充填材であるカーボンブラックやシリカとの相互作用を強め、充填材の分散性を向上させ、ゴム組成物の低ロス性、破壊特性を大幅に向上させることが開示されている（例えば、特許文献３参照）。
In addition, the demand for lower fuel consumption for tires is increasing year by year. Synthetic rubber has been developed with techniques such as terminal modification and copolymerization of functional group-containing monomers as techniques for improving the reinforcement and affinity of polymers with respect to fillers such as carbon black and silica.
Natural rubber, on the other hand, is used in large quantities taking advantage of its excellent physical properties. As a technology to improve the reinforcement and affinity for fillers by improving the natural rubber itself, the natural rubber molecule contains a polar group containing a single amount. By graft-polymerizing the body, the interaction with carbon black and silica, which are reinforcing fillers, is strengthened, the dispersibility of the filler is improved, and the low loss and fracture characteristics of the rubber composition are greatly improved. Is disclosed (for example, see Patent Document 3).
本発明は、このような状況下で、カーボンブラック及び／又はシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、耐劣化性、耐熱性、耐侯性等を向上させた変性水添天然ゴムの製造方法、変性水添天然ゴム、ゴム組成物及びそれを用いてなる空気入りタイヤを提供することを目的とするものである。 Under such circumstances, the present invention is excellent in reinforcing property and affinity to carbon black and / or silica, improves low loss and wear resistance, and greatly impairs the high strength characteristic of natural rubber. It is an object of the present invention to provide a method for producing a modified hydrogenated natural rubber having improved deterioration resistance, heat resistance, weather resistance, etc., a modified hydrogenated natural rubber, a rubber composition, and a pneumatic tire using the same. To do.
本発明者は、前記目的を達成するために鋭意研究を重ねた結果、天然ゴムに極性基をグラフトさせ、かつ天然ゴム中の不飽和結合を部分水添することにより、その目的を達成し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、
［１］ （１）天然ゴムラテックス中の天然ゴムに極性基含有単量体をグラフト重合する変性反応工程と、さらに（２）天然ゴム中の不飽和結合を部分的に水素化する水素添加反応工程と、（３）凝固、乾燥する工程よりなる変性水添天然ゴムの製造方法、
［２］ 前記極性基がアミノ基、イミノ基、ニトリル基、アンモニウム基、イミド基、アミド基、ヒドラゾ基、アゾ基、ジアゾ基、ヒドロキシル基、カルボキシル基、カルボニル基、エポキシ基、オキシカルボニル基、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、チオカルボニル基、含窒素複素環基および含酸素複素環基から選ばれる少なくとも一つである上記（１）の変性水添天然ゴムの製造方法、
［３］ 前記極性基含有単量体のグラフト量が天然ゴムラテックスのゴム分に対し、０．０１〜５．０質量％である上記（１）の変性水添天然ゴムの製造方法、
［４］ 変性水添天然ゴムが、不飽和結合の水素添加率５〜８０％のものである上記（1）の変性水添天然ゴムの製造方法、
［５］ 変性水添天然ゴムが、（ａ）酸素、空気及びヒドロペルオキシドの中から選ばれる少なくとも一種の酸化剤と、（ｂ）ヒドラジン及び／又はその水和物からなる還元剤と、（ｃ）金属イオン活性化剤との組合わせを用いて、天然ゴムを水素化してなるものである上記（１）〜（４）のいずれかの変性水添天然ゴムの製造方法、
［６］ （ａ）酸化剤が、過酸化水素である上記（５）の変性水添天然ゴムの製造方法、
［７］ （ｃ）金属イオン活性化剤が、銅、鉄、コバルト、鉛、ニッケル、銀、及び錫の中から選ばれる少なくとも一種の金属の塩である請求項５に記載の変性水添天然ゴムの製造方法、
［８］ 上記（１）〜（７）いずれかの製造方法で得られたことを特徴とする変性水添天然ゴム、
［９］ 上記（８）の変性水添天然ゴムを用いてなるゴム組成物、
［１０］ 変性水添天然ゴム３０質量％以上を含むゴム成分を含有する上記（９）のゴム組成物、
［１１］ ゴム成分１００質量部に対して、補強用充填材１０〜１２０質量部を含有する上記（９）又は（１０）のゴム組成物、
［１２］ 補強用充填材が、カーボンブラック及び／又はシリカである上記（１１）のゴム組成物、及び
［１３］ 上記（９）〜（１２）いずれかのゴム組成物を用いてなる空気入りタイヤ、
を提供するものである。
As a result of intensive studies to achieve the above object, the present inventor can achieve the object by grafting polar groups to natural rubber and partially hydrogenating unsaturated bonds in natural rubber. I found out. The present invention has been completed based on such findings.
That is, the present invention
[1] (1) Modification reaction step of graft polymerization of polar group-containing monomer to natural rubber in natural rubber latex, and (2) Hydrogenation reaction to partially hydrogenate unsaturated bonds in natural rubber And (3) a method for producing a modified hydrogenated natural rubber comprising the steps of coagulation and drying,
[2] The polar group is an amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, oxycarbonyl group, A process for producing a modified hydrogenated natural rubber according to the above (1), which is at least one selected from a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, a nitrogen-containing heterocyclic group and an oxygen-containing heterocyclic group;
[3] The method for producing a modified hydrogenated natural rubber according to (1), wherein the graft amount of the polar group-containing monomer is 0.01 to 5.0% by mass with respect to the rubber content of the natural rubber latex,
[4] The method for producing a modified hydrogenated natural rubber according to the above (1), wherein the modified hydrogenated natural rubber has an unsaturated bond hydrogenation rate of 5 to 80%,
[5] The modified hydrogenated natural rubber comprises (a) at least one oxidizing agent selected from oxygen, air and hydroperoxide, (b) a reducing agent comprising hydrazine and / or a hydrate thereof, and (c) ) A method for producing a modified hydrogenated natural rubber according to any one of the above (1) to (4), wherein the natural rubber is hydrogenated using a combination with a metal ion activator,
[6] (a) The method for producing a modified hydrogenated natural rubber according to (5), wherein the oxidizing agent is hydrogen peroxide,
[7] The modified hydrogenated natural product according to claim 5, wherein (c) the metal ion activator is a salt of at least one metal selected from copper, iron, cobalt, lead, nickel, silver, and tin. Rubber production method,
[8] A modified hydrogenated natural rubber obtained by the production method of any one of (1) to (7) above,
[9] A rubber composition using the modified hydrogenated natural rubber according to (8),
[10] The rubber composition according to (9), comprising a rubber component containing 30% by mass or more of a modified hydrogenated natural rubber,
[11] The rubber composition according to (9) or (10), containing 10 to 120 parts by mass of a reinforcing filler with respect to 100 parts by mass of the rubber component.
[12] The rubber composition according to the above (11), wherein the reinforcing filler is carbon black and / or silica, and [13] a pneumatic product using the rubber composition according to any one of (9) to (12) above. tire,
Is to provide.
本発明によれば、カーボンブラック及び／又はシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、耐劣化性、耐熱性、耐侯性等を向上させた変性水添天然ゴムの製造方法、変性水添天然ゴム、ゴム組成物及びそれを用いてなる空気入りタイヤを提供することができる。 According to the present invention, the carbon black and / or silica have excellent reinforcement and affinity, low loss and wear resistance are improved, and the high strength, which is characteristic of natural rubber, is not deteriorated so much. A method for producing a modified hydrogenated natural rubber with improved heat resistance, weather resistance, etc., a modified hydrogenated natural rubber, a rubber composition, and a pneumatic tire using the same can be provided.
以下に、本発明を詳細に説明する。
本発明の製造方法においては、（１）天然ゴムラテックス中の天然ゴムに極性基含有単量体をグラフト重合する変性反応工程（以下、変性反応工程と略記することがある）と、さらに（２）天然ゴム中の不飽和結合を部分的に水素化する水素添加反応工程（以下、水素添加反応工程と略記することがある）と、（３）凝固、乾燥する工程（以下、凝固、乾燥工程と略記することがある）によって変性水添天然ゴムが得られる。
The present invention is described in detail below.
In the production method of the present invention, (1) a modification reaction step in which a polar group-containing monomer is graft-polymerized to natural rubber in natural rubber latex (hereinafter sometimes abbreviated as a modification reaction step), and (2 ) Hydrogenation reaction step for partially hydrogenating unsaturated bonds in natural rubber (hereinafter sometimes abbreviated as hydrogenation reaction step); (3) Step for coagulation and drying (hereinafter referred to as coagulation and drying step) Modified hydrogenated natural rubber can be obtained.
本発明に用いる天然ゴムラテックスは通常のものであって、フィールドラテックス、アンモニア処理ラテックス、遠心分離濃縮ラテックス、界面活性剤や酵素で処理した脱蛋白ラテックスおよびこれらを組合せたもの等を挙げることができる。ラテックスの濃度は１〜７０質量％、より好ましくは１〜４０質量％である。 The natural rubber latex used in the present invention is ordinary, and examples thereof include field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant and an enzyme, and combinations thereof. . The concentration of the latex is 1 to 70% by mass, more preferably 1 to 40% by mass.
[（１）変性反応工程 ]
本発明における（１）変性反応工程は、天然ゴムラテックス中の天然ゴムに極性基含有単量体を添加し、さらに重合開始剤を加えた後、乳化重合によって、グラフトする。このように少量の極性基含有単量体を天然ゴムにグラフト重合（乳化重合）させているので、加工性を低下させることなく、天然ゴム本来の物理特性を維持しながら、充填剤との補強性、親和性を向上させることができる。また、この変性天然ゴムをカーボンブラックやシリカのような充填剤とともに配合してゴム組成物を形成すると、低ロス性、耐摩耗性等の物性を大幅に改良することができる。
[(1) Denaturation reaction step]
In the (1) modification reaction step in the present invention, a polar group-containing monomer is added to natural rubber in natural rubber latex, a polymerization initiator is further added, and then grafted by emulsion polymerization. In this way, a small amount of polar group-containing monomer is graft-polymerized (emulsion polymerization) onto natural rubber, so that it can be reinforced with fillers while maintaining the natural physical properties of natural rubber without reducing processability. And affinity can be improved. When this modified natural rubber is blended with a filler such as carbon black or silica to form a rubber composition, physical properties such as low loss and wear resistance can be greatly improved.
