JPS6395243A - Bead filler rubber composition - Google Patents
Bead filler rubber compositionInfo
- Publication number
- JPS6395243A JPS6395243A JP61240821A JP24082186A JPS6395243A JP S6395243 A JPS6395243 A JP S6395243A JP 61240821 A JP61240821 A JP 61240821A JP 24082186 A JP24082186 A JP 24082186A JP S6395243 A JPS6395243 A JP S6395243A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- rubber composition
- parts
- weight
- composition
- 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
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 123
- 239000005060 rubber Substances 0.000 title claims abstract description 123
- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000011324 bead Substances 0.000 title claims abstract description 36
- 239000000945 filler Substances 0.000 title claims abstract description 34
- 239000004952 Polyamide Substances 0.000 claims abstract description 29
- 229920002647 polyamide Polymers 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 26
- 229920001194 natural rubber Polymers 0.000 claims abstract description 25
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 18
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000004898 kneading Methods 0.000 abstract description 6
- 238000001125 extrusion Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 2
- 238000000034 method Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 235000019241 carbon black Nutrition 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- -1 N-vinylbenzylaminoethyl Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 229920001195 polyisoprene Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- HEXHLHNCJVXPNU-UHFFFAOYSA-N 2-(trimethoxysilylmethyl)butane-1,4-diamine Chemical compound CO[Si](OC)(OC)CC(CN)CCN HEXHLHNCJVXPNU-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ムーニー粘度（ＭＬ）が小さくて加工性に優
れ、かつ加硫物の耐屈曲亀裂成長性が良好なビードフィ
ラーゴム組成物に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a bead filler rubber composition that has a small Mooney viscosity (ML), excellent processability, and good flex crack growth resistance of vulcanizates. It is something.
最近、高速道路等の高速走行可能な道路の普及に伴い、
タイヤにはよりシビアな高速耐久性が要求されるように
なってきた。タイヤは高速で走行すればする程スタンデ
ィングウェーブ現象を発生し易くなり、ひいてはタイヤ
破裂につながることはよ（知られている。このスタンデ
ィングウェーブ現象を抑制する有効な手法の一つにビー
ド部の剛性を向上させることが考えられる。又ビード部
の高弾性率化は転がり抵抗の低減にも効果があることか
ら、ビードフィラーゴムとしては弾性率の高いものが好
ましい。Recently, with the spread of high-speed roads such as expressways,
Tires are now required to have more severe high-speed durability. It is known that the faster a tire is run, the more likely it is that standing wave phenomenon will occur, which can even lead to tire bursting.One effective method to suppress this standing wave phenomenon is to increase the rigidity of the bead. In addition, since increasing the elastic modulus of the bead portion is effective in reducing rolling resistance, it is preferable that the bead filler rubber has a high elastic modulus.
一方、スタンディングウェーブ現象が一旦発生するとビ
ード部は太き（変形するため、安全上の見地からビード
フィラーゴムの耐亀裂成長性が良くて直ぐにはタイヤ破
壊に至らないことが必要である。即ち、タイヤの高速耐
久性を改善するためのビードフィラーゴムに必要な条件
として、高弾性率であること、耐亀裂成長性の良いこと
が挙げられる。On the other hand, once the standing wave phenomenon occurs, the bead becomes thick (deformed), so from a safety standpoint, it is necessary that the bead filler rubber has good crack growth resistance and does not immediately lead to tire failure. Requirements for bead filler rubber to improve the high-speed durability of tires include a high modulus of elasticity and good crack growth resistance.
而して、高弾性率のゴムを得る方法としては従来から種
々の方法が試みられているが、それぞれ問題を有してい
る。カーボンブラックを大量に配合する方法は、加工工
程中でのゴムのまとまりが悪いこと、バンバリーミキサ
−混練時に電力負荷が増大すること、配合物ＭＬが大き
くなるのでタイヤ成型作業に困難が伴うこと等のため好
ましくない。イオウを多量に配合する方法は、イオウが
ブルームすること、架橋密度の増大による屈曲亀裂成長
性等の物性に著しい低下を来す等の問題がある。また、
熱硬化性樹脂を添加する方法もゴムに高弾性率を付与す
る一方法であるが、多量の熱硬化性樹脂は天然ゴムやジ
エン系ゴムと相溶性が低いので、熱硬化性樹脂の良好な
分散状態を得るには例えば混練時間を長くする必要があ
る等、製造条件が厳しい制約を受ける。また、多量の熱
硬化性樹脂を配合した練生地は未加硫時でも硬いので混
練・押出しの際負荷が太き（なったり成型作業性が劣っ
たりする。また、短繊維を単に配合する方法は、短繊維
とゴムとの結合が不十分なのでクリープが大きくなった
り、疲労寿命が低下したりする問題がある。Various methods have been tried in the past to obtain rubber with a high elastic modulus, but each method has its own problems. The method of blending a large amount of carbon black has problems such as poor cohesion of the rubber during the processing process, increased power load during kneading with a Banbury mixer, and difficulty in tire molding work as the compound ML increases. Therefore, it is not desirable. The method of blending a large amount of sulfur has problems such as blooming of sulfur and significant deterioration of physical properties such as flex crack growth properties due to an increase in crosslink density. Also,
Adding a thermosetting resin is also a method of imparting high elastic modulus to rubber, but since a large amount of thermosetting resin has low compatibility with natural rubber and diene rubber, it is difficult to obtain a good thermosetting resin. In order to obtain a dispersed state, the manufacturing conditions are subject to severe restrictions, such as the need to lengthen the kneading time. In addition, kneaded dough containing a large amount of thermosetting resin is hard even when unvulcanized, so the load is heavy during kneading and extrusion, and the molding workability is poor. However, since the bond between the short fibers and the rubber is insufficient, there are problems such as increased creep and reduced fatigue life.
従って、本発明の目的は、上述の従来技術の問題点、即
ち、生産性の低さ、耐亀裂成長性の低さ等の問題点を解
決し、生産性、加工性に優れ、また、加硫物の弾性率が
大きくて耐屈曲亀裂成長性が良好なビードフィラーゴム
組成物を提供することにある。Therefore, an object of the present invention is to solve the problems of the prior art described above, such as low productivity and low crack growth resistance, and to achieve excellent productivity and processability. It is an object of the present invention to provide a bead filler rubber composition having a high elastic modulus of sulfur and good resistance to flex crack growth.
