JP2008238115A - Additive for bubble-containing composition - Google Patents
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- JP2008238115A JP2008238115A JP2007085478A JP2007085478A JP2008238115A JP 2008238115 A JP2008238115 A JP 2008238115A JP 2007085478 A JP2007085478 A JP 2007085478A JP 2007085478 A JP2007085478 A JP 2007085478A JP 2008238115 A JP2008238115 A JP 2008238115A
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本発明は木目が細かくクリーミーな泡を形成して泡組織に適度な弾力感を付与し、更に泡の分散状態を良好に保ち、気泡同士の合一を防止することによって気泡の安定性を向上させることのできる気泡含有組成物用添加剤に関する。 The present invention improves the stability of the bubbles by forming fine and creamy bubbles with a fine grain and imparting a moderate elasticity to the foam structure, further maintaining a good dispersion state of the bubbles and preventing coalescence of the bubbles. It is related with the additive for bubble-containing compositions which can be made to do.
カルボキシメチルセルロースは、乳化安定剤としての機能を持ち、アイスクリームやミルクセーキなどのホイップ化食品への添加剤として用いられている。ホイップ化食品に限らず、泡を包含する食品や組成物においては、泡が急速に崩壊することを防ぐという課題を有している。ホイップ食品に関し、この課題を解決する手段が、特許文献１や特許文献２に開示されている。特許文献１では、微結晶セルロースとナトリウムカルボキシメチルセルロースの混合物を安定化剤として用いている。また、特許文献2では、空気含有量の低いアイスクリーム用の安定化剤として、エーテル化度が０．８〜２．０であって、２％水溶液の粘度が１〜３０Ｐａ・ｓのカルボキシメチルセルロース・ナトリウム塩を用いている。しかし、これらの方法では、気泡の崩壊を十分に抑制できず、上記課題解決に至っていない。また、木目細かい泡や泡へ弾力を付与させることについても十分な解決に至っていない。 Carboxymethylcellulose has a function as an emulsion stabilizer and is used as an additive to whipped foods such as ice cream and milk shakes. Not only whipped foods but also foods and compositions containing foams have the problem of preventing the foams from rapidly collapsing. With respect to whipped food, Patent Document 1 and Patent Document 2 disclose means for solving this problem. In Patent Document 1, a mixture of microcrystalline cellulose and sodium carboxymethyl cellulose is used as a stabilizer. In Patent Document 2, as a stabilizer for ice cream having a low air content, carboxymethylcellulose having a degree of etherification of 0.8 to 2.0 and a viscosity of a 2% aqueous solution of 1 to 30 Pa · s.・ Sodium salt is used. However, these methods cannot sufficiently suppress the collapse of the bubbles and have not yet solved the above problem. Moreover, it has not reached sufficient solution about giving elasticity to fine-grained bubbles and bubbles.
本発明は、上記のような従来技術の問題を解決するために創案されたものであり、木目が細かくクリーミーな泡を形成して泡組織に適度な弾力感を付与し、更に泡の分散状態を良好に保ち、気泡安定性を向上させることができ、気泡を含有する食品、化粧品、洗浄剤（固形石鹸、台所洗剤、ボディーソープ、シャンプーなど）、樹脂、土木、ボーリング（気泡シールドなど）等の様々な分野で用いる気泡含有組成物に利用できる添加剤を提供するものである。 The present invention was devised in order to solve the above-described problems of the prior art, and the grain structure forms a fine creamy foam to give the foam structure an appropriate elasticity, and further the dispersed state of the foam Keeps the air condition good and can improve the bubble stability. Foods, cosmetics, detergents (bubble soap, kitchen detergent, body soap, shampoo, etc.) containing foam, resin, civil engineering, bowling (bubble shield etc.), etc. The present invention provides an additive that can be used for a bubble-containing composition used in various fields.
本発明者等は、課題を解決するために鋭意検討を重ねた結果、軽度にカルボキシメチル化され、水不溶性・水膨潤性のカルボキシメチルセルロース又はその塩が、泡質改善、気泡安定性能を満足できることを見出し、この知見に基づいて本発明をなすに至った。 As a result of intensive studies to solve the problems, the inventors of the present invention are slightly carboxymethylated and water-insoluble / water-swellable carboxymethylcellulose or a salt thereof can satisfy foam quality improvement and bubble stability performance. The present invention has been made based on this finding.
即ち、本発明は以下を提供する。
［１］ 無水グルコース単位当りのカルボキシメチル置換度が０．０５〜０．４である水不溶性および／または水膨潤性のカルボキシメチルセルロース又はその塩を含有することを特徴とする気泡含有組成物用添加剤。
［２］ 前記カルボキシメチルセルロースが、非結晶であることを特徴とする［１］記載の気泡含有組成物用添加剤。
［３］ 前記カルボキシメチルセルロースが、レーザー回折・散乱式粒度分布計で測定される体積累計５０％粒子径に於いて、水を分散媒として測定した値のメタノールを分散媒として測定した値に対する比が２．０以上であることを特徴とする［１］記載の気泡含有組成物用添加剤。
That is, the present invention provides the following.
[1] Addition for a bubble-containing composition characterized by containing water-insoluble and / or water-swellable carboxymethylcellulose having a degree of carboxymethyl substitution per anhydroglucose unit of 0.05 to 0.4 or a salt thereof Agent.
[2] The additive for a bubble-containing composition according to [1], wherein the carboxymethylcellulose is amorphous.
[3] When the carboxymethyl cellulose has a 50% cumulative volume particle diameter measured with a laser diffraction / scattering particle size distribution meter, the ratio of the value measured with water as the dispersion medium to the value measured with methanol as the dispersion medium is The additive for a bubble-containing composition according to [1], which is 2.0 or more.
本発明の添加剤を気泡含有組成物に添加すると、木目を細かくクリーミーな気泡を調製することができ、気泡組織に適度な弾性感、ボディー感を付与するなど、泡質を改善する効果を有し、また、気泡同士の合一を防いで気泡の崩壊を防ぐので、長時間にわたって気泡が安定した状態を維持することができる。本発明の気泡含有組成物添加剤は、気泡を含有する飲食品や組成物、例えば化粧品、洗浄剤（固形石鹸、台所洗剤、ボディーソープ、シャンプーなど）、樹脂、土木、ボーリング（気泡シールドなど）等で用いられる組成物に利用できる。 When the additive of the present invention is added to the bubble-containing composition, fine and creamy bubbles can be prepared, and there is an effect of improving the foam quality such as imparting appropriate elasticity and body feeling to the bubble tissue. In addition, since the bubbles are prevented from collapsing by preventing the bubbles from being coalesced, it is possible to maintain the bubbles in a stable state for a long time. The foam-containing composition additive of the present invention is a food or drink or composition containing foam, such as cosmetics, cleaning agents (solid soap, kitchen detergent, body soap, shampoo, etc.), resin, civil engineering, bowling (bubble shield, etc.) It can utilize for the composition used by etc.