本発明に用いる極性基含有単量体としては、分子内に少なくとも一つの極性基を有する単量体であれば特に制限されない。極性基の具体例としては、アミノ基、イミノ基、ニトリル基、アンモニウム基、イミド基、アミド基、ヒドラゾ基、アゾ基、ジアゾ基、ヒドロキシル基、カルボキシル基、カルボニル基、エポキシ基、オキシカルボニル基、スルフィド基、ジスルフィド基、スルホニル基、スルフィニル基、チオカルボニル基、含窒素複素環基および含酸素複素環基を好適に挙げることができる。これら極性基を含有する単量体は、それぞれ単独で、あるいは２種またはそれ以上組み合わせて用いることができる。 The polar group-containing monomer used in the present invention is not particularly limited as long as it is a monomer having at least one polar group in the molecule. Specific examples of polar groups include amino groups, imino groups, nitrile groups, ammonium groups, imide groups, amide groups, hydrazo groups, azo groups, diazo groups, hydroxyl groups, carboxyl groups, carbonyl groups, epoxy groups, oxycarbonyl groups. Preferable examples include sulfide groups, disulfide groups, sulfonyl groups, sulfinyl groups, thiocarbonyl groups, nitrogen-containing heterocyclic groups, and oxygen-containing heterocyclic groups. These monomers containing polar groups can be used alone or in combination of two or more.
アミノ基含有単量体としては、１分子中に第１級、第２級および第３級アミノ基から選ばれる少なくとも１つのアミノ基を有する重合性単量体がある。その中でも、ジアルキルアミノアルキル（メタ）アクリレート等のような第３級アミノ基含有単量体が特に好ましい。これらアミノ基含有単量体は単独で、若しくは２種またはそれ以上を組合せて使用することができる。 As the amino group-containing monomer, there is a polymerizable monomer having at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among these, tertiary amino group-containing monomers such as dialkylaminoalkyl (meth) acrylates are particularly preferable. These amino group-containing monomers can be used alone or in combination of two or more.
第１級アミノ基含有単量体としては、アクリルアミド、メタクリルアミド、４−ビニルアニリン、アミノメチル（メタ）アクリレート、アミノエチル（メタ）アクリレート、アミノプロピル（メタ）アクリレート、アミノブチル（メタ）アクリレート等が挙げられる。 Examples of primary amino group-containing monomers include acrylamide, methacrylamide, 4-vinylaniline, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate, and the like. Is mentioned.
第２級アミノ基含有単量体としては、（１）アニリノスチレン、β−フェニル−ｐ−アニリノスチレン、β−シアノ−ｐ−アニリノスチレン、β−シアノ−β−メチル−ｐ−アニリノスチレン、β−クロロ−ｐ−アニリノスチレン、β−カルボキシ−ｐ−アニリノスチレン、β−メトキシカルボニル−ｐ−アニリノスチレン、β−（２−ヒドロキシエトキシ）カルボニル−ｐ−アニリノスチレン、β−ホルミル−ｐ−アニリノスチレン、β−ホルミル−β−メチル−ｐ−アニリノスチレン、α−カルボキシ−β−カルボキシ−β−フェニル−ｐ−アニリノスチレン等のようなアニリノスチレン類、（２）アニリノフェニルブタジエン、１−アニリノフェニル−１，３−ブタジエン、１−アニリノフェニル−３−メチル−１，３−ブタジエン、１−アニリノフェニル−３−クロロ−１，３−ブタジエン、３−アニリノフェニル−２−メチル−１，３−ブタジエン、１−アニリノフェニル−２−クロロ−１，３−ブタジエン、２−アニリノフェニル−１，３−ブタジエン、２−アニリノフェニル−３−メチル−１，３−ブタジエン、２−アニリノフェニル−３−クロロ−１，３−ブタジエン等のアニリノフェニルブタジエン類、（３）Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−（４−アニリノフェニル）メタクリルアミド等のＮ−モノ置換（メタ）アクリルアミド類等が挙げられる。 Secondary monomer-containing monomers include (1) anilinostyrene, β-phenyl-p-anilinostyrene, β-cyano-p-anilinostyrene, β-cyano-β-methyl-p-ani Linostyrene, β-chloro-p-anilinostyrene, β-carboxy-p-anilinostyrene, β-methoxycarbonyl-p-anilinostyrene, β- (2-hydroxyethoxy) carbonyl-p-anilinostyrene, anilinostyrenes such as β-formyl-p-anilinostyrene, β-formyl-β-methyl-p-anilinostyrene, α-carboxy-β-carboxy-β-phenyl-p-anilinostyrene, and the like; (2) Anilinophenyl butadiene, 1-anilinophenyl-1,3-butadiene, 1-anilinophenyl-3-methyl-1,3-butadiene, 1-anili Nophenyl-3-chloro-1,3-butadiene, 3-anilinophenyl-2-methyl-1,3-butadiene, 1-anilinophenyl-2-chloro-1,3-butadiene, 2-anilinophenyl- Anilinophenylbutadienes such as 1,3-butadiene, 2-anilinophenyl-3-methyl-1,3-butadiene, 2-anilinophenyl-3-chloro-1,3-butadiene, (3) N— Examples include N-monosubstituted (meth) acrylamides such as methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide and the like.
第３級アミノ基含有単量体としては、Ｎ，Ｎ−ジ置換アミノアルキルアクリレート、Ｎ，Ｎ−ジ置換アミノアルキルアクリルアミドおよびピリジル基を有するビニル化合物等が挙げられる。 Examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl acrylates, N, N-disubstituted aminoalkylacrylamides, and vinyl compounds having a pyridyl group.
Ｎ，Ｎ−ジ置換アミノアルキルアクリレートとしては、たとえばＮ，Ｎ−ジメチルアミノメチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノブチル（メタ）アクリレート、Ｎ−メチル−Ｎ−エチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジプロピルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジブチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジブチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジブチルアミノブチル（メタ）アクリレート、Ｎ，Ｎ−ジヘキシルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジオクチルアミノエチル（メタ）アクリレート、アクリロイルモルフォリン等のアクリル酸またはメタクリル酸のエステル等が挙げられる。特に、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジプロピルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジオクルアミノエチル（メタ）アクリレート、Ｎ―メチル―Ｎ−エチルアミノエチル（メタ）アクリレート等が好ましい。 Examples of the N, N-disubstituted aminoalkyl acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N , N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl-N- Ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dibutyl Aminobutyl (meth) acrylate DOO, N, N-dihexylaminoethyl (meth) acrylate, N, N-dioctyl aminoethyl (meth) acrylate, esters of acrylic acid or methacrylic acid such as acryloyl morpholine and the like. In particular, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-diocleaminoethyl (meth) acrylate N-methyl-N-ethylaminoethyl (meth) acrylate and the like are preferable.
Ｎ，Ｎ−ジ置換アミノアルキルアクリルアミドとしては、たとえばＮ，Ｎ−ジメチルアミノメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノブチル（メタ）アクリルアミド、Ｎ―メチル―Ｎ−エチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジプロピルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジブチルアミノブチル（メタ）アクリルアミド、Ｎ，Ｎ−ジヘキシルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ−ジヘキシルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジオクチルアミノプロピル（メタ）アクリルアミド等のアクリルアミド化合物またはメタクリルアミド化合物等が挙げられる。特に、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジオクチルアミノプロピル（メタ）アクリルアミド等が好ましい。 Examples of the N, N-disubstituted aminoalkylacrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N , N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N-methyl-N- Ethylaminoethyl (meth) acrylamide, N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylamino Acrylamide compounds or methacrylamide compounds such as butyl (meth) acrylamide, N, N-dihexylaminoethyl (meth) acrylamide, N, N-dihexylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide, etc. Is mentioned. In particular, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like are preferable.
また、アミノ基の代わりに含窒素複素環基であってもよい。含窒素複素環としては、たとえばピロール、ヒスチジン、イミダゾール、トリアゾリジン、トリアゾール、トリアジン、ピリジン、ピリミジン、ピラジン、インドール、キノリン、プリン、フェナジン、プテリジン、メラミン等が挙げられる。含窒素複素環は、他のヘテロ原子を環中に含んでいてもよい。 Moreover, a nitrogen-containing heterocyclic group may be sufficient instead of an amino group. Examples of the nitrogen-containing heterocycle include pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole, quinoline, purine, phenazine, pteridine, melamine and the like. The nitrogen-containing heterocycle may contain other heteroatoms in the ring.
ピリジル基を有するビニル化合物としては、たとえば２−ビニルピリジン、３−ビニルピリジン、４−ビニルピリジン、５−メチル−２−ビニルピリジン、５−エチル−２−ビニルピリジン等が挙げられる。特に、２−ビニルピリジン、４−ビニルピリジン等が好ましい。 Examples of the vinyl compound having a pyridyl group include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, and the like. In particular, 2-vinylpyridine, 4-vinylpyridine and the like are preferable.
ニトリル基含有単量体としては、（メタ）アクリロニトリル、シアン化ビニリデン等が挙げられる。これらは、単独または２種以上併用してもよい。 Examples of the nitrile group-containing monomer include (meth) acrylonitrile, vinylidene cyanide, and the like. These may be used alone or in combination of two or more.
