EP2327831B1 - Vernetzte fasern auf acrylatbasis und ihre herstellung - Google Patents
Vernetzte fasern auf acrylatbasis und ihre herstellung Download PDFInfo
- Publication number
- EP2327831B1 EP2327831B1 EP09812813.5A EP09812813A EP2327831B1 EP 2327831 B1 EP2327831 B1 EP 2327831B1 EP 09812813 A EP09812813 A EP 09812813A EP 2327831 B1 EP2327831 B1 EP 2327831B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- cross
- linked acrylate
- treatment
- carboxyl group
- 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.)
- Not-in-force
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- 239000000835 fiber Substances 0.000 title claims description 148
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 73
- 238000000034 method Methods 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000011282 treatment Methods 0.000 claims description 67
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 57
- 238000010521 absorption reaction Methods 0.000 claims description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 13
- -1 hydrazine compound Chemical class 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 13
- 230000003301 hydrolyzing effect Effects 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000012770 industrial material Substances 0.000 description 13
- 238000003795 desorption Methods 0.000 description 11
- 159000000003 magnesium salts Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000011835 investigation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000002560 nitrile group Chemical group 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical group C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- PTYMQUSHTAONGW-UHFFFAOYSA-N carbonic acid;hydrazine Chemical compound NN.OC(O)=O PTYMQUSHTAONGW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/63—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with hydroxylamine or hydrazine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Definitions
- the present invention relates to a cross-linked acrylate fiber and to a method for manufacturing the same. More particularly, it relates to a cross-linked acrylate fiber having a color which induces no unusual sense in the appearance when used in the industrial material field together with other fibers for industrial materials.
- Cross-linked acrylate fiber has been known to have various functions such as absorption/desorption property for moisture, moisture-absorption exothermic property, deodorant property, antibacterial property and flame-resisting property and is a fiber which is expected to be developed to various fields.
- the fiber since the fiber is in pink color and it further turns dark upon a post-treatment and with elapse of time, there is a problem that development of its use has been limited. For such a problem, many investigations have been carried out for a purpose of development to the field of clothing.
- Patent Documents 1 to 3 investigations for improving the whiteness are done in Patent Documents 1 to 3 and a cross-linked acrylate fiber having the whiteness in a practically acceptable level is achieved.
- Patent Document 4 there is disclosed a cross-linked acrylate fiber in black color prepared from black-doped acrylic fiber as a material.
- Patent Documents 5 and 6 investigations are conducted for making cross-linked acrylate fiber into various colors by dyeing.
- dyeing further investigations are still necessary for achieving the practically sufficient product in view of hue stability, uneven dyeing, fastness in dyeing, etc.
- the cross-linked acrylate fiber has a flame resisting property as mentioned above and, particularly when carboxyl group in the fiber is made into a magnesium salt type, the resulting cross-linked acrylate fiber has a very high flame resisting property which is not found in the common organic fibers (Patent Document 7).
- Such a cross-linked acrylate fiber of a magnesium salt type also has a characteristic of slow moisture absorption/desorption property or, in other words, the speed of absorption and desorption of moisture is slow (Patent Document 8). Therefore, a continued generation of heat by means of absorption of moisture is possible and that is particularly useful in the field of clothing.
- a method for producing an acrylic-group fiber having high moisture absorption property is known from JP 2004/149989 A .
- the method is based on a) cross-linking process, b) hydrolyzing process and c) oxidization treatment and alkali treatment.
- An object of the present invention is to provide a cross-linked acrylate fiber having the color causing no unusual sense in the appearance even when used together with other fibers for industrial materials in the field of industrial materials which has not been provided in the prior art and also being advantageous in terms of the cost.
- Another object of the present invention is to provide a cross-linked acrylate fiber having both of the high flame resisting property and the high speed of moisture absorption/desorption.
- the color of the cross-linked acrylate fiber of the present invention is similar to golden color, it does not cause unusual sense even when mixed with a fiber for industrial materials and, further since the manufacturing steps are fewer and the cost therefor can be suppressed, the fiber can be advantageously used in the field of industrial materials.
