JP2012236878A - Complex, method of producing the complex, rubber composition, and pneumatic tire - Google Patents
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 54
- 239000005060 rubber Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 80
- 239000004113 Sepiolite Substances 0.000 claims description 48
- 229910052624 sepiolite Inorganic materials 0.000 claims description 48
- 235000019355 sepiolite Nutrition 0.000 claims description 48
- 239000002131 composite material Substances 0.000 claims description 30
- 229920000126 latex Polymers 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 239000004816 latex Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 15
- -1 polyoxyethylene group Polymers 0.000 claims description 13
- 238000010306 acid treatment Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229920006173 natural rubber latex Polymers 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 229910052625 palygorskite Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- 229960000892 attapulgite Drugs 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000002270 dispersing agent Substances 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
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
本発明は、複合体及びその製造方法、並びに該複合体を含むゴム組成物及びそれを用いた空気入りタイヤに関する。 The present invention relates to a composite, a method for producing the same, a rubber composition containing the composite, and a pneumatic tire using the rubber composition.
無機フィラーをゴム材料に配合することでゴム組成物の物性が大幅に改善されることが知られているが、なかでも、低発熱性などが良好であるという観点から、シリカが汎用されている。しかし、シリカは、表面にシラノール基を有し、親水性を示すため、一般に疎水性を示すゴムとの親和性が低く、更に自己凝集性も強いため、ゴム中に均一に分散させることは容易ではない。 It is known that the physical properties of the rubber composition are greatly improved by blending the inorganic filler with the rubber material. Among them, silica is widely used from the viewpoint of good low heat build-up and the like. . However, since silica has silanol groups on the surface and is hydrophilic, it generally has low affinity with rubber that exhibits hydrophobic properties and strong self-aggregation properties, so it can be easily dispersed uniformly in rubber. is not.
例えば、特許文献１には、ゴムラテックスに水ガラスから製造される微粒子シリカを液体状態で混合し、複合体を製造する方法が開示されているが、シリカの分散性という点で更なる改善が求められている。 For example, Patent Document 1 discloses a method of producing a composite by mixing fine particle silica produced from water glass with rubber latex in a liquid state, but further improvement in terms of dispersibility of silica. It has been demanded.
また、タイヤ工業などで汎用されているシリカは球状であり、それを分散したゴム組成物ではあらゆる方向に平均的に力学的特性が改善されるが、その一方で特定方向に優れた力学的特性を有するゴム組成物も求められている。従って、このような作用を持つフィラーを均一に分散させ、特定方向のゴム物性を改善したゴム材料の提供が望まれている。 Silica, which is widely used in the tire industry and the like, is spherical, and the rubber composition in which it is dispersed improves the mechanical properties on average in all directions, while it has excellent mechanical properties in specific directions. There is also a need for rubber compositions having: Therefore, it is desired to provide a rubber material in which fillers having such an action are uniformly dispersed and rubber properties in a specific direction are improved.
本発明は、前記課題を解決し、棒状シリカが微細に分散し、特定方向の力学的特性が改善された複合体及びその製造方法を提供することを目的とする。また、該複合体を用いたゴム組成物及び空気入りタイヤを提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems and to provide a composite in which rod-like silica is finely dispersed and mechanical properties in a specific direction are improved, and a method for producing the same. Another object of the present invention is to provide a rubber composition and a pneumatic tire using the composite.
本発明は、平均幅３〜３５ｎｍ及び平均長さ５０ｎｍ〜５μｍの棒状シリカをゴム成分中に分散させた複合体に関する。
上記棒状シリカは、セピオライトに酸処理を施して得られるものが好ましい。
The present invention relates to a composite in which rod-like silica having an average width of 3 to 35 nm and an average length of 50 nm to 5 μm is dispersed in a rubber component.
The rod-like silica is preferably obtained by subjecting sepiolite to an acid treatment.
上記複合体は、界面活性剤の存在下で、ゴムラテックスと上記棒状シリカの分散液とを混合して調製された配合ラテックスから得られるものが好ましい。また、上記界面活性剤は、ポリオキシエチレン基及び炭化水素基を有する非イオン性界面活性剤であることが好ましい。更に、上記棒状シリカの分散液は、超音波処理が施されて調製されたものであることが好ましい。 The composite is preferably obtained from a compounded latex prepared by mixing a rubber latex and a dispersion of the rod-shaped silica in the presence of a surfactant. Moreover, it is preferable that the said surfactant is a nonionic surfactant which has a polyoxyethylene group and a hydrocarbon group. Further, the rod-like silica dispersion is preferably prepared by being subjected to ultrasonic treatment.
本発明は、界面活性剤の存在下でゴムラテックスと棒状シリカの分散液とを混合して配合ラテックスを調製する工程１、及び上記工程１で得られた配合ラテックスを凝固させる工程２を含む上記複合体の製造方法に関する。 The present invention includes the step 1 for preparing a compounded latex by mixing a rubber latex and a dispersion of rod-like silica in the presence of a surfactant, and the step 2 for coagulating the compounded latex obtained in the above step 1. The present invention relates to a method for producing a composite.
本発明は、上記複合体を含むゴム組成物に関する。
本発明はまた、上記ゴム組成物を用いて作製した空気入りタイヤに関する。
The present invention relates to a rubber composition containing the composite.
The present invention also relates to a pneumatic tire produced using the rubber composition.
