JP3947574B2 - Highly substituted hydroxyethyl cellulose composition - Google Patents
Highly substituted hydroxyethyl cellulose composition Download PDFInfo
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- JP3947574B2 JP3947574B2 JP27918594A JP27918594A JP3947574B2 JP 3947574 B2 JP3947574 B2 JP 3947574B2 JP 27918594 A JP27918594 A JP 27918594A JP 27918594 A JP27918594 A JP 27918594A JP 3947574 B2 JP3947574 B2 JP 3947574B2
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- Prior art keywords
- hydroxyethyl cellulose
- stearate
- composition
- substituted hydroxyethyl
- long
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 title claims description 36
- 239000004354 Hydroxyethyl cellulose Substances 0.000 title claims description 36
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 title claims description 36
- 239000000203 mixture Substances 0.000 title claims description 18
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- -1 hydroxyethyl group Chemical group 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000000314 lubricant Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004676 glycans Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、粉体流動性を改良し、アンチブロッキング性を付与した高置換度ヒドロキシエチルセルロース又はその誘導体組成物に関するものである。
【０００２】
【従来の技術】
高置換度ヒドロキシエチルセルロース又はその誘導体は、酵素の触媒作用による加水分解に対して増強された抵抗性を有し、塗料用の増粘剤や土木ボーリングでの保水剤などとして有用であることが知られている。通常このような高置換度ヒドロキシエチルセルロース又はその誘導体は、フレーク状、粉末状、粒状の形態で流通し、それぞれの用途に供される。
【０００３】
しかし、高置換度ヒドロキシエチルセルロース又はその誘導体は、流動性が低いため、製造プロセスにおいて機器内へ付着をしたり、粉砕時のシェアによる焦げ付きなどが起こりやすく、そのハンドリングが難しい。また、保存時には経時的に固化しやすいため、長期保存ができないほどの欠点を有する。
【０００４】
【発明が解決しようとする課題】
本発明は、上述のような不利を解決した粉体流動性、アンチブロッキング性の良好な高置換度ヒドロキシエチルセルロース又はその誘導体組成物の提供を目的とするものである。
【０００５】
【課題を解決するための手段】
本発明者らは上記の目的を達成するために鋭意研究した結果、高置換度ヒドロキシエチルセルロース又はその特定の誘導体に、特定の粒度と嵩を有するステアリン酸塩を滑剤として添加することにより、当該高置換度ヒドロキシエチルセルロース等の粉体流動性、アンチブロッキング性が飛躍的に向上することを見出し、本発明を完成するに至った。
【０００６】
即ち本発明は、高置換度ヒドロキシエチルセルロース又は長鎖アルキル基もしくは長鎖アルキルアリール基が導入された疎水化高置換度ヒドロキシエチルセルロース100 重量部当たり、 0.6〜2.0 重量部のステアリン酸塩を添加してなる高置換度ヒドロキシエチルセルロース組成物であって、前記高置換度ヒドロキシエチルセルロース又は長鎖アルキル基もしくは長鎖アルキルアリール基が導入された疎水化高置換度ヒドロキシエチルセルロースのヒドロキシエチル基のモル置換度（ＭＳ）が 2.5 以上であり、前記ステアリン酸塩が、75μｍメッシュ通過分が99％以上を占める粒度を有し、嵩が６〜10ml／ｇの範囲にある粉末状のステアリン酸カルシウム又はステアリン酸亜鉛である高置換度ヒドロキシエチルセルロース組成物を提供するものである。
【０００７】
本発明において、高置換度ヒドロキシエチルセルロース又はその誘導体100 重量部に対して添加されるべきステアリン酸塩の量が 2.0重量部より多くなると、高置換度ヒドロキシエチルセルロース又はその誘導体の特性が失われ、例えば、水に溶解したときの水溶液の透明性が低下するという不利があり、また 0.6重量部未満では、顕著な効果が期待されない。ステアリン酸塩の添加量は、好ましくは 1.0〜 1.5重量部の範囲である。
【０００８】
