JPH0827277A - Production of fine particle - Google Patents
Production of fine particleInfo
- Publication number
- JPH0827277A JPH0827277A JP18792894A JP18792894A JPH0827277A JP H0827277 A JPH0827277 A JP H0827277A JP 18792894 A JP18792894 A JP 18792894A JP 18792894 A JP18792894 A JP 18792894A JP H0827277 A JPH0827277 A JP H0827277A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- particles
- resin
- fine particles
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水不溶化多糖類微粒子の
製造方法に関する。この微粒子はフィルム等に印刷性の
良いコーティング用フィラー等として有用である。FIELD OF THE INVENTION The present invention relates to a method for producing water-insolubilized polysaccharide fine particles. The fine particles are useful as a coating filler or the like having good printability on a film or the like.
【０００２】[0002]
【従来の技術】従来、水溶性微粒子の不溶化は、一般的
には造粒した後、エピクロルヒドリン、ビスエポキシド
などの架橋剤を溶解した有機溶剤中に造粒した粒子を含
浸させて行っていた。2. Description of the Related Art Conventionally, insolubilization of water-soluble fine particles has generally been carried out by granulating and then impregnating the granulated particles in an organic solvent in which a crosslinking agent such as epichlorohydrin or bisepoxide is dissolved.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、造粒後
に液中で反応を行うため、反応後に溶剤の除去が必要と
なる。However, since the reaction is carried out in the liquid after the granulation, it is necessary to remove the solvent after the reaction.
【０００４】また、水溶性多糖類では、架橋剤に代え水
溶性樹脂を用いて不溶化を行おうとしても造粒後の形状
を保ったままの不溶化は不充分であった。Further, in the case of water-soluble polysaccharides, even if an attempt was made to insolubilize a water-soluble resin in place of the crosslinking agent, the insolubilization while maintaining the shape after granulation was insufficient.
【０００５】本発明は、この不溶化多糖微粒子の製造方
法に関して、過剰の溶剤や反応性樹脂の除去を必要とせ
ず、水溶性樹脂による不溶化を可能にする。The present invention enables insolubilization with a water-soluble resin in the method for producing the insolubilized polysaccharide fine particles, without the need to remove excess solvent or reactive resin.
【０００６】[0006]
【課題を解決するための手段】この発明は水溶性多糖類
と反応性樹脂又は水溶性架橋剤とを溶解した水溶液を噴
霧乾燥して造粒し、得られた粒子を熱処理して架橋し水
に不溶化することを特徴とする微粒子の製造方法であ
る。以下詳細に説明する。The present invention is directed to spray-drying an aqueous solution in which a water-soluble polysaccharide and a reactive resin or a water-soluble crosslinking agent are dissolved into granules, and heat-treating the resulting particles to cross-link them. It is a method for producing fine particles, which is characterized by insolubilizing in. This will be described in detail below.
【０００７】まず水溶性多糖類及び反応性樹脂を溶解し
た水溶液を調整し、これを通常の噴霧乾燥を行い造粒す
る。溶解の添加順序は問わない。First, an aqueous solution in which a water-soluble polysaccharide and a reactive resin are dissolved is prepared, and this is subjected to usual spray drying to granulate. The order of addition of dissolution does not matter.
【０００８】水溶性多糖類としては、でんぷん、カルボ
キシメチルセルロース、メチルセルロース、ヒアルロン
酸、コンドロイチン硫酸、グアーガムなどが挙げられ、
水中濃度１〜２０ｗｔ％、好ましくは５〜１５ｗｔ％と
する。Examples of the water-soluble polysaccharides include starch, carboxymethyl cellulose, methyl cellulose, hyaluronic acid, chondroitin sulfate, guar gum and the like,
The concentration in water is 1 to 20 wt%, preferably 5 to 15 wt%.
【０００９】反応性樹脂としては水溶性又は水分散性の
もので反応性官能基をもったものであり、ポリマーの
他、水中で反応してポリマーを形成するもの、初期縮合
物、オリゴマーを含むものとする。The reactive resin is a water-soluble or water-dispersible resin having a reactive functional group, and includes not only a polymer but also a polymer which reacts in water to form a polymer, an initial condensate and an oligomer. Let's assume.