本発明によれば、平均幅３〜３５ｎｍ及び平均長さ５０ｎｍ〜５μｍの棒状シリカをゴム成分中に分散させた複合体であるので、特定方向に優れたゴム物性を付与できる。また、該複合体の使用により、同様のゴム物性を持つゴム組成物及び空気入りタイヤを提供できる。 According to the present invention, since it is a composite in which rod-shaped silica having an average width of 3 to 35 nm and an average length of 50 nm to 5 μm is dispersed in a rubber component, excellent rubber physical properties can be imparted in a specific direction. Further, the use of the composite can provide a rubber composition and a pneumatic tire having similar rubber properties.
＜複合体＞
本発明の複合体は、平均幅３〜３５ｎｍ及び平均長さ５０ｎｍ〜５μｍの棒状シリカをゴム成分中に分散させたものである。該棒状シリカを使用することで、特定方向に優れた力学的特性を有する複合体が得られる。
<Composite>
The composite of the present invention is obtained by dispersing rod-like silica having an average width of 3 to 35 nm and an average length of 50 nm to 5 μm in a rubber component. By using the rod-like silica, a composite having excellent mechanical properties in a specific direction can be obtained.
上記複合体は、例えば、界面活性剤の存在下でゴムラテックスと上記棒状シリカの分散液とを混合して配合ラテックスを調製する工程１、及び上記工程１で得られた配合ラテックスを凝固させる工程２を含む製造方法により得られる。 The composite is prepared, for example, by mixing a rubber latex and a dispersion of rod-shaped silica in the presence of a surfactant to prepare a compounded latex, and a step of coagulating the compounded latex obtained in the above step 1 2 is obtained.
（工程１）
工程１で使用されるゴムラテックスとしては、天然ゴムラテックス、合成ジエン系ゴムラテックス（ブタジエンゴム、スチレンブタジエンゴム、アクリロニトリルブタジエンゴム、エチレン酢酸ビニルゴム、クロロプレンゴム、ビニルピリジンゴム、ブチルゴムなどのラテックス）などが挙げられる。なかでも、低燃費性、ゴム強度に優れるという理由から、天然ゴムラテックスが好ましい。
(Process 1)
Examples of the rubber latex used in Step 1 include natural rubber latex and synthetic diene rubber latex (latex such as butadiene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, ethylene vinyl acetate rubber, chloroprene rubber, vinyl pyridine rubber, and butyl rubber). Can be mentioned. Of these, natural rubber latex is preferred because of its low fuel consumption and excellent rubber strength.
天然ゴムラテックスとしては、従来公知のものを用いることができ、例えば、天然のゴムの木から得られるフィールドラテックスのほかアンモニア処理ラテックス（たとえばハイアンモニアタイプの天然ゴムラテックス）などを用いることができる。なお、天然ゴムラテックスは、ゴム固形分が１０〜７０質量％のものを使用することが好ましい。 As the natural rubber latex, conventionally known ones can be used. For example, ammonia-treated latex (for example, high ammonia type natural rubber latex) can be used in addition to a field latex obtained from a natural rubber tree. The natural rubber latex preferably has a rubber solid content of 10 to 70% by mass.
工程１では、特定形状の棒状シリカが液中に分散された分散液（棒状シリカの分散液）が使用される。上記分散液は、公知の方法で製造でき、例えば、棒状シリカと水性媒体（水など）の混合液を、公知の方法で分散することで調製できる。なかでも、分散性の点から、超音波ホモジナイザーなどを用いて超音波処理を施して分散することが好ましい。 In step 1, a dispersion liquid (a dispersion liquid of rod-shaped silica) in which rod-shaped silica having a specific shape is dispersed in a liquid is used. The dispersion can be produced by a known method. For example, it can be prepared by dispersing a mixed solution of rod-like silica and an aqueous medium (such as water) by a known method. Among these, from the viewpoint of dispersibility, it is preferable to disperse by applying ultrasonic treatment using an ultrasonic homogenizer or the like.
超音波処理の時間は、棒状シリカが充分に分散されるという点から、好ましくは３０分〜５時間である。なお、該処理時には、分散性の点から、分散液のｐＨを７〜９に調整することが好ましい。ｐＨの調整は公知の方法で実施できる（酸やアルカリの添加など）。ここで、上記分散液中の棒状シリカの含有量は特に限定されないが、分散液（１００質量％）中での均一分散性の点から、好ましくは１〜２０質量％、より好ましくは２〜１０質量％である。 The ultrasonic treatment time is preferably 30 minutes to 5 hours from the viewpoint that the rod-like silica is sufficiently dispersed. During the treatment, it is preferable to adjust the pH of the dispersion to 7 to 9 from the viewpoint of dispersibility. The pH can be adjusted by a known method (addition of acid or alkali, etc.). Here, the content of the rod-like silica in the dispersion is not particularly limited, but is preferably 1 to 20% by mass, more preferably 2 to 10 from the viewpoint of uniform dispersibility in the dispersion (100% by mass). % By mass.
上記棒状シリカは、球状の形状を有する通常のシリカとは異なり、棒状又は針状の形状を有し、その表面にシラノール基を有する無機材料（シリカ）である。棒状シリカとしては、例えば、セピオライト、パリゴルスカイト、アタパルジャイト、シロタイル、ラフリナイト、ファルコンドアイト、イモゴライトなどが挙げられる。なかでも、不純物が少なく、シラノール基が多いという理由から、セピオライト、アタパルジャイトが好ましい。棒状シリカ表面のシラノール基により、シランカップリング剤を介してゴム分子と棒状シリカが結合し、棒状シリカの配合による効果が充分に得られる。なお、本明細書では、単にシリカと記載する場合には、特に言及しない限り、球状のシリカをいう。 Unlike normal silica having a spherical shape, the rod-shaped silica is an inorganic material (silica) having a rod-like or needle-like shape and having a silanol group on the surface thereof. Examples of the rod-like silica include sepiolite, palygorskite, attapulgite, sirotile, rafrinite, falconite, imogolite and the like. Of these, sepiolite and attapulgite are preferred because they have few impurities and many silanol groups. The silanol group on the surface of the rod-like silica bonds the rubber molecule and the rod-like silica through the silane coupling agent, and the effect of blending the rod-like silica is sufficiently obtained. In this specification, when it is simply described as silica, it means spherical silica unless otherwise specified.
