JP2003253586A - Paper additive and water and moisture retaining paper using the same - Google Patents
Paper additive and water and moisture retaining paper using the sameInfo
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- JP2003253586A JP2003253586A JP2002058524A JP2002058524A JP2003253586A JP 2003253586 A JP2003253586 A JP 2003253586A JP 2002058524 A JP2002058524 A JP 2002058524A JP 2002058524 A JP2002058524 A JP 2002058524A JP 2003253586 A JP2003253586 A JP 2003253586A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、保水・保湿機能を
向上させるための紙用添加剤及びそれを用いた保水・保
湿紙に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper additive for improving a water retention / humidification function and a water retention / humidity paper using the same.
【０００２】[0002]
【従来の技術】近年、建築物の気密性が向上し、結露の
問題が多く発生するようになってきている。これに対し
て、建築内部の障子、ふすま、壁紙等の高い保水性また
は保湿性が要望されている。また、食品包装材料、特に
生鮮魚介類および肉類等の水分吸収を促進する食品用吸
液シートや使い捨ておむつ等の吸収性材料に用いる紙等
についても、同様な品質が要望されている。2. Description of the Related Art In recent years, the airtightness of buildings has been improved, and the problem of dew condensation has been increasing. On the other hand, high water retention or moisture retention of shoji, bran, wallpaper, and the like inside a building is required. In addition, similar qualities are required for food packaging materials, especially paper used for absorbent materials for food such as fresh fish and shellfish and meat, and absorbent materials such as disposable diapers.
【０００３】これらの問題を解決するために、高保水・
保湿性能を有する高吸水性ホ゜リマーを配合する方法(特開昭
58-186437号、特公平1-49112号)が知られている。ま
た、カルホ゛キシメチルセルロースを配合する方法としては、水に不溶
性のカルホ゛キシメチルセルロースとハ゜ルフ゜を混抄した後、アンモニアで中和
する方法(特公昭40-968号)、カルホ゛キシメチルセルロースアルミニウム塩の
ような水不溶性塩とハ゜ルフ゜を混抄した後、アルカリ金属化合
物で処理する方法(特公昭43-28766号)、カルホ゛キシメチルセルロース
ナトリウム塩とフィフ゛リル化したハ゜ルフ゜を水性有機溶媒中で均一に
混合後、抄紙する方法(特公昭56-8160号)が知られてい
る。[0003] In order to solve these problems, high water retention
Method of blending superabsorbent polymer having moisture retention performance
No. 58-186437, Tokuhei 1-49112) are known. Further, as a method of blending carboxymethylcellulose, a method of mixing carboxymethylcellulose and water-insoluble in water and then neutralizing with ammonia (Japanese Patent Publication No. 40-968), a method of mixing water-insoluble salts such as aluminum salt of carboxymethylcellulose. A method of mixing paper and treating it with an alkali metal compound (Japanese Patent Publication No. 43-28766), a method of uniformly mixing carboxymethylcellulose sodium salt and a fibrillated resin in an aqueous organic solvent, and then making a paper (Japanese Patent Publication No. 56-28766). No. 8160) is known.
【０００４】しかし、高吸水性ホ゜リマーを配合する方法
は、吸収能力は大きいが、食品用吸収シート等に使用する
場合、袋・シート等から高吸水性ホ゜リマーが脱落し、食品衛生
上問題が生じる恐れがあった。さらに、カルホ゛キシメチルセルロース
もしくはカルホ゛キシメチルセルロースナトリウム塩を混抄する方法は、連
続的な抄紙時に完全な中和あるいはアルカリ処理を行うこと
は極めて困難であり、製品品質上極めて問題が多いこ
と、また、有機溶媒を使用する場合は製造コストが大幅に
上昇するという問題があった。[0004] However, the method of blending the superabsorbent polymer has a large absorption capacity, but when used in an absorbent sheet for food, the superabsorbent polymer falls off from bags, sheets, etc., causing a problem in food hygiene. There was fear. Further, the method of mixing carboxymethylcellulose or carboxymethylcellulose sodium salt is extremely difficult to perform complete neutralization or alkali treatment during continuous papermaking, which is extremely problematic in terms of product quality. When used, there is a problem that the manufacturing cost is significantly increased.