本発明は、加硫可能なゴム１００重量部に繊維形成可能
なポリアミドの微細な短繊維５〜１００重量部が埋封さ
れており、かつ該繊維の界面において前記ポリアミドと
前記ゴムとがシランカップリング剤を介して結合してい
る強化ゴム組成物（Ａ）、ジエン系ゴム（Ｂ）、及びカ
ーボンブラック（Ｃ）を配合してなり、かつ下記（Ｉ）
乃至（ｒＶ）の条件を満足することを特徴とするビード
フィラーゴム組成物により達成したものである。In the present invention, 5 to 100 parts by weight of fine short fibers of polyamide that can be formed into fibers are embedded in 100 parts by weight of vulcanizable rubber, and at the interface of the fibers, the polyamide and the rubber meet in a silane cup. A reinforced rubber composition (A), a diene rubber (B), and carbon black (C) bonded via a ring agent, and the following (I)
This was achieved using a bead filler rubber composition characterized by satisfying the conditions of (rV) to (rV).
（Ｉ）前記ポリアミドの量は、ゴム成分の合計１００重
量部に対して２〜２０重量部であり、（ＩＩ）ゴム成分
として、少なくとも天然ゴム及び／又はポリイソプレン
を用い、該天然ゴム及び／又はポリイソプレンの合計量
の割合が、全ゴム成分に対して５５〜１００重量％であ
り、（ＩＩ＋）カーボンブラックの量は、ゴム成分の合
計１００ｍＱ部に対して５０〜７０重量部であり、（Ｉ
Ｖ）５０％モジュラスが３０ｋｇ／ｃｎ１以上の加硫物
となる。(I) The amount of the polyamide is 2 to 20 parts by weight based on a total of 100 parts by weight of the rubber component, and (II) at least natural rubber and/or polyisoprene is used as the rubber component, and the natural rubber and/or polyisoprene are used as the rubber component. Or the proportion of the total amount of polyisoprene is 55 to 100% by weight based on the total rubber components, and the amount of (II+) carbon black is 50 to 70 parts by weight based on the total 100 mQ parts of the rubber components, (I
V) A vulcanizate with a 50% modulus of 30 kg/cn1 or more.
本発明のビードフィラーゴム組成物は、ムーニー粘度Ｍ
Ｌ、、、（Ｉ００°Ｃ）（以下、単にＭＬと略記するこ
ともある）が小さく、加硫物の５０％モジュラス（以下
、単にＭ、。と略記することもある）が３０ｋｇ／−以
上であり、耐屈曲亀裂成長試験による屈曲回数が１００
０回以上であり、加工性に優れ、かつ加硫物の弾性率が
大きくて耐亀裂成長性が良好であり、これらの優れた特
性を利用して、タイヤの一内部部材であるビードフィラ
ーに使用することができる。The bead filler rubber composition of the present invention has a Mooney viscosity of M
L,... (I00°C) (hereinafter sometimes simply abbreviated as ML) is small, and the 50% modulus of the vulcanizate (hereinafter sometimes simply abbreviated as M) is 30 kg/- or more , and the number of bending in the bending crack growth test is 100.
0 times or more, it has excellent processability, and the elastic modulus of the vulcanizate is high, and crack growth resistance is good. Utilizing these excellent properties, it is suitable for bead filler, which is an internal component of tires. can be used.
以下、本発明のビードフィラーゴム組成物について詳述
する。The bead filler rubber composition of the present invention will be described in detail below.
本発明のビードフィラーゴム組成物を構成する強化ゴム
組成物に用いられる加硫可能なゴムとしては、天然ゴム
、シス−１，４ポリブタジエン、ポリイソプレン、スチ
レン−ブタジェン共重合体ゴム、イソプレン−イソブチ
レン共重合体などを挙げることができ、これらのゴムの
中でも天然ゴムが好ましい。Vulcanizable rubbers used in the reinforced rubber composition constituting the bead filler rubber composition of the present invention include natural rubber, cis-1,4 polybutadiene, polyisoprene, styrene-butadiene copolymer rubber, and isoprene-isobutylene. Examples include copolymers, and among these rubbers, natural rubber is preferred.
また、前記強化ゴム組成物に用いられるポリアミドは、
繊維形成可能なもので、融点が１５０〜２６０”Ｃ，好
ましくは１９０〜２３５°Ｃの、ナイロン６、ナイロン
６１０、ナイロン１２、ナイロン６１１、ナイロン６１
２、ナイロン６６等を挙げることができる。また、この
ポリアミドとしては繊維形成能があれば特に制限はない
が、数平均分子ｉ５，０００以上、好ましくは８，００
０以上である。分子量があまりに低いと繊維形成能が悪
く強度も低い。Furthermore, the polyamide used in the reinforced rubber composition is
Nylon 6, nylon 610, nylon 12, nylon 611, nylon 61 which can be formed into fibers and has a melting point of 150 to 260"C, preferably 190 to 235"C.
2, nylon 66, etc. The polyamide is not particularly limited as long as it has fiber-forming ability, but the number average molecular i is 5,000 or more, preferably 8,000.
It is 0 or more. If the molecular weight is too low, the fiber forming ability will be poor and the strength will also be low.
本発明における強化ゴム組成物に用いられる短繊維は、
上記のポリアミドの微細な短繊維で、この短繊維は、繊
維軸方向に分子が配列された形態のもので、その平均径
が好ましくは０．０５〜０．８μ、特に断面円形で最短
繊維長が１μ以上のものが好ましい。The short fibers used in the reinforced rubber composition of the present invention are:
The fine short fibers of the above-mentioned polyamide, the short fibers have molecules arranged in the direction of the fiber axis, preferably have an average diameter of 0.05 to 0.8μ, particularly have a circular cross section and a shortest fiber length. is preferably 1μ or more.
また、前記強化ゴム組成物に用いられるシランカップリ
ング剤としては構造式Ｙ−Ｒ１ＳｉＸｓ、あるいは、Ｙ
Ｒ＋ Ｓ ｉ Ｒｇ Ｘｚで示される化合物が使用
される。In addition, the silane coupling agent used in the reinforced rubber composition has the structural formula Y-R1SiXs, or Y
A compound represented by R+ S i Rg Xz is used.
ここで、上記構造式におけるＹ、Ｒ＋ 、Ｒｚ、χは、
各々、下記の基を示す。Here, Y, R+, Rz, and χ in the above structural formula are
Each represents the following group.
ＣＩ 、 Ｈ３、ＣＭ Ｈｓ 。CI, H3, CM Hs.