【００１０】架橋剤としては水溶性のジエポキシ化合
物、ホルマリンが挙げられる。Examples of the cross-linking agent include water-soluble diepoxy compounds and formalin.
【００１１】代表的には、反応性樹脂としてメラミン樹
脂、尿素樹脂、尿素・メラミン・ホルマリン初期縮合
物、高縮合尿素樹脂、グリオキザール系樹脂、エチレン
尿素系樹脂、トリアジン系樹脂、又は水溶性ポリアミド
樹脂、水溶性ポリアクリルアミド樹脂、ポリアクリル酸
エステル樹脂、エチレン・酢酸ビニル系樹脂、塩化ビニ
ール／エチレン／酢酸ビニル共重合体などのエマルジョ
ンが挙げられる。Typically, the reactive resin is melamine resin, urea resin, urea / melamine / formalin initial condensation product, highly condensed urea resin, glyoxal resin, ethylene urea resin, triazine resin, or water-soluble polyamide resin. , Water-soluble polyacrylamide resin, polyacrylic acid ester resin, ethylene / vinyl acetate resin, emulsion of vinyl chloride / ethylene / vinyl acetate copolymer and the like.
【００１２】又、水溶性ジエポキシ化合物としてエチレ
ングリコールジグリシジルエーテル、ソルビトールポリ
グリシジルエーテルなどが挙げられる。Examples of water-soluble diepoxy compounds include ethylene glycol diglycidyl ether and sorbitol polyglycidyl ether.
【００１３】これらを多糖類の固形分濃度に比して、３
から６０ｗｔ％好ましくは、８〜２０ｗｔ％を使用し、
さらには反応を促進するための触媒を添加してもよい。Compared to the solid content of polysaccharides, these are 3
To 60 wt%, preferably 8 to 20 wt%,
Further, a catalyst for promoting the reaction may be added.
【００１４】次に造粒された微粒子と樹脂が反応し、架
橋する温度（８０〜２００℃）に加熱することで微粒子
を不溶化する。Next, the granulated fine particles react with the resin and are heated at a temperature (80 to 200 ° C.) at which they are crosslinked to insolubilize the fine particles.
【００１５】[0015]
【作用】本発明においては、反応性樹脂をあらかじめ造
粒原液に均一に溶解又は分散させることで、造粒後、さ
らに有機溶剤中で反応を行わせることなく、造粒物をそ
のまま加熱処理して水可溶分の少ない粒子を得ることが
できる。この粒子は表面が電子顕微鏡写真によると、表
面がなめらかで、大きな陥没が数箇所見られた。In the present invention, the reactive resin is uniformly dissolved or dispersed in the granulation stock solution in advance, so that after granulation, the granulated product is heat-treated as it is without further reaction in an organic solvent. Thus, particles having a low water-soluble content can be obtained. The surface of the particles was smooth on an electron micrograph and several large depressions were observed.
【００１６】コーティングフィラーとして用いた場合、
インクの吸収性がよく、フィルム等に印刷性の良い表面
を与えた。When used as a coating filler,
The ink absorbability was good, and it gave a film or other surface with good printability.
【００１７】[0017]
【００１８】[0018]
【実施例１】デキストリン（松谷科学、バインデックス
＃１００）１０重量部を水９０重量部に溶解させた。こ
れに高縮合尿素ホルマリン樹脂（住友化学スミテックス
レジン２５０ｃｏｎｃ）を１重量部添加し、溶解させ
た。さらにアミン系触媒（住友化学ＡＣＸ）を０．０３
重量部添加し、溶解させた。Example 1 10 parts by weight of dextrin (Matsutani Kagaku, Baindex # 100) was dissolved in 90 parts by weight of water. To this, 1 part by weight of highly condensed urea formalin resin (Sumitomo Chemical Sumitex Resin 250conc) was added and dissolved. Furthermore, 0.03 of amine-based catalyst (Sumitomo Chemical ACX)
Part by weight was added and dissolved.