本発明の気泡含有組成物用添加剤は、無水グルコース単位当りのカルボキシメチル置換度が０．０５〜０．４である水不溶性および／または水膨潤性のカルボキシメチルセルロース又はその塩を主成分として含有するものである。
［カルボキシメチルセルロース又はその塩］
カルボキシメチルセルロース又はその塩は、セルロースを構成するグルコース残基中の水酸基がカルボキシメチルエーテル基に置換された構造を持つ。カルボキシルセルロースは、塩の形態であっても良く、例えばカルボキシメチルセルロースナトリウム塩などの金属塩などとすることができる。本発明においてセルロースとは、Ｄ−グルコピラノースがβ−１,４グリコシド結合で連なった構造の多糖を意味し、無水グルコースを基本単位とする。一般に起源、製法等から、天然セルロース、再生セルロース、微細セルロース、非結晶領域を除いた微結晶セルロース等に分類される。天然セルロースとしては、晒または未晒木材パルプ、精製リンター、酢酸菌等の微生物によって生産されるセルロース等が例示される。晒又は未晒パルプの原料は特に限定されず、例えば、木材、木綿、わら、竹等が挙げられる。また、晒又は未晒パルプの製造方法も特に限定されず、機械的方法、化学的方法、あるいはその中間で二つを組み合わせた方法でも良く、例えば、メカニカルパルプ、ケミカルパルプ、砕木パルプ、亜硫酸パルプ、クラフトパルプ等が挙げられる。さらに、製紙用パルプの他に、化学的に精製され、主として薬品に溶解して使用する、人造繊維、セロハンなどの主原料となる溶解パルプを用いてもよい。再生セルロースとしては、セルロースを銅アンモニア溶液、セルロースザンテート溶液、モルフォリン誘導体など何らかの溶媒に溶解し、改めて紡糸されたものが例示される。微細セルロースとは、上記天然セルロースや再生セルロースをはじめとするセルロース系素材を酸加水分解、アルカリ加水分解、酵素分解、爆砕処理、振動ボールミル処理等によって解重合処理したものや、前記セルロース系素材を機械的に処理したものが例示される。
The additive for a foam-containing composition of the present invention contains, as a main component, water-insoluble and / or water-swellable carboxymethyl cellulose having a degree of carboxymethyl substitution per anhydroglucose unit of 0.05 to 0.4 or a salt thereof. To do.
[Carboxymethylcellulose or a salt thereof]
Carboxymethyl cellulose or a salt thereof has a structure in which a hydroxyl group in a glucose residue constituting cellulose is substituted with a carboxymethyl ether group. The carboxyl cellulose may be in the form of a salt, for example, a metal salt such as carboxymethyl cellulose sodium salt. In the present invention, cellulose means a polysaccharide having a structure in which D-glucopyranose is linked by β-1,4 glycosidic bonds, and has anhydrous glucose as a basic unit. Generally, it is classified into natural cellulose, regenerated cellulose, fine cellulose, microcrystalline cellulose excluding the non-crystalline region, etc. from the origin, production method and the like. Examples of natural cellulose include cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linters, and acetic acid bacteria. The raw material of bleached or unbleached pulp is not specifically limited, For example, wood, cotton, straw, bamboo, etc. are mentioned. The method for producing bleached or unbleached pulp is not particularly limited, and may be a mechanical method, a chemical method, or a method combining two in the middle, such as mechanical pulp, chemical pulp, groundwood pulp, sulfite pulp. And kraft pulp. Furthermore, in addition to pulp for papermaking, dissolved pulp that is chemically purified and mainly used as a main raw material such as artificial fibers and cellophane, which is mainly dissolved in chemicals, may be used. Examples of the regenerated cellulose include those obtained by dissolving cellulose in some solvent such as a copper ammonia solution, a cellulose xanthate solution, and a morpholine derivative and spinning again. Fine cellulose refers to cellulose-based materials such as the above natural cellulose and regenerated cellulose that have been depolymerized by acid hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibration ball mill treatment, etc. What was processed mechanically is illustrated.
本発明においてカルボキシメチル置換度（エーテル化度ともいう）とは、セルロースを構成する無水グルコース単位１モル当りの水酸基（−ＯＨ）のうちカルボキシメチルエーテル基（−ＯＣＨ2ＣＯＯＨ）に置換されているもののモル数を示している。なお、カルボキシメチル置換度はＤＳと略すことがある。本発明のカルボキシメチルセルロース又はその塩は、カルボキシメチル置換度が０．０５〜０．４であることが必要である。カルボキシメチル置換度が０．０５未満では、カルボキシメチルエーテル基に由来する吸水、膨潤部分が十分形成されず、本発明の特徴とする泡質改善効果、気泡安定性能を発揮することができない。一方、０．４を超えると水溶性部分が増加して水への溶解が起こり易くなり、本発明の特徴を十分に発揮できない。 In the present invention, the degree of carboxymethyl substitution (also called degree of etherification) is substituted with a carboxymethyl ether group (—OCH 2 COOH) out of hydroxyl groups (—OH) per mole of anhydroglucose units constituting cellulose. The number of moles of the thing is shown. The degree of carboxymethyl substitution may be abbreviated as DS. The carboxymethyl cellulose of the present invention or a salt thereof needs to have a carboxymethyl substitution degree of 0.05 to 0.4. When the degree of carboxymethyl substitution is less than 0.05, the water absorption and swelling part derived from the carboxymethyl ether group are not sufficiently formed, and the effect of improving the foam quality and the ability to stabilize the bubbles, which are the characteristics of the present invention, cannot be exhibited. On the other hand, when it exceeds 0.4, the water-soluble part increases and the dissolution in water tends to occur, and the characteristics of the present invention cannot be fully exhibited.