棒状シリカとしては、繊維状材料であるセピオライト鉱物［Ｍｇ８Ｓｉ１２Ｏ３０（ＯＨ）４（Ｈ２Ｏ）４・８（Ｈ２Ｏ）］を解繊して得られたものを好適に使用できる。セピオライト鉱物の構造は、Ｓｉ−Ｏ四面体が３本連結して繊維方向に平行なＳｉ−Ｏ四面体リボンを形成し、このリボンは八面体配位のマグネシウムイオンによって結び付けられ、タルク構造に似た２：１型を形成する。これらが互いに粘着して繊維束を形成しており、凝集物を形成し得る。 The rod-like silica, preferably using those obtained sepiolite mineral is fibrous material [Mg 8 Si 12 O 30 ( OH) 4 (H 2 O) 4 · 8 (H 2 O)] and by defibrating it can. The structure of sepiolite mineral is formed by connecting three Si-O tetrahedrons to form a Si-O tetrahedral ribbon parallel to the fiber direction. The ribbons are connected by octahedrally coordinated magnesium ions and resemble a talc structure. Form a 2: 1 mold. These adhere to each other to form a fiber bundle, which can form an aggregate.
上記凝集物は工業的工程、例えば微粉化（粉砕）または化学的修飾（例えば、欧州特許第１７０２９９号公報を参照）などで分裂（解繊）可能であり、それによって直径がナノメートルの繊維、即ち剥離（解繊）した棒状シリカ（セピオライト）が生じ得る。本発明では、セピオライト鉱物の解繊方法は特に限定されないが、棒状シリカ（セピオライト）の繊維としての形状を実質的に壊すことなく解繊することが好ましい。このような解繊方法としては、例えば、湿式粉砕法（例えば、欧州特許第１７０２９９号公報、特開平５−９７４８８号公報、欧州特許第８５２０００９４−４号公報などに記載の方法）などが挙げられる。 The agglomerates can be broken (defibrated) by industrial processes such as pulverization (grinding) or chemical modification (see for example EP 170299), whereby fibers of nanometer diameter, That is, exfoliated (defibrated) rod-like silica (sepiolite) can be produced. In the present invention, the method for defibrating sepiolite minerals is not particularly limited, but it is preferable to defibrate without substantially breaking the shape of rod-like silica (sepiolite) as a fiber. Examples of such a defibrating method include a wet pulverization method (for example, a method described in European Patent No. 170299, Japanese Patent Laid-Open No. 5-97488, European Patent No. 85200094-4, etc.). .
湿式粉砕法の一例を具体的に説明する。まず、水分を含んだ状態の棒状シリカ（セピオライト）を２ｍｍ以下の粒度になるまで粉砕後、懸濁液の固形分濃度が５〜２５％となるように水を加えた後、分散剤（例えば、ヘキサメタリン酸アルカリ塩）を添加する。次に、高せん断力を有する撹拌機を使用して懸濁液を５〜１５分間撹拌する。撹拌の際には、まず、低速回転で２〜７分間撹拌し、次に、高速回転で２〜８分間撹拌する。続いて、上澄みをデカンテーション又は遠心分離により分離することにより、繊維としての形状を実質的に壊すことなく解繊された棒状シリカ（セピオライト）を得ることができる。 An example of the wet pulverization method will be specifically described. First, after pulverizing the rod-like silica (sepiolite) containing water until the particle size is 2 mm or less, water is added so that the solid content concentration of the suspension is 5 to 25%, and then a dispersant (for example, , Hexametaphosphate alkali salt). The suspension is then stirred for 5-15 minutes using a stirrer with high shear. At the time of stirring, the mixture is first stirred at a low speed for 2 to 7 minutes, and then at a high speed for 2 to 8 minutes. Subsequently, by separating the supernatant by decantation or centrifugation, rod-shaped silica (sepiolite) that has been defibrated without substantially breaking the shape as a fiber can be obtained.
なお、本発明におけるセピオライトは、アタパルジャイト（パリゴルスカイトとしても知られる）も含む。アタパルジャイトは、アタパルジャイトが有する単位格子の方が若干小さい（繊維長が小さい）以外はセピオライトと構造的及び化学的にほとんど同一である。 The sepiolite in the present invention includes attapulgite (also known as palygorskite). Attapulgite is structurally and chemically almost identical to sepiolite, except that the unit cell of attapulgite is slightly smaller (fiber length is shorter).
上記棒状シリカとして、セピオライトに酸処理を施して得られるもの（酸処理セピオライト）を使用することが好ましい。酸処理により、Ｍｇイオンが溶出し、組成がＳｉＯ２になった棒状シリカが得られるため、該棒状シリカ表面にシランカップリング剤との反応サイトであるシラノール基が多量に生成される。このため、表面活性が高まり、ゴムとの相互作用が向上する。 As the rod-like silica, it is preferable to use one obtained by subjecting sepiolite to an acid treatment (acid-treated sepiolite). By the acid treatment, Mg ions are eluted and rod-like silica having a composition of SiO 2 is obtained, so that a large amount of silanol groups, which are reaction sites with the silane coupling agent, are generated on the rod-like silica surface. For this reason, surface activity increases and interaction with rubber improves.