【０００５】[0005]
【発明が解決しようとする課題】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、高い保水・保湿性能を有する紙用添加剤およびそれ
を用いた保水・保湿紙を提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and has an additive for paper having high water retention and moisture retention properties and water retention using the same.・ Provides moisturizing paper.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、簡便な製
造法で高い保水・保湿性を有する紙について鋭意検討を
重ねた結果、紙用添加剤として、水膨潤性または水不溶
性のカルホ゛キシメチルセルロースナトリウム塩（以下、ＣＭＣと略）を配
合することで、上記課題を解決できることを見い出し、
この知見に基づいて本発明をなすに至った。Means for Solving the Problems The present inventors have conducted intensive studies on paper having high water retention and moisture retention by a simple manufacturing method, and as a result, water-swellable or water-insoluble carboxydioxane is used as a paper additive. By blending methylcellulose sodium salt (hereinafter abbreviated as CMC), it was found that the above problem could be solved.
The present invention has been accomplished based on this finding.
【０００７】即ち、軽度にカルホ゛キシメチル化した水膨潤性ま
たは水不溶性のＣＭＣは、水に対する親和性が、ハ゜ルフ゜
と比較し、格段に向上することで、ハ゜ルフ゜が持つ保水・保
湿性能をさらに高めることが出来、かつセルロース部分を有
するため、ハ゜ルフ゜との混抄が容易であると推定される。[0007] That is, the water-swellable or water-insoluble CMC which has been slightly carboxymethylated has a much higher affinity for water than that of the mold, thereby further enhancing the water retention and moisture retention properties of the mold. It is presumed that blending with cellulose is easy because of the presence of cellulose and a cellulose portion.
【０００８】[0008]
【発明実施の形態】本発明の水膨潤性または水不溶性の
ＣＭＣは、セルロースを発底原料とし軽度にカルホ゛キシメチル化反応
を行うことで製造される。BEST MODE FOR CARRYING OUT THE INVENTION The water-swellable or water-insoluble CMC of the present invention is produced by carrying out a mild carboxymethylation reaction using cellulose as a starting material.
【０００９】セルロース原料としては、晒または未晒木材ハ゜ル
フ゜、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
ロース等の天然セルロースや、セルロースを銅アンモニア溶液、モルホリン誘導
体等何らかの溶媒に溶解し、改めて紡糸された再生セルロー
ス、および上記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、振動ホ゛ールミル処理等によって解
重合処理した微細セルロースまたは機械的に処理した微細セルロ
ースが例示される。[0009] As a raw material for cellulose, natural cellulose such as cellulose produced by microorganisms such as bleached or unbleached wood balms, refined linters, and acetic acid bacteria, or cellulose is dissolved in a solvent such as a copper ammonia solution or a morpholine derivative, and then renewed. Examples include spun regenerated cellulose, fine cellulose obtained by depolymerizing the above-mentioned cellulosic material by acid hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibration ball mill treatment or the like, or mechanically treated fine cellulose.
【００１０】水膨潤性または水不溶性のＣＭＣは、公知
の方法、例えば、セルロース原料を水酸化ナトリウムなどのアルカリで
マーセル化し、次いでカルホ゛キシメチル化剤であるモノクロル酢酸または
モノクロル酢酸ナトリウムでエーテル化反応を行うという製法を適用す
る。Water-swellable or water-insoluble CMC can be obtained by a known method, for example, by mercerizing a cellulose raw material with an alkali such as sodium hydroxide, and then subjecting it to etherification reaction with monocarboxylic acetic acid or sodium monochloroacetate as a carboxymethylating agent. Apply the manufacturing method of doing.
