JP2944061B2 - Odorless viscose cellulose fiber and method for producing the same - Google Patents
Odorless viscose cellulose fiber and method for producing the sameInfo
- Publication number
- JP2944061B2 JP2944061B2 JP13402993A JP13402993A JP2944061B2 JP 2944061 B2 JP2944061 B2 JP 2944061B2 JP 13402993 A JP13402993 A JP 13402993A JP 13402993 A JP13402993 A JP 13402993A JP 2944061 B2 JP2944061 B2 JP 2944061B2
- Authority
- JP
- Japan
- Prior art keywords
- viscose
- copper
- cellulose fiber
- viscose cellulose
- copper ions
- 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
- 229920000297 Rayon Polymers 0.000 title claims description 70
- 229920003043 Cellulose fiber Polymers 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 230000009965 odorless effect Effects 0.000 title claims description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 43
- 229910001431 copper ion Inorganic materials 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 238000004061 bleaching Methods 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 238000009991 scouring Methods 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 235000019645 odor Nutrition 0.000 description 27
- 239000002964 rayon Substances 0.000 description 18
- 238000005406 washing Methods 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 230000001877 deodorizing effect Effects 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 generally Polymers 0.000 description 2
- 210000004251 human milk Anatomy 0.000 description 2
- 235000020256 human milk Nutrition 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
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、レーヨン臭のない無臭
性ビスコース法セルロース繊維及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an odorless viscose cellulose fiber having no rayon odor and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、ビスコース法セルロース繊維（レ
ーヨン）の製造は、一般に繊維素キサントゲン酸ソーダ
を含むビスコースを酸性紡糸浴中で紡糸し、開綿後に、
第一水洗、脱硫、第二水洗、漂白、中和、第三水洗、第
四水洗、オイリングの順の各工程で精錬されることによ
って行なわれている。前記工程に於いて二硫化炭素が溶
剤として使用されるため、製造された繊維に硫化水素、
メルカプタン臭等の硫黄化合物の残留複合臭、いわゆる
レーヨン臭が残ることが避けられなかった。2. Description of the Related Art Conventionally, in the production of viscose-processed cellulose fibers (rayon), generally, viscose containing cellulose xanthogenate is spun in an acidic spinning bath, and after opening cotton,
It is performed by refining in each of the following steps: first washing, desulfurization, second washing, bleaching, neutralization, third washing, fourth washing, and oiling. Since carbon disulfide is used as a solvent in the above process, the produced fiber has hydrogen sulfide,
A residual complex odor of sulfur compounds such as a mercaptan odor, so-called rayon odor, was inevitable.
【０００３】このレーヨン臭は、乾燥時にはほとんど感
じられないものでも、ビスコース法セルロース繊維を用
いた不織布の製造工程等において該繊維を湿潤させた
時、特に、水に分散させた場合には、強く感じられる。
この不織布の製造においては、最近、ビスコース法セル
ロース繊維の品質、特に白度が向上し、そのため漂白工
程が省略されるので、レーヨン臭の残留傾向はむしろ顕
著となっている。[0003] Even if this rayon odor is hardly perceived when dried, it is wet when the fiber is wetted in a manufacturing process of nonwoven fabric using viscose cellulose fiber, especially when the fiber is dispersed in water. I feel strongly.
In the production of this nonwoven fabric, recently, the quality of viscose cellulose fibers, especially the whiteness, has been improved, and thus the bleaching step has been omitted.
【０００４】従来、レーヨン臭のないビスコース法セル
ロース繊維を得る目的のためには、ビスコース法セルロ
ース繊維の精練工程において脱硫、漂白、中和、水洗等
を強化して硫化水素、硫黄等の臭気成分を極力除去する
方法が行なわれているが、このような処理が行なわれた
後でも該繊維中に硫黄化合物が極微量残留し、これがレ
ーヨン臭の残留する原因となっているのが現状である。
このように、従来のレーヨン臭の除去技術に満足できる
方法はなかった。Heretofore, in order to obtain viscose cellulose fibers having no rayon odor, desulfurization, bleaching, neutralization, washing and the like have been strengthened in the scouring process of the viscose cellulose fibers to reduce hydrogen sulfide, sulfur and the like. Although a method of removing odor components has been carried out as much as possible, even after such treatment, a very small amount of sulfur compound remains in the fiber, which is a cause of residual rayon odor. It is.