酸処理は、酸と棒状シリカを接触させる方法であれば特に限定されないが、例えば、酸水溶液に棒状シリカを添加し、所定温度で一定時間、撹拌する方法などが挙げられる。酸処理セピオライトは、表面活性が高く、凝集力が強いが、ゴムとの複合前に上記超音波処理を施すことで充分にほぐれ、ゴムと混合し易くなる。 The acid treatment is not particularly limited as long as it is a method in which an acid is brought into contact with rod-like silica, and examples thereof include a method in which rod-like silica is added to an acid aqueous solution and stirred at a predetermined temperature for a predetermined time. Acid-treated sepiolite has a high surface activity and a strong cohesive force, but is sufficiently loosened and easily mixed with rubber by subjecting it to the ultrasonic treatment before combining with rubber.
酸処理において、酸としては、ギ酸、硫酸、塩酸、酢酸などの無機酸及び有機酸が挙げられ、硫酸、塩酸が好ましい。塩酸を使用する場合、棒状シリカ表面の親水性をより高められる。 In the acid treatment, examples of the acid include inorganic acids and organic acids such as formic acid, sulfuric acid, hydrochloric acid, and acetic acid, and sulfuric acid and hydrochloric acid are preferable. When hydrochloric acid is used, the hydrophilicity of the rod-like silica surface can be further increased.
酸の濃度、酸処理の温度、時間は適宜設定すればよく、設定により部分的な酸処理も可能である。酸の濃度は、Ｍｇイオンの溶出が良好に進行するという点から、好ましくは１〜６ｍｏｌ／Ｌである。酸処理の温度は、Ｍｇイオンの溶出が充分に進行しうる範囲で適宜設定でき、通常３０〜９０℃、好ましくは５５〜８５℃である。酸処理の時間は、好ましくは５分〜２４時間、より好ましくは０．５〜３時間である。 What is necessary is just to set suitably the density | concentration of an acid, the temperature of acid treatment, and time, and a partial acid treatment is also possible by setting. The concentration of the acid is preferably 1 to 6 mol / L from the viewpoint that elution of Mg ions proceeds well. The temperature of the acid treatment can be appropriately set as long as the elution of Mg ions can sufficiently proceed, and is usually 30 to 90 ° C, preferably 55 to 85 ° C. The acid treatment time is preferably 5 minutes to 24 hours, more preferably 0.5 to 3 hours.
なお、上記方法などで得られた酸処理セピオライトは、通常、水洗などの方法で洗浄され、乾燥させることなく、前述の方法で棒状シリカ分散液（酸処理セピオライトの分散液）を調製し、工程１に供することが好ましい。これにより、酸処理セピオライトの凝集を防止でき、ゴム中に良好に分散できる。 In addition, the acid-treated sepiolite obtained by the above method is usually washed by a method such as water washing, and a rod-like silica dispersion (acid-treated sepiolite dispersion) is prepared by the above-described method without drying, 1 is preferably used. Thereby, aggregation of acid-treated sepiolite can be prevented and it can disperse | distribute favorably in rubber | gum.
本発明における棒状シリカの平均幅は、３ｎｍ以上、好ましくは５ｎｍ以上である。３ｎｍ未満であると、表面積が大きくなり、ゴムへの分散が悪くなる傾向がある。棒状シリカの平均幅は、３５ｎｍ以下、好ましくは３０ｎｍ以下である。３５ｎｍを超えると、補強剤としての機能が低下する傾向がある。 The average width of the rod-like silica in the present invention is 3 nm or more, preferably 5 nm or more. If it is less than 3 nm, the surface area tends to be large, and the dispersion into rubber tends to be poor. The average width of the rod-like silica is 35 nm or less, preferably 30 nm or less. When it exceeds 35 nm, the function as a reinforcing agent tends to decrease.
棒状シリカの平均長さは、５０ｎｍ以上、好ましくは１００ｎｍ以上、より好ましくは３００ｎｍ以上である。５０ｎｍ未満であると、特定方向に優れた力学的特性を示さなくなる傾向がある。棒状シリカの平均長さは、５μｍ以下、好ましくは３μｍ以下、より好ましくは２μｍ以下である。５μｍを超えると、破壊の起点になるため、ゴム強度が悪化する傾向がある。 The average length of the rod-like silica is 50 nm or more, preferably 100 nm or more, more preferably 300 nm or more. If it is less than 50 nm, there is a tendency that excellent mechanical properties are not exhibited in a specific direction. The average length of the rod-like silica is 5 μm or less, preferably 3 μm or less, more preferably 2 μm or less. When it exceeds 5 μm, it becomes a starting point of destruction, so that the rubber strength tends to deteriorate.
棒状シリカのアスペクト比（平均長さ／平均幅）は、好ましくは２以上、より好ましくは５以上である。２未満であると、特定方向についての力学的特性が充分に得られないおそれがある。棒状シリカのアスペクト比の上限は特に限定されず、上記形状の範囲内で、大きいほど好ましい。 The aspect ratio (average length / average width) of the rod-like silica is preferably 2 or more, more preferably 5 or more. If it is less than 2, mechanical properties in a specific direction may not be sufficiently obtained. The upper limit of the aspect ratio of the rod-shaped silica is not particularly limited, and it is preferably as large as possible within the range of the above shape.