ヒドロキシル基含有単量体としては、１分子中に少なくとも１つの第１級、第２級および第３級ヒドロキシル基を有する重合性単量体が挙げられる。かかる単量体としては、たとえばヒドロキシル基含有不飽和カルボン酸系単量体、ヒドロキシル基含有ビニルエーテル系単量体、ヒドロキシル基含有ビニルケトン系単量体等がある。このようなヒドロキシル基含有単量体の具体例としては、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、３−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；ポリエチレングリコール、ポリプロピレングリコール等のようなポリアルキレングリコール（アルキレングリコール単位数が、たとえば２−２３である）のモノ（メタ）アクリレート類；Ｎ−ヒドロキシメチル（メタ）アクリルアミド、Ｎ−（２−ヒドロキシエチル）（メタ）アクリルアミド、Ｎ，Ｎ−ビス（２−ヒドロキシメチル）（メタ）アクリルアミド等のヒドロキシル基含有不飽和アミド類；ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ｏ−ヒドロキシ―α―メチルスチレン、ｍ−ヒドロキシ―α―メチルスチレン、ｐ−ヒドロキシ―α―メチルスチレン、ｐ−ビニルベンジルアルコール等のヒドロキシル基含有ビニル芳香族化合物類；（メタ）アクリレート類がある。これらの中で、ヒドロキシル基含有不飽和カルボン酸系単量体、ヒドロキシアルキル（メタ）アクリレート類、ヒドロキシル基含有ビニル芳香族化合物が好ましく、特にヒドロキシル基含有不飽和カルボン酸系単量体が好ましい。ヒドロキシル基含有不飽和カルボン酸系単量体としては、たとえばアクリル酸、メタクリル酸、イタコン酸、フマル酸、マレイン酸等のエステル、アミド、無水物等の誘導体であり、特にアクリル酸、メタクリル酸等のエステル化合物が好ましい。 Examples of the hydroxyl group-containing monomer include polymerizable monomers having at least one primary, secondary, and tertiary hydroxyl group in one molecule. Examples of such monomers include hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyl group-containing vinyl ether monomers, and hydroxyl group-containing vinyl ketone monomers. Specific examples of such hydroxyl group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2- 23) mono (meth) acrylates; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxymethyl) (meth) acryl Hydroxyl group-containing unsaturated amides such as amides; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α- Examples include hydroxyl group-containing vinyl aromatic compounds such as methylstyrene and p-vinylbenzyl alcohol; (meth) acrylates. Among these, hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyalkyl (meth) acrylates, and hydroxyl group-containing vinyl aromatic compounds are preferable, and hydroxyl group-containing unsaturated carboxylic acid monomers are particularly preferable. Examples of the hydroxyl group-containing unsaturated carboxylic acid monomer include derivatives such as esters, amides, anhydrides and the like such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid, and particularly acrylic acid and methacrylic acid. The ester compound is preferred.
カルボキシル基含有単量体としては、（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、テトラコン酸、桂皮酸等の不飽和カルボン酸類；またはフタル酸、琥珀酸、アジピン酸等の非重合性多価カルボン酸と、（メタ）アリルアルコール、２−ヒドロキシエチル（メタ）アクリレート等の水酸基含有不飽和化合物とのモノエステルのような遊離カルボキシル基含有エステル類およびその塩等が挙げられる。これらの中で、不飽和カルボン酸類が特に好ましい。かかる単量体は単独で用いるか、または２種以上併用してもよい。 Carboxyl group-containing monomers include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, cinnamic acid and other unsaturated carboxylic acids; or phthalic acid, succinic acid, adipic acid and other non-polymerizable Examples thereof include free carboxyl group-containing esters such as monoesters of polyvalent carboxylic acids and hydroxyl-containing unsaturated compounds such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate, and salts thereof. Of these, unsaturated carboxylic acids are particularly preferred. Such monomers may be used alone or in combination of two or more.
エポキシ基含有単量体としては、（メタ）アリルグリシジルエーテル、グリシジル（メタ）アクリレート、３，４−オキシシクロヘキシル（メタ）アクリレート等があげられる。これら単量体は単独で用いるか、または２種以上併用してもよい。 Examples of the epoxy group-containing monomer include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, and the like. These monomers may be used alone or in combination of two or more.
グラフト重合用の開始剤としては、特に限定はなく種々の開始剤、たとえば乳化重合用の開始剤を用いることができ、その添加方法についても特に限定はない。一般に用いられる開始剤の例としては、過酸化ベンゾイル、過酸化水素、クメンヒドロパーオキサイド、ｔｅｒｔ−ブチルヒドロパーオキサイド、ジーｔｅｒｔ−ブチルパーオキサイド、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ヒドロクロライド、２，２−アゾビス（２−ジアミノプロパン）ジヒドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等が挙げられる。なお、重合温度を低減させるためには、レドックス系の重合開始剤を用いるのが好ましい。かかるレドックス系重合開始剤に用いる過酸化物と組合せる還元剤としては、たとえばテトラエチレンペンタミン、メルカプタン類、酸性亜硫酸ナトリウム、還元性金属イオン、アスコルビン酸等が挙げられる。特に、ｔｅｒｔ−ブチルヒドロパーオキサイドとテトラエチレンペンタミンとの組合せがレドックス系重合開始剤として好ましい。 The initiator for graft polymerization is not particularly limited, and various initiators such as an initiator for emulsion polymerization can be used, and the addition method is not particularly limited. Examples of commonly used initiators include benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 2,2-azobisisobutyronitrile, 2, 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2-diaminopropane) dihydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), potassium persulfate, sodium persulfate, Examples include ammonium sulfate. In order to reduce the polymerization temperature, it is preferable to use a redox polymerization initiator. Examples of the reducing agent used in combination with the peroxide used in the redox polymerization initiator include tetraethylenepentamine, mercaptans, acidic sodium sulfite, reducing metal ions, ascorbic acid and the like. In particular, a combination of tert-butyl hydroperoxide and tetraethylenepentamine is preferable as a redox polymerization initiator.
本発明で行うグラフト重合は、極性基含有単量体を天然ゴムラテックス中に添加し、所定の温度で撹拌しながら重合する一般的な乳化重合である。予め極性基含有単量体に水と乳化剤を加え、十分に乳化させたものを天然ゴムラテックス中に添加してもよいし、極性基含有単量体を直接天然ゴムラテックス中に添加し、必要に応じて単量体の添加前または添加後に乳化剤を添加してもよい。乳化剤としては、特に限定されず、ポリオキシエチレンラウリルエーテル等のようなノニオン系の界面活性剤が挙げられる。 The graft polymerization performed in the present invention is a general emulsion polymerization in which a polar group-containing monomer is added to natural rubber latex and polymerized while stirring at a predetermined temperature. Water and an emulsifier added to the polar group-containing monomer in advance and fully emulsified may be added to the natural rubber latex, or the polar group-containing monomer may be added directly to the natural rubber latex. Depending on the case, an emulsifier may be added before or after the addition of the monomer. The emulsifier is not particularly limited, and examples thereof include nonionic surfactants such as polyoxyethylene lauryl ether.
カーボンブラックやシリカと配合した時に加工性を低下させることなく、低ロス性、耐摩耗性を向上させることを考慮すると、天然ゴムの分子に対しまんべんなく少量の極性基を導入することが重要であるため、重合開始剤の添加量は極性基含有単量体１００モルに対し１〜１００モル％が好ましく、１０〜１００モル％がより好ましい。上述した各成分を反応容器に仕込み、０〜８０℃で１０分〜２４時間反応させてグラフト重合を行う。 It is important to introduce a small amount of polar groups evenly into the natural rubber molecules in consideration of improving low loss and wear resistance without reducing processability when blended with carbon black or silica. Therefore, the addition amount of the polymerization initiator is preferably 1 to 100 mol%, more preferably 10 to 100 mol% with respect to 100 mol of the polar group-containing monomer. The above-described components are charged into a reaction vessel and reacted at 0 to 80 ° C. for 10 minutes to 24 hours to perform graft polymerization.
本発明において、(１)変性反応工程における極性基含有単量体のグラフト量は、天然ゴムラテックスのゴム分に対し０．０１〜５．０質量％が好ましく、０．０１〜１．０質量％がより好ましい。極性基含有単量体のグラフト量を上記範囲にすることによって、ゴム組成物の低ロス性、耐摩耗性の改良効果が十分に得られ、粘弾性、応力−歪曲線等の天然ゴム本来の優れた物理特性を大きく変えることはない。 In the present invention, the graft amount of the polar group-containing monomer in the (1) modification reaction step is preferably 0.01 to 5.0% by mass, 0.01 to 1.0% by mass with respect to the rubber content of the natural rubber latex. % Is more preferable. By making the graft amount of the polar group-containing monomer within the above range, the rubber composition can be sufficiently improved in low loss and wear resistance, and inherent in natural rubber such as viscoelasticity and stress-strain curve. It does not significantly change the excellent physical properties.
[（２）水素添加反応工程 ]
本発明における（２）水素添加反応工程は、（１）変性反応工程同様にラテックス形態の天然ゴムを用いることが有利である。水素添加方法としては、天然ゴム中の不飽和結合を部分的に水素化し得る方法であればよく、特に制限されず、従来公知の方法の中から、任意の方法を適宣選択して用いることができる。この部分水素化法としては、例えば特開昭５９−１６１４１５号公報に記載されている方法を、好ましく採用することができる。
すなわち、（ａ）酸素、空気及びヒドロペルオキシドの中から選ばれる少なくとも一種の酸化剤と、（ｂ）ヒドラジン及び／又はその水和物からなる還元剤と、（ｃ）金属イオン活性化剤との組合わせを用いることにより、天然ゴム中の不飽和結合を、効率よく部分的に水素化することができる。この場合、天然ゴムは、ラテックス形態で用いることが有利である。
前記（ａ）成分の酸化剤において、ヒドロペルオキシドとしては、過酸化水素、クメンヒドロペルオキシド、ｔ−ブチルヒドロペルオキシド、ｐ−メンタンヒドロペルオキシド等が挙げられる。この（ａ）成分の酸化剤としては、部分水素化の性能、操作性等の観点から、過酸化水素が好適である。
[(2) Hydrogenation reaction process]
In the (2) hydrogenation reaction step in the present invention, it is advantageous to use natural rubber in the form of latex as in the (1) modification reaction step. The hydrogenation method is not particularly limited as long as it can partially hydrogenate unsaturated bonds in natural rubber, and any method selected from conventionally known methods can be appropriately selected and used. Can do. As this partial hydrogenation method, for example, the method described in JP-A-59-161415 can be preferably employed.
That is, (a) at least one oxidizing agent selected from oxygen, air and hydroperoxide, (b) a reducing agent comprising hydrazine and / or a hydrate thereof, and (c) a metal ion activator. By using the combination, the unsaturated bond in natural rubber can be efficiently partially hydrogenated. In this case, the natural rubber is advantageously used in latex form.