【００１１】例えば、セルロースを発底原料とし、溶媒に3〜
20重量倍の低級アルコール、具体的にはメタノール、エタノール、n-フ゜ロ
ヒ゜ルアルコール、イソフ゜ロヒ゜ルアルコール、n-フ゛タノール、イソフ゛タノール、第3級
フ゛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
体を使用する。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％である。マーセル化剤としては、
発底原料のク゛ルコース残基当たり0.5〜20倍モルの水酸化アルカリ
金属、具体的には水酸化ナトリウム、水酸化カリウムを使用す
る。発底原料と溶媒、マーセル化剤を混合し、反応温度0〜7
0℃、好ましくは10〜60℃、かつ反応時間15分〜8時間、
好ましくは30分〜7時間、マーセル化処理を行う。その後、カ
ルホ゛キシメチル化剤を発底原料のク゛ルコース残基当たり0.05〜2.0
倍モル添加し、反応温度30〜90℃、好ましくは40〜80℃、
かつ反応時間30分〜10時間、好ましくは1時間〜4時間、
エーテル化反応させる。[0011] For example, cellulose is used as a starting material and the solvent is 3 to
A mixture of water with a 20-fold by weight lower alcohol, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-phthalanol, isophthalanol, tertiary phthalanol, etc., or a mixture of two or more thereof and water. use. The ratio of the lower alcohol to the total of the lower alcohol and water is 60 to 95% by weight. As mercerizing agents,
0.5 to 20 times mol of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide, is used per glucose residue of the starting material. Mix the bottoming material, solvent and mercerizing agent, and react at a reaction temperature of 0 to 7.
0 ° C., preferably 10 to 60 ° C., and a reaction time of 15 minutes to 8 hours,
The mercerization treatment is preferably performed for 30 minutes to 7 hours. Thereafter, the carboxymethylating agent is added in an amount of 0.05 to 2.0 per glucose residue of the starting material.
The reaction temperature is 30 to 90 ° C, preferably 40 to 80 ° C,
And reaction time 30 minutes to 10 hours, preferably 1 hour to 4 hours,
Allow etherification reaction.
【００１２】尚、水膨潤性または水不溶性のカルホ゛キシメチルセ
ルロースナトリウム塩は必要に応じて、洗浄工程、乾燥工程、粉
砕工程、分級工程を経たものであっても問題はない。The water-swellable or water-insoluble sodium salt of carboxymethylcellulose may be subjected to a washing step, a drying step, a pulverizing step and a classification step, if necessary, without any problem.
【００１３】本発明では、ク゛ルコース残基当たりカルホ゛キシメチル
基の置換度(以下、CM-DSと略)が0.05〜0.50で、かつ１
％水溶液粘度が2〜300mPa・sの範囲にある水膨潤性また
は水不溶性のＣＭＣが好ましい。CM-DSが0.05未満もし
くは１％水溶液粘度が2mPa・s未満であれば、保水・保湿
性が低下するために好ましくない。また、CM-DSが0.50
もしくは１％水溶液粘度が300mPa・sを越えた場合、水に
対する溶解性が高まり、抄紙時、抄紙機からの剥離性が
低下するために好ましくないからである。より好ましく
は、CM-DSが0.10〜0.45、かつ１％水溶液粘度が3〜100m
Pa・sの範囲である。本発明における粘度とは、Ｂ型回転
粘度計(ローターNO.2、回転数30rpm)により、25℃にて
無水物換算１％水溶液を測定した値である。In the present invention, the degree of substitution of a carboxymethyl group per glucose residue (hereinafter abbreviated as CM-DS) is 0.05 to 0.50 and 1
A water-swellable or water-insoluble CMC having a% aqueous solution viscosity of 2 to 300 mPa · s is preferred. If the CM-DS is less than 0.05 or the 1% aqueous solution viscosity is less than 2 mPa · s, it is not preferable because water retention and moisture retention are reduced. In addition, CM-DS is 0.50
Alternatively, if the viscosity of the 1% aqueous solution exceeds 300 mPa · s, the solubility in water increases, and the removability from the paper machine at the time of papermaking decreases, which is not preferable. More preferably, CM-DS is 0.10 to 0.45, and 1% aqueous solution viscosity is 3 to 100 m
It is in the range of Pa · s. The viscosity in the present invention is a value obtained by measuring a 1% aqueous solution in terms of anhydride at 25 ° C. using a B-type rotational viscometer (rotor No. 2, rotation speed 30 rpm).