- a high moisture absorption/desorption speed can be achieved and both of the high flame resisting property and the high moisture absorption/desorption speed which could not be achieved in the conventional cross-linked acrylate fiber are available whereby it is now possible to develop to the uses where such characteristics have been demanded.
- Fig. 1 shows moisture absorption curves of the cross-linked acrylate fibers of Examples 1 and 2 and Comparative Example 1 and 2.
- the color of the cross-linked acrylate fiber of the present invention is similar to golden color which has never been achieved in the conventional cross-linked acrylate fiber, it causes no unusual sense even when mixed with a fiber for industrial materials. To be more specific, it is the color where L* is 60 to 75, a* is 5.0 to 14.5 and b* is 23.0 to 30.0 in accordance with the indication method stipulated by JIS-Z-8729 and the color where L* is 65 to 75, a* is 7.0 to 13.0 and b* is 23.5 to 27.0 is preferred.
- the cross-linked acrylate fiber of the present invention as such can be manufactured according to such a manner that each of the treatments of (a) treatment for introduction of cross-linking by a hydrazine compound, (b) treatment by a peroxide and (c) hydrolyzing treatment using an alkaline metal compound are applied to an acrylonitrile fiber in the order of (a), (b) and (c) or in such an order that, after (a) is applied, (b) and (c) are then applied together.
- the acrylonitrile fiber adopted in the present invention is manufactured from an acrylonitrile polymer by a known method and, as to the composition of said polymer, amount of acrylonitrile is preferably not less than 40% by weight, more preferably not less than 50% by weight and, still more preferably, not less than 80% by weight.
- a hydrazine compound is made to react with nitrile group of the acrylonitrile polymer forming the acrylonitrile fiber to introduce a cross-linking structure into the fiber of the present invention.
- Cross-linking structure greatly affects the properties of the fiber and, when the copolymerizing composition of acrylonitrile is too small, the cross-linking structure naturally becomes small and there is a possibility that the properties of the fiber become insufficient but, when the copolymerizing composition of the acrylonitrile is made within the above range, a good result is apt to be achieved.
- Examples of the copolymerizing component other than acrylonitrile in the acrylonitrile polymer include a sulfonic acid-containing monomer such as methallylsulfonic acid or p-styrenesulfonic acid and a salt thereof; a carboxylic acid-containing monomer such as (meth) acrylic acid or itaconic acid and a salt thereof; and a monomer such as styrene, vinyl acetate, (meth)acrylate or (meth)acrylamide and there is no particular limitation therefor so far as it is a monomer being able to be copolymerized with acrylonitrile.
- a sulfonic acid-containing monomer such as methallylsulfonic acid or p-styrenesulfonic acid and a salt thereof
- a carboxylic acid-containing monomer such as (meth) acrylic acid or itaconic acid and a salt thereof
- a monomer such as styrene, vinyl
- the form of the acrylonitrile fiber adopted by the present invention may be any of the forms of short fiber, tow, yarn, knitted/woven fabric, nonwoven fabric, etc. and even an intermediate during the manufacture, waste fiber, etc. may be adopted as well.
- hydrazine reacts with the nitrile group of the acrylonitrile fiber whereupon a cross-linking structure is formed in the fiber.
- the hydrazine compound include hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate, neutral hydrazine sulfate and hydrazine carbonate.
- An example of the treating condition is that the above acrylonitrile fiber is dipped in an aqueous solution to which the above hydrazine compound is added so as to make the hydrazine concentration 3 to 40% by weight followed by treating at 50 to 120°C for not longer than 5 hours.
- the fiber prepared by subjecting to the treatment (a) is treated with a solution containing a peroxide.
- a peroxide used for the treatment
- examples of the peroxide used for the treatment include hydrogen peroxide, ammonium persulfate and potassium persulfate.
- An example of the treating condition is that the fiber is dipped in an aqueous solution where the peroxide concentration is 1 to 15% by weight or, preferably, 3 to 8% by weight and treated at 50 to 120°C for 0.5 to 20 hour (s) . It is preferred that, before the treatment, the fiber is well washed with water so that the chemicals remained in the treatment (a) are removed as much as possible.
- the treatment (c) is a hydrolyzing treatment using an alkaline metal compound.
- nitrile group and amide group existing in the fiber are hydrolyzed to form carboxyl group.
- the carboxylic group is an important factor for expressing the characteristic such as moisture absorption/desorption property, moisture-absorption exothermic property or deodorizing property in the cross-linked acrylate fiber and it is desirable to form 1 to 12 mmol/g, preferably 3 to 10 mmol/g or, more preferably 3 to 8 mmol/g of carboxyl group in terms of the total carboxyl group amount. Amount of the carboxyl group formed thereby may be adjusted by the treating condition.
- amide group is produced from a part of nitrile group during the treatment (a).
- alkaline metal compound used in the treatment (c) examples include alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; and alkali metal carbonate such as sodium carbonate.
- An example of the treating condition is that the fiber is dipped in an aqueous solution where the alkaline metal compound is 1 to 10% by weight or, preferably, 1 to 5% by weight followed by treating at 50 to 120°C for 1 to 10 hour(s).
- Counter ion for the carboxyl group formed thereby is a metal ion corresponding to the alkaline metal compound used therefor.
- the above treatments (b) and (c) are applied at the same time.
- the fiber which was prepared by the treatment (a) may be treated by dipping in a solution containing both of the above-mentioned peroxide and the alkaline metal compound.
- the cross-linked acrylate fiber of the present invention can be prepared by applying the treatments (a), (b) and (c) to the acrylonitrile fiber and it is also possible that the carboxyl group in the fiber is made into a desired salt-type carboxyl group or H-type carboxyl group by subjecting to an ion-exchange treatment using metal salt such as nitrate, sulfate or hydrochloride, to an acid treatment using nitric acid, sulfuric acid, hydrochloric acid, formic acid, etc. or to a pH-adjusting treatment using an alkaline metal compound, etc. or that a salt-type carboxylic group of a different type is made to contain therein so that the characteristic such as moisture absorption/desorption property, exothermic property upon moisture absorption, deodorizing property, antibacterial property or flame resisting property can be adjusted.
- metal salt such as nitrate, sulfate or hydrochloride
- one or more member(s) may be selected from alkali metal such as lithium, sodium or potassium, alkali earth metal such as magnesium or calcium and other metal such as manganese, copper, zinc or silver depending upon the required characteristic.
- a salt-type carboxyl group such as sodium, potassium, magnesium or calcium is suitable and, when the cross-linked acrylate fiber of the present invention is compared with the conventional cross-linked acrylate fiber to which no peroxide treatment is applied, the cross-linked acrylate fiber of the present invention has a characteristic that the moisture absorption speed can be made relatively high whereby far better moisture absorption/desorption property can be achieved even in such a case where, in both fibers, the metals for the salt-type carboxyl group are same and the saturated moisture absorption rates are homologous as well.
- magnesium salt-type carboxyl group or zinc salt-type carboxyl group as the salt-type carboxyl group.
- amount of the salt-type carboxyl group is preferably not less than 2 mmol/g in terms of an absolute amount and not less than 50% to the total carboxyl group amount, more preferably not less than not less than 2 mmol/g in terms of an absolute amount and not less than 60% to the total carboxyl group amount or not less than not less than 3 mmol/g in terms of an absolute amount and not less than 50% to the total carboxyl group amount and, most preferably, not less than not less than 3 mmol/g in terms of an absolute amount and not less than 60% to the total carboxyl group amount.
- a method for making into such a salt-type carboxyl group will be illustrated as follows taking a magnesium salt-type carboxyl group as an example.
- a cross-linked acrylate fiber having a magnesium salt-type carboxyl group it can be manufactured by dipping the fiber after the treatment (c) into an aqueous solution containing magnesium ion such as an aqueous solution of magnesium nitrate. If the amount of the magnesium salt-type carboxylic group is to be more precisely controlled, the following method may be adopted.
- the fiber after the treatment (c) is dipped in an aqueous acid solution such as nitric acid so that the whole carboxyl group in the fiber is made into an H-type carboxyl group.
- an alkaline aqueous solution containing sodium ion such as an aqueous solution of sodium hydroxide so that the H-type carboxyl group is made into a sodium salt-type carboxyl group.
- the above is dipped in an aqueous solution containing magnesium such as an aqueous solution of magnesium nitrate to convert to a magnesium salt-type carboxyl group.
- the group which can be converted to magnesium salt-type carboxyl group is sodium salt-type carboxyl group only and an H-type carboxyl group is hardly converted to a magnesium salt-type carboxyl group.
- the amount of the sodium salt-type carboxyl group by adjusting the pH, it is possible to control the amount of the magnesium salt-type carboxyl group.
- the magnesium salt-type cross-linked acrylate fiber of the present invention prepared as such has the identical flame resisting property to that of the conventionally known magnesium salt-type cross-linked acrylate fiber and a limit oxygen index of 30 to 50 or, preferably, 35 to 50 can be achieved.
- said fiber has a saturated moisture absorption rate of 20 to 60% by weight or, preferably, 30 to 60% by weight and, with regard to the moisture absorption speed, a moisture absorption rate during five minutes under the atmosphere of 20°C and 65% RH is higher to an extent of two fold or more as compared with the conventional magnesium salt-type cross-linked acrylate fiber which has the same degree of saturated moisture absorption rate as the magnesium salt-type cross-linked acrylate fiber of the present invention, whereby the coexistence of high flame resisting property and high moisture absorption speed which has not been available in the past is now able to be achieved.
- the cross-linked acrylate fiber of a zinc salt type can also be prepared by the same method as in the case of the cross-linked acrylate fiber of a magnesium salt type mentioned above.
- an aqueous solution containing zinc ion such as aqueous solution of zinc chloride, zinc nitrate or zinc sulfate may be used in place of the above-mentioned aqueous solution containing magnesium ion such as magnesium nitrate.
- a well-dried sample (about 1 g) was precisely weighted (W1 [g]), 200 ml of 1 mol/l aqueous solution of hydrochloric acid was added thereto and the mixture was allowed to stand for 30 minutes, filtered through a glass filter and washed with water after addition of water. The treatment was repeated for three times and well washed with water until pH of the filtrate became 5 or higher. After that, this sample was placed in 200 ml of water, the mixture was adjusted to pH 2 by addition of 1 mol/l aqueous solution of hydrochloric acid thereto and a titration curve is determined by a common method using a 0. 1 mol/l aqueous solution of sodium hydroxide.
- amount (V1[ml]) of the aqueous solution of sodium hydroxide consumed by carboxyl group is determined and an amount of total carboxyl group is calculated by the following formula.
- Amount of total carboxyl group mmol / g 0.1 * V ⁇ 1 / W ⁇ 1
- a well-dried sample is precisely weighed, subjected to an acid decomposition by a common method using a mixed solution of concentrated sulfuric acid and concentrated nitric acid and metal contained in a form of a salt of carboxyl group is quantified by an atomic absorption spectroscopy by a common method and divided by atomic weight of said metal to calculate an amount of salt-type carboxyl group.
- a nonwoven fabric where the basis weight was 180 g/m 2 was prepared using a sample fiber and said nonwoven fabric was subjected to the measurement of LOI in accordance with the measuring method stipulated by JIS-K-7201-2. When the resulting value was high, it means that the flame resisting property was also high.
- Color of the sample where the fiber was opened was measured for three times using a colorimeter CR 300 (illuminant: D65) manufactured by Minolta and the mean value of each of L*, a* and b* according to the indication method according to JIS-Z-8729 was determined.
- a dope solution for spinning was prepared by dissolving an acrylonitrile polymer comprising 90% of acrylonitrile and 10% of methyl acrylate in a 48% aqueous solution of sodium thiocyanate. It was subjected to spinning, water-washing, stretching, crimping and heating treatments according to the conventional means to give a material fiber of 0.9 dtex and 70 mm. The material fiber was dipped in a 15% aqueous solution of hydrazine hydrate in a bath ratio of 1:10 and treated under the condition of 120°C for 1 hour.
- the resulting fiber was washed with water, dipped in a 4% aqueous solution of ammonium persulfate in a bath ratio of 1:10 and subjected to a peroxide treatment under the condition of 100°C for 1 hour. After that, the resulting fiber was dipped in a 5% aqueous solution of sodium hydroxide in a bath ratio of 1:10, hydrolyzed under the condition of 110°C for 1 hour and washed with water to give a cross-linked acrylate fiber of a sodium salt type. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1 and Fig. 1 .
- Example 2 The same operation as in Example 1 was carried out except that no peroxide treatment was conducted to give a cross-linked acrylate fiber of a sodium salt type. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1 and Fig. 1 .
- the cross-linked acrylate fiber prepared in Example 1 was treated with a 1 mol/l aqueous solution of nitric acid so that the carboxyl group was converted into H type, washed with water, adjusted to pH 12 with 1 mol/l sodium hydroxide and washed with water to give a fiber having a sodium salt-type carboxyl group.
- the resulting fiber was dipped in an aqueous solution containing magnesium nitrate in an amount of 1.2 times equivalent of the carboxyl group amount of said fiber to subject to a converting treatment to a magnesium salt type under the condition of 50°C for 1 hour followed by washing with water whereupon a cross-linked acrylate fiber of a magnesium salt type was prepared. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1 and Fig. 1 .
- Example 2 The same operation as in Example 2 was conducted except that the cross-linked acrylate fiber prepared in Comparative Example 1 was used in place of the cross-linked acrylate fiber prepared in Example 1 to give a cross-linked acrylate fiber of a magnesium salt type. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1 and Fig. 1 .
- Example 1 The same operation as in Example 1 was conducted except that the peroxide treatment was done using a 3% aqueous hydrogen peroxide to give a cross-linked acrylate fiber of a sodium salt type. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1.
- Example 1 The material fiber used in Example 1 was dipped in a 15% aqueous solution of hydrazine hydrate in a bath ratio of 1:10 and treated under the condition of 120°C for 1 hour followed by washing with water. The resulting fiber was dipped in an aqueous solution containing 4% of ammonium persulfate and 5% of sodium hydroxide in a bath ratio of 1:10 and subjected to a simultaneous treatment comprising a treatment with peroxide and a hydrolyzing treatment followed by washing with water to give a cross-linked acrylate fiber of a sodium salt type. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1.
- a dope solution for spinning was prepared by dissolving an acrylonitrile polymer comprising 88% of acrylonitrile and 12% of vinyl acetate in a 48% aqueous solution of sodium thiocyanate. It was subjected to spinning, water-washing, stretching, crimping and heating treatments according to the conventional means to give a material fiber of 0.9 dtex and 70 mm. The material fiber was dipped in a 15% aqueous solution of hydrazine hydrate in a bath ratio of 1:10 and treated under the condition of 120°C for 1.5 hours.
- the resulting fiber was washed with water, dipped in a 3% aqueous solution of potassium persulfate in a bath ratio of 1:10 and subjected to a peroxide treatment under the condition of 60°C for 30 minutes. After that, the resulting fiber was dipped in a 5% aqueous solution of sodium hydroxide in a bath ratio of 1:10, hydrolyzed under the condition of 110°C for 1 hour and washed with water to give a cross-linked acrylate fiber of a sodium salt type.
- the said fiber was treated with a 1 mol/l aqueous solution of nitric acid so that the carboxyl group was converted into H type, washed with water, adjusted to pH 12 with 1 mol/l sodium hydroxide and washed with water to give a fiber having a sodium salt-type carboxyl group.
- the resulting fiber was dipped in an aqueous solution containing zinc sulfate in an amount of 1.3 times equivalent of the carboxyl group amount of said fiber to subject to a converting treatment to a zinc salt type under the condition of 50°C for 1 hour followed by washing with water whereupon a cross-linked acrylate fiber of a zinc salt type was prepared. Results of evaluation for the characteristic of the resulting fiber are shown in Table 1.
- the cross-linked acrylate fiber prepared in Example 1 was treated with a 1 mol/l aqueous solution of nitric acid so that the carboxyl group was converted into H type, washed with water, adjusted to pH 12 with 1 mol/l sodium hydroxide and washed with water to give a fiber having a sodium salt carboxyl group.
- the resulting fiber was dipped in an aqueous solution containing magnesium nitrate in an amount of 1.6 times equivalent of the carboxyl group amount of said fiber to subject to a converting treatment to a magnesium salt type under the condition of 50°C for 1 hour followed by washing with water whereupon a cross-linked acrylate fiber of a magnesium salt type was prepared.
- the cross-linked acrylate fibers of Comparative Examples 1 and 2 have a pink color while the cross-linked acrylate fibers of Examples 1 to 6 being subjected to a peroxide treatment have a golden color.
- the cross-linked acrylate fibers of Examples 1 and 2 contain less amount of salt-type carboxyl group as compared with the cross-linked acrylate fibers of Comparative Examples 1 and 2, respectively, the moisture absorption rate after 5 minutes from the initiation of moisture absorption is 28% in Example 1 while that in Comparative Example 1 is 20% in the case of a sodium salt type and, in the case of a magnesium salt type, that is 6% in Example 2 while that in Comparative Example 2 is 2%.
- an increase in the moisture absorption speed is significant in a magnesium salt type.
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Claims (6)
- Vernetzte Acrylatfaser mit einer Farbe, bei der, gemessen nach dem Standard-verfahren JIS-Z-8729, L* von 60 bis 75 beträgt, a* von 5,0 bis 14,5 beträgt und b* von 23,0 bis 30,0 beträgt.
- Vernetzte Acrylatfaser nach Anspruch 1, bei der die Behandlungen (a) Behandlung zum Einbringen einer Vernetzung mit einer Hydrazinverbindung, (b) Behandlung mit einem Peroxid und (c) Hydrolysebehandlung mit einer Alkalimetallverbindung an einer Acrylnitrilfaser in der Abfolge (a), (b) und (c) oder in einer Abfolge derart vorgenommen werden, dass nachdem (a) erfolgt ist, (b) und (c) dann gemeinsam vorgenommen werden.
- Vernetzte Acrylatfaser nach Anspruch 1 oder 2, bei der das oder die Gegenion(en) für mindestens einen Teil der Carboxylgruppen in der vernetzten Acrylatfaser ein oder mehrere Magnesium- und/oder Zinkion(en) ist/sind.
- Vernetzte Acrylatfaser nach Anspruch 3, wobei das Gegenion für mindestens einen Teil der Carboxylgruppen in der vernetzten Acrylatfaser ein Magnesiumion ist, der LOI-Wert (Limiting Oxygen Index) 30 bis 50 beträgt und die Aufnahmerate zur Feuchtigkeitssättigung 20 bis 60 Gewichts-% beträgt.
- Verfahren zur Herstellung einer vernetzten Acrylatfaser, dadurch gekennzeichnet, dass die Behandlungen (a) Behandlung zum Einbringen einer Vernetzung mit einer Hydrazinverbindung, (b) Behandlung mit einem Peroxid und (c) Hydrolysebehandlung mit einer Alkalimetallverbindung an einer Acrylnitritfaser in der Abfolge (a), (b) und (c) vorgenommen werden.
- Verfahren zur Herstellung einer vernetzten Acrylatfaser, dadurch gekennzeichnet, dass die Behandlungen (a) Behandlung zum Einbringen einer Vernetzung mit einer Hydrazinverbindung, (b) Behandlung mit einem Peroxid und (c) Hydrolysebehandlung mit einer Alkalimetallverbindung an einer Acrylnitrilfaser in einer Abfolge derart vorgenommen werden, dass nachdem (a) erfolgt ist, (b) und (c) dann gemeinsam vorgenommen werden.
