JP2006265314A - Rubber composition and method for producing the same - Google Patents
Rubber composition and method for producing the same Download PDFInfo
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- JP2006265314A JP2006265314A JP2005082764A JP2005082764A JP2006265314A JP 2006265314 A JP2006265314 A JP 2006265314A JP 2005082764 A JP2005082764 A JP 2005082764A JP 2005082764 A JP2005082764 A JP 2005082764A JP 2006265314 A JP2006265314 A JP 2006265314A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 107
- 239000005060 rubber Substances 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 239000011256 inorganic filler Substances 0.000 claims abstract description 34
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 238000004073 vulcanization Methods 0.000 claims abstract description 5
- 239000004927 clay Substances 0.000 claims description 48
- 238000005096 rolling process Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229920005549 butyl rubber Polymers 0.000 claims description 12
- 229940096992 potassium oleate Drugs 0.000 claims description 8
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical group [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 8
- 229920005557 bromobutyl Polymers 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 4
- 230000035699 permeability Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 229920000126 latex Polymers 0.000 description 22
- 239000004816 latex Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- -1 polyoxyethylene lauryl ether sulfate Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000012874 anionic emulsifier Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- FVFJGQJXAWCHIE-UHFFFAOYSA-N [4-(bromomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CBr)C=C1 FVFJGQJXAWCHIE-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ホース、ガスケット、パッキング材などに有用な無機フィラーをを含有するゴム組成物及びその製造方法に関する。 The present invention relates to a rubber composition containing an inorganic filler useful for hoses, gaskets, packing materials and the like, and a method for producing the same.
ゴムにクレー等の無機フィラーを配合することは、従来からガスバリア性等の向上を目的として行われている。このように、ゴムに、例えばクレイを分散させる方法は種々知られている。例えば、(1)クレーを4級アンモニウム塩などの界面活性剤を用いて有機化処理した「有機化クレー」と、半固体状のゴムを有機溶媒に一旦溶解したものとを十分混合したした後に有機溶媒を乾燥させゴム/クレー配合物を乾燥させてゴム/クレー配合物を得る「有機化クレー/有機溶媒法」が知られている(例えば、特許文献1参照。)。この方法には以下のような欠点がある。即ち、クレーの有機化処理に多数の工程が必要であり、有機溶媒中に有機化クレーが良好に分散するときとしないときがあり、ばらつきが大きい。 Mixing an inorganic filler such as clay with rubber has been conventionally performed for the purpose of improving gas barrier properties and the like. Thus, various methods for dispersing clay, for example, in rubber are known. For example, (1) after sufficiently mixing “organized clay” obtained by organically treating clay with a surfactant such as a quaternary ammonium salt, and semi-solid rubber once dissolved in an organic solvent. An “organized clay / organic solvent method” is known in which an organic solvent is dried to dry a rubber / clay blend to obtain a rubber / clay blend (see, for example, Patent Document 1). This method has the following drawbacks. That is, many steps are required for the organic treatment of clay, and there are cases where the organic clay is dispersed well in an organic solvent, and there is a large variation.
(2)「有機化クレー」と半固体状のゴムとを、二軸混練機などの高温高せん断型ミキサーを用いて混合することにより、ゴム/クレー配合物を得る「有機化クレー/高せん断ミキサー法」は、(1)と同様にクレーの有機化処理に多数の工程が必要であり、さらに、ゴム/クレーの分散状態は、二軸混練中のせん断力のみに依存するため、分散性にばらつきがある、二軸混練機などの大型で高額な設備を必要とする、二軸混練機中に残った原材料は廃棄処理されるので、材料のロスが大きいという欠点を持つ。 (2) “Organized clay / high shear” obtained by mixing “organized clay” and semi-solid rubber using a high-temperature high-shear mixer such as a twin-screw kneader. Like the method (1), the “mixer method” requires a number of steps for the organic treatment of clay, and further, the dispersion state of rubber / clay depends only on the shearing force during biaxial kneading, and thus dispersibility. The raw material remaining in the twin-screw kneader, which requires a large and expensive equipment such as a twin-screw kneader, is disposed of, and thus has a disadvantage that the material loss is large.
(3)有機化処理されていないクレー(未処理クレー)を水に浸漬して得られるクレー/水スラリーとゴム又はポリマーとを、高温高せん断型ミキサーを用いて混合し、水を混合中に気化脱水することによりゴム/クレー配合物を得る「クレー水スラリー/高せん断型ミキサー法」(例えば、特許文献2参照。)も知られている。この方法では、有機溶剤は使用されないが、水スラリーを高温の二軸混練機へ注入する設備が必要であること、二軸混練機などの大型で高額な設備を必要とすること、二軸混練機中に残った原材料は廃棄処理されるので、材料のロスが大きいこと等の欠点がある。 (3) A clay / water slurry obtained by immersing clay that has not been organically treated (untreated clay) in water and rubber or polymer are mixed using a high-temperature high-shear mixer, and water is mixed during mixing. A “clay water slurry / high shear mixer method” (see, for example, Patent Document 2) is also known in which a rubber / clay blend is obtained by vapor dehydration. In this method, no organic solvent is used, but equipment for injecting water slurry into a high-temperature twin-screw kneader is necessary, large and expensive equipment such as a twin-screw kneader is required, and twin-screw kneading Since the raw materials remaining in the machine are disposed of, there are disadvantages such as a large material loss.
