JP5442497B2 - Method for treating cellulosic fiber or cellulosic fiber product - Google Patents
Method for treating cellulosic fiber or cellulosic fiber product Download PDFInfo
- Publication number
- JP5442497B2 JP5442497B2 JP2010050742A JP2010050742A JP5442497B2 JP 5442497 B2 JP5442497 B2 JP 5442497B2 JP 2010050742 A JP2010050742 A JP 2010050742A JP 2010050742 A JP2010050742 A JP 2010050742A JP 5442497 B2 JP5442497 B2 JP 5442497B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulosic fiber
- cellulosic
- fiber product
- group
- cellulose
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims description 192
- 238000000034 method Methods 0.000 title claims description 86
- 229920003043 Cellulose fiber Polymers 0.000 claims description 42
- -1 ester compound Chemical class 0.000 claims description 30
- 239000003431 cross linking reagent Substances 0.000 claims description 26
- 150000002148 esters Chemical class 0.000 claims description 26
- 150000001718 carbodiimides Chemical class 0.000 claims description 22
- 238000004132 cross linking Methods 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 229920001225 polyester resin Polymers 0.000 claims description 15
- 239000004645 polyester resin Substances 0.000 claims description 15
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002433 hydrophilic molecules Chemical class 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 238000005406 washing Methods 0.000 description 71
- 239000003599 detergent Substances 0.000 description 36
- 239000007788 liquid Substances 0.000 description 31
- 229920000742 Cotton Polymers 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000004744 fabric Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000005642 Oleic acid Substances 0.000 description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 9
- 238000004332 deodorization Methods 0.000 description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 108010010803 Gelatin Proteins 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 210000002374 sebum Anatomy 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RJECHNNFRHZQKU-UHFFFAOYSA-N Oelsaeurecholesterylester Natural products C12CCC3(C)C(C(C)CCCC(C)C)CCC3C2CC=C2C1(C)CCC(OC(=O)CCCCCCCC=CCCCCCCCC)C2 RJECHNNFRHZQKU-UHFFFAOYSA-N 0.000 description 1
- 241001469893 Oxyzygonectes dovii Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 description 1
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 239000004663 anionic softener Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000002752 cationic softener Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- RJECHNNFRHZQKU-RMUVNZEASA-N cholesteryl oleate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H]([C@H](C)CCCC(C)C)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)C1 RJECHNNFRHZQKU-RMUVNZEASA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- UMEJBQAJSACPLX-UHFFFAOYSA-K trisodium 4,6-dimethyl-5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [Na+].CC1=C(C(=C(C=C1C(=O)[O-])C(=O)[O-])C)S(=O)(=O)[O-].[Na+].[Na+] UMEJBQAJSACPLX-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- 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
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
- D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
-
- 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
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- 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
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Description
セルロース系繊維又はセルロース系繊維製品に、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の洗浄効果が得られるという機能を付与することができ、かつ、高い柔軟性及び洗濯耐久性を実現できるセルロース系繊維又はセルロース系繊維製品の処理方法、並びに、セルロース系繊維又はセルロース系繊維製品に関する。 Even if the cellulosic fiber or the cellulosic fiber product is washed without using a detergent, it can be given a function of obtaining almost the same cleaning effect as when using a detergent, and The present invention relates to a method for treating cellulosic fibers or cellulosic fiber products capable of realizing high flexibility and washing durability, and cellulosic fibers or cellulosic fiber products.
汚れた繊維製品は、洗剤を用いて洗濯することが常識である。これは、洗剤の主成分である界面活性剤の効果により汚れ成分と繊維の表面との剥離を促進することにより達成される。しかし、大量の洗剤が環境中に排出された場合、海や湖沼等の環境を著しく汚染する可能性が指摘されている。これに対して、近年では、洗剤中の成分を見直して、環境に与える影響の少ない成分を主成分とする洗剤や、より少ない量で従来と同等の洗浄効果が得られる洗剤等が開発され、上市されている。しかしながら、家庭用途及び産業用途で使用され排出される洗剤の量は膨大であり、環境に与える影響をいかに軽減するかは依然として大きな課題のままであった。 It is common knowledge that dirty textiles are washed with detergent. This is achieved by accelerating the peeling between the soil component and the fiber surface by the effect of the surfactant which is the main component of the detergent. However, it has been pointed out that when a large amount of detergent is discharged into the environment, it may significantly contaminate the environment such as the sea and lakes. On the other hand, in recent years, the ingredients in the detergent have been reviewed, and detergents mainly composed of ingredients that have little impact on the environment, detergents that can obtain a cleaning effect equivalent to the conventional amount in a smaller amount, etc. have been developed. It is on the market. However, the amount of detergent used and discharged for household and industrial applications is enormous, and how to reduce the environmental impact remains a major challenge.
一方で、洗濯機や洗濯方法を工夫することにより、洗剤を用いなくとも洗剤を用いた場合と同等の洗浄効果が得られる洗濯方法も検討されている。例えば、特許文献１には、ヒドロニウムイオンやヒドロキシルイオン等を含有した洗剤を入れなくとも洗浄効果を有する水と空気との混合体を高速で衣類を通過させる洗濯方法が開示されている。しかしながら、この方法は特殊な洗濯機を必要とするうえ、皮脂汚れ等の油性成分による汚れに対する洗浄効果は不充分であるとの報告もあった。 On the other hand, by devising a washing machine and a washing method, a washing method that can obtain a cleaning effect equivalent to that obtained when a detergent is used without using a detergent is also being studied. For example, Patent Document 1 discloses a washing method in which clothes are passed at high speed through a mixture of water and air having a cleaning effect without adding a detergent containing hydronium ions, hydroxyl ions, or the like. However, this method requires a special washing machine, and there has been a report that the cleaning effect on dirt due to oily components such as sebum dirt is insufficient.
これに対して、本願発明者らは、特許文献２において、繊維又は繊維製品に親水化処理を施すことによって、繊維又は繊維製品に無洗剤洗濯機能を付与する方法を開示している。このような方法で得られる繊維製品は、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の洗浄効果が得られるが、親水化処理によって柔軟性が低下することがあった。また、処理後の繊維製品は洗濯によって柔軟性が低下する等の不具合も生じていた。 On the other hand, the inventors of the present application disclose a method of imparting a detergent-free washing function to a fiber or fiber product by applying a hydrophilic treatment to the fiber or fiber product in Patent Document 2. The textile product obtained by such a method can obtain a cleaning effect almost the same as that using a detergent even when washing is performed without using a detergent, but the flexibility is reduced by the hydrophilic treatment. There was something to do. In addition, the treated fiber product also has problems such as a decrease in flexibility due to washing.
本発明は、上記現状に鑑み、セルロース系繊維又はセルロース系繊維製品に、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の洗浄効果が得られるという機能を付与することができ、かつ、高い柔軟性及び洗濯耐久性を実現できるセルロース系繊維又はセルロース系繊維製品の処理方法、並びに、セルロース系繊維又はセルロース系繊維製品を提供することを目的とする。 In view of the above situation, the present invention has a function of obtaining a cleaning effect substantially equivalent to that obtained when a detergent is used even when a cellulosic fiber or a cellulosic fiber product is washed without using a detergent. It is an object of the present invention to provide a method for treating cellulosic fibers or cellulosic fiber products, and cellulosic fibers or cellulosic fiber products that can impart high flexibility and washing durability.
本発明は、セルロース系繊維又はセルロース系繊維製品に親水化処理を施す工程、及び、親水化処理を施したセルロース系繊維又はセルロース系繊維製品を、エステル系仕上剤と、カルボジイミド系架橋剤とを用いて架橋させる工程とを有し、前記エステル系仕上剤は、酸化変性若しくは酸変性ポリエチレンと、脂肪族アルコール又は脂肪族アミンのエチレンオキシド及び／若しくはプロピレンオキシド付加物とのエステル化反応によって生成されたエステル系化合物を含有するセルロース系繊維又はセルロース系繊維製品の処理方法である。
以下に本発明を詳述する。
The present invention includes a step of subjecting a cellulose fiber or a cellulose fiber product to a hydrophilic treatment, and a cellulose fiber or a cellulose fiber product that has been subjected to a hydrophilic treatment, an ester finishing agent, and a carbodiimide crosslinking agent. And the ester finishing agent is produced by an esterification reaction of an oxidatively or acid-modified polyethylene with an ethylene oxide and / or propylene oxide adduct of an aliphatic alcohol or an aliphatic amine. It is the processing method of the cellulosic fiber or cellulosic fiber product containing an ester compound.
The present invention is described in detail below.
親水化処理を施したセルロース系繊維又はセルロース系繊維製品の柔軟性を改善する方法としては、シリコーン系柔軟剤、ポリエステル系柔軟剤、ポリアミド系柔軟剤、ポリウレタン系柔軟剤、ポリエチレン系柔軟剤等の柔軟剤を用いて処理する方法が考えられるが、これらの柔軟剤を用いてセルロース系繊維又はセルロース系繊維製品を処理した場合、セルロース系繊維又はセルロース系繊維製品の親水性が著しく低下したり、洗濯によって柔軟性が低下したりしてしまうという欠点があった。また、従来の耐久吸水柔軟剤を用いる方法も考えられるが、親水化処理を施したセルロース系繊維又はセルロース系繊維製品にこれらの耐久吸水柔軟剤を用いた場合、通常のセルロース系繊維又はセルロース系繊維製品に用いた場合と比較して洗濯耐久性に劣り、柔軟性が低下しやすい傾向にあった。さらに、繊維表面に残留する耐久吸水柔軟剤によって無洗剤洗濯機能が阻害されるという問題もあった。
これに対して、本発明者らは、鋭意検討した結果、所定のエステル系仕上剤及びカルボジイミド系架橋剤を併用し、親水化処理を施したセルロース系繊維又はセルロース系繊維製品を架橋させる工程を行うことで、優れた無洗剤洗濯機能を有しつつ、高い柔軟性が付与され、洗濯を繰り返し行った場合でも柔軟性が低下しにくいセルロース系繊維又はセルロース系繊維製品が得られることを見出し、本発明を完成するに至った。
Examples of methods for improving the flexibility of cellulose fibers or cellulose fiber products that have been subjected to a hydrophilic treatment include silicone softeners, polyester softeners, polyamide softeners, polyurethane softeners, and polyethylene softeners. Although the method of processing using a softening agent is considered, when processing a cellulosic fiber or a cellulosic fiber product using these softening agents, the hydrophilicity of a cellulosic fiber or a cellulosic fiber product falls remarkably, There was a disadvantage that flexibility was reduced by washing. In addition, although a method using a conventional durable water-absorbing softener is also conceivable, when these durable water-absorbing softeners are used for cellulosic fibers or cellulosic fiber products that have been subjected to a hydrophilic treatment, ordinary cellulosic fibers or cellulosic fibers are used. It was inferior in washing durability as compared with the case used for textile products, and the flexibility was liable to decrease. Furthermore, there is also a problem that the detergent-free washing function is hindered by the durable water-absorbing softener remaining on the fiber surface.
On the other hand, as a result of intensive investigations, the present inventors have used a predetermined ester-based finish and a carbodiimide-based crosslinking agent in combination, and a step of crosslinking the cellulose-based fiber or the cellulose-based fiber product subjected to the hydrophilic treatment. It is found that a cellulosic fiber or a cellulosic fiber product is obtained, which has an excellent detergent-free washing function, is imparted with high flexibility, and is less likely to lose flexibility even after repeated washing, The present invention has been completed.
本発明のセルロース系繊維又はセルロース系繊維製品の処理方法では、まず、セルロース系繊維又はセルロース系繊維製品に親水化処理を施す工程を行う。
上記親水化処理を行うことで、無洗剤洗濯機能を付与することができる。これは、セルロース系繊維又はセルロース系繊維製品で問題となる汚れのほとんどが皮脂汚れをはじめとする油性成分であるところ、セルロース系繊維又はセルロース系繊維製品を親水化することにより汚れ成分と繊維との結合力が弱くなり、界面活性剤を用いるまでもなく水のみによっても汚れ成分を剥離できるためと考えられる。なお、油性成分以外の汚れについては、もともと大量の水を用いて洗濯を行えば、界面活性剤を用いるまでもなく剥離することができる。
In the method for treating a cellulosic fiber or cellulosic fiber product of the present invention, first, a step of subjecting the cellulosic fiber or cellulosic fiber product to a hydrophilic treatment is performed.
By performing the hydrophilic treatment, a detergent-free washing function can be imparted. This is because most of the stains that are a problem with cellulosic fibers or cellulosic fiber products are oily components including sebum stains, and by making the cellulosic fibers or cellulosic fiber products hydrophilic, the soil components and fibers This is considered to be due to the fact that the binding force of the ink becomes weak and the soil components can be peeled off only with water without using a surfactant. In addition, about the stain | pollution | contamination other than an oil-based component, if washing was originally performed using a lot of water, it can peel, without using surfactant.
