JPS62213839A - Preparation of composite particle coated uniformly - Google Patents
Preparation of composite particle coated uniformlyInfo
- Publication number
- JPS62213839A JPS62213839A JP5780686A JP5780686A JPS62213839A JP S62213839 A JPS62213839 A JP S62213839A JP 5780686 A JP5780686 A JP 5780686A JP 5780686 A JP5780686 A JP 5780686A JP S62213839 A JPS62213839 A JP S62213839A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- particle
- core
- polymer
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011246 composite particle Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 124
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 239000007771 core particle Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims description 68
- 238000004519 manufacturing process Methods 0.000 claims description 35
- 239000010954 inorganic particle Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920002689 polyvinyl acetate Polymers 0.000 abstract description 2
- 239000011118 polyvinyl acetate Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 239000004634 thermosetting polymer Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000004816 latex Substances 0.000 description 47
- 229920000126 latex Polymers 0.000 description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000377 silicon dioxide Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000084 colloidal system Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000003995 emulsifying agent Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- -1 Alternatively Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000001246 colloidal dispersion Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 description 3
- 235000011151 potassium sulphates Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 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
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、無機質粒子又は高分子粒子からなるコア粒子
の表面を、無機質粒子又は高分子粒子からなる満足する
割合で、分散液状態で混合してコア複合体粒子の製造方
法および該複合体粒子をコア粒子として、更に満足する
割合で、分散液状態で均一に被覆することを１回以上繰
り返した複合体粒子の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention involves mixing the surfaces of core particles made of inorganic particles or polymer particles in a dispersion state with a satisfactory ratio of inorganic particles or polymer particles to form core composite particles. The present invention relates to a manufacturing method and a method for manufacturing composite particles in which the composite particles are used as core particles and uniformly coated in a dispersion state at a satisfactory ratio one or more times.
［従来技術とその欠点］
従来、無機物と樹脂を配合して加工性の改善、物理的特
性の改良、耐熱性の付与、難燃性の付与、耐薬品性及び
電気的性質の向上などが試みられてきた。しかしながら
、樹脂と無機質微粒子を単に混合するだけでは無機質微
粒子の樹脂への分散が困難なため、不均一な複合体しか
えられず、従って各種特性にムラが生じるという欠点が
ある。又、改良法として、
（イ）無機物を粉砕しながら新生表面の活性によって、
モノマーをグラフトさせるか、又はポリマーを切断しな
がらグラフトさせるメカノケミカル的改質や、
（口）高エネルギー電子線を用いて、無機質粒子表面に
ビニルポリマーを結合させる改質や、四無機物に重合開
始剤、モノマー、ポリマーなどを吸着させた後、懸濁重
合や乳化重合して改質する方法などがあるが、これらの
改質法は均一に被覆できない詐りでなく、工程が複雑に
なったりするという欠点がある。ことに、（／〜は無機
物に対する樹脂の複合化が不十分であったり、また、ポ
リマーのみの生成が多かったりして収率が低いという欠
点があった。[Prior art and its drawbacks] Previous attempts have been made to improve processability, improve physical properties, impart heat resistance, flame retardancy, improve chemical resistance and electrical properties by blending inorganic substances and resins. I've been exposed to it. However, simply mixing a resin and inorganic fine particles has the drawback that it is difficult to disperse the inorganic fine particles in the resin, so that only a non-uniform composite can be obtained, resulting in unevenness in various properties. In addition, as an improved method, (a) While pulverizing inorganic substances, by the activity of the newly generated surface,
Mechanochemical modification in which monomers are grafted or polymers are grafted while being cut, modification in which vinyl polymers are bonded to the surface of inorganic particles using high-energy electron beams, and polymerization initiated in four inorganic substances. There are methods of adsorbing agents, monomers, polymers, etc., and then modifying them through suspension polymerization or emulsion polymerization, but these modification methods do not result in uniform coating, and the process is complicated. There is a drawback that it does. In particular, (/~) had the drawback that the compounding of the resin with the inorganic substance was insufficient, and the yield was low because only a large amount of polymer was produced.
［課題解決の手段］
本発明者らは、かかる改質方法の必要性とその聞届点に
鑑み、無機質粒子の表面を高分子粒子で均一に被覆する
ばかりでなく、高分子粒子の表面を無機質粒子で混合し
てコアり、あるいは無機質粒子を無機質粒子で、又は高
分子粒子を高分子粒子で混合してコア複合体粒子をうる
べく鋭意研究を重ねた結果、反対に荷電した粒子を特定
の条件で混合することによりきわめて強固にかつ均一に
被覆された複合体粒子がえられることを見出し本発明を
完成した。[Means for Solving the Problem] In view of the need for such a modification method and the need for such a modification method, the present inventors not only uniformly coat the surface of inorganic particles with polymer particles, but also cover the surface of polymer particles with polymer particles. As a result of intensive research into creating core composite particles by mixing inorganic particles with inorganic particles, or by mixing inorganic particles with inorganic particles, or polymer particles with polymer particles, we identified oppositely charged particles. The present invention was completed based on the discovery that by mixing under these conditions, composite particles coated extremely firmly and uniformly can be obtained.
すなわち本発明は、（Ａ）荷電した無機質粒子又は高分
子粒子からなるコア粒子と、（Ｂ）コア粒子より小さく
、かつ反対に荷電した無機質粒子又は高分子粒子からな
る満足する割合で、分散液状態を、満足する割合で、分
散液状態の数をコア粒子の数で割った粒子数比（Ｒ）が
４π （ａ＋ｂ） ２
（Ｒ） ＞ ｘＯ．５２σｂ２
［ａ−コア粒子の平均半径、ｂ−満足する割合で、分散
液状態の平均半径］を満足する割合で、分散液状態で混
合することを特徴とするコア粒子を満足する割合で、分
散液状態で混合してコア複合体粒子の製造方法、および
これを複数回繰り返して多層に被覆した複合体粒子を製
造する方法である。That is, the present invention provides a dispersion solution comprising (A) core particles consisting of charged inorganic particles or polymeric particles and (B) inorganic particles or polymeric particles smaller than the core particles and oppositely charged in a satisfactory ratio. The particle number ratio (R) obtained by dividing the number of dispersion liquid states by the number of core particles satisfies the condition that 4π (a+b) 2 (R) > xO. 52σb2 [a-average radius of core particles, b-average radius in dispersion state at a satisfying rate] Core particles characterized by being mixed in a dispersion state at a rate satisfying There are two methods: a method for producing core composite particles by mixing in a liquid state, and a method for producing composite particles coated with multiple layers by repeating this process multiple times.
［構成の説明］
本発明において、無機質粒子又は高分子粒子が、他の無
機質粒子又は高分子粒子で均一に被覆された複合体粒子
をつくる要件としては、（１）被覆する粒子（以下、満
足する割合で、分散液状態という）は被覆される粒子（
以下、コア粒子という）より小さいことが必要である。[Description of structure] In the present invention, the requirements for creating composite particles in which inorganic particles or polymer particles are uniformly coated with other inorganic particles or polymer particles include (1) coating particles (hereinafter referred to as satisfactory); (referred to as the dispersion state) is coated with particles (
(hereinafter referred to as core particles).
しかして、粒径分布は狭い方がより均一に被覆される。Therefore, the narrower the particle size distribution, the more uniform the coating will be.
（′２Ｊ満足する割合で、分散液状態とコア粒子は分散
液状態で混合しなければならない。('2J The dispersion state and the core particles must be mixed in the dispersion state in a satisfactory ratio.