図１は、棒状シリカ（セピオライト）の概略構造を示す模式図である。図１に示すように、棒状シリカ（セピオライト）は、針状又は長い繊維状（棒状）の形状を有している。セピオライトの幅、厚み、長さは、それぞれ図１のＸ、Ｙ、Ｚに相当する。言い換えると、セピオライトの幅（Ｘ）とは、主面（平面視したときに面積が最大となる面）の短辺の長さであり、セピオライトの厚み（Ｙ）とは、主面に対する法線方向の長さであり、セピオライトの長さ（Ｚ）とは、主面の長辺の長さである。 FIG. 1 is a schematic diagram showing a schematic structure of rod-like silica (sepiolite). As shown in FIG. 1, rod-like silica (sepiolite) has a needle shape or a long fiber shape (rod shape). The width, thickness, and length of sepiolite correspond to X, Y, and Z in FIG. In other words, the sepiolite width (X) is the length of the short side of the main surface (the surface having the largest area when viewed in plan), and the sepiolite thickness (Y) is the normal to the main surface. It is the length in the direction, and the sepiolite length (Z) is the length of the long side of the main surface.
なお、本明細書において、棒状シリカの平均幅は、透過型電子顕微鏡により測定した棒状シリカのＸの平均値（例えば、１００個の棒状シリカのＸを測定し、算出した平均値）である。また、本明細書において、棒状シリカの平均長さは、透過型電子顕微鏡により測定した棒状シリカのＺの平均値（例えば、１００個の棒状シリカのＺを測定し、算出した平均値）である。 In the present specification, the average width of the rod-shaped silica is an average value of X of the rod-shaped silica measured by a transmission electron microscope (for example, an average value calculated by measuring X of 100 rod-shaped silica). In the present specification, the average length of the rod-shaped silica is an average value of Z of the rod-shaped silica measured by a transmission electron microscope (for example, an average value calculated by measuring Z of 100 rod-shaped silica). .
棒状シリカのチッ素吸着比表面積（Ｎ２ＳＡ）は、好ましくは２００ｍ２／ｇ以上、より好ましくは３００ｍ２／ｇ以上である。２００ｍ２／ｇ未満では、ゴム強度が悪化する傾向がある。該Ｎ２ＳＡは、好ましくは５００ｍ２／ｇ以下、より好ましくは３５０ｍ２／ｇ以下である。５００ｍ２／ｇを超えると、分散性が低下する傾向がある。
なお、棒状シリカのＮ２ＳＡは、ＡＳＴＭ Ｄ３０３７−８１に準じてＢＥＴ法で測定される値である。
The nitrogen adsorption specific surface area (N 2 SA) of the rod-like silica is preferably 200 m 2 / g or more, more preferably 300 m 2 / g or more. If it is less than 200 m 2 / g, the rubber strength tends to deteriorate. The N 2 SA is preferably 500 m 2 / g or less, more preferably 350 m 2 / g or less. When it exceeds 500 m 2 / g, the dispersibility tends to decrease.
Incidentally, N 2 SA of the silica rods is a value measured by the BET method in accordance with ASTM D3037-81.
工程１の混合工程は、界面活性剤の存在下で行われる。界面活性剤の使用で棒状シリカとゴムの相互作用が高められ、棒状シリカの凝集を抑制できる。このため、棒状シリカの良好な分散性が得られる。界面活性剤としては、分散性を良好に改善できるという理由から、非イオン性、陽イオン性界面活性剤が好ましく、非イオン性界面活性剤がより好ましい。 The mixing step of step 1 is performed in the presence of a surfactant. By using a surfactant, the interaction between the rod-like silica and the rubber is enhanced, and aggregation of the rod-like silica can be suppressed. For this reason, good dispersibility of the rod-like silica can be obtained. As the surfactant, a nonionic or cationic surfactant is preferable, and a nonionic surfactant is more preferable because the dispersibility can be improved satisfactorily.
非イオン性界面活性剤としては特に限定されず、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリプロピレンアルキルエーテル、ポリオキシエチレンポリブチレンアルキルエーテルなどのポリオキシアルキレンアルキルエーテル；ポリオキシエチレンアルケニルエーテルなどのポリオキシアルキレンアルケニルエーテル；ポリオキシエチレンアルキルフェニルエーテル；高級脂肪酸アルカノールアミドなど、従来公知のものを使用できる。なかでも、ポリオキシエチレン基により棒状シリカ表面との水素結合力が高められるという点から、親水性基としてポリオキシエチレン基、疎水性基として炭化水素基を有する非イオン性界面活性剤を好適に使用できる。 The nonionic surfactant is not particularly limited, and polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene polypropylene alkyl ethers, polyoxyethylene polybutylene alkyl ethers; polyoxyethylenes such as polyoxyethylene alkenyl ethers A conventionally well-known thing can be used, such as alkylene alkenyl ether; polyoxyethylene alkyl phenyl ether; higher fatty acid alkanolamide. Among them, a nonionic surfactant having a polyoxyethylene group as a hydrophilic group and a hydrocarbon group as a hydrophobic group is preferable because the hydrogen bond strength with the surface of the rod-like silica is enhanced by the polyoxyethylene group. Can be used.
このような非イオン性界面活性剤として、棒状シリカを良好に分散できるという点から、下記式（Ｉ）で表される化合物を好適に使用できる。 As such a nonionic surfactant, a compound represented by the following formula (I) can be suitably used from the viewpoint that rod-like silica can be favorably dispersed.
Ｒ１−Ｏ−（ＥＯ）ｘ−Ｈ （Ｉ）
（式（Ｉ）において、Ｒ１は炭素数３〜５０のアルキル基又は炭素数３〜５０のアルケニル基を表す。ＥＯはオキシエチレン基を表す。平均付加モル数ｘは３〜１００である。）
R 1 —O— (EO) x —H (I)
(In the formula (I), R 1 represents an alkyl group having 3 to 50 carbon atoms or an alkenyl group having 3 to 50 carbon atoms. EO represents an oxyethylene group. The average added mole number x is 3 to 100. )
上記Ｒ１の炭素数は、好ましくは１０〜４０、より好ましくは２０〜３５である。
上記ｘは、好ましくは５〜５０、より好ましくは８〜３０である。
The carbon number of R 1 is preferably 10 to 40, more preferably 20 to 35.
