JPS6368645A - Production of spherical particle - Google Patents
Production of spherical particleInfo
- Publication number
- JPS6368645A JPS6368645A JP61213454A JP21345486A JPS6368645A JP S6368645 A JPS6368645 A JP S6368645A JP 61213454 A JP61213454 A JP 61213454A JP 21345486 A JP21345486 A JP 21345486A JP S6368645 A JPS6368645 A JP S6368645A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- particles
- acid ester
- solvent
- org
- 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
- 239000012798 spherical particle Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920002678 cellulose Polymers 0.000 claims abstract description 55
- 239000001913 cellulose Substances 0.000 claims abstract description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003349 gelling agent Substances 0.000 claims abstract description 15
- 239000007863 gel particle Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 43
- -1 organic acid ester Chemical class 0.000 claims description 29
- 239000012736 aqueous medium Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 150000002148 esters Chemical class 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 10
- 229920002284 Cellulose triacetate Polymers 0.000 abstract description 8
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000011324 bead Substances 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000875 Dissolving pulp Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- YZBOVSFWWNVKRJ-UHFFFAOYSA-N Monobutylphthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(O)=O YZBOVSFWWNVKRJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000001042 affinity chromatography Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- PBMCLYSTXOTVKX-UHFFFAOYSA-N butanoic acid;carbamic acid Chemical compound NC(O)=O.CCCC(O)=O PBMCLYSTXOTVKX-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001641 gel filtration chromatography Methods 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PKIYFBICNICNGJ-UHFFFAOYSA-N monooctyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(O)=O PKIYFBICNICNGJ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
この発明はセルロース有Ｗ１酸エステルの多孔性球状粒
子の製造方法に関するものであり、詳しくは粒度の均一
性、真球性、多孔性などにすぐれた球状粒子の製造方法
に関するものであり、特にそれをケン化してクロマトグ
ラフィの担体などに有用なセルロース球状粒子を得るた
めのものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a method for producing porous spherical particles of cellulose W1 acid ester, and in detail, the uniformity of particle size, sphericity, porosity, etc. The present invention relates to a method for producing spherical particles with excellent properties, and in particular for saponifying them to obtain cellulose spherical particles useful as carriers for chromatography.
（ロ）従来の技術
高分子物質の微小粒子は、その形状のままでプラスチッ
クス添加剤、薬品賦形剤、ブロッキング防止剤、化粧品
、印刷などの分野に用いられているが、近年、酵素、微
生物などの担体、クロマトグラフィーの充填剤などとし
ても注目されている。(b) Conventional technology Microparticles of polymeric substances are used in fields such as plastics additives, drug excipients, anti-blocking agents, cosmetics, and printing, but in recent years, enzymes, It is also attracting attention as a carrier for microorganisms and as a packing material for chromatography.
高分子物質としてセルロース有機酸エステルは溶剤溶解
性に冨み、粒子として取得しやすいので、そのままで上
記用途に使用されるほか、加水分解してセルロースの微
小粒子に変換したり、さらに他の官能基例えばイオン交
換能を有する官能基を導入したりすることができ、それ
ぞれの機能に応じた用途に使用できる。特にこの方法で
得られるセルロース粒子について、いくつかの特許出願
がなされている。As a polymeric substance, cellulose organic acid ester has high solvent solubility and is easy to obtain as particles, so in addition to being used as is for the above purposes, it can also be hydrolyzed to convert into microparticles of cellulose, or it can be converted into other functional materials. For example, a functional group having ion exchange ability can be introduced, and the material can be used for purposes depending on its function. In particular, several patent applications have been filed regarding cellulose particles obtained by this method.
特公昭５５−３９５６５号公報、特公昭５４−４０６１
８号公報には、球状粒子の製法としてセルロース脂肪酸
エステルを乾式紡糸し、得たフィラメントを切断してチ
ップとし高沸点溶媒中で加熱して球状粒子とする方法、
ならびにセルロース脂肪酸エステルを低沸点溶媒に溶解
し、高沸点貧溶媒中に懸濁させた後、加熱して低沸点溶
媒を蒸発させ、球状粒子を得る方法が示されており、得
られたセルロース脂肪酸エステル粒子を加水分解してセ
ルロース球状粒子を得ている。これらは工程が長くエネ
ルギー消費も大きい製法である。また、得られるセルロ
ース脂肪酸エステル粒子が比較的緻密であるため、これ
から得られるセルロース粒子も比較的緻密に過ぎ、クロ
マトグラフィー担体用または薬剤徐放剤としては、空隙
率の小さすぎるものしが得られない。Special Publication No. 55-39565, Special Publication No. 54-4061
Publication No. 8 describes a method for producing spherical particles by dry spinning cellulose fatty acid ester, cutting the obtained filament into chips, heating in a high boiling point solvent, and producing spherical particles;
Also, a method is shown in which spherical particles are obtained by dissolving cellulose fatty acid ester in a low boiling point solvent, suspending it in a high boiling point poor solvent, and then heating to evaporate the low boiling point solvent. Cellulose spherical particles are obtained by hydrolyzing ester particles. These manufacturing methods require long steps and consume a lot of energy. Furthermore, since the obtained cellulose fatty acid ester particles are relatively dense, the cellulose particles obtained from them are also relatively dense, and the porosity is too small to be used as a chromatography carrier or a drug sustained release agent. do not have.