本明細書において無洗剤洗濯機能とは、洗剤を用いずに洗濯した場合であっても、洗剤を用いて洗濯した場合と略同等の洗浄効果が得られることを意味し、略同等の洗浄効果が得られるとは、本発明のセルロース系繊維又はセルロース系繊維製品の処理方法による親水化処理を施したセルロース系繊維又はセルロース系繊維製品を洗剤を用いずに洗濯した場合の洗浄効果が、未処理のセルロース系繊維又はセルロース系繊維製品を洗剤を用いて洗濯した場合の洗浄効果と同等であることを意味する。具体的には例えば、対象となるセルロース系繊維又はセルロース系繊維製品が白色である場合には、本発明のセルロース系繊維又はセルロース系繊維製品の処理方法による親水化処理を施したセルロース系繊維又はセルロース系繊維製品を汚して洗剤を用いずに洗濯した後の汚す前のセルロース系繊維又はセルロース系繊維製品との白度の変化量が、未処理のセルロース系繊維又はセルロース系繊維製品を汚して洗剤を用いて洗濯した後の汚す前のセルロース系繊維又はセルロース系繊維製品との白度の変化量の１１０％以内であることを意味する。また、対象となるセルロース系繊維又はセルロース系繊維製品が白色を含む色物である場合には、例えば、本発明のセルロース系繊維又はセルロース系繊維製品の処理方法による親水化処理を施したセルロース系繊維又はセルロース系繊維製品にオレイン酸１０％ｏ．ｗ．ｆ．、ゼラチン２．５％ｏ．ｗ．ｆ．を付着させた後洗剤を用いずに洗濯した後のオレイン酸の残留率（％）が、未処理の繊維製品にオレイン酸１０％ｏ．ｗ．ｆ．、ゼラチン２．５％ｏ．ｗ．ｆ．を付着させた後洗剤を用いて洗濯した後のオレイン酸の残留率（％）の１１０％以内であることを意味する。 In the present specification, the detergent-free washing function means that even when washing is performed without using a detergent, it is possible to obtain substantially the same cleaning effect as when washing with a detergent. Is obtained when the cellulosic fiber or cellulosic fiber product that has been subjected to hydrophilic treatment by the method for treating cellulosic fiber or cellulosic fiber product of the present invention is washed without using a detergent. This means that the cellulosic fiber or cellulosic fiber product of the treatment is equivalent to the cleaning effect when the detergent is used for washing. Specifically, for example, when the cellulosic fiber or cellulosic fiber product to be processed is white, the cellulosic fiber or the cellulosic fiber that has been subjected to a hydrophilic treatment by the method for treating cellulosic fiber or cellulosic fiber product of the present invention or After the cellulosic fiber product is soiled and washed without using a detergent, the amount of change in whiteness with the cellulosic fiber or the cellulosic fiber product before soiling stains the untreated cellulosic fiber or cellulosic fiber product. It means that it is within 110% of the amount of change in whiteness with the cellulosic fiber or cellulosic fiber product before washing after washing with a detergent. Moreover, when the cellulosic fiber or cellulosic fiber product to be used is a colored product containing white, for example, the cellulosic fiber subjected to a hydrophilic treatment by the method for treating the cellulosic fiber or cellulosic fiber product of the present invention. 10% oleic acid on fiber or cellulosic fiber product o. w. f. Gelatin 2.5% o. w. f. The residual percentage of oleic acid after laundering and without washing without detergent was 10% oleic acid in the untreated textile. w. f. Gelatin 2.5% o. w. f. It means that it is within 110% of the residual ratio (%) of oleic acid after laundering and washing with a detergent.
上記セルロース系繊維又はセルロース系繊維製品には、単繊維及び単繊維を使用した製品が包含され、上記単繊維を使用した製品としては、例えば、綿糸、綿混紡糸等の糸や、例えば、綿布等の糸から製造される製品や、綿スライバー（束）等が挙げられる。
なお、本発明のセルロース系繊維又はセルロース系繊維製品の処理方法では、上述したセルロース系繊維以外の繊維も用いることができる。上記セルロース系繊維以外の繊維としては、例えば、麻、絹、羊毛等の天然繊維からなるもの；ポリエチレンテレフタレート、レーヨン、ポリノジック、キュプラ、アセテート、ナイロン、ビニロン、ビニリデン、ポリ塩化ビニル、アクリル、アクリル系、ポリエチレン、ポリプロピレン、ポリウレタン等の合成繊維からなるものや、これらの混合繊維等が挙げられる。
また、本明細書においてセルロース系繊維製品とは、肌着、上着、靴下、手袋、帽子、ヘアバンド等の衣類の他、ハンカチ、タオル、フェイスマスク、マフラー、シーツ、枕カバー、ふとん、クッション、おむつ、おむつカバー等のセルロース系繊維が用いられる全てのものが含まれる。
The cellulose-based fiber or the cellulose-based fiber product includes single fibers and products using single fibers. Examples of the products using the single fibers include yarns such as cotton yarn and cotton blended yarn, and cotton fabric, for example. And products manufactured from yarn such as cotton sliver (bundle).
In addition, in the processing method of the cellulose fiber or cellulose fiber product of this invention, fibers other than the cellulose fiber mentioned above can also be used. Examples of fibers other than the above cellulose fibers include natural fibers such as hemp, silk, wool, etc .; polyethylene terephthalate, rayon, polynosic, cupra, acetate, nylon, vinylon, vinylidene, polyvinyl chloride, acrylic, acrylic And synthetic fibers such as polyethylene, polypropylene, and polyurethane, and mixed fibers thereof.
In addition, in the present specification, the cellulosic fiber product includes clothes such as underwear, outerwear, socks, gloves, hats, hair bands, handkerchiefs, towels, face masks, mufflers, sheets, pillowcases, futons, cushions, All the things using cellulosic fibers, such as a diaper and a diaper cover, are included.
上記親水化処理としては特に限定されないが、例えば、親水基を導入する方法、親水性分子を導入する方法、物理的に表面を改質する方法、及び、親水性物質を含有するコーティング剤でコーティングする方法からなる群より選択される少なくとも１種により行われるものであることが好ましい。 The hydrophilization treatment is not particularly limited. For example, a method for introducing a hydrophilic group, a method for introducing a hydrophilic molecule, a method for physically modifying a surface, and a coating with a coating agent containing a hydrophilic substance. Preferably, the method is carried out by at least one selected from the group consisting of methods.
上記親水基を導入する方法としては特に限定されず、例えば、セルロース系繊維又はセルロース系繊維製品を構成する分子に、カルボキシル基、アミノ基、スルホン基、水酸基、リン酸基、エポキシ基、エーテル残基等の極性基又はこれらの基を有する基等の親水基を直接結合させる方法等が挙げられる。 The method for introducing the hydrophilic group is not particularly limited. For example, a carboxyl group, an amino group, a sulfone group, a hydroxyl group, a phosphate group, an epoxy group, an ether residue may be added to the cellulose fiber or the molecule constituting the cellulose fiber product. Examples thereof include a method of directly bonding a polar group such as a group or a hydrophilic group such as a group having these groups.
上記親水性分子を導入する方法としては特に限定されないが、例えば、セルロース系繊維又はセルロース系繊維製品を構成する分子に、カルボキシル基、アミノ基、スルホン基等の極性基又はこれらの基を有する基等の親水基を有する分子を結合させたり、メタクリルアミド、ヒドロキシエチルアクリレート、アクリル酸、メタクリル酸等をグラフト重合させて親水性の高い側鎖を結合させたりする方法等が挙げられる。 The method of introducing the hydrophilic molecule is not particularly limited. For example, polar groups such as a carboxyl group, an amino group, and a sulfone group or a group having these groups may be added to a molecule constituting a cellulose fiber or a cellulose fiber product. And a method of bonding molecules having a hydrophilic group such as methacrylamide, hydroxyethyl acrylate, acrylic acid, methacrylic acid or the like to bond a highly hydrophilic side chain.
上記物理的に表面を改質する方法としては特に限定されないが、例えば、セルロース系繊維又はセルロース系繊維製品の表面にプラズマ処理、コロナ処理、紫外線、電子線、放射線、レーザー等の電離活性線処理、火炎処理、オゾン処理、酵素微生物処理等の処理を施す方法等が挙げられる。
上記親水性物質を含有するコーティング剤でコーティングする方法としては特に限定されず、例えば、アクリル樹脂、メタクリル樹脂、ウレタン樹脂、シリコーン樹脂、グリオキサール樹脂、酢酸ビニル樹脂、塩化ビニリデン樹脂、ブタジエン樹脂、メラミン樹脂、エポキシ樹脂、アクリル−シリコーン共重合体樹脂、エチレン−酢酸ビニル共重合体樹脂、イソブチレン−無水マレイン酸共重合体樹脂等のバインダー樹脂中に、親水性ビニル化合物、ポリアルキレンオキサイド系化合物、親水性天然化合物等の親水性物質を溶解したコーティング剤を用いてセルロース系繊維又はセルロース系繊維製品の表面にコーティングする方法が挙げられる。また、これらのモノマー及びオリゴマーをコーティングした後、反応させて樹脂化させてもよい。
The method for physically modifying the surface is not particularly limited. For example, the surface of a cellulosic fiber or a cellulosic fiber product is subjected to ionizing actinic radiation treatment such as plasma treatment, corona treatment, ultraviolet ray, electron beam, radiation, and laser. , Flame treatment, ozone treatment, enzyme microorganism treatment, and the like.
The method of coating with the coating agent containing the hydrophilic substance is not particularly limited. For example, acrylic resin, methacrylic resin, urethane resin, silicone resin, glyoxal resin, vinyl acetate resin, vinylidene chloride resin, butadiene resin, melamine resin , Epoxy resin, acrylic-silicone copolymer resin, ethylene-vinyl acetate copolymer resin, isobutylene-maleic anhydride copolymer resin and other binder resins, hydrophilic vinyl compounds, polyalkylene oxide compounds, hydrophilic Examples thereof include a method of coating the surface of a cellulosic fiber or cellulosic fiber product using a coating agent in which a hydrophilic substance such as a natural compound is dissolved. Moreover, after coating these monomers and oligomers, they may be reacted to form a resin.
本発明のセルロース系繊維又はセルロース系繊維製品の処理方法では、親水化処理によりセルロース系繊維の吸湿率を７．１％以上にすることが好ましい。７．１％未満であると、油性の汚れ成分とセルロース系繊維又はセルロース系繊維製品との結合力が強く、水だけでは充分に汚れ成分を落とせないことがある。より好ましくは７．５％以上である。吸湿率の上限については特に限定されないが、通常、好ましい上限は２０％、より好ましい上限は１５％である。
なお、上記吸湿率は下記式（１）により求めることができる。
In the method for treating a cellulosic fiber or cellulosic fiber product of the present invention, it is preferable that the moisture absorption rate of the cellulosic fiber is set to 7.1% or more by hydrophilic treatment. If it is less than 7.1%, the binding force between the oily soil component and the cellulosic fiber or cellulosic fiber product is strong, and the soil component may not be sufficiently removed with water alone. More preferably, it is 7.5% or more. Although the upper limit of the moisture absorption rate is not particularly limited, the preferable upper limit is usually 20%, and the more preferable upper limit is 15%.
In addition, the said moisture absorption rate can be calculated | required by following formula (1).
吸湿率（％）＝（〔公定重量〕÷〔絶乾重量〕−１）×１００ （１）
上記式（１）において、絶乾重量は、例えば、測定対象となるセルロース系繊維又はセルロース系繊維製品を秤量ビンに入れて１０５℃で２時間乾燥させた後に秤量し、予め秤量しておいた秤量ビンの重量を差し引くことにより算出することができる。また、公定重量は、例えば、秤量ビンに入れて絶乾重量を測定したセルロース系繊維又はセルロース系繊維製品を温度２０℃、湿度６５％ＲＨの雰囲気に２４時間放置した後に秤量し、秤量ビンの重量を差し引くことにより算出することができる。なお、絶乾重量及び公定重量の測定には、例えば、１０×２０ｃｍ程度の大きさの生地小片等を使用することができる。秤量は、重量が一定になるまで繰り返し測定する。
Moisture absorption rate (%) = ([official weight] ÷ [absolute dry weight] −1) × 100 (1)
In the above formula (1), the absolute dry weight is measured, for example, after the cellulosic fiber or cellulosic fiber product to be measured is placed in a weighing bottle and dried at 105 ° C. for 2 hours, and weighed in advance. It can be calculated by subtracting the weight of the weighing bottle. The official weight is determined by, for example, weighing a cellulosic fiber or a cellulosic fiber product that has been measured for absolute dry weight in a weighing bottle after leaving it in an atmosphere at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours. It can be calculated by subtracting the weight. In addition, for measurement of the absolute dry weight and the official weight, for example, a piece of dough having a size of about 10 × 20 cm can be used. Weighing is repeated until the weight is constant.