当該カルボキシメチル置換度は、試料中のカルボキシメチルセルロースを中和するのに必要な水酸化ナトリウム等の塩基の量を測定して確認することができる。この場合、カルボキシメチルエーテル塩の場合には、測定前に予めカルボキシメチルセルロースに変換しておく。測定の際には、塩基、酸を用いた逆滴定、フェノールフタレイン等の指示薬を適宜組み合わせることができる。 The degree of carboxymethyl substitution can be confirmed by measuring the amount of base such as sodium hydroxide required to neutralize carboxymethylcellulose in the sample. In this case, in the case of a carboxymethyl ether salt, it is converted into carboxymethyl cellulose in advance before measurement. In the measurement, an indicator such as back titration using a base and an acid, phenolphthalein and the like can be appropriately combined.
本発明のカルボキシメチルセルロース又はその塩は、非結晶である方が好ましい。カルボキシメチル置換度が上記範囲を満たしていても、非結晶でなければ、化学的反応性、吸水性に乏しい結晶領域が残っていることに起因して、泡質改善効果、気泡安定性能が落ちる可能性がある。 The carboxymethyl cellulose or salt thereof of the present invention is preferably amorphous. Even if the degree of carboxymethyl substitution satisfies the above range, if it is not amorphous, the crystalline region with poor chemical reactivity and water absorption remains, resulting in poor foam quality improvement effect and bubble stability performance. there is a possibility.
カルボキシメチルセルロース又はその塩が非結晶であることは、Ｘ線回折による測定により確認することができる。具体的には、Ｘ線回折の測定の結果、非結晶領域に由来する２θ＝１８．５°の回折ピーク以外には結晶領域に由来する回折ピークを生じないことが確認されれば、非結晶であるということができる。例えば、セルロースＩ型結晶では、Ｘ線回折による測定で２θ＝２２．６°に００２面の回折強度に由来するピークを生じる。これに対し、本発明のカルボキシメチルセルロース又はその塩の場合は、微結晶セルロースを原料に使用した場合でも２θ＝２２．６°の回折ピークは消失している方が好ましい。
［カルボキシメチルセルロース又はその塩の水不溶性および／または水膨潤性］
本発明のカルボキシメチルセルロース又はその塩は、水不溶性および／または水膨潤性を示す。すなわち、水不溶性及び水膨潤性のうちの少なくとも一方を示すことが必要であり、好ましくは両方を示すものである。
It can be confirmed by measurement by X-ray diffraction that carboxymethylcellulose or a salt thereof is amorphous. Specifically, if it is confirmed as a result of the X-ray diffraction measurement that a diffraction peak derived from the crystalline region other than the diffraction peak of 2θ = 18.5 ° derived from the amorphous region does not occur, non-crystalline It can be said that. For example, in cellulose I type crystal, a peak derived from the diffraction intensity of the 002 plane occurs at 2θ = 22.6 ° as measured by X-ray diffraction. On the other hand, in the case of carboxymethyl cellulose or a salt thereof of the present invention, it is preferable that the diffraction peak at 2θ = 22.6 ° disappears even when microcrystalline cellulose is used as a raw material.
[Water-insoluble and / or water-swelling property of carboxymethylcellulose or a salt thereof]
The carboxymethylcellulose or salt thereof of the present invention exhibits water insolubility and / or water swellability. That is, it is necessary to show at least one of water insolubility and water swellability, preferably both.
水不溶性とは、試料を水に１〜２重量％添加して３〜６時間撹拌後の状態を目視判定して不溶であれば水不溶性と判断することができる。 Water-insoluble can be determined to be water-insoluble if the sample is insoluble by visually judging the state after adding 1 to 2% by weight to water and stirring for 3 to 6 hours.
一方、水膨潤性とは、水に浸漬等接触した場合に体積が増加する（膨潤する）ことを示す。例えば、レーザー回折・散乱式粒度分布計で測定される体積累計５０％粒子径に於いて、水を分散媒として測定した値のメタノールを分散媒として測定した値に対する比（水を分散媒として測定した値／メタノールを分散媒として測定した値）として表現することができ、該数値が２．０以上であることが好ましい。２．０未満では吸水、膨潤が不十分となり泡質改善効果、気泡安定性能が十分発揮されない。尚、上限は、カルボキシメチルセルロース又はその塩が水不溶性を示す範囲であれば、特に限定はない。レーザー回折・散乱式粒度分布計としては、水、メタノールのそれぞれを分散媒とした場合の測定が可能であれば特に限定されず、例えば、マイクロトラック Ｍｏｄｅｌ−９２２０−ＳＲＡ（日機装（株）製）等を用いることができる。 On the other hand, water swellability indicates that the volume increases (swells) when immersed in water or the like. For example, the ratio of the value measured with water as the dispersion medium to the value measured with methanol as the dispersion medium (measured with water as the dispersion medium) at a 50% cumulative volume particle size measured with a laser diffraction / scattering particle size distribution meter Value / value measured using methanol as a dispersion medium), and the numerical value is preferably 2.0 or more. If it is less than 2.0, water absorption and swelling are insufficient, and the foam quality improving effect and the bubble stabilizing performance are not sufficiently exhibited. The upper limit is not particularly limited as long as carboxymethyl cellulose or a salt thereof is in a range showing water insolubility. The laser diffraction / scattering particle size distribution meter is not particularly limited as long as it can measure water and methanol as dispersion media. For example, Microtrac Model-9220-SRA (manufactured by Nikkiso Co., Ltd.) Etc. can be used.
［カルボキシメチルセルロース又はその塩の製造］
本発明のカルボキシメチルセルロース又はその塩を製造するにあたっては、公知のカルボキシメチルセルロース又はその塩の製法を適用することができる。即ち、原料セルロースをマーセル化剤（アルカリ）で処理してマーセル化セルロース（アルカリセルロース）を調製した後に、エーテル化剤を添加してエーテル化反応させることで本発明のカルボキシメチルセルロース又はその塩を製造することができる。
[Production of carboxymethyl cellulose or a salt thereof]
In producing the carboxymethyl cellulose or a salt thereof of the present invention, a known method for producing carboxymethyl cellulose or a salt thereof can be applied. That is, after processing raw material cellulose with a mercerizing agent (alkali) to prepare mercerized cellulose (alkali cellulose), the carboxymethyl cellulose of the present invention or a salt thereof is produced by adding an etherifying agent and causing an etherification reaction. can do.
原料のセルロースとしては、上述のセルロースであれば特に制限なく用いることができるが、セルロース純度が高いものが好ましく、特に、溶解パルプ、リンターを用いることが好ましい。これらを用いることにより、純度の高い非結晶のカルボキシメチルセルロース又はその塩を得ることができる。 As the raw material cellulose, any cellulose can be used as long as it is the above-mentioned cellulose, but those having high cellulose purity are preferable, and it is particularly preferable to use dissolved pulp and linter. By using these, highly pure amorphous carboxymethylcellulose or a salt thereof can be obtained.