(4)クレー水スラリーと、ラテックスとを混合することにより得られるラテックス/クレー水スラリーを乾燥させてゴム/クレー配合物を得る「ラテックス/クレー水スラリー法」も知られている。この方法では、有機溶剤は使用されず、クレー水スラリーとラテックスの混合は容易であり、条件をうまく設定すればかなり広範囲の混合条件においても良好な分散状態のゴム/クレー配合物が得られる。しかし、得られる成形品のガスバリアが充分でなく、実用化レベルにまで至っていないのが現状である(例えば、特許文献3参照。)。
クレー等の無機フィラーは、気体遮蔽性(ガスバリヤ性)の向上、即ちガス透過率の低減化、或いは機械的特性の向上のためゴム或いはポリマーに一般に添加されている。しかしながら、上記のクレー含有ゴム組成物においては、クレーの微分散、均一分散が充分でない場合があり、クレーを含有しているにもかかわらず気体透過率が充分に低下していない。また(3)、(4)のように比較的低い気体透過率が得られる場合でも、クレーの分散が充分でないためか、実用化レベルの気体透過率が得られていない。また、クレーの含有量を多くすることで、改善は見られるが多すぎた場合、透明性、機械特性等が低下するとの問題があった。 Inorganic fillers such as clay are generally added to rubbers or polymers in order to improve gas barrier properties (gas barrier properties), that is, to reduce gas permeability or improve mechanical properties. However, in the above clay-containing rubber composition, the fine dispersion and uniform dispersion of the clay may not be sufficient, and the gas permeability is not sufficiently lowered despite containing the clay. Moreover, even when a relatively low gas permeability is obtained as in (3) and (4), a practical level of gas permeability is not obtained because of insufficient dispersion of clay. Moreover, improvement was seen by increasing the clay content, but when it was too much, there was a problem that transparency, mechanical properties and the like deteriorated.
本発明は、これらの従来技術の欠点を克服し、以下の目的を達成することを課題とする。すなわち、
本発明は、透明性、優れた機械特性を有するとともに、気体透過率が低減されたゴム組成物及びその製造方法を提供することを目的とする。
The present invention aims to overcome these drawbacks of the prior art and achieve the following objects. That is,
An object of the present invention is to provide a rubber composition having transparency and excellent mechanical properties, and having reduced gas permeability, and a method for producing the same.
前記課題を解決するための手段は以下の通りである。すなわち、
<1> ゴムの乳化分散液と、無機フィラーとを混合して乾燥する工程を含むゴム組成物の製造方法であって、前記ゴムの乳化分散液中の乳化剤量を、ゴム100質量部に対して0.1〜3質量部に調整し、乾燥したゴム組成物を、加硫工程の前の成形加工工程において、1.0mm以下の厚みに圧延する工程を少なくとも1回含むことを特徴とするゴム組成物の製造方法である。
Means for solving the above-mentioned problems are as follows. That is,
<1> A method for producing a rubber composition comprising a step of mixing and drying an emulsified dispersion of rubber and an inorganic filler, wherein the amount of the emulsifier in the emulsified dispersion of rubber is 100 parts by weight of rubber. The step of rolling the rubber composition adjusted to 0.1 to 3 parts by mass into a thickness of 1.0 mm or less is included at least once in the molding step before the vulcanization step. It is a manufacturing method of a rubber composition.
<2> 前記ゴムが、ブチルゴム及び臭素化ブチルゴムの少なくとも1つであることを特徴とする前記<1>に記載のゴム組成物の製造方法である。 <2> The method for producing a rubber composition according to <1>, wherein the rubber is at least one of butyl rubber and brominated butyl rubber.
<3> 前記ゴムの乳化分散液中の乳化剤が、オレイン酸カリウムであることを特徴とする前記<1>または<2>に記載のゴム組成物の製造方法である。 <3> The method for producing a rubber composition according to <1> or <2>, wherein the emulsifier in the emulsified dispersion of rubber is potassium oleate.
<4> 前記無機フィラーが、クレーであることを特徴とする前記<1>から<3>のいずれかに記載のゴム組成物の製造方法である。 <4> The method for producing a rubber composition according to any one of <1> to <3>, wherein the inorganic filler is clay.
<5> 前記無機フィラーの含有量が、ゴム100質量部に対して5〜100質量部であることを特徴とする前記<1>から<4>のいずれかに記載のゴム組成物の製造方法である。 <5> The method for producing a rubber composition according to any one of <1> to <4>, wherein the content of the inorganic filler is 5 to 100 parts by mass with respect to 100 parts by mass of the rubber. It is.
<6> 前記<1>から<5>のいずれかに記載のゴム組成物の製造方法により得られるゴム組成物である。 <6> A rubber composition obtained by the method for producing a rubber composition according to any one of <1> to <5>.
本発明によれば、透明性、優れた機械特性を有するとともに、気体透過率が低減されたゴム組成物及びその製造方法を提供することができる。
また、本発明のゴム組成物は、ホース、ガスケット、パッキング材等に有利に使用される。
ADVANTAGE OF THE INVENTION According to this invention, while having transparency and the outstanding mechanical characteristic, the rubber composition by which gas permeability was reduced, and its manufacturing method can be provided.
The rubber composition of the present invention is advantageously used for hoses, gaskets, packing materials and the like.