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JP (2) | JP4487083B2 (de) |
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UA111731C2 (uk) * | 2010-10-06 | 2016-06-10 | Рідженерон Фармасьютікалз, Інк. | Стабілізована композиція, яка містить антитіло до рецептора інтерлейкіну-4 (іl-4r), варіанти |
JP6228511B2 (ja) * | 2014-05-29 | 2017-11-08 | 日本エクスラン工業株式会社 | 分散性の良好な架橋アクリレート系繊維 |
JP6247800B1 (ja) * | 2016-09-26 | 2017-12-13 | 東洋紡株式会社 | 吸湿発熱性繊維 |
TWI771378B (zh) * | 2017-03-23 | 2022-07-21 | 日商日本Exlan工業股份有限公司 | 吸溼性粒狀綿及含有該粒狀綿之中綿 |
CN114007743B (zh) * | 2019-06-20 | 2023-09-15 | 日本爱克兰工业株式会社 | 离子交换纤维和含有该纤维的离子交换过滤器 |
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JP3196577B2 (ja) * | 1995-06-05 | 2001-08-06 | 日本エクスラン工業株式会社 | pH緩衝性吸湿性アクリル系繊維及びその製造方法 |
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JP2000136432A (ja) * | 1998-10-28 | 2000-05-16 | Japan Exlan Co Ltd | 染色性に優れた耐熱複合アクリル繊維 |
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JP3334865B2 (ja) | 1999-04-16 | 2002-10-15 | 日本エクスラン工業株式会社 | 高白度吸湿性繊維及び該繊維の製造方法 |
JP3698204B2 (ja) | 2001-01-26 | 2005-09-21 | 日本エクスラン工業株式会社 | 高白度吸湿性合成繊維及び該繊維の製造方法 |
WO2002059415A1 (fr) * | 2001-01-26 | 2002-08-01 | Japan Exlan Company Limited | Fibre hygroscopique a blancheur elevee et procede de fabrication correspondant |
DE60236162D1 (de) * | 2001-07-25 | 2010-06-10 | Japan Exlan Co Ltd | Fasergebilde mit hohem weissgrad und hoher feuchtigkeitsaufnahme und -wiederabgabe und verfahren zu dessen herstellung |
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JP2004149989A (ja) * | 2002-11-01 | 2004-05-27 | Teijin Ltd | アクリル系繊維の処理方法 |
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CN100494556C (zh) * | 2004-08-03 | 2009-06-03 | 日本爱克兰工业株式会社 | 交联丙烯酸酯类纤维的染色方法以及含有用该染色方法染色的交联丙烯酸酯类纤维的纤维制品 |
JP4696724B2 (ja) | 2004-08-03 | 2011-06-08 | 日本エクスラン工業株式会社 | 架橋アクリレート系繊維の染色方法および該染色方法で染色された架橋アクリレート系繊維を含む繊維製品 |
JP4529145B2 (ja) | 2004-09-07 | 2010-08-25 | 日本エクスラン工業株式会社 | 徐吸放湿性架橋アクリル系繊維 |
WO2006027911A1 (ja) | 2004-09-07 | 2006-03-16 | Japan Exlan Company Limited | 高度難燃吸湿性繊維および繊維構造物 |
CN101389803B (zh) * | 2006-04-28 | 2011-05-04 | 日本爱克兰工业株式会社 | 制备复合纤维的方法 |
JP5056358B2 (ja) * | 2007-11-02 | 2012-10-24 | 日本エクスラン工業株式会社 | 可染性架橋アクリレート系繊維およびその製造方法ならびに該繊維を染色して得られる染色された架橋アクリレート系繊維 |
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- 2009-06-01 KR KR1020117007384A patent/KR101593726B1/ko active IP Right Grant
- 2009-06-01 WO PCT/JP2009/002428 patent/WO2010029664A1/ja active Application Filing
- 2009-06-01 JP JP2009531508A patent/JP4487083B2/ja active Active
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JPWO2010029664A1 (ja) | 2012-02-02 |
JP4487083B2 (ja) | 2010-06-23 |
CN102066649A (zh) | 2011-05-18 |
CN102066649B (zh) | 2013-05-15 |
KR20110053254A (ko) | 2011-05-19 |
JP5029975B2 (ja) | 2012-09-19 |
WO2010029664A1 (ja) | 2010-03-18 |
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KR101593726B1 (ko) | 2016-02-18 |
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