マーセル化剤としては水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ金属塩等を使用することができる。エーテル化剤としてはモノクロロ酢酸、モノクロロ酢酸ソーダ等を使用することができる。 As the mercerizing agent, alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide can be used. As the etherifying agent, monochloroacetic acid, sodium monochloroacetate or the like can be used.
水溶性の一般的なカルボキシメチルセルロース（ＤＳ０．５以上）の製法の場合のマーセル化剤とエーテル化剤のモル比は、エーテル化剤としてモノクロロ酢酸を使用する場合では２．００〜２．４５が一般的に採用される。その理由は、２．００以下であるとエーテル化反応が不十分となるため、未反応のモノクロロ酢酸が残って無駄が生じること、及び２．４５以上であると過剰のマーセル化剤とモノクロロ酢酸による副反応が進行してグリコール酸アルカリ金属塩が生成するため、不経済であることにある。 The molar ratio of mercerizing agent to etherifying agent in the production method of water-soluble general carboxymethylcellulose (DS 0.5 or more) is 2.00 to 2.45 when monochloroacetic acid is used as the etherifying agent. Generally adopted. The reason is that if it is 2.00 or less, the etherification reaction becomes insufficient, so that unreacted monochloroacetic acid remains and waste occurs, and if it is 2.45 or more, an excessive mercerizing agent and monochloroacetic acid. This is uneconomical because an alkali metal glycolate salt is produced by the side reaction due to.
しかしながら、本発明のカルボキシメチルセルロース又はその塩を得るためには極めて軽度にカルボキシメチルエーテル基を導入する必要がある。そのために、添加するエーテル化剤のモル数を低くすると、一般的に採用されているモル比ではマーセル化剤の添加モル数も少なくすることになる。その結果、セルロース内部、特に化学的反応性に乏しい結晶部分でのマーセル化は不十分となり、結晶構造が完全には破壊されないこともある。 However, in order to obtain the carboxymethyl cellulose or a salt thereof of the present invention, it is necessary to introduce a carboxymethyl ether group very lightly. Therefore, if the number of moles of the etherifying agent to be added is lowered, the number of moles of the mercerizing agent to be added is reduced at a generally employed molar ratio. As a result, mercerization inside the cellulose, particularly in a crystal part having poor chemical reactivity, becomes insufficient, and the crystal structure may not be completely destroyed.
本発明のカルボキシメチルセルロース又はその塩を調製する際には、極めて軽度にカルボキシメチル化することが必要である。さらには、セルロース内部、特に化学的反応性に乏しい結晶部分の結晶構造を破壊する、すなわち非結晶性である方が好ましい。結晶構造を破壊するためには、セルロース内部も十分なマーセル化を行うために結晶構造を完全に破壊するに十分なマーセル化剤を添加するとともに、エーテル化剤の添加モル数は少量とすることが好ましい。マーセル化剤の添加量は、原料セルロースの無水グルコース単位当り、通常は１．０〜４．０モル、好ましくは１．２〜３．０モルとなるように調整することができる。前記マーセル化剤の添加量は、本発明で添加することのできるエーテル化剤に対し、通常は過剰である。過剰のマーセル化剤はエーテル化反応の際には副反応の原因となり不経済である。従って、エーテル化剤を添加する前に、反応系中に残存するマーセル化剤と添加するエーテル化剤のモル比（マーセル化剤／エーテル化剤）が２．０〜３．０、好ましくは２．２〜２．８になるように予めマーセル化剤を圧搾脱液して除去するか、鉱酸、有機酸などで中和しておくことが好ましい。 When preparing the carboxymethylcellulose or salt thereof of the present invention, it is necessary to carboxymethylate very lightly. Furthermore, it is preferable that the inside of the cellulose, particularly the crystal structure of the crystal part having poor chemical reactivity, is destroyed, that is, it is non-crystalline. In order to destroy the crystal structure, add sufficient mercerizing agent to completely destroy the crystal structure in order to achieve sufficient mercerization inside the cellulose, and add a small number of moles of etherifying agent. Is preferred. The addition amount of the mercerizing agent can be adjusted to usually 1.0 to 4.0 mol, preferably 1.2 to 3.0 mol, per anhydroglucose unit of the raw material cellulose. The addition amount of the mercerizing agent is usually excessive with respect to the etherifying agent that can be added in the present invention. Excess mercerizing agent causes side reactions during the etherification reaction and is uneconomical. Therefore, before adding the etherifying agent, the molar ratio of the mercerizing agent remaining in the reaction system to the etherifying agent to be added (merceling agent / etherifying agent) is 2.0 to 3.0, preferably 2 It is preferable that the mercerizing agent is removed by squeezing and draining in advance so as to be 2 to 2.8, or neutralized with a mineral acid, an organic acid or the like.
本発明のセルロース誘導体の製造に使用する溶媒としては、低級アルコールを挙げることができる。具体的にはメタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブタノール、イソブタノール、第３級ブタノール等の単独、または２種以上の混合物と水の混合媒体などである。溶媒の使用量は、一般に、原料セルロースに対し３〜２０重量倍とすることができる。尚、低級アルコールと水の合計に対する低級アルコールの割合は６０〜９５重量％とすることができる。 A lower alcohol can be mentioned as a solvent used for manufacture of the cellulose derivative of this invention. Specifically, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, tertiary butanol or the like alone or a mixture medium of two or more and water are used. Generally the usage-amount of a solvent can be 3-20 weight times with respect to raw material cellulose. In addition, the ratio of the lower alcohol with respect to the sum total of a lower alcohol and water can be 60 to 95 weight%.