【００１４】なお、本発明の紙用添加剤としては、水膨
潤性または水不溶性のＣＭＣを50重量%以上配合するも
のであり、その他の成分としては、従来使用されている
非木材植物繊維、レーヨン繊維、わらハ゜ルフ゜、麻ハ゜ルフ゜、綿ハ゜
ルフ゜等の植物繊維、化学処理したマーセル化ハ゜ルフ゜や架橋ハ゜ルフ
゜、高吸水性ホ゜リマー等が挙げられ、これらは単独もしくは
併用して使用することが出来る。The paper additive of the present invention contains 50% by weight or more of water-swellable or water-insoluble CMC, and other components include non-wood plant fibers conventionally used. Examples include vegetable fibers such as rayon fiber, straw balm, hemp balm, and cotton balm, chemically treated mercerized balm, crosslinked balm, and superabsorbent polymer. These can be used alone or in combination.
【００１５】本発明では、目的とする保水・保湿紙の性
能に応じて、パルプに対して、水膨潤性または水不溶性
のＣＭＣからなる紙用添加剤20〜95重量％（対固形分）
配合し、混抄するのが好ましい。紙用添加剤の配合量が
20重量％未満であれば、保水・保湿性能の向上が見られ
ない。また、配合量が95重量％を超えると、水膨潤性ま
たは水不溶性のＣＭＣは化学処理を行っている分、ハ゜ルフ
゜を比較し、強度が若干低下しているため、製品である
保水・保湿紙の強度が低下する場合があり、好ましくな
い。より好ましくは、30〜80重量％である。According to the present invention, depending on the desired performance of the water-retaining and moisturizing paper, a paper additive composed of water-swellable or water-insoluble CMC is added to the pulp in an amount of 20 to 95% by weight (based on solid content).
It is preferable to mix and mix. The amount of additive for paper is
If it is less than 20% by weight, no improvement in water retention / moisture retention performance is observed. If the amount exceeds 95% by weight, the water-swellable or water-insoluble CMC has undergone a chemical treatment, and its strength is slightly reduced as compared to the mold. May be reduced, which is not preferable. More preferably, it is 30 to 80% by weight.
【００１６】本発明における保水・保湿紙は、目的に応
じた物性を付与するために、水膨潤性または水不溶性の
ＣＭＣからなる紙用添加剤の他に、必要に応じて、紙力
増強剤、保湿剤、合成繊維、無機繊維、顔料等を本発明
の効果を損なわない範囲で任意に配合することが出来
る。The water-retaining and moisturizing paper of the present invention may further comprise, if necessary, a paper-strengthening agent, in addition to a water-swellable or water-insoluble CMC additive, in order to impart physical properties according to the purpose. , A humectant, a synthetic fiber, an inorganic fiber, a pigment and the like can be arbitrarily compounded within a range that does not impair the effects of the present invention.
【００１７】紙力増強剤としては、澱粉、変性澱粉、水
可溶性のカルホ゛キシメチルセルロースナトリウム塩、ク゛アーカ゛ム、ホ゜リヒ゛ニルアルコ
ール、ホ゜リアクリルアミト゛、アラヒ゛アカ゛ム、アルキ゛ン酸ソータ゛、ホ゜リアクリル酸ソ
ータ゛、酢酸ヒ゛ニル系重合体やアクリル系重合体やスチレン系重合体
に代表される合成樹脂エマルション等が挙げられる。Examples of the paper strength enhancer include starch, modified starch, water-soluble sodium salt of carboxymethylcellulose, quarcum, polyalcohol, polyacrylamide, arachikam, alkionic acid sorter, polyacrylic acid sorter, phenylacetate polymer and acrylic resin. Examples include a synthetic resin emulsion represented by a polymer or a styrene-based polymer.
