JP2002201202A - Cationized carboxymethylcellulose sodium salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cationized carboxymethylcellulose sodium salt which is excellent in chemical resistance, surface modification and fixability. SOLUTION: The cationized carboxymethylcellulose sodium salt is characterized in that the substitutional degree of a carboxymethyl group is 0.4 to 2.0 per glucosic residue and the substitutional degree of a cationic group is 0.01 to 1.0 per glucosic residue.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明はカチオン化カルホ゛キシメチルセルロ
ースナトリウム塩(以下、カチオン化CMCと略す)に関するものであ
る。なお、カチオン化CMCは、増粘剤、凝析剤、凝集剤、定
着剤、分散安定剤、洗濯用仕上げ剤、泥水用調整剤、製
紙における歩留まり向上剤、濾水性向上剤、繊維および
繊布等における帯電防止剤、手触り改良剤、化粧品、シャ
ンフ゜ー、リンス、トリートメント等の配合剤、糊剤、接着剤、インク等
の配合剤等として使用できる。The present invention relates to a cationized carboxymethylcellulose sodium salt (hereinafter abbreviated as cationized CMC). The cationized CMC is a thickener, a coagulant, a flocculant, a fixing agent, a dispersion stabilizer, a finishing agent for washing, a modifier for muddy water, a retention improver in papermaking, a drainage improver, fibers and textiles, etc. And cosmetic additives such as cosmetics, shampoos, rinses and treatments, and adhesives, adhesives and inks.

【０００２】[0002]

【従来の技術】従来より、カルホ゛キシメチルセルロースナトリウム塩(以
下、CMCと略す)は、アニオン性の水溶性高分子として、増粘
性、接着性、分散性、乳化安定性、保護コロイト゛性、フィルム
形成性等の特徴を有すため、食品工業、医薬品工業、化
粧品工業、繊維工業、製紙工業等、広範な分野で使用さ
れている。2. Description of the Related Art Conventionally, sodium carboxymethylcellulose (hereinafter abbreviated as CMC) has been known as an anionic water-soluble polymer as a thickening agent, an adhesive agent, a dispersing agent, an emulsifying agent, a protective colloid, a film forming agent. Because of these features, it is used in a wide range of fields such as the food industry, the pharmaceutical industry, the cosmetics industry, the textile industry, and the paper industry.

【０００３】CMCの耐薬品性、分散安定性、保護コロイト゛
性、チキソトロヒ゜ー性等の物性を大きく左右する因子として、
カルホ゛キシメチル化反応の均一性が挙げられる。即ち、溶媒法
によるCMCの製造法は、先ずセルロースにアルカリを作用させてアル
カリセルロースを調製し、その後エーテル化剤としてモノクロル酢酸を添
加して、エーテル化反応を行うのが一般的である。[0003] Factors that greatly affect the physical properties of CMC, such as chemical resistance, dispersion stability, protective colloid properties, and thixotropic properties, are as follows:
Uniformity of the carboxymethylation reaction. That is, in the method for producing CMC by a solvent method, generally, an alkali is acted on cellulose to prepare alkali cellulose, and then monochloroacetic acid is added as an etherifying agent to carry out an etherification reaction.

【０００４】しかし、アルカリセルロースを調製後にモノクロル酢酸を
エーテル化剤として使用する場合、強酸に近いモノクロル酢酸と
強アルカリであるアルカリセルロース中の水酸化ナトリウムが急激に中和反
応を起こし、それにより発生する中和熱によって系内の
温度が局部的に上昇し、モノクロル酢酸添加中不均一にエーテル
化反応が進行するため、カルホ゛キシメチル基が不均一に置換さ
れる結果となっていた。However, when monochloroacetic acid is used as an etherifying agent after alkali cellulose is prepared, monochloroacetic acid, which is close to a strong acid, and sodium hydroxide in alkali cellulose, which is a strong alkali, suddenly cause a neutralization reaction, which is generated. Due to the heat of neutralization, the temperature inside the system was locally increased, and the etherification reaction proceeded heterogeneously during the addition of monochloroacetic acid, resulting in heterogeneous substitution of the carboxymethyl group.

【０００５】そこで、CMCの耐薬品性、分散安定性、保
護コロイト゛性、チキソトロヒ゜ー性等の物性を改良させるために、カ
ルホ゛キシメチル化反応を均一に行うことで対処する試みがなさ
れてきた(特公昭60-35361号公報等)。特公昭60-35361号
公報では、アルカリを含むアルコール水溶液中でも比較的安定で
加水分解速度の遅いエーテル化剤として、CMCの反応溶媒と
して最も一般的に使用されるイソフ゜ロヒ゜ルアルコールのモノクロル酢酸
エステル(モノクロル酢酸イソフ゜ロヒ゜ル)を用いて、CMCの製造を行う方
法が提示されている。Therefore, in order to improve the physical properties of CMC such as chemical resistance, dispersion stability, protective colloid property, and thixotropic property, attempts have been made to uniformly carry out a carboxymethylation reaction (Japanese Patent Publication No. No. 60-35361). Japanese Patent Publication No. 60-35361 discloses a monochloroacetic acid ester of isochlorohydric alcohol (monochloroacetic acid) which is most commonly used as a reaction solvent for CMC as an etherifying agent which is relatively stable even in an aqueous alcohol solution containing an alkali and has a slow hydrolysis rate. A method for producing CMC by using isopropyl) has been proposed.

【０００６】しかし、この方法で、モノクロル酢酸イソフ゜ロヒ゜ル
を得るためには、ヘ゛ンセ゛ンなどの溶媒の存在下、モノクロル酢
酸をイソフ゜ロヒ゜ルアルコールで煮沸する程の温度で、20〜24時間
反応させなければ95%程度のエステル化率のものが得られな
いなど、その調製は煩雑であり、また長時間を要する等
の問題があった。However, in order to obtain isopropyl monochloroacetate by this method, it is necessary to react monochloroacetic acid in the presence of a solvent such as benzene at a temperature such that monochloroacetic acid is boiled with isopropyl alcohol for about 20 to 24 hours without about 95%. However, there is a problem that the preparation is complicated and a long time is required, for example, the esterification rate cannot be obtained.

【０００７】また、エーテル化剤として、塩タイフ゜であるモノクロ
ル酢酸ナトリウムを使用する方法も考えられる。しかし、モノクロ
ル酢酸と比較し、添加時の中和反応に起因する発熱は生
じないものの、反応効率の低下を招く水以外の溶媒に殆
ど溶解しないこと、また高価であるという問題点があっ
た。[0007] A method using sodium monochloroacetate which is a salt type as an etherifying agent is also conceivable. However, as compared with monochloroacetic acid, although there is no heat generation due to the neutralization reaction at the time of addition, there is a problem that it hardly dissolves in a solvent other than water, which causes a reduction in reaction efficiency, and is expensive.

【０００８】一方、特公昭45-20318号公報には、第4級
窒素含有セルロースエーテルとして、カルホ゛キシル基とカチオン基を併せ持
つセルロース誘導体を提示している。しかし、定着剤や表面
改質剤として満足できるものではなかった。On the other hand, Japanese Patent Publication No. 45-20318 discloses a cellulose derivative having both a carboxyl group and a cationic group as a quaternary nitrogen-containing cellulose ether. However, it was not satisfactory as a fixing agent or a surface modifier.

【０００９】[0009]

【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、CMCの物性改良品として、定着剤や表面改質剤とし
て優れた性能を有するカチオン化CMCを提供することにあ
る。SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems of the prior art, and is excellent as a fixing agent or a surface modifier as a product having improved physical properties of CMC. An object of the present invention is to provide a cationized CMC having high performance.

【００１０】[0010]

【発明を解決するための手段】本発明者等は、CMCの耐
薬品性、分散安定性、保護コロイト゛性、チキソトロヒ゜ー性等の物
性改良について鋭意検討を重ねた結果、セルロースに特定割
合のカルホ゛キシメチル基とカチオン基を導入することで、アニオン性の
水溶性高分子であるCMCでは有さない物性を発現するこ
とを見出し、この知見に基づいて本発明を成すに至っ
た。Means for Solving the Problems The present inventors have conducted intensive studies on the improvement of physical properties such as chemical resistance, dispersion stability, protective colloid property and thixotropy property of CMC. It has been found that by introducing a group and a cationic group, physical properties not possessed by CMC, which is an anionic water-soluble polymer, are exhibited, and the present invention has been accomplished based on this finding.

【００１１】即ち、本発明は、カルホ゛キシメチル基の置換度(CM
-DS)がク゛ルコース残基当たり0.4〜2.0、かつカチオン基の置換度
(CT-DS)がク゛ルコース残基当たり0.01〜1.0であることを特徴
とするカチオン化CMCに関するものである。[0011] That is, the present invention relates to the degree of substitution of a carboxymethyl group (CM
-DS) is 0.4 to 2.0 per glucose residue, and the degree of cationic group substitution
(CT-DS) is 0.01 to 1.0 per glucose residue.

【００１２】[0012]

【発明実施の形態】本発明のカチオン化CMCは、CMCを発底原
料としカチオン化反応を行うか、セルロースを発底原料としカチオン
化反応、次いでカルホ゛キシメチル化反応を行うか、カチオン化反応
とカルホ゛キシメチル化反応を同時に行うことで製造される。即
ち、カチオン化反応はカルホ゛キシメチル化反応の前後または同時の
どの時期で反応しても良い。BEST MODE FOR CARRYING OUT THE INVENTION The cationized CMC of the present invention can be prepared by performing a cationization reaction using CMC as a starting material, a cationization reaction using cellulose as a starting material, and then performing a carboxymethylation reaction or a cationization reaction. It is produced by performing a carboxymethylation reaction simultaneously. That is, the cationization reaction may be performed at any time before, after, or simultaneously with the carboxymethylation reaction.

【００１３】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。[0013] 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 cellulose-based material by acid hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibrating wheel mill treatment or the like, or mechanically treated fine cellulose.

【００１４】CMCは溶媒法または水媒法いずれかの方法
で製造された市販品だけでなく、公知のカルホ゛キシメチル化方
法、例えば、上記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
ル化後に得られた未乾燥未精製CMCも使用可能である。ま
た、カチオン化したセルロースをカルホ゛キシメチル化することも、上記の
方法で同様にすることができる。CMC is not only a commercially available product produced by either the solvent method or the aqueous medium method, but also a known carboxymethylation method, for example, mercerizing the above cellulose material with an alkali such as sodium hydroxide, Undried crude CMC obtained after etherification with acetic acid or sodium monochloroacetate can also be used. Carboxymethylation of the cationized cellulose can be performed in the same manner as described above.

【００１５】本発明では、CM-DSが0.4〜2.0であるCMCを
用いる。この範囲を外れると、定着性、表面改質性にお
いて効果が得られない。0.4未満であれば、CMCとしての
特徴が見られず、2.0を越えると、アニオン化度が強くなり
過ぎ、カチオン基導入の効果が得られないために好ましくな
いからである。更に好ましくは、0.6〜1.8である。In the present invention, a CMC having a CM-DS of 0.4 to 2.0 is used. If the ratio is out of this range, no effect is obtained in the fixing property and the surface modifying property. If it is less than 0.4, the characteristics as CMC cannot be seen, and if it exceeds 2.0, the degree of anionization becomes too strong and the effect of introducing a cationic group is not obtained, which is not preferable. More preferably, it is 0.6 to 1.8.

【００１６】カチオン化反応は、上記セルロースまたはCMCを発底
原料に対し、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
物と水の混合媒体と発底原料のク゛ルコース残基当たり0.01〜
15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し、低級アルコールと水の合計に対する低級ア
ルコールの割合が75〜95重量%からなる組成の混合媒体中で
発底原料をマーセル化処理後、カチオン化剤を発底原料のク゛ルコース
残基当たり0.01〜5.0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時間反応させ、CT-DSが0.01〜1.0になる
ように調節する。In the cationization reaction, the above cellulose or CMC is used as a lower alcohol in an amount of 3 to 20 times by weight based on the starting material, specifically, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-ethanol,
Isophthalanol, tertiary phthalanol, etc. alone, or a mixture of two or more kinds thereof and water, and a mixture medium of water and 0.01 to 0.01% per glucose residue of the starting material
Using a 15-fold molar amount of alkali metal hydroxide, specifically sodium hydroxide and potassium hydroxide, in a mixed medium having a composition in which the ratio of lower alcohol to the total of lower alcohol and water is 75 to 95% by weight. After mercerizing the bottom material, a cationizing agent is added in an amount of 0.01 to 5.0 times mol per glucose residue of the bottom material, and the reaction temperature is 30 to 90 ° C.
The reaction is preferably performed at 40 to 80 ° C. and the reaction time is 30 minutes to 10 hours, preferably 1 hour to 4 hours, and the CT-DS is adjusted to be 0.01 to 1.0.

【００１７】本発明に使用するカチオン化剤としては、ク゛リシ
シ゛ルトリアルキルアンモニウムハライト゛あるいはそのハロヒト゛リン型のものが
使用できる。それらを例示するならば、ク゛リシシ゛ルトリメチルアン
モニウムクロライト゛、ク゛リシシ゛ルトリエチルアンモニウムクロライト゛、ク゛リシシ゛ルトリメチル
アンモニウムフ゛ロミト゛、3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト
゛、3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムフ゛ロミト゛等が挙げら
れる。この添加量は所望するCT-DSにより任意に選択さ
れるが、原料セルロースもしくはCMCのク゛ルコース残基当たり0.01
〜5.0倍モル、好ましくは0.05〜3.0倍モルが適当である。カチ
オン化剤の添加量が原料のク゛ルコース残基当たり0.01倍モル未満
であれば、導入されるカチオン基の置換度が低くなり、原料
のク゛ルコース残基当たり5.0倍モルを越えると、カチオン性が強く
なり過ぎカルホ゛キシメチル基とカチオン基のハ゛ランスが崩れ、物性低下
に繋がり好ましくない。As the cationizing agent used in the present invention, glycidyl trialkylammonium halide or its halo-human phosphorus type can be used. Examples thereof include glycidyltrimethylammonium chlorite, glycidyltriethylammonium chlorite, glycidyltrimethylammonium chromite, 3-chloro-2-human oxyfluorotrimethylammonium chlorite, and 3-chloro-2-human oxyfluorotrimethylammonium chromite. This addition amount is arbitrarily selected depending on the desired CT-DS, but is 0.01 to 0.01% of the glucose residue of the raw material cellulose or CMC.
The molar ratio is suitably from 5.0 to 5.0 times, preferably from 0.05 to 3.0 times. When the amount of the cationizing agent added is less than 0.01 times the molar amount of the raw material glucose residue, the degree of substitution of the introduced cation group becomes low. The balance between the carboxymethyl group and the cationic group is undesirably broken, leading to a decrease in physical properties, which is not preferable.

【００１８】また、カチオン化反応の触媒として、水酸化ナト
リウム、水酸化カリウムのような水酸化アルカリ金属をカチオン化剤の
種類に応じて適宜添加される。触媒量は、カチオン化剤が第
4級エホ゜キサイト゛の場合、カチオン化剤1モル当たり0.01〜1.0モルで
あるが、カチオン化剤が第4級ハロヒト゛リンの場合、カチオン化剤1モル
当たり1.0〜3.0モルである。触媒量が0.01モル(第4級エホ゜キサイ
ト゛使用時)もしくは1.0モル(第4級ハロヒト゛リン使用時)未満の場
合、触媒量が少な過ぎて反応速度が低下し実用的ではな
く、1.0モル(第4級エホ゜キサイト゛使用時)もしくは3.0モル(第4級ハ
ロヒト゛リン使用時)を越えると、副反応が促進されるためと
考えられるが、カチオン化剤の有効利用率が著しく低下し好
ましくない。よって、反応系内の水酸化アルカリ金属の含有
量が上記範囲になるように、カチオン化剤添加前後に水酸化
アルカリ金属を添加したり、また鉱酸および有機酸で中和す
ることで触媒量を調節する。As a catalyst for the cationization reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is appropriately added according to the type of the cationizing agent. The amount of catalyst is
In the case of the quaternary exoxite, the amount is 0.01 to 1.0 mol per mol of the cationizing agent, whereas when the cationizing agent is quaternary halohuman perrin, the amount is 1.0 to 3.0 mol per mol of the cationizing agent. When the amount of the catalyst is less than 0.01 mol (when using quaternary ethoxylate) or less than 1.0 mol (when using quaternary halohitoline), the amount of the catalyst is too small and the reaction rate is lowered, which is not practical. If the amount exceeds 3.0 mol (when using epoxide) or 3.0 mol (when using quaternary halothrodentin), it is considered that a side reaction is promoted, but the effective utilization rate of the cationizing agent is remarkably reduced, which is not preferable. Therefore, the amount of the catalyst is adjusted by adding the alkali metal hydroxide before and after the addition of the cationizing agent or by neutralizing with a mineral acid and an organic acid so that the content of the alkali metal hydroxide in the reaction system is within the above range. Adjust

【００１９】本発明では、CD-DSが0.01〜1.0が好まし
い。この範囲を外れると、定着性、表面改質性において
効果が得られない。CT-DSが0.01未満であれば、カチオン基
導入の効果が得られず、1.0を越えると、カチオン性が強く
為り過ぎてカルホ゛キシル基とカチオン基のハ゛ランスが崩れるために好
ましくないからである。In the present invention, the CD-DS is preferably 0.01 to 1.0. If the ratio is out of this range, no effect is obtained in the fixing property and the surface modifying property. If CT-DS is less than 0.01, the effect of introducing a cationic group cannot be obtained, and if it exceeds 1.0, the cationicity is so strong that the balance between the carboxyl group and the cationic group is lost, which is not preferable.

