JPS62240327A - Production of powdered rubber - Google Patents
Production of powdered rubberInfo
- Publication number
- JPS62240327A JPS62240327A JP8219686A JP8219686A JPS62240327A JP S62240327 A JPS62240327 A JP S62240327A JP 8219686 A JP8219686 A JP 8219686A JP 8219686 A JP8219686 A JP 8219686A JP S62240327 A JPS62240327 A JP S62240327A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- parts
- weight
- rubber latex
- latex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 71
- 239000005060 rubber Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920000126 latex Polymers 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 5
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- -1 sodium lauryl alcohol sulfuric acid ester Chemical class 0.000 abstract description 13
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 12
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 abstract description 11
- 229920001084 poly(chloroprene) Polymers 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract 1
- 239000001110 calcium chloride Substances 0.000 abstract 1
- 229910001628 calcium chloride Inorganic materials 0.000 abstract 1
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 238000005189 flocculation Methods 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 13
- 239000004816 latex Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000002563 ionic surfactant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001599 direct drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007965 rubber solvent Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PCPYTNCQOSFKGG-UHFFFAOYSA-N 1-chlorobuta-1,3-diene Chemical compound ClC=CC=C PCPYTNCQOSFKGG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LEKIODFWYFCUER-UHFFFAOYSA-N 2-methylidenebut-3-enenitrile Chemical compound C=CC(=C)C#N LEKIODFWYFCUER-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 101000650578 Salmonella phage P22 Regulatory protein C3 Proteins 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
- 101001040920 Triticum aestivum Alpha-amylase inhibitor 0.28 Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- QUEICCDHEFTIQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=N1 QUEICCDHEFTIQD-UHFFFAOYSA-N 0.000 description 1
- KLIYQWXIWMRMGR-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate Chemical compound C=CC=C.COC(=O)C(C)=C KLIYQWXIWMRMGR-UHFFFAOYSA-N 0.000 description 1
- LRTQWXGNPCHTFW-UHFFFAOYSA-N buta-1,3-diene;methyl prop-2-enoate Chemical compound C=CC=C.COC(=O)C=C LRTQWXGNPCHTFW-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-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
- 238000001694 spray drying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【発明の詳細な説明】 ［１）発明の目的 〔産業上の利用分野〕 本発明は、粉末ゴムの製造法に関するものである。[Detailed description of the invention] [1) Purpose of the invention [Industrial application field] The present invention relates to a method for producing powdered rubber.
さらに詳しくは、ゴムラテックスに陰イオン界面活性剤
を加え、安定化したのち、アルカリ土類金属の塩化物も
しくは硝酸塩を含む水溶液中に滴下することＫよって粉
末状にゴムを分離し、次いで無機充填剤の超微粒子コロ
イド溶液を添加して、ゴム粒子同志の粘着を防止するこ
とによりて粉末ゴムを製造する方法に関するものである
。More specifically, an anionic surfactant is added to the rubber latex to stabilize it, and then the rubber is separated into a powder by dropping it into an aqueous solution containing an alkaline earth metal chloride or nitrate. The present invention relates to a method for producing powdered rubber by adding an ultrafine colloidal solution of an agent to prevent rubber particles from sticking together.
ゴムは、ゴムラテックスから単離されることが多（、そ
の形状は比較的大きな塊状（ブロック状あるいはベール
状）又はチップ状の形で供給されてきた。近年、ゴムの
加工技術の進歩に伴い、自動計量や連続加工が可能な粉
末ゴムが省力化あるいは省エネルギーな目的として市場
における要望が高く、注目されてきている。Rubber is often isolated from rubber latex and is supplied in the form of relatively large lumps (blocks or veils) or chips.In recent years, with advances in rubber processing technology, Powdered rubber, which can be automatically weighed and processed continuously, is in high demand and attracting attention in the market for labor-saving and energy-saving purposes.
一般に粉末ゴムの製造法としては、機械的粉砕法、直接
乾燥法、共沈法および凝固法がある。Generally, methods for producing powdered rubber include mechanical pulverization, direct drying, coprecipitation, and coagulation.
