JPS63196769A - Novel acrylic synthetic fiber - Google Patents
Novel acrylic synthetic fiberInfo
- Publication number
- JPS63196769A JPS63196769A JP62022284A JP2228487A JPS63196769A JP S63196769 A JPS63196769 A JP S63196769A JP 62022284 A JP62022284 A JP 62022284A JP 2228487 A JP2228487 A JP 2228487A JP S63196769 A JPS63196769 A JP S63196769A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic synthetic
- synthetic fiber
- ferrocyanide
- water
- aqueous solution
- 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.)
- Pending
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 45
- 239000012209 synthetic fiber Substances 0.000 title claims description 43
- 229920002994 synthetic fiber Polymers 0.000 title claims description 43
- 150000002697 manganese compounds Chemical class 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000009987 spinning Methods 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000010828 elution Methods 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- -1 NaMn04 or NaMn04 Chemical class 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、金属化合物を担持、固定したアクリル系合成
繊維に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an acrylic synthetic fiber carrying and fixing a metal compound.
（本発明の解決すべき味題）
担持、固定した不溶性フェロシアン化物の水への再分散
を抑制するように処理されたアクリル系合成繊維を目的
とする。(Problems to be Solved by the Invention) An object of the present invention is to provide an acrylic synthetic fiber that has been treated to suppress the redispersion of supported and fixed insoluble ferrocyanide into water.
（問題を解決するための手段）
本発明者らは、アクリル系合成繊維に担持、固定した不
溶性フェロシアン化物の水への古分散を抑制する事につ
いて鋭意研究を行なった結果不溶性フェロシアン化物を
担持、固定したアクリル系合成繊維をマンガン化合物水
溶液で処理する事によって、担持、固定した不溶性フェ
ロシアン化物の水への再分散がほぼ完全に消失する事を
発見し、本発明圧到達したものである。(Means for Solving the Problem) The present inventors have conducted intensive research on suppressing the dispersion of insoluble ferrocyanide supported and fixed on acrylic synthetic fibers into water, and as a result, the insoluble ferrocyanide We have discovered that by treating supported and fixed acrylic synthetic fibers with an aqueous solution of manganese compound, the redispersion of supported and fixed insoluble ferrocyanide into water almost completely disappears, and we have achieved the pressure of the present invention. be.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明に用いられるアクリル系合成−維は、アクリロニ
トリルを４０重ｔｔＩｊ以上含有する２ＮＩｔたは、３
榛以上の共重合体または、アクリロニトリル単独重合体
から成る繊維である。ここで、共重合成分として蝶、ア
クリル酸、メタリルスルホン酸ソーダ、アリルスルホン
酸ソーダ、パラスチレンスルホン酸ソーダ、アクリルア
ミド、メタクリルアミド、塩化ビニル、塩化ビニリデン
、酢酸ビニル、アク、リル酸メチル、Ｎ、 Ｎ’−ジメ
チルアミノエチルアクリレート、Ｎ、 Ｎ’−ジエチル
アミノエチルメタクリレート等が挙けられるがこれらに
限定されるものではない。さらに、上記のアクリル系合
成繊維を水酸化ナトリウム等の塩基または、ａ醒等の酸
を用いて表向を加水分解後、本発明のアクリル系合成繊
維として用いてもよい。The acrylic synthetic fiber used in the present invention is 2NIt or 3NIt containing acrylonitrile of 40 weights ttIj or more.
It is a fiber made of a copolymer of acrylonitrile or higher or an acrylonitrile homopolymer. Here, the copolymerization components include butterfly, acrylic acid, sodium methallyl sulfonate, sodium allyl sulfonate, sodium p-styrene sulfonate, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, acrylate, methyl lylate, N , N'-dimethylaminoethyl acrylate, N,N'-diethylaminoethyl methacrylate and the like, but are not limited to these. Furthermore, the above acrylic synthetic fiber may be used as the acrylic synthetic fiber of the present invention after surface hydrolysis using a base such as sodium hydroxide or an acid such as acetic acid.
より好ましくは、カルメキシル基及び／またはスルホン
酸基を０．１〜５ｍｍｏｆｆｉ／、ｊｉｉｌ含廟するア
クリル系合成繊維を柑いる事である。このカルゼキシル
革及び／またはスルホン酸基を介して、不溶性フェロシ
アン化物がイオン的相互作用によりアクリル系合成繊維
に吸着するために、不溶性フェロシアン化物の付着量が
増大する。しかし、カルゼキシル基及び／またはスルホ
ン酸基の含有量が総量で０．１ ｍ ｍａｉｌ／ ｇ未
満では、不溶性フェロシアン化物の付着量はほとんど増
大せず５ ｍ ｍｏ Ｑ ／ ｇ以上ではアクリル系合
成繊維の単糸物性の低下が着るしいために、実用上適用
範囲が制限される結果となる。More preferably, an acrylic synthetic fiber containing carmexyl groups and/or sulfonic acid groups of 0.1 to 5 mmoff is used. Since the insoluble ferrocyanide is adsorbed to the acrylic synthetic fiber by ionic interaction via the calzexyl leather and/or the sulfonic acid group, the amount of the insoluble ferrocyanide deposited increases. However, when the total content of carzexyl groups and/or sulfonic acid groups is less than 0.1 mm/g, the amount of insoluble ferrocyanide deposited hardly increases, and when the total content is 5 mm/g/g or more, acrylic synthetic fibers Since the physical properties of single fibers tend to deteriorate, the range of practical application is limited.
不溶性フェロシアン化物は、水への溶解度が、２５℃に
おいて、０．１ ｇ７１００ ｃｃ以下であり、かつＣ
ｒ’ｅ （ＣＮ）＠ ）および金属から成る物質である
。たとえば、Ｋ２Ｃｏ ［：Ｆｅ （ＣＮ）ｓ）、Ｎａ
２Ｎｔ（Ｆｅ （ＣＮ）＠］、Ｋ１Ｚｎ３ 〔Ｆｅ （
ＣＮ）ａｃｔ、Ｃｕｌ［Ｆｅ（ＣＮ）ｓ：］、Ｚｎ鵞（
Ｆｅ （ＣＮ）ｊ、Ｃｄ５（Ｆｅ （ＣＮ）ａ〕、Ｎｉ
ｚ［Ｆｅ（ＣＮ）Ｊ、Ｆｅａ〔Ｆｅ（ＣＮ）６〕１、Ｔ
ｉ（Ｆｅ（ＣＮ）ｓ）などを挙げる事ができ、金属とし
ては、Ｌｉ、 Ｋ、 Ｎａ、 Ａｇ、 Ｚｎ、 Ｃｄ、
Ｃｕ、 Ｃｏ、 Ｎｉ、 Ｍｎ、 Ｆｅ。The insoluble ferrocyanide has a solubility in water of 0.1 g7100 cc or less at 25°C, and a C
It is a substance consisting of r'e (CN)@) and metal. For example, K2Co[:Fe(CN)s), Na
2Nt(Fe (CN)@], K1Zn3 [Fe (
CN) act, Cul[Fe(CN)s:], Zn(
Fe(CN)j, Cd5(Fe(CN)a), Ni
z[Fe(CN)J, Fea[Fe(CN)6]1, T
i(Fe(CN)s), etc., and metals include Li, K, Na, Ag, Zn, Cd,
Cu, Co, Ni, Mn, Fe.
ＴＩ、 Ｚｒ、 Ｖ、 Ｍｏ、Ｗ、 Ｕなどの１棟また
は、２ｔ１１１以上の金属を組み合せを用いる事ができ
るが、これらに限定されるものではない。A single metal such as TI, Zr, V, Mo, W, or U, or a combination of metals of 2t111 or more can be used, but the material is not limited to these.
不溶性フェロシアン化物のアクリル系合成繊維への担持
、固定は、アクリル系合成繊維自体が不溶性フェロシア
ン化物を城り囲む事、またはアクリル系合成繊維中のカ
ルゼキシル基かつ／またはスルホン酸基と不溶性フェロ
シアン化物がイオン的相互作用によって吸着する事、ま
たはその相乗作用によってアクリル系合成繊維に固定さ
れる事である。The insoluble ferrocyanide is supported and fixed on the acrylic synthetic fiber by the fact that the acrylic synthetic fiber itself surrounds the insoluble ferrocyanide, or by the fact that the calzexyl group and/or sulfonic acid group in the acrylic synthetic fiber and the insoluble ferrocyanide are supported and fixed on the acrylic synthetic fiber. This is because rusyanide is adsorbed by ionic interaction or fixed to acrylic synthetic fiber by their synergistic action.
なお、不溶性フェロシアン化物の繊維に対する担持量は
、繊維１ｇ当りＱ、００１ｇ以上あれば良い。The amount of insoluble ferrocyanide supported on the fibers should be Q,001 g or more per 1 g of fibers.
不溶性フェロシアン化物のアクリル系合成繊維への担持
、固定方法は、たとえばアクリル系合成繊維の紡糸時に
紡糸み液に不溶性フェロシアン化物を混合後、湿式法も
しくは乾式法を用い常法により紡糸する方法で紡糸用溶
媒としてジメチルホルムアミド、ジメチルアセトアミド
、ジメチルスルホキシド、硝酸、ロダン塩水溶液などを
挙げる半ができる。また、たとえばアクリル系合繊維の
紡糸時に水溶性フェロシアン化物であるに４ （）’
ｅ ＜ＣＮ）ｓ ’）、Ｎａ４（Ｆｅ（ＣＮ）ｓ：］な
どをｍ和溶解度以上の水に溶解し紡糸原液と混合する。A method for supporting and fixing insoluble ferrocyanide on acrylic synthetic fibers is, for example, by mixing insoluble ferrocyanide into the spinning solution during spinning of acrylic synthetic fibers, and then spinning in a conventional manner using a wet or dry method. As a spinning solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide, nitric acid, an aqueous solution of rhodan salt, etc. can be used. In addition, for example, when spinning acrylic synthetic fibers, water-soluble ferrocyanide is produced.
e<CN)s'), Na4(Fe(CN)s:], etc. are dissolved in water having a molar solubility or higher and mixed with the spinning stock solution.
その後１兄弐法を用い常法によって、紡糸を行なうがフ
ェロシアン化物が、不溶性フェロシアン化物となる様な
１８Ｉま九は、２拘以上のＡｇ、 Ｚｎ、 Ｃｄ、 Ｃ
ｏ、 Ｃｏ。After that, spinning is carried out in a conventional manner using the 1-2 method, but if the 18I or 18I is such that the ferrocyanide becomes insoluble ferrocyanide, Ag, Zn, Cd, C with a concentration of 2 or more is used.
o, Co.
Ｎｉ、 Ｍｎ、 Ｆｅ、 Ｔｉ、 Ｚｒ、 Ｖ、 Ｍｏ
、 Ｗ、 Ｖなどの金属イオンまたは金属錯体を凝固浴
に添加し紡糸する方法を挙げる墨ができる。Ni, Mn, Fe, Ti, Zr, V, Mo
Ink can be produced by adding metal ions or metal complexes such as , W, and V to a coagulation bath and spinning.
また、たとえばアクリル系合成繊維の紡糸時に紡糸原液
中に、その７エロシアン化物が不溶性フェロシアン化物
となる様な１拘または２拘以上のＡｇ、 Ｚｎ、 Ｃｄ
、 Ｃｕ、 Ｃｏ、 Ｎｉ、 Ｍｎ、 Ｆｅ、 Ｔｉ、
Ｚｒ、 Ｖ、 Ｍｏ。In addition, for example, when spinning acrylic synthetic fibers, one or more of Ag, Zn, and Cd is added to the spinning dope so that the 7-erocyanide becomes insoluble ferrocyanide.
, Cu, Co, Ni, Mn, Fe, Ti,
Zr, V, Mo.
Ｗ、Ｕなどの金属イオン、金属錯体を飽和溶解度以上の
水に溶解し、紡糸原液と混合する。その後湿式法を用い
常法によって紡糸を行なうが、水溶性フェロシアン化物
であるに４（Ｆｅ（ＣＮ）８”ｌ、Ｎａ４ （Ｆｅ （
ＣＮ）ａ ）などを凝固浴に冷加し紡糸する方法を挙け
る事ができる。Metal ions and metal complexes such as W and U are dissolved in water having a saturation solubility or higher, and mixed with the spinning dope. Thereafter, spinning is carried out in a conventional manner using a wet method.
An example of this method is to cool CN)a) in a coagulation bath and spin it.
また、たとえばアクリル系合成繊維を水溶性フェロシア
ン化物でおるに４（Ｆｅ （ＣＮ）ｓ 〕、Ｎａ４（Ｆ
ｅ（ＣＮ）ｓ）、などの水溶液により処理温度１０℃〜
１４０℃、処理時間３０秒〜３時間で処理を行なう。In addition, for example, acrylic synthetic fibers can be coated with water-soluble ferrocyanide (Fe (CN)s), Na4 (F
e(CN)s), etc. at a treatment temperature of 10℃~
The treatment is carried out at 140° C. for a treatment time of 30 seconds to 3 hours.
その後、そのフェロシアン化物が不溶性フェロシアン化
物となる様な１種または２棟以上のＡｇ。Thereafter, one or more types of Ag such that the ferrocyanide becomes an insoluble ferrocyanide.
Ｚｎ、 Ｃｄ、 Ｃｕ、 Ｃｏ、 Ｎｉ、 Ｍｎ、 Ｆ
ｅ、 Ｔｉ、 Ｚｒ、 Ｖ、 Ｍｏ、 Ｗ、Ｕなどの金
属イオンまたは金属錯体の水溶液により処理温度１０℃
〜１４０℃、処理時間３０秒〜３時間で処理を行なう方
法を挙げる事ができる。Zn, Cd, Cu, Co, Ni, Mn, F
Treatment temperature: 10°C with an aqueous solution of metal ions or metal complexes such as e, Ti, Zr, V, Mo, W, and U.
A method of carrying out the treatment at ~140°C for a treatment time of 30 seconds to 3 hours can be mentioned.
また、たとえばアクリル系合成繊維を、そのフェロシア
ン化物が不溶性フェロシアン化物となる様な１捏または
２種以上のＡｇ、 Ｚｎ、 Ｃｄ、 Ｃｕ、 Ｃｏ。Further, for example, acrylic synthetic fibers may be mixed with one or more types of Ag, Zn, Cd, Cu, and Co such that the ferrocyanide thereof becomes an insoluble ferrocyanide.
Ｎｉ、 Ｍｎ、 Ｆｅ、 Ｔｉ、 Ｚｒ、 Ｖ、 Ｍｏ
、 Ｗ、 Ｕなどの金属イオンまたは金属錯体の水溶液
により処理温度１０℃〜１４０℃、処理時ＩＶ］３０秒
〜３時間で処理を行なう。Ni, Mn, Fe, Ti, Zr, V, Mo
The treatment is carried out using an aqueous solution of metal ions or metal complexes such as , W, and U at a treatment temperature of 10° C. to 140° C. and a treatment time of 30 seconds to 3 hours.
その後、水溶性フェロシアン化物であるに４（Ｆｅ （
ＣＮ）ａ〕、Ｎａ４（Ｆｅ （ＣＮ）ｓ：）などの水溶
液により処理温度１０℃〜１４０℃、処理時間３０秒〜
３時間で処理を行なう方法を挙げる事ができる。Thereafter, water-soluble ferrocyanide 4(Fe(
CN)a], Na4(Fe(CN)s:), etc. at a treatment temperature of 10°C to 140°C and a treatment time of 30 seconds to
There is a method that can perform the treatment in 3 hours.
これらに挙げ六方法は一例でありこれらに限定されるも
のではない。The six methods listed above are just examples, and the method is not limited to these.
マンガン化合物水溶液による処理は、たとえばＫＭ ｎ
０４ 、 Ｎ ａ Ｍ ｎ ０４などの過マンガン酸
塩化合物を含有する水溶液を用いて、不溶性フェロシア
ン化物を担持、固定したアクリル系合成繊維を処理温度
１０℃〜１４０℃、処理時間３０秒〜３時間で処理する
方法、−またたとえば、酸性もしくは中性の水溶液に対
して可溶性であるマンガン化合物を含有する、酸性もし
くは中性水溶液を用いて、不溶性フェロシアン化物を担
持、固定したアクリル系合成繊維を処理温度ｌＯ℃〜１
４０℃、処理時間３０秒〜３時間で処理し、その後ＫＯ
Ｈ，ＮａＯＨ，ＮＨ３などの塩基性物質を含有する塩基
性水溶液を用い処理温度１０℃〜１４０℃、処理時間３
０秒〜３時間で処理し、水への溶解度が２５℃において
、０．１ｇ／１００ｃｃ以下である不溶性マンガン化合
物とする方法などを挙げる事ができるがこれらに限定さ
れるものではない。ここで、酸性もしくは、中性の水溶
液に対して可溶性であるマンガン化合物は、ＭｎＣｊ！
２゜Ｍｎ （ＮＯ３）２ 、 ＭｎＣＯ３、ＭｎＦ２
、 Ｍｎ （ＯＨ）２ 、 ＭｎＯ（ＯＨ）２゜Ｍｎ
Ｉｌ 、 ＭｎＣ０１０４、ＭｎＯ２、Ｍ ｎ２
０ｔ、 ＭｎＯ３、Ｍｎ２Ｐ２ ０？ 。Treatment with a manganese compound aqueous solution is, for example, KM n
Using an aqueous solution containing a permanganate compound such as NaMn04 or NaMn04, an acrylic synthetic fiber having an insoluble ferrocyanide supported and fixed thereon was treated at a temperature of 10°C to 140°C and a treatment time of 30 seconds to 30°C. - Also, for example, acrylic synthetic fibers carrying and fixing insoluble ferrocyanide using an acidic or neutral aqueous solution containing a manganese compound that is soluble in an acidic or neutral aqueous solution. The processing temperature is 1O℃~1
Treated at 40°C for 30 seconds to 3 hours, then KO
Using a basic aqueous solution containing basic substances such as H, NaOH, NH3, treatment temperature 10°C to 140°C, treatment time 3
Examples include, but are not limited to, a method of processing for 0 seconds to 3 hours to form an insoluble manganese compound having a solubility in water of 0.1 g/100 cc or less at 25°C. Here, manganese compounds that are soluble in acidic or neutral aqueous solutions are MnCj!
2゜Mn(NO3)2, MnCO3, MnF2
, Mn (OH)2 , MnO(OH)2゜Mn
Il, MnC0104, MnO2, Mn2
0t, MnO3, Mn2P2 0? .
ＭｎＰ、 ＭｎＳＯ４、ＭｎＳ、 Ｍｎ （ＳＣＮ）１
・３Ｈ２０などを挙げる事ができるが、これらに限定
されるものではない。なお、マンガン化合物水溶液で処
理したアクリル系合成線維中のマンガン含有量は、線維
１ｇ当り０．００１ｇ以上かつ０．５ｇ以下であれば良
い。アクリル系合成線ｔｗｉｇ中のマンガン含有量が０
．００１ｇ未満では、アクリル系合成繊維中に担持、固
定した不溶性フェロシアン化物の水への再分散を抑制す
る事は困難であり、マンガン含有量が０．５ｇ以上では
、繊維表面が不溶性マンガン化合物で完全に轡われでし
まい、不溶性フェロシアン化物の性質が有効に機能せず
、実質的に用途が制限される結果となる。MnP, MnSO4, MnS, Mn (SCN)1
-3H20, etc., but are not limited to these. Note that the manganese content in the acrylic synthetic fiber treated with the manganese compound aqueous solution may be 0.001 g or more and 0.5 g or less per 1 g of fiber. Manganese content in acrylic synthetic wire twig is 0
．． If the manganese content is less than 0.001 g, it will be difficult to suppress the redispersion of insoluble ferrocyanide supported and fixed in the acrylic synthetic fiber into water, and if the manganese content is 0.5 g or more, the fiber surface will be covered with insoluble manganese compounds. The properties of the insoluble ferrocyanide will not function effectively and its uses will be substantially limited.
さらに、不溶性フェロシアン化物を相持、固定し、マン
ガン化合物水溶液で処理したアクリル系合成繊維に、湿
熱下において、熱収縮を行なってもよい拳
この様にして製造された本発明のアクリル系合成繊維は
、綿状のままカラムに充填し九り織布、絹布等の布帛状
あるいは不織布等の形態により使用する。Furthermore, the acrylic synthetic fiber of the present invention, which is produced in this manner, may be subjected to heat shrinkage under moist heat to the acrylic synthetic fiber, which has been treated with an aqueous solution of a manganese compound and has an insoluble ferrocyanide attached thereto. is packed in a column in its cotton form and used in the form of fabrics such as woven fabrics and silk fabrics, or non-woven fabrics.
アクリル系合成［Ｍｚｏｏｇを、ＸＣ紫を精秤した３０
０ｅｅビーカーに入れさらに純水２００ｅｅを投入後、
５０℃で１０時間攪拌を行危う。Acrylic synthesis [Mzoog and XC purple were precisely weighed 30
After putting it in a 0ee beaker and adding 200ee of pure water,
Stirring was carried out at 50°C for 10 hours.
攪拌後、アクリル系合成繊維を取り出しアクリル系合成
繊維付着の水を純水５０ｃｃでビーカー内に洗い落す。After stirring, the acrylic synthetic fibers are taken out and the water adhering to the acrylic synthetic fibers is washed off into a beaker with 50 cc of pure water.
ビーカー内の水を蒸発、乾固し、ビーカー重量を精秤す
る。溶出率は下式に基づき針筒した。Evaporate the water in the beaker to dryness and accurately weigh the beaker. The elution rate was determined based on the formula below.
０１ｇ１
実施例１〜７
共重合体組成が第１表記載の組成である３デニールのア
クリル系合成繊維１０ｇおよびｌＯ重量係の第１表記載
の金属塩水溶液４００ｇを１０００ｃｃビーカー中にお
いて第１表記載の反応温度および反応時間攪拌しながら
反応させる。反応後、洗浄水の着色が消失するまで水洗
を行なう。その後、反応し次アクリル系合成繊維および
１０重量％の第１表記載の）二〇シアン酸塩水溶液４０
０ｇを１０００ｃｃビーカー中で第１表記載の反応温度
および反応時間攪拌しながら反応させる。反応後、洗浄
水の着色が消失するまで水洗を行なう。01g1 Examples 1 to 7 10 g of 3 denier acrylic synthetic fiber having the copolymer composition shown in Table 1 and 400 g of the metal salt aqueous solution shown in Table 1 with a weight ratio of 1O were placed in a 1000 cc beaker. The reaction temperature and reaction time are as follows: The reaction is carried out with stirring. After the reaction, wash with water until the color of the washing water disappears. Then, after reacting, the acrylic synthetic fiber and 10% by weight aqueous solution of 20 cyanate (listed in Table 1) 40
0 g was reacted in a 1000 cc beaker at the reaction temperature and reaction time listed in Table 1 with stirring. After the reaction, wash with water until the color of the washing water disappears.
さらに、反応後のアクリル系合成繊維および２重量悌の
第１表記載の過マンガン酸塩水溶液４００ｇを１０００
ｃｃビーカー中で第１表記載の反応温度および反応時間
攪拌しながら反応させる。反応後、洗浄水の着色が消失
するまで水洗を行なう。Furthermore, 1,000 g of the acrylic synthetic fiber after the reaction and 400 g of the permanganate aqueous solution listed in Table 1 weighing 2.
The reaction is carried out in a cc beaker at the reaction temperature and reaction time listed in Table 1 with stirring. After the reaction, wash with water until the color of the washing water disappears.
処理したアクリル系合成繊維を脱水後、８０℃、２時間
乾燥する。After the treated acrylic synthetic fibers are dehydrated, they are dried at 80° C. for 2 hours.
（比較例１〜３）
共重合体組成が第１表記載の組成である３デニールのア
クリル系合成繊維を実施例１〜７と同一の方法を用い、
第１表記載の金鵬塩水溶液、フェロシアン化物水溶液お
よび反応温度、反応時間で縦芯を行なう。さらに実施例
１〜７と同一方法で乾燥を行なう。(Comparative Examples 1 to 3) Using the same method as Examples 1 to 7, a 3-denier acrylic synthetic fiber having a copolymer composition listed in Table 1 was used.
Vertical core testing is carried out using the aqueous solution of Kinho salt, aqueous ferrocyanide solution, reaction temperature, and reaction time shown in Table 1. Further, drying is performed in the same manner as in Examples 1 to 7.
（以下余白）
第 ２ 表
得られｆｃ織繊維金属含有率および溶出率を第２表に示
した。この中で、実施例１〜７における、溶出率は０．
１８〜Ｏ，Ｓ Ｓ ＊と低い。これに対し比較例１〜３
の溶出率は１．５０〜１３８係と高く、実用上適用範囲
が制限される結果となった。(The following is a blank space) Table 2 Table 2 shows the metal content and elution rate of the obtained fc woven fibers. Among these, the elution rate in Examples 1 to 7 was 0.
It is as low as 18~O, S S *. On the other hand, Comparative Examples 1 to 3
The elution rate was as high as 1.50 to 138, which resulted in a limited practical application range.
実施例８
共重合体組成がアクリロニトリル＝９１．５重量嗟、ア
クリル酸メチル＝８重（１１およびメタリルスルホン酸
ソーダ＝０．５重量悌である３デニールのアクリル系合
成繊維４９に、３規定の水酸化ナトリウム水溶液４０２
を添加し、反応ｍ度５０℃、１時間オーツ々−マイヤー
型染色機を使用し反応させる。Example 8 A 3-denier acrylic synthetic fiber 49 having a copolymer composition of acrylonitrile = 91.5 weight units, methyl acrylate = 8 units (11 weight units), and sodium methallylsulfonate = 0.5 weight units, was coated with 3N. Sodium hydroxide aqueous solution 402
was added and allowed to react at 50° C. for 1 hour using an Oates-Meyer type dyeing machine.
反応後、洗浄水のｐＨが７．０になるまで洗浄を繰返す
。得られた繊維のカルゼキシル基およびスルホン酸基の
含有量は１３ ｍｍｏｆｉ／ ｇであってさらに、１０
重を−の硝酸コノ９ルト水溶液を４０２添加し、処理ｍ
度６０℃、１時間オーバーマイヤー型染色機を使用し処
理する。処理後、洗浄水の着色が消失するまで、洗浄を
繰返す。その後、フェロシアン酸カリウム１０重ｔチ水
溶液、４０２を添加し、処理温度６０℃、１時間オーノ
セーマイヤー型染色機を使用し処理する。処理後、洗浄
水の着色が消失するまで、洗浄を繰返す。さらＫ、その
後２重量％の過マンガン酸カリウム水溶液４０２を添加
し、処理温度６０℃、１時間オー）々−マイヤー型染色
機を使用し、処理する。処理後、洗浄水の着色が消失す
るまで洗浄を繰返す。そして、処理されたアクリル系合
成繊維を脱水後、７０℃、１０時間乾燥する。After the reaction, washing is repeated until the pH of the washing water becomes 7.0. The content of calxyl groups and sulfonic acid groups in the obtained fibers was 13 mmofi/g, and furthermore, 10 mmofi/g.
Add 402% of aqueous solution of nitric acid and treat with m
Process at 60°C for 1 hour using an Obermeyer dyeing machine. After treatment, the washing is repeated until the coloring of the washing water disappears. Thereafter, a 10-t water solution of potassium ferrocyanate, 402, is added, and the mixture is treated at a treatment temperature of 60° C. for 1 hour using an Ohnoseemeyer type dyeing machine. After treatment, the washing is repeated until the coloring of the washing water disappears. After that, 2% by weight potassium permanganate aqueous solution 402 is added, and treatment is carried out at a treatment temperature of 60° C. for 1 hour using a Mayer-type dyeing machine. After treatment, the washing is repeated until the coloring of the washing water disappears. Then, the treated acrylic synthetic fibers are dehydrated and then dried at 70° C. for 10 hours.
Ｋ、 Ｍｎ、 Ｃｏ、 Ｆｅの繊維への付着量は、それ
ぞれ繊ｍｔｇ当り、Ｋが９．８ｍｇ、Ｍｎが４８ ｍｇ
、 Ｃｏが１０ｍｇ、Ｆｅが６．８ ｍ ｇであった。The amounts of K, Mn, Co, and Fe attached to the fibers were 9.8 mg for K and 48 mg for Mn per mtg of fiber, respectively.
, Co was 10 mg, and Fe was 6.8 mg.
（比較例４）
実施例８と同一のアクリル系合成線維を用い、水酸化ナ
トリウム水溶液により実施例８と同一条件で処理した。(Comparative Example 4) Using the same acrylic synthetic fiber as in Example 8, it was treated with an aqueous sodium hydroxide solution under the same conditions as in Example 8.
反応後、洗浄水のｐＨが７．０になるまで、洗浄を練返
す。得られた繊維のカルゼキシル基およびスルホン酸基
の含有ＩＩは２−３ ｍ ｒｎｏ ｊｌ ／ ｇであっ
た。After the reaction, the washing is repeated until the pH of the washing water becomes 7.0. The content II of calzexyl groups and sulfonic acid groups in the obtained fiber was 2-3 m rno jl/g.
さらに、１０重量％の硝酸コノ々ルト水溶液、１０重量
％フェロシアン酸カリウム水溶液を用い、それぞれ実施
例８と同一条件で処理、洗浄を行なう。Furthermore, processing and cleaning are performed under the same conditions as in Example 8 using a 10% by weight aqueous solution of conolt nitrate and a 10% by weight aqueous potassium ferrocyanate solution.
そして、処理されたアクリル系合成繊維を脱水後、７０
℃、１０時間乾燥する。After dehydrating the treated acrylic synthetic fiber,
Dry at ℃ for 10 hours.
Ｋ、 Ｃｏ、 Ｆｅの繊維への付着量は、それぞれ繊維
１ｓｌす、Ｋが３８ ｍｇ、 Ｃｏが２１ｍｇ、Ｆｅが
２０ｍｇであった。The amounts of K, Co, and Fe attached to the fibers were 38 mg of K, 21 mg of Co, and 20 mg of Fe per 1 sl of fiber.
第 ３ 表
得られた繊維の溶出率を第３表に示した。実施例８の溶
出率は０，２０と極めて低い。しかし、比較例４の溶出
率は１．３０％と高く、実用上適用範囲が制限される。Table 3 Table 3 shows the dissolution rate of the obtained fibers. The elution rate of Example 8 was extremely low at 0.20. However, the elution rate of Comparative Example 4 is as high as 1.30%, which limits its practical applicability.
（発明の効果）
本発明の新規なアクリル系合成繊維は、悪臭成分ガス類
の吸着による脱臭材、各８２生物の殺菌を目的とする殺
菌材、線維および電子、’Ｎ（、気工業等に用いる訓電
、導電材、化学工業等に用いる触媒、高温耐熱性を肩す
る無機線維、織布の原料等に使用することができる。(Effects of the Invention) The novel acrylic synthetic fiber of the present invention can be used as a deodorizing material by adsorbing malodorous component gases, as a sterilizing material for the purpose of sterilizing 82 living organisms, and as a fiber, electronic, 'N(, air industry, etc.). It can be used for electrical training, conductive materials, catalysts used in the chemical industry, inorganic fibers with high temperature resistance, raw materials for woven fabrics, etc.
Claims (1)
ガン化合物水溶液で処理されたアクリル系合成繊維 ２、アクリル系合成繊維が、カルボキシル基及び／また
はスルホン酸基を総量で０．１〜５．０ｍｍｏｌ／ｇ含
有する特許請求の範囲第１項記載のアクリル系合成繊維[Scope of Claims] 1. Acrylic synthetic fibers carrying and fixing insoluble ferrocyanide and treated with an aqueous manganese compound solution 2. Acrylic synthetic fibers containing a total of 0 carboxyl groups and/or sulfonic acid groups Acrylic synthetic fiber according to claim 1 containing .1 to 5.0 mmol/g
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62022284A JPS63196769A (en) | 1987-02-04 | 1987-02-04 | Novel acrylic synthetic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62022284A JPS63196769A (en) | 1987-02-04 | 1987-02-04 | Novel acrylic synthetic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63196769A true JPS63196769A (en) | 1988-08-15 |
Family
ID=12078449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62022284A Pending JPS63196769A (en) | 1987-02-04 | 1987-02-04 | Novel acrylic synthetic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63196769A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06272174A (en) * | 1993-03-16 | 1994-09-27 | Toray Ind Inc | Deodorizing acrylonitrile synthetic fiber and its production |
| US8020469B2 (en) | 2005-08-31 | 2011-09-20 | Honda Motor Co., Ltd. | Base frame and parking brake device |
| JP2013173077A (en) * | 2012-01-24 | 2013-09-05 | National Institute Of Advanced Industrial Science & Technology | Method for manufacturing cation sorbing agent |
| JP2014091088A (en) * | 2012-11-05 | 2014-05-19 | Japan Exlan Co Ltd | Polyacrylonitrile-based film and cesium ion adsorbent containing the same |
| JP2014095164A (en) * | 2012-11-09 | 2014-05-22 | Japan Exlan Co Ltd | Porous acrylic fiber and cesium ion adsorbent containing the same |
-
1987
- 1987-02-04 JP JP62022284A patent/JPS63196769A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06272174A (en) * | 1993-03-16 | 1994-09-27 | Toray Ind Inc | Deodorizing acrylonitrile synthetic fiber and its production |
| US8020469B2 (en) | 2005-08-31 | 2011-09-20 | Honda Motor Co., Ltd. | Base frame and parking brake device |
| JP2013173077A (en) * | 2012-01-24 | 2013-09-05 | National Institute Of Advanced Industrial Science & Technology | Method for manufacturing cation sorbing agent |
| JP2014091088A (en) * | 2012-11-05 | 2014-05-19 | Japan Exlan Co Ltd | Polyacrylonitrile-based film and cesium ion adsorbent containing the same |
| JP2014095164A (en) * | 2012-11-09 | 2014-05-22 | Japan Exlan Co Ltd | Porous acrylic fiber and cesium ion adsorbent containing the same |
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