<ゴム組成物の製造方法>
本発明のゴム組成物の製造方法は、ゴムの乳化分散液と、無機フィラーとを混合して乾燥する工程を含むゴム組成物の製造方法であって、前記ゴムの乳化分散液中の乳化剤量を、ゴム100質量部に対して0.1〜3質量部に調整し、乾燥したゴム組成物を、加硫工程の前の成形加工工程において、1.0mm以下の厚みに圧延する工程を少なくとも1回含むことを特徴としている。以下、各工程について説明するとともに、各工程で使用される各配合物について説明する。
<Method for producing rubber composition>
The method for producing a rubber composition of the present invention is a method for producing a rubber composition comprising a step of mixing and drying a rubber emulsified dispersion and an inorganic filler, wherein the amount of emulsifier in the rubber emulsified dispersion is as follows. At least a step of rolling the dried rubber composition to a thickness of 1.0 mm or less in the molding step before the vulcanization step. It is characterized by including once. Hereinafter, while explaining each process, each compound used at each process is explained.
本発明において使用されるゴムの乳化分散液は、ゴム有機溶剤溶液を乳化した分散液であり、天然のゴムラテックス或いは乳化重合により得られたラテックスとは異なる。即ち、気相重合、溶液重合、塊状重合等で得られたゴム又は合成ゴムを有機溶剤に溶解させ乳化分散液としたものである。従って、特に乳化重合に不向きな合成ゴムに好適である。 The emulsified dispersion of rubber used in the present invention is a dispersion obtained by emulsifying a rubber organic solvent solution, and is different from a natural rubber latex or a latex obtained by emulsion polymerization. That is, a rubber or synthetic rubber obtained by gas phase polymerization, solution polymerization, bulk polymerization or the like is dissolved in an organic solvent to obtain an emulsified dispersion. Therefore, it is particularly suitable for a synthetic rubber unsuitable for emulsion polymerization.
上記ゴムの例として、例えば天然ゴム、スチレンブタジエンゴム(SBR)、ブタジエンゴム、イソプレンゴム、アクリロニトリル ブタジエンゴム(NBR)、クロロプレンゴム、ブチルゴム(IIR)、臭素化ブチルゴム、エチレン−プロピレンゴム、アクリルゴム、クロロスルホン化ポリエチレンゴム、フッ素ゴムラテックス、シリコーンゴム、ウレタンゴムが挙げられる。中でも優れた性能を有し、ホース等の材料に汎用材料的に使用されている材料の観点からアクリロニトリル−ブタジエンゴム(NBR)、スチレンブタジエンゴム(SBR)、ブチルゴム(IIR)、臭素化ブチルゴムが好ましく、特にブチルゴム(IIR)、臭素化ブチルゴムが好ましい。ブチルゴム(IIR)は一般にイソブチレンと少量のイソブレンとの共重合体であり、ハロゲン化されたタイプもある。上記合成ゴムは、通常の気相重合法、溶液重合法、塊状重合法等の重合手法を用いることにより得られる。上記ゴムに加えて、通常の熱可塑性樹脂等のポリマーを併用してもよい。
このような特定のゴムのラテックスを用いることにより、後述する無機フィラーの分散が良好となり、例えば無機フィラーとしてクレーを用いた場合、少量のクレーで優れたガスバリヤ性を発揮することができ好ましい。
Examples of the rubber include natural rubber, styrene butadiene rubber (SBR), butadiene rubber, isoprene rubber, acrylonitrile butadiene rubber (NBR), chloroprene rubber, butyl rubber (IIR), brominated butyl rubber, ethylene-propylene rubber, acrylic rubber, Examples include chlorosulfonated polyethylene rubber, fluorine rubber latex, silicone rubber, and urethane rubber. Among them, acrylonitrile-butadiene rubber (NBR), styrene butadiene rubber (SBR), butyl rubber (IIR), and brominated butyl rubber are preferable from the viewpoint of materials that have excellent performance and are used as general-purpose materials for hoses and the like. In particular, butyl rubber (IIR) and brominated butyl rubber are preferred. Butyl rubber (IIR) is generally a copolymer of isobutylene and a small amount of isobrene, and there are halogenated types. The synthetic rubber can be obtained by using a polymerization method such as a normal gas phase polymerization method, solution polymerization method, bulk polymerization method or the like. In addition to the rubber, a polymer such as a normal thermoplastic resin may be used in combination.
By using such a latex of a specific rubber, the dispersion of the inorganic filler described later is improved. For example, when clay is used as the inorganic filler, it is preferable because excellent gas barrier properties can be exhibited with a small amount of clay.
前記ゴムの乳化分散物に使用される乳化剤は、通常水に溶解して使用する。乳化剤としては、特に限定されることはなく、例えば、アニオン系乳化剤、カチオン系乳化剤、ノニオン系乳化剤又は分散安定剤等を適宜、単独で又は2種以上を混合して用いることができる。 The emulsifier used in the emulsified dispersion of rubber is usually used after being dissolved in water. The emulsifier is not particularly limited, and for example, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, a dispersion stabilizer, or the like can be used alone or in admixture of two or more.
上記アニオン系乳化剤として、例えば、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、アルキルベンゼンスルホン酸ナトリウム、アルキル硫酸ナトリウム、ナフタレンスルホン酸ナトリウムホルマリン縮合物、ジアルキルスルホコハク酸塩、ロジン酸カリウム、オレイン酸アンモニウム、オレイン酸ナトリウム、オレイン酸カリウム等の脂肪酸石鹸等を挙げることができる。 Examples of the anionic emulsifier include sodium polyoxyethylene lauryl ether sulfate, sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium naphthalene sulfonate formalin condensate, dialkyl sulfosuccinate, potassium rosinate, ammonium oleate, sodium oleate, Examples include fatty acid soaps such as potassium oleate.