粉砕法は塊状のゴムを原料とし、粉砕を行う方法である
が、この場合、しばしば製造の為のエネルギー消費が大
きくなる問題がある。The pulverization method is a method in which a lump of rubber is used as a raw material and is pulverized, but in this case, there is often a problem that energy consumption for production is large.
スプレー乾燥法、フラッシュ乾燥法等の直接乾燥法やラ
テックス中に硅酸塩やカーボンブラックを加えて、共沈
させて分離する共沈法では、しばしば多量の凝集防止剤
を費し、あるいは、ラテックス中の乳化剤等の非ゴム分
が乾燥品中に多量に残留する欠点がある。Direct drying methods such as spray drying and flash drying, and coprecipitation methods in which silicate or carbon black is added to latex and separated by coprecipitation, often require a large amount of anti-coagulant, or The disadvantage is that a large amount of non-rubber components such as emulsifiers remain in the dry product.
攪拌下の凝固剤にラテックスを滴下させることによって
ラテックスの凝固を行う凝固法は、物理的には良好なも
のが得られるものの、クロロプレンゴム等のような粘着
性の強いゴムの場合、粒子同志が粘着してしまい、微粒
子状での凝固は難しく、望ましい粒径の粉末ゴムが得ら
れにくかった。Although a coagulation method in which latex is coagulated by dropping the latex into a coagulant under stirring produces physically good results, in the case of highly adhesive rubbers such as chloroprene rubber, the particles may stick together. It was sticky and difficult to coagulate into fine particles, making it difficult to obtain powdered rubber with a desired particle size.
さらに１マイクロカプセル化を用いる粉末ゴムの製造方
法（特開昭５３−７５２４４）があり、本方法により製
造した粉末ゴムは、強固なマイクロカプセルのため、粒
子同志が粘着したり、貯蔵中に凝集したりすることはな
い。しかしながら、かかる粉末ゴムは、ゴム系溶剤に不
溶な成分（以後ゲルと称す）を含有しており、ゴム系溶
剤壁接着剤のゴム材料として使用するには問題があるこ
とがわかった。また、他の粉末ゴムの製造法を用いても
粒子同志の粘着や貯蔵中の凝集がなく、ゴム系溶剤型接
着剤のゴム材料を含めたすべてのゴム用途に使用できる
粉末ゴムは製造できていないのが現状である。Furthermore, there is a method for producing powdered rubber using microencapsulation (Japanese Patent Application Laid-open No. 53-75244), and because the powdered rubber produced by this method is a strong microcapsule, the particles may stick to each other or aggregate during storage. There is nothing to do. However, it has been found that such powdered rubber contains a component (hereinafter referred to as gel) that is insoluble in rubber solvents, and there is a problem in its use as a rubber material for rubber solvent wall adhesives. In addition, even if other powdered rubber manufacturing methods are used, powdered rubber that does not cause particle adhesion or agglomeration during storage and can be used for all rubber applications, including rubber materials for rubber-based solvent-based adhesives, cannot be produced. The current situation is that there is no such thing.
本発明の目的は、粒子同志の粘着や貯蔵中の凝集がな（
、ゴム系溶剤型接着剤のゴム材料を含めたすべてのゴム
用途に使用できる粉末ゴムの製造法を提供することにあ
る。The purpose of the present invention is to prevent particles from adhering to each other and from agglomerating during storage.
The object of the present invention is to provide a method for producing powdered rubber that can be used for all rubber applications, including rubber materials for rubber-based solvent-based adhesives.
