JPH0653827B2 - Water-soluble cellulose derivative composition - Google Patents
Water-soluble cellulose derivative compositionInfo
- Publication number
- JPH0653827B2 JPH0653827B2 JP63092486A JP9248688A JPH0653827B2 JP H0653827 B2 JPH0653827 B2 JP H0653827B2 JP 63092486 A JP63092486 A JP 63092486A JP 9248688 A JP9248688 A JP 9248688A JP H0653827 B2 JPH0653827 B2 JP H0653827B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble cellulose
- cellulose derivative
- viscosity
- soluble
- 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.)
- Expired - Lifetime
Links
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D9/00—Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
- E21D9/06—Making by using a driving shield, i.e. advanced by pushing means bearing against the already placed lining
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D9/00—Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
- E21D9/06—Making by using a driving shield, i.e. advanced by pushing means bearing against the already placed lining
- E21D9/0642—Making by using a driving shield, i.e. advanced by pushing means bearing against the already placed lining the shield having means for additional processing at the front end
- E21D9/0678—Adding additives, e.g. chemical compositions, to the slurry or the cuttings
Landscapes
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Excavating Of Shafts Or Tunnels (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、水に易溶性のセルロース誘導体組成物に関す
るものである。The present invention relates to a water-soluble cellulose derivative composition.
【従来の技術】 （背景） 一般に、カルボキシメチルセルロースナトリウム（以下
ＣＭＣと略す；以下同様）、メチルセルロース（Ｍ
Ｃ）、ヒドロキシエチルセルロース（ＨＥＣ）などの水
溶性セルロース誘導体は、水に対する分散性が悪いため
水中へ投入したとき継粉（ママコ）になり易く、このた
め、水に溶解しようとする際には、充分撹拌しながら少
量ずつ添加しなければならないという欠点がある。 （従来技術の問題点） そこで、従来から継粉の発生を防止する方法が種々研究
され、その一つに水溶性セルロース誘導体をグリオキザ
ールで処理する方法があるが、この処理には非常に手数
がかかり、かつ媒質である水のpHをアルカリ側にしなけ
れば完全な溶解は望めない。加えて、添加成分のグリオ
キザール自体、食品添加物として好ましいものではな
い。これらの理由から、グリオキザール処理物は食品添
加物用として自ずと制限を受ける結果となる。 また、継粉の発生を防止する別の方法として、水溶性セ
ルロース誘導体の一種であるＣＭＣを熱処理することに
より水分散性を向上させる手段が報告されている。この
方法は、遊離のカルボキシル基の加熱処理によってエス
テル結合を生成させることを特徴としているため、水溶
液のpHが酸性側になり易い。このため、食品添加物基準
の定めるpH 6.0〜8.5 に適合させるためには、例えばpH
調整などの煩雑な操作を必要とする。加えて、この方法
は、非イオン性セルロース誘導体には適応できないとい
う欠点を持つ。 このように、これまで種々の水易溶性セルロース誘導体
が開発されてきたが、従来技術で得られる水易溶性セル
ロース誘導体は、調製のため煩雑な操作を必要とするの
みでなく、用途的にも制限を受けるものであった。(Background) Generally, sodium carboxymethylcellulose (hereinafter abbreviated as CMC; the same applies hereinafter), methylcellulose (M
Water-soluble cellulose derivatives such as C) and hydroxyethyl cellulose (HEC) are poor in dispersibility in water and are liable to become powdered powder (Mamako) when added to water. Therefore, when trying to dissolve in water, It has a drawback that it must be added little by little with sufficient stirring. (Problems of the prior art) Therefore, various methods have been conventionally studied for preventing the generation of powder, and one of them is a method of treating a water-soluble cellulose derivative with glyoxal, which is very troublesome. Complete dissolution cannot be expected unless the pH of the water, which is a medium, is set to the alkaline side. In addition, glyoxal itself, which is an additive component, is not preferable as a food additive. For these reasons, the treated glyoxal is naturally limited as a food additive. Further, as another method for preventing the generation of powdered powder, a means for improving the water dispersibility by heat treatment of CMC, which is a kind of water-soluble cellulose derivative, has been reported. Since this method is characterized in that an ester bond is generated by heat treatment of a free carboxyl group, the pH of the aqueous solution tends to be acidic. Therefore, in order to comply with the pH 6.0-8.5 set by the food additive standards, for example, pH
It requires complicated operations such as adjustment. In addition, this method has the disadvantage that it is not applicable to nonionic cellulose derivatives. As described above, various water-soluble cellulose derivatives have been developed so far, but the water-soluble cellulose derivatives obtained by the conventional techniques not only require complicated operations for preparation, but also in use. It was subject to restrictions.
