JPH06183955A - Medicine coated with modified waxy fine powder and its production - Google Patents

Medicine coated with modified waxy fine powder and its production

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Publication number
JPH06183955A
JPH06183955A JP5692593A JP5692593A JPH06183955A JP H06183955 A JPH06183955 A JP H06183955A JP 5692593 A JP5692593 A JP 5692593A JP 5692593 A JP5692593 A JP 5692593A JP H06183955 A JPH06183955 A JP H06183955A
Authority
JP
Japan
Prior art keywords
fine powder
waxy
medicine
drug
wax
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
Application number
JP5692593A
Other languages
Japanese (ja)
Other versions
JPH0696517B2 (en
Inventor
Masamichi Kohitsu
櫃 正 道 小
Masumi Koishi
石 真 純 小
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Priority to JP5692593A priority Critical patent/JPH0696517B2/en
Publication of JPH06183955A publication Critical patent/JPH06183955A/en
Publication of JPH0696517B2 publication Critical patent/JPH0696517B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To obtain a medicine, capable of regulating the surface properties thereof and optionally changing the initial release rate of the contained medicine and coated with surface treated waxy fine powder. CONSTITUTION:This powdery medicine is obtained by coating the surface of a medicine with modified waxy fine powder prepared by depositing hydrophilic colloidal particles on the surface layer of waxy fine powder, composed of one or two or more waxy substances capable of melting or softening at a temperature within the range of 30-180 deg.C and having 0.1-1000mum particle diameter. Thereby, the initial release rate of the medicine is controlled. Furthermore, a granulated substance or a molded body such as a tablet is provided.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】本発明はワックスコーティング剤で被覆さ
れた薬物又は薬剤の粉末、造粒物又は錠剤等の成型体及
びその製造法に関するものである。従来から行なわれて
いるワックスコーティング法は、予め適当な有機溶剤に
ワックス状物質を溶解し、これを流動或いは転動してい
る物質にスプレーする方法であった。
The present invention relates to a drug or drug powder coated with a wax coating agent, a molded product such as a granulated product or a tablet, and a method for producing the same. The conventional wax coating method has been a method of previously dissolving a wax-like substance in an appropriate organic solvent and spraying the substance on a fluid or rolling object.

【0002】この方法を用いると、溶剤の残留、薬物の
変性等多くの問題点がある。又、用いたワックス状物質
は疎水性で、単一の物性しか有していない。従って、ワ
ックスの表面性質の改質によって、ワックス状物質のよ
り広範囲な有効利用が可能になる。表面改質の技法は、
一般に化学的、物理化学的又は物理的(機械的)処理に
よる技法に大別されるが、以下の6技法がある。 (1)コーティングによる改質、(2)トポケミカルな
改質、(3)メカノケミカルな改質、(4)カプセル化
による改質、(5)高エネルギーの利用による改質、
(6)沈澱反応による改質。
When this method is used, there are many problems such as residual solvent and denaturation of drug. The wax-like substance used is hydrophobic and has only one physical property. Therefore, the modification of the surface properties of the wax enables a wider range of effective utilization of the wax-like substance. The surface modification technique is
Generally, it is roughly classified into a technique by chemical, physicochemical or physical (mechanical) treatment, and there are the following 6 techniques. (1) Modification by coating, (2) Modification by topochemical, (3) Modification by mechanochemical, (4) Modification by encapsulation, (5) Modification by using high energy,
(6) Modification by precipitation reaction.

【0003】本発明者は、コロイドを用いて改質する、
トポケミカルな改質法と沈澱反応による改質法の原理を
組合せた複合的技法による表面処理の方法を検討した。
その結果、従来にみられない、優れた特性のワックスコ
ーティング剤を見出し種々検討の結果、このワックスコ
ーティング剤で被覆された薬物又は薬剤の粉末、造粒物
又は錠剤等の成型体及びその製造法に関する発明を完成
するに至った。
The present inventor uses a colloid to modify,
The surface treatment method by the composite technique which combined the principles of the topochemical modification method and the modification method by precipitation reaction was investigated.
As a result, the inventors have found a wax coating agent having excellent properties that has not been found in the past, and as a result of various studies, a powdered product of a drug or drug coated with this wax coating agent, a molded product such as a granulated product or a tablet, and a method for producing the same. It came to complete the invention concerning.

【0004】本発明について更に詳しく説明する。即
ち、一種類又は二種類以上のワックス状物質からなる単
品又は混合のワックス状物質を粉砕、微粉末化する。次
に、このワックス性微粉末を、親水性コロイド、例えば
シリカゾル又はシリカゾルの粒子の表面を水溶性高分子
で処理したシリカゾル或いは水溶性高分子とシリカゾル
との複合体のコロイド溶液で、表面処理した後、乾燥す
る。
The present invention will be described in more detail. That is, a single or mixed wax-like substance composed of one kind or two or more kinds of wax-like substances is crushed and made into fine powder. Next, the waxy fine powder was surface-treated with a hydrophilic colloid, for example, a silica sol or a silica sol in which the surface of particles of silica sol was treated with a water-soluble polymer or a colloidal solution of a complex of a water-soluble polymer and silica sol. After that, it is dried.

【0005】次に、この表面処理したワックス性微粉末
を用いて、薬物又は薬物を含有する薬剤の粉末、造粒物
又は錠剤等の表面を被覆するものである。このようにし
て、表面処理したワックス性微粉末によって被覆された
剤形は、その表面性質が変わることにより、含有薬物の
初期放出速度が変化することを見出した。
Next, the surface-treated waxy fine powder is used to coat the surface of powder, granules or tablets of a drug or a drug containing the drug. In this way, it was found that the dosage form coated with the surface-treated fine waxy powder changes the initial release rate of the contained drug by changing the surface property.

【0006】即ち、この表面処理したワックス性微粉末
によって被覆された剤形の表面層は、被覆するワックス
性微粉末間に形成された空隙部分によって多数の曲路が
形成される。これが毛細管となって、細孔制御ができ、
薬物の初期放出速度に著しい影響を与えることによるも
のと推測される。
That is, in the surface layer of the dosage form coated with the surface-treated waxy fine powder, a large number of curved paths are formed by the void portions formed between the waxy fine powders to be coated. This becomes a capillary tube and the pores can be controlled,
It is speculated that this is due to a significant influence on the initial release rate of the drug.

【0007】又、親水性の低いワックス性微粉末の表面
に親水性の高いシリカサイトが多数沈積することによ
り、ワックス性微粉末の表面層の親水・疎水のバランス
を変化させることが可能になった。更に、ワックス性微
粉末の表面上に沈積したシリカサイトの密度を、シリカ
ゾル類の添加条件(例えば、添加と混合の時間、添加
量、添加濃度、添加、混合後の後処理条件)を変えるこ
とにより、調節することが可能になったので、ワックス
性微粉末の表面の親水−疎水のバランスの調節が可能に
なった。
Further, by depositing a large number of highly hydrophilic silica sites on the surface of the waxy fine powder having a low hydrophilicity, it becomes possible to change the hydrophilic / hydrophobic balance of the surface layer of the waxy fine powder. It was Further, the density of silica sites deposited on the surface of the waxy fine powder should be changed by changing the addition conditions of silica sols (eg, addition and mixing time, addition amount, addition concentration, addition and post-treatment conditions after mixing). As a result, it became possible to adjust the hydrophilic-hydrophobic balance on the surface of the waxy fine powder.

【0008】ワックス状物質は、30〜180℃の温度
範囲で融解又は軟化するものが好ましい。これらワック
ス性物質の例としては、脂肪、蝋、脂肪酸、脂肪酸エス
テル、脂肪酸塩、脂肪族高級エステル、脂肪族高級アル
コール、多価アルコール等の固形の脂蝋状物質、例えば
エチレンオキサイド重合物、塩化ビニール重合物等の熱
可塑性高分子物質又は糖類の脂肪酸エステル等が挙げら
れる。
The waxy substance preferably melts or softens in the temperature range of 30 to 180 ° C. Examples of these waxy substances include solid fatty wax-like substances such as fats, waxes, fatty acids, fatty acid esters, fatty acid salts, higher aliphatic esters, higher aliphatic alcohols and polyhydric alcohols, for example, ethylene oxide polymer, chloride. Examples thereof include thermoplastic polymer substances such as vinyl polymers and fatty acid esters of sugars.

【0009】脂肪としては、カカオ脂、牛脂、豚脂、ラ
ノリン等がある。その他、アセトグリセライド、ワセリ
ン、固形パラフィン、天然樹脂、ポリフェノール類も使
用できる。蝋物質としては、黄蝋、鯨蝋、白蝋、木蝋、
カルナバ蝋等が挙げられる。脂肪酸としては、ステアリ
ン酸、パルミチン酸、ラウリン酸等の高級脂肪酸ならば
何れも用いうる。
The fat includes cocoa butter, beef tallow, lard, lanolin and the like. In addition, acetoglyceride, petrolatum, solid paraffin, natural resins and polyphenols can be used. As wax substances, yellow wax, spermaceti, white wax, wood wax,
Carnauba wax and the like can be mentioned. As the fatty acid, any higher fatty acid such as stearic acid, palmitic acid and lauric acid can be used.

【0010】脂肪酸エステルとしては、グリセリンモノ
ステアレート、グリセリンジステアレート、グリセリン
モノパルミテート等の高級脂肪酸のグリセリンエステル
等がある。脂肪酸塩としては、ステアリン酸カルシウ
ム、ステアリン酸マグネシウム等がある。
Examples of the fatty acid ester include glycerin esters of higher fatty acids such as glycerin monostearate, glycerin distearate and glycerin monopalmitate. Examples of fatty acid salts include calcium stearate and magnesium stearate.

【0011】高級アルコールとしては、ラウリルアルコ
ール、セチルアルコール、ステアリルアルコール等があ
る。多価アルコールとしては、マンニット、ソルビッ
ト、蔗糖等がある。熱可塑性高分子物質としては、塩化
ビニール重合物のようなビニール樹脂、メタアクリル酸
重合物のようなアクリル酸樹脂、スチレン重合物のよう
なスチレン樹脂、エチルセルロースのようなセルローズ
誘導体、エチレンオキサイド重合物等がある。
Examples of higher alcohols include lauryl alcohol, cetyl alcohol and stearyl alcohol. Examples of polyhydric alcohols include mannitol, sorbit, sucrose and the like. Examples of the thermoplastic polymer substance include vinyl resin such as vinyl chloride polymer, acrylic resin such as methacrylic acid polymer, styrene resin such as styrene polymer, cellulose derivative such as ethyl cellulose, ethylene oxide polymer. Etc.

【0012】又、以上の重合物、糖類脂肪酸エステル等
の固形の界面活性剤等も挙げられる。前記のワックス状
物質は、単独はもとより2種以上の物質を選択使用する
こともできる。これらワックス状物質の微粉末化後の微
粉末の粒径は、0.1〜1000μであり、1〜100
μが好ましい。
Further, the above-mentioned polymers, solid surfactants such as saccharide fatty acid esters and the like can also be mentioned. The wax-like substance may be used alone or in combination of two or more. The particle size of the fine powder after finely powdering these wax-like substances is 0.1 to 1000 μm, and is 1 to 100 μm.
μ is preferred.

【0013】親水性コロイドとしてはシリカゾル、又は
シリカゾルのシリカ粒子の表面を水溶性高分子で処理し
たシリカゾル或いはシリカゾルと水溶性高分子のコロイ
ド溶液が挙げられる。シリカゾルとしては、粒子径が3
〜100mμ、SiO2 濃度が0.1〜50重量%で、
且つSiO2 /Na2 O(モル比)が50〜2000で
あるシリカゾルであり、水又は含水のメタノール、エタ
ノール、プロパノール、ブタノールを溶媒とするシリカ
ゾルでよく、実例としてスノーテックス〔日産化学工業
(株)製〕がある。
Examples of the hydrophilic colloid include silica sol, silica sol obtained by treating the surface of silica particles of silica sol with a water-soluble polymer, or a colloid solution of silica sol and a water-soluble polymer. The particle size of silica sol is 3
~100Emumyu, of SiO 2 concentration of 0.1 to 50 wt%,
Further, it is a silica sol having a SiO 2 / Na 2 O (molar ratio) of 50 to 2000, and may be a silica sol using water, water-containing methanol, ethanol, propanol or butanol as a solvent, and Snowtex [Nissan Chemical Industry Co., Ltd. ) Made.

【0014】シリカゾルのシリカ粒子の表面を水溶性高
分子で処理したシリカゾル或いはシリカゾルと水溶性高
分子のコロイド溶液は、前記シリカゾルにポリビニルア
ルコール、ポリビニルピロリドン、ヒドロキシプロピル
セルロース、ヒドロキシプロピルメチルセルロース、セ
ルロースアセテートフタレート、ポリエチレングリコー
ル等を混合処理したものであり、添加量としてはSiO
2 100重量部に対し0.1から50重量部であり、好
ましくは2〜15重量部である。
A silica sol in which the surface of silica particles of silica sol is treated with a water-soluble polymer or a colloidal solution of silica sol and a water-soluble polymer is prepared by adding polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropylcellulose, hydroxypropylmethylcellulose, cellulose acetate phthalate to the silica sol. , Polyethylene glycol, etc. are mixed and treated.
2 0.1 to 50 parts by weight, preferably 2 to 15 parts by weight, based on 100 parts by weight.

【0015】ワックス性微粉末に親水性コロイドを処理
する時の温度は、ワックス性微粉末が融合又は著しく変
形しない範囲の温度である必要があり、使用するワック
スの融点又は軟化点によって異なる。通常は、0℃から
使用するワックス性微粉末が融合又は著しく変形しない
範囲の温度であり、15℃からワックス性微粉末が融合
又は著しく変形しない範囲の温度が好ましい。
The temperature at which the waxy fine powder is treated with the hydrophilic colloid needs to be within a range in which the waxy fine powder is not fused or significantly deformed, and depends on the melting point or softening point of the wax used. Usually, the temperature is from 0 ° C. to a range in which the waxy fine powder to be used is not fused or significantly deformed, and a temperature in a range from 15 ° C. to a range in which the waxy fine powder is not fused or significantly deformed is preferable.

【0016】このように、表面処理したワックス性微粉
末は、ワックス性微粉末が融合又は著しく変形しない範
囲の温度で、過剰の水溶液が除去された後、通常の乾燥
法、例えば風乾、向流乾燥、減圧乾燥等により乾燥さ
れ、微粉末となる。次に、表面処理次いで乾燥処理され
たワックス性微粉末で、薬物又は薬物を含有する剤形の
粉末、造粒物又は錠剤等の表面を被覆するに際しての条
件は、下記の如くである。
As described above, the surface-treated waxy fine powder is removed by removing the excess aqueous solution at a temperature within a range where the waxy fine powder does not coalesce or is not significantly deformed, and then a usual drying method such as air drying or countercurrent flow. It is dried by drying, reduced pressure drying, etc., and becomes a fine powder. Next, the conditions for coating the surface of a drug, a powder of a drug-containing dosage form, a granulated product, a tablet, or the like with a waxy fine powder that has been surface-treated and then dried are as follows.

【0017】即ち、温度はワックス性微粉末が融合しな
い範囲の温度であり、上記剤形との混合方法は常法によ
る。尚、一度上記の方法により被覆した後、加熱によ
り、被覆されたワックス性微粉末をお互いに半融合させ
た後、再度上記の方法により被覆することもある。本発
明の内容を、下記の実施例により更に詳しく説明する。 実施例1 転動造粒法で調製した粒子径1〜2mmのアスピリン含
有乳糖粒100gと参考1、2、3又は4の方法で処理
された粉末10gとを径が100mmの遠心回転皿型方
式の混合器:メルカプトMM−10型(岡田精工製)に
入れ、内皿の回転速度500r.p.mとし、20分間
室温で混合した。
That is, the temperature is within a range in which the waxy fine powder is not fused, and the mixing method with the above dosage form is a conventional method. In some cases, once the above-mentioned method is used for coating, the waxy fine powders thus coated are semi-fused with each other by heating and then coated again by the above-mentioned method. The contents of the present invention will be described in more detail by the following examples. Example 1 100 g of aspirin-containing lactose granules having a particle diameter of 1 to 2 mm prepared by the tumbling granulation method and 10 g of powder treated by the method of Reference 1, 2, 3 or 4 have a diameter of 100 mm and are a centrifugal rotating dish type system. Mixer: Put in a mercapto MM-10 type (made by Okada Seiko), and rotate the inner plate at a rotation speed of 500 r. p. m and mixed for 20 minutes at room temperature.

【0018】上記処理された乳糖粒を100kg/cm
2 の条件で打錠し、打錠した試料表面に対し水0.1m
lの液滴を付着させ、常法により接触角を測定した。参
考例1、2、3、4で得られた表面処理したワックス性
微粉末により処理された上記乳糖粒の接触角はそれぞれ
70°、65°、55°、85°であった。 比較例1 実施例1において、参考例1、2、3、4におけるコロ
イド処理を行わない他は、同様に処理した乳糖粒に対す
る接触角はそれぞれ110°、105°、110°、1
20°であった。 参考例1 平均粒子径64mμ、SiO2 含量20重量%、SiO
2 /Na2 O(モル比)が165であるシリカゾル15
mlを水で希釈し、3.0重量%のゾル分散液100m
lとする。
100 kg / cm of the treated lactose granules
Tableted under the conditions of 2 and water 0.1m against the tableted sample surface
l droplets were attached and the contact angle was measured by a conventional method. The contact angles of the lactose particles treated with the surface-treated waxy fine powders obtained in Reference Examples 1, 2, 3, and 4 were 70 °, 65 °, 55 °, and 85 °, respectively. Comparative Example 1 In Example 1, the contact angles for lactose granules treated in the same manner as in Reference Examples 1, 2, 3 and 4 were 110 °, 105 °, 110 ° and 1 °, respectively.
It was 20 °. Reference Example 1 Average particle size 64 mμ, SiO 2 content 20% by weight, SiO
Silica sol 15 having a 2 / Na 2 O (molar ratio) of 165
100 ml of sol dispersion liquid of 3.0% by weight diluted with water
Let l.

【0019】平均粒子径15μのカルナウバ蝋10g
に、上記ゾル分散液を10ml宛3〜5回に分けて加
え、各回ごとに良く練合しペースト状とする。残りのゾ
ル分散液を全部加え、更に30分間かき混ぜカルナウバ
蝋が十分に液中分散されたサスペンションとする。この
操作の後、濾過し、過剰の水溶液を除去した後、風乾し
た。 参考例2 重量比3:1のカルナウバ蝋とステアリルアルコールの
均質な混合溶融混合物を粉砕し、平均粒子径15μの粉
末を得た。
10 g of carnauba wax having an average particle diameter of 15 μ
The above sol dispersion is added to 10 ml in 3 to 5 times, and kneaded well at each time to form a paste. All of the remaining sol dispersion liquid is added, and the mixture is stirred for another 30 minutes to prepare a suspension in which carnauba wax is sufficiently dispersed in the liquid. After this operation, the mixture was filtered to remove excess aqueous solution and then air dried. Reference Example 2 A homogeneous mixed melt mixture of carnauba wax and stearyl alcohol in a weight ratio of 3: 1 was pulverized to obtain a powder having an average particle diameter of 15μ.

【0020】この粉末に参考例1と同様の処理を行っ
た。 参考例3 平均粒子径64mμ、SiO2 含量20重量%、SiO
2 /Na2 O(モル比)が165であるシリカゾル10
0gに平均分子量40,000であるポリビニルピロリ
ドンの10%水溶液25gを撹拌下に添加し、ポリビニ
ルピロリドンにより処理されたシリカゾルを用意した。
This powder was treated in the same manner as in Reference Example 1. Reference Example 3 Average particle size 64 mμ, SiO 2 content 20% by weight, SiO
Silica sol 10 having a 2 / Na 2 O (molar ratio) of 165
25 g of a 10% aqueous solution of polyvinylpyrrolidone having an average molecular weight of 40,000 was added to 0 g under stirring to prepare a silica sol treated with polyvinylpyrrolidone.

【0021】このゾル18.8gに水を添加して、3.
0wt%のゾル分散液100mlを調整した後、参考例
1と同様にして、平均粒子径15μのカルナウバ蝋10
gを処理した。 参考例4 平均粒子径15μのステアリン酸カルシウム10gに参
考例1と同様の処理を行った。
Water was added to 18.8 g of this sol, and 3.
After preparing 100 ml of 0 wt% sol dispersion, carnauba wax 10 having an average particle size of 15 μm was prepared in the same manner as in Reference Example 1.
g were processed. Reference Example 4 10 g of calcium stearate having an average particle diameter of 15 μm was treated in the same manner as in Reference Example 1.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 30〜180℃の温度範囲で融解又は軟
化するワックス状物質の一種又は二種以上から成り、粒
径が0.1〜1000μであるワックス性微粉末の表面
層に、親水性コロイドの粒子が沈積している変性したワ
ックス性微粉末により、表面が被覆され、薬物の初期放
出速度が制御された薬剤の粉末、造粒物又は錠剤等の成
型体。
1. A surface layer of a waxy fine powder having a particle size of 0.1 to 1000 μm, which is composed of one or more wax-like substances which melt or soften in the temperature range of 30 to 180 ° C., and is hydrophilic. A molded product such as a powder, a granule or a tablet of a drug, the surface of which is coated with a modified waxy fine powder in which colloidal particles are deposited and the initial release rate of the drug is controlled.
【請求項2】 30〜180℃の温度範囲で融解又は軟
化するワックス状物質の一種又は二種以上から成り、粒
径が0.1〜1000μであるワックス性微粉末の表面
層に、親水性コロイドの粒子が沈積している変性したワ
ックス性微粉末を用いて、薬剤の表面を被覆し、薬剤の
初期放出速度が制御された薬物の粉末、造粒物又は錠剤
等の成型体の製造法。
2. A waxy fine powder having a particle diameter of 0.1 to 1000 μm, which is composed of one or more wax-like substances which melt or soften in the temperature range of 30 to 180 ° C., has a hydrophilic property on the surface layer. A method for producing a molded body such as a powder of a drug, a granule, or a tablet, in which the surface of the drug is coated with a modified waxy fine powder in which colloidal particles are deposited to control the initial release rate of the drug. .
JP5692593A 1993-03-17 1993-03-17 Drug coated with modified waxy fine powder and method for producing the same Expired - Lifetime JPH0696517B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5692593A JPH0696517B2 (en) 1993-03-17 1993-03-17 Drug coated with modified waxy fine powder and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5692593A JPH0696517B2 (en) 1993-03-17 1993-03-17 Drug coated with modified waxy fine powder and method for producing the same

Publications (2)

Publication Number Publication Date
JPH06183955A true JPH06183955A (en) 1994-07-05
JPH0696517B2 JPH0696517B2 (en) 1994-11-30

Family

ID=13041082

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5692593A Expired - Lifetime JPH0696517B2 (en) 1993-03-17 1993-03-17 Drug coated with modified waxy fine powder and method for producing the same

Country Status (1)

Country Link
JP (1) JPH0696517B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040010A1 (en) * 2000-10-24 2002-05-23 Ajinomoto Co.,Inc. Nateglinide-containing hydrophilic drug preparations

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040010A1 (en) * 2000-10-24 2002-05-23 Ajinomoto Co.,Inc. Nateglinide-containing hydrophilic drug preparations
JPWO2002040010A1 (en) * 2000-10-24 2004-06-03 味の素株式会社 Nateglinide-containing hydrophilic pharmaceutical preparation

Also Published As

Publication number Publication date
JPH0696517B2 (en) 1994-11-30

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