本発明において、アニオン系乳化剤も上述のように水相に存在させて使用することができるが、上記脂肪酸石鹸を添加するときには、脂肪酸を有機溶剤中に添加しておき、その中和に必要な水酸化アルカリ金属を水中に添加しておき、乳化にあたって有機溶液相と水相とを混合する際にその境界面で両者を反応させて脂肪酸石鹸を形成させることにより乳化を行ってもよい。上記カチオン系乳化剤として、例えば、アルキルトリメチルアンモニウムクロライド、ポリオキシエチレンアルキルアミンの酢酸塩等を挙げることができる。またノニオン系乳化剤としては、例えば、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アルキルフェニルエーテル、ポリオキシエチレンソルビタンアルキレート、オキシエチレンオキシプロピレンブロック共重合体、ポングリセリンエステル等を挙げることができる。また分散安定剤としては、例えば、ポリビニルアルコール、ヒドロキシエチルセルロース、メチルセルロース、ヒドロキシプロピルセルロース、ポリアクリル酸ナトリウム、ポリメタクリル酸ナトリウム、スチレン無水マレイン酸共重合体等の高分子系分散剤等を挙げることができる。これらの乳化剤の中で、得られたゴム組成物が優れたガスバリア性を示す乳化剤としてロジン酸カリウム、オレイン酸アンモニウム、オレイン酸カリウム、オレイン酸ナトリウムを挙げることができ、さらに好ましくはオレイン酸カリウムを挙げることができる。 In the present invention, an anionic emulsifier can also be used in the aqueous phase as described above. However, when the fatty acid soap is added, the fatty acid is added to an organic solvent and is necessary for neutralization. Emulsification may be performed by adding an alkali metal hydroxide to water and reacting the organic solution phase and the aqueous phase at the interface to form a fatty acid soap when emulsifying. Examples of the cationic emulsifier include alkyltrimethylammonium chloride and polyoxyethylene alkylamine acetate. Examples of nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkylate, oxyethylene oxypropylene block copolymer, and ponglycerin ester. Examples of the dispersion stabilizer include polymer dispersants such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl cellulose, sodium polyacrylate, sodium polymethacrylate, and styrene maleic anhydride copolymer. it can. Among these emulsifiers, potassium rosinate, ammonium oleate, potassium oleate, and sodium oleate can be mentioned as emulsifiers in which the obtained rubber composition exhibits excellent gas barrier properties, more preferably potassium oleate. Can be mentioned.
本発明においては、使用する乳化剤の使用量はゴム組成物の性能面から、乳化分散液中のゴム100質量部に対して0.1〜3の質量部としており、より好ましくは0.1〜2質量部である。0.1質量部より少ない場合、乳化することができなくなる。又、3質量部より多い場合、乳化は可能であるが、ゴム組成物のガスバリア性が低下する場合が多く好ましくない。 In this invention, the usage-amount of the emulsifier to use is 0.1-3 mass parts with respect to 100 mass parts of rubber | gum in an emulsified dispersion from the performance surface of a rubber composition, More preferably, it is 0.1-0.1. 2 parts by mass. When the amount is less than 0.1 parts by mass, it cannot be emulsified. When the amount is more than 3 parts by mass, emulsification is possible, but the gas barrier property of the rubber composition is often lowered, which is not preferable.
本発明において使用される無機フィラーとしては、クレー、マイカ、カオリンクレー、タルク、炭酸カルシウム、シリカ等を挙げることができ、これらを単独で又は2種以上を混合して用いることができる。無機フィラーの中でも形状が扁平状であるクレー、マイカ、カオリンクレー、タルクが好ましく、特にクレーが好ましい。無機フィラーの平均粒径は15μm以下であることが好ましく、8〜0.01μmであることがより好ましい。 Examples of the inorganic filler used in the present invention include clay, mica, kaolin clay, talc, calcium carbonate, silica and the like, and these can be used alone or in admixture of two or more. Among inorganic fillers, clay, mica, kaolin clay, and talc having a flat shape are preferable, and clay is particularly preferable. The average particle size of the inorganic filler is preferably 15 μm or less, and more preferably 8 to 0.01 μm.
無機フィラーの量は、ゴム100質量部に対して5〜100質量部、特に5〜80質量部、さらに5〜50質量部が好ましい。無機フィラーの量が5質量部より少ないと、気体遮蔽性の効果が充分に得らないことがあり、100質量部より多いと、分散が困難となることがある。 The amount of the inorganic filler is preferably 5 to 100 parts by mass, particularly 5 to 80 parts by mass, and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the rubber. When the amount of the inorganic filler is less than 5 parts by mass, the gas shielding effect may not be sufficiently obtained. When the amount is more than 100 parts by mass, dispersion may be difficult.
本発明において、前記無機フィラーは、無機フィラーの水スラリー状で混合されることが好ましい。無機フィラーを水スラリー状とする手法としては、特に限定はなく、例えば、まず無機フィラーを水に浸漬し、攪拌する。水の量は、無機フィラーが水に分散し、攪拌が容易になる量であればよく、例えばクレーの場合、通常20gのクレーに対して、総容積が800〜1200ml、好ましくは900〜1100mlになる量である。攪拌には、スターラーミキサーなどの汎用の混合機を用いることができる。攪拌時間は、無機フィラーが水に充分浸漬する時間であればよく、無機フィラーの量にもよるが、通常0.5〜36時間である。 In the present invention, the inorganic filler is preferably mixed in the form of a water slurry of inorganic filler. There is no particular limitation on the method of making the inorganic filler into a water slurry. For example, the inorganic filler is first immersed in water and stirred. The amount of water may be an amount that allows the inorganic filler to be dispersed in water and facilitate stirring. For example, in the case of clay, the total volume is usually 800 to 1200 ml, preferably 900 to 1100 ml, with respect to 20 g of clay. Is the amount. For the stirring, a general-purpose mixer such as a stirrer mixer can be used. The stirring time may be a time for the inorganic filler to be sufficiently immersed in water, and is usually 0.5 to 36 hours although it depends on the amount of the inorganic filler.
前記ゴムの乳化分散液の調製方法は特に限定されず、たとえば1)ラテックスと水に分散した無機フィラーとを別々に調製し混合する、2)乳化剤と無機フィラーを併用して製造されたラテックスを用いる方法、3)乳化剤と無機フィラーを併用して製造されたラテックスと別途調製された水に分散した無機フィラーを混合する方法、等を挙げることができる。さらにこれに架橋剤を加えると、架縮ゴム組成物が得られる。 The method for preparing the rubber emulsified dispersion is not particularly limited. For example, 1) A latex and an inorganic filler dispersed in water are separately prepared and mixed. 2) A latex produced by using an emulsifier and an inorganic filler together. The method to use, 3) The method of mixing the latex manufactured by using an emulsifier and an inorganic filler together, and the inorganic filler disperse | distributed to the water prepared separately, etc. can be mentioned. Furthermore, when a crosslinking agent is added to this, a stretched rubber composition is obtained.
例えば、乳化剤と無機フィラーを分散剤として製造されたラテックスを得る方法として、無機フィラーを分散した水分散に所定量の乳化剤を添加した分散液と、ゴムを溶解した有機溶剤溶液とを混合後、乳化を行い、その後有機溶剤を留去することにより無機フィラーと乳化剤を分散剤として製造されたラテックスを得る。
次いでこれらのラテックスと無機フィラーの水分散液を所定濃度になるように混合する。混合は、スターラーミキサーなどの汎用の混合機を用いることができる。混合は、ラテックスが変質しない限りの高温で行なうこともできるが、室温が好ましい。混合時間は、ラテックスと無機フィラーの水分散液が均一に混合される時間であればよく、混合物の粘度にもよるが、通常0.5〜30分間である。
For example, as a method of obtaining a latex produced using an emulsifier and an inorganic filler as a dispersant, after mixing a dispersion obtained by adding a predetermined amount of an emulsifier to an aqueous dispersion in which an inorganic filler is dispersed, and an organic solvent solution in which rubber is dissolved, Emulsification is performed, and then the organic solvent is distilled off to obtain a latex produced using an inorganic filler and an emulsifier as a dispersant.
Subsequently, these latex and the aqueous dispersion of an inorganic filler are mixed so that it may become a predetermined density | concentration. For mixing, a general-purpose mixer such as a stirrer mixer can be used. The mixing can be performed at a high temperature as long as the latex does not change, but room temperature is preferred. The mixing time may be a time during which the latex and the aqueous dispersion of the inorganic filler are uniformly mixed, and is usually 0.5 to 30 minutes although it depends on the viscosity of the mixture.
攪拌後、混合物を乾燥することで、ゴム組成物を得る。乾燥方法は特に限定はなく、ラテックスの水分散体から固形物を取り出すことができればよく、例えば、水分散体を直接乾燥機に掛ける乾燥法や、水分散体に凝固剤を添加し、一旦固形物を取り出した後乾燥することができる。乾燥方法しては、熱風乾燥、真空乾燥、伝熱乾燥、高周波乾燥、マイクロ波乾燥、加熱蒸気乾燥、等を利用することができ、これらの中でもドラムドライヤーを用いて乾燥した場合、生産効率、性能面でも優れたゴム組成物を得ることができる。この理由としては定かではないが、ドラムドライヤーを用いて乾燥した場合、薄膜状で乾燥が進むために、薄いシートとしてゴム組成物が得られ、このシート内で、クレーが層状に配列しやすくするために、ガスバリア性の遮断効果がよくなると推測される。これらの乾燥によりゴム組成物を得る。 After stirring, the mixture is dried to obtain a rubber composition. The drying method is not particularly limited as long as the solid can be taken out from the latex aqueous dispersion. For example, a drying method in which the aqueous dispersion is directly applied to a dryer, or a coagulant is added to the aqueous dispersion, It can be dried after removing the object. As a drying method, hot air drying, vacuum drying, heat transfer drying, high frequency drying, microwave drying, heating steam drying, etc. can be used, and among these, when drying using a drum dryer, production efficiency, A rubber composition excellent in performance can also be obtained. The reason for this is not clear, but when dried using a drum dryer, since the drying proceeds in a thin film state, a rubber composition is obtained as a thin sheet, and within this sheet, clay is easily arranged in layers. Therefore, it is estimated that the gas barrier property blocking effect is improved. A rubber composition is obtained by these drying.
本発明においては、加硫工程の前の成形加工工程において、ゴム組成物を1.0mm以下に圧延する工程を少なくとも1回含む。圧延されたゴム組成物の厚みはより好ましくは0.7mm以下である。圧延する方法としては特に限定はされないが、通常ロール等の成形機を用いて行うことができる。また、圧延時の温度として、圧延効果を挙げるために、ゴムシートの温度を50℃〜100℃の範囲にすることが好ましい。ゴム組成物を1.0mm以下に圧延することでガスバリア性が向上する理由として、ゴム組成物を薄膜化することでシー卜内で、クレーが層状に配列しやすくするために、ガスの遮断効果が一層よくなっていると推測される。圧延する回数は好ましくは1〜30回、さらに好ましくは1〜20回である。回数が多いほど効果は期待されるが経済的でなくなる。 In the present invention, the step of rolling the rubber composition to 1.0 mm or less is included at least once in the molding step before the vulcanization step. The thickness of the rolled rubber composition is more preferably 0.7 mm or less. Although it does not specifically limit as a rolling method, Usually, it can carry out using shaping machines, such as a roll. Moreover, in order to raise a rolling effect as temperature at the time of rolling, it is preferable to make the temperature of a rubber sheet into the range of 50 to 100 degreeC. The reason why the gas barrier property is improved by rolling the rubber composition to 1.0 mm or less is that, by making the rubber composition into a thin film by making the rubber composition into a thin layer, the clay can be easily arranged in a layered manner. Is estimated to be even better. The number of times of rolling is preferably 1 to 30 times, more preferably 1 to 20 times. The greater the number of times, the better the effect, but the less economical.
<ゴム組成物>
本発明のゴム組成物は、上述の本発明のゴム組成物の製造方法により製造されるゴム組成物である。本発明のゴム組成物は、透明性、優れた機械特性を有するとともに、気体透過率が低減されている。
本発明のゴム組成物は、その気体遮蔽性を生かして、ホース、ガスケット、パッキング材等に有利に使用される。
<Rubber composition>
The rubber composition of the present invention is a rubber composition produced by the above-described method for producing a rubber composition of the present invention. The rubber composition of the present invention has transparency, excellent mechanical properties, and reduced gas permeability.
The rubber composition of the present invention is advantageously used for hoses, gaskets, packing materials and the like by taking advantage of its gas shielding properties.
以下に実施例を挙げて本発明をさらに具体的に説明するが本発明は以下の実施例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.
[実施例1]
(1)乳化分散液の作製
臭素化ブチルゴム(商品名;ポリサーX2、バイエル社製、臭素含有量1.8質量%、残存二重結合量0%)30gをトルエン200gに溶解した。別途、水150gにオレイン酸カリウム0.9gを添加し溶解した溶液を調製した。これらの二つの溶液をTKホモミキサー(M型、特殊機化工業社(株)製)を用いて回転数12000rpmで2分間攪拌混合し乳化した。この浮化液を減圧下、加熱することにより、トルエンを留去し、ブチルゴムのラテックス(固形分20質量%)を得た。得られたラテックスの平均粒子径は1.2μmであった。
[Example 1]
(1) Preparation of emulsion dispersion 30 g of brominated butyl rubber (trade name; Polycer X2, manufactured by Bayer, bromine content 1.8% by mass, residual double bond amount 0%) was dissolved in 200 g of toluene. Separately, a solution was prepared by adding 0.9 g of potassium oleate to 150 g of water and dissolving it. These two solutions were stirred and mixed for 2 minutes at a rotational speed of 12,000 rpm using a TK homomixer (M type, manufactured by Tokushu Kika Kogyo Co., Ltd.) and emulsified. By heating this floating solution under reduced pressure, toluene was distilled off to obtain a latex of butyl rubber (solid content 20% by mass). The average particle size of the obtained latex was 1.2 μm.
(2)ゴム組成物及びシートの作製
9gのクレー(クニミネ工業(株)製:クニピアF)を純水に浸漬し1000mlとして、汎用のスターラーミキサーで2時間撹拌して、クレー水スラリーを得た。このスラリーと上記(1)のラテックスとを混合し、スターラーミキサーを用いて約10分間撹拌し、均一な混合物を得た。
得られた混合物を、60cm×25cm、深さ5cmの容器に取り出し、80℃のファン付き恒温槽中で24時間乾燥し、ゴム組成物を得た。これにロールを用いて1.5gの亜鉛華と0.3gのテトラメチルチウラムジスルフィドを添加した。続いてゴム圧延用ロールの温度を調整し、ゴム組成物の温度60℃、厚みが0.7mmになるように設定して5回、圧延処理をした。
得られた圧延シートを表面が十分平滑な金型を用いて160℃、20分の条件下において架橋させ、1mm厚のシートサンプルを得た。
(2) Preparation of rubber composition and sheet 9 g of clay (Kunimine Kogyo Co., Ltd .: Kunipia F) was immersed in pure water to 1000 ml and stirred with a general-purpose stirrer mixer for 2 hours to obtain a clay water slurry. . This slurry and the latex of (1) were mixed and stirred for about 10 minutes using a stirrer mixer to obtain a uniform mixture.
The obtained mixture was taken out into a container of 60 cm × 25 cm and a depth of 5 cm and dried in a thermostatic bath with a fan at 80 ° C. for 24 hours to obtain a rubber composition. To this, 1.5 g of zinc white and 0.3 g of tetramethylthiuram disulfide were added using a roll. Then, the temperature of the roll for rubber rolling was adjusted, the temperature of the rubber composition was set to 60 ° C., and the thickness was set to 0.7 mm, and the rolling treatment was performed 5 times.
The obtained rolled sheet was crosslinked at 160 ° C. for 20 minutes using a mold having a sufficiently smooth surface to obtain a sheet sample having a thickness of 1 mm.
[実施例2]
(1)乳化分散液の作製
臭素化ブチルゴム(商品名;ポリサーX2、バイエル社製、臭素含有量1.8質量%、残存二重結合量0%)30gをトルエン200gに溶解した。別途、水150gにオレイン酸カリウム0.6gとクレー(クニミネ工業(株)製:クニピアF)0.3gを分散し、汎用のスターラーミキサーを用いて2時間撹拌して分散した溶液を作製した。これらの二つの溶液をTKホモミキサー(M型、特殊機化工業社(株)製)を用いて回転数12000rpmで2分間攪拌混合し乳化した。この乳化液を減圧下、加熱することにより、トルエンを留主し、ブチルゴムのラテックス(固形分20質量%)を得た。得られたラテックスの平均粒子径は1.1μmであった。
[Example 2]
(1) Preparation of emulsion dispersion 30 g of brominated butyl rubber (trade name; Polycer X2, manufactured by Bayer, bromine content 1.8% by mass, residual double bond amount 0%) was dissolved in 200 g of toluene. Separately, 0.6 g of potassium oleate and 0.3 g of clay (Kunimine Kogyo Co., Ltd .: Kunipia F) were dispersed in 150 g of water, and a dispersion solution was prepared by stirring for 2 hours using a general-purpose stirrer mixer. These two solutions were stirred and mixed for 2 minutes at a rotational speed of 12,000 rpm using a TK homomixer (M type, manufactured by Tokushu Kika Kogyo Co., Ltd.) and emulsified. By heating this emulsion under reduced pressure, toluene was distilled to obtain a latex of butyl rubber (solid content 20% by mass). The average particle size of the obtained latex was 1.1 μm.
(2)ゴム組成物及びシートの作製
8.7gのクレー(クニミネ工業(株)製:クニピアF)を蒸留水に浸漬し1000mlとして、汎用のスターラーミキサーで2時間撹拌して、クレー水スラリーを得た。このスラリーと218gの上記(1)のラテックスとを混合し、スターラーミキサーを用いて約10分間攪拌し、均一な混合物を得た。
得られた混合物を、60cm×25cm、深さ5cmの容器に取り出し、80℃のファン付き恒温槽中で24時間乾燥しゴム組成物を得た。これにロールを用いて1.5gの亜鉛華と0.3gのテトラメチルチウラムジスルフィドを添加した。続いてゴム圧延用ロールの温度を調整し、ゴム組成物の温度60℃、厚みが0.7mmになるように設定して5回、圧延処理をした。
得られた圧延シートを表面が十分平滑な金型を用いて160℃、20分の条件下において架橋させ、1mm厚のシートサンプルを得た。
(2) Preparation of rubber composition and sheet 8.7 g of clay (Kunimine Kogyo Co., Ltd .: Kunipia F) was immersed in distilled water to make 1000 ml, and stirred for 2 hours with a general-purpose stirrer mixer. Obtained. This slurry and 218 g of the latex of (1) were mixed and stirred for about 10 minutes using a stirrer mixer to obtain a uniform mixture.
The obtained mixture was taken out into a container having a size of 60 cm × 25 cm and a depth of 5 cm and dried in a thermostatic bath with a fan at 80 ° C. for 24 hours to obtain a rubber composition. To this, 1.5 g of zinc white and 0.3 g of tetramethylthiuram disulfide were added using a roll. Then, the temperature of the roll for rubber rolling was adjusted, the temperature of the rubber composition was set to 60 ° C., and the thickness was set to 0.7 mm, and the rolling treatment was performed 5 times.
The obtained rolled sheet was crosslinked at 160 ° C. for 20 minutes using a mold having a sufficiently smooth surface to obtain a sheet sample having a thickness of 1 mm.
[実施例3]
実施例1において、クレーの添加量を15gに変更したこと以外は実施例1と同様にしてゴム組成物及びシートを製造した。
[Example 3]
In Example 1, a rubber composition and a sheet were produced in the same manner as in Example 1 except that the amount of clay added was changed to 15 g.
[参考例1]
臭素化ブチル30gにロールを用いて1.5gの亜鉛華と0.3gのテトラメチルチウラムジスルフィドを添加した。得られたシートを表面が十分平滑な金型を用いて160℃、20分の条件下において架橋させ、1mm厚のシートサンプルを得た。
[Reference Example 1]
Using 30 g of brominated butyl, 1.5 g of zinc white and 0.3 g of tetramethylthiuram disulfide were added using a roll. The obtained sheet was crosslinked under a condition of 160 ° C. for 20 minutes using a mold having a sufficiently smooth surface to obtain a sheet sample having a thickness of 1 mm.
[比較例1]
実施例1において、乳化分散液の調製で用いるオレイン酸カリウムの量を1.5gに変更したこと以外は実施例1と同様にしてゴム組成物及びシートを製造した。
[Comparative Example 1]
In Example 1, a rubber composition and a sheet were produced in the same manner as in Example 1 except that the amount of potassium oleate used in the preparation of the emulsified dispersion was changed to 1.5 g.
[比較例2]
実施例1において、ゴム組成物及びシートの作製においてロール圧延時、ゴム組成物の厚みを1.5mmになるように圧延処理を行なったこと以外は実施例1と同様にしてゴム組成物及びシートを製造した。
[Comparative Example 2]
In Example 1, the rubber composition and the sheet were produced in the same manner as in Example 1 except that the rolling treatment was performed so that the rubber composition had a thickness of 1.5 mm during roll rolling in the production of the rubber composition and the sheet. Manufactured.
<評価方法>
1)機械特性
JIS−K6301に従い引張試験を行い、引張応力(Md100、Md300はそれぞれ伸び100%、300%時の応力)、引張強さ(Tb)、及び引張伸び(Eb)を測定した。結果を表1に示す。
2)気体透過性
気体透過性を評価するため、GTRテック(株)製ガス透過試験機(GTR30A、ガス:フロンR134a)を用い、100℃、ガス供給側圧力0.2MPaの差圧法により気体透過測定を行った。
但し、試験を開始した後、12時間経過後に気体透過測定を行い、気体透過係数(cc−cm/cm2・秒・cmHg)を得た。
<Evaluation method>
1) Mechanical properties A tensile test was performed in accordance with JIS-K6301, and tensile stress (Md100 and Md300 were elongation at 100% and 300%, respectively), tensile strength (Tb), and tensile elongation (Eb) were measured. The results are shown in Table 1.
2) Gas permeability In order to evaluate gas permeability, gas permeability was measured by a differential pressure method using a gas permeation tester (GTR30A, gas: Freon R134a) manufactured by GTR Tech Co., Ltd. at 100 ° C and a gas supply side pressure of 0.2 MPa. Measurements were made.
However, after starting the test, gas permeation measurement was performed after 12 hours to obtain a gas permeation coefficient (cc-cm / cm 2 · sec · cmHg).
表1より、実施例1〜3はいずれも、機械特性が優れるとともに、気体透過率が低減されているのに対し、乳化剤の量がゴム100質量部に対して5質量部含む比較例1は気体透過率が低減されず、圧延する工程における厚みを1.5mmとして比較例2は優れた機械特性が得られなかったことが分かる。 From Table 1, Examples 1 to 3 all have excellent mechanical properties and reduced gas permeability, whereas the amount of emulsifier is 5 parts by mass with respect to 100 parts by mass of rubber. It can be seen that the gas permeability was not reduced, and excellent mechanical properties were not obtained in Comparative Example 2 when the thickness in the rolling step was 1.5 mm.
Claims (6)
前記ゴムの乳化分散液中の乳化剤量を、ゴム100質量部に対して0.1〜3質量部に調整し、乾燥したゴム組成物を、加硫工程の前の成形加工工程において、1.0mm以下の厚みに圧延する工程を少なくとも1回含むことを特徴とするゴム組成物の製造方法。 A method for producing a rubber composition comprising a step of mixing and drying an emulsified dispersion of rubber and an inorganic filler,
The amount of the emulsifier in the emulsified dispersion of rubber is adjusted to 0.1 to 3 parts by mass with respect to 100 parts by mass of rubber, and the dried rubber composition is subjected to the following steps in the molding process step before the vulcanization step: A method for producing a rubber composition, comprising a step of rolling at a thickness of 0 mm or less at least once.
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JP2008013608A (en) * | 2006-07-03 | 2008-01-24 | Jsr Corp | Aqueous emulsified dispersion of butyl rubber and its manufacturing method |
JP2017519893A (en) * | 2014-06-30 | 2017-07-20 | アランセオ・シンガポール・プライヴェート・リミテッド | A novel anti-flocculating agent for the rubber industry. |
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JP2003321551A (en) * | 2002-05-02 | 2003-11-14 | Bridgestone Corp | Production method of rubber composition and rubber composition |
JP2003327711A (en) * | 2002-05-10 | 2003-11-19 | Bridgestone Corp | Method of producing rubber composition and rubber composition |
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JP2004051748A (en) * | 2002-07-18 | 2004-02-19 | Sumitomo Rubber Ind Ltd | Polymer composition and its production method |
JP2004263128A (en) * | 2003-03-04 | 2004-09-24 | Bridgestone Corp | Rubber composition, rubber laminated body using this, and method for manufacturing rubber composition |
JP2005029769A (en) * | 2003-06-18 | 2005-02-03 | Bridgestone Corp | Polymer composition, ball for ball games using the same, and tire tube for bicycles |
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JP2003292678A (en) * | 2002-04-05 | 2003-10-15 | Bridgestone Corp | Rubber composition and its production method |
JP2003321551A (en) * | 2002-05-02 | 2003-11-14 | Bridgestone Corp | Production method of rubber composition and rubber composition |
JP2003327711A (en) * | 2002-05-10 | 2003-11-19 | Bridgestone Corp | Method of producing rubber composition and rubber composition |
JP2004035708A (en) * | 2002-07-03 | 2004-02-05 | Bridgestone Corp | Rubber composition and high-pressure hose |
JP2004051748A (en) * | 2002-07-18 | 2004-02-19 | Sumitomo Rubber Ind Ltd | Polymer composition and its production method |
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JP2017519893A (en) * | 2014-06-30 | 2017-07-20 | アランセオ・シンガポール・プライヴェート・リミテッド | A novel anti-flocculating agent for the rubber industry. |
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