空隙率の大きい粒子を得る方法として、特開昭５４−５
５０５５号公報や特開昭５６−２４４２９号公報にみら
れるようにセルロース脂肪酸エステルを低沸点溶媒に溶
解する際に高沸点溶媒やセルロースエステルとは溶剤溶
解性の異る高分子化合物、例えば水溶性高分子化合物を
添加し、その混合溶液を水性溶液中に分散懸濁させて液
滴化した模、加熱して低沸点溶媒を蒸発させ液滴を凝固
せしめて、高分子化合物もしくは高沸点溶剤を含有する
セルロース脂肪酸エステルの微小球体を得、これをケン
化する前かケン化後に高分子化合物又は高沸点溶媒を洗
浄によって除去し空隙率の大きいセルロース粒子を得る
方法が提案されている。As a method for obtaining particles with a large porosity, JP-A-54-5
5055 and JP-A No. 56-24429, when dissolving cellulose fatty acid ester in a low-boiling point solvent, a high-boiling point solvent or a polymer compound having a different solvent solubility from that of cellulose ester, such as a water-soluble After adding a polymer compound and dispersing and suspending the mixed solution in an aqueous solution to form droplets, the polymer compound or high boiling point solvent is heated to evaporate the low boiling point solvent and solidify the droplets. A method has been proposed in which microspheres containing cellulose fatty acid ester are obtained, and the polymer compound or high-boiling solvent is removed by washing before or after saponification to obtain cellulose particles with a large porosity.
（ハ）発明が解決しようとする問題点
上記従来の技術において、空隙率の大きい粒子を得るた
めになされた後者の方法には次のような問題点がある。(c) Problems to be Solved by the Invention Among the conventional techniques described above, the latter method used to obtain particles with a large porosity has the following problems.
液滴あるいは液滴からの凝固粒子を加熱して低沸点溶媒
を除去する場合に、セルロース脂肪酸エステルの熱可塑
性のために、空孔の大きざ、粒子径、密度などの物性が
変動しやすく、再現性のある物性値を得るための工程管
理が面倒である。また、凝固粒子から洗浄により高分子
化合物を除去する方法は、空隙率としては大きい数値か
えられるが個々の空孔が大ぎく、且つその数も限られた
ものになる。すなわち個々の空孔が比較的大きすぎる粒
子が得られる。このような粒子は、酵素固定担体やイオ
ン交換セルース誘導体用原料としては使用できるがクロ
マトグラフィー用担体としてはあまり好適とは言えない
。When a low boiling point solvent is removed by heating droplets or coagulated particles from droplets, physical properties such as pore size, particle diameter, and density are likely to fluctuate due to the thermoplasticity of cellulose fatty acid ester. Process control to obtain reproducible physical property values is troublesome. Further, in the method of removing the polymer compound from the coagulated particles by washing, the porosity can be increased to a large value, but the individual pores are large and the number thereof is limited. That is, particles are obtained in which the individual pores are relatively too large. Although such particles can be used as enzyme-immobilized carriers or raw materials for ion-exchanged cellulose derivatives, they are not very suitable as carriers for chromatography.
この発明の発明者らは、セルロース有機酸エステルを適
当な条件でゲル化させると、立体的網状構造を形成し、
この構造が比較的安定であるため多数の小空孔の形成に
有利な条件となることを見出し、この発明に到達した。The inventors of this invention have discovered that when cellulose organic acid ester is gelled under appropriate conditions, it forms a three-dimensional network structure,
The inventors have discovered that this structure is relatively stable, which provides favorable conditions for the formation of a large number of small pores, and has thus arrived at the present invention.