本発明の組成物を構成するヒドロキシエチルセルロース又はその誘導体は、多糖繰り返し単位当たりのヒドロキシエチル基の平均モル数であるモル置換度（ＭＳ）が 2.5以上である高置換度ヒドロキシエチルセルロース又はその誘導体であることを条件とする。ＭＳ 2.5に満たないヒドロキシエチルセルロース又はその誘導体は、本来、低流動性、ブロッキング性によるハンドリングのしにくさは確認されず、滑剤の添加の必要性がない。
【０００９】
本発明の組成物を構成する高置換度ヒドロキシエチルセルロース誘導体には、長鎖アルキル基や長鎖アルキルアリール基が導入された疎水化高置換度ヒドロキシエチルセルロースも包含される。これらの誘導体は、特公平１−２８０４２号公報や特開平３−１９７５３５号公報に記載されている。
【００１０】
粉体の流動性改良、アンチブロッキング性付与を行う滑剤としては、様々な種類のものが一般に知られているが、本発明のような高置換度ヒドロキシエチルセルロース又はその誘導体の粉体に対して有効と認められる滑剤は、ステアリン酸塩である。ステアリン酸塩としては、カルシウム塩、マグネシウム塩、アルミニウム塩、亜鉛塩などが例示される。好ましくはカルシウム塩、亜鉛塩であり、特に好ましいステアリン酸塩は、ステアリン酸カルシウムである。
【００１１】
ステアリン酸カルシウム、ステアリン酸亜鉛は、75μｍ通過分99％以上の粒度を有し、嵩が６〜10ml／ｇの範囲にあるものを使用する。ここで「嵩」とは単位質量の体積であり、比容積としても表現される。このような粒度と嵩を有するステアリン酸塩は、高置換度ヒドロキシエチルセルロースと混合した際の分散性に優れる。
【００１２】
本発明の組成物の流動性は、例えば安息角を測定することにより評価できる。本発明の組成物の安息角は40度以下であることが好ましい。
【００１３】
本発明の組成物のアンチブロッキング性は、例えば、錠剤成形用プレス機などで強制的に固化させた組成物に、くさび型のプランジャーを差し込み、その時の最大応力（硬さ）を検出することにより評価できる。最大応力（硬さ）は、式(1) に示されるhardness indexと呼ばれる無次元化した値で表現できる。
硬さ(hardness index)＝Ｈ／感度係数 … (1)
本発明の組成物において、アンチブロッキング性の指標となる硬さは10以下であることが好ましい。
【００１４】
【実施例】
以下に、実施例で本発明の説明を行うが、本発明はこれらの実施例に限定されるものではない。
【００１５】
実施例１〜２及び比較例１〜４
表１に示す高置換度ヒドロキシエチルセルロース100 重量部に対し、ステアリン酸カルシウム又はステアリン酸亜鉛を表１に示す量添加して得られた組成物の流動性の試験を行った。ステアリン酸カルシウムは、粒度が75μｍ通過分99％以上で、嵩が９ml／ｇのものを、またステアリン酸亜鉛は粒度が75μｍ通過分99％以上で、嵩が8.5 ml／ｇのものを使用した。比較例として、ＭＳ 2.5に満たないヒドロキシエチルセルロース、或いは滑剤として超微粒子状シリカを用いた試験を行った。
流動性の評価は、安息角を測定することにより行った。安息角の測定は、三輪式円筒回転法を用いた。これらの結果を表１にまとめた。
【００１６】
【表１】
実施例３〜４及び比較例５〜７
高置換度ヒドロキシエチルセルロースとして、長鎖アルキルアリール（ドデシルフェニル）化ヒドロキシエチルセルロースを用い、表２に示す滑剤を添加して実施例１と同様の評価を行なった。その結果を表２に示す。
【００１８】
【表２】
実施例５〜６及び比較例８〜11
高置換度ヒドロキシエチルセルロース又はその誘導体に対し、100 重量部に対し、ステアリン酸カルシウム又はステアリン酸亜鉛を表３に示す量添加して得られた組成物のアンチブロッキング性の試験を行った。ステアリン酸カルシウムは、粒度が75μｍ通過分99％以上で、嵩が９ml／ｇのものを、またステアリン酸亜鉛は粒度が75μｍ通過分99％以上で、嵩が8.5 ml／ｇのものを使用した。比較例として、ＭＳ 2.5に満たないヒドロキシエチルセルロース、及び滑剤として超微粒子状シリカを用いた試験を行った。
【００２０】
アンチブロッキング性の評価は以下の通り行なった。
まず、滑剤を添加したヒドロキシエチルセルロース組成物を錠剤成形用プレス機で強制的に固化させた。次に、固化組成物の硬さを、レオロユニットを計測部とする物性解析システム（飯尾電機株式会社製）を用い、テクスチャー解析と呼ばれる方法で測定した。硬さは、固化物へくさび型のプランジャーを差し込んだ時にロードセルで検出される最大応力（Ｈ）を、式(1) に示されるhardness indexと呼ばれる無次元化した値で表現した。
硬さ(hardness index)＝Ｈ／感度係数 … (1)
これらの結果を表３にまとめた。
【００２１】
【表３】
実施例７〜８及び比較例12〜14
高置換度ヒドロキシエチルセルロースとして、長鎖アルキルアリール（ドデシルフェニル）化ヒドロキシエチルセルロースを用い、表４に示す滑剤を添加して実施例３と同様の評価を行なった。その結果を表４に示す。
【００２３】
【表４】
[Industrial application fields]
The present invention relates to a highly substituted hydroxyethyl cellulose or a derivative composition thereof having improved powder flowability and imparted antiblocking properties.
[0002]
[Prior art]
Highly substituted hydroxyethylcellulose or its derivatives have enhanced resistance to enzyme-catalyzed hydrolysis and are known to be useful as thickeners for paints and water retaining agents for civil engineering boring. It has been. Usually, such a highly substituted hydroxyethyl cellulose or a derivative thereof is distributed in the form of flakes, powders, or granules, and is provided for each use.
[0003]
However, since the highly substituted hydroxyethyl cellulose or its derivative has low fluidity, it easily adheres to the equipment in the manufacturing process, or burns due to the shear during pulverization, and is difficult to handle. Moreover, since it is easy to solidify with time at the time of storage, it has a drawback that it cannot be stored for a long time.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a highly substituted hydroxyethyl cellulose or a derivative composition thereof having excellent powder flowability and antiblocking properties, which solves the above disadvantages.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have added a stearic acid salt having a specific particle size and bulk as a lubricant to a highly substituted hydroxyethyl cellulose or a specific derivative thereof. powder fluidity of such substituted hydroxypropyl ethylcellulose row scan, anti-blocking property found that remarkably improved, and have completed the present invention.
[0006]
That is, in the present invention, 0.6 to 2.0 parts by weight of stearate is added per 100 parts by weight of a highly substituted hydroxyethyl cellulose or a hydrophobized highly substituted hydroxyethyl cellulose into which a long-chain alkyl group or a long-chain alkylaryl group is introduced. A highly substituted hydroxyethyl cellulose composition comprising the above-mentioned highly substituted hydroxyethyl cellulose, or the molar substitution degree (MS) of the hydroxyethyl group of the hydrophobized high substituted hydroxyethyl cellulose into which a long-chain alkyl group or a long-chain alkylaryl group has been introduced. ) Is 2.5 or more, and the stearate is a powdered calcium stearate or zinc stearate having a particle size with a 75 μm mesh passage of 99% or more and a bulk in the range of 6 to 10 ml / g A highly substituted hydroxyethyl cellulose composition is provided.
[0007]
In the present invention, if the amount of stearate to be added to 100 parts by weight of high-substituted hydroxyethyl cellulose or a derivative thereof exceeds 2.0 parts by weight, the characteristics of the high-substituted hydroxyethyl cellulose or a derivative thereof are lost. There is a disadvantage that the transparency of the aqueous solution is lowered when dissolved in water, and if it is less than 0.6 parts by weight, a remarkable effect is not expected. The amount of stearate added is preferably in the range of 1.0 to 1.5 parts by weight.
[0008]
The hydroxyethyl cellulose or a derivative thereof constituting the composition of the present invention is a highly substituted hydroxyethyl cellulose or a derivative thereof having a molar substitution degree (MS) which is an average number of moles of hydroxyethyl groups per polysaccharide repeating unit is 2.5 or more. On the condition. Hydroxyethyl cellulose or a derivative thereof less than MS 2.5 is not inherently difficult to handle due to low fluidity and blocking properties, and does not require the addition of a lubricant.
[0009]
The highly substituted hydroxyethyl cellulose derivative constituting the composition of the present invention includes a hydrophobic high-substituted hydroxyethyl cellulose into which a long-chain alkyl group or a long-chain alkylaryl group is introduced. These derivatives are described in JP-B-1-28042 and JP-A-3-197535.
[0010]
Various types of lubricants that improve the fluidity of the powder and impart anti-blocking properties are generally known, but are effective for powders of high-substituted hydroxyethyl cellulose or its derivatives as in the present invention. A recognized lubricant is stearate. Examples of stearates include calcium salts, magnesium salts, aluminum salts, and zinc salts. Calcium salts and zinc salts are preferred, and a particularly preferred stearate is calcium stearate.