【００１９】上記水溶液をニロアトマイザー社製モービ
ルマイナー型スプレードライヤーで噴霧乾燥を行った。
噴霧装置は、直径５センチのロータリーディスクアトマ
イザーを用いた。回転数は２万ｒｐｍとした。The above aqueous solution was spray-dried with a mobile minor type spray dryer manufactured by Niro Atomizer.
The atomizer used was a rotary disk atomizer with a diameter of 5 cm. The rotation speed was 20,000 rpm.
【００２０】得られた微粒子は、最大粒径３０μｍ、平
均粒径１４．３μｍであった。The obtained fine particles had a maximum particle size of 30 μm and an average particle size of 14.3 μm.
【００２１】また、電子顕微鏡での観察では、粒子の表
面はなめらかであるが、大きな陥没が数箇所に見られ
た。この微粒子は、水溶性であるが、１００℃の棚型乾
燥機で１時間熱処理をすることで不溶性となった。化粧
品原料基準、第二版注解、日本公定書協会編（薬事日報
社、１９８４）の方法で水可溶分を測定したところ、
６．５％であった。In addition, under observation with an electron microscope, although the surface of the particles was smooth, large depressions were found at several places. These fine particles were water-soluble, but became insoluble by heat treatment for 1 hour in a 100 ° C. shelf dryer. When the water-soluble content was measured by the method of Cosmetic Raw Material Standards, Second Edition Note, Japan Official Book Association (Yakuji Nipposha, 1984),
It was 6.5%.
【００２２】また、以下のようにして測った保水率の値
は、３００％であった。The water retention value measured as described below was 300%.
【００２３】（保水率の測定方法）サンプルを５Ｇのガ
ラスフィルター上に２ｇとり、イオン交換水を１０ｍｌ
加える。水流アスピレーターで脱気をし、水を粒子に充
分しみこませる。濾過操作により、濾過器上の水を除去
する。遠心分離機で２０００Ｇを２０分間与え、粒子間
の水を除去する。ガラスフィルター上から重量をはかっ
た秤量瓶（重量Ａ）に粒子を移す。秤量する。（重量
Ｂ） １０５℃で恒量になるまで乾燥させる。恒量になったと
きの重量（重量Ｃ）から絶乾粒子の重量を計算する。(Measurement method of water retention rate) A sample of 2 g was put on a 5 G glass filter, and 10 ml of ion-exchanged water was used.
Add. Degas with a water aspirator and allow water to soak into the particles. Water on the filter is removed by a filtration operation. Gently apply 2000 G for 20 minutes to remove water between particles. Transfer the particles from the glass filter into a weighed weighing bottle (weight A). Weigh. (Weight B) Dry at 105 ° C. until constant weight. The weight of the absolutely dried particles is calculated from the weight when the weight becomes constant (weight C).
【００２４】[0024]
【数１】保水率＝（Ｂ−Ａ）÷（Ｃ−Ａ）×１００[Equation 1] Water retention rate = (B−A) ÷ (C−A) × 100
【００２５】[0025]
【実施例２〜７】同様の実験を行い結果を第１表に示し
た。Examples 2 to 7 The same experiment was conducted and the results are shown in Table 1.
【００２６】[0026]
【比較例１】実施例１と同じデキストリン１０重量部を
水９０重量部に溶解させた。反応性樹脂は用いなかっ
た。Comparative Example 1 10 parts by weight of the same dextrin as in Example 1 was dissolved in 90 parts by weight of water. No reactive resin was used.
【００２７】上記水溶液をニロアトマイザー社製モービ
ルマイナー型スプレードライヤーで噴霧乾燥を行った。
噴霧装置は、直径５センチのロータリーディスクアトマ
イザーを用いた。回転数は２万ｒｐｍとした。The above aqueous solution was spray-dried with a mobile minor type spray dryer manufactured by Niro Atomizer.
The atomizer used was a rotary disk atomizer with a diameter of 5 cm. The rotation speed was 20,000 rpm.
【００２８】得られた微粒子は、最大粒径３０μｍ、平
均粒径１３．２μｍであった。The resulting fine particles had a maximum particle size of 30 μm and an average particle size of 13.2 μm.
【００２９】また、電子顕微鏡での観察では、粒子の表
面はなめらかであるが、大きな陥没が数箇所に見られ
た。この微粒子は、速やかに水に溶けた。In addition, when observed with an electron microscope, the surface of the particles was smooth, but large depressions were observed at several places. The fine particles quickly dissolved in water.