マーセル化処理は、原料セルロースと溶媒、マーセル化剤を混合して行うことができる。この際、反応温度は、通常０〜７０℃、好ましくは１０〜６０℃である。また、反応時間は通常１５分〜４時間、好ましくは３０分〜２時間である。その後エーテル化処理を行うが、その前に必要に応じて、過剰のマーセル化剤を圧搾脱液して除去するか、鉱酸か有機酸で中和しておいてもよい。エーテル化処理では、エーテル化剤を原料セルロースに添加してエーテル化反応を行う。得られるカルボキシメチルセルロース又はその塩の性質、特にカルボキシメチル置換度は、原料セルロースの種類、エーテル化反応の反応系の溶媒組成、機械的条件、反応温度及び反応時間、その他の要因によって変化する。そのため、前記置換度が０．０５〜０．４の範囲となるように、反応条件、特にエーテル化剤の添加量を調整することが必要となる。前記置換度にする際のエーテル化剤の添加量は、一般的には、無水グルコース単位当たり０．０５〜１．０モルとすることができる。エーテル化反応の反応温度は、通常５０〜９０℃、好ましくは６０〜８０℃である。反応時間は通常３０分〜６時間、好ましくは１時間〜３時間である。 The mercerization treatment can be performed by mixing raw material cellulose, a solvent, and a mercerizing agent. Under the present circumstances, reaction temperature is 0-70 degreeC normally, Preferably it is 10-60 degreeC. The reaction time is usually 15 minutes to 4 hours, preferably 30 minutes to 2 hours. Thereafter, an etherification treatment is carried out. Before that, if necessary, excess mercerizing agent may be removed by squeezing and draining, or neutralized with a mineral acid or an organic acid. In the etherification treatment, an etherification agent is added to the raw material cellulose to perform an etherification reaction. The properties of the obtained carboxymethyl cellulose or a salt thereof, particularly the degree of carboxymethyl substitution, varies depending on the type of raw cellulose, the solvent composition of the reaction system of the etherification reaction, mechanical conditions, reaction temperature and reaction time, and other factors. Therefore, it is necessary to adjust the reaction conditions, particularly the addition amount of the etherifying agent, so that the degree of substitution is in the range of 0.05 to 0.4. In general, the addition amount of the etherifying agent in the substitution degree can be 0.05 to 1.0 mol per anhydroglucose unit. The reaction temperature of the etherification reaction is usually 50 to 90 ° C, preferably 60 to 80 ° C. The reaction time is usually 30 minutes to 6 hours, preferably 1 hour to 3 hours.
反応終了後、残存するアルカリ金属塩を鉱酸または有機酸で中和する。必要に応じて副生する無機塩、有機酸塩等を含水メタノールで洗浄して除去し、乾燥、粉砕、分級して本発明のカルボキシメチルセルロース又はその塩を得る。特に乾式粉砕や湿式粉砕を施すと、より微細化されたカルボキシメチルセルロース又はその塩を得ることができる。乾式粉砕で用いる装置としてはハンマーミル、ピンミル等の衝撃式ミル、ボールミル、タワーミル等の媒体ミル、ジェットミル等が例示される。湿式粉砕で用いる装置としてはホモジナイザー、マスコロイダー、パールミル等の装置が例示される。 After completion of the reaction, the remaining alkali metal salt is neutralized with a mineral acid or an organic acid. If necessary, by-product inorganic salts, organic acid salts and the like are removed by washing with water-containing methanol, dried, pulverized and classified to obtain the carboxymethyl cellulose of the present invention or a salt thereof. In particular, when dry pulverization or wet pulverization is performed, more refined carboxymethyl cellulose or a salt thereof can be obtained. Examples of the apparatus used in the dry pulverization include impact mills such as a hammer mill and a pin mill, medium mills such as a ball mill and a tower mill, and jet mills. Examples of the apparatus used in the wet pulverization include apparatuses such as a homogenizer, a mass collider, and a pearl mill.
本発明のカルボキシメチルセルロース又はその塩は、高い親水性を示ため、水中では吸水、膨潤して容積比の高いゲル状物質となり、メタノール等の有機溶媒中では吸液も膨潤もしないことが多い。この変化は、レーザー回折・散乱式粒度分布計で測定すると、その平均粒子径は水を分散媒として測定した値とメタノールを分散媒として測定した値の比が２．０以上のときに顕著である。 Since the carboxymethyl cellulose or salt thereof of the present invention exhibits high hydrophilicity, it absorbs and swells in water to form a gel material having a high volume ratio, and often does not absorb or swell in an organic solvent such as methanol. This change is noticeable when the ratio of the value measured with water as the dispersion medium and the value measured with methanol as the dispersion medium is 2.0 or more when measured with a laser diffraction / scattering particle size distribution analyzer. is there.
［本発明の添加剤中のカルボキシメチルセルロース又はその塩の含有量］
本発明の添加剤の主成分は、カルボキシメチルセルロース又はその塩であり、添加剤中の含有量は、５０重量％以上、好ましくは８０重量％以上、より好ましくは９０重量％以上である。
[Content of carboxymethyl cellulose or salt thereof in the additive of the present invention]
The main component of the additive of the present invention is carboxymethylcellulose or a salt thereof, and the content in the additive is 50% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
［本発明の添加剤中のその他の成分］
本発明の添加剤には、カルボキシメチルセルロースまたはその塩の他に、必要に応じて、界面活性剤、水溶性高分子などを添加しても良い。
[Other components in the additive of the present invention]
In addition to carboxymethylcellulose or a salt thereof, a surfactant, a water-soluble polymer, or the like may be added to the additive of the present invention as necessary.
［気泡含有組成物中の本発明の添加剤の含有量］
気泡含有組成物中の本発明の添加剤の含有量は、０.０５重量％以上、好ましくは０.１重量％以上である。含有量が０.０５重量より少ないと十分な泡質改善効果、気泡安定性能を発揮しない。
[Content of the additive of the present invention in the bubble-containing composition]
The content of the additive of the present invention in the bubble-containing composition is 0.05% by weight or more, preferably 0.1% by weight or more. If the content is less than 0.05 weight, sufficient foam quality improvement effect and bubble stabilization performance are not exhibited.
以下、本発明の実施の形態を実施例により説明するが、本発明はこれによって限定されるものではない。尚、配合量を示す「部」はすべて「重量部」を示す。 Hereinafter, the embodiments of the present invention will be described by way of examples, but the present invention is not limited thereto. The “parts” indicating the blending amounts all represent “parts by weight”.
［実施例１］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム３０部を水５８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、酢酸を２６部添加して過剰のマーセル化剤を中和する。更に攪拌しつつ９０％ＩＰＡ４５部に溶解したモノクロロ酢酸１１部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕して無水グルコース単位当りのカルボキシメチル置換度（ＤＳ）０．１６のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。
[Example 1]
Add 522 parts of isopropyl alcohol (IPA) and 30 parts of sodium hydroxide in 58 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 26 parts of acetic acid is added to neutralize excess mercerizing agent. Further, 11 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was added with stirring, and the mixture was heated to 70 ° C. and subjected to etherification reaction for 90 minutes. After completion of the reaction, neutralization, liquid removal, drying and pulverization were carried out to obtain sodium carboxymethyl cellulose having a degree of carboxymethyl substitution (DS) of 0.16 per anhydroglucose unit. This was used as the additive of the present invention.