上記親水化処理の方法としては特に限定されないが、高い吸湿率を比較的容易に付与できることから、カルボキシル基を導入する方法が好適である。なお、本明細書においてカルボキシル基には、ナトリウム塩、カリウム塩等の塩も含まれる。 The hydrophilic treatment method is not particularly limited, but a method of introducing a carboxyl group is preferable because a high moisture absorption rate can be imparted relatively easily. In the present specification, the carboxyl group includes salts such as sodium salt and potassium salt.
上記セルロース系繊維にカルボキシル基を導入する方法の好ましい態様の１つを説明する。カルボキシル基は、例えば、セルロース系繊維にモノクロル酢酸又はモノクロル酢酸のアルカリ金属塩（例えば、ナトリウム塩、カリウム塩）を含有する処理液を接触させることによりカルボキシメチル基の形で容易にセルロース系繊維に導入することができる。このようにカルボキシメチル基を導入することを、以下、カルボキシメチル化ともいう。 One preferred embodiment of the method for introducing a carboxyl group into the cellulose fiber will be described. The carboxyl group can be easily converted into the cellulosic fiber in the form of carboxymethyl group by contacting the cellulosic fiber with a treatment liquid containing monochloroacetic acid or an alkali metal salt of monochloroacetic acid (for example, sodium salt or potassium salt). Can be introduced. The introduction of a carboxymethyl group in this way is hereinafter also referred to as carboxymethylation.
上記カルボキシメチル化を行う場合の処理液中における、モノクロル酢酸又はモノクロル酢酸のアルカリ金属塩の濃度としては、目的の加工度が得られるよう処理液の条件を適宜定めればよいが、１０〜５００ｇ／Ｌであることが好ましく、より好ましくは５０〜３００ｇ／Ｌ、更に好ましくは１００〜２００ｇ／Ｌである。 The concentration of monochloroacetic acid or the alkali metal salt of monochloroacetic acid in the treatment liquid in the case of carrying out the carboxymethylation may be determined as appropriate in order to obtain the desired degree of processing. / L, more preferably 50 to 300 g / L, still more preferably 100 to 200 g / L.
上記カルボキシメチル化を行う場合の処理液には、アルカリ金属の水酸化物、例えば、水酸化ナトリウムを配合することが好ましい。水酸化ナトリウムを配合することにより、得られる処理繊維のカルボキシメチル化度を向上させることができる。上記処理液中における水酸化ナトリウム濃度を上げるほど反応度が上がる傾向があり、通常は２０ｇ／Ｌ以上とすることが好ましい。ただし、大量の水酸化ナトリウムを配合すると、得られる繊維の風合いが悪化する傾向があるので注意を要する。 It is preferable to mix | blend alkali metal hydroxide, for example, sodium hydroxide, in the process liquid in the case of performing the said carboxymethylation. By blending sodium hydroxide, the degree of carboxymethylation of the resulting treated fiber can be improved. The reactivity tends to increase as the concentration of sodium hydroxide in the treatment liquid is increased, and it is usually preferably 20 g / L or more. However, if a large amount of sodium hydroxide is blended, the texture of the resulting fiber tends to deteriorate, so care must be taken.
セルロース系繊維と上記処理液とを接触させる方法としては、例えば、処理液中で繊維を回転させる液流法；繊維を処理液中に浸漬した後にパディング（絞り）する方法等が挙げられる。使用効率の点で、浴比（処理液の使用割合）を下げることが有効であり、この点で浸漬した後にパディングする方法が有効である。なお、セルロース系繊維と処理液とを接触させる際の温度条件としては特に限定されず、例えば、５〜５０℃の範囲内とすることができる。 Examples of the method of bringing the cellulosic fiber into contact with the treatment liquid include a liquid flow method in which the fiber is rotated in the treatment liquid; a method of padding (squeezing) after immersing the fiber in the treatment liquid, and the like. In terms of use efficiency, it is effective to lower the bath ratio (use ratio of the treatment liquid), and a method of padding after dipping in this respect is effective. In addition, it does not specifically limit as temperature conditions at the time of making a cellulosic fiber and a process liquid contact, For example, it can be in the range of 5-50 degreeC.
上記セルロース系繊維と処理液とを接触させる時間としては目的とするカルボキシメチル化度や処理中のモノクロル酢酸濃度、水酸化ナトリウム濃度等の諸条件から適宜選択すればよい。常温で数時間〜数日間程度接触させていてもよいし、熱処理することにより要する時間を短縮することもできる。 The time for contacting the cellulosic fiber with the treatment liquid may be appropriately selected from various conditions such as the desired degree of carboxymethylation, the concentration of monochloroacetic acid during treatment, the concentration of sodium hydroxide, and the like. It may be contacted at room temperature for several hours to several days, and the time required can be shortened by heat treatment.
肌着等の衣類等、とりわけ風合いが求められる場合には、処理液中のモノクロル酢酸又はモノクロル酢酸のアルカリ金属塩の濃度、処理液中のアルカリ金属の水酸化物の濃度、処理温度、及び、処理時間を調整することが好ましい。なかでも処理液中のアルカリ金属の水酸化物の濃度が高くなると、セルロース系繊維にダメージを与えて風合いを硬化させる傾向がある。従って、処理液中のアルカリ金属の水酸化物の濃度をできる限り低くし、かつ、処理温度を低温にしてアルカリ金属の水酸化物による影響を抑制することが好ましい。一方、アルカリ金属の水酸化物の濃度を低く抑えた状態でも充分なカルボキシメチル化度を得るためには、処理液中のモノクロル酢酸又はモノクロル酢酸のアルカリ金属塩の濃度を比較的高く設定し、処理時間を長くする必要がある。具体的には、セルロース系繊維を、アルカリ金属の水酸化物の濃度が２０〜１００ｇ／Ｌ、モノクロル酢酸又はモノクロル酢酸のアルカリ金属塩の濃度が１００〜４００ｇ／Ｌの処理液と１０〜４０℃、６〜４８時間接触させる場合には、充分な吸湿度と風合いとを両立させることができる。 In the case of clothing such as underwear, especially when a texture is required, the concentration of monochloroacetic acid or alkali metal salt of monochloroacetic acid in the treatment liquid, the concentration of alkali metal hydroxide in the treatment liquid, the treatment temperature, and the treatment It is preferable to adjust the time. In particular, when the concentration of the alkali metal hydroxide in the treatment liquid is increased, the cellulosic fibers tend to be damaged and the texture is cured. Therefore, it is preferable that the concentration of the alkali metal hydroxide in the treatment liquid be as low as possible and the treatment temperature be lowered to suppress the influence of the alkali metal hydroxide. On the other hand, in order to obtain a sufficient degree of carboxymethylation even when the concentration of alkali metal hydroxide is kept low, the concentration of monochloroacetic acid or the alkali metal salt of monochloroacetic acid in the treatment liquid is set to be relatively high, It is necessary to lengthen the processing time. Specifically, the cellulosic fiber is treated with a treatment solution having an alkali metal hydroxide concentration of 20 to 100 g / L, monochloroacetic acid or an alkali metal salt of monochloroacetic acid of 100 to 400 g / L, and 10 to 40 ° C. When contacting for 6 to 48 hours, sufficient moisture absorption and texture can be achieved.
上記カルボキシメチル化度の好ましい下限は０．１モル％である。０．１モル％未満であると、充分な吸湿度が得られないことがある。より好ましい下限は１モル％である。カルボキシメチル化度の上限は特に限定されないが、好ましい上限は１０モル％、より好ましい上限は５モル％である。 A preferable lower limit of the carboxymethylation degree is 0.1 mol%. If it is less than 0.1 mol%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 1 mol%. The upper limit of the degree of carboxymethylation is not particularly limited, but the preferable upper limit is 10 mol%, and the more preferable upper limit is 5 mol%.
なお、本明細書においてカルボキシメチル化度とは、カルボキシメチル化反応したセルロースの水酸基の割合（％）、即ち、未処理セルロースの水酸基の数に対するカルボキシメチル化した後のＣＯＯ基の数の割合（％）を意味する。また、セルロース系繊維中のＣＯＯ基の数は、セルロース系繊維の全ＣＯＯ基をＣＯＯＨ基とし、水酸化ナトリウム水溶液（０．１Ｎ）に浸漬した後、その置換に使用されたＮａを定量することにより求めることができる。置換に使用されたＮａ量は、処理済のセルロース系繊維又はセルロース系繊維製品を浸漬した水酸化ナトリウム水溶液を、例えば、塩酸（０．１Ｎ）を使用して滴定することにより、定量することができる。具体的には、以下の測定方法を採用することができる。 In this specification, the degree of carboxymethylation means the ratio (%) of hydroxyl groups of cellulose subjected to carboxymethylation reaction, that is, the ratio of the number of COO groups after carboxymethylation to the number of hydroxyl groups of untreated cellulose ( %). The number of COO groups in the cellulosic fiber is determined by quantifying the amount of Na used for the substitution after immersing it in a sodium hydroxide aqueous solution (0.1N) with all the COO groups of the cellulosic fiber as COOH groups. It can ask for. The amount of Na used for substitution can be quantified by titrating an aqueous sodium hydroxide solution in which treated cellulose fibers or cellulose fiber products are immersed using, for example, hydrochloric acid (0.1N). it can. Specifically, the following measurement methods can be employed.
まず、処理済のセルロース系繊維（例えば、生地小片）を、０．３Ｎの塩酸に、浴比１：５０、液温２０℃の条件で１時間浸漬して全ＣＯＯ基をＣＯＯＨ基とし、脱水し、乾燥して残留ＨＣｌを除去し、約４ｇをサンプリングして絶乾重量（Ｗ（ｇ））を秤量する。次いで、絶乾重量を秤量したセルロース繊維等を、精秤した０．１Ｎの水酸化ナトリウム水溶液５０ｍＬ（Ｂ（ｍＬ））に浸漬して液温２０℃で１晩放置することにより、全ＣＯＯＨ基をＣＯＯＮａに置換する。更に、置換に使用されたＮａを定量するため、０．１Ｎ塩酸を使用して液を滴定し、滴定値をＸ（ｍＬ）とする。指示薬としてはフェノールフタレインを使用することができる。 First, the treated cellulosic fibers (for example, dough pieces) are immersed in 0.3N hydrochloric acid for 1 hour under conditions of a bath ratio of 1:50 and a liquid temperature of 20 ° C. to make all COO groups COOH groups, and dehydrated. And dry to remove residual HCl, sample approximately 4 g and weigh the absolute dry weight (W (g)). Next, the cellulose fibers and the like weighed in absolute dry weight are immersed in 50 mL (B (mL)) of 0.1 N sodium hydroxide aqueous solution that has been precisely weighed and left overnight at a liquid temperature of 20 ° C. Is replaced with COONa. Further, in order to quantify Na used in the substitution, the liquid is titrated using 0.1N hydrochloric acid, and the titration value is set to X (mL). Phenolphthalein can be used as an indicator.
カルボキシメチル化度は、セルロース系繊維等の絶乾重量（Ｗ（ｇ））、水酸化ナトリウム水溶液の体積（Ｂ（ｍＬ））、滴定に要した塩酸の体積（Ｘ（ｍＬ））から、下記式（２）に従って算出することができる。 The degree of carboxymethylation was determined from the absolute dry weight (W (g)) of the cellulose fiber, the volume of sodium hydroxide aqueous solution (B (mL)), and the volume of hydrochloric acid required for titration (X (mL)) as follows. It can be calculated according to equation (2).
カルボキシメチル化度（モル％）
＝１６２．１４×（Ｂ−Ｘ）÷〔１００００Ｗ−５９．０４×（Ｂ−Ｘ）〕÷３×１００
（２）
上記親水化処理方法としては、セルロース系繊維にメタクリルアミド、ヒドロキシエチルアクリレート、アクリル酸、及び、メタクリル酸からなる群より選択される少なくとも１種のモノマーをグラフト重合する方法も好適である。
Carboxymethylation degree (mol%)
= 162.14 × (B−X) ÷ [10000 W−59.04 × (B−X)] ÷ 3 × 100
(2)
As the hydrophilic treatment method, a method in which at least one monomer selected from the group consisting of methacrylamide, hydroxyethyl acrylate, acrylic acid, and methacrylic acid is graft-polymerized on the cellulose fiber is also suitable.
