JP3239146B2 - Modified cellulose fiber and method for producing the same - Google Patents
Modified cellulose fiber and method for producing the sameInfo
- Publication number
- JP3239146B2 JP3239146B2 JP32478792A JP32478792A JP3239146B2 JP 3239146 B2 JP3239146 B2 JP 3239146B2 JP 32478792 A JP32478792 A JP 32478792A JP 32478792 A JP32478792 A JP 32478792A JP 3239146 B2 JP3239146 B2 JP 3239146B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- modified cellulose
- cellulose fiber
- methacrylic acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、改質セルロース繊維及
びその製造方法に関するものである。The present invention relates to a modified cellulose fiber and a method for producing the same.
【０００２】[0002]
【従来の技術】セルロース繊維にカルボキシル基を導入
するために、モノクロル酢酸をセルロース繊維に反応さ
せて、カルボキシメチル化させる方法は知られている。
このようにして得られたカルボキシメチル化セルロース
繊維は、そのカルボキシル基の導入により、繊維の親水
性が向上するとともに、アンモニアやアミン等の塩基性
悪臭物質を吸着脱臭する機能を有する。しかしながら、
このモノクロル酢酸とセルロース繊維とを反応させる方
法は、発熱反応であるために、バルク状（塊状）の繊維
を均一に反応させるのに大きな技術的困難を伴ない。実
用的方法とは言えない。また、セルローズ繊維にビニル
化合物をミカエル反応させてエーテル結合を持ったセル
ロース繊維を製造する方法も知られている。しかし、こ
の方法では、ビニル化合物の種類によりその反応性が大
きく変り、アクリロニトリルや、アクリルアミド、ビニ
ルスルホン等は比較的反応性が高く、反応を効率よく行
うことが可能であるものの、アクリル酸やマレイン酸等
のビニル化合物は反応性が低く、反応を効率よく行うこ
とができない。即ち、アクリル酸やマレイン酸等の不飽
和カルボン酸をミカエル反応によりセルロース繊維に効
率よく結合させることはできない。ミカエル反応を利用
してカルボキシル基をセルロース繊維に効率よく導入す
るには、アクリロニトリルをミカエル反応によりセルロ
ース繊維に反応させて、シアノエチルエーテル基を持っ
た繊維とした後、そのシアノ基を加水分解してカルボキ
シル基に変換させる方法があるが、この場合には、多工
程を要するために経済的ではない。2. Description of the Related Art In order to introduce a carboxyl group into a cellulose fiber, a method of reacting monochloroacetic acid with the cellulose fiber to carry out carboxymethylation is known.
The carboxymethylated cellulose fiber thus obtained has a function of improving the hydrophilicity of the fiber and introducing and deodorizing basic malodorous substances such as ammonia and amine by introducing the carboxyl group. However,
This method of reacting monochloroacetic acid with cellulose fibers is an exothermic reaction, so that there is no great technical difficulty in uniformly reacting bulk (bulk) fibers. It is not a practical method. There is also known a method for producing a cellulose fiber having an ether bond by subjecting a cellulose compound to a Michael reaction with a cellulose fiber. However, in this method, the reactivity varies greatly depending on the type of vinyl compound, and acrylonitrile, acrylamide, vinyl sulfone, and the like have relatively high reactivity, and although it is possible to carry out the reaction efficiently, acrylic acid or maleic acid is used. Vinyl compounds such as acids have low reactivity and cannot be reacted efficiently. That is, unsaturated carboxylic acids such as acrylic acid and maleic acid cannot be efficiently bound to cellulose fibers by the Michael reaction. In order to efficiently introduce carboxyl groups into cellulose fibers using the Michael reaction, acrylonitrile is reacted with the cellulose fibers by the Michael reaction to produce fibers having cyanoethyl ether groups, and then the cyano groups are hydrolyzed. Although there is a method of converting to a carboxyl group, this method is not economical because it requires multiple steps.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、カルボキシ