【００２０】特に、本発明のカチオン化CMCはCM-DSとCT-DS
が下記式1の関係になるものがより好ましい。式１の関
係を満たす場合が、特にカルホ゛キシメチル基（アニオン性）とカチオン
基（カチオン性）のイオンのハ゛ランスが取れ、定着性、表面改質性
等に効果を発揮する。 0.01 ≦ (CT-DS / CM-DS) ≦ 0.5 …式１In particular, the cationized CMC of the present invention comprises CM-DS and CT-DS
Are more preferably those having the relationship of the following formula 1. When the relationship of Formula 1 is satisfied, in particular, the balance between the ions of the carboxymethyl group (anionic) and the cationic group (cationic) can be balanced, and the effect on the fixability, the surface modification property and the like is exerted. 0.01 ≤ (CT-DS / CM-DS) ≤ 0.5… Equation 1

【００２１】カルホ゛キシメチル化反応およびカチオン化反応終了
後、残存した水酸化アルカリ金属を鉱酸または有機酸により
中和後、常法により洗浄、精製、乾燥、粉砕することで
目的とするカチオン化CMCを得ることができる。After the completion of the carboxymethylation reaction and the cationization reaction, the remaining alkali metal hydroxide is neutralized with a mineral acid or an organic acid, and then washed, purified, dried and pulverized by a conventional method to obtain the desired cationized CMC. Can be obtained.

【００２２】本発明のカチオン化CMCは、増粘剤、凝析剤、
凝集剤、定着剤、分散安定剤、洗濯用仕上げ剤、泥水用
調整剤、製紙における歩留まり向上剤、濾水性向上剤、
繊維および繊布等における帯電防止剤、手触り改良剤、
化粧品、シャンフ゜ー、リンス、トリートメント等の配合剤、糊剤、接着
剤、インク等の配合剤等として使用できる。配合量は、用
途により適宜求めることができる。The cationized CMC of the present invention comprises a thickener, a coagulant,
Flocculant, fixing agent, dispersion stabilizer, finishing agent for washing, conditioner for muddy water, retention agent in papermaking, drainage improver,
Antistatic agents in fibers and textiles, touch improvers,
It can be used as a compounding agent for cosmetics, shampoos, rinses, treatments, etc., and a compounding agent for sizing agents, adhesives, inks and the like. The blending amount can be appropriately determined depending on the use.

【００２３】[0023]

【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。なお、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 by these examples. In addition, all "parts" indicating the blending amount are "parts by weight".

【００２４】［実施例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1270部と水酸化ナトリウム85.0部
を水192部に溶解したものとを加え、市販の溶解ハ゜ルフ゜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15
0部に溶解したモノクロル酢酸87.0部を添加し、30分で70℃に
昇温し、90分間反応させた。その後、水酸化ナトリウム5.0
部、3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト゛50%水溶液4
6.5部を添加し、さらに70℃で120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、粉砕
し、CM-DS 0.58、CT-DS 0.051のカチオン化CMCを得た。Example 1 To a biaxial neater whose rotation speed was adjusted to 100 rpm, 1270 parts of 99% isopropanol and 85.0 parts of sodium hydroxide dissolved in 192 parts of water were added, and a commercially available dissolved resin was dried to dryness. 200 parts were charged. After stirring and mixing at 30 ° C. for 90 minutes to prepare alkaline cellulose, 90% isopropyl alcohol 15
87.0 parts of monochloroacetic acid dissolved in 0 parts was added, the temperature was raised to 70 ° C. in 30 minutes, and the reaction was carried out for 90 minutes. Then sodium hydroxide 5.0
Part, 3-chloro-2-human peroxyfluorotrimethylammonium chloride 50% aqueous solution 4
6.5 parts were added, and the mixture was further reacted at 70 ° C. for 120 minutes. After completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried, and pulverized to obtain a cationized CMC of CM-DS 0.58 and CT-DS 0.051.

【００２５】［実施例２］回転数を500rpmに調節したセハ
゜ラフ゛ルフラスコに99%イソフ゜ロヒ゜ルアルコール680部と水酸化ナトリウム30.0
部を水85.0部に溶解したものとを加え、市販のCMC(サンロー
ス゛F300HC、日本製紙製)を絶乾で200部仕込んだ。30℃で
90分間攪拌後、さらに、攪拌しつつ3-クロロ-2-ヒト゛ロキシフ゜ロヒ
゜ルトリメチルアンモニウムクロリト゛50%水溶液140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、粉砕し、CM-DS 0.87、C
T-DS 0.120のカチオン化CMCを得た。Example 2 In a separatory flask whose rotation speed was adjusted to 500 rpm, 680 parts of 99% isopropyl alcohol and 30.0% of sodium hydroxide were placed.
A part thereof dissolved in 85.0 parts of water was added thereto, and 200 parts of a commercially available CMC (Sanrose F300HC, manufactured by Nippon Paper Industries) were charged to dryness. At 30 ° C
After stirring for 90 minutes, 140 parts of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was further added with stirring, and 70 minutes in 30 minutes.
The temperature was raised to ° C., and the reaction was performed for 90 minutes. After the reaction, wash twice with 80% methanol, neutralize, drain, dry and pulverize, CM-DS 0.87, C
A cationized CMC of T-DS 0.120 was obtained.

【００２６】［実施例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1900部と水酸化ナトリウム99.0部
を水100部に溶解したものとを加え、市販の溶解ハ゜ルフ゜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、酢酸70.0部と3-クロ
ロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト゛50%水溶液465部を添
加し、30分で70℃に昇温し、90分間反応させた。その
後、水酸化ナトリウム138部、モノクロル酢酸ナトリウム430部を添加
し、さらに70℃で120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、粉砕し、CM-DS 1.
41、CT-DS 0.313のカチオン化CMCを得た。[Example 3] To a biaxial neater whose rotation speed was adjusted to 100 rpm, 1900 parts of 99% isopropyl alcohol and 99.0 parts of sodium hydroxide dissolved in 100 parts of water were added, and a commercially available dissolved resin was dried to dryness. 200 parts were charged. After stirring and mixing at 30 ° C. for 90 minutes to prepare an alkali cellulose, while stirring, 70.0 parts of acetic acid and 465 parts of a 50% aqueous solution of 3-chloro-2-human peroxyfluorotrimethylammonium chloride were added, and 70 ° C. in 30 minutes. And reacted for 90 minutes. Thereafter, 138 parts of sodium hydroxide and 430 parts of sodium monochloroacetate were added, and the mixture was further reacted at 70 ° C. for 120 minutes. 80% after reaction
Wash twice with methanol, neutralize, drain, dry, pulverize, CM-DS 1.
41. Cationized CMC of CT-DS 0.313 was obtained.

【００２７】［比較例１］市販CMCとして、サンロース゛F300H
C(日本製紙製 CM-DS 0.87)を用いた。[Comparative Example 1] As a commercially available CMC, Sanroth F300H
C (Nippon Paper Industries CM-DS 0.87) was used.

【００２８】［比較例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2500部と水酸化ナトリウム199部
を水200部に溶解したものとを加え、市販の溶解ハ゜ルフ゜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、酢酸145部と3-クロロ
-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト゛50%水溶液930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、粉砕
し、CT-DS 0.723のカチオン化セルロースを得た。このカチオン化セルロー
ス200部を発底原料として、再度回転数を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1900部と水酸化ナトリウム9
9.0部を水100部に溶解したものとを加え、30℃で90分間
攪拌、混合後、さらに、攪拌しつつ、酢酸70.0部と3-クロ
ロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト゛50%水溶液465部を添
加し、30分で70℃に昇温し、90分間反応させた。その
後、水酸化ナトリウム141部、モノクロル酢酸ナトリウム460部を添加
し、さらに70℃で120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、粉砕し、CM-DS 1.
41、CT-DS 1.037のカチオン化CMCを得た。[Comparative Example 2] To a biaxial neater whose rotational speed was adjusted to 100 rpm, 2500 parts of 99% isopropyl alcohol and 199 parts of sodium hydroxide dissolved in 200 parts of water were added, and a commercially available dissolved resin was dried to dryness. 200 parts were charged. After stirring and mixing at 30 ° C. for 90 minutes to prepare alkali cellulose, further stirring, 145 parts of acetic acid and 3-chloroform
930 parts of a 50% aqueous solution of 2-hydroxypropyltrimethylammonium chloride-2-human was added, the temperature was raised to 70 ° C. in 30 minutes, and the reaction was carried out for 90 minutes. After the completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried and pulverized to obtain a cationized cellulose having CT-DS 0.723. Using 200 parts of this cationized cellulose as a bottoming material, 1900 parts of 99% isopropyl alcohol and sodium hydroxide 9 were added to a biaxial neater whose rotation speed was again adjusted to 100 rpm.
A solution obtained by dissolving 9.0 parts in 100 parts of water was added, and the mixture was stirred at 30 ° C. for 90 minutes, mixed, and further, with stirring, 70.0 parts of acetic acid and 465 parts of a 3-chloro-2-human peroxyfluorotrimethylammonium chloride 50% aqueous solution were further added. Was added, the temperature was raised to 70 ° C. in 30 minutes, and the reaction was carried out for 90 minutes. Thereafter, 141 parts of sodium hydroxide and 460 parts of sodium monochloroacetate were added, and further reacted at 70 ° C. for 120 minutes. 80% after reaction
Wash twice with methanol, neutralize, drain, dry, pulverize, CM-DS 1.
41. Cationized CMC of CT-DS 1.037 was obtained.

【００２９】［比較例３］回転数を500rpmに調節したセハ
゜ラフ゛ルフラスコに99%イソフ゜ロヒ゜ルアルコール950部と水酸化ナトリウム4.5部
を水50部に溶解したものとを加え、市販のNa-CMC(サンロース
゛F300HC、日本製紙製)を絶乾で200部仕込んだ。30℃で9
0分間攪拌後、さらに、攪拌しつつ3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜
ルトリメチルアンモニウムクロリト゛50%水溶液20部を添加し、30分で70℃
に昇温し、30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、粉砕し、CM-DS 0.87、CT-
DS 0.009のカチオン化CMCを得た。[Comparative Example 3] A 950 parts of 99% isopropanol alcohol and 4.5 parts of sodium hydroxide dissolved in 50 parts of water were added to a separatory flask having a rotation speed of 500 rpm, and commercially available Na-CMC (San 200 parts of loin (F300HC, made by Nippon Paper) were dry-dried. 9 at 30 ° C
After stirring for 0 minutes, 20 parts of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was further added with stirring, and the mixture was heated to 70 ° C for 30 minutes.
And reacted for 30 minutes. After completion of the reaction, add 80% methanol
Wash twice, neutralize, drain, dry, pulverize, CM-DS 0.87, CT-
A cationized CMC with a DS of 0.009 was obtained.

【００３０】［比較例４］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711部と水酸化ナトリウム53.5部
を水89部に溶解したものとを加え、市販の溶解ハ゜ルフ゜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12
0部に溶解したモノクロル酢酸59.0部を添加し、30分で70℃に
昇温し、90分間反応させた。その後、水酸化ナトリウム12.0
部、3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチルアンモニウムクロリト゛50%水溶液1
42部を添加し、さらに70℃で120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、粉砕
し、CM-DS 0.35、CT-DS 0.114のカチオン化CMCを得た。[Comparative Example 4] To a biaxial neater whose rotation speed was adjusted to 100 rpm, a solution prepared by dissolving 711 parts of 99% isopropyl alcohol and 53.5 parts of sodium hydroxide in 89 parts of water was added, and a commercially available dissolved bag was dried to dryness. 200 parts were charged. After stirring and mixing at 30 ° C. for 90 minutes to prepare alkali cellulose, 90% isopropanol alcohol 12 is further stirred.
59.0 parts of monochloroacetic acid dissolved in 0 parts was added, the temperature was raised to 70 ° C. in 30 minutes, and the reaction was performed for 90 minutes. Then sodium hydroxide 12.0
Part, 3-chloro-2-human peroxyfluorotrimethylammonium chloride 50% aqueous solution 1
42 parts were added and further reacted at 70 ° C. for 120 minutes. After completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried, and pulverized to obtain a cationized CMC of CM-DS 0.35 and CT-DS 0.114.

【００３１】［比較例５］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2500部と水酸化ナトリウム318部
を水300部に溶解したものとを加え、市販の溶解ハ゜ルフ゜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、攪拌しつつモノクロル酢酸ナトリウム450
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、
粉砕し、CM-DS 1.51のNa-CMCを得た。このNa-CMC200部
を発底原料として、再度、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2810部と水酸化ナトリウム210部
を水190部に溶解したものとを加え、30℃で90分間攪
拌、混合後、さらに、攪拌しつつモノクロル酢酸ナトリウム298部
を添加し、30分で70℃に昇温し、90分間反応させた。そ
の後、水酸化ナトリウム16.0部、3-クロロ-2-ヒト゛ロキシフ゜ロヒ゜ルトリメチル
アンモニウムクロリト゛50%水溶液151部を添加し、さらに70℃で120
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、粉砕し、CM-DS 2.03、CT-DS 0.107のカ
チオン化CMCを得た。[Comparative Example 5] To a biaxial neater whose rotation speed was adjusted to 100 rpm, 2,500 parts of 99% isopropyl alcohol and 318 parts of sodium hydroxide dissolved in 300 parts of water were added, and a commercially available dissolved resin was dried to dryness. 200 parts were charged. After stirring and mixing at 30 ° C. for 90 minutes to prepare alkali cellulose, further stirring, sodium monochloroacetate 450
Then, the mixture was heated to 70 ° C. in 30 minutes and reacted for 90 minutes.
After the reaction, wash twice with 80% methanol, neutralize, drain, dry,
It was pulverized to obtain Na-CMC of CM-DS 1.51. Using 200 parts of this Na-CMC as a starting material, again, 2810 parts of 99% isopropanol alcohol and 210 parts of sodium hydroxide dissolved in 190 parts of water were added to a biaxial neater whose rotation speed was adjusted to 100 rpm, and 30 ° C. After stirring and mixing for 90 minutes, 298 parts of sodium monochloroacetate was further added with stirring, the temperature was raised to 70 ° C. in 30 minutes, and the mixture was reacted for 90 minutes. Thereafter, 16.0 parts of sodium hydroxide and 151 parts of a 50% aqueous solution of 3-chloro-2-human peroxyfluorotrimethylammonium chloride were added, and the mixture was further added at 70 ° C for 120 parts.
Allowed to react for minutes. After the completion of the reaction, the resultant was washed twice with 80% methanol, neutralized, drained, dried and pulverized to obtain a cationized CMC of CM-DS 2.03 and CT-DS 0.107.

【００３２】［試験法］ 1)カルホ゛キシメチル化度(CM-DS)の測定方法 以下に示す２種の方法により、CM-DSを求めた。なお、C
M-DSが1.0以下の場合は、硝酸メタノール法で、CM-DSが1.0を
越える場合は、灰分アルカリ法で測定した。 <硝酸メタノール法>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、カ
ルホ゛キシメチルセルロースナトリウム（Na-CMC）をカルホ゛キシメチルセルロース（H-CM
C）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-H2SO4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-CMC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 <灰分アルカリ法>試料約0.5gを精秤し、白金皿に入れ、電熱
器上で炭化した。その後、電気炉(750±25℃)で１〜２
分灼熱した。冷却後、温水で可溶分を抽出し、さらに温
水で洗浄しながら、完全に可溶分をヒ゛ーカーへ移した。温
水可溶分に0.1N-H₂SO₄100mlを加え、10分間煮沸後、冷
却し、指示薬としてフェノールフタレインを用いて、0.1N-NaOHで
過剰のH₂SO₄を滴定した。なお、CM-DSは、次式によって
算出した。 A=(100×F'−0.1N-NaOH(ml)×F)/試料の絶乾重量(g) CM-DS=162×A/(1000−80×A) F:0.1N-H₂SO₄のfactor F':0.1N-NaOHのfactor[Test Method] 1) Method of Measuring Degree of Carboxymethylation (CM-DS) CM-DS was determined by the following two methods. Note that C
When the M-DS was 1.0 or less, the measurement was performed by the nitric acid methanol method, and when the CM-DS exceeded 1.0, the measurement was performed by the ash alkali method. <Methanol nitrate method> About 2.0 g of a sample was precisely weighed and placed in a 300 ml Erlenmeyer flask with a stopper. Add 100 ml of methanol nitrate (1 liter of anhydrous methanol and 100 ml of special grade concentrated nitric acid) and shake for 3 hours to remove sodium carboxymethylcellulose (Na-CMC) from carboxymethylcellulose (H-CM
C). 1.5-2.0 g of the absolutely dried H-CMC is precisely weighed and 300 ml
The flask was placed in a stoppered Erlenmeyer flask. H-CMC was wet 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. Excess NaOH was back titrated with 0.1N-H2SO4 using phenolphthalein as an indicator. CM-DS was calculated by the following equation. A = ((100 × F′−0.1NH ₂ SO ₄ (ml) × F) × 0.1) / absolute dry weight of H-CMC (g) CM-DS = 0.162 × A / (1-0.058 × A) A : the amount of 1N-NaOH required to neutralize the H-CMC1g (ml) F: 0.1NH 2 SO 4 the factor F ': 0.1N-NaOH of factor <ash alkali method> a sample is precisely weighed about 0.5g Then, it was placed in a platinum dish and carbonized on an electric heater. Then, 1-2 in an electric furnace (750 ± 25 ° C)
Burning. After cooling, the soluble matter was extracted with warm water, and the soluble matter was completely transferred to a heater while washing with warm water. 100 ml of 0.1NH ₂ SO ₄ was added to the hot water-soluble matter, the mixture was boiled for 10 minutes, cooled, and excess H ₂ SO ₄ was titrated with 0.1N-NaOH using phenolphthalein as an indicator. Note that CM-DS was calculated by the following equation. A = (100 × F′−0.1N-NaOH (ml) × F) / absolute dry weight of sample (g) CM-DS = 162 × A / (1000−80 × A) F: 0.1 NH ₂ SO ₄ factor F ': factor of 0.1N-NaOH

【００３３】2)カチオン化度(CT-DS)の測定方法ケルタ゛ール 分析法に従い、窒素含有量を測定し、CT-DSを次
式によって、算出した。なお、次式はカチオン化剤として、
ク゛リシシ゛ルトリメチルアンモニウムハライト゛あるいはそのハロヒト゛リン型を用い
た場合の式である。 CT-DS=(162+80×(CM-DS))×B/(1400-133.1×B) B:窒素含有量2) Method of Measuring Degree of Cationization (CT-DS) The nitrogen content was measured according to the Keltahl analysis method, and CT-DS was calculated by the following equation. The following formula is used as a cationizing agent.
This is a formula in the case of using glycidyltrimethylammonium halide or its halohantulin type. CT-DS = (162 + 80 × (CM-DS)) × B / (1400-133.1 × B) B: Nitrogen content

【００３４】3)耐薬品性試験 1000mlヒ゛ーカーに純水990gを注ぎ、トライアンク゛ル攪拌棒を用い
て攪拌しながら、精秤したカチオン化CMC(無水物)10gを添加
し、完全に溶解させた。溶解後、液温を25±0.2℃に調
整し、BM型粘度計(東京計器社製)を用いて、回転数30rp
m、3分間後の粘度η1を読みとった。また、1000mlヒ゛ーカー
に4%食塩水990gを注ぎ、トライアンク゛ル攪拌棒を用いて攪拌し
ながら、精秤したカチオン化CMC(無水物)10gを添加し、完全
に溶解させた。溶解後、液温を25±0.2℃に調整し、BM
型粘度計(東京計器社製)を用いて、回転数30rpm、3分間
後の粘度η2を読みとり、粘度変化率、即ちη2/η1を計
算し、耐薬品性の指標とした。なお、η2/η1の値が1に
近いほど、耐薬品性は良好である。3) Chemical Resistance Test 990 g of pure water was poured into a 1000 ml shaker, and 10 g of cationized CMC (anhydride), which was precisely weighed, was added while stirring using a triangular stirring bar, and completely dissolved. After dissolution, the solution temperature was adjusted to 25 ± 0.2 ° C., and using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the rotation speed was 30 rp.
m, and the viscosity η1 after 3 minutes was read. Further, 990 g of 4% saline solution was poured into a 1000 ml shaker, and 10 g of cationized CMC (anhydride), which was precisely weighed, was added thereto while stirring using a triangular stirring rod, and completely dissolved. After dissolution, adjust the solution temperature to 25 ± 0.2 ° C,
Using a viscometer (manufactured by Tokyo Keiki Co., Ltd.), the viscosity η2 after 3 minutes of rotation at 30 rpm was read, and the viscosity change rate, that is, η2 / η1, was calculated and used as an index of chemical resistance. Note that the closer the value of η2 / η1 is to 1, the better the chemical resistance.

【００３５】4)表面改質性試験カチオン 化CMC5部、濃ク゛リセリン1部、エタノール10部、メチルハ゜ラヘ゛ン0.1
部、香料および精製水からなる原液(100部)に1,2-シ゛メトキ
シエタンを加え、1,2-シ゛メトキシエタン/原液が30/70である組成の
毛髪化粧料(スフ゜レー剤)を定法により製造した。長さ18c
m、重さ10gの毛髪束を水で濡らし、タオルト゛ライした後、上
記毛髪化粧料を2g塗布し、直径2cmのロット゛に巻いた後、
自然乾燥させた。この毛髪束について、10名のハ゜ネラーが
下記の基準で感触（手触り感）を評価した。 ◎：未塗布毛より非常に良い、○：未塗布毛より良い、
△：未塗布毛と変わらない、×：未塗布毛より悪い4) Surface modification test 5 parts of cationized CMC, 1 part of concentrated glycerin, 10 parts of ethanol, 0.1 parts of methyl alcohol
1,2-dimethoxyethane is added to a stock solution (100 parts) consisting of 1 part, perfume and purified water to produce a hair cosmetic (spray agent) with a composition of 1,2-dimethoxyethane / stock solution of 30/70 by a standard method. did. Length 18c
m, a hair bundle weighing 10 g is moistened with water, toweled, coated with 2 g of the above hair cosmetic, and wound into a 2 cm diameter lot.
Air dried. About this hair bundle, 10 panelists evaluated the feeling (touch feeling) based on the following criteria. ◎: Very good than uncoated hair, ○: Better than uncoated hair,
△: Same as uncoated hair, ×: worse than uncoated hair

【００３６】5)定着性試験 広葉樹晒クラフトハ゜ルフ゜を実験用ナイアカ゛ラヒ゛ーターで濾水度を480m
lCSF(カナタ゛標準フリーネス)に調成した。2%濃度のハ゜ルフ゜スラリー
に、スリーワンモーターにて450rpmの速度で攪拌しながら、濃度1
%カチオン化CMC水溶液の状態でカチオン化CMCを0.2%、カチオン化澱
粉0.5%、硫酸ハ゛ント゛0.3%、アルキルケテンタ゛イマーを主成分とする
中性抄紙用サイス゛剤0.05%、ホ゜リアミト゛・エヒ゜クロルヒト゛リン樹脂を成
分とする紙力増強剤0.1%、軽質炭酸カルシウム10%、ホ゜リアクリルア
ミト゛を成分とする歩留まり向上剤0.01%を、この順番で添
加し、添加終了後、3分間攪拌を続けた。このハ゜ルフ゜紙料
を用いてTAPPI標準の角形シートマシンで坪量60g/m2の紙を抄
き、ト゛ラム式乾燥機にて120℃3分間乾燥した。この手抄き
シートを温度20℃、相対湿度65%にて24時間調湿後、紙の引
っ張り強度(TAPPI T205に準じて測定し、列断長で示す)
とステキヒトサイス゛度(JIS P8122に準じて測定)を測定した。な
お、列断長、ステキヒトサイス゛度ともに値が大きいほど良好で
あり、製紙用薬剤がハ゜ルフ゜へよく定着し、機能を発現し
たことを示す。5) Fixing property test Hardwood bleached craft halves were tested for freeness with a laboratory niagar heater to a freeness of 480 m.
Formulated to lCSF (Kanata II Standard Freeness). While stirring at a speed of 450 rpm with a three-one motor, a 1%
0.2% cationized CMC in the form of an aqueous solution of cationized CMC, 0.5% of cationized starch, 0.3% of sulfate sulfate, 0.05% of a neutral paper-making sieve agent containing an alkyl ketene dimer as a main component, and a polyamidoxychlorohuman phosphorus resin as a component. Then, 0.1% of a paper strength enhancer, 10% of light calcium carbonate, and 0.01% of a retention aid containing polyacrylamide were added in this order, and after the addition was completed, stirring was continued for 3 minutes. A paper having a basis weight of 60 g / m2 was made using this half paper stock with a TAPPI standard square sheet machine, and dried at 120 ° C. for 3 minutes with a tram dryer. After conditioning this handmade sheet at a temperature of 20 ° C and a relative humidity of 65% for 24 hours, the tensile strength of the paper (measured according to TAPPI T205, indicated by the row length)
And the stiffness of the specimen (measured according to JIS P8122). It should be noted that the larger the values for both the row length and the stiffness size, the better the results, indicating that the papermaking agent was well fixed to the palm and exhibited its function.

【００３７】[0037]

【表１】表１ [Table 1] Table 1

【００３８】[0038]

【発明の効果】本発明のカチオン化CMCは、両性イオンホ゜リマーと
して、耐薬品性、表面改質性、定着性に優れ、これらの
物性の釣り合いがとれたものである。従って、増粘剤、
凝析剤、凝集剤、定着剤、分散安定剤、洗濯用仕上げ
剤、泥水用調整剤、製紙における歩留まり向上剤、濾水
性向上剤、繊維および繊布等における帯電防止剤、手触
り改良剤、化粧品、シャンフ゜ー、リンス、トリートメント等の配合剤、
糊剤、接着剤、インク等の配合剤等として有用である。The cationized CMC of the present invention, as a zwitterion polymer, has excellent chemical resistance, surface modification properties and fixing properties, and balances these properties. Therefore, thickeners,
Coagulants, flocculants, fixing agents, dispersion stabilizers, finishing agents for washing, modifiers for muddy water, retention improvers in papermaking, drainage improvers, antistatic agents in fibers and textiles, touch improvers, cosmetics, Compounding agents such as shampoo, rinse and treatment,
It is useful as a compounding agent for pastes, adhesives, inks and the like.

【手続補正書】[Procedure amendment]

【提出日】平成１３年３月５日（２００１．３．５）[Submission date] March 5, 2001 (2001.3.5)

【手続補正１】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００３３[Correction target item name] 0033

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００３３】２）カチオン化度（CT-DS）の測定方法ケ゛ルタ゛ール 分析法に従い、窒素含有量を測定し、CT-DSを次
式によって、算出した。なお、次式は、カチオン化剤として
ク゛リシシ゛ルトリメチルアンモニウムクロライト゛あるいはそのクロロヒト゛リン型を用
いた場合の式である。 CT-DS=(162+80×(CM-DS))×B／(1400-151.6×B) Ｂ：窒素含有量 ─────────────────────────────────────────────────────
2) Method of Measuring Degree of Cationization (CT-DS) The nitrogen content was measured in accordance with the Kjeldahl analysis method, and CT-DS was calculated by the following equation. The following formula is used as a cationizing agent.
This is a formula in the case of using glycidyltrimethylammonium chlorite or its chlorohuman perrin type . CT-DS = (162 + 80 × (CM-DS)) × B / ( 1400-151.6 × B) B: Nitrogen content ──────────────────── ─────────────────────────────────

【手続補正書】[Procedure amendment]

【提出日】平成１３年３月５日（２００１．３．５）[Submission date] March 5, 2001 (2001.3.5)

【手続補正１】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００３３[Correction target item name] 0033

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００３３】２）カチオン化度（CT-DS）の測定方法ケ゛ルタ゛ール 分析法に従い、窒素含有量（％）を測定し、CT-
DSを次式によって、算出した。なお、次式は、カチオン化剤
としてク゛リシシ゛ルトリメチルアンモニウムクロライト゛あるいはそのクロロヒト゛リン
型を用いた場合の式である。 CT-DS=(162+80×(CM-DS))×B／(1400-151.6×B) Ｂ：窒素含有量（％） 2) Method for measuring the degree of cationization (CT-DS) According to the Kjeldahl analysis method, the nitrogen content (%) is measured and the CT-DS is measured.
DS was calculated by the following equation. In addition, the following formula is used as a cationizing agent for glycidyltrimethylammonium chlorite or its chlorohuman phosphorus.
This is an expression when a type is used. CT-DS = (162 + 80 × (CM-DS)) × B / ( 1400-151.6 × B) B: Nitrogen content (%)

───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 伸治 島根県江津市江津町1280 日本製紙株式会 社内化成品開発研究所内 Ｆターム(参考） 4C090 AA05 BA29 BB12 BB36 BB52 BB62 BB99 BD06 BD18 BD34 CA28 DA26 4L033 AA01 AA04 AB01 AB03 AB04 AC06 AC12 CA05 4L055 AG46 AH18 AH50 EA29 FA08 FA30  ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Shinji Sato 1280, Etsu-cho, Gotsu-shi, Shimane Prefecture Nippon Paper Industries Co., Ltd. F-term (in reference) 4C090 AA05 BA29 BB12 BB36 BB52 BB62 BB99 BD06 BD18 BD34 CA28 DA26 4L033 AA01 AA04 AB01 AB03 AB04 AC06 AC12 CA05 4L055 AG46 AH18 AH50 EA29 FA08 FA30

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 カルホ゛キシメチル基の置換度がク゛ルコース残基当た
り0.4〜2.0、かつカチオン基の置換度がク゛ルコース残基当たり0.
01〜1.0であることを特徴とするカチオン化カルホ゛キシメチルセルロースナ
トリウム塩。(1) The degree of substitution of a carboxymethyl group is 0.4 to 2.0 per glucose residue, and the degree of substitution of a cationic group is 0.4 to 0.2 per glucose residue.
A cationized carboxymethylcellulose sodium salt, which is 01 to 1.0. 【請求項２】 カルホ゛キシメチル基の置換度(CM-DS)とカチオン基の
置換度(CT-DS)が下記式1を満たす請求項1記載のカチオン化カ
ルホ゛キシメチルセルロースナトリウム塩。 0.01≦(CT-DS/CM-DS)≦0.5 …式１2. The cationized carboxymethyl cellulose sodium salt according to claim 1, wherein the degree of carboxymethyl group substitution (CM-DS) and the degree of cation group substitution (CT-DS) satisfy the following formula 1. 0.01 ≦ (CT-DS / CM-DS) ≦ 0.5… Equation 1