（３）満足する割合で、分散液状態とコア粒子は互いに
反対に荷電していなければならない。そのためには、分
散液のｐＨが重要なポイントとなることがある。(3) In a satisfactory proportion, the dispersion state and the core particles must be oppositely charged. For this purpose, the pH of the dispersion liquid may be an important point.
（４）満足する割合で、分散液状態およびコア粒子は、
無機質粒子、高分子粒子のいずれでもよい。しかし、実
用上は無機質粒子を高分子粒子で被覆した複合体粒子、
又は高分子粒子を無機質粒子で被覆した複合体粒子が好
ましい。(4) In a satisfactory proportion, the dispersion state and the core particles are
Either inorganic particles or polymer particles may be used. However, in practice, composite particles consisting of inorganic particles coated with polymer particles,
Alternatively, composite particles in which polymer particles are coated with inorganic particles are preferable.
（５）均一に被覆するための最も大切な要件は、満足す
る割合で、分散液状態とコア粒子の粒子数の比、すなわ
ち満足する割合で、分散液状態の数をコア粒子の数で割
った粒子数比（Ｒ）が次式を満足することである。(5) The most important requirement for uniform coverage is the ratio of the number of particles in the dispersion state to the number of core particles, that is, the number in the dispersion state divided by the number of core particles in a satisfactory ratio. The particle number ratio (R) satisfied the following formula.
（Ｒ） ＞ＮＸ Ｏ，５
Ｎ：コア粒子１ケの表面を最密に被覆するに要する満足
する割合で、分散液状態の数Ｐ：コア粒子１ケの表面に
、満足する割合で、分散液状態が被覆したときの表面積
−半径（ａ＋ｂ）の球面−（Ｒ）２・・・・・・（第１
図）Ｑニジエル形成用粒子がコア粒子の表面を最密に被
覆したときの満足する割合で、分散液状態１ヶ当りの占
める方形の面９−２ｂｘｉｂ−２ＩＢｂ２・・・・・
・（第２図）本発明に於て、均一に被覆するということ
は最密に被覆する必要はなく、偏りなく、平均的に被覆
していることが大切である。そのためには（Ｒ）はＮの
５０％以上、好ましくは７０％以上でなければならない
。これを模型図として示すと第３図のようになる。(R) > N Surface area when covered by liquid state - spherical surface with radius (a + b) - (R)2... (first
Figure) Q Niziel-forming particles cover the surface of the core particles in a satisfactory ratio, and the rectangular surface occupied by one dispersion state 9-2bxib-2IBb2... (Second Figure) In the present invention, uniform coating does not necessarily mean dense coating, but it is important to cover evenly and evenly. For this purpose, (R) must be at least 50% of N, preferably at least 70%. This is shown as a model diagram as shown in Fig. 3.
（Ｒ）がＮの５０％未満では、露出部分が多くなり、そ
のため大きい凝集体を形成することになる。これを模型
図として示すと第４図のようになる。すなわち、露出し
ているコア粒子の負のイオン性により疎らに被覆した正
の粒子を介して他のコア粒子が密着し、凝集して大きい
凝集体となる。（Ｒ）の上限はとくに制限はないが、余
分の満足する割合で、分散液状態はいたずらに浮遊して
いるだけであるから、実用的には１５０％程度が適当で
ある。If (R) is less than 50% of N, there will be a large amount of exposed parts, resulting in the formation of large aggregates. This is shown as a model diagram as shown in Fig. 4. That is, due to the negative ionicity of the exposed core particles, other core particles adhere to each other through the loosely coated positive particles, and aggregate to form a large aggregate. There is no particular upper limit to the upper limit of (R), but since the dispersion state is only suspended at a satisfactory level, approximately 150% is practically appropriate.
本発明で用いる無機質粒子としては、金、銀、銅、鉄、
アルミニウムなどの金属粉、シリカ、アルミナ、酸化鉄
、酸化チタン、酸化亜鉛などの金属酸化物、炭酸カルシ
ウム、蓚酸カルシウム、硫酸バリウムなどの塩などが適
当である。Inorganic particles used in the present invention include gold, silver, copper, iron,
Suitable examples include metal powders such as aluminum, silica, alumina, metal oxides such as iron oxide, titanium oxide, and zinc oxide, and salts such as calcium carbonate, calcium oxalate, and barium sulfate.
しかして、これらの無機質粒子は、平均粒径０．００５
〜１００」のものが適当である。However, these inorganic particles have an average particle size of 0.005
~100'' is suitable.
本発明で用いる高分子粒子としては、ポリ酢酸ビニル、
ポリアクリル酸エステル、ポリエチレン、ポリプロピレ
ン、ポリスチレン、酢酸ビニル−エチレンコポリマー、
酢酸ビニル−（メタ）アクリル酸エステルコポリマー、
スチレン−（メタ）アクリル酸エステルコポリマー、酢
酸ビニルーベオバ（シェル化学■製のビニルエステル）
コポリマーなどの熱可塑性高分子粒子やポリエステル、
エポキシ樹脂、尿素樹脂、メラミン樹脂、シリコン樹脂
、フッ素樹脂などの熱硬化性高分子粒子などがある。こ
れらの高分子粒子は、平均粒径０．０１〜５０屡のもの
が適当である。The polymer particles used in the present invention include polyvinyl acetate,
Polyacrylic acid ester, polyethylene, polypropylene, polystyrene, vinyl acetate-ethylene copolymer,
Vinyl acetate-(meth)acrylic acid ester copolymer,
Styrene-(meth)acrylic acid ester copolymer, vinyl acetate Rubeova (vinyl ester manufactured by Shell Chemical ■)
Thermoplastic polymer particles such as copolymers and polyester,
Examples include thermosetting polymer particles such as epoxy resin, urea resin, melamine resin, silicone resin, and fluororesin. These polymer particles suitably have an average particle size of 0.01 to 50 mm.
これらの粒子の分散液としては水性分散液が最もよいが
、イオンに解離できる程度の水分が含有されていれば非
水性分散液でもよい。使用できる非水溶剤としてはシク
ロヘキサン、ヘプタン、ヘキサンなどの無極性有機溶剤
が好ましい。Although an aqueous dispersion is best as a dispersion of these particles, a non-aqueous dispersion may also be used as long as it contains enough water to dissociate into ions. As the non-aqueous solvent that can be used, non-polar organic solvents such as cyclohexane, heptane, and hexane are preferred.
無機質粒子の分散液を作るには、前述の無機質物質を粉
砕し、三本ロール、ペブルミル、超音波分散などの公知
の方法で水又は含水した非水溶剤に分散させるか、又は
コロイドゾル合成法により合成すればよい。To make a dispersion of inorganic particles, the above-mentioned inorganic substance is pulverized and dispersed in water or a water-containing non-aqueous solvent by a known method such as a three-roll mill, a pebble mill, or an ultrasonic dispersion, or by a colloidal sol synthesis method. All you have to do is synthesize.
このようにして、粒子径０．００５〜１００ρの範囲の
無機質粒子の分散液かえられる。In this way, a dispersion of inorganic particles having a particle size in the range of 0.005 to 100 ρ is changed.