以上の事情に鑑み、本発明が解決しようとする課題は、
調製が簡単で、しかも用途的にも制限のない水易溶性セ
ルロース誘導体を提供することである。In view of the above circumstances, the problems to be solved by the present invention include
An object of the present invention is to provide a readily water-soluble cellulose derivative which is easy to prepare and has no limitation in use.
（概要） 以上の課題を解決するため、本発明に係る水易溶性セル
ロース誘導体組成物は、高粘度水溶性セルロース誘導体
と、ＢＭ型粘度計を用い、濃度１％、３０ｒｐｍ、２５
℃の条件で測定したときの低粘度水溶性セルロース誘導
体の粘度が、同条件で測定した高粘度水溶性セルロース
誘導体の粘度の１／５０以下である低粘度水溶性セルロ
ース誘導体との粉末状混合物（高粘度水溶性セルロース
誘導体と低粘度水溶性セルロース誘導体の重量比配合割
合は、５：９５〜９５：５）であることを特徴とする。 （水溶性セルロース誘導体） 本発明に用いる水溶性セルロース誘導体は、セルロース
中に含まれる水酸基を種々の化学的残基で置換したもの
であって、その主なものとしては、上記ＣＭＣの他、例
えばＭＣ、ＨＥＣ、ヒドロキシプロピルセルロース（Ｈ
ＰＣ）等を挙げることができるが、水溶性を有するもの
である限り別段例示のもののみに限られるものではな
く、かつ、これらのグルコース当りの置換度又は置換モ
ル数にも限定されるものではない。 （配合比及び粘度差） 本発明によれば、種々の高粘度水溶性セルロース誘導体
と低粘度水溶性セルロース誘導体とを、単に粉末状態で
混合するだけで得られた組成物が対象水溶性セルロース
誘導体の種類は問わず水易溶性となる。発明者の知見に
よれば、一般に高粘度水溶性セルロース誘導体と低粘度
水溶性セルロース誘導体との間の粘度比が大きければ大
きい程組成物の水易溶性が増加する傾向にある。殊に発
明目的上、ＢＭ型粘度計を用い測定したときの１％水溶
液粘度において、低粘度水溶性セルロース誘導体の粘度
が、高粘度水溶性セルロース誘導体のそれに対して1/50
以下であることが望ましい。かつこの際、両セルロース
誘導体の配合比は任意であるが、比が一方に偏ると配合
割合の多い方のセルロース誘導体単品としての性能しか
現れなくなり、水易溶性が失われて継粉を形成するよう
になる。従って、実用上の見地から、高粘度水溶性セル
ロース誘導体と低粘度水溶性セルロース誘導体の配合割
合は、５：95〜95：５（重量比）の範囲、殊に20：80〜
80：20の範囲が最も好ましい。なお、高粘度水溶性セル
ロース誘導体と低粘度水溶性誘導体は、同種のものでも
異種のものでも同様の効果を期待できる。 （用途） 本発明に係る水易溶性セルロース誘導体組成物は、既に
水溶性セルロース誘導体が使用されている分野、例え
ば、土木ボーリング用泥水増粘安定化剤、釉薬安定化
剤、シャンプー、リンス等の安定化剤、乳飲料等の食品
用増粘剤、錠剤用崩壊剤、パップ剤、繊維壁用糊剤、飼
料用バインダ、染毛、歯磨等の香粧品などの分野に使用
される。但し、用途はこれらの分野に限定されない。(Outline) In order to solve the above problems, the easily water-soluble cellulose derivative composition according to the present invention uses a high-viscosity water-soluble cellulose derivative and a BM type viscometer, and has a concentration of 1%, 30 rpm, and 25 rpm.
A powdery mixture with a low-viscosity water-soluble cellulose derivative in which the viscosity of the low-viscosity water-soluble cellulose derivative when measured under the condition of 1/50 is 1/50 or less of the viscosity of the high-viscosity water-soluble cellulose derivative measured under the same condition ( The weight ratio of the high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble cellulose derivative is 5:95 to 95: 5). (Water-Soluble Cellulose Derivative) The water-soluble cellulose derivative used in the present invention is obtained by substituting hydroxyl groups contained in cellulose with various chemical residues, and the main ones thereof include the above-mentioned CMC and, for example, MC, HEC, hydroxypropyl cellulose (H
PC) and the like, but the compounds are not limited to those exemplified above as long as they have water solubility, and are not limited to the substitution degree or the substitution mole number per glucose. Absent. (Blending Ratio and Viscosity Difference) According to the present invention, a composition obtained by simply mixing various high-viscosity water-soluble cellulose derivatives and low-viscosity water-soluble cellulose derivatives in a powder state is a target water-soluble cellulose derivative. It is easily soluble in water regardless of the type. According to the knowledge of the inventor, generally, the larger the viscosity ratio between the high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble cellulose derivative, the higher the water solubility of the composition. Particularly, for the purpose of the invention, the viscosity of the low-viscosity water-soluble cellulose derivative is 1/50 of that of the high-viscosity water-soluble cellulose derivative at the viscosity of 1% aqueous solution measured by using a BM type viscometer.
The following is desirable. And at this time, the compounding ratio of both cellulose derivatives is arbitrary, but if the ratio is biased to one side, only the performance of the cellulose derivative as a single compound having a larger compounding ratio will appear, and the water-soluble property will be lost to form a flour. Like Therefore, from a practical point of view, the mixing ratio of the high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble cellulose derivative is in the range of 5:95 to 95: 5 (weight ratio), particularly 20:80 to
The range of 80:20 is most preferred. The high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble derivative may be the same or different, and similar effects can be expected. (Use) The water-soluble cellulose derivative composition according to the present invention is used in fields where water-soluble cellulose derivatives have already been used, for example, mud thickening stabilizers for civil engineering boring, glaze stabilizers, shampoos, rinses, etc. It is used in the fields of stabilizers, thickeners for foods such as milk drinks, disintegrants for tablets, poultices, pastes for fiber walls, binders for feeds, hair dyes, cosmetics such as toothpaste. However, the use is not limited to these fields.
本発明により、高粘度水溶性セルロース誘導体と低粘度
水溶性セルロース誘導体との粉末状組成物が易水溶化す
ることの理論的説明は今のところ不可能であるが、恐ら
く共存している高分子量の高粘度水溶性セルロース誘導
体と低分子量の低粘度水溶性セルロース誘導体の各分子
中の活性基同士が何らかの相互作用をし、これにより親
水性が瞬間的に低下するため継粉が生成し難くなり、全
体として水に対し易溶性となるためであろう。According to the present invention, a theoretical explanation that the powdery composition of the high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble cellulose derivative is easily water-solubilized is not possible so far, but it is presumed that the coexisting high molecular weight The active groups in each molecule of the high-viscosity water-soluble cellulose derivative of and the low-molecular-weight low-viscosity water-soluble cellulose derivative interact with each other in some way, and the hydrophilicity is instantaneously reduced, making it difficult to produce a powdered powder. , Because it is easily soluble in water as a whole.
以下、実施例及び比較列により発明を具体的に説明する
が、例示は当然説明用のものであって、発明思想の内
包、外延を画するものではない。 （実験方法） 水溶性セルロース誘導体の水にする溶解性の評価方法に
は特に定まった方法がないので、以下の方法で測定し
た。 1.5 容のビーカー中に１の水を入れ、回転式撹拌装
置により400 rpm で撹拌する。この水中にサンプルを添
加し、最高粘度に達するまでの時間を溶解所要時間とし
て、水溶性セルロース誘導体組成物の水に対する溶解性
の代表値とした。粘度はＢＭ型粘度計を用い、30rpm 、
25℃の条件で測定した。 溶解所要時間測定の際添加するサンプルの量は、イオン
性水溶性セルロース誘導体を用いた実施例１では１ｇと
し、非イオン性水溶性セルロース誘導体を用いる実施例
２及び３では10ｇとした。 実施例１〜３及び比較例１〜３ 種々のＣＭＣ粉末を表１のように種々を混合して水易容
性ＣＭＣ組成物を作り、溶解所要時間を測定、比較し
た。その結果を表２に示す。 上表２より、本発明によるＣＭＣ組成物の溶解所要時間
は、混合前の夫々同粘度の単品の溶解時間よりも短くな
っているので、発明の効果が確認される。 実施例４〜６及び比較例４〜６ 前例と同様に、下表４の通り種々のＭＣ粉末を異なった
割合で混合し、水易溶性ＭＣ組成物を作成して溶解所要
時間を測定、比較した。その結果を下表４に示す。 上表４中の実施例と比較例にのデータから、本発明によ
るＭＣ組成物の溶解所要時間は、混合前の夫々同粘度の
単品の溶解時間よりも短くなっているので、発明の効果
が確認される。 実施例７〜８及び比較例７ 次に、高粘度水溶性セルロース誘導体としてＣＭＣ、低
粘度水溶性セルロース誘導体としてＨＥＣを用い、本発
明に従って下表５の水易溶性セルロース誘導体組成物を
作成し、溶解所要時間を測定、比較した、結果を下表６
に示す。 上表６中の実施例７〜８及び比較例７より、異種の水溶
性セルロース誘導体の混合による水易溶性セルロース誘
導体組成物でも、溶解所要時間が混合前の同粘度の単品
より短くなっているので、本発明の効果は明らかであ
る。Hereinafter, the invention will be specifically described with reference to examples and comparative columns, but the exemplification is, of course, for the purpose of description, and does not depict the inclusion or extension of the inventive idea. (Experimental Method) Since there is no specific method for evaluating the solubility of the water-soluble cellulose derivative in water, the following method was used for the measurement. Add 1 water into a 1.5 volume beaker and stir at 400 rpm with a rotary stirrer. The sample was added to this water, and the time required until the maximum viscosity was reached was taken as the time required for dissolution, and was taken as the representative value of the water solubility of the water-soluble cellulose derivative composition. Use a BM type viscometer to measure the viscosity at 30 rpm,
It was measured under the condition of 25 ° C. The amount of the sample added in the measurement of the time required for dissolution was 1 g in Example 1 using the ionic water-soluble cellulose derivative, and 10 g in Examples 2 and 3 using the nonionic water-soluble cellulose derivative. Examples 1 to 3 and Comparative Examples 1 to 3 Various CMC powders were mixed as shown in Table 1 to prepare water-acceptable CMC compositions, and required dissolution times were measured and compared. The results are shown in Table 2. From Table 2 above, the time required for dissolution of the CMC composition according to the present invention is shorter than the time required for dissolution of a single product having the same viscosity before mixing, thus confirming the effect of the present invention. Examples 4 to 6 and Comparative Examples 4 to 6 As in the previous example, various MC powders were mixed at different ratios as shown in Table 4 below to prepare water-soluble MC compositions, and the time required for dissolution was measured and compared. did. The results are shown in Table 4 below. From the data of Examples and Comparative Examples in Table 4 above, the time required for dissolution of the MC composition according to the present invention is shorter than the dissolution time of individual products having the same viscosity before mixing, so that the effect of the invention is It is confirmed. Examples 7 to 8 and Comparative Example 7 Next, using CMC as the high-viscosity water-soluble cellulose derivative and HEC as the low-viscosity water-soluble cellulose derivative, water-soluble cellulose derivative compositions shown in Table 5 below were prepared according to the present invention. The time required for dissolution was measured and compared, and the results are shown in Table 6 below.