In the oxidizing agent of the component (a), examples of the hydroperoxide include hydrogen peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and p-menthane hydroperoxide. As the oxidizing agent for the component (a), hydrogen peroxide is preferable from the viewpoint of partial hydrogenation performance, operability, and the like.
前記（ｃ）成分の金属イオン活性化剤としては、例えば銅、鉄、コバルト、鉛、ニッケル、銀及び錫の中から選ばれる少なくとも一種の金属の塩等を用いることができるが、これらの中で、部分水素化の性能等の観点から硫酸銅が好適である。なお、（ａ）成分の酸化剤として、過酸化水素を使用する場合、この（ｃ）成分の金属イオン活性化剤は、用いなくともよい。
前記（ｂ）成分であるヒドラジンやその水和物の使用量は、天然ゴムの所望水素添加率によって異なるが、天然ゴム１モルに対して、通常０．２〜４．０モル、好ましくは０．５〜１．５モルの範囲である。また、（ｃ）成分の金属イオン活性化剤の使用量は、天然ゴムに対して、通常０．５〜５質量％程度であり、（ａ）成分の酸化剤の使用量は、所望する水素添加率に対応して適宜調整すればよい。
As the metal ion activator of the component (c), for example, a salt of at least one metal selected from copper, iron, cobalt, lead, nickel, silver and tin can be used. In view of the performance of partial hydrogenation and the like, copper sulfate is preferable. When hydrogen peroxide is used as the oxidizing agent for component (a), the metal ion activator for component (c) need not be used.
The amount of hydrazine or hydrate used as the component (b) varies depending on the desired hydrogenation rate of natural rubber, but is usually 0.2 to 4.0 mol, preferably 0, per 1 mol of natural rubber. The range is from 5 to 1.5 mol. In addition, the amount of the component (c) metal ion activator used is usually about 0.5 to 5% by mass relative to the natural rubber, and the amount of the component (a) oxidizing agent used is the desired hydrogen What is necessary is just to adjust suitably according to an addition rate.
本発明においては、天然ゴムの部分水素化反応は、例えば以下に示す方法により行うことができる。
天然ゴムラテックス中に、（ｂ）成分であるヒドラジンやその水和物の所定量を加え、反応液の温度を、通常２０℃以上、還流温度以下、好ましくは４０〜９０℃の温度に維持しながら、（ａ）成分である過酸化水素水の所定量を滴状で反応時間の間に添加し、反応を行う。反応時間は、反応温度によって左右され、一概に定めることはできないが、通常０．５〜１０時間程度である。
このように、天然ゴムの不飽和結合を水素添加することにより、様々な条件で不安定なイソプレン主鎖を安定化することができ、その結果として、分子鎖切断やゲル化が抑制され、耐劣化性、耐熱性、耐候性等が向上する。
本発明においては、水添天然ゴムの水素添加率は、天然ゴムの不飽和結合に対して、５〜８０％が好ましく、１０〜６０％がより好ましい。この水素添加率が５％以上であれば、本発明の効果が良好に発揮され、また８０％以下であれば、伸長結晶性の阻害による強度の低下を抑制することができると共に、二重結合の極端な減少による加硫挙動に対する悪影響を抑制することもできる。
なお、この水素添加率は、水素添加前後の天然ゴムのＮＭＲ（核磁気共鳴分光）を測定することにより、求めることができる。
In the present invention, the partial hydrogenation reaction of natural rubber can be performed, for example, by the following method.
A predetermined amount of hydrazine or its hydrate as component (b) is added to natural rubber latex, and the temperature of the reaction solution is usually maintained at a temperature of 20 ° C. or higher and a reflux temperature or lower, preferably 40 to 90 ° C. However, a predetermined amount of the hydrogen peroxide solution as the component (a) is added dropwise during the reaction time to carry out the reaction. The reaction time depends on the reaction temperature and cannot be determined in general, but is usually about 0.5 to 10 hours.
In this way, by hydrogenating unsaturated bonds of natural rubber, it is possible to stabilize the unstable isoprene main chain under various conditions, and as a result, molecular chain scission and gelation are suppressed, and resistance is improved. Degradability, heat resistance, weather resistance, etc. are improved.
In the present invention, the hydrogenation rate of the hydrogenated natural rubber is preferably 5 to 80% and more preferably 10 to 60% with respect to the unsaturated bond of the natural rubber. If the hydrogenation rate is 5% or more, the effect of the present invention is exhibited satisfactorily, and if it is 80% or less, a decrease in strength due to inhibition of elongation crystallinity can be suppressed, and a double bond It is also possible to suppress adverse effects on the vulcanization behavior due to an extreme decrease in the amount.
In addition, this hydrogenation rate can be calculated | required by measuring NMR (nuclear magnetic resonance spectroscopy) of the natural rubber before and after hydrogenation.
本発明の変性水添天然ゴムの製造方法においては、（１）変性反応工程及び（２）水素添加反応工程をラテックスの状態で別々に行なうことができ、どちらの工程を先に行なってもよい。
また、水素添加反応が終了後に極性基を導入する場合は、前記グラフトラジカル重合以外に下記の手法をとることができる。
水素添加された天然ゴムラテックスを蟻酸により凝固・洗浄・乾燥し、得られた固形ゴムを原料として、反応性極性基含有化合物をグラフト重合又は付加することができる。また、機械的せん断力をかけることにより反応性極性基含有単量体を導入することができる。固形状天然ゴムに機械的せん断力をかける手段としてはドライプリブレーカー、２軸混練押出し機等が挙げられる。
In the method for producing a modified hydrogenated natural rubber of the present invention, (1) the modification reaction step and (2) the hydrogenation reaction step can be performed separately in a latex state, and either step may be performed first. .
Moreover, when introducing a polar group after completion | finish of hydrogenation reaction, the following method can be taken besides the said graft radical polymerization.
The hydrogenated natural rubber latex can be coagulated, washed and dried with formic acid, and the resulting solid rubber can be used as a raw material to graft or add a reactive polar group-containing compound. Moreover, a reactive polar group containing monomer can be introduce | transduced by applying a mechanical shearing force. Examples of means for applying a mechanical shear force to the solid natural rubber include a dry prebreaker and a twin-screw kneading extruder.
[（３）凝固、乾燥工程 ]
上述のように（１）変性反応工程及び（２）水素添加反応工程を終えた変性水添天然ゴムを含むラテックスを常法、例えば蟻酸、硫酸などの酸や、塩化ナトリウムなどの塩の凝固剤を用いてラテックスを凝固させたのち、洗浄後、固形物を取り出し、真空乾燥機、エアドライヤー、ドラムドライヤー等の乾燥機、せん断による、連続混練機、好ましくは多軸混練押出機、より好ましくは二軸混練押出機を用いることで乾燥処理することにより、変性水添天然ゴムが得られる。
[(3) Solidification and drying process]
As described above, the latex containing the modified hydrogenated natural rubber after finishing the (1) modification reaction step and (2) hydrogenation reaction step is treated with a conventional method, for example, a coagulant of an acid such as formic acid or sulfuric acid, or a salt such as sodium chloride. After the latex is coagulated using a solid, the solid material is taken out and dried, such as a vacuum dryer, an air dryer, a drum dryer, a shearing continuous kneader, preferably a multi-screw kneading extruder, more preferably A modified hydrogenated natural rubber can be obtained by drying using a twin-screw kneading extruder.
本発明の変性水添天然ゴムは、タイヤ用途を始め、防振ゴム、ベルト、ホースその他の工業用品等の用途のゴム組成物として用いることができる。特にタイヤ用ゴムとして好適に使用され、例えばトレッドゴム、サイドゴム、プライコーティングゴム、ビードフイラーゴム、ベルトコーティングゴムなどあらゆるタイヤ部材に適用することができる。 The modified hydrogenated natural rubber of the present invention can be used as a rubber composition for applications such as anti-vibration rubbers, belts, hoses and other industrial articles as well as tire applications. In particular, it is suitably used as tire rubber, and can be applied to all tire members such as tread rubber, side rubber, ply coating rubber, bead filler rubber, and belt coating rubber.
本発明のゴム組成物においては、ゴム成分として、前記変性水添天然ゴムを３０質量％以上の割合で含むものを用いることが好ましい。この量が３０質量％以上では、カーボンブラック及び／又はシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、高強度を有し、かつ耐劣化性、耐熱性及び耐候性等に優れるゴム組成物を得ることができる。ゴム成分中の変性水添天然ゴムの含有量は、好ましくは５０質量％以上、より好ましくは７０〜１００質量％である。
また、当該変性水添天然ゴムと併用されるゴム成分としては未変性水添天然ゴム及びジエン系合成ゴムが挙げられジエン系合成ゴムとしては、例えばスチレン−ブタジエン共重合体（ＳＢＲ）、ポリブタジエン（ＢＲ）、ポリイソプレン（ＩＲ）、ブチルゴム（ＩＩＲ）、エチレン−プロピレン共重合体及びこれらの混合物等が挙げられる。また、その一部が変性剤により末端変性されたものであってもよい。
In the rubber composition of the present invention, it is preferable to use a rubber component containing the modified hydrogenated natural rubber in a proportion of 30% by mass or more. When this amount is 30% by mass or more, it has excellent reinforcing properties and affinity for carbon black and / or silica, and has improved low loss and wear resistance, without significantly impairing the high strength characteristic of natural rubber. A rubber composition having high strength and excellent in deterioration resistance, heat resistance, weather resistance and the like can be obtained. The content of the modified hydrogenated natural rubber in the rubber component is preferably 50% by mass or more, more preferably 70 to 100% by mass.
Examples of the rubber component used in combination with the modified hydrogenated natural rubber include unmodified hydrogenated natural rubber and diene synthetic rubber. Examples of the diene synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene ( BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, and mixtures thereof. Further, a part thereof may be terminal-modified with a modifier.