［実施例２］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム３３部を水５８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、酢酸を１６部添加して過剰のマーセル化剤を中和する。更に攪拌しつつ９０％ＩＰＡ４５部に溶解したモノクロロ酢酸１９部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．２８のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。
[Example 2]
Add 522 parts of isopropyl alcohol (IPA) and 33 parts of sodium hydroxide in 58 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 16 parts of acetic acid is added to neutralize excess mercerizing agent. Further, 19 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was added with stirring, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethylcellulose having a DS of 0.28. This was used as the additive of the present invention.
［実施例３］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム３８部を水５８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、酢酸を１３部添加して過剰のマーセル化剤を中和する。更に攪拌しつつ９０％ＩＰＡ４５部に溶解したモノクロロ酢酸２６部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．３８のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。。
[Example 3]
Add 522 parts of isopropyl alcohol (IPA) and 38 parts of sodium hydroxide in 58 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 13 parts of acetic acid is added to neutralize excess mercerizing agent. Further, 26 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was added with stirring, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.38. This was used as the additive of the present invention. .
［実施例４］
回転数１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）４３５部と水酸化ナトリウム３９．５部を水６５部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。４５℃で３０分攪拌、混合しマーセル化セルロースを調整後、５０％モノクロル酢酸のＩＰＡ溶液９．０部を加え、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．０６のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。
[Example 4]
To a biaxial kneader adjusted to a rotational speed of 100 rpm, 435 parts of isopropyl alcohol (IPA) and 39.5 parts of sodium hydroxide dissolved in 65 parts of water were added, and commercially available dissolved pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) ) Was completely dried and 100 parts were charged. After stirring and mixing at 45 ° C. for 30 minutes to prepare mercerized cellulose, 9.0 parts of an IPA solution of 50% monochloroacetic acid was added, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.06. This was used as the additive of the present invention.
［実施例５］
回転数１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）４３５部と水酸化ナトリウム２９．６部を水６５部に溶解したものを加え、市販の晒クラフトパルプ（日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で１時間攪拌、混合しマーセル化セルロースを調整後、５０％モノクロル酢酸のＩＰＡ溶液１４．０部を加え、７０℃に昇温し９０分反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．１１のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。
[Example 5]
Add 435 parts of isopropyl alcohol (IPA) and 29.6 parts of sodium hydroxide in 65 parts of water to a biaxial kneader adjusted to a rotational speed of 100 rpm, and commercially available bleached kraft pulp (manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 1 hour to prepare mercerized cellulose, 14.0 parts of an IPA solution of 50% monochloroacetic acid was added, and the mixture was heated to 70 ° C. and reacted for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.11. This was used as the additive of the present invention.
［実施例６］
回転数１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム４４．４部を水７８部に溶解したものを加え、脱脂木粉１００部を仕込んだ。４５℃で３０分攪拌、混合しマーセル化セルロースを調整後、５０％モノクロル酢酸のＩＰＡ溶液２８．０部を加え、７０℃に昇温し９０分反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．２３のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。。
[Example 6]
To a biaxial kneader adjusted to a rotational speed of 100 rpm, 522 parts of isopropyl alcohol (IPA) and 44.4 parts of sodium hydroxide dissolved in 78 parts of water were added, and 100 parts of defatted wood flour was charged. After stirring and mixing at 45 ° C. for 30 minutes to prepare mercerized cellulose, 28.0 parts of an IPA solution of 50% monochloroacetic acid was added, and the mixture was heated to 70 ° C. and reacted for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.23. This was used as the additive of the present invention. .
［実施例７］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム２３部を水５８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、更に攪拌しつつ９０％ＩＰＡ４５部に溶解したモノクロロ酢酸２３部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．３４のカルボキシメチルセルロースナトリウムを得た。これを本発明の添加剤とした。。
[Example 7]
Add 522 parts of isopropyl alcohol (IPA) and 23 parts of sodium hydroxide in 58 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 23 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was added with further stirring, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethylcellulose having a DS of 0.34. This was used as the additive of the present invention. .
［比較例１］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム３０部を水５８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、更に攪拌しつつ９０%ＩＰＡ４５部に溶解したモノクロロ酢酸９部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．０３のカルボキシメチルセルロースナトリウムを得た。これを添加剤とした。
[Comparative Example 1]
Add 522 parts of isopropyl alcohol (IPA) and 30 parts of sodium hydroxide in 58 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 9 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was added with further stirring, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.03. This was used as an additive.
［比較例２］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム４９部を水７８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、更に攪拌しつつ９０％ＩＰＡ４５部に溶解したモノクロロ酢酸３７部を添加し、７０℃に昇温して９０分間エーテル化反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．４５のカルボキシメチルセルロースナトリウムを得た。これを添加剤とした。
[Comparative Example 2]
Add 522 parts of isopropyl alcohol (IPA) and 49 parts of sodium hydroxide in 78 parts of water to a biaxial kneader whose rotational speed is adjusted to 100 rpm, and add commercially available dissolving pulp (NDPS, manufactured by Nippon Paper Chemicals Co., Ltd.) 100 parts were completely dried. After stirring and mixing at 30 ° C. for 90 minutes to prepare mercerized cellulose, 37 parts of monochloroacetic acid dissolved in 45 parts of 90% IPA was further added while stirring, and the mixture was heated to 70 ° C. and subjected to an etherification reaction for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and pulverized to obtain a sodium carboxymethyl cellulose having a DS of 0.45. This was used as an additive.
［比較例３］
回転数を１００ｒｐｍに調節した二軸ニーダーにイソプロピルアルコール（ＩＰＡ）５２２部と水酸化ナトリウム３２．４部を水７８部に溶解したものを加え、市販の溶解パルプ（ＮＤＰＳ、日本製紙ケミカル（株）製）を絶乾で１００部仕込んだ。３０℃で９０分間攪拌、混合しマーセル化セルロースを調製後、５０％モノクロル酢酸のＩＰＡ溶液５．０部を加え、７０℃に昇温し９０分反応させた。反応終了後、中和、脱液、乾燥、粉砕してＤＳ０．００５のカルボキシメチルセルロースナトリウムを得た。これを添加剤とした。
[Comparative Example 3]
To a biaxial kneader whose rotational speed is adjusted to 100 rpm, 522 parts of isopropyl alcohol (IPA) and 32.4 parts of sodium hydroxide dissolved in 78 parts of water are added, and commercially available dissolving pulp (NDPS, Nippon Paper Chemicals Co., Ltd.) 100 parts) was completely dried. After stirring and mixing at 30 ° C for 90 minutes to prepare mercerized cellulose, 5.0 parts of an IPA solution of 50% monochloroacetic acid was added, and the mixture was heated to 70 ° C and reacted for 90 minutes. After completion of the reaction, the solution was neutralized, drained, dried and ground to obtain sodium carboxymethylcellulose having a DS of 0.005. This was used as an additive.
[無水グルコース単位当りのカルボキシメチル置換度（ＤＳ）の測定]
試料約２．０ｇを精秤して、３００ｍｌ共栓付き三角フラスコに入れた。硝酸メタノール（無水メタノール１Ｌに特級濃硝酸１００ｍｌを加えた液）１００ｍｌを加え、３時間振とうして、カルボキシメチルセルロースナトリウム（Ｎａ−ＣＭＣ）をカルボキシメチルセルロース（Ｈ−ＣＭＣ）にした。その絶乾Ｈ−ＣＭＣ１．５〜２．０ｇを精秤し、３００ｍｌ共栓付き三角フラスコに入れた。８０％メタノール１５ｍｌでＨ−ＣＭＣを湿潤し、０．１Ｎ−ＮａＯＨ１００ｍｌを加え、室温で３時間振とうした。指示薬として、フェノールフタレインを用いて、０．１Ｎ−Ｈ2ＳＯ4で過剰のＮａＯＨを逆滴定した。ＤＳは滴定に要した０．１Ｎ−Ｈ2ＳＯ4の量（ｍｌ）を次式に代入して算出した。
Ａ＝（（１００×Ｆ'−０．１Ｎ−Ｈ2ＳＯ4（ｍｌ）×Ｆ）×０．１）／Ｈ−ＣＭＣの絶乾重量（ｇ）
ＤＳ＝０．１６２×Ａ／（１−０．０５８×Ａ）（ｍｏｌ／Ｃ6）
Ａ：Ｈ−ＣＭＣ１ｇを中和するのに必要な１Ｎ−ＮａＯＨの量（ｍｌ）
Ｆ：０．１Ｎ−Ｈ2ＳＯ4のｆａｃｔｏｒ
Ｆ'：０．１Ｎ−ＮａＯＨのｆａｃｔｏｒ
[Measurement of degree of carboxymethyl substitution (DS) per anhydroglucose unit]
About 2.0 g of the sample was precisely weighed and placed in a 300 ml Erlenmeyer flask with a stopper. 100 ml of methanol nitric acid (a solution obtained by adding 100 ml of special concentrated nitric acid to 1 L of anhydrous methanol) was added and shaken for 3 hours to convert sodium carboxymethylcellulose (Na-CMC) to carboxymethylcellulose (H-CMC). The absolute dry H-CMC 1.5-2.0 g was precisely weighed and put into a 300 ml Erlenmeyer flask with a stopper. H-CMC was moistened with 15 ml of 80% methanol, 100 ml of 0.1N NaOH was added, and the mixture was shaken at room temperature for 3 hours. As an indicator, using phenolphthalein was back titrated excess NaOH with 0.1N-H 2 SO 4. The DS was calculated by substituting the amount (ml) of 0.1N—H 2 SO 4 required for titration into the following equation.
A = ((100 × F′−0.1N—H 2 SO 4 (ml) × F) × 0.1) / absolute dry weight of H-CMC (g)
DS = 0.162 × A / (1-0.058 × A) (mol / C 6)
A: Amount of 1N NaOH required to neutralize 1 g of H-CMC (ml)
F: factor of 0.1N—H 2 SO 4
F ′: 0.1N-NaOH factor
[結晶化度の測定]
セルロースＩ型の結晶化度は、試料のＸ線回折を測定することで求めた。Ｘ線回折の測定は、試料をガラスセルに乗せ、Ｘ線回折測定装置（ＲＡＤ−２Ｃシステム、理学電気社製）を用いて測定した。結晶化度の算出はＳｅａｇｅｌらの手法（Ｌ．Ｓｅａｇｅｌ，Ｊ．Ｊ．Ｇｒｅｅｌｙ ｅｔ ａｌ，Ｔｅｘｔ．Ｒｅｓ．Ｊ．，２９，７８６，１９５９）、並びにＫａｍｉｄｅらの手法（Ｋ．Ｋａｍｉｄｅ，ｅｔ ａｌ，ｐｏｌｙｍｅｒ Ｊ．，１７，９０９，１９８５）を用いて行い、Ｘ線回折図の２θ＝４°〜３２°の回折強度をベースラインとして、２θ＝２２．６°の００２面の回折強度と２θ＝１８．５°のアモルファス部分の回折強度から次式により算出した。
ｘｃ＝（Ｉ００２Ｃ−Ｉａ）／Ｉ００２Ｃ×１００
ｘｃ＝セルロースＩ型の結晶化度（％）
Ｉ００２Ｃ：２θ＝２２．６°，００２面の回折強度
Ｉａ ：２θ＝１８．５°，アモルファス部分の回折強度
[Measurement of crystallinity]
The crystallinity of cellulose type I was determined by measuring the X-ray diffraction of the sample. The X-ray diffraction was measured by placing the sample on a glass cell and using an X-ray diffraction measurement apparatus (RAD-2C system, manufactured by Rigaku Corporation). The crystallinity is calculated by the method of Seagel et al. (L. Seagel, JJ Greery et al, Text. Res. J., 29, 786, 1959) and the method of Kamide et al. (K. Kamide, et al, polymer J., 17, 909, 1985), with the diffraction intensity of 2θ = 4 ° to 32 ° of the X-ray diffraction diagram as the baseline, the diffraction intensity of the 002 plane of 2θ = 22.6 ° and 2θ = It calculated from the following formula from the diffraction intensity of the amorphous portion at 18.5 °.
xc = (I 002C -I a ) / I 002C × 100
xc = crystallinity of cellulose type I (%)
I 002C : 2θ = 22.6 °, diffraction intensity of 002 plane I a : 2θ = 18.5 °, diffraction intensity of amorphous part
[膨潤度の測定]
レーザー回折・散乱式粒度分布計（マイクロトラック Ｍｏｄｅｌ−９２２０−ＳＲＡ、日機装（株）製）により測定される体積累計５０％粒子径（平均粒子径）において、膨潤溶媒である水を分散媒に用いて測定した値の非膨潤溶媒であるメタノールを分散媒に用いて測定した値に対する比を膨潤度とした。
[Measurement of swelling degree]
In a cumulative volume of 50% particle diameter (average particle diameter) measured by a laser diffraction / scattering particle size distribution analyzer (Microtrac Model-9220-SRA, manufactured by Nikkiso Co., Ltd.), water as a swelling solvent is used as a dispersion medium. The ratio of the measured value to the value measured using methanol, which is a non-swelling solvent, as the dispersion medium was defined as the degree of swelling.
[溶解性試験]
実施例および比較例の添加剤２ｇを水１００ｍｌ中に加え、スターラーで３時間撹拌後、その状態を目視判定した。尚、評価は以下の様に定めた。尚、試料のうち一部でも不溶性を示せばその部分を分離、抽出等して不溶性のカルボキシメチルセルロース又はその塩として利用可能である。よって、下記評価のうち「×」のほか「△」である試料は、水不溶性を示すものと判断できる。
○：溶解、△：一部溶解、×：不溶
[Solubility test]
2 g of the additives of Examples and Comparative Examples were added to 100 ml of water, and after stirring for 3 hours with a stirrer, the state was visually determined. The evaluation was determined as follows. If any part of the sample shows insolubility, the part can be separated, extracted, etc., and used as insoluble carboxymethylcellulose or a salt thereof. Therefore, in the following evaluations, samples with “Δ” in addition to “x” can be judged to show water insolubility.
○: dissolved, Δ: partially dissolved, ×: insoluble
［気泡安定性試験］
１Ｌ（リットル）容ポリ容器に水３００ｍｌを入れ、ホモミキサー（８，０００ｒｐｍ）で攪拌しながら、実施例および比較例の添加剤を６ｇ添加し、５分間攪拌して溶解または分散させる。起泡剤としてラウリル硫酸ナトリウムを２ｇ添加し、更に２分間攪拌して気泡を調整する。調整直後、１０分後、１２０分後の気泡の安定性を目視判定した。なお、結果は以下のように定めた。
◎：気泡が均一に分散しており、気泡の合一もない
○：気泡は液体中に分散しているが、気泡が一部合一している
△：気泡と液体が一部分離している
×：気泡と液体が完全に分離している
[Bubble stability test]
Add 300 g of water to a 1 L (liter) container, add 6 g of the additives of Examples and Comparative Examples while stirring with a homomixer (8,000 rpm), and dissolve or disperse by stirring for 5 minutes. 2 g of sodium lauryl sulfate is added as a foaming agent, and the mixture is further stirred for 2 minutes to adjust bubbles. Immediately after the adjustment, the stability of the bubbles after 10 minutes and 120 minutes was visually determined. The results were determined as follows.
A: Bubbles are uniformly dispersed, and there is no coalescence of the bubbles. B: The bubbles are dispersed in the liquid, but some of the bubbles are united. Δ: The bubbles and the liquid are partly separated. : Bubbles and liquid are completely separated
［気泡の弾力性試験］
１Ｌ（リットル）容ポリ容器に水３００ｍｌを入れ、ホモミキサー（８，０００ｒｐｍ）で攪拌しながら、実施例および比較例の添加剤を６ｇ添加し、５分間攪拌して溶解または分散させる。起泡剤としてラウリル硫酸ナトリウムを２ｇ添加し、更に２分間攪拌して気泡を調整する。調整直後の気泡を手で触り気泡の弾力性を判定した。なお、結果は以下のように定めた。
◎：気泡は、スポンジ様の強い弾力を持っている
○：気泡は、スポンジほどではないがある程度の弾力を持っている。
△：気泡は、若干弾力を持っている。
×：気泡には、全く弾力がない。
[Bubble elasticity test]
Add 300 g of water to a 1 L (liter) container, add 6 g of the additives of Examples and Comparative Examples while stirring with a homomixer (8,000 rpm), and dissolve or disperse by stirring for 5 minutes. 2 g of sodium lauryl sulfate is added as a foaming agent, and the mixture is further stirred for 2 minutes to adjust bubbles. The elasticity of the bubbles was judged by touching the bubbles immediately after the adjustment. The results were determined as follows.
A: Bubbles have a strong elasticity like a sponge B: Bubbles have some elasticity, although not as much as a sponge.
Δ: The bubbles have some elasticity.
X: The bubbles have no elasticity at all.
表１の結果から明らかなように、実施例の添加剤は、気泡の合一を抑制し、長時間気泡の安定性を保ち、弾力性があることが分かる。また、図１、図２から実施例２の気泡は、細かく、時間が経過しても気泡の合一は抑制されていることがわかる。 As is apparent from the results in Table 1, it can be seen that the additives of the examples suppress the coalescence of bubbles, maintain the stability of the bubbles for a long time, and have elasticity. Moreover, it turns out that the bubble of Example 2 is fine from FIG. 1, FIG. 2, and coalescence of the bubble is suppressed even if time passes.
Claims (3)
When the carboxymethyl cellulose has a cumulative volume of 50% measured by a laser diffraction / scattering particle size distribution meter, the ratio of the value measured with water as the dispersion medium to the value measured with methanol as the dispersion medium is 2.0. It is the above, The additive for bubble-containing compositions of Claim 1 characterized by the above-mentioned.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010057393A (en) * | 2008-09-02 | 2010-03-18 | Nippon Paper Chemicals Co Ltd | Gel-like food and method for producing the same |
| JP2011121916A (en) * | 2009-12-11 | 2011-06-23 | Kao Corp | Dentifrice composition |
| JP2013253203A (en) * | 2012-06-08 | 2013-12-19 | Kao Corp | Detergent composition |
| EP3459366A4 (en) * | 2016-05-16 | 2020-03-11 | Nippon Paper Industries Co., Ltd. | Additive for food |
| WO2022114076A1 (en) * | 2020-11-27 | 2022-06-02 | 日本製紙株式会社 | Additive for use in production of air bubble-containing composition |
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| JP2011121916A (en) * | 2009-12-11 | 2011-06-23 | Kao Corp | Dentifrice composition |
| JP2013253203A (en) * | 2012-06-08 | 2013-12-19 | Kao Corp | Detergent composition |
| EP3459366A4 (en) * | 2016-05-16 | 2020-03-11 | Nippon Paper Industries Co., Ltd. | Additive for food |
| WO2022114076A1 (en) * | 2020-11-27 | 2022-06-02 | 日本製紙株式会社 | Additive for use in production of air bubble-containing composition |
| CN116615465A (en) * | 2020-11-27 | 2023-08-18 | 日本制纸株式会社 | Additive for producing composition containing air bubbles |
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