えられた分散液は無機物質の種類によって正又は負に荷
電しているが、中にはｐＩ■を変えることによってζ電
位が変り、負又は正に変るものがある。このような荷電
は、水素イオン、水酸イオン、電位決定イオン、又は高
原子価を有する対イオンによってもたらされる。その強
さはζ電位として測定することができる。このことは後
述する高分子粒子についても同様である。The obtained dispersion is positively or negatively charged depending on the type of inorganic substance, and in some cases, the ζ potential changes by changing the pI■, which changes to negative or positive. Such charges are provided by hydrogen ions, hydroxide ions, potential-determining ions, or counterions with high valences. Its strength can be measured as ζ potential. This also applies to the polymer particles described below.
高分子粒子の分散液は、乳化重合法や懸濁重合法によっ
て作ることができる。又、ポリマーを後乳化することに
よっても作ることができる。A dispersion of polymer particles can be produced by an emulsion polymerization method or a suspension polymerization method. It can also be made by post-emulsifying the polymer.
このようにして平均粒子径０．０１〜５０ρの範囲の高
分子粒子の分散液かえられる。In this way, a dispersion of polymer particles having an average particle diameter in the range of 0.01 to 50 ρ is changed.
えられる分散液は、組成や製法によって正又は負に荷電
させることができる。荷電させる方法としては、カチオ
ン性又はアニオン性単量体、および正又は負のポリマー
末端を与える重合開始剤、およびカチオン性又はアニオ
ン性の重合性乳化剤のいずれかを選択的に単独又は併用
して、必要により非イオン性単量体や他の乳化剤ととも
にラジカル重合する方法が用いられる。The resulting dispersion can be positively or negatively charged depending on the composition and manufacturing method. As a charging method, a cationic or anionic monomer, a polymerization initiator giving a positive or negative polymer terminal, and a cationic or anionic polymerizable emulsifier are selectively used alone or in combination. If necessary, a method of radical polymerization with nonionic monomers and other emulsifiers is used.
カチオン性単量体としては、たとえばジエチルアミノエ
チルメタクリレート、ジメチルアミノエチルメタクリレ
ートなどがあげられ、アニオン性単量体としては、たと
えばアクリル酸、メタクリル酸などがあげられる。これ
らのイオン性単量体はそれぞれ単独で重合してもよく、
又他の非イオン性単量体と組合せて用いてもよい。Examples of cationic monomers include diethylaminoethyl methacrylate and dimethylaminoethyl methacrylate, and examples of anionic monomers include acrylic acid and methacrylic acid. These ionic monomers may be polymerized individually,
It may also be used in combination with other nonionic monomers.
イオン性単量体だけで荷電させるためには、非イオン性
単量体１００ｆｆｉ量部に対して、イオン性単量体０．
０１ ｉｉ量郡部以上ことに０．２ｆｆｉ量部以上の使
用が好ましい。０．０１重量部未満ではえられた粒子の
帯電量が不足し、本発明の目的に使用できない。In order to charge with only the ionic monomer, 0.00 parts of the ionic monomer should be added to 100 parts of the non-ionic monomer.
It is preferable to use more than 0.01 parts, especially more than 0.2 parts. If the amount is less than 0.01 part by weight, the resulting particles will have insufficient charge and cannot be used for the purpose of the present invention.
正のポリマー末端を与える重合開始剤としては、たとえ
ば２，２°−アゾビス（２−アミジノプロパン）塩酸塩
などがあげられる。負のポリマー末端を与える重合開始
剤としては、たとえば過硫酸ナトリウム、過硫酸カリウ
ム、過硫酸アンモニウムなどがあげられる。これらの重
合開始剤は、ラジカル重合性単量体１００重量部に対し
て０．０１〜２０重量部、ことに０．２〜１０重量部の
使用が好ましい。Examples of the polymerization initiator that provides a positive polymer terminal include 2,2°-azobis(2-amidinopropane) hydrochloride. Examples of the polymerization initiator that provides negative polymer terminals include sodium persulfate, potassium persulfate, and ammonium persulfate. These polymerization initiators are preferably used in an amount of 0.01 to 20 parts by weight, particularly 0.2 to 10 parts by weight, based on 100 parts by weight of the radically polymerizable monomer.
また、正又は負のポリマー末端を与えない重合開始剤、
たとえば過酸化ベンゾイル、過酸化ラウリルなどを併用
してもよい。Also, a polymerization initiator that does not give a positive or negative polymer end,
For example, benzoyl peroxide, lauryl peroxide, etc. may be used in combination.
カチオン性の重合性乳化剤としては、アルキルジメチル
アンモニウムクロライドとアリルエーテル化合物との合
成化合物があり、アニオン性の重合性乳化剤としては、
アルキルアリルスルホサクシネートのアルカリ塩や、ビ
ニルスルホン酸のアルカリ塩などがある。勿論他の乳化
剤と併用してもよい。Examples of cationic polymerizable emulsifiers include synthetic compounds of alkyldimethylammonium chloride and allyl ether compounds, and examples of anionic polymerizable emulsifiers include:
Examples include alkali salts of alkylaryl sulfosuccinate and alkali salts of vinyl sulfonic acid. Of course, it may be used in combination with other emulsifiers.
しかし乍ら、重合性乳化剤を使用するか又は全く乳化剤
を使用せずに重合した、所謂ソープフリー重合法でえら
れた乳化重合体は、とくに均一に被覆された複合体粒子
を作るために好適である。However, emulsion polymers obtained by the so-called soap-free polymerization method, which are polymerized with polymerizable emulsifiers or without any emulsifier, are particularly suitable for producing uniformly coated composite particles. It is.
本発明の複合体粒子を作るには、無機質粒子を高分子粒
子で混合してコア複合体粒子を作る場合を例にとって説
明すると、たとえば水に分散させた、平均粒子径１．５
．ｃｍのシリカ粒子のごとき無機質粒子をコア粒子とし
て選び、その表面を正又は負に帯電させるために酸又は
塩基を加え撹拌混合して９Ｈを調整し、目的の電荷、た
とえば負に帯電させる。つぎに、同−ｐＨで正に荷電し
ている、たとえば水に分散させた平均粒子径０．３虜の
ポリスチレン粒子を満足する割合で、分散液状態として
選び、この場合Ｎは１３０なので、この粒子数をシリカ
粒子に対して１３０Ｘ Ｏ，５−６５以上になるように
両方の分散液を調整して混合し、緩やかに１０分〜２時
間撹拌すればコア粒子に満足する割合で、分散液状態が
きわめて均一に、かつ強固に付着し、無機質粒子を高分
子粒子で混合してコア複合体粒子の分散液かえられる。To make the composite particles of the present invention, an example is explained in which core composite particles are made by mixing inorganic particles with polymer particles.
．． An inorganic particle such as a silica particle with a diameter of 1 cm is selected as a core particle, and in order to charge the surface positively or negatively, an acid or base is added and mixed with stirring to adjust 9H, and the target charge is charged, for example, negatively. Next, select positively charged polystyrene particles at the same pH and, for example, dispersed in water and with an average particle diameter of 0.3 mm, as a dispersion liquid in a satisfying ratio. In this case, N is 130, so Adjust both dispersions so that the number of particles is 130X O, 5-65 or more relative to the silica particles, mix them, and stir gently for 10 minutes to 2 hours. The state is extremely uniform and strongly adhered, and the dispersion of core composite particles can be changed by mixing inorganic particles with polymer particles.