本発明のゴム組成物においては、前記ゴム成分１００質量部に対して、補強用充填材１０〜１２０質量部を含有させることができる。この補強用充填材の含有量が１０質量部以上であれば、補強性や他の物性の改良効果が良好に発揮され、一方１２０質量部以下であれば、加工性も良好である。当該補強用充填材の好ましい含有量は、補強性、他の物性及び加工性等を考慮すると、２０〜１００質量部の範囲である。
当該補強用充填材としては、従来、ゴム組成物において、補強用充填材として使用されている公知のものの中から、任意のものを適宜選択して用いることができるが、カーボンブラック及び／又はシリカが好適である。
前記カーボンブラックとしては、例えばＦＥＦ、ＧＰＦ、ＳＲＦ、ＨＡＦ、ＩＩＳＡＦ、ＩＳＡＦ、ＳＡＦ等が挙げられる。カーボンブラックの窒素吸着比表面積（Ｎ2ＳＡ、ＪＩＳ Ｋ ６２１７−２：２００１に準拠する）は２０〜１６０ｍ2／ｇであることが好ましく、７０〜１６０ｍ2／ｇであることがより好ましい。また、好ましくはジブチルフタレート吸油量（ＤＢＰ、ＪＩＳ Ｋ ６２１７−４：２００１に準拠する）が８０〜１７０ｃｍ3／１００ｇのカーボンブラックである。これらのカーボンブラックを用いることにより、諸物性の改良効果は大きくなる。好ましいカーボンブラックは、特に耐摩耗性に優れるＨＡＦ、ＩＩＳＡＦ、ＩＳＡＦ、ＳＡＦである。
In the rubber composition of this invention, 10-120 mass parts of reinforcing fillers can be contained with respect to 100 mass parts of the rubber component. If the content of the reinforcing filler is 10 parts by mass or more, the effect of improving the reinforcing property and other physical properties is exhibited well, while if it is 120 parts by mass or less, the workability is also good. The preferable content of the reinforcing filler is in the range of 20 to 100 parts by mass in consideration of reinforcing properties, other physical properties, workability, and the like.
As the reinforcing filler, any one of conventionally known fillers used as reinforcing fillers in rubber compositions can be appropriately selected and used. Carbon black and / or silica Is preferred.
Examples of the carbon black include FEF, GPF, SRF, HAF, IISAF, ISAF, and SAF. Nitrogen adsorption specific surface area of the carbon black (N 2 SA, JIS K 6217-2 : conforms to 2001) is preferably from 20~160m 2 / g, more preferably 70~160m 2 / g. Further, preferably dibutyl phthalate oil absorption: a (DBP, JIS K 6217-4 compliant to 2001) of carbon black 80~170cm 3 / 100g. By using these carbon blacks, the effect of improving various physical properties is increased. Preferred carbon blacks are HAF, IISAF, ISAF, and SAF, which are particularly excellent in wear resistance.
一方、シリカとしては、例えば湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）等が挙げられるが、中でも破壊特性の改良効果並びにウェットグリップ性の両立効果が最も顕著である湿式シリカが好ましい。そして、シリカの窒素吸着比表面積（Ｎ2ＳＡ、ＢＥＴ法による）は１００〜５００ｍ2／ｇであることが好ましい。好適な湿式シリカとしては、東ソー・シリカ（株）製のＡＱ、ＶＮ３、ＬＰ、ＮＡ等、デグッサ社製のウルトラジルＶＮ３（Ｎ2ＳＡ：２１０ｍ2／ｇ）等が挙げられる。 On the other hand, examples of the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), etc. Among them, wet silica is most preferable because it has the most remarkable effect of improving the fracture characteristics and the wet grip. . Then, the nitrogen adsorption specific surface area of the silica (N 2 SA, according to the BET method) is preferably 100 to 500 m 2 / g. Suitable wet silica includes AQ, VN3, LP, NA, etc. manufactured by Tosoh Silica Co., Ltd., Ultrazil VN3 (N 2 SA: 210 m 2 / g) manufactured by Degussa, and the like.
上述以外の無機充填材として、所望により、一般式（Ｉ）
ｎＭ・ｘＳｉＯy・ｚＨ2Ｏ ・・・（Ｉ）
［式中、Ｍは、アルミニウム、マグネシウム、チタン、カルシウム及びジルコニウムから選ばれる金属、これらの金属の酸化物又は水酸化物、それらの水和物、及び前記金属の炭酸塩の中から選ばれる少なくとも一種であり、ｎ、ｘ、ｙ及びｚは、それぞれ１〜５の整数、０〜１０の整数、２〜５の整数、及び０〜１０の整数である。］で表される無機充填材の中から選ばれる少なくとも一種の充填材を用いることができる。
一般式（Ｉ）で表される無機充填剤としては、例えば、γ−アルミナ、α−アルミナ等のアルミナ（Ａｌ2Ｏ3）、ベーマイト、ダイアスポア等のアルミナ一水和物（Ａｌ2Ｏ3・Ｈ2Ｏ）、ギブサイト、バイヤライト等の水酸化アルミニウム［Ａｌ（ＯＨ）3］、炭酸アルミニウム［Ａｌ2（ＣＯ3）2］、水酸化マグネシウム［Ｍｇ（ＯＨ）2］、酸化マグネシウム（ＭｇＯ）、炭酸マグネシウム（ＭｇＣＯ3）、タルク（３ＭｇＯ・４ＳｉＯ2・Ｈ2Ｏ）、アタパルジャイト（５ＭｇＯ・８ＳｉＯ2・９Ｈ2Ｏ）、チタン白（ＴｉＯ2）、チタン黒（ＴｉＯ2n-1）、酸化カルシウム（ＣａＯ）、水酸化カルシウム［Ｃａ（ＯＨ）2］、酸化アルミニウムマグネシウム（ＭｇＯ・Ａｌ2Ｏ3）、クレー（Ａｌ2Ｏ3・２ＳｉＯ2）、カオリン（Ａｌ2Ｏ3・２ＳｉＯ2・２Ｈ2Ｏ）、パイロフィライト（Ａｌ2Ｏ3・４ＳｉＯ2・Ｈ2Ｏ）、ベントナイト（Ａｌ2Ｏ3・４ＳｉＯ2・２Ｈ2Ｏ）、ケイ酸アルミニウム（Ａｌ2ＳｉＯ5 、Ａｌ4・３ＳｉＯ4・５Ｈ2Ｏ等）、ケイ酸マグネシウム（Ｍｇ2ＳｉＯ4、ＭｇＳｉＯ3等）、ケイ酸カルシウム（Ｃａ2・ＳｉＯ4等）、ケイ酸アルミニウムカルシウム（Ａｌ2Ｏ3・ＣａＯ・２ＳｉＯ2等）、ケイ酸マグネシウムカルシウム（ＣａＭｇＳｉＯ4）、炭酸カルシウム（ＣａＣＯ3）、酸化ジルコニウム（ＺｒＯ2）、水酸化ジルコニウム［ＺｒＯ（ＯＨ）2・ｎＨ2Ｏ］、炭酸ジルコニウム［Ｚｒ（ＣＯ3）2］、各種ゼオライトのように電荷を補正する水素、アルカリ金属又はアルカリ土類金属を含む結晶性アルミノケイ酸塩等が使用できる。また、上記一般式（Ｉ）中のＭがアルミニウム金属、アルミニウムの酸化物又は水酸化物、及びそれらの水和物、又はアルミニウムの炭酸塩から選ばれる無機充填材を含有してもよい。特に水酸化アルミニウムが好ましい。
As inorganic fillers other than those described above, if desired, the general formula (I)
nM · xSiO y · zH 2 O (I)
[Wherein M is at least selected from metals selected from aluminum, magnesium, titanium, calcium and zirconium, oxides or hydroxides of these metals, hydrates thereof, and carbonates of the metals. N, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. ] At least 1 type of filler chosen from the inorganic filler represented by this can be used.
Examples of the inorganic filler represented by the general formula (I) include alumina (Al 2 O 3 ) such as γ-alumina and α-alumina, and alumina monohydrate such as boehmite and diaspore (Al 2 O 3. H 2 O), gibbsite, aluminum hydroxide [Al (OH) 3] such as bayerite, aluminum carbonate [Al 2 (CO 3) 2 ], magnesium hydroxide [Mg (OH) 2], magnesium oxide (MgO) , magnesium carbonate (MgCO 3), talc (3MgO · 4SiO 2 · H 2 O), attapulgite (5MgO · 8SiO 2 · 9H 2 O), titanium white (TiO 2), titanium black (TiO 2n-1), calcium oxide (CaO), calcium hydroxide [Ca (OH) 2], magnesium aluminum oxide (MgO · Al 2 O 3) , clay (Al 2 O 3 · 2SiO 2 ), kaolin Al 2 O 3 · 2SiO 2 · 2H 2 O), pyrophyllite (Al 2 O 3 · 4SiO 2 · H 2 O), bentonite (Al 2 O 3 · 4SiO 2 · 2H 2 O), aluminum silicate (Al 2 SiO 5 , Al 4 · 3SiO 4 · 5H 2 O, etc.), magnesium silicate (Mg 2 SiO 4 , MgSiO 3 etc.), calcium silicate (Ca 2 · SiO 4 etc.), aluminum calcium silicate (Al 2 O 3 · CaO · 2SiO 2 etc.), magnesium calcium silicate (CaMgSiO 4 ), calcium carbonate (CaCO 3 ), zirconium oxide (ZrO 2 ), zirconium hydroxide [ZrO (OH) 2 · nH 2 O], zirconium carbonate [ Zr (CO 3) 2], hydrogen to correct electric charge as various zeolites, crystalline aluminosilicates such as containing alkali metal or alkaline earth metal is used It can be. Further, M in the general formula (I) may contain an inorganic filler selected from aluminum metal, aluminum oxide or hydroxide, and hydrates thereof, or aluminum carbonate. Aluminum hydroxide is particularly preferable.