Said x becomes like this. Preferably it is 5-50, More preferably, it is 8-30.
工程１の混合工程では、界面活性剤の存在下でゴムラテックスと棒状シリカとを、公知の方法により混合し、その後、配合ラテックスが均一な溶液になるまで十分に攪拌することで、配合ラテックス（混合液）を調製できる。 In the mixing step of Step 1, the rubber latex and the rod-like silica are mixed by a known method in the presence of a surfactant, and then sufficiently stirred until the compounded latex becomes a uniform solution. Liquid mixture) can be prepared.
上記混合工程では、ゴム１００質量部（固形分）に対して棒状シリカが５〜１５０質量部となるように棒状シリカ分散液を混合することが好ましい。５質量部未満であると、棒状シリカの配合量が少なく、本発明の効果が充分に得られない傾向がある。１５０質量部を超えると、棒状シリカの均一分散性が低下する傾向がある。該混合量の下限はより好ましくは３０質量部以上であり、上限はより好ましくは１００質量部以下、更に好ましくは７０質量部以下である。 In the said mixing process, it is preferable to mix a rod-shaped silica dispersion so that rod-shaped silica will be 5-150 mass parts with respect to 100 mass parts (solid content) of rubber | gum. When the amount is less than 5 parts by mass, the amount of the rod-like silica is small, and the effects of the present invention tend not to be sufficiently obtained. When it exceeds 150 parts by mass, the uniform dispersibility of the rod-shaped silica tends to be lowered. The lower limit of the mixing amount is more preferably 30 parts by mass or more, and the upper limit is more preferably 100 parts by mass or less, still more preferably 70 parts by mass or less.
上記混合工程において、界面活性剤の添加量は、棒状シリカ１００質量部に対して、１〜３０質量部であることが好ましい。１質量部未満であると、界面活性剤の配合量が少なく、分散性の改善効果が充分に得られないおそれがある。３０質量部を超えると、棒状シリカの均一分散性が低下する傾向がある。該添加量の下限はより好ましくは３質量部以上であり、上限はより好ましくは２０質量部以下である。 In the mixing step, the amount of the surfactant added is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the rod-like silica. If the amount is less than 1 part by mass, the blending amount of the surfactant is small, and the effect of improving dispersibility may not be sufficiently obtained. When it exceeds 30 mass parts, there exists a tendency for the uniform dispersibility of rod-shaped silica to fall. The lower limit of the addition amount is more preferably 3 parts by mass or more, and the upper limit is more preferably 20 parts by mass or less.
（工程２）
工程２では、工程１で得られた配合ラテックスを凝固させる。凝固は公知の方法により実施できるが、配合ラテックスのｐＨを５〜７（好ましくは６〜７）に調整することが好ましい。ｐＨが５未満であると、ラテックスが急速に凝固するため、棒状シリカとゴムが分離してしまい、棒状シリカの分散が悪化する傾向がある。またｐＨが７を超えると、ラテックスの凝固反応が遅く実用的でない傾向がある。
(Process 2)
In step 2, the compounded latex obtained in step 1 is coagulated. Coagulation can be carried out by a known method, but it is preferable to adjust the pH of the compounded latex to 5 to 7 (preferably 6 to 7). When the pH is less than 5, the latex is rapidly solidified, so that the rod-like silica and the rubber are separated, and the dispersion of the rod-like silica tends to deteriorate. On the other hand, if the pH exceeds 7, the latex coagulation reaction tends to be slow and impractical.
ｐＨ５〜７に調整し、配合ラテックスを凝固させる方法としては、通常、酸が使用され、これを配合ラテックスに添加することで凝固する。凝固させるための酸としては、硫酸、塩酸、蟻酸、酢酸などが挙げられる。 As a method for adjusting the pH to 5 to 7 and coagulating the compounded latex, an acid is usually used, and the acid is coagulated by adding it to the compounded latex. Examples of the acid for coagulation include sulfuric acid, hydrochloric acid, formic acid, acetic acid and the like.
得られた凝固物（凝集ゴム及び棒状シリカを含む凝集物）を公知の方法でろ過、乾燥させ、更に乾燥後、２軸ロール、バンバリーなどでゴム練りを行うと、棒状シリカがゴムマトリックスに均一に分散した複合体を得ることができる。
なお、本発明の複合体は、本発明の効果を阻害しない範囲で他の成分を含んでもよい。
The obtained coagulated material (aggregated material containing agglomerated rubber and rod-like silica) is filtered and dried by a known method, and further dried and then kneaded with a biaxial roll, a banbury, etc., and the rod-like silica is uniformly formed in the rubber matrix. A complex dispersed in can be obtained.
In addition, the composite_body | complex of this invention may contain another component in the range which does not inhibit the effect of this invention.
＜ゴム組成物＞
本発明のゴム組成物は、上記複合体を含有する。上記複合体はマスターバッチとして使用できる。上記複合体はゴム中に棒状シリカが均一に分散しているので、他の成分と混合したゴム組成物においても棒状シリカを均一に分散できる。そのため、効果的な性能の向上が期待できる。
<Rubber composition>
The rubber composition of the present invention contains the above composite. The composite can be used as a masterbatch. In the above composite, the rod-like silica is uniformly dispersed in the rubber, so that the rod-like silica can be evenly dispersed in the rubber composition mixed with other components. Therefore, effective performance improvement can be expected.