As described above, there is no method that can satisfy the conventional rayon odor removal technology.
【０００５】一方、周囲の臭気を消臭する目的でセルロ
ース繊維に消臭効果を付与する技術が既に開発されてい
る。このような技術には、例えば、セルロース繊維に金
属フタロシアニン化合物を担持させる方法（特開平２−
２４５０３９号公報、特開平２−３０７９８３号公
報）、セルロース繊維にトリポリリン酸２水素アルミニ
ウムを添加する方法（特開平２−３００３１０号公
報）、銅塩を含むセルロース繊維をヨウ素化合物にて処
理する方法（特開平４−１４６２０７号公報、特開平１
−３２００５９号公報）、セルロース繊維に酸化銅粉末
を付着させる方法（特開昭６２−２３８８６６号公
報）、銅イオン錯体をセルロース繊維と結合させる方法
（特開昭６３−２３５５７１号公報）等が知られてい
る。On the other hand, techniques for imparting a deodorizing effect to cellulose fibers have been developed for the purpose of deodorizing ambient odors. Such techniques include, for example, a method of supporting a metal phthalocyanine compound on cellulose fibers (Japanese Patent Laid-Open No.
JP-A-245039, JP-A-2-307983), a method of adding aluminum dihydrogen tripolyphosphate to cellulose fibers (JP-A-2-300310), and a method of treating a cellulose fiber containing a copper salt with an iodine compound ( JP-A-4-146207, JP-A-1-146207
No.-320059), a method of adhering copper oxide powder to cellulose fibers (Japanese Patent Application Laid-Open No. 62-238866), a method of bonding a copper ion complex to cellulose fibers (Japanese Patent Application Laid-Open No. 63-235571), and the like. Have been.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、前記従
来のセルロース繊維の各処理方法は、ビスコース法セル
ロース繊維自体を消臭する目的の技術ではなく、周囲の
臭気を除去するためにビスコース法セルロース繊維を処
理する技術であるため、例えば、銅についていえば、ビ
スコース法セルロース繊維に添着される銅の添着量が多
く、このため銅イオンが脱落して周囲を汚染したり、染
色工程における発色異常等の問題点があった。However, the above-mentioned conventional methods for treating cellulose fibers are not techniques for deodorizing the viscose cellulose fibers themselves, but for removing the odor from the surroundings. Because it is a technology for treating fibers, for example, in the case of copper, the amount of copper adhering to the viscose cellulose fiber is large, so that copper ions fall off and contaminate the surroundings, and color development in the dyeing process There were problems such as abnormalities.
【０００７】そこで本発明は、前記した問題点を除去
し、銅イオンの脱落の問題がなく、且つ染色工程におけ
る発色等の問題のない、しかも、ビスコース法セルロー
ス繊維自体にレーヨン臭が永続的に残留することがな
い、無臭性のビスコース法セルロース繊維を提供するこ
とおよびその製造方法を提供することを目的とする。Therefore, the present invention eliminates the above-mentioned problems, eliminates the problem of falling off of copper ions, and does not cause the problem of color development in the dyeing process, and furthermore, the viscose method cellulose fiber itself has a permanent rayon odor. It is an object of the present invention to provide an odorless viscose-processed cellulose fiber which does not remain in the cellulose and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】上記した問題点を解決す
るために、本発明は、銅換算で０．１〜２００ｐｐｍの
銅イオンを担持した無臭性ビスコース法セルロース繊維
とするものである。In order to solve the above-mentioned problems, the present invention provides an odorless viscose cellulose fiber carrying 0.1 to 200 ppm of copper ions in terms of copper.
【０００９】また本発明は、ビスコース法セルロース繊
維の製造方法において、精練工程で漂白した後、ｐＨ３
〜６の条件下で、銅換算で０．１〜２００ｐｐｍの銅イ
オンをビスコース法セルロース繊維に担持させることを
特徴とする無臭性ビスコース法セルロース繊維の製造方
法とするものである。Further, according to the present invention, in a process for producing a viscose-processed cellulose fiber, after bleaching in a scouring step, the pH is adjusted to 3
A method for producing an odorless viscose cellulose fiber, characterized in that 0.1 to 200 ppm of copper ion in terms of copper is supported on the viscose cellulose fiber under the conditions of to 6.
