JP2005205864A - Easily water-soluble cellulose ether and its production method - Google Patents
Easily water-soluble cellulose ether and its production method Download PDFInfo
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Abstract
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本発明は、水中で容易に分散して溶解する水易溶性セルロースエーテルに関するもので、特に微量のアルカリ添加により溶解する水易溶性セルロースエーテル及びその製法に関する。 The present invention relates to a readily water-soluble cellulose ether that is easily dispersed and dissolved in water, and particularly relates to a readily water-soluble cellulose ether that is dissolved by adding a small amount of alkali and a method for producing the same.
水溶性セルロースエーテルの粉末は、水に投入溶解する際に塊状物ができる。これは最初に水と接触した部分が直ちに溶解してゲル状の層で覆われ、未溶解の粉末部分内部まで水が浸透し難くなるためである（ママコ現象と呼ぶ）。
このママコ現象を防止するため、水溶性セルロースエーテルの粉末をあらかじめグリオキサールと有機酸で表面処理することにより、粒子を水中で分散状態とした後、少量のアルカリを添加し、ｐＨを８〜１０にして溶解増粘させる方法が特公昭５８−１１８８２号公報に開示されている。
In order to prevent this Mamako phenomenon, the water-soluble cellulose ether powder is surface-treated with glyoxal and an organic acid in advance to make the particles dispersed in water, and then a small amount of alkali is added to adjust the pH to 8-10. A method for dissolving and increasing the viscosity is disclosed in Japanese Patent Publication No. 58-11882.
然しながらグリオキサール自体については、労働安全衛生法の既存化学物質点検変異原性の分類で強度の変異原性が認められている。化学物質排出把握管理促進法（ＰＲＴＲ法）の第１種指定化学物質にも該当する。またシックハウス症候群に関する建築基準法施行令規制物質であるホルムアルデヒドをかなり含有している、という問題がある。
一方、グリオキザール架橋でん粉は、労働安全衛生法の既存化学物質点検変異原性の分類では該当しない。またグリオキザール付加でん粉は、米国連邦規定のＦＤＡ（米国食品衛生局）では乾燥食品と接触する紙・板紙の構成成分で無制限の使用が認可されている（２１ＣＦＲ １７６．１８０）。また水性及び油性食品と接触する紙・板紙の構成成分の場合は、全コート量に対してバインダーに対し２５％を超えない使用のみ承認されている（２１ＣＦＲ１７６．１７０）。ホルムアルデヒドは極低含有である。このような事からグリオキザール付加でん粉はグリオキサールに比べて人体、環境面への安全性が優れている。However, glyoxal itself is recognized as having strong mutagenicity in the existing chemical substance inspection mutagenicity classification of the Industrial Safety and Health Law. It also falls under Class 1 designated chemical substances under the PRTR Law. In addition, there is a problem that it contains a considerable amount of formaldehyde, a substance regulated by the Building Standard Law Enforcement Order concerning sick house syndrome.
On the other hand, glyoxal cross-linked starch does not fall under the existing chemical substance inspection mutagenicity classification of the Industrial Safety and Health Law. Glyoxal-added starch is approved for unlimited use by the US Federal Food and Drug Administration (FDA) as a constituent of paper and paperboard that comes into contact with dried food (21 CFR 176.180). In the case of paper / paperboard components that come into contact with aqueous and oil-based foods, only the use not exceeding 25% of the binder with respect to the total coating amount is approved (21 CFR 176.170). Formaldehyde is extremely low. For this reason, glyoxal-added starch is superior to glyoxal in terms of safety to the human body and the environment.
そこで上記の技術的問題を解決するために、本発明者らはグリオキサールに代えてグリオキザール付加でん粉を用いることを研究し、本発明を完成した。
すなわち、本発明の水易溶性セルロースエーテルの製法は、粉末状の水溶性セルロースエーテルに対しグリオキザール付加でん粉（グリオキザール付加デキストリン含む）で表面処理をすることを特徴とする。また本発明の水易溶性セルロースエーテルは、水溶性セルロースエーテルに対しグリオキザール付加でん粉（グリオキザール付加デキストリン含む）で処理をしたことを特徴とし、水中で容易に分散して微量のアルカリ添加で溶解するものである。In order to solve the above technical problem, the present inventors studied the use of glyoxal-added starch instead of glyoxal, and completed the present invention.
That is, the method for producing a readily water-soluble cellulose ether of the present invention is characterized in that the powdered water-soluble cellulose ether is surface-treated with glyoxal-added starch (including glyoxal-added dextrin). The water-soluble cellulose ether of the present invention is characterized in that it is treated with glyoxal-added starch (including glyoxal-added dextrin) to water-soluble cellulose ether, and is easily dispersed in water and dissolved by adding a small amount of alkali. It is.
水溶性セルロースエーテルとしてはヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、ヒドロキシエチルメチルセルロース（ＨＥＭＣ）、メチルセルロース（ＭＣ）、ヒドロキシエチルセルロース（ＨＥＣ）、カルボキシメチルセルロース（ＣＭＣ）などが使用できる。
グリオキザール付加でん粉（グリオキザール付加デキストリン含む）としては、でん粉（デキストリン含む）の−ＯＨ基にグリオキサールが架橋あるいはペンダント状に付加したもので、なおアセタール化架橋の働きを残しているものである。好ましくは、変異原性の分類では該当しないグリオキザール架橋でん粉を使用する。As the water-soluble cellulose ether, hydroxypropylmethylcellulose (HPMC), hydroxyethylmethylcellulose (HEMC), methylcellulose (MC), hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC) and the like can be used.
Glyoxal-added starch (including glyoxal-added dextrin) is a product in which glyoxal is added to the —OH group of starch (including dextrin) in a cross-linked or pendant form, and still has the function of acetalization cross-linking. Preferably, glyoxal cross-linked starch that is not applicable in the mutagenic classification is used.
本発明では、水溶性セルロースエーテルに対して、グリオキザール付加でん粉を通常１〜１０％使用して処理する。分散性が良好で、且つ粘度の低下が少ない最適使用量は１．５〜５％である。
この処理により、グリオキザール付加でん粉が水溶性セルロースエーテルの−ＯＨ基にアセタール化架橋を行って水溶性セルロースエーテルの粒子表面の溶解性を僅かに低下させる。
例えば、加温状態の水溶性セルロースエーテル粉末にグリオキザール架橋でん粉水溶液を８０℃に加熱して噴霧、添加後６０℃で乾燥する。この粉末を水に撒布し軽く攪拌する時、塊状化することなく容易に水中に分散する。この２％水溶液はｐＨが４．４であり、グリオキザール処理品のｐＨ３．８に比べて高い。従って、このあと溶解させるために使用されるアルカリ添加量も少なくてすむメリットがある。In the present invention, glyoxal-added starch is usually used in an amount of 1 to 10% for water-soluble cellulose ether. The optimum use amount with good dispersibility and little decrease in viscosity is 1.5 to 5%.
By this treatment, the glyoxal-added starch performs acetalization crosslinking on the —OH group of the water-soluble cellulose ether to slightly reduce the solubility of the water-soluble cellulose ether on the particle surface.
For example, a water-soluble cellulose ether powder in a heated state is sprayed with a glyoxal cross-linked starch aqueous solution heated to 80 ° C. and dried at 60 ° C. after addition. When this powder is spread in water and stirred lightly, it is easily dispersed in water without agglomeration. This 2% aqueous solution has a pH of 4.4, which is higher than the pH 3.8 of the glyoxal-treated product. Therefore, there is an advantage that the amount of alkali added to be used for the subsequent dissolution can be reduced.
本発明の水易溶性セルロースエーテルの用途はモルタル、吹付コンクリート、漆喰、石膏プラスター、壁装材、樹脂接着剤、塗料、捺染糊、洗剤、化粧品用などの増粘剤として使用できる。 The water-soluble cellulose ether of the present invention can be used as a thickener for mortar, sprayed concrete, plaster, gypsum plaster, wall covering, resin adhesive, paint, printing paste, detergent, cosmetics and the like.
以下、実施例をあげて本発明を説明する。Hereinafter, the present invention will be described with reference to examples.
原料の水溶性セルロースエーテルとして、５００ミクロン以下の粒度で２％水溶液の粘度が４４００ｍＰａ・ｓのヒドロキシプロピルメチルセルロース（ＨＰＭＣ）について水分散の状態、また熱水分散→冷却溶解による粘度測定（２０℃）を行った。 Hydroxypropyl methylcellulose (HPMC) with a particle size of 500 microns or less and a 2% aqueous solution viscosity of 4400 mPa · s as a raw material water-soluble cellulose ether is in a state of water dispersion, and hot water dispersion → viscosity measurement by cooling dissolution (20 ° C.) Went.
５００ミクロン以下の粒度で２％水溶液の粘度が４４００ｍＰａ・ｓのヒドロキシプロピルメチルセルロース（ＨＰＭＣ）１００ｇを８０℃に加温しミキサーに仕込む。高速攪拌しながら固形分４０％のグリオキサール３ｇとグリコール酸溶液（７０％）１ｇと水７ｇを混ぜ８０℃に加熱して噴霧する。噴霧時間も入れて２０分間高速攪拌する。その後６０℃で１時間熱風乾燥して水分４％以下で終了し、グリオキザール処理品を製造した。 100 g of hydroxypropylmethylcellulose (HPMC) having a particle size of 500 microns or less and a 2% aqueous solution having a viscosity of 4400 mPa · s is heated to 80 ° C. and charged into a mixer. While stirring at high speed, 3 g of glyoxal having a solid content of 40%, 1 g of glycolic acid solution (70%) and 7 g of water are mixed and heated to 80 ° C. and sprayed. Stir at high speed for 20 minutes, including spraying time. Thereafter, it was dried with hot air at 60 ° C. for 1 hour and finished with a moisture content of 4% or less to produce a glyoxal-treated product.
５００ミクロン以下の粒度で２％水溶液の粘度が４４００ｍＰａ・ｓのヒドロキシプロピルメチルセルロース（ＨＰＭＣ）１００ｇを６０℃に加温しミキサーに仕込む。高速攪拌しながらグリオキザール架橋でん粉（固形分５５重量％、ｐＨ４．５、２０℃粘度２００ｍＰａ・ｓ）を表１に記載の配合量と水量で混ぜ、８０℃に加熱して噴霧する。噴霧時間も入れて２０分間高速攪拌する。その後６０℃で１時間熱風乾燥して水分４％以下で終了とする。
外観及び粒子の大きさは仕込まれたヒドロキシプロピルメチルセルロースと区別できない粉末が得られた。100 g of hydroxypropyl methylcellulose (HPMC) having a particle size of 500 microns or less and a 2% aqueous solution having a viscosity of 4400 mPa · s is heated to 60 ° C. and charged into a mixer. Glyoxal cross-linked starch (solid content 55% by weight, pH 4.5, 20 ° C. viscosity 200 mPa · s) is mixed at the blending amount and water amount shown in Table 1, heated to 80 ° C. and sprayed. Stir at high speed for 20 minutes, including spraying time. Thereafter, it is dried with hot air at 60 ° C. for 1 hour, and is finished when the water content is 4% or less.
A powder whose appearance and particle size were indistinguishable from the charged hydroxypropylmethylcellulose was obtained.
５００ミクロン以下の粒度で２％水溶液の粘度が４４００ｍＰａ・ｓのヒドロキシプロピルメチルセルロース（ＨＰＭＣ）１００ｇを６０℃に加温しミキサーに仕込む。高速攪拌しながら固形分５５％のグリオキザール架橋デキストリン３ｇと水１７ｇを混ぜ８０℃に加熱して噴霧する。噴霧時間も入れて２０分間高速攪拌する。その後６０℃で１時間熱風乾燥して水分４％以下で終了とする。
外観及び粒子の大きさは仕込まれたヒドロキシプロピルメチルセルロースと区別できない粉末が得られた。100 g of hydroxypropyl methylcellulose (HPMC) having a particle size of 500 microns or less and a 2% aqueous solution having a viscosity of 4400 mPa · s is heated to 60 ° C. and charged into a mixer. While stirring at high speed, 3 g of glyoxal crosslinked dextrin having a solid content of 55% and 17 g of water are mixed and heated to 80 ° C. and sprayed. Stir at high speed for 20 minutes, including spraying time. Thereafter, it is dried with hot air at 60 ° C. for 1 hour, and is finished when the water content is 4% or less.
A powder whose appearance and particle size were indistinguishable from the charged hydroxypropylmethylcellulose was obtained.
ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）に代えて５００ミクロン以下の粒度で２％水溶液の粘度が４８０ｍＰａ・ｓのメチルセルロース（ＭＣ）を用いる以外、実施例２と同様にしてグリオキザール架橋でん粉で処理した。
外観及び粒子の大きさは仕込まれたメチルセルロースと区別できない粉末が得られた。It was treated with glyoxal crosslinked starch in the same manner as in Example 2 except that methylcellulose (MC) having a particle size of 500 microns or less and a viscosity of a 2% aqueous solution of 480 mPa · s was used instead of hydroxypropylmethylcellulose (HPMC).
A powder whose appearance and particle size were indistinguishable from the charged methylcellulose was obtained.
ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）に代えて３００ミクロン以下の粒度で２％水溶液の粘度が１６３００ｍＰａ・ｓのヒドロキシエチルセルロース（ＨＥＣ）を用いる以外、実施例２と同様にしてグリオキザール架橋でん粉で処理した。
外観及び粒子の大きさは仕込まれたヒドロキシエチルセルロースと区別できない粉末が 得られた。Instead of hydroxypropylmethylcellulose (HPMC), it was treated with glyoxal crosslinked starch in the same manner as in Example 2 except that hydroxyethylcellulose (HEC) having a particle size of 300 microns or less and a 2% aqueous solution having a viscosity of 16300 mPa · s was used.
A powder whose appearance and particle size were indistinguishable from the charged hydroxyethyl cellulose was obtained.
本発明の実施例１〜７および比較例１，２について配合条件と評価結果を表１に示す。
本発明は、水中で容易に分散して、特に微量のアルカリ添加により溶解する水易溶性セルロースエーテルであり、安全衛生上なんら心配することなく、モルタル、吹付コンクリート、接着剤、塗料などの増粘剤として有用である。The present invention is a readily water-soluble cellulose ether that is easily dispersed in water and dissolves in particular by addition of a small amount of alkali, and does not worry about safety and hygiene, and thickened mortar, shotcrete, adhesive, paint, etc. Useful as an agent.
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| KR20140011794A (en) * | 2012-07-19 | 2014-01-29 | 삼성정밀화학 주식회사 | Thickener composition and adhesive including the same |
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| KR20140011794A (en) * | 2012-07-19 | 2014-01-29 | 삼성정밀화학 주식회사 | Thickener composition and adhesive including the same |
| KR101956643B1 (en) * | 2012-07-19 | 2019-03-11 | 롯데정밀화학 주식회사 | Thickener composition and adhesive including the same |
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