本発明のゴム組成物には、上記複合体以外に、タイヤ工業において一般的に用いられているカーボンブラックなどの充填剤、シランカップリング剤、酸化亜鉛、ステアリン酸、老化防止剤、硫黄、加硫促進剤、別途配合する他のゴム成分等の各種材料を適宜配合できる。 In addition to the above composite, the rubber composition of the present invention includes fillers such as carbon black generally used in the tire industry, silane coupling agents, zinc oxide, stearic acid, anti-aging agents, sulfur, additives. Various materials such as a sulfur accelerator and other rubber components added separately can be appropriately added.
＜空気入りタイヤ＞
本発明のゴム組成物は空気入りタイヤに好適に使用できる。上記空気入りタイヤは、上記ゴム組成物を用いて通常の方法によって製造される。すなわち、必要に応じて各種添加剤を配合したゴム組成物を、未加硫の段階でタイヤの各部材の形状に合わせて押し出し加工し、タイヤ成型機上にて通常の方法にて成形することにより未加硫タイヤを形成した後、加硫機中で加熱加圧してタイヤを製造することができる。
<Pneumatic tire>
The rubber composition of the present invention can be suitably used for a pneumatic tire. The pneumatic tire is manufactured by a normal method using the rubber composition. That is, a rubber composition containing various additives as necessary is extruded in accordance with the shape of each member of the tire at an unvulcanized stage and molded by a normal method on a tire molding machine. After forming an unvulcanized tire by heating, the tire can be manufactured by heating and pressing in a vulcanizer.
実施例に基づいて、本発明を具体的に説明するが、本発明はこれらのみに限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
以下、実施例及び比較例で使用した各種薬品について、まとめて説明する。
天然ゴムラテックス：ハイアンモニアタイプ（ゴム固形分濃度６０質量％）
天然ゴム：ＴＳＲ２０
セピオライト（棒状シリカ）：ＴＯＬＳＡ社製のＰＡＮＧＥＬ（長さ：２００〜２０００ｎｍ、幅：５〜３０ｎｍ、Ｎ２ＳＡ：３２０ｍ２／ｇ、純度９９％以上、スペイン産、セピオライト鉱物の湿式粉砕品）
界面活性剤（１）：ハンツマン（株）製のｔｅｒｉｃ １６Ａ２９（ＣＨ３（Ｃ２Ｈ４）１６（ＯＣ２Ｈ４）２９−ＯＨ）
界面活性剤（２）：花王（株）製のＰＤ−４３０（Ｒ−（ＯＣ４Ｈ８）ｐ（ＯＣ２Ｈ４）ｑ−ＯＨ：Ｒ＝長鎖アルキル基）
界面活性剤（３）：花王（株）製のＥｍｕｌｇｅｎ４２０（Ｃ８Ｈ１７ＣＨ＝ＣＨＣ８Ｈ１６（ＯＣ２Ｈ４）ｒ−ＯＨ）
界面活性剤（４）：エボニックデグッサ社製のＳｉ３６３（下記式で表される界面活性剤）
１０％硫酸：和光純薬工業（株）製
ＮａＯＨ：関東化学（株）製
Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
Natural rubber latex: high ammonia type (rubber solid content concentration 60 mass%)
Natural rubber: TSR20
Sepiolite (rod-like silica): PANGEL manufactured by TOLSA (length: 200 to 2000 nm, width: 5 to 30 nm, N 2 SA: 320 m 2 / g, purity 99% or more, wet pulverized product of sepiolite mineral from Spain)
Surfactant (1): Huntsman Corp. of teric 16A29 (CH 3 (C 2 H 4) 16 (OC 2 H 4) 29 -OH)
Surfactant (2): PD-430 (R- (OC 4 H 8 ) p (OC 2 H 4 ) q —OH: R = long chain alkyl group) manufactured by Kao Corporation
Surfactant (3): manufactured by Kao Corp. of Emulgen420 (C 8 H 17 CH = CHC 8 H 16 (OC 2 H 4) r -OH)
Surfactant (4): Si363 (surfactant represented by the following formula) manufactured by Evonik Degussa
（酸処理セピオライトの調製）
９５％硫酸１５０ｇを３ｍｏｌ／Ｌになるまで純水で希釈し、これにセピオライト１５０ｇを添加し、８０℃で１時間攪拌した。その後、遠心分離により固形分を取り出し、該固形分を純水２Ｌに再分散し、攪拌することで余分な塩を除去した（洗浄）。この洗浄操作を３回行い、酸処理セピオライト（未乾燥）を得た。
(Preparation of acid-treated sepiolite)
150 g of 95% sulfuric acid was diluted with pure water to 3 mol / L, and 150 g of sepiolite was added thereto, followed by stirring at 80 ° C. for 1 hour. Thereafter, the solid content was taken out by centrifugation, and the solid content was redispersed in 2 L of pure water and stirred to remove excess salt (washing). This washing operation was performed three times to obtain acid-treated sepiolite (undried).
（実施例１）
酸処理セピオライト（９０ｇ）を乾燥させずに、純水１７００ｇに分散させた。分散液のｐＨが２となったので、ＮａＯＨを添加し、ｐＨを８に調整した。これに、超音波ホモジナイザーを用いて、２００Ｗ、１時間の条件で超音波を照射した（超音波処理）。
超音波処理後の分散液に、界面活性剤（１）９ｇ、天然ゴムラテックス３３３ｇ（ゴム固形分２００ｇ）を加えて１時間攪拌した。攪拌後、１０％硫酸を加え、ｐＨ７に調整し、凝固物を得た。これをろ過（ろ紙＃２）し、６０℃で乾燥して酸処理セピオライト・天然ゴム複合体を得た。
Example 1
The acid-treated sepiolite (90 g) was dispersed in 1700 g of pure water without drying. Since the pH of the dispersion reached 2, NaOH was added to adjust the pH to 8. This was irradiated with ultrasonic waves using an ultrasonic homogenizer at 200 W for 1 hour (ultrasonic treatment).