ル基を導入した改質セルロース繊維及びその製造方法を
提供することをその課題とする。An object of the present invention is to provide a modified cellulose fiber having a carboxyl group introduced therein and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明者は、前記課題を
解決すべく鋭意研究を重ねた結果、本発明を完成するに
至った。即ち、本発明によれば、木綿繊維、麻繊維又は
レーヨン繊維に、メタクリル酸をグラフト共重合反応さ
せたものであって、該セルロース繊維に対するメタクリ
ル酸のグラフト化率が７〜１５重量％であることを特徴
とする改質セルロース繊維が提供される。また、本発明
によれば、過酸化水素と二価鉄塩を含む水溶液中におい
て、木綿繊維、麻繊維又はレーヨン繊維に、メタクリル
酸をグラフト共重合させることを特徴とする改質セルロ
ース繊維の製造方法が提供される。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a methacrylic acid is subjected to a graft copolymerization reaction with a cotton fiber, a hemp fiber or a rayon fiber, and the graft ratio of methacrylic acid to the cellulose fiber is 7 to 15 % by weight. A modified cellulose fiber is provided. Further, according to the present invention, in an aqueous solution containing hydrogen peroxide and a ferrous iron salt, a cotton fiber, a hemp fiber or a rayon fiber is graft-copolymerized with methacrylic acid to produce a modified cellulose fiber. A method is provided.
【０００５】本発明で用いる繊維は、木綿や麻等の各種
のセルロース含有繊維であることができ、その形状は、
糸状や綿状、布状、トウ状、不織布状であることができ
る。また、繊維には、他の繊維が混合されていてもよ
い。[0005] The fibers used in the present invention can be various cellulose-containing fibers such as cotton and hemp.
It can be in the form of a thread, cotton, cloth, tow, or nonwoven. Further, other fibers may be mixed with the fibers.
【０００６】本発明においては、木綿繊維、麻繊維又は
レーヨン繊維（以下、単に繊維とも言う）にカルボキシ
ル基を導入するために、過酸化水素と二価鉄塩を含有す
る水溶液中で、繊維に対してメタクリル酸をグラフト共
重合させる。二価鉄塩としては、水中において２価鉄イ
オンを放出し得るものであれば任意のものが用いられ
る。このようなものとしては、硫酸第一鉄、塩化第一
鉄、硫酸第一鉄アンモニウム、硝酸第一鉄等がある。こ
の二価鉄塩と過酸化水素の組合せは、レドックス系触媒
を構成し、メタクリル酸のグラフト共重合反応を促進さ
せる。水溶液中の過酸化水素濃度は、０．０１〜０．１
モル／ｌ、好ましくは０．０２〜０．０５モル／ｌであ
る。また、鉄塩濃度は、０．７〜５．０ミリモル／ｌ、
好ましくは１．０〜２．５ミリモル／ｌである。In the present invention, cotton fiber , hemp fiber or
In order to introduce a carboxyl group into rayon fiber (hereinafter also simply referred to as fiber), methacrylic acid is graft-copolymerized onto the fiber in an aqueous solution containing hydrogen peroxide and a ferrous salt. As the ferrous salt, any one can be used as long as it can release ferrous ions in water. Such materials include ferrous sulfate, ferrous chloride, ferrous ammonium sulfate, ferrous nitrate, and the like. The combination of the divalent iron salt and hydrogen peroxide constitutes a redox catalyst and promotes a methacrylic acid graft copolymerization reaction. The concentration of hydrogen peroxide in the aqueous solution is 0.01 to 0.1
Mol / l, preferably 0.02 to 0.05 mol / l. The iron salt concentration is 0.7 to 5.0 mmol / l,
Preferably it is 1.0 to 2.5 mmol / l.