【００１０】また本発明は、ビスコース法セルロース繊
維の製造方法において、精練工程で漂白した後、ｐＨ３
〜６の条件下で、ビスコース法セルロース繊維に銅の塩
類溶液を付与し、水洗し、銅換算で０．１〜２００ｐｐ
ｍの銅イオンを該繊維に担持させることを特徴とする無
臭性ビスコース法セルロース繊維の製造方法とするもで
ある。[0010] The present invention also relates to a method for producing a viscose cellulose fiber, comprising the steps of:
Under conditions of ~ 6, a copper salt solution is applied to the viscose method cellulose fiber, washed with water, and 0.1 to 200 pp in terms of copper.
The present invention also provides a method for producing an odorless viscose cellulose fiber, wherein m copper ions are supported on the fiber.
【００１１】本発明のビスコース法セルロース繊維は、
レーヨン特有のいわゆるレーヨン臭が除去されているこ
とを特徴とし、さらに同時に、本発明のビスコース法セ
ルロース繊維と共存する他の繊維の臭気成分も無臭化さ
せることを特徴とする。[0011] The viscose cellulose fiber of the present invention comprises:
It is characterized in that so-called rayon odor peculiar to rayon is removed, and at the same time, odor components of other fibers coexisting with the viscose cellulose fiber of the present invention are also deodorized.
【００１２】本発明において、ビスコース法セルロース
繊維に担持された銅イオンは、銅換算で０．１〜２００
ｐｐｍ、好ましくは、０．５〜１００ｐｐｍであること
が必要である。その理由は、銅イオンが０．１未満であ
るとビスコース法セルロース繊維に残留するレーヨン臭
の消臭効果がなく、また銅イオンが２００ｐｐｍを越え
ると、銅イオンが例えば水などによって脱落しやすくな
り好ましくないからである。本発明における銅イオンの
このような担持量は、前記従来技術における銅のセルロ
ース繊維に対する担持量、０．２〜５０重量％と比べ
て、極端にその担持量が少ない。In the present invention, the copper ions carried on the viscose cellulose fibers are 0.1 to 200 in terms of copper.
ppm, preferably 0.5-100 ppm. The reason is that when the copper ion is less than 0.1, there is no deodorizing effect of rayon odor remaining on the viscose cellulose fiber, and when the copper ion exceeds 200 ppm, the copper ion is easily dropped off by, for example, water. This is not preferred. Such a supported amount of copper ions in the present invention is extremely small as compared with the supported amount of copper to cellulose fibers in the prior art, which is 0.2 to 50% by weight.
【００１３】本発明においては、ビスコース法セルロー
ス繊維に含まれる銅イオンの形態は特に制限されない。In the present invention, the form of copper ions contained in the viscose cellulose fibers is not particularly limited.
【００１４】本発明の繊維は次の方法によって製造され
る。The fiber of the present invention is produced by the following method.
【００１５】本発明のビスコース法セルロース繊維に銅
イオンを担持させる方法は、ビスコース法セルロース繊
維の一般的な精錬工程、即ち、ビスコースを酸性紡糸浴
中で紡糸し開綿後に行なわれる、第一水洗工程、脱硫工
程、第二水洗工程、漂白工程、中和工程、第三水洗工
程、第四水洗工程、オイリング工程のいずれの工程にお
いても添加することが可能であるが、特に、硫黄化合物
が十分に脱硫工程において脱硫され、漂白工程において
漂白された後の、即ち、ビスコース法セルロース繊維の
綿中の残留Ｓが０．０２％以下となるまで漂白された後
の、中和工程、第三水洗工程、第四水洗工程、オイリン
グ工程等からなる１以上の工程において、それらの浴に
微量の銅イオンを添加することによって行なうことが好
ましい。The method for supporting copper ions on the viscose cellulose fiber according to the present invention is carried out after a general refining step of the viscose cellulose fiber, that is, after spinning viscose in an acidic spinning bath and opening cotton. It can be added in any of the first washing step, desulfurization step, second washing step, bleaching step, neutralization step, third washing step, fourth washing step, and oiling step. A neutralization step after the compound is sufficiently desulfurized in the desulfurization step and bleached in the bleaching step, that is, after bleaching until the residual S in the viscose cellulose fiber in cotton becomes 0.02% or less. , A third rinsing step, a fourth rinsing step, an oiling step and the like, it is preferable to add a trace amount of copper ions to these baths.