本発明のゴム組成物においては、補強用充填材としてシリカを用いる場合、その補強性をさらに向上させる目的で、シランカップリング剤を配合することができる。このシランカップリング剤としては、例えばビス（３−トリエトキシシリルプロピル）テトラスルフィド、ビス（３−トリエトキシシリルプロピル）トリスルフィド、ビス（３−トリエトキシシリルプロピル）ジスルフィド、ビス（２−トリエトキシシリルエチル）テトラスルフィド、ビス（３−トリメトキシシリルプロピル）テトラスルフィド、ビス（２−トリメトキシシリルエチル）テトラスルフィド、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、２−メルカプトエチルトリメトキシシラン、２−メルカプトエチルトリエトキシシラン、３−トリメトキシシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、３−トリエトキシシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、２−トリエトキシシリルエチル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、３−トリメトキシシリルプロピルベンゾチアゾリルテトラスルフィド、３−トリエトキシシリルプロピルベンゾチアゾリルテトラスルフィド、３−トリエトキシシリルプロピルメタクリレートモノスルフィド、３−トリメトキシシリルプロピルメタクリレートモノスルフィド、ビス（３−ジエトキシメチルシリルプロピル）テトラスルフィド、３−メルカプトプロピルジメトキシメチルシラン、ジメトキシメチルシリルプロピル−Ｎ，Ｎ−ジメチルチオカルバモイルテトラスルフィド、ジメトキシメチルシリルプロピルベンゾチアゾリルテトラスルフィド等が挙げられるが、これらの中で補強性改善効果等の点から、ビス（３−トリエトキシシリルプロピル）テトラスルフィド及び３−トリメトキシシリルプロピルベンゾチアゾリルテトラスルフィドが好適である。これらのシランカップリング剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
このシランカップリング剤の配合量は、カップリング剤としての効果及びゴム成分のゲル化防止等の観点から、シリカに対して、１〜２０質量％が好ましく、５〜１５質量％がより好ましい。
In the rubber composition of the present invention, when silica is used as the reinforcing filler, a silane coupling agent can be blended for the purpose of further improving the reinforcing property. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Silylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthioca Vamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3- Triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthio Examples include carbamoyl tetrasulfide and dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. 3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide are preferable. These silane coupling agents may be used singly or in combination of two or more.
The blending amount of the silane coupling agent is preferably 1 to 20% by mass and more preferably 5 to 15% by mass with respect to silica from the viewpoint of the effect as a coupling agent and the prevention of gelation of the rubber component.
本発明のゴム組成物には、本発明の目的が損なわれない範囲で、所望により、通常ゴム工業界で用いられる各種薬品、例えば加硫剤、加硫促進剤、プロセス油、老化防止剤、スコーチ防止剤、亜鉛華、ステアリン酸等を含有させることができる。
上記加硫剤としては、硫黄等が挙げられ、その使用量は、ゴム成分１００質量部に対し、硫黄分として０．１〜１０．０質量部が好ましく、０．５〜５．０質量部がより好ましい。
In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, vulcanizing agents, vulcanization accelerators, process oils, anti-aging agents, as long as the object of the present invention is not impaired. A scorch inhibitor, zinc white, stearic acid and the like can be contained.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of rubber components, 0.5-5.0 mass parts is preferable. Is more preferable.
本発明で使用できる加硫促進剤は、特に限定されるものではないが、例えば、Ｍ（２−メルカプトベンゾチアゾール）、ＤＭ（ジベンゾチアジルジスルフィド）、ＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド）等のチアゾール系、あるいはＤＰＧ（ジフェニルグアニジン）等のグアジニン系の加硫促進剤等を挙げることができ、その使用量は、ゴム成分１００質量部に対し、０．１〜５．０質量部が好ましく、さらに好ましくは０．２〜３．０質量部である。 The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine-based vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.
また、本発明のゴム組成物で使用できるプロセス油としては、例えばパラフィン系、ナフテン系、アロマチック系等を挙げることができる。引張強度、耐摩耗性を重視する用途にはアロマチック系が、ヒステリシスロス、低温特性を重視する用途にはナフテン系又はパラフィン系が用いられる。その使用量は、ゴム成分１００質量部に対して、０〜１００質量部が好ましく、１００質量部以下であれば加硫ゴムの引張強度、低発熱性が良好となる。 Examples of the process oil that can be used in the rubber composition of the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount of use is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component.
本発明のゴム組成物は、前述のように、極性基により変性し、さらに不飽和結合を部分的に水素化してなる変性水添天然ゴムを含むゴム成分を用いることにより、カーボンブラック及び／又はシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、耐劣化性、耐熱性、耐候性等を向上させることができ、例えばトラック／バス用タイヤ等の大型タイヤの全部材や、小型タイヤのケース部材等として用いられる。 As described above, the rubber composition of the present invention is modified with a polar group, and further, by using a rubber component containing a modified hydrogenated natural rubber obtained by partially hydrogenating an unsaturated bond, carbon black and / or Excellent reinforcement and affinity for silica, improved low loss and wear resistance, and improved deterioration resistance, heat resistance, weather resistance, etc. without significantly damaging the high strength characteristic of natural rubber. For example, it can be used as all members of large tires such as truck / bus tires and case members of small tires.
本発明のゴム組成物は、バンバリーミキサー、ロール、インターナルミキサー等の混練り機を用いて混練りすることによって得られ、成形加工後、加硫を行い、タイヤ用途として、例えばタイヤトレッド、アンダートレッド、サイドウォール、カーカスコーティングゴム、ベルトコーティングゴム、ビードフィラー、チェーファー、ビードコーティングゴム等に用いることができる。
本発明の空気入りタイヤは、前述の本発明のゴム組成物を用いて通常の方法によって製造される。すなわち、必要に応じて、上記のように各種薬品を含有させた本発明のゴム組成物が未加硫の段階で各部材に加工され、タイヤ成形機上で通常の方法により貼り付け成形され、生タイヤが成形される。この生タイヤを加硫機中で加熱加圧して、タイヤが得られる。
このようにして得られた本発明の空気入りタイヤは、シリカ及び／又はカーボンブラックなどの補強性充填剤に対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、優れた耐劣化性、耐熱性、耐候性等を有している。
The rubber composition of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, roll, internal mixer, etc., and after molding and vulcanizing, for tire use, for example, tire tread, under It can be used for tread, sidewall, carcass coating rubber, belt coating rubber, bead filler, chafer, bead coating rubber and the like.
The pneumatic tire of the present invention is produced by a usual method using the above-described rubber composition of the present invention. That is, if necessary, the rubber composition of the present invention containing various chemicals as described above is processed into each member at an unvulcanized stage, and is pasted and molded by a normal method on a tire molding machine, A green tire is formed. The green tire is heated and pressed in a vulcanizer to obtain a tire.
The pneumatic tire of the present invention thus obtained has excellent reinforcing properties and affinity for reinforcing fillers such as silica and / or carbon black, and has improved low loss and wear resistance. It has deterioration resistance, heat resistance, weather resistance, etc.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例で得られたゴム組成物の加硫ゴム物性は、下記の方法に従って測定した。
（１）初期破壊特性
ＪＩＳ Ｋ ６２５１：２００４に準拠し、加硫ゴムのダンベル状３号形試験片を用いて引張り試験を行い、切断時引張応力（ＴＳｂ）を測定し、この数値を比較例１のデータを１００として指数表示した。指数値が大きいほど切断時引張応力が高く、初期破壊特性が良好である。評価結果を第３表及び第４表に示す。
（２）耐熱劣化試験
加硫ゴム試験片を、空気の存在下、１００℃で４８時間保持して、耐熱劣化試験を行ったのち、ＪＩＳ Ｋ ６２５１：２００４に準拠し、ダンベル状３号形試験片を用いて引張り試験を行い、切断時伸び（Ｅｂ−２）を測定した。また、耐熱劣化試験前の試験片についても、同様にして切断時伸び（Ｅｂ−１）を測定し、下記の式により、耐熱劣化試験後のＥｂ保持率を求めた。評価結果を第３表及び第４表に示す。
Ｅｂ保持率（％）＝［（Ｅｂ−２）／（Ｅｂ−１）］×１００
（３）ｔａｎδ
粘弾性測定装置（レオメトリックス社製）を使用し、温度５０℃、歪み５％、周波数１５Ｈｚでｔａｎδを測定した。この値が小さいほど、低ロスである。評価結果を第３表及び第４表に示す。
（４）耐摩耗性
ランボーン型摩耗試験機を用い、室温におけるスリップ率６０％の摩耗量を測定し、比較例１の耐摩耗性を１００として指数表示した。数値が高いほど、耐摩耗性が良好である。評価結果を第３表及び第４表に示す。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In addition, the vulcanized rubber physical property of the rubber composition obtained in each example was measured according to the following method.
(1) Initial fracture characteristics In accordance with JIS K 6251: 2004, a tensile test was performed using a dumbbell-shaped No. 3 test piece of vulcanized rubber, and the tensile stress (TSb) at cutting was measured. The data of 1 is shown as an index with 100 as the index. The larger the index value, the higher the tensile stress at cutting and the better the initial fracture characteristics. The evaluation results are shown in Tables 3 and 4.
(2) Heat-resistant deterioration test After holding the vulcanized rubber test piece at 100 ° C for 48 hours in the presence of air and conducting a heat-resistant deterioration test, the dumbbell-shaped No. 3 test was conducted in accordance with JIS K 6251: 2004. A tensile test was performed using the piece, and the elongation at break (Eb-2) was measured. Further, the elongation at break (Eb-1) was measured in the same manner for the test piece before the heat deterioration test, and the Eb retention after the heat deterioration test was obtained by the following formula. The evaluation results are shown in Tables 3 and 4.
Eb retention (%) = [(Eb-2) / (Eb-1)] × 100
(3) tan δ
Using a viscoelasticity measuring device (Rheometrics), tan δ was measured at a temperature of 50 ° C., a strain of 5%, and a frequency of 15 Hz. The smaller this value, the lower the loss. The evaluation results are shown in Tables 3 and 4.
(4) Abrasion resistance Using a Ramborn type abrasion tester, the amount of wear at a slip rate of 60% at room temperature was measured, and the abrasion resistance of Comparative Example 1 was shown as an index. The higher the value, the better the wear resistance. The evaluation results are shown in Tables 3 and 4.
製造例１
（１）変性反応工程
フィールドラテックスをラテックスセパレーター（斎藤遠心工業製）を用いて回転数７５００ｒｐｍで遠心分離して乾燥ゴム濃度６０％の濃縮ラテックスを得た。この濃縮ラテックス５００ｇを、撹拌機、温調ジャケットを備えた上部開放のガラス反応容器に投入し、予め２０ｍｌの水と６０ｍｇの乳化剤「エマルゲン１１０８」（花王株式会社製）をＮ，Ｎ−ジエチルアミノエチルメタクリレート３．０ｇに加えて乳化したものを上記反応容器に添加し窒素置換しながら３０分間攪拌した。次いで、重合開始剤としてtert−ブチルヒドロパーオキサイド１．０ｇとテトラエチレンペンタミン１．０ｇとを添加し、４０℃で２時間反応させることにより、変性天然ゴムラテックスを得た。
（２）水素添加反応工程
上記変性天然ゴムラテックスに０．１ＦのＣｕＳＯ4開始剤および７５０ｇのヒドラジン水和物を加えた。この反応混合物中に空気を９００ｍｌ／分で注入し、７０℃で３時間過熱攪拌し、変性水添された天然ゴムのラテックス（ａ）を得た。
Production Example 1
(1) Modification reaction step The field latex was centrifuged at a rotation speed of 7500 rpm using a latex separator (manufactured by Saito Centrifugal Co., Ltd.) to obtain a concentrated latex having a dry rubber concentration of 60%. 500 g of this concentrated latex was put into a glass reaction vessel with an open top equipped with a stirrer and a temperature control jacket, and 20 ml of water and 60 mg of emulsifier “Emulgen 1108” (manufactured by Kao Corporation) were added in advance to N, N-diethylaminoethyl. What was emulsified in addition to 3.0 g of methacrylate was added to the reaction vessel and stirred for 30 minutes while purging with nitrogen. Next, 1.0 g of tert-butyl hydroperoxide and 1.0 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C. for 2 hours to obtain a modified natural rubber latex.
(2) Hydrogenation reaction step 0.1F CuSO 4 initiator and 750 g hydrazine hydrate were added to the modified natural rubber latex. Air was injected into the reaction mixture at 900 ml / min, followed by superheated stirring at 70 ° C. for 3 hours to obtain a modified hydrogenated natural rubber latex (a).
製造例２
（１）変性反応工程
極性基含有単量体Ｎ，Ｎ−ジエチルアミノエチルメタクリレート３．０ｇを加えるかわりに２−ヒドロキシエチルメタクリレート２．１ｇ、２−ビニルピリジン１．７ｇそれぞれ加えた以外は、製造例１と同様な条件で製造し変性水添された天然ゴムのラテックス（ｂ）及び（ｃ）を得た。
Production Example 2
(1) Modification reaction step Production example, except that instead of adding 3.0 g of polar group-containing monomer N, N-diethylaminoethyl methacrylate, 2.1 g of 2-hydroxyethyl methacrylate and 1.7 g of 2-vinylpyridine were added. Natural rubber latexes (b) and (c) produced under the same conditions as in No. 1 and modified and hydrogenated were obtained.
製造例３
（１）水素添加反応工程
フィールドラテックスをラテックスセパレーター（斎藤遠心工業製）を用いて回転数７５００ｒｐｍで遠心分離して乾燥ゴム濃度６０％の濃縮ラテックスを得た。この濃縮ラテックス５００ｇを、撹拌機、温調ジャケットを備えた上部開放のガラス反応器に投入し、５００ｇの水を加えた。次いで０．１ＦのＣｕＳＯ4開始剤および７５０ｇのヒドラジン水和物を加えた。この反応混合物中に空気を９００ｍｌ／分で注入し、８０℃で３時間過熱攪拌し、水添された天然ゴムのラテックスを得た。
（２）変性反応工程
予め２０ｍｌの水と６０ｍｇの乳化剤（エマルゲン１１０８，花王株式会社製）をＮ，Ｎ−ジエチルアミノエチルメタクリレート３．０ｇに加えて乳化したもの
を上記水素添加反応で得られた水添された天然ゴムのラテックスが入っているガラス反応器に添加し窒素置換しながら３０分間攪拌した。ついで重合開始剤tert−ブチルハイドロパーオキサイド１．０ｇとテトラエチレンペンタミン１．０ｇを加え、４０℃で２時間反応させることで、変性水添された天然ゴムのラテックス（ｄ）を得た。
Production Example 3
(1) Hydrogenation reaction process The field latex was centrifuged at a rotational speed of 7500 rpm using a latex separator (manufactured by Saito Centrifugal Co., Ltd.) to obtain a concentrated latex having a dry rubber concentration of 60%. 500 g of this concentrated latex was charged into an open top glass reactor equipped with a stirrer and a temperature control jacket, and 500 g of water was added. Then 0.1 F CuSO 4 initiator and 750 g hydrazine hydrate were added. Air was injected into the reaction mixture at 900 ml / min and stirred for 3 hours at 80 ° C. to obtain a hydrogenated natural rubber latex.
(2) Denaturation reaction step Water obtained by the above hydrogenation reaction in which 20 ml of water and 60 mg of emulsifier (Emulgen 1108, manufactured by Kao Corporation) were added and emulsified in 3.0 g of N, N-diethylaminoethyl methacrylate. The mixture was added to a glass reactor containing the added natural rubber latex and stirred for 30 minutes while purging with nitrogen. Next, 1.0 g of a polymerization initiator tert-butyl hydroperoxide and 1.0 g of tetraethylenepentamine were added and reacted at 40 ° C. for 2 hours to obtain a modified hydrogenated natural rubber latex (d).
製造例４
（１）変性反応工程
フィールドラテックスをラテックスセパレーター（斎藤遠心工業製）を用いて回転数７５００ｒｐｍで遠心分離して乾燥ゴム濃度６０％の濃縮ラテックスを得た。この濃縮ラテックス５００ｇを、撹拌機、温調ジャケットを備えたステンレス製反応容器に投入し、予め２０ｍｌの水と６０ｍｇの乳化剤「エマルゲン１１０８」（花王株式会社製）をＮ，Ｎ−ジエチルアミノエチルメタクリレート３．０ｇに加えて乳化したものを上記反応容器に添加し、窒素置換しながら３０分間撹拌した。次いで、重合開始剤としてtert−ブチルヒドロパーオキサイド１．０ｇとテトラエチレンペンタミン１．０ｇとを加え、４０℃で２時間反応させることにより、変性天然ゴムラテックス（ｅ）を得た。
Production Example 4
(1) Modification reaction step The field latex was centrifuged at a rotation speed of 7500 rpm using a latex separator (manufactured by Saito Centrifugal Co., Ltd.) to obtain a concentrated latex having a dry rubber concentration of 60%. 500 g of this concentrated latex is put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 20 ml of water and 60 mg of emulsifier “Emulgen 1108” (manufactured by Kao Corporation) are added in advance to N, N-diethylaminoethyl methacrylate 3 What was emulsified in addition to 0.0 g was added to the reaction vessel and stirred for 30 minutes while purging with nitrogen. Next, 1.0 g of tert-butyl hydroperoxide and 1.0 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C. for 2 hours to obtain a modified natural rubber latex (e).
製造例５及び６
（１）変性反応工程
極性基含有単量体Ｎ，Ｎ−ジエチルアミノエチルメタクリレート３．０ｇを加えるかわりに２−ヒドロキシエチルメタクリレート２．１ｇ、２−ビニルピリジン１．７ｇそれぞれ加えた以外は、製造例４と同様な条件で製造し変性された天然ゴムのラテックス（ｆ）及び（ｇ）を得た。
Production Examples 5 and 6
(1) Modification reaction step Production example, except that instead of adding 3.0 g of polar group-containing monomer N, N-diethylaminoethyl methacrylate, 2.1 g of 2-hydroxyethyl methacrylate and 1.7 g of 2-vinylpyridine were added. Natural rubber latexes (f) and (g) produced and modified under the same conditions as in No. 4 were obtained.
製造例７
製造例３記載の水素添加反応工程のみをおこない水添された天然ゴムのラテックス（ｈ）をえた。
Production Example 7
Only the hydrogenation reaction step described in Production Example 3 was performed to obtain a hydrogenated natural rubber latex (h).
（３）凝固・乾燥工程
製造例１〜７得られたラテックスａ，ｂ，ｃ，ｄ，ｅ，ｆ及びｈに蟻酸を添加してｐＨを４．７に調製することにより、それぞれのラテックスを凝固させた。このようにして得た凝固物をクレーパーで２０回処理することで洗浄し、熱風乾燥機により１１０℃で２１０分間乾燥しそれぞれ天然ゴムＡ，Ｂ，Ｃ，Ｄ，Ｅ，Ｆ，Ｇ及びＨを得た。
これらの天然ゴムの水素添添加率は、核磁気共鳴（ＮＭＲ）にて測定した。
極性基含有単量体の天然ゴムに対するグラフト量については、変性天然ゴムの重量から極性基含有単量体のグラフト量として概算し、該変性天然ゴムを石油エーテルで抽出し、さらにアセトンとメタノールの２：１混合溶媒で抽出することにより得られるホモポリマーの量を差し引いて極性基含有単量体のグラフト量を求めた。両者の測定結果を第２表に示す。
(3) Coagulation / drying step By adding formic acid to the latexes a, b, c, d, e, f and h obtained in Production Examples 1 to 7 and adjusting the pH to 4.7, the respective latexes were prepared. Solidified. The coagulated material thus obtained was washed by treating it with a creper 20 times and dried with a hot air dryer at 110 ° C. for 210 minutes to give natural rubbers A, B, C, D, E, F, G and H, respectively. Obtained.
The hydrogenation rate of these natural rubbers was measured by nuclear magnetic resonance (NMR).
The grafting amount of the polar group-containing monomer to the natural rubber is estimated as the grafting amount of the polar group-containing monomer from the weight of the modified natural rubber, the modified natural rubber is extracted with petroleum ether, and further, acetone and methanol. The graft amount of the polar group-containing monomer was determined by subtracting the amount of the homopolymer obtained by extraction with a 2: 1 mixed solvent. Both measurement results are shown in Table 2.
製造例８
尚、比較のためコントロールとして変性及び水素添加反応をおこなわず、天然ゴムラテックスをそのまま凝固・乾燥した天然ゴムをＩとして用いた。
Production Example 8
For comparison, as a control, natural rubber obtained by coagulating and drying natural rubber latex as it was was used as I without any modification or hydrogenation reaction.
実施例１〜８、比較例１〜１０
製造例１〜７で得た変性天然ゴムＡ〜Ｈをそれぞれ用いて第１表に示す配合処方ＩまたはＩＩに従ってゴム組成物を作成した。比較のため、製造例８の天然ゴムＩを用いて上記と同じ配合処方によりゴム組成物を作成した。
各ゴム組成物を、１４５℃、３３分間の条件で加硫し、加硫ゴムの初期破壊特性（Ｔｂ）、劣化後の（Ｅｂ）保持率、ｔａｎδ及び耐摩耗性を測定した。その結果を表３に示す。
Examples 1-8, Comparative Examples 1-10
Using the modified natural rubbers A to H obtained in Production Examples 1 to 7, rubber compositions were prepared according to the compounding recipe I or II shown in Table 1. For comparison, a rubber composition was prepared by using the natural rubber I of Production Example 8 with the same formulation as described above.
Each rubber composition was vulcanized at 145 ° C. for 33 minutes, and the initial fracture characteristics (Tb), the (Eb) retention after deterioration, tan δ, and wear resistance of the vulcanized rubber were measured. The results are shown in Table 3.
＊１．製造例１〜８で得られたものを用いた。
＊２．Ｎ３３９：「シーストＫＨ」東海カーボン社製
＊３．「ＡＱ」東ソー・シリカ社製
＊４．「Ｓｉ６９」デグッサ社製、ビス（３−トリエトキシシリルプロピル）テトラスルフィド
＊５．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
＊６．Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド
＊７．ジフェニルグアニジン
＊８．ジベンゾチアジルジスルフィド
＊９．Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアジルスルフェンアミド
* 1. Those obtained in Production Examples 1 to 8 were used.
* 2. N339: “Seast KH” manufactured by Tokai Carbon Co., Ltd. * 3. “AQ” manufactured by Tosoh Silica Co., Ltd. * 4. “Si69” manufactured by Degussa, bis (3-triethoxysilylpropyl) tetrasulfide * 5. N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine * 6. N-cyclohexyl-2-benzothiazylsulfenamide * 7. Diphenylguanidine * 8. Dibenzothiazyl disulfide * 9. N-tert-butyl-2-benzothiazylsulfenamide
＊１０．ｔｅｒｔ−ブチルヒドロパーオキサイド
＊１１．テトラエチレンペンタミン
* 10. tert-butyl hydroperoxide * 11. Tetraethylenepentamine
第３表から分かるように充填材としてカーボンブラックを使用した実施例１〜４は比較例５のゴム組成物（未変性、未水添天然ゴム）に比べて加硫ゴムの初期破壊特性（Ｔｂ）、劣化後の（Ｅｂ）保持率、ｔａｎδ及び耐摩耗性いずれも優れていることが分かる。極性基含有単量体による変性のみの比較例１〜３のゴム組成物は比較例５のゴム組成物対比、初期破壊特性（Ｔｂ）、劣化後の（Ｅｂ）保持率、ｔａｎδ及び耐摩耗性いずれも改良されているが、その改良の度合いは、実施例１〜４がさらに優れており、特に劣化後の（Ｅｂ）保持率が大幅に改善されていることが分かる。
また、第４表に示すように充填材としてシリカを使用した実施例５〜８の組成物についても同様ことが言える。とくにｔａｎδの改良効果が大きいことがわかる。
As can be seen from Table 3, Examples 1 to 4 using carbon black as a filler are compared with the rubber composition of Comparative Example 5 (unmodified, non-hydrogenated natural rubber). ), (Eb) retention, tan δ, and wear resistance after deterioration are all excellent. The rubber compositions of Comparative Examples 1 to 3 only modified with a polar group-containing monomer were compared with the rubber composition of Comparative Example 5, initial fracture characteristics (Tb), (Eb) retention after deterioration, tan δ and abrasion resistance. Although all are improved, the degree of the improvement is further excellent in Examples 1 to 4, and it can be seen that the (Eb) retention rate after deterioration is greatly improved.
The same applies to the compositions of Examples 5 to 8 using silica as a filler as shown in Table 4. It can be seen that the improvement effect of tan δ is particularly great.
本発明の製造方法により得られる変性水添天然ゴムを含むゴム成分を用いることで、カーボンブラック及び／又はシリカに対する補強性、親和性に優れ、また低ロス性、耐摩耗性を改善し、天然ゴムの特徴である高強度をあまり損なうことなく、耐劣化性、耐熱性、耐候性等を向上させることができ、空気入りタイヤのトレッド部、サイドウォール部、ベルト部、カーカス部等に用いることにより、低ロス性、耐摩耗性、耐劣化性、耐熱性、耐候性等に優れる空気入りタイヤを与えることができる。 By using a rubber component containing a modified hydrogenated natural rubber obtained by the production method of the present invention, it is excellent in reinforcing property and affinity for carbon black and / or silica, and has improved low loss and wear resistance. Deterioration resistance, heat resistance, weather resistance, etc. can be improved without significantly damaging the high strength characteristic of rubber, and used for tread parts, sidewall parts, belt parts, carcass parts, etc. of pneumatic tires Thus, it is possible to provide a pneumatic tire excellent in low loss, wear resistance, deterioration resistance, heat resistance, weather resistance, and the like.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831034A (en) * | 2010-05-11 | 2010-09-15 | 中国热带农业科学院农产品加工研究所 | Natural rubber/N-vinyl pyrrolidone graft copolymer and preparation method thereof |
| KR20110103946A (en) * | 2008-12-15 | 2011-09-21 | 스미토모 고무 고교 가부시키가이샤 | Natural rubber, manufacturing method thereof, rubber composition and pneumatic tire using same, modified natural rubber and manufacturing method thereof, and rubber composition for tread or carcass cord coating and pneumatic tire using them |
| JP2018141090A (en) * | 2017-02-28 | 2018-09-13 | 大塚化学株式会社 | Rubber composition and tire using the same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59161415A (en) * | 1983-02-22 | 1984-09-12 | ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− | Hydrogenation of carbon-carbon double bond in unsaturated polymer |
| JPH02175705A (en) * | 1988-12-28 | 1990-07-09 | Japan Synthetic Rubber Co Ltd | Modified hydrogenated conjugated diene polymer and its composition and production |
| WO2002083746A1 (en) * | 2001-04-11 | 2002-10-24 | Asahi Kasei Kabushiki Kaisha | Hydrogenated polymer and process for producing the same |
| JP2004359716A (en) * | 2003-06-02 | 2004-12-24 | Bridgestone Corp | Rubber composition and pneumatic tire |
| WO2005040236A1 (en) * | 2003-10-24 | 2005-05-06 | Jsr Corporation | Ionomer, method for producing same, and formed article |
| JP2006131807A (en) * | 2004-11-08 | 2006-05-25 | Nitta Ind Corp | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same |
| JP2006219618A (en) * | 2005-02-14 | 2006-08-24 | Bridgestone Corp | Modified natural rubber masterbatch, method for producing the same, rubber composition and tire |
| JP2007084662A (en) * | 2005-09-21 | 2007-04-05 | Yokohama Rubber Co Ltd:The | Modified polymer and method for producing the same |
-
2007
- 2007-01-31 JP JP2007021080A patent/JP2008184572A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59161415A (en) * | 1983-02-22 | 1984-09-12 | ザ・グツドイヤ−・タイヤ・アンド・ラバ−・カンパニ− | Hydrogenation of carbon-carbon double bond in unsaturated polymer |
| JPH02175705A (en) * | 1988-12-28 | 1990-07-09 | Japan Synthetic Rubber Co Ltd | Modified hydrogenated conjugated diene polymer and its composition and production |
| WO2002083746A1 (en) * | 2001-04-11 | 2002-10-24 | Asahi Kasei Kabushiki Kaisha | Hydrogenated polymer and process for producing the same |
| JP2004359716A (en) * | 2003-06-02 | 2004-12-24 | Bridgestone Corp | Rubber composition and pneumatic tire |
| WO2005040236A1 (en) * | 2003-10-24 | 2005-05-06 | Jsr Corporation | Ionomer, method for producing same, and formed article |
| JP2006131807A (en) * | 2004-11-08 | 2006-05-25 | Nitta Ind Corp | Modified latex and natural polyisoprenoid hydrogenation product or modified product containing the same |
| JP2006219618A (en) * | 2005-02-14 | 2006-08-24 | Bridgestone Corp | Modified natural rubber masterbatch, method for producing the same, rubber composition and tire |
| JP2007084662A (en) * | 2005-09-21 | 2007-04-05 | Yokohama Rubber Co Ltd:The | Modified polymer and method for producing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110103946A (en) * | 2008-12-15 | 2011-09-21 | 스미토모 고무 고교 가부시키가이샤 | Natural rubber, manufacturing method thereof, rubber composition and pneumatic tire using same, modified natural rubber and manufacturing method thereof, and rubber composition for tread or carcass cord coating and pneumatic tire using them |
| KR101695039B1 (en) * | 2008-12-15 | 2017-01-10 | 스미토모 고무 고교 가부시키가이샤 | Natural rubber and manufacturing method thereof, rubber composition and pneumatic tire utilizing the same, modified natural rubber and manufacturing method thereof, and rubber composite for covering treads or carcass cords and pneumatic tire utilizing the same |
| CN101831034A (en) * | 2010-05-11 | 2010-09-15 | 中国热带农业科学院农产品加工研究所 | Natural rubber/N-vinyl pyrrolidone graft copolymer and preparation method thereof |
| CN101831034B (en) * | 2010-05-11 | 2012-06-27 | 中国热带农业科学院农产品加工研究所 | Natural rubber/N-vinyl pyrrolidone graft copolymer and preparation method thereof |
| JP2018141090A (en) * | 2017-02-28 | 2018-09-13 | 大塚化学株式会社 | Rubber composition and tire using the same |
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