上記グラフト化の方法としては、例えば、上記モノマーを、セルロース系繊維と接触させた状態で、重合反応させる方法等が挙げられる。具体的には、例えば、上記モノマー及び重合開始剤（例えば、ペルオキソ２硫酸アンモニウム等）を含有する液中に、セルロース系繊維を浸漬して絞った後、加熱することにより、親水性分子がグラフトしたセルロース系繊維を得ることができる。 Examples of the grafting method include a method of polymerizing the monomer in a state where the monomer is brought into contact with the cellulosic fiber. Specifically, for example, a cellulose-based fiber is immersed and squeezed in a liquid containing the monomer and a polymerization initiator (for example, ammonium peroxodisulfate), and then the hydrophilic molecule is grafted by heating. Cellulosic fibers can be obtained.
上記グラフト化により導入する親水性分子の量としては、親水性分子の種類、セルロース系繊維に要求される吸湿率等を考慮して適宜選択することができるが、グラフト率の好ましい下限は１％である。１％未満であると、充分な吸湿度が得られないことがある。より好ましい下限は２％である。グラフト率の上限については特に限定されないが、好ましい上限は３０％、より好ましい上限は２５％、更に好ましい上限は２０％である。
なお、本明細書においてグラフト率は、グラフトさせる前のセルロース系繊維等の絶乾重量（処理前絶乾重量）とグラフトさせた後の絶乾重量（処理後絶乾重量）から、下記式（３）により算出することができる。
The amount of the hydrophilic molecule to be introduced by the grafting can be appropriately selected in consideration of the kind of the hydrophilic molecule, the moisture absorption rate required for the cellulosic fiber, etc. The preferred lower limit of the graft rate is 1%. It is. If it is less than 1%, sufficient moisture absorption may not be obtained. A more preferred lower limit is 2%. The upper limit of the graft ratio is not particularly limited, but a preferable upper limit is 30%, a more preferable upper limit is 25%, and a further preferable upper limit is 20%.
In the present specification, the graft ratio is calculated from the following formula (absolute dry weight before treatment) and the absolute dry weight after treatment (absolute dry weight after treatment): 3).
グラフト率（％）＝（〔処理後絶乾重量〕÷〔処理前絶乾重量〕−１）×１００ （３）
上記式（３）において、絶乾重量は、例えば１０×２０ｃｍ程度の大きさの生地小片を、秤量ビンに入れ１０５℃で２時間乾燥後、秤量し、予め秤量しておいた秤量ビンの重量を差し引いくことにより、算出することができる。
Graft rate (%) = ([absolute dry weight after treatment] ÷ [absolute dry weight before treatment] −1) × 100 (3)
In the above formula (3), the absolute dry weight is the weight of a weighing bottle that has been weighed in advance by weighing a dough piece of about 10 × 20 cm in a weighing bottle, drying it at 105 ° C. for 2 hours, weighing it, and so on. Can be calculated by subtracting.
本発明のセルロース系繊維又はセルロース系繊維製品の処理方法では、次いで、親水化処理を施したセルロース系繊維又はセルロース系繊維製品を、所定のエステル系仕上剤と、カルボジイミド系架橋剤とを用いて架橋させる工程を行う。以下、この工程を架橋工程ともいう。 In the method for treating cellulosic fibers or cellulosic fiber products of the present invention, the cellulose fiber or cellulosic fiber product that has been subjected to a hydrophilic treatment is then treated with a predetermined ester finish and a carbodiimide crosslinker. A cross-linking step is performed. Hereinafter, this process is also referred to as a crosslinking process.
本発明において、上記架橋工程の具体例としては、例えば、上記エステル系仕上剤、カルボジイミド系架橋剤、触媒を含有する架橋処理液に、親水化処理を施したセルロース系繊維又はセルロース系繊維製品を浸漬した後にパディング（絞り）、乾燥を行う方法、架橋処理液中でセルロース系繊維又はセルロース系繊維製品を回転させる液流法等が挙げられる。このなかでは、浸漬した後にパディングする方法が有効である。 In the present invention, as a specific example of the crosslinking step, for example, a cellulose fiber or a cellulose fiber product obtained by subjecting a crosslinking treatment liquid containing the ester finish, a carbodiimide crosslinking agent, and a catalyst to a hydrophilic treatment. Examples of the method include padding (squeezing) after drying, drying, and a liquid flow method in which cellulosic fibers or cellulosic fiber products are rotated in a crosslinking treatment liquid. Of these, the padding method after immersion is effective.
上記エステル系仕上剤は、酸化変性若しくは酸変性ポリエチレンと、脂肪族アルコール又は脂肪族アミンのエチレンオキシド及び／若しくはプロピレンオキシド付加物とのエステル化反応によって生成されたエステル系化合物を含有する。上記エステル系仕上剤を用いることで、優れた無洗剤洗濯機能を有しつつ、高い柔軟性も有する。さらに後述するカルボジイミド系架橋剤と併用することで、繰り返し洗濯後も柔軟性を維持することが可能となる。
以下、上記エステル系化合物をＡ成分ともいう。
The ester-based finish contains an ester-based compound produced by an esterification reaction between an oxidatively-modified or acid-modified polyethylene and an aliphatic alcohol or an ethylene amine and / or propylene oxide adduct of an aliphatic amine. By using the above-mentioned ester-based finish, it has high flexibility while having an excellent detergent-free washing function. Furthermore, by using together with the carbodiimide type crosslinking agent mentioned later, it becomes possible to maintain a softness | flexibility after repeated washing.
Hereinafter, the ester compound is also referred to as component A.
上記酸化変性若しくは酸変性ポリエチレンとしては、例えば、ポリエチレンを空気酸化又は熱分解することによりカルボキシル基を導入したもの、ポリエチレンとアクリル酸、メタクリル酸等のビニルカルボン酸を共重合させたもの等が挙げられる。市販品としては、例えば、ＡＣ−６２９、ＡＣ−５８０、ＡＣ−５４０（何れもハネウェル・インターナショナル社製）、三井ハイワックス４２０２Ｅ、１１０５Ａ（何れも三井化学社製）、サンワックスＥ−３１０（三洋化成工業社製）等が挙げられる。 Examples of the oxidation-modified or acid-modified polyethylene include those obtained by introducing a carboxyl group by subjecting polyethylene to air oxidation or thermal decomposition, and those obtained by copolymerizing polyethylene and vinyl carboxylic acid such as acrylic acid or methacrylic acid. It is done. Examples of commercially available products include AC-629, AC-580, AC-540 (all manufactured by Honeywell International), Mitsui High Wax 4202E, 1105A (all manufactured by Mitsui Chemicals), Sun Wax E-310 (SANYO) Kasei Kogyo Co., Ltd.).
上記脂肪族アルコール又は脂肪族アミンのエチレンオキシド及び／若しくはプロピレンオキシド付加物としては、脂肪族アルコール又は脂肪族アミンに、エチレンオキシド及び／若しくはプロピレンオキシドをブロック又はランダムで付加したエチレンオキシド及び／若しくはプロピレンオキシド付加物を用いる。
これらのなかでは、セルロース繊維又はセルロース繊維製品への加工時に白度低下が少なくなる点から、脂肪族アルコールのエチレンオキシド及び／若しくはプロピレンオキシド付加物がより好適である。吸水性を発現させるためには、上記エチレンオキシド及び／若しくはプロピレンオキシド付加物は、ＨＬＢが１０〜１９であることが好ましく、１２〜１７であることがより好ましい。更に、ＨＬＢが上記範囲内であると、エステル系仕上剤としてより安定したエマルジョンが得られる。なお、本明細書におけるＨＬＢは、グリフィンの式による値である。
The ethylene oxide and / or propylene oxide adduct of the aliphatic alcohol or aliphatic amine is an ethylene oxide and / or propylene oxide adduct obtained by blocking or randomly adding ethylene oxide and / or propylene oxide to an aliphatic alcohol or aliphatic amine. Is used.
Among these, aliphatic alcohol ethylene oxide and / or propylene oxide adducts are more preferable because the decrease in whiteness during processing into cellulose fibers or cellulose fiber products is reduced. In order to develop water absorption, the ethylene oxide and / or propylene oxide adduct preferably has an HLB of 10 to 19, and more preferably 12 to 17. Further, when the HLB is within the above range, a more stable emulsion can be obtained as an ester finish. In addition, HLB in this specification is a value according to the Griffin equation.
上記酸化変性若しくは酸変性ポリエチレンと、上記エチレンオキシド及び／若しくはプロピレンオキシド付加物との反応は、例えば、反応容器に上記酸化変性若しくは酸変性ポリエチレンの酸化当量と当モルの上記エチレンオキシド及び／若しくはプロピレンオキシド付加物を仕込み、さらに触媒としてパラトルエンスルホン酸を添加し、窒素気流下に、１８０〜２２０℃で３〜５時間脱水反応させることにより行うことができる。反応率は、キシレン／ジメチルスルホキシド（２／１〜９／１）の混合溶媒による酸化測定により追跡することができる。本発明では、反応物の反応率が７０〜９５％であることが好ましい。さらに好ましくは８０〜９０％である。エステル化の反応率が前記下限未満であると、安定したエマルジョンを得られないことがあり、さらにセルロース系繊維又はセルロース系繊維製品に処理した時に、吸水性を阻害することがある。また、前記上限を超えると、エステル系仕上剤とカルボジイミド系架橋剤との架橋反応が充分進行せず、セルロース系繊維又はセルロース系繊維製品に処理した時に、洗濯耐久性を損なうことがある。 For example, the reaction between the oxidatively modified or acid-modified polyethylene and the ethylene oxide and / or propylene oxide adduct is carried out by adding, for example, an oxidation equivalent of the oxidatively modified or acid-modified polyethylene and an equimolar amount of the ethylene oxide and / or propylene oxide to a reaction vessel. The product can be charged, and paratoluenesulfonic acid is added as a catalyst, followed by dehydration reaction at 180 to 220 ° C. for 3 to 5 hours under a nitrogen stream. The reaction rate can be monitored by oxidation measurement using a mixed solvent of xylene / dimethyl sulfoxide (2/1 to 9/1). In the present invention, the reaction rate of the reactant is preferably 70 to 95%. More preferably, it is 80 to 90%. If the esterification reaction rate is less than the lower limit, a stable emulsion may not be obtained, and further, when the cellulose fiber or cellulose fiber product is processed, water absorption may be inhibited. When the upper limit is exceeded, the crosslinking reaction between the ester-based finish and the carbodiimide-based crosslinking agent does not proceed sufficiently, and the washing durability may be impaired when the cellulose-based fiber or the cellulose-based fiber product is processed.
上記エチレンオキシド又はプロピレンオキシド付加物において、脂肪族アルコール又は脂肪族アミンは、飽和であっても不飽和であってもよく、好ましくは飽和のものである。その炭素数は好ましくは４〜２２、より好ましくは８〜２０である。炭素数が前記下限より小さいものを用いると、セルロース系繊維又はセルロース系繊維製品に処理した時に柔軟性に劣ることがあり、前記上限を超えるものを用いると、セルロース系繊維又はセルロース系繊維製品に処理した時に吸水性に劣ることがある。 In the above-mentioned ethylene oxide or propylene oxide adduct, the aliphatic alcohol or aliphatic amine may be saturated or unsaturated, and is preferably saturated. The carbon number is preferably 4 to 22, more preferably 8 to 20. If the carbon number is smaller than the lower limit, the flexibility may be inferior when processed into cellulosic fiber or cellulosic fiber product. If the carbon number exceeds the upper limit, the cellulosic fiber or cellulosic fiber product may be used. It may have poor water absorption when treated.
上記エステル系仕上剤は、更に、下記式［１］に示す水溶性ポリエステル樹脂を含有することが好ましい。
以下、上記水溶性ポリエステル樹脂をＢ成分ともいう。
The ester-based finish preferably further contains a water-soluble polyester resin represented by the following formula [1].
Hereinafter, the water-soluble polyester resin is also referred to as B component.
上記一般式［１］中、Ｒ１はＨＯ−基又はＨＯ（Ｒ２Ｏ）ａ−基を表し、Ｒ２は炭素数２〜４のアルキレン基を表す。
上記炭素数２〜４のアルキレン基としては、例えば、エチレン、トリメチレン、プロピレン、テトラメチレン、ブチレンが挙げられるが、水に対する溶解度や分散性の観点から、特にエチレン基が好ましい。
In the general formula [1], R 1 represents a HO— group or a HO (R 2 O) a — group, and R 2 represents an alkylene group having 2 to 4 carbon atoms.
Examples of the alkylene group having 2 to 4 carbon atoms include ethylene, trimethylene, propylene, tetramethylene, and butylene, and an ethylene group is particularly preferable from the viewpoint of water solubility and dispersibility.
上記ａは１〜２００の整数を表すが、１〜１５０がより好ましい。上記ａが前記上限を超えると、ポリエステル樹脂の粘度が高くなり過ぎて、取り扱いが困難となることがある。
上記ａが２以上の場合にはＲ２Ｏは同一でも異なっていてもよく、Ｒ２Ｏが２種以上の場合にはランダム付加でも、ブロック付加でもよい。
また、上記ｂは１〜１００の整数を表すが、１〜５０がより好ましい。前記上限を超えると、ポリエステル樹脂の粘度が高くなり過ぎて、取り扱いが困難となる。
Although a represents an integer of 1 to 200, 1 to 150 is more preferable. When said a exceeds the said upper limit, the viscosity of a polyester resin will become high too much and handling may become difficult.
When a is 2 or more, R 2 O may be the same or different, and when R 2 O is 2 or more, random addition or block addition may be used.
Moreover, although said b represents the integer of 1-100, 1-50 are more preferable. When the upper limit is exceeded, the viscosity of the polyester resin becomes too high and handling becomes difficult.
さらに、Ｒ４は同一でも異なっていてもよく、それぞれ水素原子又は−ＳＯ３Ｘ基を表し、−ＳＯ３Ｘ基のうち、Ｘは水素原子、アルカリ金属又はアミンを表す。
上記アルカリ金属としては、例えば、リチウム、ナトリウム、カリウムが挙げられ、上記アミンとしては、例えば、アンモニア、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、アリルアミン等の１級アミン；ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジアリルアミン等の２級アミン；トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン等の３級アミン；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミンが挙げられる。
Furthermore, R 4 may be the same or different, each represents a hydrogen atom or an -SO 3 X group, among -SO 3 X group, X represents a hydrogen atom, an alkali metal or an amine.
Examples of the alkali metal include lithium, sodium and potassium. Examples of the amine include primary amines such as ammonia, methylamine, ethylamine, propylamine, butylamine and allylamine; dimethylamine, diethylamine and dipropyl. Secondary amines such as amine, dibutylamine and diallylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine.
また、Ｒ３は水素原子又は上記一般式［２］で表される基を表す。そして、上記一般式［２］において、Ｒ４は式［１］中のＲ４と同一のものを表す。 R 3 represents a hydrogen atom or a group represented by the above general formula [2]. Then, in the general formula [2], R 4 represents the same as R 4 in the formula [1].
上記水溶性ポリエステル樹脂は、芳香族ジカルボン酸又はその誘導体とアルキレングリコール及び／又はポリアルキレングリコールより、公知の方法により製造することができる。
上記芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、フタル酸及びスルホイソフタル酸を挙げることができ、その誘導体としては、例えば、これらのジカルボン酸のジメチルエステル、ジエチルエステル、ジプロピルエステル、ジブチルエステル等の低級アルキルエステル、これらのジカルボン酸のクロライド、無水フタル酸を挙げることができる。これらの芳香族ジカルボン酸又はその誘導体は、単独で使用してもよく、２種以上を併用してもよい。
上記芳香族ジカルボン酸又はその誘導体の重合比率には特に制限はないが、−ＳＯ３Ｘ基を有する芳香族ジカルボン酸又はその誘導体を使用する場合には、その重合比率は５０モル％以下であることが好ましい。−ＳＯ３Ｘ基を有する芳香族ジカルボン酸誘導体の重合比率が前記上限を超えると、水溶性ポリエステル樹脂の重縮合反応が困難となることや、洗濯による脱落が激しく、無洗剤洗濯性の更なる向上効果が得られないことがある。
The water-soluble polyester resin can be produced by a known method from aromatic dicarboxylic acid or a derivative thereof and alkylene glycol and / or polyalkylene glycol.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, and sulfoisophthalic acid, and examples of the derivatives thereof include dimethyl ester, diethyl ester, dipropyl ester of these dicarboxylic acids, Examples thereof include lower alkyl esters such as dibutyl ester, chlorides of these dicarboxylic acids, and phthalic anhydride. These aromatic dicarboxylic acids or derivatives thereof may be used alone or in combination of two or more.
There is no particular limitation on the polymerization ratio of the aromatic dicarboxylic acid or a derivative thereof, in the case of using an aromatic dicarboxylic acid or a derivative thereof having a -SO 3 X group, the polymerization ratio is 50 mol% or less It is preferable. When the polymerization ratio of the aromatic dicarboxylic acid derivative having a —SO 3 X group exceeds the above upper limit, the polycondensation reaction of the water-soluble polyester resin becomes difficult, the falling off due to washing is severe, and the detergent-free washing property is further improved. The improvement effect may not be obtained.
上記水溶性ポリエステル樹脂の重量平均分子量は、３０００〜６００００であることが好ましく、５０００〜３００００であることがより好ましい。
上記水溶性ポリエステル樹脂の重量平均分子量が前記下限未満であると、洗濯による脱落が激しく、無洗剤洗濯性の更なる向上効果が得られないことがある。一方、前記上限を超えると、水溶性ポリエステル樹脂の粘度が高くなり過ぎて、取り扱いが困難となる。なお、水溶性ポリエステル樹脂の重量平均分子量は、分子量既知の単分散のポリエチレングリコールを測定標準物質として、ゲルパーミューションクロマトグラフィーにより求めることができる。
The water-soluble polyester resin preferably has a weight average molecular weight of 3000 to 60000, and more preferably 5000 to 30000.
When the weight average molecular weight of the water-soluble polyester resin is less than the lower limit, dropping off due to washing is severe, and a further improvement effect of non-detergent washing properties may not be obtained. On the other hand, when the above upper limit is exceeded, the viscosity of the water-soluble polyester resin becomes too high and handling becomes difficult. The weight average molecular weight of the water-soluble polyester resin can be determined by gel permeation chromatography using monodispersed polyethylene glycol having a known molecular weight as a measurement standard substance.
本発明において、上記Ａ成分とＢ成分とを併用する場合、Ａ成分：Ｂ成分の質量比としては、１：０．０１〜１：１が好ましい。上記範囲内とすることで、良質で安定なエマルジョンを得ることができ、セルロース系繊維又はセルロース系繊維製品に処理した場合に、無洗剤洗濯性を更に向上することができる。 In the present invention, when the A component and the B component are used in combination, the mass ratio of the A component to the B component is preferably 1: 0.01 to 1: 1. By setting it within the above range, a high-quality and stable emulsion can be obtained, and when it is processed into cellulosic fibers or cellulosic fiber products, the detergent-free washability can be further improved.
本発明においては、上記Ａ成分とＢ成分とを併用し、これらを水に乳化して使用することも可能であるが、更に、グリセリド、多価アルコール脂肪酸エステル、ポリアミン高級脂肪酸アミド、パラフィン、水溶性アクリル樹脂、アミノ変性シリコーン等を配合することにより、さらに良質で安定なエマルジョンを得ることができる。 In the present invention, the A component and the B component may be used in combination and emulsified in water. However, glycerides, polyhydric alcohol fatty acid esters, polyamine higher fatty acid amides, paraffin, water soluble By blending a functional acrylic resin, amino-modified silicone, etc., an even better and more stable emulsion can be obtained.
本発明において、上記エステル系仕上剤の処理量は、Ａ成分の繊維製品への付着量が、不揮発分として０．１〜５％ｏ．ｗ．ｆ．となることが好ましく、０．５〜２％ｏ．ｗ．ｆ．となることがより好ましい。上記Ａ成分の付着量が前記下限未満であると、処理後のセルロース系繊維又はセルロース系繊維製品の洗濯耐久性が不充分となり、前記上限を超えると、処理後のセルロース系繊維又はセルロース系繊維製品にそれ以上の柔軟性向上が得られず不経済であったり、無洗剤洗濯機能が損なわれることがある。なお、不揮発分とは、１０５℃で３時間乾燥後の残分を示したものであり、％ｏ．ｗ．ｆ．は繊維の重量に対する割合を示したものである。 In the present invention, the treatment amount of the ester finish is such that the adhesion amount of the component A to the fiber product is 0.1 to 5% o. w. f. Preferably 0.5 to 2% o. w. f. More preferably. When the adhesion amount of the component A is less than the lower limit, the washing durability of the cellulose fiber or cellulose fiber product after treatment becomes insufficient, and when the upper limit is exceeded, the cellulose fiber or cellulose fiber after treatment. The product cannot be further improved in flexibility and is uneconomical or the detergent-free washing function may be impaired. The non-volatile content indicates the residue after drying at 105 ° C. for 3 hours. w. f. Indicates the ratio to the weight of the fiber.
本発明では、上記エステル系仕上剤と同時に、架橋剤としてカルボジイミド系架橋剤を用いる。上記カルボジイミド系架橋剤が架橋反応を起こすことで、セルロース系繊維又はセルロース系繊維製品に洗濯耐久性を付与して、柔軟性の低下を防止することが可能となる。 In the present invention, a carbodiimide-based crosslinking agent is used as a crosslinking agent simultaneously with the ester-based finishing agent. When the carbodiimide-based crosslinking agent causes a crosslinking reaction, it becomes possible to impart washing durability to the cellulosic fiber or the cellulosic fiber product and prevent a decrease in flexibility.
上記カルボジイミド系架橋剤とは、（−Ｎ＝Ｃ＝Ｎ−）で表されるカルボジイミド基を含む架橋剤をいう。上記カルボジイミド系架橋剤としては、１分子中にカルボジイミド基が複数含有するものが好ましい。さらに、作業性の観点と吸湿性の観点から、水溶性を有するものがより好適である。
上記カルボジイミド系架橋剤としては、ジイソシアネートを触媒存在下脱炭酸縮合反応することによって得られるポリカルボジイミド化合物等の分子中に少なくとも２個のカルボジイミド基を有する化合物が挙げられる。
市販品としては例えば、「カルボジライトＳＶ−０２」、「カルボジライトＶ−０２」、「カルボジライトＶ−０２−Ｌ１」、「カルボジライトＶ−０４」、「カルボジライトＥ−０１」、「カルボジライトＥ−０２」（何れも日清紡ケミカル社製）等が挙げられる。
これらのなかでも、処理浴での安定性の観点から「カルボジライトＥ−０１」、「カルボジライトＥ−０２」がより好適である。
The said carbodiimide type crosslinking agent means the crosslinking agent containing the carbodiimide group represented by (-N = C = N-). As said carbodiimide type crosslinking agent, what contains multiple carbodiimide groups in 1 molecule is preferable. Furthermore, from the viewpoint of workability and hygroscopicity, those having water solubility are more suitable.
Examples of the carbodiimide-based crosslinking agent include compounds having at least two carbodiimide groups in the molecule such as a polycarbodiimide compound obtained by decarboxylation condensation reaction of diisocyanate in the presence of a catalyst.
Examples of commercially available products include “Carbodilite SV-02”, “Carbodilite V-02”, “Carbodilite V-02-L1”, “Carbodilite V-04”, “Carbodilite E-01”, “Carbodilite E-02” ( All of them are manufactured by Nisshinbo Chemical Co., Ltd.).
Among these, “Carbodilite E-01” and “Carbodilite E-02” are more preferable from the viewpoint of stability in the treatment bath.
上記カルボジイミド系架橋剤の処理量は、セルロース系繊維又はセルロース系繊維製品への付着量が、不揮発分として０．０１〜０．５％ｏ．ｗ．ｆ．となることが好ましい。上記カルボジイミド系架橋剤の付着量が前記下限未満であると、処理後のセルロース系繊維又はセルロース系繊維製品の洗濯耐久性が不充分となり、前記上限を超えると、処理後のセルロース系繊維又はセルロース系繊維製品に、それ以上の洗濯耐久性が得られず、不経済であったり、柔軟性が損なわれたりすることがある。 The treatment amount of the carbodiimide crosslinking agent is such that the adhesion amount to the cellulosic fiber or the cellulosic fiber product is 0.01 to 0.5% o. w. f. It is preferable that When the adhesion amount of the carbodiimide-based crosslinking agent is less than the lower limit, the washing durability of the cellulose fiber or cellulose fiber product after treatment becomes insufficient, and when the upper limit is exceeded, the cellulose fiber or cellulose after treatment. The fiber-based textile product may not be able to obtain further washing durability, which may be uneconomical and may lose flexibility.
上記架橋工程においては、架橋反応を促進させるため、触媒を含有させてもよい。
また、上記架橋処理液には、必要に応じて、抗カビ剤、抗酸化剤、光安定剤、制電剤、導電剤、難燃剤、顔料等の添加剤を含有させてもよい。
In the crosslinking step, a catalyst may be contained in order to promote the crosslinking reaction.
Moreover, you may contain additives, such as an antifungal agent, an antioxidant, a light stabilizer, an antistatic agent, a electrically conductive agent, a flame retardant, and a pigment, in the said crosslinking process liquid as needed.
上記架橋工程における架橋処理液への浸漬時間、浸漬後のセルロース系繊維又はセルロース系繊維製品を絞る際の絞り率については、所望の性能に応じて適宜選択することができる。
また、上記架橋工程において、乾燥を行う際の温度の好ましい下限は８０℃、好ましい上限は１５０℃である。８０℃未満であると、上記架橋剤が充分に架橋せず、洗濯耐久性が低下することがある。１５０℃を超えると、薬剤の劣化が起こることがある。
The dipping time in the cross-linking treatment liquid in the cross-linking step and the drawing ratio when drawing the cellulosic fiber or cellulosic fiber product after dipping can be appropriately selected according to the desired performance.
In the crosslinking step, the preferable lower limit of the temperature for drying is 80 ° C., and the preferable upper limit is 150 ° C. When the temperature is less than 80 ° C., the crosslinking agent is not sufficiently crosslinked, and the washing durability may be lowered. When the temperature exceeds 150 ° C., deterioration of the drug may occur.
本発明のセルロース系繊維又はセルロース系繊維製品の処理方法によれば、セルロース系繊維又はセルロース系繊維製品に、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の効果が得られるという機能を付与することができる。また、洗剤を用いずに洗濯を行う場合には、洗剤を除去する操作（すすぎ操作）を省略することができることから、より短い時間で洗濯を行うことができる。このような洗濯時間の短縮により、水や電気等の資源を大幅に節約することができる。更に、本発明のセルロース系繊維又はセルロース系繊維製品の処理方法が施された繊維製品は、吸放湿性に極めて優れ、着衣の際の快適性に優れるという副次的な効果もある。
また、本発明によれば、所定のエステル系仕上剤とカルボジイミド系架橋剤とを併用して架橋工程を行うことで、優れた無洗剤洗濯機能を有しつつ、高い柔軟性と洗濯耐久性とを兼ね備えたセルロース系繊維又はセルロース系繊維製品が得られる。
According to the method for treating a cellulosic fiber or cellulosic fiber product of the present invention, even if the cellulosic fiber or cellulosic fiber product is washed without using a detergent, it is almost the same as when the detergent is used. A function of obtaining an equivalent effect can be provided. In addition, when washing is performed without using a detergent, an operation (rinsing operation) for removing the detergent can be omitted, so that the washing can be performed in a shorter time. By shortening the washing time, resources such as water and electricity can be saved greatly. Furthermore, the fiber product to which the processing method of the cellulosic fiber or the cellulosic fiber product of the present invention is applied is extremely excellent in moisture absorption and desorption and has a secondary effect that it is excellent in comfort in clothing.
In addition, according to the present invention, by performing a crosslinking step in combination with a predetermined ester finish and a carbodiimide crosslinking agent, while having an excellent detergent-free washing function, high flexibility and washing durability Cellulosic fibers or cellulosic fiber products having both of the above are obtained.
本発明のセルロース系繊維又はセルロース系繊維製品の処理方法を用いて得られるセルロース系繊維又はセルロース系繊維製品もまた、本発明の１つである。 The cellulosic fiber or cellulosic fiber product obtained using the method for treating cellulosic fiber or cellulosic fiber product of the present invention is also one aspect of the present invention.
本発明のセルロース系繊維又はセルロース系繊維製品は、更に消臭剤を含有してもよい。親水化処理としてカルボキシル基が導入された場合には高い消臭効果があるが、消臭剤を配合することにより、更に高い消臭効果を得ることができる。 The cellulosic fiber or cellulosic fiber product of the present invention may further contain a deodorant. When a carboxyl group is introduced as a hydrophilic treatment, there is a high deodorizing effect, but a higher deodorizing effect can be obtained by adding a deodorant.
上記消臭剤としては特に限定されず、例えば、酸化亜鉛系、酸化チタン系、銀系、ゼオライト系、植物抽出物系等の従来公知のものを用いることができる。なかでも、繊維への加工が容易であることから酸化亜鉛系の消臭剤を用いることが好ましい。 The deodorizer is not particularly limited, and conventionally known deodorizers such as zinc oxide, titanium oxide, silver, zeolite, and plant extract can be used. Among them, it is preferable to use a zinc oxide-based deodorant because it can be easily processed into fibers.
本発明によれば、セルロース系繊維又はセルロース系繊維製品に、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の洗浄効果が得られるという機能を付与することができ、かつ、高い柔軟性及び洗濯耐久性を実現できるセルロース系繊維又はセルロース系繊維製品の処理方法、並びに、セルロース系繊維又はセルロース系繊維製品を提供することができる。 According to the present invention, the cellulose fiber or the cellulosic fiber product is provided with a function that even when washing is performed without using a detergent, almost the same cleaning effect as that obtained when using the detergent can be obtained. In addition, it is possible to provide a cellulosic fiber or a cellulosic fiber product processing method, and a cellulosic fiber or cellulosic fiber product that can achieve high flexibility and washing durability.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
元生地として綿ニット（綿１００％ ４０／１（４０番手単糸）フライスニット）を使用し、モノクロル酢酸ナトリウム（２００ｇ／Ｌ）及び水酸化ナトリウム（７０ｇ／Ｌ）を含有する処理液中に１：２０の浴比で浸漬し、パッダーで絞った後、２５℃、２４時間放置して反応させた。水洗して未反応物を除去し、乾燥させることにより親水化綿ニットを得た。
得られた親水化綿ニットについてカルボキシメチル化度を測定したところ２．６７であり、また、吸湿率を測定したところ８．９％であった。
Example 1
Cotton knit (100% cotton 40/1 (40th single yarn) milling knit) is used as the base fabric, and 1 in a treatment liquid containing sodium monochloroacetate (200 g / L) and sodium hydroxide (70 g / L). : It was immersed in a bath ratio of 20, and after squeezing with a padder, it was left to react at 25 ° C. for 24 hours. Unreacted substances were removed by washing with water and dried to obtain a hydrophilized cotton knit.
It was 2.67 when the degree of carboxymethylation was measured about the obtained hydrophilic cotton knit, and it was 8.9% when the moisture absorption rate was measured.
酸化変性ポリエチレンであるハイワックス１１０５Ａ（三井化学社製、酸価６０）１８７ｇにセチルアルコールのエチレンオキサイド１５モル付加物（ＨＬＢ １４．６）１６８ｇおよびパラトルエンスルホン酸０．６ｇを仕込み、窒素気流下で昇温し、１８０〜２２０℃で４時間脱水反応して反応率８３％の生成物（Ｉ）３４２．８ｇを得た。 188 g of high wax 1105A (Mitsui Chemicals, acid value 60), which is an oxidation-modified polyethylene, is charged with 168 g of cetyl alcohol ethylene oxide 15 mol adduct (HLB 14.6) and 0.6 g of paratoluenesulfonic acid under a nitrogen stream. The product was dehydrated at 180 to 220 ° C. for 4 hours to obtain 342.8 g of product (I) having a reaction rate of 83%.
テレフタル酸ジメチル７７．６ｇ（０．４モル）、５−スルホイソフタル酸ジメチルエステルナトリウム塩２９．６ｇ（０．１モル）、ポリエチレングリコール（ＰＥＧ４０００、三洋化成工業（株）製、商品名、平均分子量：約３１００）２７９ｇ（０．０９モル）、モノエチレングリコール６８．２ｇ（１．１モル）及び三酸化アンチモン０．１ｇ、酢酸亜鉛０．１ｇを仕込み、窒素気流下で昇温し、１３０〜１８０℃まで２時間かけてゆっくり昇温しエステル交換反応を行った。さらに１８０℃〜２５０℃まで２時間かけてゆっくり昇温後、窒素気流を停止し、２５０〜２６０℃、約５ｍｍＨｇの減圧下で２時間反応したのち、さらに２６０℃、約２ｍｍＨｇの減圧下で３０分間反応し、水溶性ポリエステル樹脂（ＩＩ）４００ｇを得た。この水溶性ポリエステル樹脂（ＩＩ）の重量平均分子量は、ゲルパーミエーションクロマトグラフィー［東ソー社製高速ＧＰＣ、ＨＬＣ−８１２０型、測定標準物質：ポリエチレングリコール］で測定の結果、約１４０００であった。 77.6 g (0.4 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of dimethyl 5-sulfoisophthalic acid sodium salt, polyethylene glycol (PEG 4000, manufactured by Sanyo Chemical Industries, Ltd., trade name, average molecular weight) : About 3100) 279 g (0.09 mol), monoethylene glycol 68.2 g (1.1 mol), antimony trioxide 0.1 g, and zinc acetate 0.1 g were charged, and the temperature was increased under a nitrogen stream. The temperature was slowly raised to 180 ° C. over 2 hours to conduct a transesterification reaction. Further, after slowly raising the temperature from 180 ° C. to 250 ° C. over 2 hours, the nitrogen stream was stopped, and after reacting at 250 to 260 ° C. under reduced pressure of about 5 mmHg for 2 hours, further under reduced pressure of 260 ° C. and about 2 mmHg. Reaction was performed for minutes, and 400 g of water-soluble polyester resin (II) was obtained. The weight average molecular weight of the water-soluble polyester resin (II) was about 14,000 as a result of measurement by gel permeation chromatography [High-speed GPC manufactured by Tosoh Corporation, HLC-8120 type, measurement standard substance: polyethylene glycol].
生成物（Ｉ）１００ｇを、水溶性ポリエステル樹脂（ＩＩ）２０ｇとともに８５〜９０℃にて融解し、８５〜９０℃の熱水を２８０ｇ仕込んで乳化し、合計４００ｇのエステル系仕上剤を得た。このエステル系仕上剤に含まれるＡ成分は、不揮発分として２５質量％である。 100 g of product (I) was melted at 85 to 90 ° C. together with 20 g of water-soluble polyester resin (II), and 280 g of hot water at 85 to 90 ° C. was added and emulsified to obtain a total of 400 g of ester finish. . The component A contained in the ester finish is 25% by mass as a nonvolatile content.
次いで、得られたエステル系仕上剤を３質量％、カルボジイミド系架橋剤としてポリカルボジイミド系架橋剤（カルボジライトＥ−０１、日清紡ケミカル株式会社製、不揮発分は３９．７質量％）を０．４質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、３質量％×２５質量％×１００％＝０．７５％ｏ．ｗ．ｆ．となり、カルボジイミド系架橋剤の付着量（不揮発分として）が、０．４質量％×３９．７質量％×１００％＝０．１６％ｏ．ｗ．ｆ．となる条件である。 Next, 3% by mass of the obtained ester-based finishing agent, and 0.4% by mass of a polycarbodiimide-based crosslinking agent (carbodilite E-01, manufactured by Nisshinbo Chemical Co., Ltd., non-volatile content is 39.7% by mass) as a carbodiimide-based crosslinking agent. The obtained hydrophilized cotton knit was immersed in a treatment solution containing 1%, and then squeezed with a padder at a squeezing rate of 100%. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the component A (as non-volatile content) is 3% by mass × 25% by mass × 100% = 0.75% o. w. f. The adhesion amount of the carbodiimide-based crosslinking agent (as a non-volatile content) is 0.4 mass% × 39.7 mass% × 100% = 0.16% o. w. f. This is a condition.
（実施例２）
実施例１と同様の方法で親水化綿ニットを得た後、実施例１で得られたエステル系仕上剤を５質量％、カルボジイミド系架橋剤としてポリカルボジイミド系架橋剤（カルボジライトＥ−０１、日清紡ケミカル株式会社製）を０．４質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、５質量％×２５質量％×１００％＝１．２５％ｏ．ｗ．ｆ．となり、カルボジイミド系架橋剤の付着量（不揮発分として）が、０．４質量％×３９．７質量％×１００％＝０．１６％ｏ．ｗ．ｆ．となる条件である。
(Example 2)
After obtaining a hydrophilized cotton knit by the same method as in Example 1, 5% by mass of the ester finish obtained in Example 1 and a polycarbodiimide-based crosslinking agent (Carbodilite E-01, Nisshinbo Co., Ltd.) as a carbodiimide-based crosslinking agent. The obtained hydrophilized cotton knit was immersed in a treatment solution containing 0.4% by mass of Chemical Co., Ltd., and then squeezed at a squeezing rate of 100% using a padder. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the A component (as non-volatile content) is 5% by mass × 25% by mass × 100% = 1.25% o.d. w. f. The adhesion amount of the carbodiimide-based crosslinking agent (as a non-volatile content) is 0.4 mass% × 39.7 mass% × 100% = 0.16% o. w. f. This is a condition.
（実施例３）
実施例１と同様の方法で親水化綿ニットを得た後、実施例１で得られたエステル系仕上剤を７質量％、カルボジイミド系架橋剤としてポリカルボジイミド系架橋剤（カルボジライトＥ−０１、日清紡ケミカル株式会社製）を０．４質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、７質量％×２５質量％×１００％＝１．７５％ｏ．ｗ．ｆ．となり、カルボジイミド系架橋剤の付着量（不揮発分として）が、０．４質量％×３９．７質量％×１００％＝０．１６％ｏ．ｗ．ｆ．となる条件である。
(Example 3)
After obtaining a hydrophilized cotton knit in the same manner as in Example 1, 7% by mass of the ester-based finish obtained in Example 1, and a polycarbodiimide-based crosslinking agent (Carbodilite E-01, Nisshinbo Co., Ltd.) as a carbodiimide-based crosslinking agent. The obtained hydrophilized cotton knit was immersed in a treatment solution containing 0.4% by mass of Chemical Co., Ltd., and then squeezed at a squeezing rate of 100% using a padder. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the A component (as non-volatile content) is 7% by mass × 25% by mass × 100% = 1.75% o.d. w. f. The adhesion amount of the carbodiimide-based crosslinking agent (as a non-volatile content) is 0.4 mass% × 39.7 mass% × 100% = 0.16% o. w. f. This is a condition.