9 g of surfactant (1) and 333 g of natural rubber latex (200 g of rubber solid content) were added to the dispersion after the ultrasonic treatment, followed by stirring for 1 hour. After stirring, 10% sulfuric acid was added to adjust the pH to 7 to obtain a coagulated product. This was filtered (filter paper # 2) and dried at 60 ° C. to obtain an acid-treated sepiolite / natural rubber composite.
（実施例２）
超音波処理をしなかった点以外は実施例１と同様の方法により、酸処理セピオライト・天然ゴム複合体を得た。
(Example 2)
An acid-treated sepiolite / natural rubber composite was obtained in the same manner as in Example 1 except that the ultrasonic treatment was not performed.
（比較例１）
天然ゴム１００質量部に対して、乾燥した酸処理セピオライトを４５質量部混合し、バンバリーを用いてゴム練りを行ない、酸処理セピオライト・天然ゴム複合体を得た。
(Comparative Example 1)
45 parts by mass of dried acid-treated sepiolite was mixed with 100 parts by mass of natural rubber, and rubber kneading was performed using Banbury to obtain an acid-treated sepiolite / natural rubber composite.
得られた複合体を、ミクロトームを用いて、薄片を切り出し、ＴＥＭ分析によりセピオライトの分散状態を観察した。 From the obtained composite, a thin piece was cut out using a microtome, and the dispersion state of sepiolite was observed by TEM analysis.
調製した酸処理セピオライトについては、ＳＥＭ−ＥＤＸよりＭｇイオン成分の消失（溶出）を確認し、ＦＴ−ＩＲのＳｉＯ骨格振動より棒状形態のＳｉＯ２が残っていることを確認した（図２）。
なお、酸処理の反応は、下記反応式のようにすすむと考えられる。
（セピオライトの組成：Ｍｇ８Ｈ２（Ｓｉ４Ｏ１１）３・８Ｈ２Ｏ）
反応式
Ｍｇ８Ｈ２（Ｓｉ４Ｏ１１）３・８Ｈ２Ｏ＋１６Ｈ＋→８Ｍｇ２＋＋１２ＳｉＯ２＋１７Ｈ２Ｏ
With respect to the prepared acid-treated sepiolite, disappearance (elution) of the Mg ion component was confirmed from SEM-EDX, and it was confirmed that rod-like SiO 2 remained from the SiO skeleton vibration of FT-IR (FIG. 2).
In addition, it is thought that reaction of an acid treatment advances like the following reaction formula.
(Composition of sepiolite: Mg 8 H 2 (Si 4 O 11 ) 3 · 8H 2 O)
Reaction formula Mg 8 H 2 (Si 4 O 11 ) 3 · 8H 2 O + 16H + → 8Mg 2+ + 12SiO 2 + 17H 2 O
図６（実施例２のＴＥＭ写真）から、界面活性剤（１）の存在下で、天然ゴムラテックスと酸処理セピオライトの分散液とを混合することで、酸処理セピオライトを良好に分散できることが明らかとなった。また、図４（実施例１のＴＥＭ写真）から、超音波処理を施すことで、酸処理セピオライトの分散性を一層向上できること、図５（実施例１のＡ部の拡大ＴＥＭ写真）から、酸処理セピオライトが棒状形態のまま分散されることが明らかとなった。 From FIG. 6 (TEM photograph of Example 2), it is clear that the acid-treated sepiolite can be dispersed well by mixing the natural rubber latex and the acid-treated sepiolite dispersion in the presence of the surfactant (1). It became. Further, from FIG. 4 (TEM photograph of Example 1), it is possible to further improve the dispersibility of the acid-treated sepiolite by applying ultrasonic treatment. From FIG. 5 (enlarged TEM photograph of Part A of Example 1), acid It was revealed that the treated sepiolite was dispersed in a rod-like form.
なお、実施例１、２の界面活性剤（１）に代えて、界面活性剤（２）〜（５）を用いて得られた複合体も、酸処理セピオライトを良好に分散できること、酸処理セピオライトが棒状形態のまま分散されることを確認した。 In addition, it replaces with surfactant (1) of Example 1, 2, and the composite_body | complex obtained using surfactant (2)-(5) can also disperse | distribute acid-treated sepiolite favorably, acid-treated sepiolite. It was confirmed that was dispersed in a rod-like form.
一方、図３（比較例１のＴＥＭ写真）では、酸処理セピオライトの凝集塊が形成されていた。この結果から、酸処理セピオライトが乾燥することにより凝集塊が形成され、ゴム練りでは該凝集塊を分散できないことが明らかとなった。 On the other hand, in FIG. 3 (TEM photograph of Comparative Example 1), aggregates of acid-treated sepiolite were formed. From this result, it was clarified that the agglomerates were formed by drying the acid-treated sepiolite, and the agglomerates could not be dispersed by rubber kneading.
以上より、実施例の複合体は、特定方向に優れたゴム物性を付与できると期待できる。また、分散性に優れるため、補強性などの性能改善も期待できる。 From the above, it can be expected that the composites of the examples can impart excellent rubber properties in a specific direction. Moreover, since it is excellent in dispersibility, improvement in performance such as reinforcement can be expected.
Claims (8)
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