両分散液を混合する場合、硫酸カリウム、塩化マグネシ
ウム、塩化アルミニウムなどの無機電解質を添加すると
、より均一に、かつ緻密に被覆することができる。これ
は無機電解質が満足する割合で、分散液状態のシャドー
効果を減少させるため被覆率の増加をもたらすものと考
えられる。When both dispersions are mixed, adding an inorganic electrolyte such as potassium sulfate, magnesium chloride, or aluminum chloride allows for more uniform and dense coating. It is believed that this is a ratio that is satisfactory for the inorganic electrolyte, and that it reduces the shadow effect in the dispersion state, resulting in an increase in coverage.
また、ソープフリー製法による高分子粒子分散液を使用
すると、より均一に、かつ強く被覆することができる。In addition, when a polymer particle dispersion prepared by a soap-free manufacturing method is used, it is possible to coat more uniformly and strongly.
これは高分子分散液中にポリビニルアルコール、メチル
セルロースなどの高分子物質や、その他いわゆる乳化剤
が含まれていないので、これらによる被覆の阻害がない
ためと考えられる。This is thought to be because the polymer dispersion does not contain polymer substances such as polyvinyl alcohol, methyl cellulose, or other so-called emulsifiers, so that coating is not inhibited by these substances.
又、本発明によればさらに多層に複合した粒子を作るこ
とができる。その製造方法としては、前述によってえら
れた粒子表面が正又は負に荷電し、かつ均一に被覆され
た複合体粒子の分散液に、この複合体粒子より小さく、
かつ反対に荷電した無機質粒子又は高分子粒子の分散液
を添加し、ゆるやかに撹拌混合すればよい。Further, according to the present invention, it is possible to produce particles having even more layers. The manufacturing method includes adding particles smaller than the composite particles to a dispersion of the composite particles whose surfaces are positively or negatively charged and uniformly coated, obtained as described above.
A dispersion of oppositely charged inorganic particles or polymer particles may be added and mixed by gentle stirring.
この操作を繰り返すことにより、より多層に被覆した複
合体粒子かえられる。By repeating this operation, composite particles coated with more layers can be obtained.
［効 果］
本発明によって均一に被覆された複合体粒子がえられる
生成機構に・ついては、コア粒子の表面電荷と満足する
割合で、分散液状態の反対電荷との静電的相互作用によ
るものと思われるが、普通反対電荷に荷電した分散液同
士を混合すると、凝集沈殿を起こすものであるが、本発
明によるときわめて均一に被覆された複合体粒子が凝集
することなく安定に個々に分散した分散液かえられ、粒
子の比重などによって沈降することがあっても、軽く振
盪するだけで容易に再分散させることができる。又、被
覆はきわめて強固であり数度の水洗によっても満足する
割合で、分散液状態が殆んど脱離することがないという
すぐれた効果を示す。[Effect] The production mechanism for obtaining uniformly coated composite particles according to the present invention is due to electrostatic interaction between the surface charge of the core particle and the opposite charge in the dispersion state in a satisfactory ratio. However, when dispersions charged with opposite charges are mixed together, they usually coagulate and precipitate, but according to the present invention, the extremely uniformly coated composite particles are stably dispersed individually without agglomeration. Even if the dispersion solution is changed and sedimentation occurs due to the specific gravity of the particles, it can be easily redispersed by simply shaking it lightly. Furthermore, the coating is extremely strong and exhibits an excellent effect in that the dispersion state hardly comes off at a satisfactory rate even after several washings with water.
これは加え合わすコア粒子と満足する割合で、分散液状
態の粒子数比（Ｒ）を限定したことによるものである。This is because the particle number ratio (R) in the dispersion liquid state is limited to a ratio that satisfies the core particles to be added.
複合体粒子の完成後は、コア粒子と付着した粒子の電荷
を異符号に保ちさえすれば殆んど脱離することがなく、
付着粒子の電荷で安定化された複合体粒子の安定な分散
系となる。 ′つぎに製造例、実施例、比較例を
あげて本発明を説明する。After the composite particle is completed, as long as the charges of the core particle and the attached particle are kept with opposite signs, there will be almost no detachment.
This results in a stable dispersion of composite particles stabilized by the charge of the attached particles. 'Next, the present invention will be explained with reference to production examples, examples, and comparative examples.
製造例１
撹拌器、還流冷却器、滴下漏斗、温度計を備えた容量２
ｇの四ツロフラスコ中に水３８．１ｇ 。Preparation Example 1 Capacity 2 with stirrer, reflux condenser, addition funnel and thermometer
38.1 g of water in a four-piece flask.
２８％アンモニア水２８０．４ｇ 、エタノール７９３
ｇを加えて撹拌したのち、５８．Ｉｇのオルトケイ酸エ
チルを加え３０分間撹拌した。ついで４ｅｅ、ｅｇのオ
ルトケイ酸エチルを添加撹拌後、透析して固形分１９．
２％、平均粒子径１．５９ Ｉａのシリカコロイド水性
分散液をえた。28% ammonia water 280.4g, ethanol 793
After adding and stirring 58. Ethyl orthosilicate of Ig was added and stirred for 30 minutes. Next, 4ee and eg of ethyl orthosilicate was added and stirred, followed by dialysis to reduce the solid content to 19.
A silica colloid aqueous dispersion having a concentration of 2% and an average particle size of 1.59 Ia was obtained.
製造例２
製造例１で用いたものと同様の四ツロフラスコ中に水１
７５０ｇ 、ジエチルアミノエチルメタクリレート１７
．５ｇを入れ、この混合液のｐＨが１．２になるように
塩酸を加える。ついでスチレン１５８．８ｇ 、過硫酸
カリウム３．５ｇを入れ、窒素置換後、７０℃まで昇温
し、６時間重合反応を行なった。冷却後、凝集塊を除去
し、透析して固形分９．８％、平均粒子径０．２５ ａ
ｍのラテックスをえた。Production Example 2 In a Yotsuro flask similar to that used in Production Example 1, add 1 part of water.
750g, diethylaminoethyl methacrylate 17
．． Add 5 g of hydrochloric acid so that the pH of this mixture becomes 1.2. Next, 158.8 g of styrene and 3.5 g of potassium persulfate were added, and after purging with nitrogen, the temperature was raised to 70°C and a polymerization reaction was carried out for 6 hours. After cooling, the agglomerates were removed and dialyzed to give a solid content of 9.8% and an average particle size of 0.25 a.
I got m latex.
製造例３
製造例１で用いたものと同様の四ツロフラスコ中に水１
５１２ｇ 、アクリルアミド１４ｇ１ジメチルホルムア
ミド１６８ｇ、塩化ナトリウム４ｇ１過硫酸カリウム６
ｇを入れ、窒素置換後７０℃まで昇温し、１時間重合反
応を行なった。ついでスチレン２８０ｇを添加し、７０
℃で４時間重合反応を行ない、つぎにジエチルアミノエ
チルメタクリレートを１４ｇ加え、さらに１時間重合反
応を行なった。冷却後、凝集塊を除去し、透析し平均粒
子径が１．８．ｃａｎのラテックスをえた。Production Example 3 In a Yotsuro flask similar to that used in Production Example 1, add 1 part of water.
512g, acrylamide 14g1 dimethylformamide 168g, sodium chloride 4g1 potassium persulfate 6g
After purging with nitrogen, the temperature was raised to 70°C, and a polymerization reaction was carried out for 1 hour. Next, 280g of styrene was added, and the
The polymerization reaction was carried out at ℃ for 4 hours, then 14 g of diethylaminoethyl methacrylate was added, and the polymerization reaction was further carried out for 1 hour. After cooling, the aggregates were removed and dialyzed until the average particle size was 1.8. I got the can latex.
製造例４
製造例１で用いたものと同様の四ツ目フラスコ中に水１
４４０ｇ 、スチレン１３０ｇ、過硫酸カリウム０．１
２ｇを入れ、７０℃まで昇温し、８時間重合反応を行な
った。冷却後、凝集塊を除去し、透析して平均粒子径が
０．４４ 屡のラテックスをえた。Production Example 4 In a four-eye flask similar to that used in Production Example 1, add 1 part of water.
440g, styrene 130g, potassium persulfate 0.1
2 g was added, the temperature was raised to 70°C, and a polymerization reaction was carried out for 8 hours. After cooling, the agglomerates were removed and dialyzed to obtain a latex with an average particle size of 0.44 degrees.
製造例５
製造例１で用いたものと同様の四ツ目フラスコ中に水１
３００ｇ 、ジエチルアミノエチルメタクリレート９３
ｇ、スチレン５２ｇ１ラテムルに−１８０（花王石鹸■
製のカチオン性重合性乳化剤）１８．５ｇを入れ、８０
℃まで昇温し、Ｖ−５０（和光純薬工業■製、２，２°
−アゾビス（２−アミジノプロパン）塩酸塩の商品名）
の５％水溶液３０ｇを入れ、５時間重合反応を行なった
。冷却後、凝集塊を除去し、平均粒子径ｏ、ｏｅ 刷の
ラテックスをえた。Production Example 5 In a four-eye flask similar to that used in Production Example 1, add 1 part of water.
300g, diethylaminoethyl methacrylate 93
g, styrene 52g 1 latemul -180 (Kao soap■
Add 18.5 g of cationic polymerizable emulsifier manufactured by
The temperature was raised to ℃, and V-50 (manufactured by Wako Pure Chemical Industries, Ltd., 2.2°
- Trade name of azobis(2-amidinopropane) hydrochloride)
30 g of a 5% aqueous solution of was added thereto, and a polymerization reaction was carried out for 5 hours. After cooling, the agglomerates were removed to obtain a latex with an average particle diameter of o and oe.
製造例６
製造例１で用いたものと同様の四ツ目フラスコ中に水１
４００ｇ 、スチレン７０ｇ１メチルメタクリレート７
０ｇ１ コータミソ８８Ｐコンク （花王石鹸■製のカ
チオン乳化剤）１２ｇを入れ、７０℃まで昇温し、ｖ−
５０の５％水溶液２８ｇを加えて、６時間重合反応を行
なった。冷却後、凝集塊を除去し、粒子径０．１−のラ
テックスをえた。Production Example 6 In a four-eye flask similar to that used in Production Example 1, add 1 part of water.
400g, 70g of styrene, 70g of methyl methacrylate
0g1 12g of Kotamiso 88P Conc (cationic emulsifier manufactured by Kao Soap ■) was added, the temperature was raised to 70°C, and v-
28 g of a 5% aqueous solution of 50 was added, and a polymerization reaction was carried out for 6 hours. After cooling, the agglomerates were removed to obtain a latex with a particle size of 0.1-.
製造例１〜６の粒子について、ｐｌ＋と電荷の関係は第
１表の通りであった。Regarding the particles of Production Examples 1 to 6, the relationship between pl+ and charge was as shown in Table 1.
［以下余白］
実施例１
製造例１でえたシリカコロイド分散液を水で５％に稀釈
し、その２．０ｇをとり、塩酸でｐＨを６に調整し、緩
やかに撹拌した。この稀釈コロイド分散液は負に帯電し
ていた。別に製造例２でえたラテックスを水で２％に稀
釈し、塩酸でｐｌ＋を６に調製した。この稀釈ラテック
スは正に帯電していた。[Margin below] Example 1 The silica colloid dispersion obtained in Production Example 1 was diluted to 5% with water, 2.0 g of it was taken, the pH was adjusted to 6 with hydrochloric acid, and the mixture was gently stirred. This diluted colloidal dispersion was negatively charged. Separately, the latex obtained in Production Example 2 was diluted with water to 2%, and the pl+ was adjusted to 6 with hydrochloric acid. This diluted latex was positively charged.
この稀釈ラテックスの１．７４ｇを、前記の稀釈コロイ
ド分散液に徐々に加え、緩やかに撹拌して、無機質粒子
が高分子粒子で均一に被覆された複合体粒子の分散液を
えた。この分散液は正に帯電していた。このときの、粒
子数比（Ｒ）はＮの約１００％に当る。1.74 g of this diluted latex was gradually added to the diluted colloidal dispersion and gently stirred to obtain a dispersion of composite particles in which inorganic particles were uniformly coated with polymeric particles. This dispersion was positively charged. At this time, the particle number ratio (R) corresponds to approximately 100% of N.
顕微鏡で観察すると、シリカコロイドの粒子表面が充分
均一にラテックス粒子で覆われており、静置により沈降
しても軽く振盪するだけで容易に再分散した。When observed under a microscope, the surface of the silica colloid particles was sufficiently uniformly covered with latex particles, and even if they settled when left to stand still, they were easily redispersed by only slight shaking.
実施例２
製造例３でえたラテックスを水で１０％に稀釈し、塩酸
でｐｉを５に調整した。この稀釈のラテックスは正に帯
電していた。Example 2 The latex obtained in Production Example 3 was diluted to 10% with water, and the pi was adjusted to 5 with hydrochloric acid. The latex at this dilution was positively charged.
別に平均粒子径０．０１Ｊｃａ＋＋のスノーテックスＯ
（日産化学工業■製のシリカゾル）の１０％分散液をｐ
Ｈ５に調整した。このスノーテックス分散液は負に帯電
していた。この分散液０．４２ｇを、前記の稀釈ラテッ
クスＬＯｇに添加し、緩やかに撹拌して、高分子粒子が
無機質粒子で均一に被覆された複合体粒子の分散液をえ
た。こ°のときの、粒子数比（Ｒ）はＮの約８０％に当
る。走査型電子顕微鏡で観察すると、ラテックス粒子表
面がシリカ粒子で充分均一に覆われており、静置により
沈降しても軽く振盪するだけで容易に再分散した。Separately, Snowtex O with an average particle diameter of 0.01 Jca++
(Silica sol manufactured by Nissan Chemical Industries ■) 10% dispersion of p
Adjusted to H5. This Snowtex dispersion liquid was negatively charged. 0.42 g of this dispersion was added to the diluted latex LOg and gently stirred to obtain a dispersion of composite particles in which polymer particles were uniformly coated with inorganic particles. At this time, the particle number ratio (R) corresponds to about 80% of N. Observation with a scanning electron microscope revealed that the surfaces of the latex particles were sufficiently uniformly covered with silica particles, and even if they settled when left to stand still, they were easily redispersed by gentle shaking.
実施例３
平均粒子径が０．０１５虜のスノーテックスＯの１０％
分散液をｐＨ４に調整した。このスノーテックス分散液
は負に帯電していた。このスノーテックス分散液０．１
９ｇを実施例１でえた正に帯電しているシリカコロイド
／ラテックス複合体粒子の分散液１０ｇに徐々に添加し
、緩やかに撹拌して、高分子粒子で均一に被覆された無
機質粒子をさらに無機質粒子で混合してコア多層複合体
粒子の分散液をえた。Example 3 10% of Snowtex O with an average particle size of 0.015
The dispersion was adjusted to pH4. This Snowtex dispersion liquid was negatively charged. This Snowtex dispersion 0.1
9 g of the positively charged silica colloid/latex composite particle dispersion obtained in Example 1 was gradually added to 10 g of the positively charged silica colloid/latex composite particle dispersion, and gently stirred to further coat the inorganic particles uniformly coated with the polymer particles. The particles were mixed to obtain a dispersion of core multilayer composite particles.
この分散液を電気泳動装置で電荷を測定すると添加した
シリカコロイドと同じ負の電荷を示し、多層複合体粒子
が生成していることを証明した。静置により沈降しても
軽く振盪するだけで容易に再分散した。When the charge of this dispersion was measured using an electrophoresis device, it showed the same negative charge as the added silica colloid, proving that multilayer composite particles were produced. Even if it settled when left to stand still, it was easily redispersed by shaking lightly.
実施例４
製造例３でえたラテックスを水で１０％に稀釈し、ｐＨ
を６．５に調整した。この稀釈ラテックスは正に帯電し
ていた。Example 4 The latex obtained in Production Example 3 was diluted to 10% with water, and the pH
was adjusted to 6.5. This diluted latex was positively charged.
別に酸化チタンＪＲ（帝国化工■製の平均粒子径０．３
１ｓのルチル型酸化チタン）をボールミルで水に分散さ
せて５％の水性分散液を作り、ｐｌ＋を６．５に調整し
た。この分散液は負に帯電していた。Separately, titanium oxide JR (manufactured by Teikoku Kako ■, average particle diameter 0.3
1s rutile type titanium oxide) was dispersed in water using a ball mill to prepare a 5% aqueous dispersion, and the pl+ was adjusted to 6.5. This dispersion was negatively charged.
この分散液４７ｇを前記の稀釈ラテックス１０ｇに添加
し、緩やかに撹拌して高分子粒子が無機質粒子で均一に
被覆された複合体粒子の分散液をえた。47 g of this dispersion was added to 10 g of the diluted latex and gently stirred to obtain a dispersion of composite particles in which polymer particles were uniformly coated with inorganic particles.
顕微鏡で観察すると、ラテックス粒子表面が酸化チタン
粒子で充分均一に被覆されており、静置により沈降して
も軽く振盪するだけで容易に再分散した。When observed under a microscope, the surfaces of the latex particles were sufficiently uniformly coated with titanium oxide particles, and even if they settled when left to stand still, they were easily redispersed by only slight shaking.
実施例５
実施例１において、稀釈ラテックスとともに０．１モル
／Ｒの硫酸カリウム水溶液１ｇを添加した以外は、実施
例１と同様に行なって、無機質粒子が高分子粒子で均一
に被覆された複合体粒子の分散液をえた。Example 5 A composite in which inorganic particles were uniformly coated with polymer particles was prepared in the same manner as in Example 1 except that 1 g of a 0.1 mol/R potassium sulfate aqueous solution was added together with the diluted latex. A dispersion of body particles was obtained.
静置により沈降しても軽く振盪するだけで容易に再分散
した。顕微鏡で観察すると、シリカコロイド粒子の表面
がきわめて密にラテックス粒子で覆われていた。この複
合体粒子を沈降させて採取し、示差熱分析法によりシリ
カとラテックス樹脂の比率を調べたところ、実施例１で
えたものよりも約ｌＯ％多くラテックス樹脂が検出され
た。これは硫酸カリウムの作用によるものと考えられる
。Even if it settled when left to stand still, it was easily redispersed by shaking lightly. When observed under a microscope, the surface of the silica colloid particles was extremely densely covered with latex particles. When the composite particles were collected by sedimentation and the ratio of silica to latex resin was examined by differential thermal analysis, about 10% more latex resin than that obtained in Example 1 was detected. This is thought to be due to the action of potassium sulfate.
実施例６
製造例４でえたラテックスを水で５％に稀釈し、塩酸で
ｐＨを５に調整した。このラテックスは負に帯電してい
た。Example 6 The latex obtained in Production Example 4 was diluted to 5% with water, and the pH was adjusted to 5 with hydrochloric acid. This latex was negatively charged.
別に製造例２でえたラテックスを水で５％に稀釈し、塩
酸でｐＨを５に調整した。このラテックスは正に帯電し
ていた。Separately, the latex obtained in Production Example 2 was diluted to 5% with water, and the pH was adjusted to 5 with hydrochloric acid. This latex was positively charged.
この正に帯電しているラテックス７６ｇと、前記の負に
帯電し゛ているラテックスｌＯｇを混合し、緩やかに撹
拌して、高分子粒子が高分子粒子で均一に被覆された複
合体粒子の分散液をえた。76 g of this positively charged latex and 10 g of the negatively charged latex described above are mixed and gently stirred to create a dispersion of composite particles in which polymer particles are uniformly coated with polymer particles. I got it.
えられた複合体粒子を電気泳動装置で測定すると正の電
位を有しており、顕微鏡では小さいラテックス粒子が大
きいラテックス粒子を充分均一に被覆しているのが観察
された。When the resulting composite particles were measured using an electrophoresis device, they had a positive potential, and using a microscope, it was observed that the small latex particles were sufficiently uniformly covering the large latex particles.
実施例７
製造例１でえたシリカコロイド分散液を、水で５％に稀
釈し、その１００ｇをとり塩酸でｐＨを７に調整した。Example 7 The silica colloid dispersion obtained in Production Example 1 was diluted to 5% with water, 100 g of it was taken, and the pH was adjusted to 7 with hydrochloric acid.
この稀釈コロイド分散液は負に帯電していた。This diluted colloidal dispersion was negatively charged.
別に製造例５でえたラテックスを水で２％に稀釈し、水
酸化ナトリウムでｐＨを７に調整した。Separately, the latex obtained in Production Example 5 was diluted to 2% with water, and the pH was adjusted to 7 with sodium hydroxide.
この稀釈ラテックスは正に帯電していた。この稀釈ラテ
ックス３２．８ｇを前記の稀釈コロイド分散液に徐々に
加え、緩やかに撹拌して、無機質粒子が高分子粒子で均
一に被覆された複合体粒子の分散液をえた。このときの
粒子数比（Ｒ）はＮの約２００％に当る。This diluted latex was positively charged. 32.8 g of this diluted latex was gradually added to the diluted colloidal dispersion and gently stirred to obtain a dispersion of composite particles in which inorganic particles were uniformly coated with polymer particles. The particle number ratio (R) at this time corresponds to about 200% of N.
え、られた複合体粒子を走査型電子顕微鏡で観察すると
、シリカ粒子表面がラテックス粒子で充分均一に被覆さ
れており、静置により沈降した複合体粒子は軽く振盪す
るだけで容易に再分散した。When the composite particles were observed using a scanning electron microscope, the surfaces of the silica particles were sufficiently uniformly coated with latex particles, and the composite particles that had settled due to standing were easily redispersed by shaking lightly. .
比較例１
実施例１において、系のｐＨを９に調整した以外は、実
施例１と同様に行なった。このとき、シリカコロイドは
負に帯電しており、ラテックスも負に帯電していた。Comparative Example 1 The same procedure as in Example 1 was conducted except that the pH of the system was adjusted to 9. At this time, the silica colloid was negatively charged, and the latex was also negatively charged.
混合液中には、シリカコロイド、ラテックスともにそれ
ぞれ個々に分散しており、シリカ粒子をラテックスで被
覆したものは見られなかった。Both the silica colloid and the latex were individually dispersed in the mixed liquid, and no silica particles coated with latex were observed.
比較例２
実施例１において、稀釈ラテックスの添加量１．７４ｇ
を０．３５ｇに変えた以外は、実施例１と同様に行なっ
た。この時の粒子数比（Ｒ）はＮの約２０％であった。Comparative Example 2 In Example 1, the amount of diluted latex added was 1.74 g.
The same procedure as in Example 1 was carried out except that the amount was changed to 0.35 g. The particle number ratio (R) at this time was about 20% of N.
顕微鏡で観察すると、シリカコロイドとラテックスとが
凝集して大きい凝集塊が多く生成しており、シリカ粒子
をラテックス粒子で混合してコアものは殆んど見られな
かった。When observed under a microscope, the silica colloid and latex aggregated to form many large aggregates, and the silica particles were mixed with latex particles, with almost no core particles observed.
比較例３
実施例７において、使用した稀釈ラテックス３２、ｌ１
ｇの代りに、製造例６でえたラテッスを水で２％に稀釈
し、水酸化ナトリウムでｐｌを７に調整した稀釈ラテッ
クス５７．８ｇに変えた以外は、実施例７と同様に行な
った。この時、シリカコロイドは負に、ラテックスは正
に帯電していた。Comparative Example 3 Diluted latex 32, l1 used in Example 7
The same procedure as in Example 7 was carried out, except that instead of 57.8 g of the latex obtained in Production Example 6, the latex obtained in Production Example 6 was diluted to 2% with water and the PL was adjusted to 7 with sodium hydroxide. At this time, the silica colloid was negatively charged and the latex was positively charged.
混合後の粒子を走査型電子顕微鏡で観察すると、シリカ
粒子表面をラテックス粒子が１０〜２Ｑａ程度覆ってい
るものも見られたが、殆んどのシリカ粒子には数個のラ
テックスが被覆しているにすぎなかった。When the mixed particles were observed with a scanning electron microscope, some latex particles were seen covering the surface of the silica particles by about 10 to 2 Qa, but most silica particles were covered with several pieces of latex. It was nothing more than
実施例および比較例について、製造諸元と結果をまとめ
ると第２表の通りである。Table 2 summarizes the manufacturing specifications and results for Examples and Comparative Examples.
［以下余白］[Margin below]
【図面の簡単な説明】
第１図と第２図は、コア粒子１ケの表面を最密に被覆す
るに要する満足する割合で、分散液状態の数Ｎの算出を
説明する図面であるが、第１図の点線が１回転した面積
がＰであり、第２図は満足する割合で、分散液状態１ヶ
当りの占める面積Ｑを示す。
第３図は、均一に被覆された複合体粒子の模型図であり
、第４図は、疎らに被覆された複合体粒子の凝集状態を
示す。
なお、図面において用いられている符号において、１は
コア粒子であり、２は満足する割合で、分散液状態であ
る。又、■は正電荷を示し、ｅは負電荷を示す。[Brief explanation of the drawings] Figures 1 and 2 are diagrams illustrating the calculation of the number N of dispersion liquid states at a satisfactory ratio required to cover the surface of one core particle most densely. , the area of one rotation of the dotted line in FIG. 1 is P, and FIG. 2 shows the area Q occupied by one dispersion state at a satisfactory rate. FIG. 3 is a schematic diagram of uniformly coated composite particles, and FIG. 4 shows an agglomerated state of sparsely coated composite particles. In addition, in the symbols used in the drawings, 1 is a core particle, and 2 is a dispersion state at a satisfactory ratio. Further, ■ indicates a positive charge, and e indicates a negative charge.
Claims (1)
コア粒子と、 （Ｂ）コア粒子より小さく、かつ反対に荷電した無機質
粒子又は高分子粒子からなるシェル形成用粒子を、シェ
ル形成用粒子の数をコア粒子の数で割った粒子数比（Ｒ
）が （Ｒ）＞（４π（ａ＋ｂ）＾２）／（２√３ｂ＾２）×
０．５〔ａ＝コア粒子の平均半径〕 〔ｂ＝シェル形成用粒子の平均半径〕 を満足する割合で、分散液状態で混合することを特徴と
するコア粒子をシェル形成用粒子で均一に被覆された複
合体粒子の製造方法。 ２ I （Ａ）荷電した無機質粒子又は高分子粒子から
なるコア粒子と、 （Ｂ）コア粒子より小さく、かつ反対に荷電した無機質
粒子又は高分子粒子からなるシェル形成用粒子を、シェ
ル形成用粒子の数をコア粒子の数で割った粒子数比（Ｒ
）が （Ｒ）＞（４π（ａ＋ｂ）＾２）／（２√３ｂ＾２）×
０．５〔ａ＝コア粒子の平均半径〕 〔ｂ＝シェル形成用粒子の平均半径〕 を満足する割合で、分散液状態で混合してコア粒子をシ
ェル形成用粒子で均一に被覆した粒子とし、この粒子を
２次コア粒子として、II２次コア粒子より小さく、かつ
反対に荷電した無機質粒子又は高分子粒子からなる２次
シェル形成用粒子を、２次シェル形成用粒子の数を２次
コア粒子の数で割った粒子数比 （Ｒ′）が （Ｒ′）＞（４π（ａ′＋ｂ′）＾２）／（２√３ｂ′
＾２）×０．５〔ａ′＝２次コア粒子の平均半径〕 〔ｂ′＝２次シェル形成用粒子の平均半径〕を満足する
割合で、分散液状態で混合することを１回以上繰り返す
ことを特徴とする２次コア粒子を２次シェル形成用粒子
で均一に被覆された複合体粒子の製造方法。 ３ 高分子粒子がソープフリー製法によってえたもので
ある特許請求の範囲第１項又は第２項記載の複合体粒子
の製造方法。[Scope of Claims] 1. (A) A core particle consisting of a charged inorganic particle or a polymer particle; (B) A shell-forming particle consisting of an inorganic particle or a polymer particle smaller than the core particle and oppositely charged. , the particle number ratio (R
) is (R)>(4π(a+b)^2)/(2√3b^2)×
0.5 [a = average radius of core particles] [b = average radius of shell-forming particles] The core particles are uniformly mixed with shell-forming particles in a dispersion state. Method of manufacturing coated composite particles. 2 I (A) Core particles consisting of charged inorganic particles or polymer particles; (B) Shell-forming particles consisting of inorganic particles or polymer particles smaller than the core particles and oppositely charged; Particle number ratio (R
) is (R)>(4π(a+b)^2)/(2√3b^2)×
0.5 [a = average radius of core particles] [b = average radius of shell-forming particles] The core particles are mixed in a dispersion state at a ratio that satisfies the following: core particles are uniformly coated with shell-forming particles. , with this particle as the secondary core particle, the secondary shell-forming particles consisting of inorganic particles or polymer particles smaller than the II secondary core particle and oppositely charged, and the number of secondary shell-forming particles as the secondary core particle. The particle number ratio (R') divided by the number of particles is (R')>(4π(a'+b')^2)/(2√3b'
^2) x 0.5 [a' = average radius of secondary core particles] [b' = average radius of secondary shell forming particles] Mixing in a dispersion state at least once A method for producing composite particles in which secondary core particles are uniformly coated with secondary shell-forming particles, the method comprising repeating the steps. 3. The method for producing composite particles according to claim 1 or 2, wherein the polymer particles are obtained by a soap-free production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61057806A JPH0640951B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniformly coated composite particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61057806A JPH0640951B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniformly coated composite particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62213839A true JPS62213839A (en) | 1987-09-19 |
| JPH0640951B2 JPH0640951B2 (en) | 1994-06-01 |
Family
ID=13066162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61057806A Expired - Fee Related JPH0640951B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniformly coated composite particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640951B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63240937A (en) * | 1986-10-27 | 1988-10-06 | Japan Synthetic Rubber Co Ltd | Microencapsulated fine particle and production thereof |
| JPH0724306A (en) * | 1993-07-07 | 1995-01-27 | Agency Of Ind Science & Technol | Production of composite ultra-fine particle |
| JP2001323070A (en) * | 2000-03-08 | 2001-11-20 | Catalysts & Chem Ind Co Ltd | Spherical composite particle and cosmetic blended with the same |
| EP1160300A2 (en) * | 2000-05-18 | 2001-12-05 | JSR Corporation | Aqueous dispersion for chemical mechanical polishing |
| JP2002506719A (en) * | 1998-03-19 | 2002-03-05 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Fabrication of nanocapsules and microcapsules by layered polyelectrolyte self-assembly |
| JP2002520151A (en) * | 1998-07-15 | 2002-07-09 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Polyelectrolytes on biological templates |
| EP1243611A1 (en) * | 1999-11-22 | 2002-09-25 | JSR Corporation | Composited particles and aqueous dispersions for chemical mechanical polishing |
| JP2003522621A (en) * | 1998-03-19 | 2003-07-29 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Fabrication of multilayer coated particles and hollow shells by electrostatic self-assembly of nanocomposite multilayers on degradable colloid prototypes |
| WO2007094271A1 (en) * | 2006-02-17 | 2007-08-23 | Kaneka Corporation | Process for producing polymer powder with excellent nonblocking property |
| JP2008255318A (en) * | 2007-02-19 | 2008-10-23 | Sanyo Chem Ind Ltd | Method for manufacturing multilayer-structural resin particle |
| JP2009030000A (en) * | 2007-07-30 | 2009-02-12 | Sanyo Chem Ind Ltd | Method for producing nonaqueous resin dispersion |
| JP2010525930A (en) * | 2006-10-25 | 2010-07-29 | ウィリアム エム． カーティー， | Controlled distribution of chemicals in ceramic systems. |
| US8092836B2 (en) | 1998-03-19 | 2012-01-10 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V. | Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly |
| WO2012133696A1 (en) * | 2011-03-31 | 2012-10-04 | 国立大学法人豊橋技術科学大学 | Device for producing composite particles and process for producing composite particles |
| WO2018060649A1 (en) * | 2016-09-30 | 2018-04-05 | Compagnie Generale Des Etablissements Michelin | Method for obtaining a coagulum and a masterbatch of elastomer and polymer filler |
| CN114276642A (en) * | 2021-12-09 | 2022-04-05 | 浙江邦德管业有限公司 | Silicon core pipe resistant to environmental stress cracking and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6145250A (en) * | 1984-08-09 | 1986-03-05 | Toshiba Corp | Microencapsulated electrophotographic toner and its preparation |
-
1986
- 1986-03-14 JP JP61057806A patent/JPH0640951B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6145250A (en) * | 1984-08-09 | 1986-03-05 | Toshiba Corp | Microencapsulated electrophotographic toner and its preparation |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63240937A (en) * | 1986-10-27 | 1988-10-06 | Japan Synthetic Rubber Co Ltd | Microencapsulated fine particle and production thereof |
| JPH0724306A (en) * | 1993-07-07 | 1995-01-27 | Agency Of Ind Science & Technol | Production of composite ultra-fine particle |
| JP2003522621A (en) * | 1998-03-19 | 2003-07-29 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Fabrication of multilayer coated particles and hollow shells by electrostatic self-assembly of nanocomposite multilayers on degradable colloid prototypes |
| US8168226B2 (en) * | 1998-03-19 | 2012-05-01 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V. | Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly |
| US8092836B2 (en) | 1998-03-19 | 2012-01-10 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften E.V. | Production of nanocapsules and microcapsules by layer-wise polyelectrolyte self-assembly |
| JP2002506719A (en) * | 1998-03-19 | 2002-03-05 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Fabrication of nanocapsules and microcapsules by layered polyelectrolyte self-assembly |
| JP2002520151A (en) * | 1998-07-15 | 2002-07-09 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Polyelectrolytes on biological templates |
| JP4650976B2 (en) * | 1998-07-15 | 2011-03-16 | マックス−プランク−ゲゼルシャフト・ツア・フェルデルング・デア・ヴィッセンシャフテン・エー・ファオ | Polyelectrolytes on biological templates |
| EP1243611A1 (en) * | 1999-11-22 | 2002-09-25 | JSR Corporation | Composited particles and aqueous dispersions for chemical mechanical polishing |
| JP2001323070A (en) * | 2000-03-08 | 2001-11-20 | Catalysts & Chem Ind Co Ltd | Spherical composite particle and cosmetic blended with the same |
| EP1160300A2 (en) * | 2000-05-18 | 2001-12-05 | JSR Corporation | Aqueous dispersion for chemical mechanical polishing |
| EP1160300A3 (en) * | 2000-05-18 | 2003-11-26 | JSR Corporation | Aqueous dispersion for chemical mechanical polishing |
| WO2007094271A1 (en) * | 2006-02-17 | 2007-08-23 | Kaneka Corporation | Process for producing polymer powder with excellent nonblocking property |
| JP2010525930A (en) * | 2006-10-25 | 2010-07-29 | ウィリアム エム． カーティー， | Controlled distribution of chemicals in ceramic systems. |
| JP2008255318A (en) * | 2007-02-19 | 2008-10-23 | Sanyo Chem Ind Ltd | Method for manufacturing multilayer-structural resin particle |
| JP2009030000A (en) * | 2007-07-30 | 2009-02-12 | Sanyo Chem Ind Ltd | Method for producing nonaqueous resin dispersion |
| WO2012133696A1 (en) * | 2011-03-31 | 2012-10-04 | 国立大学法人豊橋技術科学大学 | Device for producing composite particles and process for producing composite particles |
| JP6083610B2 (en) * | 2011-03-31 | 2017-02-22 | 国立大学法人豊橋技術科学大学 | Composite particle manufacturing apparatus and composite particle manufacturing method |
| WO2018060649A1 (en) * | 2016-09-30 | 2018-04-05 | Compagnie Generale Des Etablissements Michelin | Method for obtaining a coagulum and a masterbatch of elastomer and polymer filler |
| FR3056984A1 (en) * | 2016-09-30 | 2018-04-06 | Compagnie Generale Des Etablissements Michelin | PROCESS FOR OBTAINING A COAGULUM AND A MASTER MIXTURE OF ELASTOMER AND POLYMERIC LOAD |
| CN114276642A (en) * | 2021-12-09 | 2022-04-05 | 浙江邦德管业有限公司 | Silicon core pipe resistant to environmental stress cracking and preparation method thereof |
| CN114276642B (en) * | 2021-12-09 | 2024-03-22 | 浙江邦德管业有限公司 | Silicon core tube resistant to environmental stress cracking and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0640951B2 (en) | 1994-06-01 |
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