（ＩＩ）発明の構成
〔問題を解決するための手段〕
本発明の粒子同志の粘着や貯蔵中の凝集がなく、ゲル分
を含有しない粉末ゴムの製法は、アニオンもしくはノニ
オン性のゴムラテックスに、その乾燥重量で１００重量
部当り、１〜３０重量部の陰イオン界面活性剤を加えて
得られる混合物を、該ゴムラテックスの乾燥重量で１０
０ｉｉ１１部当り１〜２０重量部のアルカリ土類金属の
塩化物もしくは硝酸塩を含む水溶液中Ｖｃｈ！ｉ下混合
して、該ゴムラテックスからゴムを粉末状に分離させ、
ついで、これに該ゴムラテックスの乾燥重量当り１１５
〜５０重量部の無機充填剤の超微粒子をコロイド溶液と
して添加することを特徴とする。(II) Structure of the Invention [Means for Solving the Problem] The method for producing powder rubber of the present invention, which does not cause adhesion of particles to each other or agglomeration during storage and does not contain a gel component, involves adding anionic or nonionic rubber latex to anionic or nonionic rubber latex. A mixture obtained by adding 1 to 30 parts by weight of an anionic surfactant per 100 parts by dry weight of the rubber latex is added to 100 parts by dry weight of the rubber latex.
Vch! in an aqueous solution containing 1 to 20 parts by weight of alkaline earth metal chloride or nitrate per 11 parts of Oii! i mixing to separate the rubber from the rubber latex into a powder;
Then, to this, 115 per dry weight of the rubber latex was added.
It is characterized in that ~50 parts by weight of ultrafine particles of an inorganic filler are added as a colloidal solution.
以下その詳細について説明する。The details will be explained below.
本発明において対象とするゴムは、アニオンあるいはノ
ニオン性のラテックスとして得られるものであればすべ
て使用可能である。Any rubber targeted in the present invention can be used as long as it can be obtained as an anionic or nonionic latex.
例えば、天然ゴムあるいは従来の乳化重合で製造される
共役ジエン化合物の単独重合体であるポリイソプレンゴ
ム、ポリブタジェンゴム、ポリクロロプレンゴム、前記
共役ジエン化合物とスチレン、アクリロニトリル、ビニ
ルピリジン、アクリル酸、メタクリル酸、アルキルアク
リレート、アルキルメタクリレート等のビニル化合物と
の共重合体であるスチレンブタジェンゴム、アクリロニ
トリルブタジェンゴム、ビニルピリジンブタジェンスチ
レンゴム、アクリル酸ブタジェンゴム、メタクリル酸ブ
タジェンゴム、メチルアクリレートブタジェンゴム、メ
チルメタクリレートブタジェンゴム、あるいはエチレン
、プロピレン、インブチレン等のオレフィン類と共役ジ
エン化合物との共重合体であるイソブチレンイソプレン
ゴム等がある。好ましいゴムは、粘着性が強い 又はゴ
ム系溶剤型接着剤としての用途の多いゴムで、例えば、
ポリクロロプレンゴム等が挙げられる。For example, natural rubber or polyisoprene rubber, which is a homopolymer of a conjugated diene compound produced by conventional emulsion polymerization, polybutadiene rubber, polychloroprene rubber, the above conjugated diene compound and styrene, acrylonitrile, vinylpyridine, acrylic acid, Styrene butadiene rubber, acrylonitrile butadiene rubber, vinylpyridine butadiene styrene rubber, butadiene acrylate rubber, butadiene methacrylate rubber, methyl acrylate butadiene rubber, which is a copolymer with a vinyl compound such as methacrylic acid, alkyl acrylate, or alkyl methacrylate. Examples include methyl methacrylate butadiene rubber, and isobutylene isoprene rubber, which is a copolymer of olefins such as ethylene, propylene, and inbutylene and a conjugated diene compound. Preferred rubbers are those that have strong tack or are often used as rubber-based solvent-based adhesives, such as:
Examples include polychloroprene rubber.