【０００７】また、この水溶液中には、必要に応じ、酸
を添加することができる。この酸の添加により、メタク
リル酸の反応率(グラフト化率)を向上させることができ
る。酸としては、例えば、硫酸、塩酸、リン酸、ギ酸等
が挙げられる。水溶液中の酸濃度は、２〜４ミリモル／
ｌ、好ましくは２．５〜３．５ミリモル／ｌである。さ
らに、この水溶液中には、従来公知の金属封鎖剤、例え
ば、リン酸系やホスホン酸の他、ＥＤＴＡ、ＮＴＡ等を
添加することができる。繊維（絶乾重量）に対する水溶
液の重量比（浴比）は、５〜５０、好ましくは５〜２０
である。反応温度は、４０〜１００℃、好ましくは４０
〜８０℃であり、反応時間は、６０〜２４０分、好まし
くは９０〜１８０分である。本発明において用いるメタ
クリル酸の使用割合は、繊維(絶乾重量)１００重量部に
対して、１０〜１００重量部、好ましくは１０〜６０重
量部である。メタクリル酸の使用割合がこれより少ない
と、カルボキシル基の導入割合が少なすぎるために、改
質効果が十分でなく、一方、多ければ多いほど導入割合
は増加するが、効果の格別の向上は得られず、経済的に
不利である。[0007] If necessary, an acid can be added to the aqueous solution. By adding this acid, the reaction rate (grafting rate) of methacrylic acid can be improved. Examples of the acid include sulfuric acid, hydrochloric acid, phosphoric acid, formic acid and the like. The acid concentration in the aqueous solution is 2 to 4 mmol /
l, preferably 2.5 to 3.5 mmol / l. Further, in this aqueous solution, conventionally known sequestering agents such as phosphoric acid and phosphonic acid, as well as EDTA and NTA can be added. The weight ratio (bath ratio) of the aqueous solution to the fiber (absolute dry weight) is 5 to 50, preferably 5 to 20.
It is. The reaction temperature is 40 to 100 ° C, preferably 40 to 100 ° C.
To 80 ° C., and the reaction time is 60 to 240 minutes, preferably 90 to 180 minutes. The methacrylic acid used in the present invention is used in an amount of 10 to 100 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of the fiber (absolute dry weight). If the use ratio of methacrylic acid is less than this, the modification effect is not sufficient because the introduction ratio of the carboxyl group is too small.On the other hand, the introduction ratio increases as the ratio increases, but the effect is particularly improved. Not economically disadvantageous.
【０００８】本発明の改質セルロース繊維において、メ
タクリル酸のグラフト化率（セルロース繊維に対するメ
タクリル酸の反応重量比）は、７〜１５重量％である。
このグラフト化率が前記範囲を超えると、グラフト共重
合反応に長時間を要し、経済的に不利である。一方、前
記範囲より少ないと、十分な改質効果を得ることができ
ない。グラフト化率は、繊維に対するメタクリル酸の使
用割合及び反応条件で調節することができる。In the modified cellulose fiber of the present invention, the grafting ratio of methacrylic acid (reaction weight ratio of methacrylic acid to cellulose fiber) is 7 to 15% by weight.
If the grafting ratio exceeds the above range, the graft copolymerization reaction requires a long time, which is economically disadvantageous. On the other hand, if it is less than the above range, a sufficient reforming effect cannot be obtained. The grafting ratio can be adjusted by the ratio of methacrylic acid to the fiber and the reaction conditions.
【０００９】[0009]
【発明の効果】本発明による改質セルロース繊維の製造
方法においては、前記のように、触媒として用いる鉄塩
の量が極めて少ないことから、改質繊維には着色もな
く、改質繊維から鉄塩を水洗除去するような脱鉄処理は
特に必要とされない。また、反応温度の制御も容易であ
るため、繊維に対するメタクリル酸のグラフト共重合を
均一に行うことができる。本発明の改質セルロース繊維
は、その分子中にカルボキシル基を導入したことから、
親水性の向上したものであると同時に、アンモニアやア
ミン、屎尿臭等の塩基性悪臭物質に対する吸着性にすぐ
れたもので、脱臭性繊維としての作用を示すものであ
る。また、種々の金属イオンを捕捉する効果も示す。In the method for producing modified cellulose fibers according to the present invention, as described above, since the amount of iron salt used as a catalyst is extremely small, the modified fibers are not colored, and There is no particular need for iron removal treatment such as washing and removing salts. Further, since the reaction temperature can be easily controlled, the graft copolymerization of methacrylic acid onto the fibers can be uniformly performed. Since the modified cellulose fiber of the present invention has a carboxyl group introduced into its molecule,
While having improved hydrophilicity, it is also excellent in adsorptivity to basic malodorous substances such as ammonia, amines, and urine odor, and exhibits an action as a deodorizing fiber. It also has the effect of trapping various metal ions.
【００１０】[0010]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。Next, the present invention will be described in more detail with reference to examples.
【００１１】実施例１ 過酸化水素（Ｈ2Ｏ2）：０．３％（０．０３モル／
ｌ）、硫酸第一鉄アンモニウム（ＦｅＳＯ4（ＮＨ4）2
ＳＯ4６Ｈ2Ｏ、モール塩）：０．０３％（０．１１ミリ
モル／ｌ）、メタクリル酸（ＭＡＡ）：１．３％（０．
１５モル／ｌ）、キレストＮＴＢ（キレスト化学（株）
製金属封鎖剤）：０．０３％（０．００１モル／ｌ）
を、硫酸（５０°Ｂｅ′）：０．０６％（０．００３モ
ル／ｌ）を含む水溶液１５０ｍｌに精練した綿糸１０ｇ
を浸漬し、８０℃で２時間処理した。湯洗、水洗して、
モノマー及びホモポリマーを除去して乾燥する。得られ
た改質繊維のグラフト化率は１０．８７％であった。Example 1 Hydrogen peroxide (H 2 O 2 ): 0.3% (0.03 mol /
l), ferrous ammonium sulfate (FeSO 4 (NH 4 ) 2 )
SO 4 6H 2 O, Mohr salt): 0.03% (0.11 mmol / l), methacrylic acid (MAA): 1.3% (0.1%).
15 mol / l), Kyrest NTB (Kyrest Chemical Co., Ltd.)
Sequestering agent): 0.03% (0.001 mol / l)
10 g of cotton yarn refined in 150 ml of an aqueous solution containing sulfuric acid (50 ° Be ′): 0.06% (0.003 mol / l)
Was treated at 80 ° C. for 2 hours. Wash with hot water, wash with water,
The monomer and homopolymer are removed and dried. The grafting ratio of the obtained modified fiber was 10.87%.
【００１２】実施例２ Ｈ2Ｏ2：０．３％、硫酸第一鉄（ＦｅＳＯ4７Ｈ20）：
０．０２％ ＭＡＡ：１．３％、キレストＮＴＢ：０．０３％を硫酸
（５０°Ｂｅ′）０．０６７％含む水溶液１５０ｍｌに
レーヨンステープル１０ｇを浸漬し、８０℃で２時間グ
ラフト処理を行った。湯洗、水洗によりモノマーを除
去、乾燥する。得られたグラフトレーヨンステープルの
グラフト化率は９．３０％であった。Example 2 H 2 O 2 : 0.3%, ferrous sulfate (FeSO 4 7H 20 ):
10 g of rayon staples is immersed in 150 ml of an aqueous solution containing 0.02% of MAA: 1.3% and 0.03% of chiles NTB: 0.03% of sulfuric acid (50 ° Be ′), and grafting is performed at 80 ° C. for 2 hours. Was. The monomer is removed by washing with hot water and water, followed by drying. The graft ratio of the obtained graph tray staple was 9.30%.
【００１３】実施例３ 実施例２のレーヨンステープルの代りに麻（ラミースラ
イバー）を用いて同様な処理を行った。グラフト化率は
８．７％であった。Example 3 A similar process was performed using hemp (ramie sliver) in place of the rayon staple of Example 2. The grafting ratio was 8.7%.
Claims (4)
メタクリル酸をグラフト共重合反応させたものであっ
て、該繊維に対するメタクリル酸のグラフト化率が７〜
１５重量％であることを特徴とする改質セルロース繊
維。Claims 1. A cotton fiber, a hemp fiber or a rayon fiber,
A graft copolymerization reaction of methacrylic acid, wherein the grafting ratio of methacrylic acid to the fiber is 7 to
A modified cellulose fiber, which is 15 % by weight.
不織布状である請求項１の改質セルロース繊維。 2. The fiber may be in the form of a thread, cotton, cloth or
The modified cellulose fiber according to claim 1, which is in the form of a nonwoven fabric.
いて、木綿繊維、麻繊維又はレーヨン繊維にメタクリル
酸をグラフト共重合させることを特徴とする請求項１の
改質セルロース繊維の製造方法。3. The modified cellulose fiber according to claim 1, wherein methacrylic acid is graft-copolymerized onto cotton fiber, hemp fiber or rayon fiber in an aqueous solution containing hydrogen peroxide and a ferrous salt. Method.
の方法。the method of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32478792A JP3239146B2 (en) | 1992-11-10 | 1992-11-10 | Modified cellulose fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32478792A JP3239146B2 (en) | 1992-11-10 | 1992-11-10 | Modified cellulose fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06184941A JPH06184941A (en) | 1994-07-05 |
| JP3239146B2 true JP3239146B2 (en) | 2001-12-17 |
Family
ID=18169677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32478792A Expired - Lifetime JP3239146B2 (en) | 1992-11-10 | 1992-11-10 | Modified cellulose fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3239146B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009101995A1 (en) | 2008-02-15 | 2009-08-20 | Opelontex Co., Ltd. | Deodorizing material |
| JP2010284441A (en) * | 2009-06-15 | 2010-12-24 | Machiko Tsukamoto | Deodorizing cover for stoma |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69428980D1 (en) * | 1994-04-29 | 2001-12-13 | Nippon Sanmo Sensyoku Co Ltd | Carboxy group modified cellulose or acrylic fibers and process for making the same |
| KR19980702256A (en) * | 1995-12-19 | 1998-07-15 | 마에다 카쯔노수케 | Fiber structure and manufacturing method |
| JP4718719B2 (en) * | 2001-05-10 | 2011-07-06 | グンゼ株式会社 | Method for processing cellulosic fiber or cellulosic fiber product with wash-resistant deodorant function |
| JP2007023458A (en) * | 2005-07-21 | 2007-02-01 | Toho Tenax Co Ltd | Flame-retardant blended yarn |
| JP5923808B2 (en) * | 2011-01-05 | 2016-05-25 | 富士紡ホールディングス株式会社 | Clothing material with deodorant performance |
| JP5543945B2 (en) * | 2011-06-06 | 2014-07-09 | 東洋紡Ｓｔｃ株式会社 | Deodorant cellulose fiber knitted fabric and method for producing the same |
| CN102277755B (en) * | 2011-06-29 | 2013-01-02 | 湖南华升株洲雪松有限公司 | Dyeing technology of ramie strips and manufacturing method of spinning |
| JP6070216B2 (en) * | 2013-01-25 | 2017-02-01 | 京都府公立大学法人 | Regeneration method of pathogenic factor production suppression fiber |
| JP6324667B2 (en) * | 2013-05-29 | 2018-05-16 | ユニチカトレーディング株式会社 | Double layer spun yarn with deodorant performance |
| KR102649214B1 (en) * | 2023-12-07 | 2024-03-19 | 임병열 | Manufacturing method of fiber with excellent deodorizing function |
-
1992
- 1992-11-10 JP JP32478792A patent/JP3239146B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009101995A1 (en) | 2008-02-15 | 2009-08-20 | Opelontex Co., Ltd. | Deodorizing material |
| JP2010284441A (en) * | 2009-06-15 | 2010-12-24 | Machiko Tsukamoto | Deodorizing cover for stoma |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06184941A (en) | 1994-07-05 |
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