Ｒ＋ ＋Ａ、ｃ、Ｈｚｌｌ Ｂ−Ｃ−Ｈｚ−Ｂ−ＣＩ
Ｈｚｔ（Ａ： Ｃ６Ｈ４、Ｂ ： Ｏ，ＮＨ
ｐ＝０〜２．ｎ＝０〜５．ｑ＝Ｏ〜２゜ｍ＝０〜５．
ｆｆ１＝０〜５ 〕Ｒ＊ ： ＣＲ
Ｈｚｅ−＋ （ＩＩ ＝ １〜４ 〕Ｘ ： Ｄｒ
Ｃ１ｌ Ｈｚ、ｌ Ｅ−Ｃ−Ｈｚ−−１（ｏ：ｏ、
Ｃ１，Ｅｇ。R+ +A, c, Hzll B-C-Hz-B-CI
Hzt(A: C6H4, B: O, NH p=0~2.n=0~5.q=O~2゜m=0~5.
ff1=0~5]R*: CR
Hz-+ (II = 1 to 4) X: Dr
C1l Hz, l E-C-Hz--1 (o:o,
C1, Eg.
ｒ＝０〜２． ｎ＝０−５． ｓ＝１〜２゜ｍ＝１
〜５ 〕従って、シラ
ンカップリング剤としては、具体的には、γ−アミノプ
ロピルトリメトキシシラン、Ｔ−アミノプロピルトリエ
トキシシラン、Ｎ−β（アミノエチル）Ｔ−アミノプロ
ピルトリメトキシシラン、Ｎ−β（アミノエチル）Ｔ−
アミノプロピルメチルジメトキシシラン、Ｔ−（ジエチ
レントリアミノ）プロピルトリメトキシシラン、Ｔ−ウ
レイドープロビルトリエトキシシランービニルトリエト
キシシラン、ビニルトリメトキシシラン、ビニルトリス
（βメトキシエトキシ）シラン、Ｔ−グリシドキシプロ
ピルメチルジェトキシシラン、γ−グリシドキシプロピ
ルトリメトキシシラン、β−（３，４エポキシシクロヘ
キシル）エチルトリメトキシシラン、Ｔ−メタクリロキ
シプロピルトリメトキシシラン、Ｔ−クロロプロピルト
リメトキシシラン、Ｔ−メルカプトプロピルトリメトキ
シシラン、Ｎ−フェニル−Ｔ−アミノプロピルトリエト
キシシラン、Ｎ−β（Ｎ−ビニルベンジルアミノエチル
）−γ−アミノプロピルトリメトキンシラン塩酸塩など
を挙げることができる。r=0-2. n=0-5. s=1~2゜m=1
~5] Therefore, specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, T-aminopropyltriethoxysilane, N-β(aminoethyl)T-aminopropyltrimethoxysilane, N- β(aminoethyl)T-
Aminopropylmethyldimethoxysilane, T-(diethylenetriamino)propyltrimethoxysilane, T-ureidoprobyltriethoxysilane-vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, T-glycidoxy Propylmethyljethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, T-methacryloxypropyltrimethoxysilane, T-chloropropyltrimethoxysilane, T-mercapto Examples include propyltrimethoxysilane, N-phenyl-T-aminopropyltriethoxysilane, and N-β(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethquinsilane hydrochloride.
而して、本発明に用いられる強化ゴム組成物は、前記の
加硫可能なゴム１００重量部に、前記のポリアミドの微
細な短繊維５〜１００重量部、好ましくは５〜７０重星
部、特に好ましくは３０〜７０重量部が埋封されており
、かつ前記ポリアミドと前記ゴムとがシランカンブリン
グ剤を介して結合しているもので、前記短繊維の界面に
おいて前記ポリアミドと前記ゴムとが前記シランカップ
リング剤を介して結合している。Thus, the reinforced rubber composition used in the present invention contains 5 to 100 parts by weight, preferably 5 to 70 parts by weight of the fine short polyamide fibers, to 100 parts by weight of the vulcanizable rubber. Particularly preferably, 30 to 70 parts by weight are embedded, and the polyamide and the rubber are bonded via a silane cambling agent, and the polyamide and the rubber are bonded at the interface of the short fibers. They are bonded via the silane coupling agent.
加硫可能なゴムに埋封されている短繊維の割合が前記下
限より少ないと、ビードフィラー組成物の強度及びモジ
ュラスが改善されず、加硫可能なゴムに埋封されている
短繊維の割合が前記上限より多いと、耐亀裂成長性が低
下する。If the proportion of short fibers embedded in vulcanizable rubber is less than the lower limit, the strength and modulus of the bead filler composition will not be improved, and the proportion of short fibers embedded in vulcanizable rubber will not improve. When the amount is more than the above upper limit, crack growth resistance decreases.
また、加硫可能なゴムに埋封されているポリアミドの微
細な短繊維の重量に対する加硫可能なゴムの重量の割合
（加硫可能なゴム／ポリアミドの微細な短繊維）が、１
０〜３０重量％、特に１５〜３０重λ％となるように短
繊維を形成するポリアミドと加硫可能なゴムとがシラン
カップリング剤を介して結合していることが好ましい。In addition, the ratio of the weight of the vulcanizable rubber to the weight of the polyamide fine short fibers embedded in the vulcanizable rubber (vulcanizable rubber/polyamide fine short fibers) is 1.
It is preferable that the short fiber-forming polyamide and the vulcanizable rubber are bonded via a silane coupling agent so that the weight is 0 to 30% by weight, particularly 15 to 30% by weight.
上述の如く、本発明で用いる強化ゴム組成物においては
、加硫可能なゴムにポリアミドの微細な短繊維が埋封さ
れており、且つ該短繊維の界面において前記ポリアミド
と加硫可能なゴムとがシランカップリング剤を介して結
合しているため、加硫物の弾性率及び屈曲回数が大きく
、ＭＬの小さい本発明のゴム組成物を得ることができる
。As mentioned above, in the reinforced rubber composition used in the present invention, fine short fibers of polyamide are embedded in vulcanizable rubber, and the polyamide and vulcanizable rubber are bonded at the interface of the short fibers. are bonded via a silane coupling agent, it is possible to obtain the rubber composition of the present invention with a high elastic modulus and bending frequency of the vulcanizate and a small ML.