【００３０】[0030]
【比較例２】実施例１と同じデキストリン１０重量部を
水９０重量部に溶解させた。これに実施例１と同じ高縮
合尿素ホルマリン樹脂を１重量部添加し、溶解させた。
さらにアミン系触媒を０．０３重量部添加し、溶解させ
た。Comparative Example 2 10 parts by weight of the same dextrin as in Example 1 was dissolved in 90 parts by weight of water. To this, 1 part by weight of the same highly condensed urea formalin resin as in Example 1 was added and dissolved.
Further, 0.03 part by weight of an amine catalyst was added and dissolved.
【００３１】上記水溶液をニロアトマイザー社製モービ
ルマイナー型スプレードライヤーで噴霧乾燥を行った。The above aqueous solution was spray-dried with a mobile minor type spray dryer manufactured by Nilo Atomizer.
【００３２】噴霧装置は、直径５センチのロータリーデ
ィスクアトマイザーを用いた。回転数は２万ｒｐｍであ
った。造粒後の熱処理は行わなかった。As the spraying device, a rotary disk atomizer having a diameter of 5 cm was used. The rotation speed was 20,000 rpm. No heat treatment was performed after granulation.
【００３３】得られた微粒子は、最大粒径３０μｍ、平
均粒径１４．３μｍであった。The resulting fine particles had a maximum particle size of 30 μm and an average particle size of 14.3 μm.
【００３４】また、電子顕微鏡での観察では、粒子の表
面はなめらかであるが、大きな陥没が数箇所に見られ
た。この微粒子は速やかに水に溶けた。In addition, in the observation with an electron microscope, although the surface of the particle was smooth, large depressions were found at several places. The fine particles quickly dissolved in water.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【発明の効果】本発明は簡略な製造方法で、水可溶分の
少ない、水不溶性で表面がなめらかで一部陥没のある、
コーティングフィラーとして有用な多糖類の微粒子を製
造できる。INDUSTRIAL APPLICABILITY The present invention is a simple manufacturing method, has a low water-soluble content, is water-insoluble, has a smooth surface and is partially depressed.
Microparticles of polysaccharide useful as a coating filler can be produced.
Claims (1)
橋剤とを溶解した水溶液を噴霧乾燥して造粒し、得られ
た粒子を熱処理して架橋し水に不溶化することを特徴と
する微粒子の製造方法。1. An aqueous solution in which a water-soluble polysaccharide and a reactive resin or a water-soluble cross-linking agent are dissolved is spray-dried to be granulated, and the obtained particles are heat-treated to cross-link and insolubilize in water. Method for producing fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18792894A JP3267060B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18792894A JP3267060B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0827277A true JPH0827277A (en) | 1996-01-30 |
| JP3267060B2 JP3267060B2 (en) | 2002-03-18 |
Family
ID=16214654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18792894A Expired - Fee Related JP3267060B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3267060B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006051950A1 (en) * | 2004-11-15 | 2006-05-18 | Shiseido Co., Ltd. | Method for producing crosslinked hyaluronic acid gel |
| WO2009099120A1 (en) | 2008-02-06 | 2009-08-13 | Toray Industries, Inc. | Aqueous dispersion containing polysaccharide particulate gel and method for producing the same |
-
1994
- 1994-07-19 JP JP18792894A patent/JP3267060B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006051950A1 (en) * | 2004-11-15 | 2006-05-18 | Shiseido Co., Ltd. | Method for producing crosslinked hyaluronic acid gel |
| JPWO2006051950A1 (en) * | 2004-11-15 | 2008-05-29 | 株式会社資生堂 | Method for producing crosslinked hyaluronic acid gel |
| JP4875988B2 (en) * | 2004-11-15 | 2012-02-15 | 株式会社 資生堂 | Method for producing crosslinked hyaluronic acid gel |
| WO2009099120A1 (en) | 2008-02-06 | 2009-08-13 | Toray Industries, Inc. | Aqueous dispersion containing polysaccharide particulate gel and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3267060B2 (en) | 2002-03-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |