JP2010195969A - Isobutylene based block copolymer - Google Patents
Isobutylene based block copolymer Download PDFInfo
- Publication number
- JP2010195969A JP2010195969A JP2009043920A JP2009043920A JP2010195969A JP 2010195969 A JP2010195969 A JP 2010195969A JP 2009043920 A JP2009043920 A JP 2009043920A JP 2009043920 A JP2009043920 A JP 2009043920A JP 2010195969 A JP2010195969 A JP 2010195969A
- Authority
- JP
- Japan
- Prior art keywords
- isobutylene
- block copolymer
- block
- polymer
- weight
- 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.)
- Granted
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims abstract description 31
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims abstract description 31
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims abstract description 31
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229930006722 beta-pinene Natural products 0.000 claims abstract description 31
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 229920005604 random copolymer Polymers 0.000 claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- -1 aromatic vinyl compound Chemical class 0.000 claims description 19
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 27
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000004073 vulcanization Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000009864 tensile test Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000010538 cationic polymerization reaction Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- MLMSLISKKHDEOV-UHFFFAOYSA-N 1,2,3-tris(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC=CC(C(C)(C)Cl)=C1C(C)(C)Cl MLMSLISKKHDEOV-UHFFFAOYSA-N 0.000 description 4
- PIOPMKDWXJORAY-UHFFFAOYSA-N 1,2-bis(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC=CC=C1C(C)(C)Cl PIOPMKDWXJORAY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920006132 styrene block copolymer Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SRNQAQUOOIZPJL-UHFFFAOYSA-N 1,3,5-tris(2-chloropropan-2-yl)benzene Chemical compound CC(C)(Cl)C1=CC(C(C)(C)Cl)=CC(C(C)(C)Cl)=C1 SRNQAQUOOIZPJL-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical group COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- KPJKMUJJFXZGAX-UHFFFAOYSA-N 2-chloropropan-2-ylbenzene Chemical compound CC(C)(Cl)C1=CC=CC=C1 KPJKMUJJFXZGAX-UHFFFAOYSA-N 0.000 description 2
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical compound [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 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 2
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- 229960002447 thiram Drugs 0.000 description 2
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- HGOUNPXIJSDIKV-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl 2-methylprop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C(C)=C HGOUNPXIJSDIKV-UHFFFAOYSA-N 0.000 description 1
- OKVWYBALHQFVFP-UHFFFAOYSA-N 2,3,3-trimethylpentane Chemical compound CCC(C)(C)C(C)C OKVWYBALHQFVFP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、空気バリア性、柔軟性、靱性、および接着性に優れたイソブチレン系ブロック共重合体と組成物に関する。さらにはカーカスへの接着性に優れたタイヤ用インナーライナーに関する。 The present invention relates to an isobutylene block copolymer and a composition excellent in air barrier properties, flexibility, toughness, and adhesiveness. Furthermore, the present invention relates to an inner liner for a tire excellent in adhesion to a carcass.
従来、空気バリア性、柔軟性、および靱性に優れる共重合体としてイソブチレンとスチレンのブロック共重合体が知られている（例えば特許文献１）。しかし、その機械強度と接着性のバランスが十分とはいえず、その用途には限界があった。 Conventionally, a block copolymer of isobutylene and styrene is known as a copolymer excellent in air barrier properties, flexibility, and toughness (for example, Patent Document 1). However, the balance between the mechanical strength and the adhesiveness cannot be said to be sufficient, and its use has a limit.
また従来、耐気体透過性材料としてブチルゴムは種々の分野で利用されている。例えば、薬栓やタイヤインナーライナー用材料として使用されている。しかし、タイヤインナーライナー用材料として使用する場合には、加硫操作を必要とするため操作性に劣るという問題点があった。 Conventionally, butyl rubber has been used in various fields as a gas-permeable material. For example, it is used as a material for medicine plugs and tire inner liners. However, when used as a material for a tire inner liner, there is a problem that the operability is poor because a vulcanization operation is required.
特許文献２には芳香族ビニル化合物とイソブチレンとのブロック共重合体とカーボンブラックとを含有するタイヤインナーライナー用ゴム組成物が開示されている。これは加硫工程を必要とせず、ガスバリア性には優れているものの未だカーカス層を構成するゴムとの接着は不十分であった。 Patent Document 2 discloses a rubber composition for a tire inner liner containing a block copolymer of an aromatic vinyl compound and isobutylene and carbon black. This does not require a vulcanization step and is excellent in gas barrier properties, but is still insufficiently bonded to the rubber constituting the carcass layer.
本発明は、上記の課題に鑑みてなされたものであって、空気バリア性、柔軟性、靱性、および接着性に優れたイソブチレン系ブロック共重合体と組成物を提供することにある。さらに加硫工程を必要としない空気入りタイヤのインナーライナー層として空気バリア性、柔軟性、靱性とカーカスへの接着性のバランスに優れたインナーライナーを提供することにある。 This invention is made | formed in view of said subject, Comprising: It is providing the isobutylene type block copolymer and composition excellent in air barrier property, a softness | flexibility, toughness, and adhesiveness. Another object of the present invention is to provide an inner liner excellent in the balance of air barrier properties, flexibility, toughness and adhesion to a carcass as an inner liner layer of a pneumatic tire that does not require a vulcanization process.
本発明者らは、鋭意検討した結果、本発明を完成するに至った。すなわち本発明は、イソブチレンを主体とする重合体ブロック（ａ）と芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）とからなるイソブチレン系ブロック共重合体であって、少なくとも一つのブロックがβ−ピネンを含むランダム共重合体であることを特徴とするイソブチレン系ブロック共重合体に関する。 As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention is an isobutylene block copolymer comprising a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound, wherein at least one block is The present invention relates to an isobutylene block copolymer, which is a random copolymer containing β-pinene.
好ましい実施態様としては、前記イソブチレン系ブロック共重合体のβ−ピネン含有量が、０．５〜２５重量％であることを特徴とするイソブチレン系ブロック重合体に関する。 A preferred embodiment relates to an isobutylene block polymer, wherein the isobutylene block copolymer has a β-pinene content of 0.5 to 25% by weight.
好ましい実施態様としては、前記芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）がβ−ピネンを含むランダム共重合体であることを特徴とするイソブチレン系ブロック重合体に関する。 A preferred embodiment relates to an isobutylene block polymer, wherein the polymer block (b) mainly composed of the aromatic vinyl compound is a random copolymer containing β-pinene.
好ましい実施態様としては、前記イソブチレンを主体とする重合体ブロック（ａ）がβ−ピネンを含むランダム共重合体であることを特徴とするイソブチレン系ブロック重合体に関する。 As a preferred embodiment, the present invention relates to an isobutylene block polymer, wherein the polymer block (a) mainly comprising isobutylene is a random copolymer containing β-pinene.
好ましい実施態様としては、前記イソブチレン系ブロック共重合体のブロック構造が、（ａ）−（ｂ）のジブロック体、または（ｂ）−（ａ）−（ｂ）のトリブロック体であることを特徴とするイソブチレン系ブロック共重合体に関する。 In a preferred embodiment, the block structure of the isobutylene block copolymer is a diblock body of (a)-(b) or a triblock body of (b)-(a)-(b). The present invention relates to a characteristic isobutylene block copolymer.
好ましい実施態様としては、重量平均分子量が３０，０００〜３００，０００であり、かつ分子量分布（重量平均分子量／数平均分子量）が１．３以下であることを特徴とするイソブチレン系ブロック共重合体に関する。 In a preferred embodiment, the isobutylene block copolymer has a weight average molecular weight of 30,000 to 300,000 and a molecular weight distribution (weight average molecular weight / number average molecular weight) of 1.3 or less. About.
好ましい実施態様としては、イソブチレンを主体とする重合体ブロック（ａ）を６０〜９０重量％、および芳香族ビニル系化合物を主体とするブロック（ｂ）を１０〜４０重量％含むことを特徴とするイソブチレン系ブロック共重合体に関する。 A preferred embodiment is characterized in that it contains 60 to 90% by weight of the polymer block (a) mainly composed of isobutylene and 10 to 40% by weight of the block (b) mainly composed of an aromatic vinyl compound. The present invention relates to an isobutylene block copolymer.
好ましい実施態様としては、前記芳香族ビニル系化合物がスチレンであることを特徴とするイソブチレン系ブロック共重合体に関する。 As a preferred embodiment, the present invention relates to an isobutylene block copolymer, wherein the aromatic vinyl compound is styrene.
さらには、上記イソブチレン系ブロック共重合体を含むことを特徴とする組成物に関する。 Furthermore, it is related with the composition characterized by including the said isobutylene type block copolymer.
さらには、上記イソブチレン系ブロック共重合体１００重量部に対してエチレン−ビニルアルコール共重合体を１〜４００重量部を含有することを特徴とする組成物に関する。 Furthermore, the present invention relates to a composition comprising 1 to 400 parts by weight of an ethylene-vinyl alcohol copolymer with respect to 100 parts by weight of the isobutylene block copolymer.
さらには、上記組成物によって作られることを特徴とするタイヤ用インナーライナーに関する。 Furthermore, it is related with the inner liner for tires characterized by being made with the said composition.
本発明のイソブチレン系ブロック共重合体は、イソブチレンを主体とする重合体ブロック（ａ）と芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）とからなり、β−ピネンを含まない従来のイソブチレン系ブロック共重合体の特徴である空気バリア性、柔軟性、および靱性に加え、接着性に優れる。特に本発明のタイヤ用インナーライナーは、加硫工程を必要とせず、空気バリア性、柔軟性、靱性とカーカスへの接着性のバランスに優れており、タイヤの組み立て容易化、あるいはガス圧の保持力の向上に好適である。 The isobutylene block copolymer of the present invention comprises a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound, and does not contain β-pinene. In addition to air barrier properties, flexibility, and toughness, which are the characteristics of isobutylene block copolymers, it has excellent adhesion. In particular, the inner liner for tires of the present invention does not require a vulcanization step, and has an excellent balance of air barrier properties, flexibility, toughness and adhesion to carcass, and facilitates tire assembly or maintains gas pressure. It is suitable for improving power.
本発明は、イソブチレンを主体とする重合体ブロック（ａ）と芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）とからなるイソブチレン系ブロック共重合体であって、少なくとも一つのブロックがβ−ピネンを含むランダム共重合体であることを特徴とするイソブチレン系ブロック共重合体である。 The present invention is an isobutylene block copolymer comprising a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound, wherein at least one block is β -A random copolymer containing pinene, which is an isobutylene block copolymer.
イソブチレンを主成分とする重合体ブロック（ａ）は、イソブチレンに由来するユニットが６０重量％以上、好ましくは８０重量％以上から構成される重合体ブロックである。 The polymer block (a) containing isobutylene as a main component is a polymer block composed of 60% by weight or more, preferably 80% by weight or more of units derived from isobutylene.
いずれの重合体ブロックも、共重合成分として、相互の単量体を使用することができるほか、その他のカチオン重合可能な単量体成分を使用することができる。このような単量体成分としては、脂肪族オレフィン類、ジエン類、ビニルエーテル類、シラン類、ビニルカルバゾール、アセナフチレン等の単量体が例示できる。これらはそれぞれ単独で又は２種以上を組み合わせて使用することができる。 Any of the polymer blocks can use mutual monomers as copolymerization components, and other monomer components capable of cationic polymerization. Examples of such monomer components include monomers such as aliphatic olefins, dienes, vinyl ethers, silanes, vinyl carbazole, and acenaphthylene. These can be used alone or in combination of two or more.
芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）は、芳香族ビニル系化合物に由来するユニットが６０重量％以上、好ましくは８０重量％以上から構成される重合体ブロックである。 The polymer block (b) mainly composed of an aromatic vinyl compound is a polymer block composed of 60% by weight or more, preferably 80% by weight or more of units derived from an aromatic vinyl compound.
芳香族ビニル系化合物としては、スチレン、ｏ−、ｍ−又はｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、２，６−ジメチルスチレン、２，４−ジメチルスチレン、α−メチル−ｏ−メチルスチレン、α−メチル−ｍ−メチルスチレン、α−メチル−ｐ−メチルスチレン、β−メチル−ｏ−メチルスチレン、β−メチル−ｍ−メチルスチレン、β−メチル−ｐ−メチルスチレン、２，４，６−トリメチルスチレン、α−メチル−２，６−ジメチルスチレン、α−メチル−２，４−ジメチルスチレン、β−メチル−２，６−ジメチルスチレン、β−メチル−２，４−ジメチルスチレン、ｏ−、ｍ−又はｐ−クロロスチレン、２，６−ジクロロスチレン、２，４−ジクロロスチレン、α−クロロ−ｏ−クロロスチレン、α−クロロ−ｍ−クロロスチレン、α−クロロ−ｐ−クロロスチレン、β−クロロ−ｏ−クロロスチレン、β−クロロ−ｍ−クロロスチレン、β−クロロ−ｐ−クロロスチレン、２，４，６−トリクロロスチレン、α−クロロ−２，６−ジクロロスチレン、α−クロロ−２，４−ジクロロスチレン、β−クロロ−２，６−ジクロロスチレン、β−クロロ−２，４−ジクロロスチレン、ｏ−、ｍ−又はｐ−ｔ−ブチルスチレン、ｏ−、ｍ−又はｐ−メトキシスチレン、ｏ−、ｍ−又はｐ−クロロメチルスチレン、ｏ−、ｍ−又はｐ−ブロモメチルスチレン、シリル基で置換されたスチレン誘導体、インデン、ビニルナフタレン等が挙げられる。これらの中でも、工業的な入手性やガラス転移温度の点から、スチレン、α−メチルスチレン、および、これらの混合物が好ましく、特にスチレンが好ましい。 Aromatic vinyl compounds include styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o. -Methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2 , 4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethyl Styrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m- Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or p- t-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene And vinyl naphthalene. Among these, styrene, α-methylstyrene, and a mixture thereof are preferable from the viewpoint of industrial availability and glass transition temperature, and styrene is particularly preferable.
本発明のイソブチレン系ブロック共重合体は（ａ），（ｂ）のうち少なくとも一つのブロックがβ−ピネンとのランダム共重合体である。低温特性を考慮すると芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）において共重合しているのが好ましい。接着性を考慮するとイソブチレンを主体とする重合体ブロック（ａ）において共重合しているのが好ましい。接着性の観点からβ−ピネンの共重合量としてはイソブチレン系ブロック共重合体の０．５〜２５重量％が好ましく、２〜２５重量％がさらに好ましく、５〜１０重量％が特に好ましい。０．５重量％を下回ると接着性に問題が起こる可能性があり、２５重量％を上回ると脆くなりゴム弾性に乏しくなる可能性がある。 The isobutylene block copolymer of the present invention is a random copolymer in which at least one block of (a) and (b) is β-pinene. Considering the low temperature characteristics, it is preferable that copolymerization is performed in the polymer block (b) mainly composed of an aromatic vinyl compound. In view of adhesiveness, it is preferable that copolymerization is performed in the polymer block (a) mainly composed of isobutylene. From the viewpoint of adhesion, the copolymerization amount of β-pinene is preferably 0.5 to 25% by weight, more preferably 2 to 25% by weight, and particularly preferably 5 to 10% by weight of the isobutylene block copolymer. If the amount is less than 0.5% by weight, there may be a problem in adhesion, and if it exceeds 25% by weight, the material may become brittle and the rubber elasticity may be poor.
本発明のイソブチレン系ブロック共重合体はイソブチレンを主体とする重合体ブロック（ａ）と芳香族ビニル系化合物を主体とする重合体ブロック（ｂ）から構成されている限り、その構造には特に制限はなく、例えば、直鎖状、分岐状、星状等の構造を有するブロック共重合体、トリブロック共重合体、マルチブロック共重合体等のいずれも選択可能である。好ましい構造としては、物性バランス及び成形加工性の点から、（ａ）−（ｂ）で構成されるジブロック共重合体、（ｂ）−（ａ）−（ｂ）で構成されるトリブロック共重合体が挙げられる。これらは所望の物性・成形加工性を得る為に、それぞれ単独で又は２種以上を組み合わせて使用することができる。 As long as the isobutylene block copolymer of the present invention is composed of a polymer block (a) mainly composed of isobutylene and a polymer block (b) mainly composed of an aromatic vinyl compound, its structure is particularly limited. For example, any of a block copolymer, a triblock copolymer, a multiblock copolymer, and the like having a linear, branched, or star structure can be selected. Preferred structures include a diblock copolymer composed of (a)-(b) and a triblock copolymer composed of (b)-(a)-(b) from the viewpoint of physical property balance and molding processability. A polymer is mentioned. These may be used alone or in combination of two or more in order to obtain desired physical properties and moldability.
またイソブチレン系ブロック共重合体の分子量にも特に制限はないが、流動性、成形加工性、ゴム弾性等の面から、ＧＰＣ測定による重量平均分子量で３０，０００〜３００，０００であることが好ましく、３０，０００〜１５０，０００であることが特に好ましい。重量平均分子量が３０，０００よりも低い場合には機械的な物性が十分に発現されない傾向があり、一方３００，０００を超える場合には流動性、加工性が悪化する傾向がある。さらには加工安定性の観点からイソブチレン系ブロック共重合体の重量平均分子量／数平均分子量が１．３以下であることが好ましい。 The molecular weight of the isobutylene block copolymer is not particularly limited, but is preferably 30,000 to 300,000 in terms of weight average molecular weight by GPC measurement from the viewpoint of fluidity, molding processability, rubber elasticity and the like. 30,000 to 150,000 is particularly preferable. When the weight average molecular weight is lower than 30,000, mechanical properties tend not to be sufficiently exhibited, whereas when it exceeds 300,000, fluidity and workability tend to deteriorate. Furthermore, the weight average molecular weight / number average molecular weight of the isobutylene block copolymer is preferably 1.3 or less from the viewpoint of processing stability.
イソブチレン系ブロック共重合体の製造方法については特に制限はないが、例えば、下記一般式（Ｉ）で表される化合物の存在下に、単量体成分を重合させることにより得られる。
（ＣＲ1Ｒ2Ｘ）ｎＲ3 （Ｉ）
［式中Ｘはハロゲン原子、炭素数１〜６のアルコキシ基またはアシロキシ基から選ばれる置換基、Ｒ1、Ｒ2はそれぞれ水素原子または炭素数１〜６の１価炭化水素基でＲ1、Ｒ2は同一であっても異なっていても良く、Ｒ3は一価若しくは多価芳香族炭化水素基または一価若しくは多価脂肪族炭化水素基であり、ｎは１〜６の自然数を示す。］
上記一般式（Ｉ）で表わされる化合物は開始剤となるものでルイス酸等の存在下炭素陽イオンを生成し、カチオン重合の開始点になると考えられる。本発明で用いられる一般式（Ｉ）の化合物の例としては、次のような化合物等が挙げられる。
Although there is no restriction | limiting in particular about the manufacturing method of an isobutylene type block copolymer, For example, it can obtain by polymerizing a monomer component in presence of the compound represented by the following general formula (I).
(CR 1 R 2 X) nR 3 (I)
[Wherein X is a halogen atom, a substituent selected from an alkoxy group having 1 to 6 carbon atoms or an acyloxy group, R 1 and R 2 are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R 1 , R 2 may be the same or different, R 3 is a monovalent or polyvalent aromatic hydrocarbon group or a monovalent or polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6. . ]
The compound represented by the above general formula (I) serves as an initiator, and is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization. The following compounds etc. are mentioned as an example of the compound of general formula (I) used by this invention.
（１−クロル−１−メチルエチル）ベンゼン［Ｃ6Ｈ5Ｃ（ＣＨ3）2Ｃｌ］、１，４−ビス（１−クロル−１−メチルエチル）ベンゼン［１，４−Ｃｌ（ＣＨ3）2ＣＣ6Ｈ4Ｃ（ＣＨ3）2Ｃｌ］、１，３−ビス（１−クロル−１−メチルエチル）ベンゼン［１，３−Ｃｌ（ＣＨ3）2ＣＣ6Ｈ4Ｃ（ＣＨ3）2Ｃｌ］、１，３，５−トリス（１−クロル−１−メチルエチル）ベンゼン［１，３，５−（ＣｌＣ（ＣＨ3）2）3Ｃ6Ｈ3］、１，３−ビス（１−クロル−１−メチルエチル）−５−（ｔｅｒｔ−ブチル）ベンゼン［１，３−（Ｃ（ＣＨ3）2Ｃｌ）2-５−（Ｃ（ＣＨ3）3）Ｃ6Ｈ3］
これらの中でも特に好ましいのはビス（１−クロル−１−メチルエチル）ベンゼン［Ｃ6Ｈ4（Ｃ（ＣＨ3）2Ｃｌ）2］、トリス（１−クロル−１−メチルエチル）ベンゼン［（ＣｌＣ（ＣＨ3）2）3Ｃ6Ｈ3］である。［なおビス（１−クロル−１−メチルエチル）ベンゼンは、ビス（α−クロロイソプロピル）ベンゼン、ビス（２−クロロ−２−プロピル）ベンゼンあるいはジクミルクロライドとも呼ばれ、トリス（１−クロル−１−メチルエチル）ベンゼンは、トリス（α−クロロイソプロピル）ベンゼン、トリス（２−クロロ−２−プロピル）ベンゼンあるいはトリクミルクロライドとも呼ばれる］。
(1-Chloro-1-methylethyl) benzene [C 6 H 5 C (CH 3 ) 2 Cl], 1,4-bis (1-chloro-1-methylethyl) benzene [1,4-Cl (CH 3 ) 2 CC 6 H 4 C (CH 3 ) 2 Cl], 1,3-bis (1-chloro-1-methylethyl) benzene [1,3-Cl (CH 3 ) 2 CC 6 H 4 C (CH 3 ) 2 Cl], 1,3,5-tris (1-chloro-1-methylethyl) benzene [1,3,5- (ClC (CH 3 ) 2 ) 3 C 6 H 3 ], 1,3-bis (1-Chloro-1-methylethyl) -5- (tert-butyl) benzene [1,3- (C (CH 3 ) 2 Cl) 2 -5- (C (CH 3 ) 3 ) C 6 H 3 ]
Of these, bis (1-chloro-1-methylethyl) benzene [C 6 H 4 (C (CH 3 ) 2 Cl) 2 ], tris (1-chloro-1-methylethyl) benzene [( ClC (CH 3 ) 2 ) 3 C 6 H 3 ]. [Bis (1-chloro-1-methylethyl) benzene is also called bis (α-chloroisopropyl) benzene, bis (2-chloro-2-propyl) benzene or dicumyl chloride, and tris (1-chloro- 1-methylethyl) benzene is also referred to as tris (α-chloroisopropyl) benzene, tris (2-chloro-2-propyl) benzene, or tricumyl chloride.
イソブチレン系ブロック共重合体を製造する際には、さらにルイス酸触媒を共存させることもできる。このようなルイス酸としてはカチオン重合に使用できるものであれば良く、ＴｉＣｌ4、ＴｉＢｒ4、ＢＣｌ3、ＢＦ3、ＢＦ3・ＯＥｔ2、ＳｎＣｌ4、ＳｂＣｌ5、ＳｂＦ5、ＷＣｌ6、ＴａＣｌ5、ＶＣｌ5、ＦｅＣｌ3、ＺｎＢｒ2、ＡｌＣｌ3、ＡｌＢｒ3等の金属ハロゲン化物；Ｅｔ2ＡｌＣｌ、ＥｔＡｌＣｌ2等の有機金属ハロゲン化物を好適に使用することができる。中でも触媒としての能力、工業的な入手の容易さを考えた場合、ＴｉＣｌ4、ＢＣｌ3、ＳｎＣｌ4が好ましい。ルイス酸の使用量は、特に限定されないが、使用する単量体の重合特性あるいは重合濃度等を鑑みて設定することができる。通常は一般式（Ｉ）で表される化合物に対して０．１〜１００モル当量使用することができ、好ましくは１〜５０モル当量の範囲である。 In producing the isobutylene block copolymer, a Lewis acid catalyst can be further present. Such Lewis acid may be any one that can be used for cationic polymerization. TiCl 4 , TiBr 4 , BCl 3 , BF 3 , BF 3 .OEt 2 , SnCl 4 , SbCl 5 , SbF 5 , WCl 6 , TaCl 5 , VCl 5 , FeCl 3 , ZnBr 2 , AlCl 3 , AlBr 3, etc .; metal halides such as Et 2 AlCl, EtAlCl 2, etc. can be preferably used. Of these, TiCl 4 , BCl 3 , and SnCl 4 are preferable in view of the ability as a catalyst and industrial availability. The amount of Lewis acid used is not particularly limited, but can be set in view of the polymerization characteristics or polymerization concentration of the monomer used. Usually, it is 0.1-100 mol equivalent with respect to the compound represented with general formula (I), Preferably it is the range of 1-50 mol equivalent.
イソブチレン系ブロック共重合体の製造に際しては、さらに必要に応じて電子供与体成分を共存させることもできる。この電子供与体成分は、カチオン重合に際して、成長炭素カチオンを安定化させる効果があるものと考えられており、電子供与体の添加によって、分子量分布の狭い、構造が制御された重合体を生成することができる。使用可能な電子供与体成分としては特に限定されないが、例えば、ピリジン類、アミン類、アミド類、スルホキシド類、エステル類、または金属原子に結合した酸素原子を有する金属化合物等を挙げることができる。 In the production of the isobutylene block copolymer, an electron donor component can be allowed to coexist if necessary. This electron donor component is believed to have the effect of stabilizing the growth carbon cation during cationic polymerization, and the addition of an electron donor produces a polymer with a narrow molecular weight distribution and a controlled structure. be able to. The electron donor component that can be used is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom.
イソブチレン系ブロック共重合体の重合は必要に応じて有機溶媒中で行うことができ、有機溶媒としてはカチオン重合を本質的に阻害しなければ、特に制約なく使用することができる。具体的には、塩化メチル、ジクロロメタン、クロロホルム、塩化エチル、ジクロロエタン、ｎ−プロピルクロライド、ｎ−ブチルクロライド、クロロベンゼン等のハロゲン化炭化水素；ベンゼン、トルエン、キシレン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン等のアルキルベンゼン類；エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等の直鎖式脂肪族炭化水素類；２−メチルプロパン、２−メチルブタン、２，３，３−トリメチルペンタン、２，２，５−トリメチルヘキサン等の分岐式脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の環式脂肪族炭化水素類；石油留分を水添精製したパラフィン油等を挙げることができる。 The polymerization of the isobutylene-based block copolymer can be carried out in an organic solvent as necessary, and the organic solvent can be used without particular limitation as long as it does not essentially inhibit cationic polymerization. Specifically, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene; benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, etc. Alkylbenzenes; linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane; 2-methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, 2 Branched aliphatic hydrocarbons such as 1,2,5-trimethylhexane; cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and ethylcyclohexane; paraffin oil obtained by hydrorefining petroleum fractions, etc. .
これらの溶媒は、イソブチレン系ブロック共重合体を構成する単量体の重合特性及び生成する重合体の溶解性等のバランスを考慮して、それぞれ単独で又は２種以上を組み合わせて使用することができる。 These solvents may be used alone or in combination of two or more in consideration of the balance of the polymerization characteristics of the monomers constituting the isobutylene block copolymer and the solubility of the resulting polymer. it can.
上記溶媒の使用量は、得られる重合体溶液の粘度や除熱の容易さを考慮して、重合体の濃度が１〜５０ｗｔ％、好ましくは５〜３５ｗｔ％となるように決定される。 The amount of the solvent used is determined so that the concentration of the polymer is 1 to 50 wt%, preferably 5 to 35 wt%, in consideration of the viscosity of the resulting polymer solution and the ease of heat removal.
実際の重合を行うに当たっては、各成分を冷却下例えば−１００℃以上０℃未満の温度で混合する。エネルギーコストと重合の安定性を釣り合わせるために、特に好ましい温度範囲は−３０℃〜−８０℃である。 In carrying out the actual polymerization, the respective components are mixed at a temperature of, for example, −100 ° C. or more and less than 0 ° C. under cooling. In order to balance the energy cost and the stability of polymerization, a particularly preferred temperature range is −30 ° C. to −80 ° C.
本発明の組成物は、本発明のイソブチレン系ブロック共重合体を含む組成物であり、インナーライナー用組成物、特に空気入りタイヤ用インナーライナー用組成物として好適に使用できる。 The composition of the present invention is a composition containing the isobutylene block copolymer of the present invention, and can be suitably used as a composition for an inner liner, particularly a composition for an inner liner for a pneumatic tire.
本発明の組成物にはガスバリア性の向上の観点からさらにエチレン−ビニルアルコール共重合体を含有しても良い。エチレン−ビニルアルコール共重合体は、エチレン含有量は２０〜７０モル％であることが好ましい。エチレン含有量が２０モル％を下回ると水分バリア性と柔軟性に劣り耐屈曲性に劣る恐れがある上熱成形性に劣る恐れがある。また、７０モル％を上回るとガスバリア性が不足する恐れがある。エチレン−ビニルアルコール共重合体の配合量はイソブチレン系ブロック共重合体１００重量部に対して好ましくは１〜４００重量部、さらに好ましくは１０〜４００重量部含有することが好ましい。エチレン−ビニルアルコール共重合体の配合量が４００重量部を超えると柔軟性が失われ長期での屈曲疲労特性に劣る可能性がある。 The composition of the present invention may further contain an ethylene-vinyl alcohol copolymer from the viewpoint of improving gas barrier properties. The ethylene-vinyl alcohol copolymer preferably has an ethylene content of 20 to 70 mol%. If the ethylene content is less than 20 mol%, the moisture barrier property and flexibility may be inferior and the flex resistance may be inferior, and the thermoformability may be inferior. Moreover, when it exceeds 70 mol%, there exists a possibility that gas barrier property may be insufficient. The blending amount of the ethylene-vinyl alcohol copolymer is preferably 1 to 400 parts by weight, more preferably 10 to 400 parts by weight, based on 100 parts by weight of the isobutylene block copolymer. When the blending amount of the ethylene-vinyl alcohol copolymer exceeds 400 parts by weight, the flexibility is lost and the bending fatigue characteristics in the long term may be inferior.
本発明の組成物にはさらに架橋剤と架橋助剤を添加しても良い。架橋剤は単体硫黄、テトラメチルチウラムジスルフィド、４，４−ジチオビスモルホリン、有機過酸化物、フェノールホルムアルデヒド樹脂、ハロメチルフェノールが例示される。これらの中でも好ましいのは単体硫黄、テトラメチルチウラムジスルフィド、４，４−ジチオビスモルホリンである。架橋助剤は例えば、スルフェンアミド、ベンゾチアゾール、グアニジン、ジチオカルバミン酸、酸化亜鉛などの金属酸化物、ステアリン酸などの脂肪酸、含窒素化合物、トリアリルイソシアヌレート、エチレングリコールジメタクリレート、トリメチロールプロパンメタクリレートが挙げられる。これらの中でも好ましいのはスルフェンアミド、ベンゾチアゾール、グアニジン、ジチオカルバミン酸、酸化亜鉛などの金属酸化物、ステアリン酸などの脂肪酸である。架橋剤と架橋助剤の配合量としてそれぞれ好ましくはイソブチレン系ブロック共重合体１００重量部に対して０．５〜５重量部である。 A crosslinking agent and a crosslinking aid may be further added to the composition of the present invention. Examples of the crosslinking agent include elemental sulfur, tetramethylthiuram disulfide, 4,4-dithiobismorpholine, organic peroxide, phenol formaldehyde resin, and halomethylphenol. Among these, simple sulfur, tetramethylthiuram disulfide, and 4,4-dithiobismorpholine are preferable. Examples of the crosslinking aid include metal oxides such as sulfenamide, benzothiazole, guanidine, dithiocarbamic acid and zinc oxide, fatty acids such as stearic acid, nitrogen-containing compounds, triallyl isocyanurate, ethylene glycol dimethacrylate, and trimethylolpropane methacrylate. Is mentioned. Among these, preferred are metal oxides such as sulfenamide, benzothiazole, guanidine, dithiocarbamic acid and zinc oxide, and fatty acids such as stearic acid. The blending amount of the crosslinking agent and the crosslinking assistant is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the isobutylene block copolymer.
本発明の組成物にはカーカスゴムへの密着性の点から、さらに粘着付与剤を含有していても良い。粘着付与剤には天然のロジン、テルペン、合成のクマロンインデン樹脂、石油樹脂、アルキルフェノール樹脂などが挙げられる。粘着付与剤の配合量はイソブチレン系ブロック共重合体１００重量部に対して好ましくは１〜８０重量部である。 The composition of the present invention may further contain a tackifier from the viewpoint of adhesion to carcass rubber. Examples of the tackifier include natural rosin, terpene, synthetic coumarone indene resin, petroleum resin, and alkylphenol resin. The blending amount of the tackifier is preferably 1 to 80 parts by weight with respect to 100 parts by weight of the isobutylene block copolymer.
本発明の組成物にはさらに目的に応じて充填剤、老化防止剤、軟化剤、加工助剤を添加しても良い。例えば充填剤には、カーボンブラック、湿式シリカ、乾式シリカ、炭酸カルシウム、カオリン、タルク、クレー等が挙げられ、老化防止剤には酸化防止剤、紫外線吸収剤、光安定剤が挙げられ、軟化剤にはパラフィン系オイル、ナフテン系オイル、アロマ系オイル、ナタネ油、ジオクチルフタレート、ジオクチルアジペートなどが挙げられ、加工助剤には高級脂肪酸、脂肪酸エステル、脂肪酸金属塩、脂肪酸アミド、パラフィンワックス、脂肪アルコール、フッ素・シリコーン系樹脂、高分子量ポリエチレンが挙げられる。 The composition of the present invention may further contain a filler, an anti-aging agent, a softening agent, and a processing aid depending on the purpose. For example, fillers include carbon black, wet silica, dry silica, calcium carbonate, kaolin, talc, clay, etc. Antiaging agents include antioxidants, ultraviolet absorbers, light stabilizers, softeners Include paraffinic oil, naphthenic oil, aroma oil, rapeseed oil, dioctyl phthalate, dioctyl adipate, etc., and processing aids include higher fatty acids, fatty acid esters, fatty acid metal salts, fatty acid amides, paraffin wax, fatty alcohols , Fluorine / silicone resin, and high molecular weight polyethylene.
本発明の組成物からなる配合物を得るには、公知の溶融混練の方法が適用できる。例えばイソブチレン系ブロック共重合体、エチレン−ビニルアルコール共重合体、さらに所定の物性を得るために配合される他の成分を、加熱混練機、例えば、一軸押出機、二軸押出機、ロール、バンバリーミキサー、ブラベンダー、ニーダー、高剪断型ミキサー等を用いて溶融混練することで製造することができる。溶融混練の温度は、１００〜２４０℃が好ましい。１００℃よりも低い温度ではイソブチレン系ブロック共重合体、エチレン−ビニルアルコール共重合体の溶融が不十分となり、混練が不均一となる傾向がある。２４０℃よりも高い温度では、イソブチレン系ブロック共重合体、エチレン−ビニルアルコール共重合体の熱分解、熱架橋が起こる傾向がある。得られた組成物を次に押出成形、カレンダー成形といった熱可塑性樹脂、熱可塑性エラストマーをフィルム化する通常の方法によってフィルム化すれば良い。 In order to obtain a composition comprising the composition of the present invention, a known melt-kneading method can be applied. For example, an isobutylene block copolymer, an ethylene-vinyl alcohol copolymer, and other components blended in order to obtain predetermined physical properties are mixed with a heating kneader, for example, a single screw extruder, a twin screw extruder, a roll, a banbury. It can be produced by melt-kneading using a mixer, Brabender, kneader, high shear mixer or the like. The temperature for melt kneading is preferably 100 to 240 ° C. When the temperature is lower than 100 ° C., the isobutylene block copolymer and the ethylene-vinyl alcohol copolymer are not sufficiently melted, and the kneading tends to be uneven. When the temperature is higher than 240 ° C., thermal decomposition and thermal crosslinking of the isobutylene block copolymer and the ethylene-vinyl alcohol copolymer tend to occur. What is necessary is just to film-form the obtained composition by the normal method of film-forming thermoplastic resin and thermoplastic elastomer, such as extrusion molding and calendar molding.
本発明の組成物は、インナーライナー、特にタイヤ用インナーライナーに好適に使用できる。 The composition of the present invention can be suitably used for an inner liner, particularly a tire inner liner.
本発明のインナーライナーの厚みは合計２０μｍ〜１５００μｍの範囲に有ることが好ましい。厚みが２０μｍを下回るとインナーライナーの耐屈曲性が低下しタイヤ転動時の屈曲変形による破断や亀裂が生じる恐れがある。一方厚みが１５００μｍを超えるとタイヤ重量低減のメリットが少なくなる。 The thickness of the inner liner of the present invention is preferably in the range of 20 μm to 1500 μm in total. When the thickness is less than 20 μm, the bending resistance of the inner liner is lowered, and there is a risk of breakage or cracking due to bending deformation at the time of tire rolling. On the other hand, when the thickness exceeds 1500 μm, the merit of reducing the tire weight is reduced.
以下、実施例にて本発明をさらに詳しく説明するが、これらの実施例によって本発明は何ら限定されるものではない。
尚、実施例に先立ち各種測定法、評価法、実施例について説明する。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
Prior to the examples, various measurement methods, evaluation methods, and examples will be described.
（引張弾性率）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。弾性率は歪みが０．５％〜５％の応力を基に算出した。
(Tensile modulus)
In accordance with JIS K 6251, a test piece prepared by punching a sheet into a No. 7 type with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min. The elastic modulus was calculated based on the stress having a strain of 0.5% to 5%.
（引張強度）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。
(Tensile strength)
In accordance with JIS K 6251, a test piece prepared by punching a sheet into a No. 7 type with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min.
（引張伸び）
ＪＩＳ Ｋ ６２５１に準拠し、試験片としてシートをダンベルで７号型に打抜いたものを用意し、これを測定に使用した。引張速度は１００ｍｍ／分とした。
(Tensile elongation)
In accordance with JIS K 6251, a test piece prepared by punching a sheet into a No. 7 type with a dumbbell was prepared and used for measurement. The tensile speed was 100 mm / min.
（ガスバリア性）
ガスバリア性は気体透過性を評価し、酸素の透過度を評価した。酸素の透過度は、得られたシートから１００ｍｍ×１００ｍｍの試験片を切り出し、ＪＩＳＫ７１２６に準拠して、２３℃、０％ＲＨ、１ａｔｍの差圧法にて測定した。
(Gas barrier properties)
For gas barrier properties, gas permeability was evaluated, and oxygen permeability was evaluated. The oxygen permeability was measured by cutting out a 100 mm × 100 mm test piece from the obtained sheet and measuring it at 23 ° C., 0% RH, 1 atm in accordance with JISK7126.
（接着性）
イソプレンゴムとの接着性を評価した。（製造例１）のイソプレンゴムの２ｍｍ厚未加硫シートと貼り合わせ、１５０℃、５０ＭＰａで４０分加熱加圧加硫を行った後、幅２ｃｍ×６ｃｍに切り出した後、１８０°剥離試験を行った際の応力を測定した。試験速度は２００ｍｍ／ｍｉｎで行い、剥離開始後３ｃｍ〜５ｃｍの応力の平均値を採用した。
(Adhesiveness)
The adhesion with isoprene rubber was evaluated. After bonding with a 2 mm thick unvulcanized sheet of isoprene rubber of (Production Example 1), heating and pressure vulcanization at 150 ° C. and 50 MPa for 40 minutes, and then cutting out to a width of 2 cm × 6 cm, a 180 ° peel test The stress during the run was measured. The test speed was 200 mm / min, and an average value of stress of 3 cm to 5 cm was adopted after the start of peeling.
（実施例等記載成分の内容）
成分（Ａ）−１（イソブチレン系ブロック共重合体）：（スチレン／β−ピネン）−イソブチレン−（スチレン／β−ピネン）ブロック共重合体 β−ピネン含量９．７重量％ 数平均分子量１０，３０００ （製造例２）
成分（Ａ）―２（イソブチレン系ブロック共重合体）：（スチレン／β−ピネン）−イソブチレン−（スチレン／β−ピネン）ブロック共重合体 β−ピネン含量５．３重量％ 数平均分子量１０，７０００（製造例３）
成分（Ａ）―３（イソブチレン系ブロック共重合体）：スチレン−（イソブチレン／β−ピネン）−スチレンブロック共重合体 β−ピネン含量５．３重量％ 数平均分子量１０，９０００（製造例４）
成分（Ｂ）（エチレン−ビニルアルコール共重合体）：エチレン含量４４ｍｏｌ％エチレン−ビニルアルコール共重合体（株式会社クラレ社製 商品名「ＥＶＡＬ Ｅ１０５Ｂ」）
架橋剤：硫黄（関東化学社製）
架橋助剤１：ジ-２-ベンゾチアゾリルジスルフィド
架橋助剤２：酸化亜鉛
架橋助剤３：ステアリン酸
粘着付与剤：脂環族飽和炭化水素樹脂（荒川化学社製「アルコンＰ−７０」）
老化防止剤：株式会社アデカ社製「ＡＯ−５０」
ＳＩＢＳ：スチレン−イソブチレン−スチレンブロック共重合体（製造例５）。
(Contents of description components such as Examples)
Component (A) -1 (isobutylene block copolymer): (styrene / β-pinene) -isobutylene- (styrene / β-pinene) block copolymer β-pinene content 9.7% by weight Number average molecular weight 10, 3000 (Production Example 2)
Component (A) -2 (isobutylene block copolymer): (styrene / β-pinene) -isobutylene- (styrene / β-pinene) block copolymer β-pinene content 5.3% by weight Number average molecular weight 10, 7000 (Production Example 3)
Component (A) -3 (isobutylene block copolymer): Styrene- (isobutylene / β-pinene) -styrene block copolymer β-pinene content 5.3 wt% Number average molecular weight 10,9000 (Production Example 4)
Component (B) (ethylene-vinyl alcohol copolymer): ethylene content 44 mol% ethylene-vinyl alcohol copolymer (trade name “EVAL E105B” manufactured by Kuraray Co., Ltd.)
Crosslinking agent: Sulfur (manufactured by Kanto Chemical)
Crosslinking aid 1: Di-2-benzothiazolyl disulfide crosslinking aid 2: Zinc oxide crosslinking aid 3: Stearic acid tackifier: Alicyclic saturated hydrocarbon resin ("Arcon P-70" manufactured by Arakawa Chemical Co., Ltd.) )
Anti-aging agent: “AO-50” manufactured by Adeka Co., Ltd.
SIBS: Styrene-isobutylene-styrene block copolymer (Production Example 5).
（製造例１）イソプレンゴムシートの作製
イソプレンゴム（株式会社ＪＳＲ社製 商品名「ＩＲ２２００」）を４００ｇ、カーボンブラック（旭カーボン旭♯５０）２００ｇを４０℃に設定した１Ｌニーダー（株式会社モリヤマ社製）に投入し５０ｒｐｍで５分間混練した後、硫黄６ｇ、N-ｔｅｒｔ-ブチル-２-ベンゾチアゾルスルフェンアミド８ｇ、酸化亜鉛８ｇ、ステアリン酸８ｇを投入し２分間混練した後排出し、８０℃で加熱プレス（神藤金属社製）にて２ｍｍ厚のシート状に成形した。
(Production Example 1) Production of isoprene rubber sheet 1 L kneader (Molyama Co., Ltd.) in which 400 g of isoprene rubber (trade name “IR2200” manufactured by JSR Corporation) and 200 g of carbon black (Asahi Carbon Asahi # 50) were set at 40 ° C. And then kneaded for 5 minutes at 50 rpm, 6 g of sulfur, 8 g of N-tert-butyl-2-benzothiazolsulfenamide, 8 g of zinc oxide and 8 g of stearic acid were added, kneaded for 2 minutes and then discharged. The sheet was formed into a sheet having a thickness of 2 mm at 80 ° C. with a heating press (manufactured by Shinto Metal Co., Ltd.).
（製造例２）［（スチレン／β−ピネン）−イソブチレン−（スチレン／β−ピネン）ブロック共重合体（成分（Ａ）−１）］の製造］
２Ｌのセパラブルフラスコの重合容器内を窒素置換した後、注射器を用いて、ｎ−ヘキサン（モレキュラーシーブスで乾燥したもの）３１．０ｍＬ及び塩化ブチル（モレキュラーシーブスで乾燥したもの）２９４．６ｍＬを加え、重合容器を−７０℃のドライアイス／メタノールバス中につけて冷却した後、イソブチレンモノマー８８．９ｍＬ（９４１．６ｍｍｏｌ）が入っている三方コック付耐圧ガラス製液化採取管にテフロン(登録商標）製の送液チューブを接続し、重合容器内にイソブチレンモノマーを窒素圧により送液した。ｐ−ジクミルクロライド０．１４８ｇ（０．６ｍｍｏｌ）及びα−ピコリン０．０７ｇ（０．８ｍｍｏｌ）を加えた。次にさらに四塩化チタン０．８７ｍＬ（７．９ｍｍｏｌ）を加えて重合を開始した。重合開始から１．５時間同じ温度で撹拌を行った後、重合溶液からサンプリング用として重合溶液約１ｍＬを抜き取った。続いて、あらかじめ−７０℃に冷却しておいたスチレンモノマー１０．４ｇ（９９．４ｍｍｏｌ）とβ−ピネン６．８ｇ（４９．７ｍｍｏｌ）をよく混ぜ均一にした後重合容器内に添加した。スチレンとβ−ピネン添加４５分後に約４０ｍＬのメタノールを加えて反応を終了させた。反応溶液から溶剤等を留去した後、トルエンに溶解し２回水洗を行った。さらにトルエン溶液を多量のメタノールに加えて重合体を沈殿させ、得られた重合体を６０℃で２４時間真空乾燥することにより目的のブロック共重合体を得た。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により得られた重合体の分子量を測定した。Ｍｎが１０３，０００、Ｍｗ／Ｍｎが１．２１であるブロック共重合体が得られた。
(Production Example 2) [Production of ((styrene / β-pinene) -isobutylene- (styrene / β-pinene) block copolymer (component (A) -1)])
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 31.0 mL of n-hexane (dried with molecular sieves) and 294.6 mL of butyl chloride (dried with molecular sieves) were added using a syringe. The polymerization vessel was placed in a dry ice / methanol bath at −70 ° C. and cooled, and then a Teflon (registered trademark) made of a pressure-resistant glass liquefied collection tube with a three-way cock containing isobutylene monomer 88.9 mL (941.6 mmol) The liquid feeding tube was connected, and the isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.148 g (0.6 mmol) of p-dicumyl chloride and 0.07 g (0.8 mmol) of α-picoline were added. Next, 0.87 mL (7.9 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 10.4 g (99.4 mmol) of styrene monomer that had been cooled to −70 ° C. in advance and 6.8 g (49.7 mmol) of β-pinene were mixed well and then added to the polymerization vessel. About 40 mL of methanol was added 45 minutes after addition of styrene and β-pinene to terminate the reaction. After distilling off the solvent from the reaction solution, it was dissolved in toluene and washed twice with water. Further, the toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. A block copolymer having Mn of 103,000 and Mw / Mn of 1.21 was obtained.
（製造例３）［（スチレン／β−ピネン）−イソブチレン−（スチレン／β−ピネン）ブロック共重合体（成分（Ａ）−２）］の製造］
２Ｌのセパラブルフラスコの重合容器内を窒素置換した後、注射器を用いて、ｎ−ヘキサン（モレキュラーシーブスで乾燥したもの）３１．０ｍＬ及び塩化ブチル（モレキュラーシーブスで乾燥したもの）２９４．６ｍＬを加え、重合容器を−７０℃のドライアイス／メタノールバス中につけて冷却した後、イソブチレンモノマー８８．９ｍＬ（９４１．６ｍｍｏｌ）が入っている三方コック付耐圧ガラス製液化採取管にテフロン(登録商標）製の送液チューブを接続し、重合容器内にイソブチレンモノマーを窒素圧により送液した。ｐ−ジクミルクロライド０．１４８ｇ（０．６ｍｍｏｌ）及びα−ピコリン０．０７ｇ（０．８ｍｍｏｌ）を加えた。次にさらに四塩化チタン０．８７ｍＬ（７．９ｍｍｏｌ）を加えて重合を開始した。重合開始から１．５時間同じ温度で撹拌を行った後、重合溶液からサンプリング用として重合溶液約１ｍＬを抜き取った。続いて、あらかじめ−７０℃に冷却しておいたスチレンモノマー１０．４ｇ（９９．４ｍｍｏｌ）とβ−ピネン３．６ｇ（２６．３ｍｍｏｌ）をよく撹拌し均一にした後重合容器内に添加した。スチレンとβ−ピネン添加４５分後に約４０ｍＬのメタノールを加えて反応を終了させた。反応溶液から溶剤等を留去した後、トルエンに溶解し２回水洗を行った。さらにトルエン溶液を多量のメタノールに加えて重合体を沈殿させ、得られた重合体を６０℃で２４時間真空乾燥することにより目的のブロック共重合体を得た。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により得られた重合体の分子量を測定した。Ｍｎが１０７，０００、Ｍｗ／Ｍｎが１．２３であるブロック共重合体が得られた。
(Production Example 3) [Production of ((styrene / β-pinene) -isobutylene- (styrene / β-pinene) block copolymer (component (A) -2)])
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 31.0 mL of n-hexane (dried with molecular sieves) and 294.6 mL of butyl chloride (dried with molecular sieves) were added using a syringe. After the polymerization vessel was placed in a -70 ° C dry ice / methanol bath and cooled, a pressure-resistant glass liquefied collection tube with a three-way cock containing 88.9 mL (941.6 mmol) of isobutylene monomer was made of Teflon (registered trademark). The liquid feeding tube was connected, and the isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.148 g (0.6 mmol) of p-dicumyl chloride and 0.07 g (0.8 mmol) of α-picoline were added. Next, 0.87 mL (7.9 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 10.4 g (99.4 mmol) of styrene monomer that had been cooled to −70 ° C. in advance and 3.6 g (26.3 mmol) of β-pinene were well stirred and added to the polymerization vessel. About 40 mL of methanol was added 45 minutes after addition of styrene and β-pinene to terminate the reaction. After distilling off the solvent from the reaction solution, it was dissolved in toluene and washed twice with water. Further, the toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. A block copolymer having Mn of 107,000 and Mw / Mn of 1.23 was obtained.
（製造例４）［スチレン−（イソブチレン／β−ピネン）−スチレンブロック共重合体（成分（Ａ）−３）］の製造］
２Ｌのセパラブルフラスコの重合容器内を窒素置換した後、注射器を用いて、ｎ−ヘキサン（モレキュラーシーブスで乾燥したもの）３１．０ｍＬ及び塩化ブチル（モレキュラーシーブスで乾燥したもの）２９４．６ｍＬを加え、重合容器を−７０℃のドライアイス／メタノールバス中につけて冷却した後、β−ピネン３．６ｇ（２６．３ｍｍｏｌ）を添加し次いでイソブチレンモノマー８８．９ｍＬ（９４１．６ｍｍｏｌ）が入っている三方コック付耐圧ガラス製液化採取管にテフロン(登録商標）製の送液チューブを接続し、重合容器内にイソブチレンモノマーを窒素圧により送液した。さらにｐ−ジクミルクロライド０．１４８ｇ（０．６ｍｍｏｌ）及びα−ピコリン０．０７ｇ（０．８ｍｍｏｌ）を加えた。次にさらに四塩化チタン０．８７ｍＬ（７．９ｍｍｏｌ）を加えて重合を開始した。重合開始から４５分後、あらかじめ−７０℃に冷却しておいたスチレンモノマー１０．４ｇ（９９．４ｍｍｏｌ）を重合容器内に添加した。スチレンを添加してから４５分後に約４０ｍＬのメタノールを加えて反応を終了させた。反応溶液から溶剤等を留去した後、トルエンに溶解し２回水洗を行った。さらにトルエン溶液を多量のメタノールに加えて重合体を沈殿させ、得られた重合体を６０℃で２４時間真空乾燥することにより目的のブロック共重合体を得た。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により得られた重合体の分子量を測定した。Ｍｎが１０９，０００、Ｍｗ／Ｍｎが１．２１であるブロック共重合体が得られた。
(Production Example 4) [Production of styrene- (isobutylene / β-pinene) -styrene block copolymer (component (A) -3)]
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 31.0 mL of n-hexane (dried with molecular sieves) and 294.6 mL of butyl chloride (dried with molecular sieves) were added using a syringe. The polymerization vessel was placed in a dry ice / methanol bath at −70 ° C. and cooled, and then 3.6 g (26.3 mmol) of β-pinene was added, followed by three-way containing 88.9 mL (941.6 mmol) of isobutylene monomer. A Teflon (registered trademark) feeding tube was connected to a pressure-resistant glass liquefied collection tube with a cock, and isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. Further, 0.148 g (0.6 mmol) of p-dicumyl chloride and 0.07 g (0.8 mmol) of α-picoline were added. Next, 0.87 mL (7.9 mmol) of titanium tetrachloride was further added to initiate polymerization. 45 minutes after the start of the polymerization, 10.4 g (99.4 mmol) of a styrene monomer that had been cooled to -70 ° C in advance was added to the polymerization vessel. About 40 mL of methanol was added 45 minutes after the addition of styrene to terminate the reaction. After distilling off the solvent from the reaction solution, it was dissolved in toluene and washed twice with water. Further, the toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. A block copolymer having Mn of 109,000 and Mw / Mn of 1.21 was obtained.
（製造例５）［スチレン−イソブチレン−スチレンブロック共重合体（ＳＩＢＳ）］の製造］
２Ｌのセパラブルフラスコの重合容器内を窒素置換した後、注射器を用いて、ｎ−ヘキサン（モレキュラーシーブスで乾燥したもの）３１．０ｍＬ及び塩化ブチル（モレキュラーシーブスで乾燥したもの）２９４．６ｍＬを加え、重合容器を−７０℃のドライアイス／メタノールバス中につけて冷却した後、イソブチレンモノマー８８．９ｍＬ（９４１．６ｍｍｏｌ）が入っている三方コック付耐圧ガラス製液化採取管にテフロン(登録商標）製の送液チューブを接続し、重合容器内にイソブチレンモノマーを窒素圧により送液した。ｐ−ジクミルクロライド０．１４８ｇ（０．６ｍｍｏｌ）及びα−ピコリン０．０７ｇ（０．８ｍｍｏｌ）を加えた。次にさらに四塩化チタン０．８７ｍＬ（７．９ｍｍｏｌ）を加えて重合を開始した。重合開始から１．５時間同じ温度で撹拌を行った後、重合溶液からサンプリング用として重合溶液約１ｍＬを抜き取った。続いて、あらかじめ−７０℃に冷却しておいたスチレンモノマー１０．４ｇ（９９．４ｍｍｏｌ）を重合容器内に添加した。スチレンを添加４５分後に約４０ｍＬのメタノールを加えて反応を終了させた。反応溶液から溶剤等を留去した後、トルエンに溶解し２回水洗を行った。さらにトルエン溶液を多量のメタノールに加えて重合体を沈殿させ、得られた重合体を６０℃で２４時間真空乾燥することにより目的のブロック共重合体を得た。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により得られた重合体の分子量を測定した。Ｍｎが１０１，０００、Ｍｗ／Ｍｎが１．２３であるブロック共重合体が得られた。
(Production Example 5) [Production of styrene-isobutylene-styrene block copolymer (SIBS)]
After the inside of the polymerization vessel of the 2 L separable flask was purged with nitrogen, 31.0 mL of n-hexane (dried with molecular sieves) and 294.6 mL of butyl chloride (dried with molecular sieves) were added using a syringe. The polymerization vessel was placed in a dry ice / methanol bath at −70 ° C. and cooled, and then a Teflon (registered trademark) made of a pressure-resistant glass liquefied collection tube with a three-way cock containing isobutylene monomer 88.9 mL (941.6 mmol) The liquid feeding tube was connected, and the isobutylene monomer was fed into the polymerization vessel by nitrogen pressure. 0.148 g (0.6 mmol) of p-dicumyl chloride and 0.07 g (0.8 mmol) of α-picoline were added. Next, 0.87 mL (7.9 mmol) of titanium tetrachloride was further added to initiate polymerization. After stirring at the same temperature for 1.5 hours from the start of polymerization, about 1 mL of the polymerization solution was extracted from the polymerization solution for sampling. Subsequently, 10.4 g (99.4 mmol) of a styrene monomer that had been cooled to −70 ° C. in advance was added to the polymerization vessel. About 40 mL of methanol was added 45 minutes after the addition of styrene to terminate the reaction. After distilling off the solvent from the reaction solution, it was dissolved in toluene and washed twice with water. Further, the toluene solution was added to a large amount of methanol to precipitate a polymer, and the obtained polymer was vacuum-dried at 60 ° C. for 24 hours to obtain a target block copolymer. The molecular weight of the polymer obtained by the gel permeation chromatography (GPC) method was measured. A block copolymer having Mn of 101,000 and Mw / Mn of 1.23 was obtained.
（実施例１）
成分（Ａ）−１、老化防止剤を表１の割合で配合し、２軸押出機を用いて１７０℃で混練しペレットを得た。得られたペレットはＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）を取り付け、ダイ温度１８０℃に設定した単軸押出機に投入され出てきたフィルムをロールにて引き取り１０００μｍの厚みのフィルムを得た。得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
Example 1
Component (A) -1 and an antioxidant were blended in the proportions shown in Table 1 and kneaded at 170 ° C. using a twin-screw extruder to obtain pellets. The obtained pellet was attached with a T die (die lip diameter of 2000 μm, width of 200 mm), and the film introduced into a single-screw extruder set at a die temperature of 180 ° C. was taken out with a roll to obtain a film having a thickness of 1000 μm. The tensile test, gas barrier property, and adhesiveness of the obtained film were measured.
（実施例２）
成分（Ａ）−１を成分（Ａ）−２に変更した以外は実施例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 2)
A film was obtained in the same manner as in Example 1 except that the component (A) -1 was changed to the component (A) -2, and the tensile test, gas barrier property, and adhesiveness of the obtained film were measured.
（実施例３）
成分（Ａ）−１を成分（Ａ）−３に変更した以外は実施例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 3)
A film was obtained in the same manner as in Example 1 except that the component (A) -1 was changed to the component (A) -3, and the tensile test, gas barrier property, and adhesiveness of the obtained film were measured.
（実施例４）
成分（Ａ）−１、成分（Ｂ）、老化防止剤を表１の割合で配合し実施例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
Example 4
A component (A) -1, a component (B), and an antioxidant were blended in the proportions shown in Table 1, and a film was obtained in the same manner as in Example 1, and the tensile test, gas barrier property, and adhesion of the obtained film were measured. Went.
（実施例５）
成分（Ｂ）の配合量を表１に従って変更した以外は実施例４と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 5)
Except having changed the compounding quantity of the component (B) according to Table 1, it carried out similarly to Example 4, and obtained the film, and measured the tensile test of the obtained film, gas barrier property, and adhesiveness.
（実施例６）
成分（Ａ）−２、架橋助剤１〜３と老化防止剤を表１の割合で配合し実施例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 6)
Ingredient (A) -2, crosslinking aids 1 to 3 and anti-aging agent were blended in the proportions shown in Table 1 to obtain a film in the same manner as in Example 1, and a tensile test, gas barrier properties, and adhesiveness of the obtained film were obtained. Was measured.
（実施例７）
成分（Ａ）−１、粘着付与剤と老化防止剤を表１の割合で配合し実施例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Example 7)
Ingredient (A) -1, a tackifier and an anti-aging agent were blended in the proportions shown in Table 1, and a film was obtained in the same manner as in Example 1, and the tensile test, gas barrier property and adhesiveness of the obtained film were measured. went.
（比較例１）
ＳＩＢＳと老化防止剤を表１の割合で配合し２軸押出機を用いて１７０℃で混練しペレットを得た。得られたペレットをＴダイ（ダイリップ径２０００μｍ、幅２００ｍｍ）を取り付け、ダイ温度１８０℃に設定した単軸押出機に投入し出てきたフィルムをロールにて引き取り１０００μｍの厚みのフィルムを得た。得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Comparative Example 1)
SIBS and an antioxidant were blended in the proportions shown in Table 1 and kneaded at 170 ° C. using a twin screw extruder to obtain pellets. A T-die (die lip diameter: 2000 μm, width: 200 mm) was attached to the obtained pellet, and the film that had been put out into a single-screw extruder set at a die temperature of 180 ° C. was taken up with a roll to obtain a film having a thickness of 1000 μm. The tensile test, gas barrier property, and adhesiveness of the obtained film were measured.
（比較例２）
ＳＩＢＳ、架橋助剤１〜３と老化防止剤を表１の割合で配合し比較例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Comparative Example 2)
SIBS, crosslinking aids 1 to 3 and an anti-aging agent were blended in the proportions shown in Table 1, and a film was obtained in the same manner as in Comparative Example 1, and the tensile test, gas barrier properties, and adhesion of the obtained film were measured. .
（比較例３）
ＳＩＢＳ、成分（Ｂ）、老化防止剤を表１の割合で配合し比較例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Comparative Example 3)
SIBS, component (B), and anti-aging agent were blended in the proportions shown in Table 1, and a film was obtained in the same manner as in Comparative Example 1, and the tensile test, gas barrier properties, and adhesiveness of the obtained film were measured.
（比較例４）
ＳＩＢＳ、粘着付与剤と老化防止剤を表１の割合で配合し比較例１と同様にして、フィルムを得て、得たフィルムの引張試験、ガスバリア性、接着性の測定を行った。
(Comparative Example 4)
SIBS, a tackifier, and an anti-aging agent were blended in the proportions shown in Table 1, and a film was obtained in the same manner as in Comparative Example 1, and the tensile test, gas barrier properties, and adhesiveness of the obtained film were measured.
（比較例５）
ブチルゴム（株式会社ＪＳＲ社製 商品名「ブチル２６８」）を４００ｇ、カーボンブラック（旭カーボン旭♯５０）１２０ｇを４０℃に設定した１Ｌニーダー（株式会社モリヤマ社製）に投入し５０ｒｐｍで５分間混練した後、硫黄８ｇ、N-ｔｅｒｔ-ブチル-２-ベンゾチアゾリルスルフェンアミド８ｇ、酸化亜鉛１２ｇ、ステアリン酸８ｇ、プロセスオイル（株式会社出光興産社製 商品名「ＰＷ３８０」）８０ｇを投入し２分間混練した後排出し、８０℃で加熱プレス（神藤金属にて１０００μｍ厚のシート状に成形した。一部はシートを１５０℃２０分間加熱プレスした後、引張試験、ガスバリア性の測定を行った。残りのシートを用いて比較例１と同様にして接着性の評価を行った。
(Comparative Example 5)
400 g of butyl rubber (trade name “butyl 268” manufactured by JSR Corporation) and 120 g of carbon black (Asahi Carbon Asahi # 50) are charged into a 1 L kneader (manufactured by Moriyama Co., Ltd.) set at 40 ° C. and kneaded at 50 rpm for 5 minutes. After that, 8 g of sulfur, 8 g of N-tert-butyl-2-benzothiazolylsulfenamide, 12 g of zinc oxide, 8 g of stearic acid, and 80 g of process oil (trade name “PW380” manufactured by Idemitsu Kosan Co., Ltd.) After kneading for a minute, the product was discharged and heated at 80 ° C. (formed into a sheet having a thickness of 1000 μm by Shinto Metal. Part of the sheet was heated and pressed at 150 ° C. for 20 minutes, and then a tensile test and gas barrier properties were measured. Using the remaining sheets, the adhesion was evaluated in the same manner as in Comparative Example 1.
実施例１〜７は剥離強度が６５Ｎ／２０ｍｍ以上であるのに対し、β−ピネンを有さない重合体を用いた比較例１〜４は３〜８Ｎ／２０ｍｍと低い接着強度である。また、実施例１〜７は通常のプラスチック用の押出機を用いて成形されており比較例５の従来の加硫ゴムのプロセスと比較して生産性に優れている。また、成分（Ｂ）を用いた実施例４，５はガスバリア性に非常に優れておりインナーライナーの薄肉化、軽量化に貢献できる。 Examples 1 to 7 have a peel strength of 65 N / 20 mm or more, while Comparative Examples 1 to 4 using a polymer having no β-pinene have a low adhesive strength of 3 to 8 N / 20 mm. In addition, Examples 1 to 7 are molded using an ordinary plastic extruder, and are superior in productivity to the conventional vulcanized rubber process of Comparative Example 5. In addition, Examples 4 and 5 using the component (B) are very excellent in gas barrier properties and can contribute to the reduction in thickness and weight of the inner liner.
これらの事から本発明のインナーライナー組成物はカーカスゴムへの接着とインナーライナーの生産性に優れていることが分かる。 From these facts, it can be seen that the inner liner composition of the present invention is excellent in adhesion to carcass rubber and productivity of the inner liner.
Claims (11)
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| WO2012057051A1 (en) | 2010-10-29 | 2012-05-03 | 株式会社カネカ | Isobutylene-based block copolymer |
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