[0011]
Calcium stearate and zinc stearate have a particle size of 75% or more of 99% or more and a bulk in the range of 6 to 10 ml / g. Here, “bulk” is a volume of unit mass, and is also expressed as a specific volume. A stearate having such a particle size and bulk is excellent in dispersibility when mixed with high-substituted hydroxyethyl cellulose.
[0012]
The fluidity of the composition of the present invention can be evaluated, for example, by measuring the angle of repose. The angle of repose of the composition of the present invention is preferably 40 degrees or less.
[0013]
The anti-blocking property of the composition of the present invention is to detect the maximum stress (hardness) at that time by inserting a wedge-shaped plunger into the composition forcibly solidified by, for example, a tablet press. Can be evaluated. The maximum stress (hardness) can be expressed by a non-dimensional value called a hardness index shown in Equation (1).
Hardness index = H / sensitivity coefficient… (1)
In the composition of the present invention, the hardness that is an index of anti-blocking property is preferably 10 or less.
[0014]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
[0015]
Examples 1-2 and Comparative Examples 1-4
The fluidity test of the composition obtained by adding calcium stearate or zinc stearate in an amount shown in Table 1 to 100 parts by weight of high-substituted hydroxyethyl cellulose shown in Table 1 was conducted. Calcium stearate having a particle size of 99% or more of 75 μm passage and a bulk of 9 ml / g, and zinc stearate having a particle size of 99 μm or more of 75 μm and a bulk of 8.5 ml / g were used. As a comparative example, a test using hydroxyethyl cellulose less than MS 2.5 or ultrafine silica as a lubricant was conducted.
The fluidity was evaluated by measuring the angle of repose. The angle of repose was measured using a three-wheeled cylinder rotation method. These results are summarized in Table 1.
[0016]
[Table 1]
Examples 3-4 and Comparative Examples 5-7
A long-chain alkylaryl (dodecylphenyl) -modified hydroxyethyl cellulose was used as the high-substituted hydroxyethyl cellulose, and the same evaluation as in Example 1 was performed by adding the lubricant shown in Table 2. The results are shown in Table 2.
[0018]
[Table 2]
Examples 5-6 and Comparative Examples 8-11
The anti-blocking property of the composition obtained by adding calcium stearate or zinc stearate in an amount shown in Table 3 to 100 parts by weight of high-substituted hydroxyethyl cellulose or a derivative thereof was tested. Calcium stearate having a particle size of 99% or more of 75 μm passage and a bulk of 9 ml / g, and zinc stearate having a particle size of 99 μm or more of 75 μm and a bulk of 8.5 ml / g were used. As a comparative example, a test was conducted using hydroxyethyl cellulose less than MS 2.5 and ultrafine silica as a lubricant.
[0020]
The anti-blocking property was evaluated as follows.
First, the hydroxyethyl cellulose composition to which the lubricant was added was forcibly solidified with a tablet press. Next, the hardness of the solidified composition was measured by a method called texture analysis using a physical property analysis system (manufactured by Iio Electric Co., Ltd.) having a Leoro unit as a measurement unit. The hardness was expressed as a non-dimensional value called the hardness index shown in Equation (1), which is the maximum stress (H) detected by the load cell when a wedge-shaped plunger was inserted into the solidified product.
Hardness index = H / sensitivity coefficient… (1)
These results are summarized in Table 3.
[0021]
[Table 3]
Examples 7-8 and Comparative Examples 12-14
As high-substituted hydroxyethyl cellulose, long-chain alkylaryl (dodecylphenyl) -modified hydroxyethyl cellulose was used, and the same evaluation as in Example 3 was performed by adding the lubricant shown in Table 4. The results are shown in Table 4.
[0023]
[Table 4]
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27918594A JP3947574B2 (en) | 1994-11-14 | 1994-11-14 | Highly substituted hydroxyethyl cellulose composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27918594A JP3947574B2 (en) | 1994-11-14 | 1994-11-14 | Highly substituted hydroxyethyl cellulose composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08134102A JPH08134102A (en) | 1996-05-28 |
| JP3947574B2 true JP3947574B2 (en) | 2007-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27918594A Expired - Fee Related JP3947574B2 (en) | 1994-11-14 | 1994-11-14 | Highly substituted hydroxyethyl cellulose composition |
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| Country | Link |
|---|---|
| JP (1) | JP3947574B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7175717B2 (en) * | 2018-11-07 | 2022-11-21 | 松本油脂製薬株式会社 | Cellulose composite powder |
-
1994
- 1994-11-14 JP JP27918594A patent/JP3947574B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH08134102A (en) | 1996-05-28 |
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