Shown in. From Examples 7 to 8 and Comparative Example 7 in Table 6 above, even in the easily water-soluble cellulose derivative composition obtained by mixing different water-soluble cellulose derivatives, the time required for dissolution is shorter than that of a single product having the same viscosity before mixing. Therefore, the effect of the present invention is clear.
本発明によれば、調製が簡単で、しかも用途的にも制限
のない水易溶性のセルロース誘導体を提供することがで
きるので、関係産業界に多大の貢献を成し得る。According to the present invention, it is possible to provide a water-soluble cellulose derivative which is easy to prepare and has no limitation in use. Therefore, it can make a great contribution to the related industries.
Claims (1)
粘度計を用い、濃度１％、３０ｒｐｍ、２５℃の条件で
測定したときの低粘度水溶性セルロース誘導体の粘度
が、同条件で測定した高粘度水溶性セルロース誘導体の
粘度の１／５０以下である低粘度水溶性セルロース誘導
体との粉末状混合物（高粘度水溶性セルロース誘導体と
低粘度水溶性セルロース誘導体の重量比配合割合は、
５：９５〜９５：５）であることを特徴とする水易溶性
セルロース誘導体組成物。1. A high-viscosity water-soluble cellulose derivative and a viscosity of a low-viscosity water-soluble cellulose derivative when measured under the conditions of a concentration of 1%, 30 rpm and 25 ° C. using a BM type viscometer. A powdery mixture with a low-viscosity water-soluble cellulose derivative which is 1/50 or less of the viscosity of the high-viscosity water-soluble cellulose derivative (the weight ratio mixing ratio of the high-viscosity water-soluble cellulose derivative and the low-viscosity water-soluble cellulose derivative is
5:95 to 95: 5), which is a water-soluble cellulose derivative composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092486A JPH0653827B2 (en) | 1988-04-14 | 1988-04-14 | Water-soluble cellulose derivative composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092486A JPH0653827B2 (en) | 1988-04-14 | 1988-04-14 | Water-soluble cellulose derivative composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01263132A JPH01263132A (en) | 1989-10-19 |
| JPH0653827B2 true JPH0653827B2 (en) | 1994-07-20 |
Family
ID=14055634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63092486A Expired - Lifetime JPH0653827B2 (en) | 1988-04-14 | 1988-04-14 | Water-soluble cellulose derivative composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653827B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19530077A1 (en) * | 1995-08-16 | 1997-02-20 | Wolff Walsrode Ag | Preparations from non-ionic and ionic hydrocolloids and their use as auxiliary materials for tunnel construction |
| JP4717241B2 (en) * | 2001-03-30 | 2011-07-06 | 小林製薬株式会社 | Aqueous gel composition |
| JP2008228696A (en) * | 2007-03-23 | 2008-10-02 | Taiyo Kagaku Co Ltd | Easily soluble CMC composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4846889A (en) * | 1988-02-02 | 1989-07-11 | The Dow Chemical Company | Polymeric blend useful in thin-bed mortar compositions comprising a water-soluble cellulose ether and a water-insoluble, but water-dispersible polymer |
-
1988
- 1988-04-14 JP JP63092486A patent/JPH0653827B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01263132A (en) | 1989-10-19 |
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