【００１８】保湿剤としては、ク゛リセリン、シ゛ク゛リセリン、平均
分子量200〜1000のホ゜リエチレンク゛リコール、ソルヒ゛ット、フ゜ロヒ゜レンク゛リ
コール、1,3-フ゛チレンク゛リコール、ク゛リシンヘ゛タイン、ヒ゜ロリト゛ンカルホ゛ン酸、
ヒ゜ロリト゛ンカルホ゛ン酸塩、マルチトール、乳酸ナトリウム等が挙げられ、
特に、ク゛リセリン単独、またはク゛リセリン及びソルヒ゛ットの併用が好
ましい。Examples of the humectant include glycerin, polyglycerin, polyethylene glycol having an average molecular weight of 200 to 1,000, sorbitol, propylene glycol, 1,3-butylene glycol, glycine heptaine, chlorotonic carboxylic acid,
Hydrolitonic acid carbonate, maltitol, sodium lactate and the like,
In particular, glycerin alone or a combination of glycerin and sorbitol is preferred.
【００１９】合成繊維としては、ホ゜リアミト゛繊維、ホ゜リフ゜ロヒ
゜レン繊維、ホ゜リエステル繊維等、無機繊維としては、カ゛ラス繊
維、マックウール、スラク゛ウール、シリカウール、シリカアルミウール等が挙げられ
る。Examples of the synthetic fibers include polyamide fibers, polypropylene fibers, polyester fibers and the like, and examples of the inorganic fibers include glass fibers, mac wool, slack wool, silica wool and silica aluminum wool.
【００２０】顔料としては、クレー、炭酸カルシウム、カオリン、酸
化チタン、タルク、酸化亜鉛、活性白土、セ゛オライト、サチンホワイト、
水酸化アルミニウム、シリカ、シラスハ゛ルーン、ヘ゛ントナイト等の無機顔料や
尿素樹脂、スチレン重合体、スチレン/フ゛タシ゛エン系共重合体または
スチレン/アクリル系共重合体からなるフ゜レスチックヒ゜ク゛メント、中空ヒ゜ク
゛メント等の有機顔料が挙げられる。Examples of pigments include clay, calcium carbonate, kaolin, titanium oxide, talc, zinc oxide, activated clay, seolite, satin white,
Inorganic pigments such as aluminum hydroxide, silica, silica glass, pentonite and the like, and organic pigments such as urea resin, styrene polymer, styrene / phthalic acid copolymer or styrene / acrylic copolymer, plastic pigment and hollow pigment. No.
【００２１】[0021]
【実施例】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」を示し
た。The embodiments of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, all "parts" indicating the blending amount are "parts by weight".
【００２２】製造例１
回転数を100rpmに調節した二軸ニータ゛ーに99%イソフ゜ロヒ゜ルアルコー
ル911部と水酸化ナトリウム78.7部を水189部に溶解したものと
を加え、市販の溶解ハ゜ルフ゜(NDPS、日本製紙（株）製)を
絶乾で200部仕込んだ。30℃で90分間攪拌、混合しアルカリセ
ルロースを調製後、さらに、攪拌しつつ90%イソフ゜ロヒ゜ルアルコール90
部に溶解したモノクロル酢酸26部を添加し、30分で70℃に昇
温し、90分間反応させた。反応終了後、80%メタノールで2回
洗浄、中和、脱液、乾燥し、CM-DS 0.18、１％水溶液粘
度5mPa・sのCMC（１）を得た。得られたCMC（１）につい
て、以下の水溶解性試験を行った。結果を表１に示す。Production Example 1 A mixture of 911 parts of 99% isopropanol and 78.7 parts of sodium hydroxide dissolved in 189 parts of water was added to a biaxial neater whose rotation speed was adjusted to 100 rpm, and a commercially available dissolving valve (NDPS, Nippon Paper Industries) was used. 200 parts) was prepared in an absolutely dry state. After stirring and mixing at 30 ° C. for 90 minutes to prepare alkali cellulose, 90% isopropyl alcohol 90 is further stirred.
26 parts of the dissolved monochloroacetic acid was added, the temperature was raised to 70 ° C. in 30 minutes, and the mixture was reacted for 90 minutes. After completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, and dried to obtain CMC (1) having a CM-DS of 0.18 and a 1% aqueous solution viscosity of 5 mPa · s. The following CMC (1) was subjected to the following water solubility test. Table 1 shows the results.
【００２３】製造例２
回転数を100rpmに調節した二軸ニータ゛ーに99%イソフ゜ロヒ゜ルアルコー
ル1044部と水酸化ナトリウム69.8部を水162部に溶解したもの
とを加え、市販の溶解ハ゜ルフ゜（NDPS、日本製紙（株）
製）を絶乾で200部仕込んだ。30℃で90分間攪拌、混合
しアルカリセルロースを調製後、さらに、攪拌しつつ90%イソフ゜ロヒ゜ル
アルコール90部に溶解したモノクロル酢酸34部を添加し、30分で70
℃に昇温し、90分間反応させた。反応終了後、中和、脱
液、乾燥、粉砕し、CM-DS 0.27、１％水溶液粘度12mPa・
sのCMC（２）を得た。Production Example 2 To a biaxial neater whose rotation speed was adjusted to 100 rpm, 1044 parts of 99% isopropyl alcohol and 69.8 parts of sodium hydroxide dissolved in 162 parts of water were added, and a commercially available dissolving valve (NDPS, Nippon Paper Industries) was used. (stock)
200 parts) After stirring and mixing at 30 ° C. for 90 minutes to prepare alkali cellulose, 34 parts of monochloroacetic acid dissolved in 90 parts of 90% isopropyl alcohol were added while stirring, and 70 minutes in 30 minutes.
The temperature was raised to ° C., and the reaction was carried out for 90 minutes. After completion of the reaction, neutralize, drain, dry and pulverize, CM-DS 0.27, 1% aqueous solution viscosity 12mPa ·
s CMC (2) was obtained.
【００２４】製造例３
回転数を100rpmに調節した二軸ニータ゛ーに99%イソフ゜ロヒ゜ルアルコー
ル932部と水酸化ナトリウム56.2部を水218部に溶解したものと
を加え、市販の溶解ハ゜ルフ゜（NDPS、日本製紙（株）製）
を絶乾で200部仕込んだ。30℃で90分間攪拌、混合しアルカ
リセルロースを調製後、さらに、攪拌しつつ90%イソフ゜ロヒ゜ルアルコール
90部に溶解したモノクロル酢酸57部を添加し、30分で70℃に
昇温し、90分間反応させた。反応終了後、中和、脱液、
乾燥し、CM-DS 0.42、１％水溶液粘度43mPa・sのCMC
（３）を得た。Production Example 3 932 parts of 99% isopropyl alcohol and 56.2 parts of sodium hydroxide dissolved in 218 parts of water were added to a biaxial neater whose rotation speed was adjusted to 100 rpm, and a commercially available dissolving valve (NDPS, Nippon Paper Industries) was used. (Made by Corporation)
200 parts were dry-blown. After stirring and mixing at 30 ° C. for 90 minutes to prepare an alkali cellulose, further, while stirring, 90% isopropanol alcohol
57 parts of monochloroacetic acid dissolved in 90 parts were added, the temperature was raised to 70 ° C. in 30 minutes, and the mixture was reacted for 90 minutes. After completion of the reaction, neutralization, drainage,
Dry, CM-DS 0.42, CMC with 1% aqueous solution viscosity 43mPa · s
(3) was obtained.
【００２５】＜CM-DSの測定方法＞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、ＣＭＣをカルホ゛キシメチルセルロース（H-CMC）に
した。その絶乾H-CMCを1.5〜2.0g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-H2SO 4で過剰
のNaOHを逆滴定した。CM-DSは次式によって、算出し
た。
A =（（100×F' − 0.1N- H2SO4 (ml)×F)×0.1）/ H-C
MCの絶乾重量(g)
CM-DS = 0.162×A / (1−0.058×A)
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 method of CM-DS> About 2.0 g of a sample is precisely weighed.
And placed in a 300 ml Erlenmeyer flask with a stopper. Methanol nitrate (anhydrous
100 ml of a solution obtained by adding 100 ml of special grade concentrated nitric acid to 1 L of methanol)
Shake for 3 hours to convert CMC to carboxymethylcellulose (H-CMC)
did. 1.5-2.0 g of the absolutely dried H-CMC is precisely weighed, and 300 ml stoppered
In an Erlenmeyer flask equipped with Wet H-CMC with 15 ml of 80% methanol
Then, 100 ml of 0.1N-NaOH was added, and the mixture was shaken at room temperature for 3 hours.
Using phenolphthalein as an indicator, 0.1N-HTwoSO FourIn excess
Of NaOH was back titrated. CM-DS is calculated by the following formula.
Was.
A = ((100 x F '-0.1N-HTwoSOFour (ml) × F) × 0.1) / H-C
Absolute dry weight of MC (g)
CM-DS = 0.162 × A / (1−0.058 × A)
A: The amount of 1N-NaOH required to neutralize 1 g of H-CMC (ml)
F: 0.1N- HTwoSOFourFactor
F ': 0.1N-NaOH factor
【００２６】＜水溶解性試験＞得られたCMC試料2gを水1
00ml中に添加し、スターラーで10分間撹拌後、その状態を目
視で判断した。尚、評価は以下のように定めた。
○：不溶または一部溶解
×：溶解<Water solubility test> 2 g of the obtained CMC sample was
After stirring for 10 minutes with a stirrer, the condition was judged visually. The evaluation was determined as follows. ○: insoluble or partially dissolved ×: dissolved
【００２７】実施例１
NBKP10重量部とCMC(1)90重量部を混合し、フリーネス(CSF)が
650〜660mlになるように叩解した。その後、JIS P 8209
に従い、手抄きシートを作製した。得られたシートについ
て、以下の試験（保水・保湿性能、裂断長）を行った。
結果を表１に示す。Example 1 NBKP (10 parts by weight) and CMC (1) (90 parts by weight) were mixed to give a freeness (CSF).
Beated to 650-660 ml. After that, JIS P 8209
In accordance with the above, a hand-made sheet was prepared. The following tests (water retention / moisture retention performance, tear length) were performed on the obtained sheet.
Table 1 shows the results.
【００２８】実施例２〜３、比較例１〜３
表１における配合で、実施例１と同様にして手抄きシート
を作成した。試験結果を表１に示す。Examples 2 to 3 and Comparative Examples 1 to 3 Hand-made sheets were prepared in the same manner as in Example 1 with the composition shown in Table 1. Table 1 shows the test results.
【００２９】＜保水・保湿性能試験＞前処理として、手
抄きシートを相対湿度22%、25℃条件下で5時間放置し、そ
の重量(W0)を測定した。その後、相対湿度100%、25℃条
件下で3.5時間放置し、そのときの重量(W1)を測定し、
再度、相対湿度22%、25℃条件下で3.5時間放置し、重量
(W2)を測定した。次式により、保湿量を算出し、保水・
保湿性能の評価とした。なお、保湿量が高いほど、保水
・保湿性能が高いといえる。
保湿量（％）＝（（W2−W0）／(W1-W0)）×100<Water retention / moisture retention test> As a pretreatment, a hand-made sheet was left under a condition of 22% relative humidity and 25 ° C. for 5 hours, and its weight (W0) was measured. After that, it was left for 3.5 hours under the condition of 100% relative humidity and 25 ° C, and the weight (W1) at that time was measured.
Again, leave for 3.5 hours at 22% relative humidity and 25 ° C,
(W2) was measured. Calculate the amount of moisture by
The moisturizing performance was evaluated. In addition, it can be said that the higher the moisture retention, the higher the water retention / humidification performance. Moisturizing amount (%) = ((W2-W0) / (W1-W0)) x 100
【００３０】＜強度試験、裂断長＞JIS P 8113に基づ
き、ショッパー式引張試験機（東西精器（株）製）を用
いて、手抄きシートの引張り強さを測定し、下式により列
断長を求めた。
裂断長（ｋｍ）＝（引張り強さ／（試験片の幅×坪
量））×1000<Strength test, tear length> Based on JIS P 8113, the tensile strength of the hand-made sheet was measured using a shopper type tensile tester (manufactured by Tozai Seiki Co., Ltd.), and the following formula was used. The row length was determined. Breaking length (km) = (tensile strength / (width of test piece x basis weight)) x 1000
【００３１】[0031]
【表１】表１ [Table 1] Table 1
【００３２】粉末セルロース※１：商品名 KCフロック W-200G、
日本製紙（株）製
市販CMC※２：商品名サンロース゛F50MC、日本製紙（株）製、
CM-DS 0.70、水可溶性Powdered cellulose * 1 : KC Floc W-200G, trade name
Commercially available CMC manufactured by Nippon Paper Co., Ltd. * 2 : Trade name: Sunloose @ F50MC, manufactured by Nippon Paper Co., Ltd.