（ニ）問題点を解決するための手段と作用この発明は、
セルロース有機酸エステルとセルロース有機酸エステル
のゲル化剤とを溶解した有機溶媒溶液を、水性媒体中に
加えて液滴を形成させ、該液滴が水性媒体中に存在する
間に液滴中のセルロース有機酸エステルをゲル化させて
球状ゲル粒子とし、生成した粒子からゲル化剤及び有機
溶媒を除去することを特徴とする多孔性球状粒子の製造
法を提供するものである。(d) Means and operation for solving the problems This invention has the following features:
An organic solvent solution in which a cellulose organic acid ester and a cellulose organic acid ester gelling agent are dissolved is added to an aqueous medium to form droplets, and while the droplets exist in the aqueous medium, the The present invention provides a method for producing porous spherical particles, which comprises gelling a cellulose organic acid ester to form spherical gel particles, and removing a gelling agent and an organic solvent from the resulting particles.
この発明に使用するセルロース有機酸エステルを例示す
れば、セルローストリアセテート、セルロースジアセテ
ート、セルロースベンゾエート、セルロースカルバメー
ト
ブチレートなどがある。いずれも溶剤溶解性及び熱可塑
性を有し、アルカリで処理すると加水分解してセルロー
スを再生する。この発明の目的には価格、溶剤溶解性、
ゲル形成性などの点でセルローストリアセテートが特に
適している。Examples of cellulose organic acid esters used in this invention include cellulose triacetate, cellulose diacetate, cellulose benzoate, and cellulose carbamate butyrate. Both have solvent solubility and thermoplasticity, and when treated with alkali, they hydrolyze and regenerate cellulose. The objectives of this invention include price, solvent solubility,
Cellulose triacetate is particularly suitable in terms of gel-forming properties.
セルロース有機酸エステルを溶解する有機溶媒としては
、水に溶解しない溶媒であることが必要であり、塩化メ
チレン、クロロホルムなどのハロゲン化炭化水素、およ
びハロゲン化炭化水素を主体としこれに脂肪族アルコー
ル、ケトン、エステル又は炭化水素を少量添加した混合
溶媒の中から選択して使用することができる。有機溶媒
の使用団はセルロース有機酸エステルの濃度が３〜１５
重量％となる程度が適当である。一般に濃度が低い方が
空隙率の高い粒子が得られる傾向がある。 １ゲル化
剤とは、セルロース有機酸エステルと相溶性があり、共
通溶剤に溶解して混合溶液を形成するが、溶媒の溶解力
が減少すると、セルロース有機酸エステルをゲル化させ
る能力を有する物質を指す。ゲル化剤としては、長鎖脂
肪族カルボン酸、長鎖脂肪族アルコール及び芳香族カル
ボン酸脂肪族エステル等から選択することができる。The organic solvent for dissolving the cellulose organic acid ester must be a solvent that does not dissolve in water, and must be a halogenated hydrocarbon such as methylene chloride or chloroform, or a halogenated hydrocarbon that is mainly composed of aliphatic alcohol, A mixed solvent to which a small amount of ketone, ester, or hydrocarbon is added can be selected and used. The concentration of cellulose organic acid ester in the organic solvent used is 3 to 15.
A suitable level is % by weight. Generally, particles with higher porosity tend to be obtained when the concentration is lower. 1. A gelling agent is a substance that is compatible with cellulose organic acid ester and forms a mixed solution when dissolved in a common solvent, but has the ability to gel the cellulose organic acid ester when the solvent's dissolving power decreases. refers to The gelling agent can be selected from long-chain aliphatic carboxylic acids, long-chain aliphatic alcohols, aromatic carboxylic acid aliphatic esters, and the like.
長鎖脂肪族カルボン酸としては、オレイン酸、ラウリン
酸、ミリスチン酸、バルミチン酸、ステアリン酸、ベヘ
ニン酸、イソステアリン酸、ｎ −オクタン酸などが挙
げられる。Examples of long-chain aliphatic carboxylic acids include oleic acid, lauric acid, myristic acid, balmitic acid, stearic acid, behenic acid, isostearic acid, n-octanoic acid, and the like.
長鎖脂肪族アルコールとしては、ｎ−ヘキサノール、ｎ
−ヘプタツール、ｎ−オクタツール、デシルアルコール
、トリデカノール、２−エチルヘキサノール、０−ノナ
ノールなどが挙げられる。Long chain aliphatic alcohols include n-hexanol, n
-heptatool, n-octatool, decyl alcohol, tridecanol, 2-ethylhexanol, 0-nonanol and the like.
芳香族カルボン酸脂肪族エステルとしては、安息香酸ブ
チル、安息香酸ヘキシル、フタル酸モノブチル、フタル
酸モノオクチル、フタル酸ジブチル、フタル酸ジオクチ
ル、フタル酸ジエチル、フタル酸ジラウリル、フタル酸
ブチルベンジル、フタル酸ジヘブチル、フタル酸ジシク
ロヘキシルなどが挙げられる。Aromatic carboxylic acid aliphatic esters include butyl benzoate, hexyl benzoate, monobutyl phthalate, monooctyl phthalate, dibutyl phthalate, dioctyl phthalate, diethyl phthalate, dilauryl phthalate, butylbenzyl phthalate, and phthalate. Examples include dihebutyl and dicyclohexyl phthalate.
これらゲル化剤の添加ｌは有機溶媒に対して５〜３０容
量％が適当である。The appropriate amount of these gelling agents added is 5 to 30% by volume relative to the organic solvent.
この発明に使用する水性媒体としては、水又は水に少量
の例えば０．２〜１０重ω％のゼラチン、ＣＭＣ，ＰＶ
Ａなとの水溶性高分子又は／及び０．０５〜３重量％の
界面活性剤、消泡剤を溶解した溶液が用いられる。水に
添加するこれらの薬剤に生成する液滴を安定化させるた
めのものである。The aqueous medium used in this invention includes water or a small amount of gelatin, CMC, PV, etc.
A solution containing a water-soluble polymer such as A or/and 0.05 to 3% by weight of a surfactant and an antifoaming agent is used. This is to stabilize the droplets that form when these drugs are added to water.
この発明の方法で得られるセルロース有！Ｉ′Ｍエステ
ルの球状粒子の大きさは、原則として１個の液滴から１
個の粒子が生成するので液滴の大きざに依存するが、水
性媒体中で生成する液滴の大きさは水性媒体中に有機溶
媒溶液を添加する際の撹拌効率に依存し、撹拌効率がよ
いはど液滴の大きさは小さい。溶液中のセルロース有ｉ
酸エステルの濃度が小ざい場合、溶液の粘度が小さくな
るので同じ撹拌回転数でも効率がよくなり小さな液滴が
えられる。尚、セルロース有ａ！酸エステルの濃度は、
同時に粒子の空隙率を決定する因子でもあり、溶質濃度
の小さいはど空隙率は大きくなる。Cellulose obtained by the method of this invention! In principle, the size of the spherical particles of I'M ester is from 1 droplet to 1
The size of the droplets generated in an aqueous medium depends on the agitation efficiency when adding the organic solvent solution to the aqueous medium, and the agitation efficiency depends on the size of the droplets. Good droplet size is small. Cellulose in solution
When the concentration of acid ester is low, the viscosity of the solution is low, so even with the same stirring speed, efficiency is improved and small droplets can be obtained. In addition, there is cellulose! The concentration of acid ester is
At the same time, it is also a factor that determines the porosity of particles, and the smaller the solute concentration, the larger the porosity.
この発明のセルロース有機酸エステルの多孔性球状粒子
の生成機構を、有機溶媒としてメタノールを含有する塩
化メチレンを用いた場合で説明すれば以下の通りである
。The production mechanism of porous spherical particles of cellulose organic acid ester of the present invention will be explained as follows when methylene chloride containing methanol is used as the organic solvent.
塩化メチレン／メタノール溶媒にセルロース有機酸エス
テルとゲル化剤を溶解させ、この溶液を撹拝下に水性媒
体中に常温で添加して液滴を生成させ、常温で撹拌をつ
寸ける。こ間に液滴中のメタノールの一部およびごく少
量の塩化メチレンが水性媒体中に拡散して失われ、且つ
ごく少量の水が液滴内に溶解して来る。この状態になっ
たとき液滴中のセルロース有機酸エステルがゲル化し、
網状構造をもつ粒子を形成する。この粒子は既に固体で
あり、弾性があり指で押して変形させても力を除くとも
との形に戻る。水性媒体中から粒子を回収し、適当な溶
媒で洗浄して粒子に含有されているゲル化剤及び塩化メ
チレンを除去する。この状態で多孔構造を有する粒子が
得られる。この粒子はまだ塩化メチレンを含有している
ので、水性媒体中で加熱して残留溶媒を追出すこの条件
下では、セルロース有機酸エステルは十分な熱可塑性を
示すに至らないため生成空孔の閉塞は起らない。A cellulose organic acid ester and a gelling agent are dissolved in a methylene chloride/methanol solvent, and this solution is added to an aqueous medium at room temperature while stirring to form droplets, and stirring is continued at room temperature. During this time, some of the methanol and a very small amount of methylene chloride in the droplets are lost by diffusion into the aqueous medium, and a very small amount of water dissolves into the droplets. When this state is reached, the cellulose organic acid ester in the droplet gels,
Forms particles with a network structure. These particles are already solid and have elasticity, so even if you push them with your fingers and deform them, they will return to their original shape when the force is removed. The particles are recovered from the aqueous medium and washed with a suitable solvent to remove the gelling agent and methylene chloride contained in the particles. In this state, particles having a porous structure are obtained. Since the particles still contain methylene chloride, the residual solvent is expelled by heating in an aqueous medium. Under these conditions, the cellulose organic acid ester does not exhibit sufficient thermoplasticity and the resulting pores are blocked. doesn't happen.
（ホ）実施例
以下に実施例をあげて本発明を説明するが本発明はこれ
によって限定されるものではない。(e) Examples The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
実施例１
セルローストリアセテート〔ダイセル化学工業（［、酢
化度６１％ ） ２５Ｇ ヲメタ／−ル３０ｘｌｔｒ含
ム塩化メチレン１７０ ｘｉに溶解した。この溶液にジ
ブチルフタレート３０ｘｌと塩化メチレン３０１！の混
合物を加え撹拌して均一な溶液としたものを、消泡剤の
アンチホームＥ −２０（花王■製〕を１％及びゼ、ラ
チンを１％含有する水０．５Ω中に、約７５０Ｏｒｐｍ
の回転数にて撹拌しながら分散させた。得られた懸濁液
を１％ゼラチン水１ρ中にゆっくりと撹拌しながら投入
し、１時間撹拌をつづけた。静置後上澄みをのぞき、水
−イソプロパツール（１：１）混合物１Ωを加え、しば
らく撹拌した。ろ過した後、水で十分に洗浄する。つい
で、セルロースエステルビーズをイソプロパツール１ｇ
中に懸濁させ７０℃〜８０℃に加熱し２−３時間撹拌し
た。濾過後、イソプロパツール０．５ｇで２回洗浄しさ
らに水中に懸濁させて加熱する。８０℃で２時間処理し
た後、ろ過し十分な水で洗浄する。湿潤状態において分
離したところ、径１０〜３０４の粒子１０１ノ、３０４
〜７５膚の粒子４０１ノ、７５〜１５０４の粒子８０１
！、１５０〜２５０膚の粒子２０１！が得られた。得ら
れたセルロースアセテートビーズ（粒径７５〜１５０ｍ
）を、ビーズ１００ｇに対し７５％エタノール３００
ｘｌと １．０％ＮａＯＨ６００シ！を加え、室温で１
日間撹拌して加水分解した。次いで希酢酸を用いて中和
し水で十分洗浄しセルロースビーズを得た。このセルロ
ースビーズの密度を以下の方法によって測定したところ
０．３２であった。Example 1 Cellulose triacetate (Daicel Chemical Co., Ltd., degree of acetylation 61%) 25G methane/-ol 30xltr was dissolved in methylene chloride 170xi. Add 30xl of dibutyl phthalate and 301ml of methylene chloride to this solution! The mixture was added and stirred to make a homogeneous solution, and the mixture was added to 0.5Ω of water containing 1% of the antifoaming agent Antiform E-20 (manufactured by Kao Corporation) and 1% of Antifoam E-20 (manufactured by Kao) at approximately 750 rpm.
The mixture was dispersed while stirring at a rotation speed of . The resulting suspension was slowly poured into 1 ρ of 1% gelatin water with stirring, and stirring was continued for 1 hour. After standing still, the supernatant was removed, and 1Ω of a water-isopropanol (1:1) mixture was added, followed by stirring for a while. After filtering, wash thoroughly with water. Next, add 1 g of isopropanol to the cellulose ester beads.
The mixture was suspended in the liquid, heated to 70°C to 80°C, and stirred for 2 to 3 hours. After filtration, the mixture is washed twice with 0.5 g of isopropanol, and further suspended in water and heated. After treatment at 80° C. for 2 hours, filter and wash with sufficient water. When separated in a wet state, 101 particles with a diameter of 10 to 304, 304
~75 skin particles 401, 75-1504 particles 801
! , 150-250 skin particles 201! was gotten. Obtained cellulose acetate beads (particle size 75-150m)
), 300 g of 75% ethanol per 100 g of beads.
xl and 1.0% NaOH600shi! 1 at room temperature.
Hydrolysis was carried out by stirring for several days. Next, the beads were neutralized using dilute acetic acid and thoroughly washed with water to obtain cellulose beads. The density of the cellulose beads was measured by the following method and was found to be 0.32.
膨潤状態の試料を内径８ｍｍのガラスカラムに約１０ｃ
ｍの高さに充填する。カラムの内径（８ｉｎ ）と充填
したセルロース粒子の高さよりセルロース粒子の容積ｖ
Ｏを算出する。Place the swollen sample in a glass column with an inner diameter of 8 mm for about 10 cm.
Fill to a height of m. The volume of cellulose particles v is calculated from the inner diameter of the column (8 inches) and the height of the packed cellulose particles.
Calculate O.
ＶＯ−（０，４）２７ｒｈ ｈ ：充ＲシｔＣセル
ロース粒子の高さく１）
ついで、分子ｆｆｉ ２，０００，０００のブルーでデ
キストリン（０，５％水溶液を用いた）を溶出させその
♂出量（Ｖｔｙｆ）を求める。充填したセルロース粒子
をカラムより取り出しろ過し十分に洗浄後、乾燥してそ
の＠山を求める（ Ｗ ＋ｑ＋ ）。これらのデータよ
り次式によって密度を算出した。VO-(0,4)27rh h: Height of cellulose particles 1) Next, dextrin (using a 0.5% aqueous solution) was eluted with blue having a molecular ffi of 2,000,000 to release the male. Find the amount (Vtyf). The packed cellulose particles are taken out from the column, filtered, thoroughly washed, and dried to determine the @ mountain (W + q+). The density was calculated from these data using the following formula.
ＣＤ（％） ＝ −Ｘ １００
Ｖｏ−Ｖも
なお得られたセルロースピーズのゲルろ適用カラムクロ
マトグラフィー充填剤としての評価をおこなったところ
、その排除限界分子旦はデキストラン分子で約７０，０
００であった。CD (%) = -X 100 When the obtained cellulose peas were evaluated as a gel filtration column chromatography packing material, the exclusion limit molecular weight was approximately 70.0 for dextran molecules.
It was 00.
比較例（ゲル化剤を添加しない場合）
セルローストリアセテート（ダイセル化学工業■製、酢
化度６１％）２５ｇをメタノール３０１！を含む塩化メ
チレン２００ ｘｌに溶解した。この溶液を消泡剤アン
チホームＥ−２０を含む１％ゼラチン水０．５Ω中に７
５００ｒｐｍの回転数にて分散させ、得られた懸濁液を
１％ゼラチン水１ρ中にゆっくりと撹拌しながら加え、
１時間撹拌をつづけた。実施例１と同様の処理を行なっ
たところ、処理中に液滴の凝集がおこり、セルロースエ
ステルの粒子は全く得られず、セルローストリアセテー
トの固まりが得られたのみであった。Comparative example (when no gelling agent is added) 25 g of cellulose triacetate (manufactured by Daicel Chemical Industries, Ltd., acetylation degree 61%) was mixed with 301 g of methanol! was dissolved in 200 xl of methylene chloride containing This solution was dissolved in 0.5Ω of 1% gelatin water containing the antifoaming agent Antiform E-20.
Dispersion was performed at a rotation speed of 500 rpm, and the resulting suspension was slowly added to 1 μl of 1% gelatin water with stirring.
Stirring was continued for 1 hour. When the same treatment as in Example 1 was carried out, droplets agglomerated during the treatment, and no cellulose ester particles were obtained, but only cellulose triacetate lumps were obtained.
実施例２
セルローストリアセテート（ダイセル化学工業＠Ｊ製、
酢化度６１％）２５Ｑをメタノール３０１！を含む塩化
メチレン１７０ｘＩに溶解した。この溶液にオレインｇ
３０ｘｌと塩化メチレン３０１！よりなる混合液を加え
撹拌して均一な溶液としたものを消泡剤アンチホームＥ
−２０を含む１％ゼラチン水０６５ρ中に約７５０Ｏｒ
ｐｍの回転数にて撹拌し分散させた。得られた懸濁液を
１％ゼラチン水１ｇ中にゆっくりと撹拌しながら投入し
約１時間撹拌した。次いで実施例１と同様の処理により
実施例１と同等のセルローストリアセテート粒子が得ら
れた。粒径７５〜１５０）ａの粒子のセルロースエステ
ルを実施例１と同様にして加水分解し密度０．３のセル
ロースビーズを得た。Example 2 Cellulose triacetate (manufactured by Daicel Chemical Industries @J,
Acetylation degree 61%) 25Q to methanol 301! was dissolved in 170xI of methylene chloride containing Add olein to this solution
30xl and methylene chloride 301! The antifoaming agent Antifoam E is obtained by adding a mixture of
Approximately 750Or in 1% gelatin water containing -20
The mixture was stirred and dispersed at a rotational speed of pm. The resulting suspension was slowly poured into 1 g of 1% gelatin water with stirring, and stirred for about 1 hour. Cellulose triacetate particles equivalent to those in Example 1 were then obtained by the same treatment as in Example 1. Cellulose ester particles having a particle size of 75 to 150)a were hydrolyzed in the same manner as in Example 1 to obtain cellulose beads with a density of 0.3.
（へ）発明の効果
この発明は、セルロース有機酸エステルの多孔性球状粒
子を簡単且つ経済的に製造する方法であり、再現性が極
めてよい。従来の方法では低沸点溶媒を除去するときの
温度条件により粒子の物性が影響されたが、この発明の
方法では、溶媒組成、セルロース有機酸エステル及びゲ
ル化剤の濃度、粒子生成時の撹拌条件などを規定するこ
とにより真球性の高い球状粒子が再現性よく得られる。(f) Effects of the Invention The present invention is a method for producing porous spherical particles of cellulose organic acid ester simply and economically, and has extremely good reproducibility. In conventional methods, the physical properties of particles were affected by the temperature conditions when removing the low-boiling point solvent, but in the method of this invention, the solvent composition, the concentration of cellulose organic acid ester and gelling agent, and the stirring conditions during particle generation can be changed. By specifying the following, spherical particles with high sphericity can be obtained with good reproducibility.
この発明の方法で得られるセルロース有！ＩＭエステル
粒子にブロッキング防止剤、プラスチック添加剤、土壌
改良材などに使用できる。さらにエステル粒子を加水分
解して得るセルロース粒子に小さい突孔を多数有するの
で化粧品、ゲルろ過クロマトグラフィー担体、徐放性薬
剤担体などに好適である。さらにセルロース粒子に化学
修飾を施し、イオン交換クロマトグラフ担体、アフイニ
ティクロマトグラフ担体などに応用できる。Cellulose obtained by the method of this invention! It can be used as an anti-blocking agent, plastic additive, soil improvement material, etc. for IM ester particles. Furthermore, since the cellulose particles obtained by hydrolyzing ester particles have many small holes, they are suitable for cosmetics, gel filtration chromatography carriers, sustained release drug carriers, and the like. Furthermore, cellulose particles can be chemically modified and applied to ion exchange chromatography carriers, affinity chromatography carriers, etc.
Claims (1)
テルのゲル化剤とを溶解した有機溶媒溶液を、水性媒体
中に加えて液滴を形成させ、該液滴が水性媒体中に存在
する間に液滴中のセルロース有機酸エステルをゲル化さ
せて、球状ゲル粒子とし、生成した粒子からゲル化剤及
び有機溶媒を除去することを特徴とする多孔性球状粒子
の製造法。 ２、有機溶媒がメタノールを含有する塩化メチレンであ
る特許請求の範囲第１項記載の球状粒子の製造法。 ３、ゲル化剤が長鎖脂肪族カルボン酸、長鎖脂肪族アル
コールまたは芳香族カルボン酸脂肪族エステルである特
許請求の範囲第１項記載の球状粒子の製造法。[Claims] 1. An organic solvent solution in which a cellulose organic acid ester and a cellulose organic acid ester gelling agent are dissolved is added to an aqueous medium to form droplets, and the droplets are formed in the aqueous medium. A method for producing porous spherical particles, which comprises gelling a cellulose organic acid ester in droplets to form spherical gel particles while the cellulose organic acid ester is present, and removing a gelling agent and an organic solvent from the resulting particles. 2. The method for producing spherical particles according to claim 1, wherein the organic solvent is methylene chloride containing methanol. 3. The method for producing spherical particles according to claim 1, wherein the gelling agent is a long-chain aliphatic carboxylic acid, a long-chain aliphatic alcohol, or an aromatic carboxylic acid aliphatic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213454A JP2506682B2 (en) | 1986-09-09 | 1986-09-09 | Manufacturing method of spherical particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61213454A JP2506682B2 (en) | 1986-09-09 | 1986-09-09 | Manufacturing method of spherical particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6368645A true JPS6368645A (en) | 1988-03-28 |
| JP2506682B2 JP2506682B2 (en) | 1996-06-12 |
Family
ID=16639482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61213454A Expired - Lifetime JP2506682B2 (en) | 1986-09-09 | 1986-09-09 | Manufacturing method of spherical particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2506682B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316270A2 (en) * | 1987-10-26 | 1989-05-17 | Ciba-Geigy Ag | Finely divided cellulosic esters of aromatic or aromatic-aliphatic carboxylic acids, process for their preparation and their use |
| JPH01275641A (en) * | 1988-04-27 | 1989-11-06 | Kanegafuchi Chem Ind Co Ltd | Polymer particle |
| JP2002236278A (en) * | 2000-12-08 | 2002-08-23 | Sony Corp | Liquid crystal display device, liquid crystal projector device, and method for cooling panel |
| US7123334B2 (en) | 2000-12-08 | 2006-10-17 | Sony Corporation | Liquid crystal display device and liquid crystal projector device |
| KR20220025101A (en) * | 2019-07-10 | 2022-03-03 | 다이니치 세이카 고교 가부시키가이샤 | Manufacturing method of resin beads, resin beads, and products using resin beads |
| US11926718B2 (en) | 2020-09-01 | 2024-03-12 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Resin beads, method for producing resin beads, and product using resin beads |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624429A (en) * | 1979-08-03 | 1981-03-09 | Yoshiaki Motozato | Preparation of porous spherical particle of cellulose |
| JPS6395237A (en) * | 1986-10-11 | 1988-04-26 | Daicel Chem Ind Ltd | Production of porous spherical particle |
-
1986
- 1986-09-09 JP JP61213454A patent/JP2506682B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624429A (en) * | 1979-08-03 | 1981-03-09 | Yoshiaki Motozato | Preparation of porous spherical particle of cellulose |
| JPS6395237A (en) * | 1986-10-11 | 1988-04-26 | Daicel Chem Ind Ltd | Production of porous spherical particle |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0316270A2 (en) * | 1987-10-26 | 1989-05-17 | Ciba-Geigy Ag | Finely divided cellulosic esters of aromatic or aromatic-aliphatic carboxylic acids, process for their preparation and their use |
| JPH01275641A (en) * | 1988-04-27 | 1989-11-06 | Kanegafuchi Chem Ind Co Ltd | Polymer particle |
| JP2002236278A (en) * | 2000-12-08 | 2002-08-23 | Sony Corp | Liquid crystal display device, liquid crystal projector device, and method for cooling panel |
| US7123334B2 (en) | 2000-12-08 | 2006-10-17 | Sony Corporation | Liquid crystal display device and liquid crystal projector device |
| KR20220025101A (en) * | 2019-07-10 | 2022-03-03 | 다이니치 세이카 고교 가부시키가이샤 | Manufacturing method of resin beads, resin beads, and products using resin beads |
| EP3998300A4 (en) * | 2019-07-10 | 2022-08-31 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Method for manufacturing resin beads, resin beads, and product employing resin beads |
| US11548999B2 (en) | 2019-07-10 | 2023-01-10 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Method for manufacturing resin beads, resin beads, and product employing resin beads |
| US11926718B2 (en) | 2020-09-01 | 2024-03-12 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Resin beads, method for producing resin beads, and product using resin beads |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2506682B2 (en) | 1996-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4118336A (en) | Novel cellulose microcapsules and preparation thereof | |
| WO2013016982A1 (en) | Cellulose acetate microsphere preparation method and product prepared thereby | |
| US4888420A (en) | Water soluble cellulose acetate microspheres | |
| JP3287798B2 (en) | Method for producing spherical cellulose fine particles | |
| JPH0739441B2 (en) | Novel chitosan derivatives useful in coating compositions for feed additives for ruminants | |
| CN104624130A (en) | Method for preparing regenerated chitin microspheres | |
| JPS6368645A (en) | Production of spherical particle | |
| JPH082992B2 (en) | Manufacturing method of porous spherical particles | |
| CN1160398C (en) | High-molecular microspheres or acicular microparticles with uniform granularity and its shaping process | |
| US4937081A (en) | Process for producing porous, spherical particles | |
| JPH0730203B2 (en) | Method for producing cellulose particles | |
| JPS62288602A (en) | Production of modified chitosan particle | |
| JPH01301701A (en) | Production of granular porous chitosan | |
| JPS5857401A (en) | Production of particulate porous chitosan | |
| US4948814A (en) | Ion exchanger based on cross-linked glucomannan | |
| JPS6395238A (en) | Production of spherical particle | |
| EP0298171A1 (en) | Beads of cross-linked glucomannan and production thereof | |
| JP2010236975A (en) | Method for producing microbial cellulose particle having pore | |
| JPH0629336B2 (en) | Process for producing cellulose ester ester beads | |
| JPH0762042B2 (en) | Manufacturing method of cellulose microspheres | |
| JP2002526579A (en) | Method for producing polysaccharide beads | |
| US4997599A (en) | Preparation of water soluble cellulose acetate microspheres | |
| JPH0212961B2 (en) | ||
| JPS62253601A (en) | Production of spherical particle of cellulose | |
| JPH0578577B2 (en) |