ポリクロロプレンゴムは、少な（とも５０重ｉ％が２−
クロル−１，３−ブタジェン（以下クロロプレンと略す
）からなるゴムを意味する。クロロプレンに対して使用
できる代表的な共重合し得る単量体には、スチレン、ア
クリロニトリル、酢酸ビニル、アクリル酸およびメタク
リル酸のアルキルエステル、ブタジェン、イソプレン、
１−クロル−１，５−フタジエン、 ２．５−シｌロル
ー１．３−ブタジェン。Polychloroprene rubber has a small amount (both 50% by weight is 2-
It means a rubber made of chloro-1,3-butadiene (hereinafter abbreviated as chloroprene). Typical copolymerizable monomers that can be used with chloroprene include styrene, acrylonitrile, vinyl acetate, alkyl esters of acrylic and methacrylic acids, butadiene, isoprene,
1-chloro-1,5-phtadiene, 2,5-silol-1,3-butadiene.
２−シアノ−１，３−ブタジェン等がある。Examples include 2-cyano-1,3-butadiene.
本発明において用いられる隘イオン界面活性剤とは、ラ
ウリルアルコールＷｔａｔエステルソーダ、アルキル硫
酸エステルソーダ、高級アルコール硫酸エステルソーダ
、ポリオキシエチレンアルキルエーテル硫酸エステルソ
ーダ、アルキルスルホネート、アルキル了りルスルホネ
ート、アルキルベンゼンスルホネート、アルキルアリル
スルホン酸ソーダ、アルキルナフタレンスルホン酸ソー
ダ、す７タレンスルホン酸ン一ダーホルマリンｍ合物、
）”デシルベンゼンスルホン酸ソーダ、アルキルベンゼ
ンスルホン酸ソーダ、リグニンスルホン酸ソ〜ダ、リグ
ニンスルホン酸カルシウム。The ionic surfactants used in the present invention include lauryl alcohol Wtat ester soda, alkyl sulfate ester soda, higher alcohol sulfate ester soda, polyoxyethylene alkyl ether sulfate ester soda, alkyl sulfonate, alkyl ester sulfonate, and alkylbenzene sulfonate. , sodium alkylaryl sulfonate, sodium alkylnaphthalene sulfonate, monomer formalin m compound,
)” Sodium decylbenzenesulfonate, sodium alkylbenzenesulfonate, sodium ligninsulfonate, calcium ligninsulfonate.
ジアルキルスルホサクシネート、ジオクチルスルホクサ
シネートソーダ塩、高級アルコールスルホン酸ソーダ塩
、アルキルアリルエーテルスルホン酸ソーダ、アルキル
ホスフェート等がある。Examples include dialkyl sulfosuccinate, dioctyl sulfoxacinate sodium salt, higher alcohol sulfonic acid sodium salt, alkyl allyl ether sulfonate sodium salt, and alkyl phosphate.
これらの陰イオン界面活性剤は、ゴムラテックスの乾燥
型１１００３１１部に対して１〜３０ｉ量部、好ましく
は１〜２５＠ｉ１１部の範囲で用いられる。隘イオン界
面活性剤が、１重量部未満では、アルカリ土類金属の塩
化物もしくは硝酸塩を含む水溶液中に滴下した際、目的
とする微粒子状粉末ゴムとならず、粗大粒子となったり
、あるいは粘着性の強い塊を形成し好ましくない。又、
隘イオン界面活性剤が３０重量部を越えて使用した場合
、得られた粉末ゴム粒子が凝集することはないが、ゲル
が増加するなどしてゴム物性が低下してしまう。These anionic surfactants are used in an amount of 1 to 30 parts, preferably 1 to 25 parts per 11 parts of dry rubber latex. If the ionic surfactant is less than 1 part by weight, when dropped into an aqueous solution containing alkaline earth metal chlorides or nitrates, the intended fine-grained powdered rubber may not be formed, but may become coarse particles or become sticky. It forms strong clumps and is undesirable. or,
If the ionic surfactant is used in an amount exceeding 30 parts by weight, the obtained powdered rubber particles will not aggregate, but the physical properties of the rubber will deteriorate due to an increase in gel formation.
本発明で用いられるアルカリ土類金属の塩化物もしくは
硝酸塩とは、たとえばＭｇＣ４。The alkaline earth metal chloride or nitrate used in the present invention is, for example, MgC4.
Ｃａ０４ 、 ＢａＣ４、Ｂａ（ＮＯ晶、 Ｍｇ（ＮＯ
，％ 、 ｃａ（Ｎｏ、）。Ca04, BaC4, Ba(NO crystal, Mg(NO
,%, ca(No,).
等である。etc.
これらのアルカリ土類金属の塩化物もしくは硝酸塩は水
溶液として使用され、その水溶液の濃度は１１〜２０重
ｔ％、好ましくはα５〜１０重ｉ％の範囲で用いられる
。これらのアルカリ土類金属の塩化物もしくは硝酸塩は
、ゴムラテックスの乾燥型［１００重量部に対して１〜
２０重量部、好ましくは２〜１５重量部の範囲で用いら
れる。These alkaline earth metal chlorides or nitrates are used as an aqueous solution, and the concentration of the aqueous solution is 11 to 20% by weight, preferably α5 to 10% by weight. These alkaline earth metal chlorides or nitrates are used in the dry form of rubber latex [1 to 100 parts by weight].
It is used in an amount of 20 parts by weight, preferably 2 to 15 parts by weight.
アルカリ土類金属の塩化物もしくは硝酸塩が１重量部未
満では、ゴムラテックスを滴下した際、目的とする微粒
子状粉末ゴムとならず、粗大粒子となったり、あるいは
粘着性の強い塊を形成し、好ましくない。又アルカリ土
類金属の塩化物もしくは硝酸塩が２０重量部を越えて使
用した場合、得られた粉末ゴム粒子が凝集することはな
いが、ゲルが増加するなどしてゴム物性が低下してしま
う。If the alkaline earth metal chloride or nitrate is less than 1 part by weight, when the rubber latex is dropped, it will not form the desired fine particulate powder rubber, but will become coarse particles, or will form a highly sticky lump, Undesirable. If more than 20 parts by weight of the alkaline earth metal chloride or nitrate is used, the resulting powdered rubber particles will not aggregate, but the physical properties of the rubber will deteriorate due to an increase in gel formation.
粉末分離操作は、ゴムラテックスをアルカリ土類金属の
塩化物もしくは硝酸塩の水溶液に攪拌下で滴下すること
によっ【行う。こうして、ゴムラテックスからゴムを速
やかに、かつ容易に粉末状に分離することができる。The powder separation operation is carried out by dropping the rubber latex into an aqueous solution of an alkaline earth metal chloride or nitrate under stirring. In this way, rubber can be quickly and easily separated into powder form from rubber latex.
次いで、該粉末ゴム分散液に１無機充填剤の超微粒子コ
ロイド溶液を添加する。Next, an ultrafine colloidal solution of an inorganic filler is added to the powdered rubber dispersion.
本発明で用いられる無機充填剤の超微粒子コロイド溶液
としては、無水硅酸（ｓｌｏ、）の超微粒子コロイド溶
液、アルミナ（Ａ４ｏｓ）の超微粒子コロイド溶液、酸
化リチウム（Ｌｉｄ、）の超微粒子コロイド溶液および
上記コロイド溶液の混合物がある。The ultrafine particle colloidal solution of the inorganic filler used in the present invention includes an ultrafine colloidal solution of silicic anhydride (slo), an ultrafine colloidal solution of alumina (A4os), and an ultrafine colloidal solution of lithium oxide (Lid). and mixtures of the above colloidal solutions.
本発明において用いられる無機充填剤の超微粒子コロイ
ド溶液は、ゴムラテックスの乾燥重量当り、乾燥重量と
して、（１５〜５０重量部、好ましくは１．０〜３０重
量部の範囲で用いられる。無機充填剤の超微粒子コロイ
ドｆ６ｇ、がα５未満の場合、粉末状に分離した粉末ゴ
ム分散液を脱水、乾燥した際、ゴム粒子同志が粘着して
しまい、流動性のある粉末ゴムは得られない。又５０重
量部を越えて添加した場合、得られた粉末ゴムが凝集す
ることはないが、ゲルが増加するなどしてゴム物性が低
下してしまう。The ultrafine colloidal solution of the inorganic filler used in the present invention is used in an amount of (15 to 50 parts by weight, preferably 1.0 to 30 parts by weight) based on the dry weight of the rubber latex. If the ultrafine colloidal particle f6g of the agent is less than α5, when the powdered rubber dispersion separated into powder is dehydrated and dried, the rubber particles will stick to each other, making it impossible to obtain a fluid powdered rubber. If more than 50 parts by weight is added, the obtained powdered rubber will not aggregate, but the physical properties of the rubber will deteriorate due to an increase in gel content.
以上の操作で得られる粉末ゴム分散液は、遠心分離機等
を用いて容易に脱水でき、流動性のある、あるいは軽度
の力で粉砕して湿潤粉末ゴム圧することができる。The powdered rubber dispersion obtained by the above operations can be easily dehydrated using a centrifuge or the like, and can be fluidized or crushed with light force to form wet powder rubber.
次いで乾燥されるが、乾燥の方法は特に限定されろもの
でな（、通風乾燥、熱風乾燥。The material is then dried, but the drying method is not particularly limited (ventilation drying, hot air drying, etc.).
真空乾燥、流動乾燥等の方法を自由に選択して用いるこ
とができる。Methods such as vacuum drying and fluidized drying can be freely selected and used.
以下に実施例を示して説明するが、本発明はこれらに限
定されるものでない。実施例中特に記載のない限り、部
とチはすべて重量による。な：ｔｌＪ ｓ実施例に使用
したゴムラテックスは次のとおりである。Examples will be described below, but the present invention is not limited thereto. In the examples, all parts and units are by weight unless otherwise specified. The rubber latex used in the examples is as follows.
Ａ）クロロプレンゴムラテックス（ＯＲと略す） 窒素気流中でロジンカリ石ケン４．０部。A) Chloroprene rubber latex (abbreviated as OR) 4.0 parts of rosin potassium soap in a nitrogen stream.
苛性ソーダ１１４部、ホルムアルデヒド・ナフタレンス
ルホン酸ソーダの縮合物（Ｌ４部を水１００部に溶解し
、次いでｎ−ドデシルメルカプタンα２部、２．６−ジ
ーｔ−ブチル−ｐ−クレゾール（Ｌ１部を溶解したクロ
ロプレンを加えて乳化し、４０℃で過硫酸カリウムの１
チ水溶液を滴下しながら重合を行った。重合は、７０％
転化率で停止させ、未反応クロロプレンを留去して乾燥
重量が５５−のクロロプレンゴムラテックスを得た。114 parts of caustic soda, a condensate of formaldehyde/sodium naphthalene sulfonate (4 parts of L were dissolved in 100 parts of water, and then 2 parts of n-dodecylmercaptan α, 2 parts of 2,6-di-t-butyl-p-cresol (1 part of L was dissolved) Add chloroprene to emulsify, and add potassium persulfate at 40°C.
Polymerization was carried out while dropping the aqueous solution. Polymerization is 70%
The conversion was stopped and unreacted chloroprene was distilled off to obtain a chloroprene rubber latex with a dry weight of 55.
Ｂ）アクリロニトリル・ブタジェンゴムラテックス（Ｎ
ＢＲと略す）
日本ゼオン社製の高アクリロニトリル・ブタジェンゴム
ラテックス（商品名Ｎ１ｐＱ１１５７１）を乾燥ｉｆが
３５％になるように調製した。B) Acrylonitrile-butadiene rubber latex (N
A high acrylonitrile butadiene rubber latex (trade name N1pQ11571) manufactured by Nippon Zeon Co., Ltd. (abbreviated as BR) was prepared to have a dry if of 35%.
Ｃ）ブタジェンゴムラテックス（ＢＲと略す）日本合成
ゴム社製のブタジェンゴムラテックス（商品名、ＴＳＲ
Ｏ７００）を乾燥重量が３５％になるように調整した。C) Butadiene rubber latex (abbreviated as BR) Butadiene rubber latex (trade name, TSR) manufactured by Japan Synthetic Rubber Co., Ltd.
O700) was adjusted to have a dry weight of 35%.
Ｄ） スチレン・ブタジェンゴムラテックス（８ＢＲ
と略す）
日本合成ゴム社製のスチレン・ブタジェンゴムラテック
ス（商品名ＪＳＲＯ５６１）を乾燥重量が３５チになる
ように調整した。D) Styrene-butadiene rubber latex (8BR
) Styrene-butadiene rubber latex (trade name JSRO561) manufactured by Japan Synthetic Rubber Co., Ltd. was adjusted to have a dry weight of 35 inches.
さらに粉末ゴムの貯蔵下における凝集性は、以下のよう
にして評価した。Furthermore, the cohesiveness of the powdered rubber during storage was evaluated as follows.
貯蔵安定性テスト（ｋｇ／ｃＩＩｔ） 乾燥粉末ゴム約１３０ｇを縦、横６０ｙｕｓ。Storage stability test (kg/cIIt) Approximately 130g of dry powder rubber, length and width 60yus.
深さ７０ｇ１ｍの箱に充てんし、これに２０に９詰袋、
８袋積の最下部Ｋかかる荷重に相当する力、４８９／ｃ
ＩＩｌの荷重をかけた状態で、恒温室内（５０℃）で２
４時間貯蔵する。その後、粉末ゴムを箔から取り出し、
これを崩すのに要する力を測定することによって評価し
た。Fill a box with a depth of 70 g and 1 m, and add 9 bags to 20.
Force equivalent to the load applied to the bottom K of 8 bags stacked, 489/c
2 in a constant temperature room (50℃) with a load of IIl applied.
Store for 4 hours. Then, remove the powdered rubber from the foil and
Evaluation was made by measuring the force required to break this.
実施例１〜５
表−１に示した各試薬の組み合せで、粉末ゴムの製造を
行った。ゴムラテックス
＆０００９に隘イオン界面活性剤５０ ９を加え、さら
に１０チ酢酸水溶液を加えてｐＨ＆０に調節した。次い
でこのゴムラテックスを１５０ｇのアルカリ土類金属の
塩化物もしくは硝酸塩を含む５ｔの水中に攪拌下で５分
間にわたって滴下した。ゴムは直ちに微粉末状に分離し
た。Examples 1 to 5 Powdered rubber was produced using the combinations of reagents shown in Table 1. An ionic surfactant 509 was added to the rubber latex &0009, and an aqueous solution of 10 thiacetic acid was added to adjust the pH to &0. This rubber latex was then added dropwise over 5 minutes to 5 tons of water containing 150 g of alkaline earth metal chloride or nitrate under stirring. The rubber immediately separated into fine powder.
無機充填剤の超微粒子コロイド溶液を添加した後、３０
分間攪拌した。After adding the ultrafine colloidal solution of inorganic filler, 30
Stir for a minute.
次いで遠心分離機で脱水し、さらに流動乾燥機で乾燥し
て粉末ゴムを得た。The mixture was then dehydrated using a centrifugal separator and further dried using a fluidized bed dryer to obtain powdered rubber.
得られた粉末ゴムは、上記操作中粒子同志が粘着したり
、又貯蔵中に凝集したりすることはなかった。また、こ
の粉末ゴムを２００メツシユの金網で作ったカゴの中に
入れ、ベンゼン中に室温下で４０時間浸漬してベンゼン
に不溶なゲル分を測定したところ、粉末ゴムは全て溶解
しており、ゲル分は０チであった。In the obtained powdered rubber, the particles did not stick to each other during the above-mentioned operation, nor did they aggregate during storage. In addition, when this powdered rubber was placed in a basket made of 200 mesh wire mesh and immersed in benzene at room temperature for 40 hours, the gel content insoluble in benzene was measured, and all of the powdered rubber was dissolved. The gel content was 0.
貯蔵安定性テストを行ったが、箱から取り出す際に警部
れしてしまう。従って崩すのに要する力はＯｋｇ／ｄで
あった。本発明の粉末ゴムは貯蔵中に凝集することはな
かった。I did a storage stability test, but the inspector was confused when I took it out of the box. Therefore, the force required to break it was Okg/d. The powdered rubber of the present invention did not agglomerate during storage.
比較例１〜２
表−１に示した各試薬の組み合せで、実施例と同様の操
作で行った。貯蔵安定性テストを行ったが、スポンジ状
に凝集してしまい、もとの粉末状にならなかった。Comparative Examples 1 and 2 The same operations as in Examples were carried out using the combinations of reagents shown in Table 1. A storage stability test was conducted, but the product agglomerated into a spongy shape and did not return to its original powder state.
ＣＩＩＩ）発明の効果
以上の説明で明らかなように、本発明の方法により粒子
同志の粘着や貯蔵中の凝集がなく、ゲル分のない粉末ゴ
ムを得ることが出来る。CIII) Effects of the Invention As is clear from the above explanation, the method of the present invention makes it possible to obtain powdered rubber without adhesion between particles or agglomeration during storage, and without any gel content.
Claims (1)
その乾燥重量で１００重量部当り、１〜３０重量部の陰
イオン界面活性剤を加えて得られる混合物を、該ゴムラ
テックスの乾燥重量で１００重量部当り１〜２０重量部
のアルカリ土類金属の塩化物もしくは硝酸塩を含む水溶
液中に混合して、該ゴムラテックスからゴムを粉末状に
分離させ、ついで、これに該ゴムラテックスの乾燥重量
当り０．５〜５０重量部の無機充填剤の超微粒子をコロ
イド溶液として添加することを特徴とする粉末ゴムの製
造方法。1) Anionic or nonionic rubber latex,
A mixture obtained by adding 1 to 30 parts by weight of an anionic surfactant per 100 parts by weight of the rubber latex is mixed with 1 to 20 parts by weight of an alkaline earth metal per 100 parts by weight of the rubber latex. Rubber is separated from the rubber latex into a powder by mixing in an aqueous solution containing chloride or nitrate, and then 0.5 to 50 parts by weight of ultrafine particles of an inorganic filler per dry weight of the rubber latex are added thereto. 1. A method for producing powdered rubber, which comprises adding as a colloidal solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8219686A JPS62240327A (en) | 1986-04-11 | 1986-04-11 | Production of powdered rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8219686A JPS62240327A (en) | 1986-04-11 | 1986-04-11 | Production of powdered rubber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62240327A true JPS62240327A (en) | 1987-10-21 |
Family
ID=13767670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8219686A Pending JPS62240327A (en) | 1986-04-11 | 1986-04-11 | Production of powdered rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62240327A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006233106A (en) * | 2005-02-28 | 2006-09-07 | Kaneka Corp | Method for producing resin particulate |
| WO2007125597A1 (en) * | 2006-04-28 | 2007-11-08 | Kaneka Corporation | Process for producing resin particulate |
| US20130192746A1 (en) * | 2008-07-24 | 2013-08-01 | Peter J. Wallen | Processes for Making Silane, Hydrophobated Silica, Silica Masterbatch and Rubber Products |
-
1986
- 1986-04-11 JP JP8219686A patent/JPS62240327A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006233106A (en) * | 2005-02-28 | 2006-09-07 | Kaneka Corp | Method for producing resin particulate |
| JP4656965B2 (en) * | 2005-02-28 | 2011-03-23 | 株式会社カネカ | Method for producing resin powder |
| WO2007125597A1 (en) * | 2006-04-28 | 2007-11-08 | Kaneka Corporation | Process for producing resin particulate |
| US20130192746A1 (en) * | 2008-07-24 | 2013-08-01 | Peter J. Wallen | Processes for Making Silane, Hydrophobated Silica, Silica Masterbatch and Rubber Products |
| US8865799B2 (en) * | 2008-07-24 | 2014-10-21 | Industrias Negromex, S.A. De C.V. | Processes for making silane, hydrophobated silica, silica masterbatch and rubber products |
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