CM-DS 0.70, water soluble
【００３３】[0033]
【発明の効果】本発明の紙用添加剤を用いることによ
り、簡便な方法で高い保水・保湿性能を有し、さらに強
度においても十分満足できる、保水・保湿紙を提供する
ことができる。By using the paper additive of the present invention, it is possible to provide a water-retaining and moisture-retaining paper which has high water-retaining and moisture-retaining performances by a simple method and which is sufficiently satisfactory in strength.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 花田 宣弘 島根県江津市江津町1280 日本製紙株式会 社化成品開発研究所内 (72)発明者 把田 雅彦 島根県江津市江津町1280 日本製紙株式会 社化成品開発研究所内 Ｆターム(参考） 4L055 AA02 AC06 AG46 AH50 BD10 EA29 EA32 FA11 GA23 GA30 GA46 GA50 ────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Nobuhiro Hanada 1280 Gotsu-cho, Gotsu-shi, Shimane Nippon Paper Industries Association In-house Chemical Development Laboratory (72) Inventor Masahiko Handa 1280 Gotsu-cho, Gotsu-shi, Shimane Nippon Paper Industries Association In-house Chemical Development Laboratory F term (reference) 4L055 AA02 AC06 AG46 AH50 BD10 EA29 EA32 FA11 GA23 GA30 GA46 GA50
Claims (3)
ースナトリウム塩を含むことを特徴とする紙用添加剤。1. A paper additive comprising water-swellable or water-insoluble sodium salt of carboxymethylcellulose.
ス残基当たりのカルホ゛キシメチル置換度が0.05〜0.50であり、か
つ１％水溶液粘度が2〜300mPa・sである請求項１記載の
紙用添加剤。2. The paper additive according to claim 1, wherein the carboxymethylcellulose sodium salt has a degree of carboxymethyl substitution per glucose residue of 0.05 to 0.50 and a 1% aqueous solution viscosity of 2 to 300 mPa · s. Agent.
パルプに対して、20〜95重量％（対固形分）配合するこ
とを特徴とする保水・保湿紙。3. The paper additive according to claim 1 or 2,
A water-retaining and moisture-retaining paper, which is blended with pulp in an amount of 20 to 95% by weight (based on solid content).
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|---|---|---|---|
| JP2002058524A JP3941545B2 (en) | 2002-03-05 | 2002-03-05 | Paper additive and water / moisturizing paper using the same |
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| JP3941545B2 JP3941545B2 (en) | 2007-07-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185216A (en) * | 2008-02-07 | 2009-08-20 | San-Dia Polymer Ltd | Absorbent resin particle and method of producing the same |
| JP2018150564A (en) * | 2018-07-06 | 2018-09-27 | 東ソー株式会社 | Vinyl chloride polymer latex, polyol composition and method for producing the same |
| JPWO2019230177A1 (en) * | 2018-05-29 | 2021-06-10 | 日本製紙株式会社 | Paper containing carboxymethylated cellulose |
-
2002
- 2002-03-05 JP JP2002058524A patent/JP3941545B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185216A (en) * | 2008-02-07 | 2009-08-20 | San-Dia Polymer Ltd | Absorbent resin particle and method of producing the same |
| JPWO2019230177A1 (en) * | 2018-05-29 | 2021-06-10 | 日本製紙株式会社 | Paper containing carboxymethylated cellulose |
| JP7323515B2 (en) | 2018-05-29 | 2023-08-08 | 日本製紙株式会社 | Paper containing carboxymethylated cellulose |
| JP2018150564A (en) * | 2018-07-06 | 2018-09-27 | 東ソー株式会社 | Vinyl chloride polymer latex, polyol composition and method for producing the same |
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| Publication number | Publication date |
|---|---|
| JP3941545B2 (en) | 2007-07-04 |
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