【００１６】その理由は、これらの工程においては硫黄
化合物が残存せず、ビスコース法セルロース繊維に対し
て異常着色等の発生の問題がないからである。なお、前
記脱硫工程は、硫化ソーダと苛性ソーダの混合浴中、７
０℃±２℃で行なわれ、また前記漂白工程は、次亜塩素
酸ソーダ浴中、３０℃で行なわれる。The reason is that no sulfur compound remains in these steps, and there is no problem of occurrence of abnormal coloring or the like on viscose cellulose fibers. The desulfurization step was performed in a mixed bath of sodium sulfide and caustic soda.
The bleaching step is performed at 30 ° C. in a sodium hypochlorite bath.
【００１７】銅イオンの添加形態は、塩水溶液の形で添
加し、その銅塩の種類には、例えば硫酸銅ＣｕＳＯ4 、
硝酸銅Ｃｕ（ＮＯ3 ）2 、燐酸第二銅Ｃｕ2 （ＰＯ4 ）
2 、酢酸銅Ｃｕ（ＣＨ3 ＣＯＯ）2 等が用いられる。The copper ions are added in the form of an aqueous salt solution, and the type of the copper salt includes, for example, copper sulfate CuSO 4 ,
Copper nitrate Cu (NO 3 ) 2 , cupric phosphate Cu 2 (PO 4 )
2 , copper acetate Cu (CH 3 COO) 2 or the like is used.
【００１８】添加浴のｐＨはｐＨ３〜６、特に好ましく
はｐＨ４〜６にて行なうことが必要である。その理由
は、添加浴のｐＨが３未満であると、ビスコース法セル
ロース繊維に銅イオンが全く吸着せず、また該繊維自体
も酸性となるからである。セルロース繊維が酸性になる
と、乾燥、その他の熱処理により黄変したり、繊維自体
が脆化する等の問題の原因となり好ましくない。通常、
精練工程では最後の仕上げ浴にてｐＨ６を調整し、ｐＨ
を順次７に近づけ、最終の製品綿のｐＨを７に調整して
いるため、ｐＨ６を越える条件で銅イオンの付与を行な
うと、再度ｐＨ調整のための工程が必要となり、工程が
繁雑となる。The pH of the addition bath must be pH 3 to 6, particularly preferably pH 4 to 6. The reason is that when the pH of the addition bath is less than 3, no copper ions are adsorbed on the viscose cellulose fibers, and the fibers themselves become acidic. When the cellulose fibers become acidic, they cause problems such as yellowing due to drying and other heat treatments and embrittlement of the fibers themselves, which is not preferable. Normal,
In the scouring process, adjust pH 6 in the final finishing bath,
Are sequentially adjusted to 7, and the pH of the final cotton product is adjusted to 7. Therefore, if copper ions are applied under conditions exceeding pH 6, a step for adjusting the pH is required again, and the process becomes complicated. .
【００１９】また銅イオンの吸着量は、繊維の結晶化や
漂白条件によって左右され漂白は十分に行なう必要があ
る。The amount of copper ions adsorbed depends on the crystallization and bleaching conditions of the fiber, and it is necessary to perform bleaching sufficiently.
【００２０】本発明は、湿式で製造される不織布用レー
ヨンに特に効果があることは当然であるが、他の用途の
普通レーヨン、強力レーヨン、ポリノジック繊維や製紙
用繊維に適用できる。The present invention is of course particularly effective for rayon for nonwoven fabrics produced by a wet process, but can be applied to ordinary rayon, high-strength rayon, polynosic fiber and papermaking fiber for other uses.
【００２１】[0021]
【実施例】本発明において、臭気の測定は以下の方法に
よった。EXAMPLES In the present invention, odor was measured by the following method.
【００２２】臭気測定法：サンプルを５０ｇ採り、３Ｌ
臭気袋に入れ、内部を真空にした後、純水５００ｃｃを
注入し、窒素ガス２Ｌを注入し、４５℃で、３時間放置
後、臭気をガステック検知管を用いて測定した。この
時、注入する純水は窒素置換などの方法により、予め溶
存酸素を含まない状態としておくことが微量の硫化水素
の酸化を防ぐため望ましい。Odor measurement method: Take 50 g of sample, 3 L
After putting in an odor bag and evacuating the inside, 500 cc of pure water was injected, 2 L of nitrogen gas was injected, the mixture was left at 45 ° C. for 3 hours, and the odor was measured using a gas tech detector tube. At this time, it is desirable that the pure water to be injected be previously free of dissolved oxygen by a method such as nitrogen replacement in order to prevent oxidation of a trace amount of hydrogen sulfide.
【００２３】なお、このような微量の銅イオンの含有量
の測定には、銅イオン付着綿を塩酸で処理して銅イオン
を溶出させ、その塩酸酸性溶液中の銅を原子吸光法で定
量し求めた。In order to measure the content of such a trace amount of copper ions, the cotton ion-adhered cotton is treated with hydrochloric acid to elute the copper ions, and the copper in the hydrochloric acid acid solution is quantified by atomic absorption. I asked.
【００２４】〔実施例１〕通常の方法により、ビスコー
スを酸性紡糸浴で紡糸し、カットした後開綿し、綿中の
残留Ｓ濃度が０．０２％となるまで脱硫した。Example 1 Viscose was spun by an ordinary method in an acidic spinning bath, cut, opened, and desulfurized until the residual S concentration in the cotton became 0.02%.
【００２５】次に、脱硫されたビスコース法セルロース
繊維をＯＨ濃度が０．５ｇ／ｌ以下となるまで、水洗し
た後、Ｃｌ２ １．５ｇ／１、３０℃の漂白浴に２分間浸
漬し脱水し、Ｃｌ濃度が０．０１ｇ／ｌ以下となるまで
十分水洗した。Next, the desulfurized viscose cellulose fibers were washed with water until the OH concentration became 0.5 g / l or less, and then immersed in a bleach bath of 1.5 g of Cl 2 at 30 ° C. for 2 minutes. It was dehydrated and thoroughly washed with water until the Cl concentration became 0.01 g / l or less.
【００２６】次いで、前記水洗されたビスコース法セル
ロース繊維をＣｕＳＯ4 ０．５ｍｇ／ｌに２分間浸漬
し、脱水水洗乾燥することによって、このセルロース繊
維に対し、銅イオンを３０ｐｐｍ吸着させた。この銅イ
オンが吸着されたセルロース繊維を通常の方法に従って
オイリングし、乾燥し、無臭性ビスコース法セルロース
繊維を得た。Next, the viscose-processed cellulose fibers washed with water were immersed in 0.5 mg / l of CuSO 4 for 2 minutes, and were washed with dewatered water and dried to adsorb 30 ppm of copper ions to the cellulose fibers. The cellulose fiber to which the copper ions had been adsorbed was oiled and dried according to a usual method to obtain an odorless viscose cellulose fiber.
【００２７】得られたビスコース法セルロース繊維につ
いて、Ｈ2 Ｓガス濃度を上記の臭気測定法で測定したと
ころ、０．００ｐｐｍ以下であり、硫化水素臭は全くな
かった。When the H 2 S gas concentration of the obtained viscose method cellulose fiber was measured by the above-mentioned odor measurement method, it was 0.00 ppm or less, and there was no hydrogen sulfide odor.
【００２８】〔比較例〕前記実施例１と同じ操作で、銅
イオンの吸着を行なわず、綿中の残留Ｓが０．０２％と
なるまで水洗（中和後の第三、第四水洗）するだけにと
どめ、その他は前記実施例１と同様に操作した。得られ
た銅イオンが吸着されたビスコース法セルロース繊維に
ついてＨ2 Ｓガス濃度を上記の臭気測定法で測定したと
ころ、Ｈ2 Ｓガス濃度は０．１５ｐｐｍであり、強い硫
化水素臭が感じられた。[Comparative Example] The same operation as in Example 1 was carried out, but the copper ions were not adsorbed, and water was washed until the residual S in cotton became 0.02% (third and fourth water washing after neutralization). The operation was the same as in Example 1 except for the above. When the H 2 S gas concentration of the obtained viscose cellulose fibers to which copper ions were adsorbed was measured by the above-mentioned odor measurement method, the H 2 S gas concentration was 0.15 ppm, and a strong hydrogen sulfide smell was felt. Was.
【００２９】〔実施例２〕前記実施例１と同様の操作
で、ビスコース法セルロース繊維に対する銅イオン吸着
量を変えて吸着させた。各々吸着量の異なる繊維から発
生したＨ2 Ｓガス濃度を調べると次の表１の如くなっ
た。Example 2 In the same manner as in Example 1, adsorption was performed by changing the amount of copper ions adsorbed on the viscose cellulose fibers. Table 1 shows the concentration of H 2 S gas generated from the fibers having different adsorption amounts.
【００３０】[0030]
【表１】 表１によれば、ビスコース法セルロース繊維に対する銅
イオンの吸着量が５ｐｐｍ以上あれば、硫化水素がない
ことがわかる。[Table 1] According to Table 1, it can be seen that there is no hydrogen sulfide when the adsorption amount of copper ions to the viscose cellulose fiber is 5 ppm or more.
【００３１】次に、各々吸着量の異なるビスコース法セ
ルロース繊維を２０倍の純水に浸し、水への銅イオンの
溶出を調べた。その結果を次の表２に示す。Next, viscose cellulose fibers having different adsorption amounts were immersed in 20 times the volume of pure water, and the elution of copper ions into the water was examined. The results are shown in Table 2 below.
【００３２】[0032]
【表２】 表２によれば、ビスコース法セルロース繊維に対する銅
イオンの吸着量が１００ｐｐｍ以下であれば、水への銅
イオンの溶出量は少ないことが分かる。[Table 2] According to Table 2, when the adsorption amount of copper ions to the viscose cellulose fibers is 100 ppm or less, the elution amount of copper ions into water is small.
【００３３】〔実施例３〕常法によりビスコースを酸性
紡糸浴で紡糸し、カットした後、開綿し、精練機に通し
た。精練機上では脱硫−水洗（第二水洗）−漂白−中和
工程を経た後、ＣｕＳＯ4 ５ｍｇ／ｌの水溶液を２５
℃、２分間シャワーし、水洗−オイリング工程を経た
後、乾燥した。得られたセルロース繊維には銅イオン
が、セルロース当たり０．９ｐｐｍ吸着されていた。得
られた銅イオンが吸着されたビスコース法セルロース繊
維についてＨ2 Ｓガス濃度を上記の臭気測定法で測定し
たところ、Ｈ2 Ｓ濃度が０．０ｐｐｍであり、Ｈ2 Ｓ臭
は全く感じられなかった。Example 3 Viscose was spun in an acidic spinning bath according to a conventional method, cut, opened, and passed through a scouring machine. The scouring machine desulfurization - washing (Second water washing) - bleach - after a neutralization step, an aqueous solution of CuSO 4 5mg / l 25
After showering at 2 ° C. for 2 minutes, washing and oiling steps, the product was dried. Copper ions were adsorbed to the obtained cellulose fibers at 0.9 ppm per cellulose. When the H 2 S gas concentration of the obtained viscose cellulose fiber to which copper ions were adsorbed was measured by the above-mentioned odor measurement method, the H 2 S concentration was 0.0 ppm, and the H 2 S odor was not felt at all. Did not.
【００３４】[0034]
【発明の効果】本発明によれば、ビスコース法セルロー
ス繊維が強く銅イオンを吸着し、含有するＨ2 Ｓやメル
カプタンを反応除去するので、ビスコース法セルロース
繊維のレーヨン臭は無臭化する。According to the present invention, the viscose cellulose fiber strongly adsorbs copper ions and reacts and removes H 2 S and mercaptan contained therein, so that the rayon odor of the viscose cellulose fiber is deodorized.
【００３５】本発明のビスコース法セルロース繊維に吸
着された銅イオンは、乾燥して製品化した後も強く吸着
されているので、この製品を水洗、染色、漂白、および
反復して洗濯しても、銅イオンは脱落せず、無臭化され
たビスコース法セルロース繊維の効果は半永久的であ
る。また、本発明の銅イオンが吸着されたビスコース法
セルロース繊維は、銅イオンの水への溶出量も０．４ｐ
ｐｍ以下と極めて少なく、通常の母乳に含まれている銅
イオンの量よりも少ないので、このビスコース法セルロ
ース繊維を使用した製品の人体への安全性に問題がな
い。Since the copper ions adsorbed on the viscose cellulose fibers of the present invention are strongly adsorbed even after drying and commercializing, the product is washed with water, dyed, bleached and repeatedly washed. However, the copper ions do not fall off, and the effect of the deodorized viscose cellulose fibers is semi-permanent. In addition, the viscose cellulose fibers to which the copper ions of the present invention have been adsorbed have a copper ion elution amount into water of 0.4 p.
pm or less, which is less than the amount of copper ions contained in normal breast milk, so that there is no problem in the safety of a product using this viscose cellulose fiber to the human body.
【００３６】銅イオンの添加工程は、ビスコース法レー
ヨンのいずれの場合でも一応さしつかえはないが、漂白
工程を終わって、硫黄化合物が大部分除去された後が好
ましく、異常着色等の問題がない。The addition step of copper ions may be irrelevant in any case of the viscose rayon, but it is preferable that the bleaching step has been completed and most of the sulfur compounds have been removed, and there is no problem such as abnormal coloring. .
【００３７】銅を微量吸着したレーヨンは、水に浸漬し
ても極わずかしか溶出せず、セルロースに対して銅イオ
ンを３０ｐｐｍ吸着した繊維は水中へは０．０４ｐｐｍ
しか溶出せず、０．０６ｐｐｍ銅が含まれている、通常
の母乳よりも低く安全性が高い。Rayon adsorbing trace amounts of copper elutes very little even when immersed in water, and fibers adsorbing 30 ppm of copper ions to cellulose have 0.04 ppm of fibers adsorbed in water.
It only elutes and contains 0.06 ppm copper, which is lower and safer than normal breast milk.
【００３８】また、この消臭効果を有する本発明の銅イ
オンの担持されたビスコース法セルロース繊維を、本発
明の無臭化処理が施されていない他の普通のレーヨン、
または臭気のある他の繊維と混合しても、レーヨン臭ま
たは他の臭気成分を吸着除去することができる。Further, the viscose-processed cellulose fiber carrying copper ions of the present invention having the deodorizing effect can be replaced with another ordinary rayon not subjected to the deodorizing treatment of the present invention,
Alternatively, even when mixed with other odorous fibers, rayon odor or other odor components can be adsorbed and removed.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−177209（ＪＰ，Ａ) 特開 平４−289274（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) D06M 11/00 - 11/84 ────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-62-177209 (JP, A) JP-A-4-289274 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) D06M 11/00-11/84
Claims (3)
ンを担持した無臭性ビスコース法セルロース繊維。1. An odorless viscose cellulose fiber carrying 0.1 to 200 ppm of copper ions in terms of copper.
において、精練工程で漂白した後、ｐＨ３〜６の条件下
で、銅換算で０．１〜２００ｐｐｍの銅イオンをビスコ
ース法セルロース繊維に担持させることを特徴とする無
臭性ビスコース法セルロース繊維の製造方法。2. A method for producing a viscose cellulose fiber, in which, after bleaching in a scouring step, 0.1 to 200 ppm of copper ion in terms of copper is carried on the viscose cellulose fiber under conditions of pH 3 to 6. A process for producing an odorless viscose cellulose fiber.
において、精練工程で漂白した後、ｐＨ３〜６の条件下
で、ビスコース法セルロース繊維に銅の塩類溶液を付与
し、水洗し、銅換算で０．１〜２００ｐｐｍの銅イオン
を該繊維に担持させることを特徴とする無臭性ビスコー
ス法セルロース繊維の製造方法。3. A method for producing a viscose cellulose fiber, wherein after bleaching in a scouring step, a copper salt solution is applied to the viscose cellulose fiber under conditions of pH 3 to 6, washed with water, and converted to copper. A method for producing an odorless viscose cellulose fiber, wherein 0.1 to 200 ppm of copper ions is supported on the fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13402993A JP2944061B2 (en) | 1993-05-11 | 1993-05-11 | Odorless viscose cellulose fiber and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13402993A JP2944061B2 (en) | 1993-05-11 | 1993-05-11 | Odorless viscose cellulose fiber and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06322662A JPH06322662A (en) | 1994-11-22 |
| JP2944061B2 true JP2944061B2 (en) | 1999-08-30 |
Family
ID=15118717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13402993A Expired - Lifetime JP2944061B2 (en) | 1993-05-11 | 1993-05-11 | Odorless viscose cellulose fiber and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2944061B2 (en) |
-
1993
- 1993-05-11 JP JP13402993A patent/JP2944061B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06322662A (en) | 1994-11-22 |
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