本発明で用いる上述の強化ゴム組成物は、例えば次のよ
うにして製造される。加硫可能なゴム、該加硫可能なゴ
ム１００重量部当り５〜１００重量部のポリアミド、及
び該ポリアミド１００重量部当りシランカップリング剤
０．１〜５．５重量部を、前記ポリアミドの融点以上の
温度で混練し、得られた混練物を前記ポリアミドの融点
以上の温度で押し出すことにより、或いは更に、適宜前
記押出物を前記ポリアミドの融点より高い温度で又は前
記ポリアミドの融点より低い温度で延伸することにより
得られる。更に、前記押出物を前記ポリアミドの融点よ
り高い温度で延伸し且つ前記押出物を前記ポリアミドの
融点より低い温度で延伸することによっても得られる。The above-mentioned reinforced rubber composition used in the present invention is produced, for example, as follows. A vulcanizable rubber, 5 to 100 parts by weight of polyamide per 100 parts by weight of the vulcanizable rubber, and 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight of the polyamide, at a temperature of 0.1 to 5.5 parts by weight of a silane coupling agent per 100 parts by weight of the vulcanizable rubber; By kneading at the above temperature and extruding the obtained kneaded product at a temperature equal to or higher than the melting point of the polyamide, or further, as appropriate, extruding the extrudate at a temperature higher than the melting point of the polyamide or lower than the melting point of the polyamide. Obtained by stretching. Furthermore, it can also be obtained by stretching the extrudate at a temperature higher than the melting point of the polyamide and stretching the extrudate at a temperature lower than the melting point of the polyamide.
本発明のビードフィラーゴム組成物は、前記の強化ゴム
組成物（Ａ）に、ジエン系ゴム（Ｂ）及びカーボンブラ
ック（Ｃ）を配合してなるものである。The bead filler rubber composition of the present invention is obtained by blending the above-mentioned reinforced rubber composition (A) with a diene rubber (B) and carbon black (C).
前記のジエン系ゴム（Ｂ）としては、天然ゴム、ポリイ
ソプレン、シス−１，４ポリブタジエン、スチレン−ブ
タジェン共重合体ゴム、イソプレン−イソブチレン共重
合体などが挙げられる。Examples of the diene rubber (B) include natural rubber, polyisoprene, cis-1,4 polybutadiene, styrene-butadiene copolymer rubber, isoprene-isobutylene copolymer, and the like.
前記カーボンブラックとしては、粒子径９０ｍμ以下、
ジブチルフタレー） （ＤＢＰ）吸油量７Ｑｒｎ１７１
００ｇ以上のものが好適に使用され、例えばＨＡＦＳＦ
Ｆ、ＦＥＦＳＧＰＦ、ＳＡＦ、ｌ５ＡＦ、ＳＲＦなどの
各種カーボンブラックが挙げられる。The carbon black has a particle size of 90 mμ or less,
dibutyl phthale) (DBP) oil absorption 7Qrn171
00g or more is preferably used, for example HAFSF
Examples include various carbon blacks such as F, FEFSGPF, SAF, 15AF, and SRF.
また、本発明のビードフィラーゴム組成物は、下記条件
（Ｉ）〜（ＩＶ）を満足するように、前記各成分が配合
される。Moreover, the bead filler rubber composition of the present invention is blended with the above-mentioned components so as to satisfy the following conditions (I) to (IV).
（Ｉ）前記ポリアミド（短繊維）の量は、ゴム成分の合
計１００重量部に対して２〜２０重量部、好ましくは２
〜１５重量部であり、（ＩＩ）ゴム成分として、少なく
とも天然ゴム及び／又はポリイソプレンを用い、該天然
ゴム及び／又はポリイソプレンの合計量の割合が、全ゴ
ム成分に対して５５〜１００重量％であり、Ｃｍ＞カー
ボンブランクの量は、ゴム成分の合計１００重量部に対
して５０〜７０重量部であり、（ｆＶ）５０％モジュラ
スが３０ ｋｇ ／ ｃ＋ａ以上の加硫物となる。(I) The amount of the polyamide (short fiber) is 2 to 20 parts by weight, preferably 2 to 20 parts by weight, based on the total 100 parts by weight of the rubber components.
(II) At least natural rubber and/or polyisoprene is used as the rubber component, and the total amount of the natural rubber and/or polyisoprene is 55 to 100 parts by weight based on the total rubber component. %, Cm>The amount of carbon blank is 50 to 70 parts by weight based on the total 100 parts by weight of the rubber components, resulting in a vulcanizate with a (fV) 50% modulus of 30 kg/c+a or more.
前記ポリアミドの量が、前記範囲の下限より少ないとＭ
Ｌが小さく、加硫物の弾性率及び屈曲回数の大きいゴム
組成物が得られず、ポリアミドの星が前記範囲の上限よ
り多いと組成物のＭＬが大きくなり、加工性が悪化する
。また、ゴム成分としては、少なくとも天然ゴム及び／
またはポリイソプレンを用いる必要があり、それらの配
合割合が前記範囲外であると加硫物の屈曲回数が小さく
なる傾向にある。カーボンブラックの量が前記範囲の下
限より少ないと加硫物の弾性率が小さくなり、前記範囲
の上限より多いとゴム組成物のＭＬが大きく・なり、加
工性が悪化する。また、加硫物のＭ５゜が前記範囲外で
あると加硫物の弾性率が小さくなるため、ビードフィラ
ーゴム組成物として適当ではない。When the amount of the polyamide is less than the lower limit of the range, M
If L is small and the vulcanizate has a large elastic modulus and bending frequency, a rubber composition cannot be obtained, and if the number of polyamide stars is greater than the upper limit of the above range, the ML of the composition becomes large and processability deteriorates. Further, as the rubber component, at least natural rubber and/or
Alternatively, it is necessary to use polyisoprene, and if the blending ratio thereof is outside the above range, the number of bends of the vulcanizate tends to decrease. If the amount of carbon black is less than the lower limit of the above range, the elastic modulus of the vulcanizate will be small, and if it is more than the upper limit of the above range, the ML of the rubber composition will become large and processability will deteriorate. Furthermore, if the M5° of the vulcanizate is outside the above range, the modulus of elasticity of the vulcanizate will be low, making it unsuitable for use as a bead filler rubber composition.
本発明のビードフィラーゴム組成物は、前記各成分（Ａ
） 、（Ｉｔ）及び（Ｃ）をバンバリーミキサ−、ロー
ルなどの混練機を用い５０〜１８０°Ｃで１〜６０分間
程分間線することによって得ることができる。The bead filler rubber composition of the present invention has the above-mentioned components (A
), (It) and (C) can be obtained by stirring at 50 to 180°C for about 1 to 60 minutes using a kneader such as a Banbury mixer or a roll.
本発明のビードフィラーゴム組成物には、加硫剤などの
添加剤が配合される。Additives such as a vulcanizing agent are blended into the bead filler rubber composition of the present invention.
加硫剤としては、公知の加硫剤、たとえばイオウ、有機
過酸化剤、含イオウ化合物などを使用することができる
。加硫剤をゴム組成物に配合する方法については特に制
限はなく、それ自体公知の配合方法を採用することがで
きる。As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxidants, sulfur-containing compounds, etc. can be used. There are no particular restrictions on the method of blending the vulcanizing agent into the rubber composition, and any known blending method can be employed.
また、本発明のビードフィラーゴム組成物には、加硫剤
と共に、熱硬化性樹脂、ホワイトカーボン、活性化炭酸
カルシウム、超微粉けい酸マグネシウム、ハイスチレン
樹脂、クマロンインデン樹脂、フェノール樹脂、リグニ
ン、変性メラミン樹脂、石油樹脂などの補強剤、各種グ
レードの炭酸カルシウム、塩ｗ竹炭酸マグネシウム、ク
レー、亜鉛華、けいそう土、再生ゴム、粉末ゴム、エボ
ナイト粉末などの充填剤、アルデヒド、アンモニア類、
アルデヒド・アミン類、グアニジン類、チオウレア類、
チアゾール類、チウラム類、ジチオカーバメート類、キ
サンテート類などの加硫促進剤、金属酸化物、脂肪酸な
どの加硫促進助剤、アミン・アルデヒド類、アミン・ケ
トン類、アミン類、フェノール類、イミダゾール類、含
イオウ系あるいは含リン系老化防止剤、ナフテン系やア
ロマティック系のプロセス油等を、本発明の効果を損な
わない範囲で配合することができる。In addition to the vulcanizing agent, the bead filler rubber composition of the present invention also contains a thermosetting resin, white carbon, activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, coumaron indene resin, phenolic resin, and lignin. , reinforcing agents such as modified melamine resin and petroleum resin, various grades of calcium carbonate, salt and bamboo magnesium carbonate, fillers such as clay, zinc white, diatomaceous earth, recycled rubber, powdered rubber, and ebonite powder, aldehydes, and ammonia. ,
Aldehydes/amines, guanidines, thioureas,
Vulcanization accelerators such as thiazoles, thiurams, dithiocarbamates, xanthates, metal oxides, vulcanization accelerators such as fatty acids, amines/aldehydes, amines/ketones, amines, phenols, imidazoles , sulfur-containing or phosphorus-containing anti-aging agents, naphthenic or aromatic process oils, etc. can be blended within the range that does not impair the effects of the present invention.
特に、本発明のゴム組成物には、ゴム１００重量部に対
して１〜３０重量部のノボラック型フェノール系樹脂の
ような熱硬化性樹脂を配合するのが好ましい。In particular, it is preferable to mix 1 to 30 parts by weight of a thermosetting resin such as a novolac type phenolic resin with respect to 100 parts by weight of rubber in the rubber composition of the present invention.
以下に実施例及び比較例を示す、以下の記載において部
は重量部を示す。Examples and comparative examples are shown below. In the following description, parts indicate parts by weight.
また、ビードフィラーゴム組成物のムーニー粘度ＭＬ＋
−４（Ｉ００°Ｃ）はＪＩＳＫ６３００に従って測定し
、加硫物の物性（引張弾性率、引張強さ、屈曲回数、硬
さ）はＪＩＳＫ６３０１に従って測定した。In addition, the Mooney viscosity ML+ of the bead filler rubber composition
-4 (I00°C) was measured according to JISK6300, and the physical properties of the vulcanized product (tensile modulus, tensile strength, number of bends, hardness) were measured according to JISK6301.
尚、下記実施例１−１６及び比較例Ｉ〜２における強化
ゴム組成物の組成（配合割合）、本発明のビードフィラ
ーゴム組成物の組成（配合割合）、及び本発明のビード
フィラーゴム組成物の物性等については、後記第１表及
び第２表にまとめて記載した。In addition, the composition (blending ratio) of the reinforced rubber composition in Examples 1-16 and Comparative Examples I to 2 below, the composition (blending ratio) of the bead filler rubber composition of the present invention, and the bead filler rubber composition of the present invention The physical properties and the like are summarized in Tables 1 and 2 below.
実施例１
２２０ ’Ｃ１５Ｑｒ、ｐ、ｍ、にセットしたゲラベン
ダーブラストグラフ中に、粘度が１×１０ｂポイズの天
然ゴム（ＮＲ）１００部、及び老化防止剤としてＮ−（
３−メタクリロイルオキシ−２−ヒドロキシプロピル）
−Ｎ’ −フェニル−Ｐ−フ二二レンジアミン〔商品名
ツクランクＧ−１、入内新興化学工業（＋１製〕１．０
部を投入し、これらを３０秒間混練後、ナイロン６（商
品名ＩＱ３０Ｂ、宇部興産Ｇ潰裂、融点２２１°Ｃ１分
子量３０，０００）１００重量部当たり２重量部のＮ〜
β（アミノエチル）γ−アミノプロピルトリメトキシシ
ラン（商品名ＫＢＭ６０３、信越化学工業０＠製、以下
シランＡ）をあらかじめ練り込んだペレット５１部を投
入し、１３分間混練しくこの間、プラベンダー内の温度
は２３０°Ｃまで上昇）、混練物を得た。得られた混練
物を、ノズルの内径２鰭、ノズルの長さと内径との比（
Ｌ／Ｄ）が２の円形ダイを有する２０１ｍφ押出ａ 押
出ｌａａｋｅ社製）を用いてグイ設定温度２３５°Ｃで
紐状に押出し、次いで、押出物をノズル直下３ｍに設置
したガイドロールを経て、ボビンにドラフト比ｔｏ（３
８，８ｍ／分の速度）で巻取った。この巻取物約５００
本を束ねてシート状（厚さ約２鰭、巾約１５（Ｉｍｓ）
とし、このシート状物をロール間隙０．２ ｍ■、温度
６０°Ｃの一対の圧延ロールで約１０倍に圧延して、強
化ゴム組成物（マスターバッチ）（試料ｌ）を得た。Example 1 100 parts of natural rubber (NR) having a viscosity of 1 x 10 b poise and N-(
3-methacryloyloxy-2-hydroxypropyl)
-N'-Phenyl-P-phinyl diamine [Product name Tsurank G-1, manufactured by Iriuchi Shinko Kagaku Kogyo (+1)] 1.0
After kneading these for 30 seconds, 2 parts by weight of N per 100 parts by weight of nylon 6 (trade name IQ30B, Ube Industries G crush, melting point 221°C, molecular weight 30,000).
51 parts of pellets pre-mixed with β(aminoethyl)γ-aminopropyltrimethoxysilane (trade name KBM603, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as silane A) were added and kneaded for 13 minutes. The temperature rose to 230°C) to obtain a kneaded product. The obtained kneaded material was mixed with the two fins of the inner diameter of the nozzle, and the ratio of the length of the nozzle to the inner diameter (
The extrudate was extruded into a string at a set temperature of 235°C using a 201 mφ extrusion a (manufactured by Extrusion LAAKE Co., Ltd.) having a circular die with L/D) of 2, and then the extrudate was passed through a guide roll installed 3 m directly below the nozzle. Draft ratio to (3) on the bobbin
It was wound up at a speed of 8.8 m/min). Approximately 500 rolls of this
Bundle books into a sheet (approx. 2 fins thick, approx. 15 ms wide)
This sheet-like material was rolled about 10 times with a pair of rolling rolls with a roll gap of 0.2 m and a temperature of 60°C to obtain a reinforced rubber composition (masterbatch) (sample 1).
次に、９０°Ｃ，７７ｒ、ｐ、ａ＋、にセットしたバン
バリーにより、第２表に示す配合処方のうち加硫促進剤
、イオウを除く配合成分を混練して混練物を得、次いで
、この混練物に１０インチロール上で加硫促進剤、イオ
ウを混練し、これをシート状にロール出しした後、金型
に入れて加硫し、加硫物を得た。加硫は、１４５℃下に
４０分間行った。Next, in a Banbury set at 90°C, 77r, p, a+, the ingredients listed in Table 2 except for the vulcanization accelerator and sulfur were kneaded to obtain a kneaded product. A vulcanization accelerator and sulfur were kneaded into the kneaded material on a 10-inch roll, and this was rolled out into a sheet shape, then placed in a mold and vulcanized to obtain a vulcanized product. Vulcanization was performed at 145° C. for 40 minutes.
実施例２
シランＡに代えてビニルトリス（β−メトキシエトキシ
）シラン（商品名ＫＢＣ１００３、信越化学工業（裸製
、シランＢ）を用いた他は実施例１と同様にして強化ゴ
ム組成物（試料２）を得、この試料２を強化ゴム組成物
として使用した他は実施例１と同様にしてビードフィラ
ーゴム組成物を得た。Example 2 A reinforced rubber composition (Sample 2) was prepared in the same manner as in Example 1, except that vinyltris(β-methoxyethoxy)silane (trade name KBC1003, Shin-Etsu Chemical Co., Ltd. (Naked, Silane B) was used in place of Silane A. ), and a bead filler rubber composition was obtained in the same manner as in Example 1, except that Sample 2 was used as the reinforced rubber composition.
実施例３
シランＡに代えてＴ−メタクリロキシプロピルトリメト
キシシラン（商品名ＫＢＭ５０３、信越化学工業＋＋＊
！！１！！、シランＣ）を用いた他は実施例１と同様
にして強化ゴム組成物（試料３）を得、この試料３を強
化ゴム組成物として使用した他は実施例１と同様にして
ビードフィラーゴム組成物を得た。Example 3 Silane A was replaced with T-methacryloxypropyltrimethoxysilane (trade name KBM503, Shin-Etsu Chemical ++*
! ! 1! ! A reinforced rubber composition (Sample 3) was obtained in the same manner as in Example 1, except that silane C) was used, and a bead filler rubber was obtained in the same manner as in Example 1, except that Sample 3 was used as the reinforced rubber composition. A composition was obtained.
実施例４
シランＡに代えてＴ−メルカプトプロピルトリメトキシ
シラン（商品名ＫＢＭ８０３、信越化学工業（蚤萄製、
シランＤ）を用いた他は実施例１と同様にして強化ゴム
組成物（試料４）を得、この試料４を強化ゴム組成物と
して使用した他は実施例１と同様にしてビードフィラー
ゴム組成物を得た。Example 4 T-mercaptopropyltrimethoxysilane (trade name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.
A reinforced rubber composition (sample 4) was obtained in the same manner as in Example 1, except that silane D) was used, and a bead filler rubber composition was prepared in the same manner as in Example 1, except that this sample 4 was used as the reinforced rubber composition. I got something.
実施例５
シランＡに代えてβ−（３，４−エポキシシクロヘキシ
ル）エチルトリメトキシシラン（商品名ＫＢＭ３０３、
信越化学工業■製、シランＥ）を用いた他は実施例１と
同様にして強化ゴム組成物（試料５）を得、この試料５
を強化ゴム組成物として使用した他は実施例１と同様に
してビードフィラーゴム組成物を得た。Example 5 β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name KBM303,
A reinforced rubber composition (Sample 5) was obtained in the same manner as in Example 1 except that Silane E) manufactured by Shin-Etsu Chemical Co., Ltd. was used.
A bead filler rubber composition was obtained in the same manner as in Example 1, except that the following was used as the reinforced rubber composition.
実施例６
ナイロン６（商品名１０１３Ｂ、宇部興産Ｇｉｌ製、融
点２２１°Ｃ１分子量１３，０００）１００重量部当り
４重量部のシランＡをあらかじめ練り込んだペレット５
２部を使用した他は実施例１と同様に実施して強化ゴム
組成物（試料６）を得、この試料６を強化ゴム組成物と
して使用した他は実施例１と同様にしてビードフィラー
ゴム組成物を得た。Example 6 Pellets 5 in which 4 parts by weight of silane A were kneaded in advance per 100 parts by weight of nylon 6 (trade name 1013B, manufactured by Ube Industries Gil, melting point 221°C, molecular weight 13,000)
A reinforced rubber composition (sample 6) was obtained in the same manner as in Example 1, except that 2 parts of the rubber were used, and a bead filler rubber was obtained in the same manner as in Example 1, except that Sample 6 was used as the reinforced rubber composition. A composition was obtained.
実施例７
天然ゴムに投入する６−ナイロンの量を１００部にかえ
た他は実施例１と同様にして強化ゴム組成物（試料７）
を得、この試料７を強化ゴム組成物として使用した他は
実施例１と同様にしてビードフィラーゴム組成物を得た
。Example 7 A reinforced rubber composition (sample 7) was prepared in the same manner as in Example 1 except that the amount of 6-nylon added to the natural rubber was changed to 100 parts.
A bead filler rubber composition was obtained in the same manner as in Example 1 except that Sample 7 was used as a reinforced rubber composition.
実施例日
天然ゴムに投入する６−ナイロンの量を２０部にかえた
他は実施例１と同様にして強化ゴム組成物（試料８）を
得、この試料８を強化ゴム組成物として使用した他は実
施例１と同様にしてビードフィラーゴム組成物を得た。Example Day A reinforced rubber composition (Sample 8) was obtained in the same manner as in Example 1, except that the amount of 6-nylon added to the natural rubber was changed to 20 parts, and this Sample 8 was used as the reinforced rubber composition. Otherwise, a bead filler rubber composition was obtained in the same manner as in Example 1.
実施例９〜１３
各成分の組成（配合割合）を第２表に示すように変えた
他は実施例１と同様にしてビードフィラーゴム組成物を
得た。Examples 9 to 13 Bead filler rubber compositions were obtained in the same manner as in Example 1, except that the composition (blending ratio) of each component was changed as shown in Table 2.
実施例１４〜１６
配合するカーボンブラックの種類を変えた他は実施例１
と同様にしてビードフィラーゴム組成物を得た。Examples 14 to 16 Example 1 except that the type of carbon black to be blended was changed
A bead filler rubber composition was obtained in the same manner as above.
比較例１〜２
強化ゴム組成物を使用しないで各成分の使用割合（組成
）を第２表に示すように変えた他は実施例１と同様にし
てビードフィラーゴム組成物を得た。Comparative Examples 1-2 Bead filler rubber compositions were obtained in the same manner as in Example 1, except that the reinforcing rubber composition was not used and the proportions (compositions) of each component were changed as shown in Table 2.
尚、第１表に示す各試料１〜８（強化ゴム組成物）にお
ける結合ゴム量の測定は、次のようにして行った。The amount of bonded rubber in each of Samples 1 to 8 (reinforced rubber compositions) shown in Table 1 was measured as follows.
強化ゴム組成物２ｇをそれぞれトルエン２０〇−に８０
°Ｃで添加し、強化ゴム組成物中のゴム分を溶解させ、
得られたスラリーを室温で遠心分離して溶液部分と沈澱
部分とに分けた。沈澱部分について前記の操作を７回繰
り返し行った後、沈澱部分を乾燥してナイロン繊維を得
た。このナイロン繊維をフェノールとオルソジクロルヘ
ンゼンの混合溶媒に溶解させて、 ′Ｈの核磁気共鳴ス
ペクトル（ＮＭＲ）で分析（内部標準テトラメチルシラ
ン）し、ＮＭＲチャートからゴムに起因するメチル基及
びメチレン基、６−ナイロンに起因するＣＯ基に隣接し
たメチレン基、ＮＨ基に隣接したメチレン基及び他の３
個のメチレン基の各々のピークについて、切り取り面積
法により６−ナイロンと天然ゴムとのモル比をもとめて
、結合ゴム量を算出した。また、前記のナイロン繊維の
形状を、繊維約２００本について１０，０００倍の倍率
で走査型顕微鏡を用いて測定した。繊維は断面円形の極
めて細い短繊維であった。Add 2g of the reinforced rubber composition to 200-80% of toluene, respectively.
°C to dissolve the rubber content in the reinforced rubber composition,
The resulting slurry was centrifuged at room temperature to separate it into a solution portion and a precipitate portion. After repeating the above operation seven times on the precipitated portion, the precipitated portion was dried to obtain nylon fibers. This nylon fiber was dissolved in a mixed solvent of phenol and orthodichlorohenzene and analyzed by 'H nuclear magnetic resonance spectrum (NMR) (internal standard: tetramethylsilane). Methyl groups and methylene groups originating from rubber were determined from the NMR chart. group, the methylene group adjacent to the CO group resulting from 6-nylon, the methylene group adjacent to the NH group, and the other 3
For each peak of methylene groups, the molar ratio of 6-nylon to natural rubber was determined by the cut area method, and the amount of bonded rubber was calculated. Further, the shape of the nylon fibers was measured using a scanning microscope at a magnification of 10,000 times for about 200 fibers. The fibers were extremely thin short fibers with a circular cross section.
また、第２表における（注１）〜（注４）は次の通りで
ある。In addition, (Note 1) to (Note 4) in Table 2 are as follows.
（注１） ＢＲ：ポリブタジェン（ＵＢＥＰＯＬ−Ｂ
Ｒ１００，宇部興産０１製）
（注２）ＳＢＲ：スチレン−ブタジェン共重合体ゴム（
ＳＤＲ−１５００、日本
合成ゴム■製）
（注３）Ｎ−３３０： ＨＡＦ、粒子径３０ｍμ、ＤＢ
Ｐ吸油量１１０ｍｌ／１００ｇ
Ｎ−４４０： ＦＦ、粒子径３８ｍμ、ＤＢＰ吸油３７
５ｍ１７１００ ｇ
Ｎ−５５０： ＦＥＦ、粒子径４１ｍμ、ＤＢＰ吸油遣
１２２ｍｌ／ １００ ｇＮ−６６０：ＧＰＦ、粒子径
８４ｍμ、ＤＢＰ吸油１８１ｍｌ／ １００ ｇ
（注４）他の配合剤
亜鉛華＝５部、ステアリン酸＝２部、老化防止剤 Ｎ−
フェニル−Ｎ゛−イソプロピル−Ｐ−フェニレンジアミ
ン １部、加硫促進剤 Ｎ−オキシジエチレンベンゾチ
アジル−２−スルフェンアミド ０．８部、イオウ ３
部（比較例１のみ、４部）
〔本発明の効果〕
本発明のゴム組成物は、ムーニー粘度が小さいため加工
性が悟れており、しかも加硫物のＭ、。が３０ｋｇ／−
以上で屈曲回数が１０００回以上であり、弾性率が大き
く耐屈曲亀裂成長性が優れており、乗用車、バス、トラ
ック、飛行機などのタイヤ部材として、他のタイヤ部材
（サイドウオール、トレッド、チェーファ−、リムなど
）とともに使用することができる。(Note 1) BR: Polybutadiene (UBEPOL-B
R100, manufactured by Ube Industries 01) (Note 2) SBR: Styrene-butadiene copolymer rubber (
SDR-1500, manufactured by Japan Synthetic Rubber ■) (Note 3) N-330: HAF, particle size 30 mμ, DB
P oil absorption 110ml/100g N-440: FF, particle size 38mμ, DBP oil absorption 37
5m17100 g N-550: FEF, particle size 41 mμ, DBP oil absorption 122 ml/100 g N-660: GPF, particle size 84 mμ, DBP oil absorption 181 ml/100 g (Note 4) Other ingredients Zinc white = 5 parts, stearic acid = 2 parts, anti-aging agent N-
Phenyl-N-isopropyl-P-phenylenediamine 1 part, vulcanization accelerator N-oxydiethylenebenzothiazyl-2-sulfenamide 0.8 part, sulfur 3
parts (Comparative Example 1 only, 4 parts) [Effects of the present invention] The rubber composition of the present invention has low Mooney viscosity, so it has good processability, and moreover, it has excellent processability. is 30kg/-
As a result, it can be bent more than 1000 times, has a large elastic modulus, and has excellent bending crack growth resistance. , rim, etc.).
Claims (1)
ドの微細な短繊維５〜１００重量部が埋封されており、
かつ前記ポリアミドと前記ゴムとがシランカップリング
剤を介して結合している強化ゴム組成物（Ａ）、ジエン
系ゴム（Ｂ）、及びカーボンブラック（Ｃ）を配合して
なり、かつ下記（ I ）乃至（IV）の条件を満足するこ
とを特徴とするビードフィラーゴム組成物。 （ I ）前記ポリアミドの量は、ゴム成分の合計１００
重量部に対して２〜２０重量部であり、（II）ゴム成分
として、少なくとも天然ゴム及び／又はポリイソプレン
を用い、該天然ゴム及び／又はポリイソプレンの合計量
の割合が、全ゴム成分に対して５５〜１００重量％であ
り、 （III）カーボンブラックの量は、ゴム成分の合計１０
０重量部に対して５０〜７０重量部であり、（IV）５０
％モジュラスが３０ｋｇ／ｃｍ＾２以上の加硫物となる
。[Claims] 100 parts by weight of vulcanizable rubber is embedded with 5 to 100 parts by weight of fine short fibers of polyamide that can be formed into fibers,
and a reinforced rubber composition (A) in which the polyamide and the rubber are bonded via a silane coupling agent, a diene rubber (B), and carbon black (C), and the following (I A bead filler rubber composition characterized by satisfying the conditions of ) to (IV). (I) The amount of the polyamide is 100% of the total rubber component.
(II) At least natural rubber and/or polyisoprene is used as the rubber component, and the ratio of the total amount of the natural rubber and/or polyisoprene to the total rubber component is 2 to 20 parts by weight. (III) The amount of carbon black is 55 to 100% by weight based on the rubber component.
50 to 70 parts by weight relative to 0 parts by weight, and (IV) 50 parts by weight.
The vulcanizate has a % modulus of 30 kg/cm^2 or more.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61240821A JPH0749495B2 (en) | 1986-10-09 | 1986-10-09 | Bead filler-rubber composition |
| EP87308206A EP0265070B1 (en) | 1986-09-26 | 1987-09-16 | Fiber-reinforced rubber composition and production process and use thereof |
| DE8787308206T DE3773608D1 (en) | 1986-09-26 | 1987-09-16 | FIBER REINFORCED RUBBER MIXTURE, METHOD FOR THE PRODUCTION AND USE THEREOF. |
| US07/097,101 US5006603A (en) | 1986-09-26 | 1987-09-16 | Fiber-reinforced rubber composition and production process and use thereof |
| US07/437,811 US5049610A (en) | 1986-09-26 | 1989-11-17 | Fiber-reinforced rubber composition and production process and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61240821A JPH0749495B2 (en) | 1986-10-09 | 1986-10-09 | Bead filler-rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6395243A true JPS6395243A (en) | 1988-04-26 |
| JPH0749495B2 JPH0749495B2 (en) | 1995-05-31 |
Family
ID=17065196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61240821A Expired - Lifetime JPH0749495B2 (en) | 1986-09-26 | 1986-10-09 | Bead filler-rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749495B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001146532A (en) * | 1999-09-16 | 2001-05-29 | Goodyear Tire & Rubber Co:The | Rubber containing short-fiber reinforcing material having adhesion promotor, and product including tire having member made of composite material with the rubber |
| JP2001191755A (en) * | 2000-01-06 | 2001-07-17 | Bridgestone Corp | Pneumatic tire |
| WO2001057493A1 (en) * | 2000-01-31 | 2001-08-09 | Mitsui Chemicals, Inc. | Method of testing rubber composition for kneaded state and process for producing rubber composition |
| JP2002080641A (en) * | 2000-09-06 | 2002-03-19 | Bridgestone Corp | Bead filler rubber composition and pneumatic tire obtained using the same |
| JP2011017013A (en) * | 2010-08-30 | 2011-01-27 | Bridgestone Corp | Modified natural rubber and method for producing the same, rubber composition, and tire |
| JP2011042774A (en) * | 2008-10-16 | 2011-03-03 | Ube Industries Ltd | Rubber composition and method for producing the same |
| JP2012532946A (en) * | 2009-07-10 | 2012-12-20 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Compositions based on natural rubber and polyamine compounds |
-
1986
- 1986-10-09 JP JP61240821A patent/JPH0749495B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001146532A (en) * | 1999-09-16 | 2001-05-29 | Goodyear Tire & Rubber Co:The | Rubber containing short-fiber reinforcing material having adhesion promotor, and product including tire having member made of composite material with the rubber |
| JP2001191755A (en) * | 2000-01-06 | 2001-07-17 | Bridgestone Corp | Pneumatic tire |
| JP4519973B2 (en) * | 2000-01-06 | 2010-08-04 | 株式会社ブリヂストン | Pneumatic tire |
| WO2001057493A1 (en) * | 2000-01-31 | 2001-08-09 | Mitsui Chemicals, Inc. | Method of testing rubber composition for kneaded state and process for producing rubber composition |
| JP2002080641A (en) * | 2000-09-06 | 2002-03-19 | Bridgestone Corp | Bead filler rubber composition and pneumatic tire obtained using the same |
| JP2011042774A (en) * | 2008-10-16 | 2011-03-03 | Ube Industries Ltd | Rubber composition and method for producing the same |
| JP2012532946A (en) * | 2009-07-10 | 2012-12-20 | コンパニー ゼネラール デ エタブリッスマン ミシュラン | Compositions based on natural rubber and polyamine compounds |
| JP2011017013A (en) * | 2010-08-30 | 2011-01-27 | Bridgestone Corp | Modified natural rubber and method for producing the same, rubber composition, and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0749495B2 (en) | 1995-05-31 |
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