（比較例１）
実施例１と同様の方法で親水化綿ニットを得た後、実施例１で得られたエステル系仕上剤を３質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、３質量％×２５質量％×１００％＝０．７５％ｏ．ｗ．ｆ．となる条件である。
(Comparative Example 1)
After obtaining the hydrophilized cotton knit by the same method as in Example 1, and then immersing the obtained hydrophilized cotton knit in the treatment liquid containing 3% by mass of the ester-based finish obtained in Example 1 Using a padder, the squeezing rate was 100%. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the component A (as non-volatile content) is 3% by mass × 25% by mass × 100% = 0.75% o. w. f. This is a condition.
（比較例２）
実施例１と同様の方法で親水化綿ニットを得た後、実施例１で得られたエステル系仕上剤を５質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、５質量％×２５質量％×１００％＝１．２５％ｏ．ｗ．ｆ．となる条件である。
(Comparative Example 2)
After obtaining a hydrophilized cotton knit by the same method as in Example 1, and then immersing the resulting hydrophilized cotton knit in a treatment liquid containing 5% by mass of the ester-based finish obtained in Example 1 Using a padder, the squeezing rate was 100%. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the A component (as non-volatile content) is 5% by mass × 25% by mass × 100% = 1.25% o.d. w. f. This is a condition.
（比較例３）
実施例１と同様の方法で親水化綿ニットを得た後、実施例１で得られたエステル系仕上剤を７質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥して、処理布を得た。これは、Ａ成分の付着量（不揮発分として）が、７質量％×２５質量％×１００％＝１．７５％ｏ．ｗ．ｆ．となる条件である。
(Comparative Example 3)
After obtaining a hydrophilized cotton knit by the same method as in Example 1, and then immersing the resulting hydrophilized cotton knit in a treatment solution containing 7% by mass of the ester-based finish obtained in Example 1 Using a padder, the squeezing rate was 100%. Then, it dried at 120 degreeC for 3 minute (s), and obtained the process cloth. This is because the adhesion amount of the A component (as non-volatile content) is 7% by mass × 25% by mass × 100% = 1.75% o.d. w. f. This is a condition.
（比較例４）
実施例１と同様の方法で得られた親水化綿ニットを処理布とした。
(Comparative Example 4)
A hydrophilized cotton knit obtained by the same method as in Example 1 was used as a treated fabric.
（比較例５）
実施例１と同様の方法で親水化綿ニットを得た後、シリコーン系柔軟剤（ソフテックスＡ−１５００、北広ケミカル社製）を２質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥することにより、処理布を得た。
(Comparative Example 5)
After obtaining a hydrophilized cotton knit by the same method as in Example 1, the hydrophilized cotton knit obtained in a treatment liquid containing 2% by mass of a silicone softener (Softex A-1500, manufactured by Kitahiro Chemical Co., Ltd.) Then, the film was squeezed with a padder at a squeezing rate of 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
（比較例６）
実施例１と同様の方法で親水化綿ニットを得た後、耐久シリコーン系柔軟剤（ＴＫシリコンＥＰ−３０１Ｅ、高松油脂社製）を３質量％、カルボジイミド系架橋剤としてポリカルボジイミド系架橋剤（カルボジライトＥ−０１、日清紡ケミカル株式会社製）を０．４質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥することにより、処理布を得た。
(Comparative Example 6)
After obtaining a hydrophilized cotton knit in the same manner as in Example 1, 3% by weight of a durable silicone softener (TK Silicon EP-301E, manufactured by Takamatsu Yushi Co., Ltd.), a polycarbodiimide crosslinker (carbodiimide crosslinker ( The obtained hydrophilized cotton knit was immersed in a treatment solution containing 0.4% by mass of Carbodilite E-01 (manufactured by Nisshinbo Chemical Co., Ltd.), and then squeezed at a drawing rate of 100% using a padder. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
（比較例７）
実施例１と同様の方法で親水化綿ニットを得た後、耐久カチオン系柔軟剤（Ｓｏｌｕｓｏｆｔ １２００、クラリアント社製）を３質量％含有する処理液に、得られた親水化綿ニットを浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥することにより、処理布を得た。
(Comparative Example 7)
After obtaining a hydrophilized cotton knit by the same method as in Example 1, the obtained hydrophilized cotton knit was immersed in a treatment solution containing 3% by mass of a durable cationic softener (Solussoft 1200, manufactured by Clariant). After that, it was squeezed at a squeezing rate of 100% using a padder. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
（比較例８）
アニオン系柔軟剤（サンソフナーＭＡＸ−９０Ａ、三洋化成社製）を１質量％含有する処理液に、綿ニット（綿１００％ ４０／１（４０番手単糸）フライスニット）を浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥することにより、処理布を得た。
(Comparative Example 8)
After immersing a cotton knit (cotton 100% 40/1 (40th single yarn) milling knit) in a treatment liquid containing 1% by mass of an anionic softener (Sansofner MAX-90A, manufactured by Sanyo Chemical Co., Ltd.) Using a padder, the squeezing rate was 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
（比較例９）
耐久シリコーン系柔軟剤（ＴＫシリコンＥＰ−３０１Ｅ、高松油脂社製）を３質量％含有する処理液に、綿ニット（綿１００％ ４０／１（４０番手単糸）フライスニット）を浸漬させた後、パッダ−を用いて絞り率１００％で絞った。その後、１２０℃で３分間乾燥することにより、処理布を得た。
(Comparative Example 9)
After dipping a cotton knit (100% cotton 40/1 (40th single yarn) milling knit) in a treatment liquid containing 3% by mass of a durable silicone softener (TK silicon EP-301E, manufactured by Takamatsu Yushi Co., Ltd.) Using a padder, the squeezing rate was 100%. Then, the process cloth was obtained by drying at 120 degreeC for 3 minute (s).
（評価）
実施例及び比較例で得られた処理布について以下の方法により、評価を行った。結果を表１に示した。
(Evaluation)
The treatment cloths obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 1.
（１）オレイン酸洗浄性試験
処理布にオレイン酸１０％ｏ．ｗ．ｆ．、ゼラチン２．５％ｏ．ｗ．ｆ．を付着させた後、通常の家庭用洗濯機（シャープ社製、ＥＳ−Ｓ４Ａ）を用いて、水のみの場合と、洗剤（花王社製、アタック）を０．６７ｇ／Ｌの濃度となるように加えた場合とで洗濯を行った。
洗濯後の各試験布を天日乾燥した後、試験布上に残存するオレイン酸をメタノールで抽出し、ガスクロマトグラフ（島津製作所社製、ＧＣ−１７Ａ）によりオレイン酸の残留量を測定し、オレイン酸残留率（％）を求めた。
(1) Oleic acid detergency test cloth treated with 10% oleic acid o. w. f. Gelatin 2.5% o. w. f. After adhering, using a normal household washing machine (manufactured by Sharp, ES-S4A), the concentration of 0.67 g / L of water only and detergent (made by Kao, Attack) Laundry was performed when added to the case.
After drying each test cloth after washing in the sun, the oleic acid remaining on the test cloth was extracted with methanol, and the residual amount of oleic acid was measured with a gas chromatograph (manufactured by Shimadzu Corporation, GC-17A). The acid residual ratio (%) was determined.
（２）剛軟度
ＪＩＳ Ｌ １０１８に準拠した方法で剛軟度を測定した。まず、得られた処理布について、試料幅２００ｍｍ、試料長２００ｍｍの試料片を３枚準備し、風合メーター（大栄科学精器製作所社製）を用い、１０ｍｍ幅のスリット上に試料片を置いて、ア−ムが試料をスリット間に押し込む時に、最高何ｃＮの力が必要かを試料の表裏について、縦横方向、４個所で測定し、その合計値を求めた。試料片３枚の平均値を剛軟度とした。なお、剛軟度は、処理直後の状態（Ｌ０）、洗濯を３０回行った後（Ｌ３０）、洗濯を５０回行った後（Ｌ５０）、洗濯を１００回行った後（Ｌ１００）について測定した。また、得られた剛軟度について以下の基準で評価した。
(2) Bending softness Bending softness was measured by a method based on JIS L 1018. First, with respect to the obtained treated cloth, three sample pieces having a sample width of 200 mm and a sample length of 200 mm were prepared, and a sample piece was placed on a 10 mm wide slit using a texture meter (manufactured by Daiei Scientific Instruments). Then, when the arm pushed the sample between the slits, the maximum cN force required was measured at four points in the vertical and horizontal directions on the front and back of the sample, and the total value was obtained. The average value of three sample pieces was defined as the bending resistance. The bending resistance was measured for the state immediately after the treatment (L0), after washing 30 times (L30), after washing 50 times (L50), and after washing 100 times (L100). . Further, the obtained bending resistance was evaluated according to the following criteria.
◎ 剛軟度が４０ｃＮ未満
○ 剛軟度が４０〜６０ｃＮ
× 剛軟度が６０ｃＮを超える
◎ Bending softness is less than 40 cN ○ Bending softness is 40-60 cN
× The bending resistance exceeds 60 cN
（３）繰り返し洗濯試験
処理布を、オレイン酸４０．６質量％、トリオレイン２２．４質量％、コレステロールオレート１７．５質量％、流動パラフィン３．６質量％、コレステロール２．３質量％及びゼラチン１０．０質量％を主成分とする人工汗に浴比が１：３０となるように浸漬した後、絞り率１３０％で絞り、１０５℃、３０分間乾燥した。
通常の家庭用洗濯機（シャープ社製、ＥＳ−Ｓ４Ａ）を用いて、水のみの場合と、洗剤（花王社製、アタック）を０．６７ｇ／Ｌの濃度となるように加えた場合とで洗濯を行った。
洗濯後の各処理布を天日乾燥した。この操作を繰り返し３回行い、それぞれの回について処理布の白度の変化を調べた。白度の測定には測色機（マクベス社製、ホワイトアイ３０００）を用いた。また、洗濯前の白度と３回洗濯した後の白度との差（低下白度）を算出した。また、得られた低下白度について以下の基準で評価した。
(3) Repeated laundering test treatment cloth is made from oleic acid 40.6% by mass, triolein 22.4% by mass, cholesterol oleate 17.5% by mass, liquid paraffin 3.6% by mass, cholesterol 2.3% by mass and gelatin. The film was immersed in artificial sweat containing 10.0% by mass as a main component so that the bath ratio would be 1:30, then drawn with a drawing rate of 130% and dried at 105 ° C. for 30 minutes.
Using a normal household washing machine (manufactured by Sharp Corporation, ES-S4A) with water only and when adding detergent (Kao Corporation, attack) to a concentration of 0.67 g / L Laundry was done.
Each treated cloth after washing was dried in the sun. This operation was repeated three times, and the change in the whiteness of the treated cloth was examined each time. A colorimeter (manufactured by Macbeth, White Eye 3000) was used to measure whiteness. Moreover, the difference (decrease whiteness) between the whiteness before washing and the whiteness after washing three times was calculated. Further, the obtained reduced whiteness was evaluated according to the following criteria.
◎ 低下白度が１０ポイント未満
○ 低下白度が１０〜１２．５ポイント
△ 低下白度が１２．５〜１５．０ポイント
× 低下白度が１５．０を超える
◎ Decreasing whiteness is less than 10 points ○ Decreasing whiteness is 10 to 12.5 points △ Decreasing whiteness is 12.5 to 15.0 points x Decreasing whiteness is more than 15.0
（４）消臭効果試験
５００ｍＬ（実容積６２５ｍＬ）の三角フラスコにマグネチィックスターラーバーを入れ、４ｃｍ×５ｃｍに切り取った試験布に糸をつけ、糸の端を三角フラスコの外側にセロハンテープで止めることにより、試験布を三角フラスコ内に吊り下げた。次いで、アンモニア消臭の場合には２％アンモニア溶液を、酢酸消臭の場合には３％酢酸溶液をそれぞれマイクロピペットで５μＬ、三角フラスコの内側壁に垂らした。２重のラップで覆ったシリコン栓ですばやく三角フラスコを密栓し、更にそのラップを３重にした輪ゴムで密栓した。その後、マグネチィックスターラーで攪拌しながら２０℃、１２０分間放置した。
１２０分放置した後、ラップがはがれないようにしてシリコン栓を抜き、測定用シリコン栓付検知管（ガステック社製、Ｎｏ．３Ｌａ／アンモニア用：ガステック社製、Ｎｏ．８１／酢酸用）を用いて三角フラスコ内のガス濃度を測定した。
同様の試験を、試験布を三角フラスコ内に吊り下げない状態で行い、これをブランク測定値とした。下記式を用いて消臭率（％）を求めた。また、得られた消臭率について以下の基準で評価した。
(4) Deodorizing effect test Put a magnetic stirrer bar in a 500 mL Erlenmeyer flask (actual volume: 625 mL), attach a thread to a test cloth cut to 4 cm x 5 cm, and attach the end of the thread to the outside of the Erlenmeyer flask with cellophane tape. By stopping, the test cloth was suspended in the Erlenmeyer flask. Then, 2% ammonia solution for ammonia deodorization and 3 μl acetic acid solution for acetic acid deodorization were dropped on the inner wall of the Erlenmeyer flask by 5 μL with a micropipette. The Erlenmeyer flask was quickly sealed with a silicon stopper covered with a double wrap, and further sealed with a rubber band made of triple wrap. Then, it was left to stand at 20 ° C. for 120 minutes while stirring with a magnetic stirrer.
After leaving for 120 minutes, the silicon stopper is pulled out so that the wrap is not peeled off, and a measuring tube with a silicon stopper for measurement (Gastech, No.3La / ammonia: Gastech, No.81 / Acetic acid) Was used to measure the gas concentration in the Erlenmeyer flask.
A similar test was performed without suspending the test cloth in the Erlenmeyer flask, and this was used as a blank measurement value. The deodorization rate (%) was calculated | required using the following formula. The obtained deodorization rate was evaluated according to the following criteria.
◎ 消臭率が９０〜１００％
○ 消臭率が８０〜９０％
△ 消臭率が７０〜８０％
× 消臭率が７０％未満
◎ Deodorization rate is 90-100%
○ Deodorization rate is 80-90%
△ Deodorization rate is 70-80%
× Deodorization rate is less than 70%
消臭率（％）＝｛（ブランク測定値−試験布測定値）／ブランク測定値｝×１００ Deodorization rate (%) = {(blank measurement value−test cloth measurement value) / blank measurement value} × 100
表１に示すように、比較例５では、洗濯耐久性（Ｌ１００の剛軟度）が不良であるが、繰り返し洗濯試験後の白度低下が少なく無洗剤洗濯機能を維持している現象が見られる。これは、耐久性の無い柔軟剤は、セルロース系繊維又はセルロース系繊維製品で問題となる油性の汚れと親和性があまり高くないため、更には汚れが付着した柔軟剤自体が少ない洗濯回数で脱落してしまい、少ない洗濯回数で比較例４の柔軟剤未処理と同じような状態になったことによるものと考えられる。
比較例６、比較例７、比較例９では、洗濯耐久性（Ｌ１００の剛軟度）が良好であるが、繰り返し洗濯試験後の白度低下が大きく無洗剤洗濯機能が劣る現象が見られる。これは従来の耐久柔軟剤はセルロース系繊維又はセルロース系繊維製品で問題となる油性の汚れと親和性が高く、汚れが付着した柔軟剤自体が洗濯により脱落しにくいために起こるためであるものと考えられる。
このように従来の柔軟剤を用いた場合は、洗濯耐久性と無洗剤洗濯機能は相反する傾向にあり両立することは困難であった。これに対して、実施例では、従来の柔軟剤を用いた場合以上の洗濯耐久性を実現しつつ、無洗剤洗濯機能も維持しており、洗濯耐久性と無洗剤洗濯機能という相反する機能を両立することが可能となった。
As shown in Table 1, in Comparative Example 5, the washing durability (the bending resistance of L100) was poor, but there was a phenomenon that the whiteness decrease after repeated washing tests was small and the detergent-free washing function was maintained. It is done. This is because non-durable softeners do not have a high affinity with oily soils that are a problem in cellulosic fibers or cellulosic fiber products. Therefore, it is considered that the same state as that of the softener untreated in Comparative Example 4 was obtained with a small number of washings.
In Comparative Example 6, Comparative Example 7, and Comparative Example 9, although washing durability (L100 bending resistance) is good, a phenomenon in which the whiteness decrease after repeated washing tests is large and the detergent-free washing function is inferior is observed. This is because conventional durable softeners have a high affinity with oil-based stains that are a problem in cellulosic fibers or cellulosic fiber products, and the softeners to which the stains are attached are not easily removed by washing. Conceivable.
Thus, when the conventional softening agent was used, washing durability and the detergent-free washing function tend to contradict each other and it was difficult to achieve both. On the other hand, in the examples, while maintaining the washing durability more than when using the conventional softener, the detergent-free washing function is maintained, and the contradictory functions of the washing durability and the no-detergent washing function are provided. It became possible to achieve both.
本発明によれば、セルロース系繊維又はセルロース系繊維製品に、洗剤を用いずに洗濯を行った場合であっても、洗剤を用いた場合とほぼ同等の洗浄効果が得られるという機能を付与することができ、かつ、高い柔軟性及び洗濯耐久性を実現できるセルロース系繊維又はセルロース系繊維製品の処理方法、並びに、セルロース系繊維又はセルロース系繊維製品を提供できる。 According to the present invention, the cellulose fiber or the cellulosic fiber product is provided with a function that even when washing is performed without using a detergent, almost the same cleaning effect as that obtained when using the detergent can be obtained. It is possible to provide a cellulosic fiber or a cellulosic fiber product treatment method and a cellulosic fiber or cellulosic fiber product that can achieve high flexibility and washing durability.
Claims (10)
親水化処理を施したセルロース系繊維又はセルロース系繊維製品を、エステル系仕上剤と、カルボジイミド系架橋剤とを用いて架橋させる工程とを有し、
前記エステル系仕上剤は、酸化変性若しくは酸変性ポリエチレンと、脂肪族アルコール又は脂肪族アミンのエチレンオキシド及び／若しくはプロピレンオキシド付加物とのエステル化反応によって生成されたエステル系化合物を含有する
ことを特徴とするセルロース系繊維又はセルロース系繊維製品の処理方法。 A step of subjecting the cellulosic fiber or cellulosic fiber product to a hydrophilic treatment, and
A step of cross-linking a cellulose fiber or a cellulose fiber product subjected to a hydrophilization treatment using an ester finishing agent and a carbodiimide cross-linking agent,
The ester finishing agent contains an ester compound produced by an esterification reaction of an oxidatively or acid-modified polyethylene with an aliphatic alcohol or an ethylene amine and / or propylene oxide adduct of an aliphatic amine. A method for treating cellulosic fibers or cellulosic fiber products.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010050742A JP5442497B2 (en) | 2010-03-08 | 2010-03-08 | Method for treating cellulosic fiber or cellulosic fiber product |
| PCT/JP2011/055255 WO2011111658A1 (en) | 2010-03-08 | 2011-03-07 | Cellulosic fiber or cellulosic fiber product treatment method |
| CN201180012950.0A CN102791922B (en) | 2010-03-08 | 2011-03-07 | Cellulosic fiber or cellulosic fiber product treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010050742A JP5442497B2 (en) | 2010-03-08 | 2010-03-08 | Method for treating cellulosic fiber or cellulosic fiber product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011184823A JP2011184823A (en) | 2011-09-22 |
| JP5442497B2 true JP5442497B2 (en) | 2014-03-12 |
Family
ID=44563460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010050742A Active JP5442497B2 (en) | 2010-03-08 | 2010-03-08 | Method for treating cellulosic fiber or cellulosic fiber product |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5442497B2 (en) |
| CN (1) | CN102791922B (en) |
| WO (1) | WO2011111658A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6073151B2 (en) * | 2013-02-20 | 2017-02-01 | 日華化学株式会社 | Method for producing functional fiber product and ultraviolet absorbent for fiber used therefor |
| JP6450237B2 (en) * | 2014-05-02 | 2019-01-09 | 出光興産株式会社 | Cross-linked body, cross-linking agent composition, fibrous cross-linked body, manufacturing method of fibrous cross-linked body, cell culture bed, cell culturing method using cell culture bed, and manufacturing method of cell sheet for transplantation using cell culture bed |
| KR101837373B1 (en) * | 2017-08-04 | 2018-03-13 | 박명복 | Functional Fashion Wig |
| KR102085297B1 (en) * | 2017-08-25 | 2020-03-05 | (주)에너지플래닛 | Carbon composition for lead-carbon hybrid batteries, coated electrode with carbon composition for lead-carbon hybrid batteries, lead-carbon hybrid batteries with the coated electrode. |
| WO2019119296A1 (en) * | 2017-12-20 | 2019-06-27 | 日华化学株式会社 | Method for manufacturing functional fiber product, and water-absorbing quick-dry processing agent |
| TWI798567B (en) * | 2020-07-13 | 2023-04-11 | 財團法人紡織產業綜合研究所 | Functional resin material, fabricating method thereof, and moisture-sensed contracting fabric |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0811868B2 (en) * | 1988-12-28 | 1996-02-07 | 日華化学株式会社 | Flexible smoothing agent |
| KR101144685B1 (en) * | 2003-07-14 | 2012-05-25 | 군제 가부시키가이샤 | Method of providing non-detergent washing function and fiber product washable without using detergent |
| JP4630955B2 (en) * | 2004-05-19 | 2011-02-09 | 大原パラヂウム化学株式会社 | Processing method of fiber fabric treated with hydrophilic / oil repellent finishing agent |
| JP4761760B2 (en) * | 2004-11-29 | 2011-08-31 | 日華化学株式会社 | Manufacturing method of durable antifouling fiber products |
| JP2006152508A (en) * | 2004-12-01 | 2006-06-15 | Nisshinbo Ind Inc | Stain-proofing fiber structure and its processing method |
| JP2006336145A (en) * | 2005-06-01 | 2006-12-14 | Gunze Ltd | Method for producing polyester fiber with function for improving cleanability of dirt |
| JP2010236142A (en) * | 2009-03-31 | 2010-10-21 | Gunze Ltd | Method for producing dirt cleanability improving function-imparted elastic fiber |
-
2010
- 2010-03-08 JP JP2010050742A patent/JP5442497B2/en active Active
-
2011
- 2011-03-07 WO PCT/JP2011/055255 patent/WO2011111658A1/en active Application Filing
- 2011-03-07 CN CN201180012950.0A patent/CN102791922B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102791922B (en) | 2014-03-19 |
| JP2011184823A (en) | 2011-09-22 |
| WO2011111658A1 (en) | 2011-09-15 |
| CN102791922A (en) | 2012-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5442497B2 (en) | Method for treating cellulosic fiber or cellulosic fiber product | |
| CN1222601C (en) | Fabric care composition | |
| CN101545208A (en) | Antimicrobial and odor adsorbing textile | |
| Prorokova et al. | Chemical method of fibrous materials surface activation on the basis of polyethylene terephthalate (PET) | |
| JP2015089975A (en) | Deodorant and processing method of the deodorant to fabric or yarn | |
| EP0328287A2 (en) | A method of altering the surface of a solid synthetic polymer | |
| JP3385399B2 (en) | Method for imparting yellowing suppression function to wear of cellulosic fiber or cellulosic fiber product | |
| JP4861700B2 (en) | Detergent-free washing function | |
| US20020120988A1 (en) | Abrasion-and wrinkle-resistant finish for textiles | |
| JP3426432B2 (en) | Fiber softening agent and method for softening fibers and fiber products | |
| JPH11247067A (en) | Process for hydrophilizing polyester-based synthetic fiber product | |
| EP2089570A1 (en) | Benefit compositions and methods | |
| JP3900705B2 (en) | Cellulosic fiber-containing fabric | |
| JP3991476B2 (en) | Cellulosic fiber-containing fabric | |
| JP2021011661A (en) | Anti-static fiber product and method for producing anti-static fiber product | |
| JP4554550B2 (en) | Textile treatment composition | |
| JP2006336145A (en) | Method for producing polyester fiber with function for improving cleanability of dirt | |
| JP6725103B2 (en) | Finishing agent composition for clothing | |
| JP2652691B2 (en) | Durable soft finish | |
| JP2021107598A (en) | Durability and antistaticity agent for synthetic fiber, durable and antistatic fiber product, and method for producing durable and antistatic fiber product | |
| JPH04100973A (en) | Soft-finishing agent | |
| JPH09158049A (en) | Antielectric, sweat-absorbing and antifouling fabric improved in durability to washing | |
| JP2000129576A (en) | Cellulosic fiber-containing cloth | |
| JPH05163678A (en) | Fiber-finishing agent composition | |
| JPH02154073A (en) | Treating agent for synthetic fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121219 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131218 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5442497 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |