JP6391552B2 - Functional fiber product and manufacturing method thereof - Google Patents
Functional fiber product and manufacturing method thereof Download PDFInfo
- Publication number
- JP6391552B2 JP6391552B2 JP2015225066A JP2015225066A JP6391552B2 JP 6391552 B2 JP6391552 B2 JP 6391552B2 JP 2015225066 A JP2015225066 A JP 2015225066A JP 2015225066 A JP2015225066 A JP 2015225066A JP 6391552 B2 JP6391552 B2 JP 6391552B2
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- JP
- Japan
- Prior art keywords
- meth
- poly
- acrylic acid
- acid polymer
- maleic anhydride
- 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.)
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- 239000000835 fiber Substances 0.000 title claims description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims description 55
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 39
- 239000004753 textile Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 239000004744 fabric Substances 0.000 claims description 27
- 229920002125 Sokalan® Polymers 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 230000001877 deodorizing effect Effects 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000004711 α-olefin Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004581 coalescence Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 82
- 238000012545 processing Methods 0.000 description 38
- -1 acryl Chemical group 0.000 description 20
- 235000019645 odor Nutrition 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 238000009940 knitting Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 15
- 239000004584 polyacrylic acid Substances 0.000 description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002781 deodorant agent Substances 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 6
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 6
- 238000004332 deodorization Methods 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methyl-1-pentene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- CWNNYYIZGGDCHS-UHFFFAOYSA-N 2-methylideneglutaric acid Chemical compound OC(=O)CCC(=C)C(O)=O CWNNYYIZGGDCHS-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- RYKZRKKEYSRDNF-UHFFFAOYSA-N 3-methylidenepentane Chemical compound CCC(=C)CC RYKZRKKEYSRDNF-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- WHMVGOHVHHTUIU-UHFFFAOYSA-N N-ethenyl-3-methyl-2-methylidenebutanamide Chemical class C(=C)NC(C(=C)C(C)C)=O WHMVGOHVHHTUIU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N butyl vinyl ether Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、消臭性、吸湿性等の効果を持つ樹脂皮膜を有する機能性繊維製品及びその製造方法に関するものである。 The present invention relates to a functional fiber product having a resin film having effects such as deodorizing properties and hygroscopicity, and a method for producing the same.
衣料用素材、生活資材、衛生材料には使用時の快適性が求められている。例えば、発汗時に蒸れにくく、空気が乾燥したときに肌を乾燥しにくくするために高い吸湿性であったり、悪臭を発しない、また汗や汚れの付着したことにより生地ｐＨが酸性やアルカリ性を呈しこの刺激による肌がカブレやすくなることを防ぐために生地ｐＨを中性に保つｐＨ緩衝機能等の特性が期待されている。このような要求に応えるものとして、カルボキシル基を有する架橋重合体微粒子を繊維に付与した衛生材料用基布が提案されている（特許文献１参照）。しかしながら、この方法では、機能性微粒子を繊維製品に付着させるため、粒子が脱落し易く、洗濯耐久性良く繊維製品に担持することが難しかった。 Comfortable materials are required for clothing materials, daily life materials, and hygiene materials. For example, it is difficult to stuffy when sweating, it is highly hygroscopic in order to make it difficult to dry the skin when the air is dry, it does not emit bad odors, and the fabric pH is acidic or alkaline due to the attachment of sweat or dirt In order to prevent the skin from being easily fogged by this stimulation, characteristics such as a pH buffering function that keeps the dough pH neutral are expected. In order to meet such a demand, a sanitary material base fabric in which crosslinked polymer fine particles having a carboxyl group are imparted to a fiber has been proposed (see Patent Document 1). However, in this method, the functional fine particles are adhered to the fiber product, so that the particles easily fall off, and it is difficult to carry the particles on the fiber product with good washing durability.
かかる洗濯耐久性の問題を克服するために、２−オキサゾリン基を有する重合体を介して高吸放湿性有機微粒子を繊維表面に固着させた繊維構造体が提案されている（特許文献２参照）。この方法では、高い洗濯耐久性を得ることができるが、風合いが硬くなる問題があった。このように、比較的粒子径が大きな有機微粒子を風合いを硬化させずに洗濯耐久性良く繊維に固着させることは難しかった。 In order to overcome the problem of washing durability, a fiber structure in which highly hygroscopic organic fine particles are fixed to the fiber surface through a polymer having a 2-oxazoline group has been proposed (see Patent Document 2). . In this method, high washing durability can be obtained, but there is a problem that the texture becomes hard. As described above, it has been difficult to fix organic fine particles having a relatively large particle size to the fiber with good washing durability without curing the texture.
一方、消臭成分の一つとしてポリカルボン酸及び／又はポリカルボン酸塩を含有する分散液を繊維素材に付与することによって消臭性繊維製品を得る方法が提案されている（特許文献２参照）。しかしながら、ポリカルボン酸は、親水性が高いため、洗濯耐久性が低い問題があった。また、バインダー樹脂としてアクリル系樹脂、シリコーン系樹脂、ウレタン系樹脂、ポリエステル系樹脂が挙げられているが、これらの一般的なバインダーでは、ポリアクリル酸の消臭機能を維持したまま高い洗濯耐久性を得ることが難しかった。 On the other hand, a method for obtaining a deodorant fiber product by applying a dispersion containing a polycarboxylic acid and / or a polycarboxylate as one of deodorant components to a fiber material has been proposed (see Patent Document 2). ). However, since polycarboxylic acid has high hydrophilicity, there has been a problem that washing durability is low. In addition, acrylic resins, silicone resins, urethane resins, and polyester resins are listed as binder resins, but these general binders have high washing durability while maintaining the deodorizing function of polyacrylic acid. It was difficult to get.
本発明は、上記従来技術の現状に鑑み創案されたものであり、その目的は、消臭性や吸湿性に優れるポリ（メタ）アクリル酸系重合体を、洗濯耐久性良く、風合いも硬くならずに繊維に固着させた機能性繊維製品及びその製造方法を提供することにある。 The present invention was devised in view of the above-mentioned state of the art, and its purpose is to provide a poly (meth) acrylic acid polymer excellent in deodorizing properties and hygroscopicity with good washing durability and a hard texture. It is an object of the present invention to provide a functional fiber product that is fixed to a fiber and a manufacturing method thereof.
本発明者らは、かかる目的を達成するために鋭意検討した結果、微粒子状でない特定の重量平均分子量のポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体を混用し、無水マレイン酸の中和度をコントロールしながら繊維上に皮膜化させて繊維に固定することにより、高い洗濯耐久性と高い機能性だけでなく、風合いも満足した繊維製品を提供できることを見出し、本発明の完成に至った。 As a result of intensive studies to achieve the above object, the present inventors have mixed a poly (meth) acrylic acid polymer having a specific weight average molecular weight that is not in the form of fine particles and an α-olefin-maleic anhydride copolymer. In addition, by controlling the degree of neutralization of maleic anhydride, forming a film on the fiber and fixing it to the fiber, it was found that not only high washing durability and high functionality, but also a fiber product that satisfies the texture can be provided. The present invention has been completed.
即ち、本発明は、以下の（１）〜（６）の構成を有するものである。
（１）ポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体の混合皮膜を表面に有する繊維製品であって、ポリ（メタ）アクリル酸系重合体がポリアクリル酸重合体、ポリメタアクリル酸重合体、またはその塩から選択され、ポリ（メタ）アクリル酸系重合体の７５重量％以上が重量平均分子量３０００〜５００００であり、混合皮膜中のポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の重量比率が１０：９０〜９０：１０であることを特徴とする繊維製品。
（２）αオレフィン−無水マレイン酸系共重合体が、イソブチレン−無水マレイン酸系共重合体であることを特徴とする（１）に記載の繊維製品。
（３）繊維製品の生地ｐＨが４〜１１であり、ＪＩＳ−Ｌ−１０９６Ｆ２法の高温洗濯５０回後のアンモニア消臭性が８０％以上であることを特徴とする（１）または（２）に記載の繊維製品。
（４）２０℃６５％ＲＨにおける生地水分率が０．７％以上、且つ生地ｐＨが５．５〜１１であり、ＪＩＳ−Ｌ−１０９６Ｆ２法の高温洗濯５０回後の生地水分率が０．６％以上であることを特徴とする（１）〜（３）のいずれかに記載の繊維製品。
（５）ポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体が多価アミンで架橋されていることを特徴とする（１）〜（４）のいずれかに記載の繊維製品。
（６）重量平均分子量３０００〜５００００のポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体の混合皮膜を繊維製品の表面に形成する方法であって、ポリ（メタ）アクリル酸系重合体がポリアクリル酸重合体、ポリメタアクリル酸重合体、またはその塩から選択され、α−オレフィン−無水マレイン酸系共重合体の中和物を溶解した水溶液と、ポリ（メタ）アクリル酸系重合体の中和物を溶解した水溶液を調製し、これらの水溶液を混合した後、この混合水溶液を繊維製品に付着させて加熱乾燥することによって繊維製品の表面に混合皮膜を形成することを特徴とする繊維製品の製造方法。
That is, the present invention has the following configurations (1) to (6).
(1) A fiber product having a mixed film of a poly (meth) acrylic acid polymer and an α-olefin-maleic anhydride copolymer on the surface, wherein the poly (meth) acrylic acid polymer is polyacrylic acid A polymer, a polymethacrylic acid polymer, or a salt thereof is selected , and 75% by weight or more of the poly (meth) acrylic acid polymer has a weight average molecular weight of 3000 to 50000, and the poly (meth) acryl in the mixed film A fiber product, wherein the weight ratio of the acid polymer to the α-olefin-maleic anhydride copolymer is 10:90 to 90:10.
(2) The fiber product according to (1), wherein the α-olefin / maleic anhydride copolymer is an isobutylene / maleic anhydride copolymer.
(3) The fabric pH of the textile product is 4 to 11, and the ammonia deodorizing property after 50 times of high-temperature washing by the JIS-L-1096F2 method is 80% or more (1) or (2) Textile products as described in.
(4) The moisture content of the dough at 20 ° C. and 65% RH is 0.7% or more, the dough pH is 5.5 to 11, and the moisture content of the fabric after 50 high-temperature washings of the JIS-L-1096F2 method is 0.00. It is 6% or more, The textiles in any one of (1)-(3) characterized by the above-mentioned.
(5) The poly (meth) acrylic acid polymer and the α-olefin-maleic anhydride copolymer are crosslinked with a polyvalent amine, according to any one of (1) to (4) Textile products.
(6) Weight and poly (meth) acrylic acid polymer of average molecular weight 3,000 to 50,000, alpha-olefin - A method of mixing coating maleic anhydride copolymer is formed on the surface of the textile, poly (meth ) An acrylic acid polymer is selected from a polyacrylic acid polymer, a polymethacrylic acid polymer, or a salt thereof, and an aqueous solution in which a neutralized product of an α-olefin-maleic anhydride copolymer is dissolved; After preparing an aqueous solution in which a neutralized product of a (meth) acrylic acid polymer is dissolved, and mixing these aqueous solutions, the mixed aqueous solution is attached to the fiber product and dried by heating to form a mixed film on the surface of the fiber product. A method for producing a textile product, characterized in that it is formed.
本発明によれば、高い洗濯耐久性を持ちながら、消臭性、吸湿性等の機能を有し、かつ風合いも良好な機能性繊維製品が提供される。 ADVANTAGE OF THE INVENTION According to this invention, while having high washing durability, it has functions, such as a deodorizing property and moisture absorption, and a functional fiber product with a favorable feel is provided.
以下、本発明の繊維製品及びその製造方法について詳細に説明する。 Hereinafter, the fiber product of the present invention and the manufacturing method thereof will be described in detail.
本発明の繊維製品は、特定の重量平均分子量のポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体を特定の重量比率で混合した機能性の樹脂皮膜を表面に有することを特徴とするものである。かかる特徴の本発明の繊維製品は、α−オレフィン−無水マレイン酸系共重合体の中和物と、ポリ（メタ）アクリル酸系重合体の中和物との混合水溶液を作製し、この混合水溶液を繊維製品に付着させて皮膜化させることによって繊維製品の表面に強固な機能性混合皮膜を形成することによって得られる。 The fiber product of the present invention has a functional resin film on the surface in which a poly (meth) acrylic acid polymer having a specific weight average molecular weight and an α-olefin-maleic anhydride copolymer are mixed at a specific weight ratio. It is characterized by having. The fiber product of the present invention having such characteristics is prepared by preparing a mixed aqueous solution of a neutralized product of an α-olefin-maleic anhydride copolymer and a neutralized product of a poly (meth) acrylic acid polymer. It is obtained by forming a strong functional mixed film on the surface of the fiber product by attaching an aqueous solution to the fiber product to form a film.
上記のポリ（メタ）アクリル酸系重合体は、（メタ）アクリル酸由来の構造を含む重合体を表し、該（メタ）アクリル酸由来の構造とは、（メタ）アクリル酸がラジカル重合することにより形成される構造であって、−ＣＨ２ＣＲ（ＣＯＯＭ）−の形で表される構造である。該構造中、Ｒは、水素原子又はメチル基を表し、Ｍは、水素原子、金属原子、アンモニウム塩、又は有機アミン塩を表す。上記金属原子としては、Ｌｉ、Ｎａ、Ｋ等のアルカリ金属原子、Ｃａ、Ｍｇ等のアルカリ土類金属原子等が例示される。上記（メタ）アクリル酸とは、アクリル酸、メタクリル酸、又はその塩を表し、これらの中でも、アクリル酸、アクリル酸塩が好ましい。これら（メタ）アクリル酸は、１種を用いてもよく、２種以上を用いてもよい。 The above poly (meth) acrylic acid polymer represents a polymer containing a structure derived from (meth) acrylic acid, and the structure derived from (meth) acrylic acid means that (meth) acrylic acid undergoes radical polymerization. Is a structure represented by the form of —CH 2 CR (COOM) —. In the structure, R represents a hydrogen atom or a methyl group, and M represents a hydrogen atom, a metal atom, an ammonium salt, or an organic amine salt. Examples of the metal atom include alkali metal atoms such as Li, Na and K, and alkaline earth metal atoms such as Ca and Mg. The (meth) acrylic acid represents acrylic acid, methacrylic acid, or a salt thereof, and among these, acrylic acid and acrylate are preferable. These (meth) acrylic acids may be used alone or in combination of two or more.
本発明のポリ（メタ）アクリル酸系重合体は、（メタ）アクリル酸由来の構造のみを有していても構わないが、（メタ）アクリル酸と共重合可能なその他の単量体由来の構造を含んでいても構わない。その他の単量体としては、具体的にはマレイン酸、フマル酸、イタコン酸、クロトン酸、２−メチレングルタル酸、及びそれらの塩等の（メタ）アクリル酸以外のカルボキシル基含有単量体及びその塩；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、α−ヒドロキシメチルエチル（メタ）アクリレート等の水酸基含有アルキル（メタ）アクリレート類；（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ラウリル等の（メタ）アクリル酸の炭素数１〜１８のアルキル基のエステルである、アルキル（メタ）アクリレート類；ジメチルアミノエチル（メタ）アクリレート及びその４級化物等のアミノ基含有アクリレート；（メタ）アクリルアミド、ジメチルアクリルアミド、イソプロピルアクリルアミド等のアミド基含有単量体類；酢酸ビニル等のビニルエステル類；エチレン、プロピレン等のアルケン類；スチレン等の芳香族ビニル系単量体類；マレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド誘導体；（メタ）アクリロニトリル等のニトリル基含有ビニル系単量体類；３−アリルオキシ−２−ヒドロキシプロパンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、スチレンスルホン酸、ビニルスルホン酸等のスルホン酸基を有する単量体及びそれらの塩；ビニルホスホン酸、（メタ）アリルホスホン酸等のホスホン酸基を有する単量体；（メタ）アクロレイン等のアルデヒド基含有ビニル系単量体類；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のアルキルビニルエーテル類；塩化ビニル、塩化ビニリデン、アリルアルコール、ビニルピロリドン等のその他の官能基含有単量体類；ポリアルキレングリコール（メタ）アクリレート、モノアルコキシポリアルキレングリコール（メタ）アクリレート、ビニルアルコール、（メタ）アリルアルコール、イソプレノール等の不飽和アルコールにアルキレンオキシドが１〜３００モル付加した構造を有する単量体等のポリアルキレングリコール鎖含有単量体等が挙げられる。これらその他の単量体についても、１種のみが単独で用いられてもよいし、２種以上が併用されてもよい。 The poly (meth) acrylic acid polymer of the present invention may have only a structure derived from (meth) acrylic acid, but is derived from another monomer copolymerizable with (meth) acrylic acid. It may contain a structure. Examples of other monomers include carboxyl group-containing monomers other than (meth) acrylic acid, such as maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. Salt thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α- Hydroxyl group-containing alkyl (meth) acrylates such as hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid such as lauryl acid having 1 to 18 carbon atoms Alkyl (meth) acrylates which are esters of alkyl groups; amino group-containing acrylates such as dimethylaminoethyl (meth) acrylate and quaternized products thereof; amide group-containing single quantities such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide Vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitriles such as (meth) acrylonitrile Group-containing vinyl monomers; monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, and the like of Salts: Monomers having a phosphonic acid group such as vinylphosphonic acid and (meth) allylphosphonic acid; Aldehyde group-containing vinyl monomers such as (meth) acrolein; Alkyl such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether Vinyl ethers; other functional group-containing monomers such as vinyl chloride, vinylidene chloride, allyl alcohol, vinyl pyrrolidone; polyalkylene glycol (meth) acrylate, monoalkoxypolyalkylene glycol (meth) acrylate, vinyl alcohol, (meth) Examples thereof include polyalkylene glycol chain-containing monomers such as monomers having a structure in which 1 to 300 mol of alkylene oxide is added to unsaturated alcohol such as allyl alcohol and isoprenol. Also about these other monomers, only 1 type may be used independently and 2 or more types may be used together.
本発明のポリ（メタ）アクリル酸系重合体は、本発明のポリ（メタ）アクリル酸系重合体に含まれる全単量体由来の構造（すなわち、（メタ）アクリル酸（塩）由来の構造とその他の単量体由来の構造との合計）１００重量％に対して、（メタ）アクリル酸由来の構造を酸型換算で８０重量％以上含むことが好ましい。より好ましくは９０重量％以上である。この重量％以上であれば、本発明の繊維製品の吸湿性や消臭性等の機能を有意に高めることができる。ここで、酸型換算とは、塩型の単量体を対応する酸型単量体として質量割合を計算することをいい、例えば（メタ）アクリル酸ナトリウム由来の構造であれば、（メタ）アクリル酸由来の構造として質量割合を計算する。その他の単量体も同様に酸型換算で計算する。 The poly (meth) acrylic acid polymer of the present invention has a structure derived from all monomers contained in the poly (meth) acrylic acid polymer of the present invention (that is, a structure derived from (meth) acrylic acid (salt)). And (meth) acrylic acid-derived structure is preferably 80% by weight or more in terms of the acid type with respect to 100% by weight. More preferably, it is 90 weight% or more. If it is this weight% or more, functions, such as a hygroscopic property and deodorizing property, of the textiles of this invention can be improved significantly. Here, acid type conversion means calculating a mass ratio using a salt type monomer as a corresponding acid type monomer. For example, if the structure is derived from sodium (meth) acrylate, (meth) The mass ratio is calculated as a structure derived from acrylic acid. The other monomers are similarly calculated in terms of acid type.
本発明のポリ（メタ）アクリル酸系重合体は、本発明のポリ（メタ）アクリル酸系重合体に含まれる全単量体由来の構造１００重量％に対して、その他の単量体由来の構造が０〜２０重量％であることが好ましく、０〜１０重量％であることがより好ましい。 The poly (meth) acrylic acid polymer of the present invention is derived from other monomers with respect to 100% by weight of the structure derived from all monomers contained in the poly (meth) acrylic acid polymer of the present invention. The structure is preferably 0 to 20% by weight, and more preferably 0 to 10% by weight.
本発明のポリ（メタ）アクリル酸系重合体の重量平均分子量は、３０００〜５００００であり、好ましくは４０００〜３００００であり、更に好ましくは５０００〜２００００である。この重量平均分子量が上記範囲を超えると、粘度が高くなり、取扱いが煩雑になるおそれがある。一方、この重量平均分子量が上記範囲より小さいと、洗濯耐久性が低下しやすくなる。また、重量平均分子量が上記範囲を超えると加工液の粘度が高くなりすぎて均一な加工が難しくなったり、風合が硬くなりすぎる場合がある。但しポリ（メタ）アクリル酸系重合体の重量全体に対して２５重量％未満の範囲で重量平均分子量が３０００未満または５００００超のポリ（メタ）アクリル酸系重合体を含めることは構わない。特に重量平均分子量が５００００を超えるポリ（メタ）アクリル酸を少量加えることで皮膜強度を高めることができる場合もあるので、適宜使用してよい。上記のようなポリ（メタ）アクリル酸の具体的な市販商品としては、アクアリック（登録商標）Ｌシリーズ、Ｈシリーズ（日本触媒製）、モイスキャッチャーＲＤ−１４８（互応化学工業製）、アロンＨＭ１１０（アロン化成製）等が挙げられる。 The weight average molecular weight of the poly (meth) acrylic acid polymer of the present invention is 3000 to 50000, preferably 4000 to 30000, and more preferably 5000 to 20000. When the weight average molecular weight exceeds the above range, the viscosity becomes high and handling may be complicated. On the other hand, when the weight average molecular weight is smaller than the above range, the washing durability tends to be lowered. On the other hand, if the weight average molecular weight exceeds the above range, the viscosity of the working fluid becomes too high, and uniform processing may be difficult, or the texture may become too hard. However, a poly (meth) acrylic acid polymer having a weight average molecular weight of less than 3000 or more than 50000 may be included in the range of less than 25% by weight with respect to the total weight of the poly (meth) acrylic acid polymer. In particular, the coating strength may be increased by adding a small amount of poly (meth) acrylic acid having a weight average molecular weight exceeding 50,000, and therefore, it may be used appropriately. Specific commercial products of the poly (meth) acrylic acid as described above include Aquaric (registered trademark) L series, H series (manufactured by Nippon Shokubai), Moiscatcher RD-148 (manufactured by Kyogo Chemical Industry), Aron HM110. (Aron Kasei) and the like.
なお、本発明のポリ（メタ）アクリル酸系重合体の重量平均分子量の値は、ゲルパーミーエーションクロマトグラフィーによるポリエチレングリコール換算の重量平均分子量であり、以下のＧＰＣ測定条件により測定したものである。使用カラム：東ソー社製ＴＳＫｇｕａｒｄＣｏｌｕｍｎ ＳＷＸＬ＋ＴＳＫｇｅ１ Ｇ４０００ＳＷＸＬ＋Ｇ３０００ＳＷＸＬ＋Ｇ２０００ＳＷＸＬ。 In addition, the value of the weight average molecular weight of the poly (meth) acrylic acid polymer of the present invention is a weight average molecular weight in terms of polyethylene glycol by gel permeation chromatography, and is measured under the following GPC measurement conditions. Column used: TSK guard Column SWXL + TSKge1 G4000SWXL + G3000SWXL + G2000SWXL manufactured by Tosoh Corporation.
本発明の繊維製品において、繊維に付着した状態におけるポリ（メタ）アクリル酸系重合体は、全部が酸型カルボキシル基であっても構わないが、吸湿性と各種臭気の消臭性を両立するために、ポリ（メタ）アクリル酸系重合体が有するカルボキシル基の一部が中和された構造になっていることが好ましい。繊維製品のｐＨを３以下まで低くするとポリ（メタ）アクリル酸系重合体が有するカルボキシル基を全て酸型にすることができ、同じくｐＨを１２以上にするとカルボキシル基を殆ど塩型にすることができるので、繊維製品のｐＨをコントロールすることにより酸型／塩型の比率を適宜調整することができる。繊維に付着するポリ（メタ）アクリル酸系重合体が有するカルボキシル基のうち、塩型カルボキシル基／全カルボキシル基の割合は限定されないが、吸湿性や酸性臭の消臭性をより高めたいときは塩型カルボキシル基を増やすことが好ましい。その場合には塩型カルボキシル基はＮａ塩型、Ｌｉ塩型等の一価の金属塩型が好ましい。より好ましくはＮａ塩型である。また、アンモニア臭等の塩基性臭の消臭性をより高めたいときは酸型カルボキシル基を増やすことが好ましい。これらの場合の好ましい繊維製品ｐＨは後述する。各種消臭性のバランスや吸湿性を両立したい場合、（メタ）アクリル酸に由来する構造とナトリウム塩やアミン塩の塩型に由来する構造とのモル比が９０：１０〜１０：９０であることが好ましい。より好ましくは、８０：２０〜２０：８０である。 In the fiber product of the present invention, the poly (meth) acrylic acid polymer attached to the fiber may be all of an acid-type carboxyl group, but is compatible with hygroscopicity and deodorization of various odors. Therefore, it is preferable that a part of the carboxyl groups of the poly (meth) acrylic acid polymer is neutralized. When the pH of the fiber product is lowered to 3 or less, all the carboxyl groups of the poly (meth) acrylic acid polymer can be converted to acid form, and when the pH is increased to 12 or more, the carboxyl group is almost converted to salt form. Therefore, the ratio of the acid type / salt type can be appropriately adjusted by controlling the pH of the fiber product. Of the carboxyl groups of the poly (meth) acrylic acid polymer attached to the fiber, the ratio of salt-type carboxyl groups / total carboxyl groups is not limited, but when you want to further improve the hygroscopicity and deodorization of acidic odors It is preferable to increase the salt-type carboxyl group. In that case, the salt type carboxyl group is preferably a monovalent metal salt type such as Na salt type or Li salt type. More preferably, it is Na salt type. Further, when it is desired to further improve the deodorizing property of a basic odor such as ammonia odor, it is preferable to increase the acid type carboxyl group. The preferred fiber product pH in these cases will be described later. When it is desired to balance various deodorizing properties and hygroscopicity, the molar ratio of the structure derived from (meth) acrylic acid and the structure derived from the salt type of sodium salt or amine salt is 90:10 to 10:90. It is preferable. More preferably, it is 80: 20-20: 80.
上記のポリ（メタ）アクリル酸系重合体が有するカルボキシル基は、繊維製品に加工する時点では少なくとも一部が有機アミン塩で中和されていることが好ましい。有機アミン塩にすることで、加工液の粘度上昇を低減することができ、その結果、αオレフィン−無水マレイン酸系共重合体と均一に混合しやすく、また、均一な加工を行いやすくできる利点がある。但し、繊維製品の吸湿性や消臭性をより高めたい場合には、繊維上に皮膜を形成した後にポリ（メタ）アクリル酸系重合体の少なくとも一部をＮａ塩等の一価の金属塩型に置換することが好ましい。 The carboxyl group of the poly (meth) acrylic acid polymer is preferably at least partially neutralized with an organic amine salt at the time of processing into a fiber product. By using an organic amine salt, it is possible to reduce the increase in the viscosity of the processing liquid, and as a result, it is easy to uniformly mix with the α-olefin-maleic anhydride copolymer, and to facilitate uniform processing. There is. However, when it is desired to further increase the hygroscopicity and deodorant property of the textile product, after forming a film on the fiber, at least a part of the poly (meth) acrylic acid polymer is a monovalent metal salt such as Na salt. Substitution with a mold is preferred.
上記の有機アミン（塩）としては、１級アミン、２級アミン、３級アミン、４級アミン、及びそれらの塩のいずれでもよく、１種が単独で用いられても良いし、２種以上を併用しても構わない。そのような有機アミンとしては、例えば、モノエタノールアミン、モノプロパノールアミン、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；メチルアミン、エチルアミン、ブチルアミン、ジメチルアミン、ジエチルアミン等のアルキルアミン；シクロヘキシルアミン等のシクロアルキルアミン；ピロリジン、ピペリジン、ピリジン、ピラジン、ピロール、モルホリン等の環状アミン；エチレンジアミン、ジエチレントリアミン等のポリアルキレンアミンが例示される。この中でも、重合体水溶液の経時的な顔料分散性能が顕著に向上すること、取扱いのしやすさ、比較的安価であること等の点から、ポリ（メタ）アクリル酸系重合体の水溶液は、アルカノールアミン又はその塩に由来する構造を含むことが好ましい。 The organic amine (salt) may be any of primary amines, secondary amines, tertiary amines, quaternary amines, and salts thereof, and one kind may be used alone, or two or more kinds. May be used in combination. Examples of such organic amines include alkanolamines such as monoethanolamine, monopropanolamine, diethanolamine, and triethanolamine; alkylamines such as methylamine, ethylamine, butylamine, dimethylamine, and diethylamine; cycloalkyl such as cyclohexylamine. Examples include amines; cyclic amines such as pyrrolidine, piperidine, pyridine, pyrazine, pyrrole and morpholine; and polyalkyleneamines such as ethylenediamine and diethylenetriamine. Among these, the aqueous dispersion of the poly (meth) acrylic acid polymer is significantly improved in terms of the pigment dispersion performance over time of the aqueous polymer solution, ease of handling, and relatively inexpensive. It preferably contains a structure derived from alkanolamine or a salt thereof.
本発明のαオレフィン−無水マレイン酸系共重合体におけるα−オレフィンとしては、直鎖状または分岐状の炭素数２〜１２、好ましくは２〜８を有する不飽和炭化水素が挙げられる。その例としては、エチレン、プロピレン、ブテン−１、ブテン−２、イソブチレン（リターンＢ．Ｂ．を含む）、イソプレン、２−メチル−１−ブテン、ｎ−ペンテン、ｎ−ヘキセン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、２−エチル−１−ブテン、ジイソブチレン、１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエン、１，３−オクタジエン、２−メチル−４−ジメチル−１−ペンテン、２−メチル−４−ジメチル−２−ペンテン等が挙げられるが、イソブチレンが本発明の目的を達成するためには好適である。 Examples of the α-olefin in the α-olefin-maleic anhydride copolymer of the present invention include linear or branched unsaturated hydrocarbons having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Examples include ethylene, propylene, butene-1, butene-2, isobutylene (including return BB), isoprene, 2-methyl-1-butene, n-pentene, n-hexene, 2-methyl- 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, diisobutylene, 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1 , 3-octadiene, 2-methyl-4-dimethyl-1-pentene, 2-methyl-4-dimethyl-2-pentene and the like, and isobutylene is preferable for achieving the object of the present invention.
本発明のαオレフィン−無水マレイン酸系共重合体における無水マレイン酸系（化合物）は、αオレフィン−無水マレイン酸系共重合体を製造する原料として、無水マレイン酸、マレイミド、及びマレイン酸エステル等を指す。ここで、マレイン酸エステルとしては、マレイン酸モノエステルまたはジエステルが挙げられ、エステルとしては、メチルエステル、エチルエステル等が挙げられるが、本発明では無水マレイン酸、マレイミドが好適に用いられる。特に好適なものは無水マレイン酸である。 The maleic anhydride system (compound) in the α-olefin-maleic anhydride copolymer of the present invention is a maleic anhydride, maleimide, maleic ester, etc. as a raw material for producing an α-olefin-maleic anhydride copolymer. Point to. Here, maleic acid esters include maleic acid monoesters or diesters, and examples of esters include methyl esters and ethyl esters. In the present invention, maleic anhydride and maleimide are preferably used. Particularly preferred is maleic anhydride.
αオレフィン−無水マレイン酸系共重合体におけるα−オレフィンと無水マレイン酸系化合物との組成比は、共重合体とアルカリ金属水酸化物との反応物が水に溶解するようなものであればいかなる程度のものであっても良い。本発明において好ましく用いられるエチレン、イソブチレン、スチレン又はメチルビニルエーテルと無水マレイン酸との共重合体の場合には、無水マレイン酸１モルに対してエチレン、イソブチレン、スチレン又はメチルビニルエーテル１〜３モル程度、多くの場合１モル程度である。このような共重合体は１種あるいは２種以上を組合わせて使用することができる。 The composition ratio of the α-olefin to the maleic anhydride compound in the α olefin-maleic anhydride copolymer is such that the reaction product of the copolymer and the alkali metal hydroxide is soluble in water. Any degree is acceptable. In the case of a copolymer of ethylene, isobutylene, styrene or methyl vinyl ether and maleic anhydride preferably used in the present invention, about 1 to 3 moles of ethylene, isobutylene, styrene or methyl vinyl ether per mole of maleic anhydride, In many cases, it is about 1 mole. Such copolymers can be used alone or in combination of two or more.
αオレフィン−無水マレイン酸系共重合体の分子量は、ジメチルホルムアミド溶液中、３０℃で測定した極限粘度〔η〕が０．２〜１０（ｄｌ／ｇ）、さらには０．３〜８（ｄｌ／ｇ）に相当するものが好ましい。これらの共重合体のなかでも反応溶液の粘度が低く、高濃度での反応が可能である点からイソブチレン−無水マレイン酸系共重合体が好ましい。上記のαオレフィン−無水マレイン酸系共重合体として好ましく使用できる市販品としては、イソバン（登録商標）シリーズ（クラレ製）等が挙げられる。 The molecular weight of the α-olefin-maleic anhydride copolymer is such that the intrinsic viscosity [η] measured at 30 ° C. in a dimethylformamide solution is 0.2 to 10 (dl / g), and further 0.3 to 8 (dl / G) is preferred. Among these copolymers, an isobutylene-maleic anhydride copolymer is preferable because the viscosity of the reaction solution is low and a reaction at a high concentration is possible. Examples of commercially available products that can be preferably used as the α-olefin-maleic anhydride copolymer include Isoban (registered trademark) series (manufactured by Kuraray).
これらの共重合体をアルカリ性化合物と反応させることにより、共重合体のカルボキシル基がアルカリ中和物となって親水性を持たせることができる。これは、例えば共重合体をアンモニアやアルカリ金属の水酸化物の水溶液に添加して反応させることによって行われる。ここで、アルカリ金属の水酸化物とは、水酸化ナトリウム、水酸化カリウム、水酸化リチウムなどをいい、水溶性、または水に完溶しなくても親水性を付与するものである。共重合体に対する中和度（反応割合）は０．５〜１．０が好ましい。さらには０．６〜０．８が好適である。この共重合体は、加工後にはマレイン酸がカルボキシル基となって存在するので、中和度により酸性臭気とアルカリ臭の消臭効果をコントロールすることができる。 By reacting these copolymers with an alkaline compound, the carboxyl group of the copolymer can be made into an alkali neutralized product to be hydrophilic. This is performed, for example, by adding the copolymer to an aqueous solution of ammonia or an alkali metal hydroxide and reacting it. Here, the alkali metal hydroxide refers to sodium hydroxide, potassium hydroxide, lithium hydroxide or the like, and is water-soluble or imparts hydrophilicity even if it is not completely dissolved in water. The neutralization degree (reaction ratio) for the copolymer is preferably 0.5 to 1.0. Furthermore, 0.6 to 0.8 is preferable. Since the copolymer has maleic acid as a carboxyl group after processing, the deodorizing effect of acidic odor and alkali odor can be controlled by the degree of neutralization.
本発明では、多価アミン化合物や、エポキシ化合物、カルボジイミド、オキサゾリン基を持つ化合物を用いて、前記ポリ（メタ）アクリル酸系共重合体と、αオレフィン−無水マレイン酸系共重合体を架橋させることによって、洗濯耐久性をさらに向上させることができる。例えば、多価アミン化合物は、共重合体１００重量部に対し０．５〜２０重量部使用することが好ましく、好適には５〜１５重量部である。多価アミン化合物の使用量が上記範囲未満では皮膜の耐久性を高める効果が低い。多価アミン化合物の使用量が上記範囲を超えると、風合いが硬くなったり、変色が起こりやすくなる。 In the present invention, the poly (meth) acrylic acid copolymer and the α-olefin-maleic anhydride copolymer are crosslinked using a polyvalent amine compound, an epoxy compound, a carbodiimide, or a compound having an oxazoline group. As a result, the washing durability can be further improved. For example, the polyvalent amine compound is preferably used in an amount of 0.5 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the copolymer. When the amount of the polyvalent amine compound used is less than the above range, the effect of enhancing the durability of the film is low. When the use amount of the polyvalent amine compound exceeds the above range, the texture becomes hard and discoloration easily occurs.
このような多価アミン化合物は、分子中に２個以上のアミノ基を有する水溶性多価アミンであり、その例としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、直鎖状又は分岐を有するポリエチレンイミンなどが挙げられる。 Such a polyvalent amine compound is a water-soluble polyvalent amine having two or more amino groups in the molecule. Examples thereof include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, Examples include linear or branched polyethyleneimine.
ポリ（メタ）アクリル酸系重合体は、親水性が高いため、ポリ（メタ）アクリル酸系重合体の高い機能性を維持したままに繊維製品に洗濯耐久性よく固着させることが非常に難しかった。本発明者らは、αオレフィン−無水マレイン酸系共重合体を使用することによってポリ（メタ）アクリル酸系重合体を洗濯耐久性良く繊維上に固着させることができることを見出した。本発明によれば、ポリ（メタ）アクリル酸系重合体と、αオレフィン−無水マレイン酸系共重合体との混合皮膜を繊維上に形成させているので、繊維の風合いが良く、ポリ（メタ）アクリル酸系重合体の吸湿性や消臭性を維持したまま、高い洗濯耐久性を得ることができる。ポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の混合皮膜の好ましい形態は、ポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体が混ざり合った水溶液を繊維に付与することで両者が完全に混ざり合った混合皮膜として繊維上に形成されたものである。その他の形態としては、予めポリ（メタ）アクリル酸系重合体の皮膜を形成しておいて、その上からαオレフィン−無水マレイン酸系共重合体の皮膜を形成させる二層構造の皮膜が挙げられる。 Since the poly (meth) acrylic acid polymer has high hydrophilicity, it was very difficult to fix it to the textile product with good washing durability while maintaining the high functionality of the poly (meth) acrylic acid polymer. . The present inventors have found that a poly (meth) acrylic acid polymer can be fixed on a fiber with good washing durability by using an α-olefin-maleic anhydride copolymer. According to the present invention, since the mixed film of the poly (meth) acrylic acid polymer and the α-olefin-maleic anhydride copolymer is formed on the fiber, the texture of the fiber is good, and the poly (meta) ) High washing durability can be obtained while maintaining the hygroscopicity and deodorizing property of the acrylic acid polymer. The preferred form of the mixed film of poly (meth) acrylic acid polymer and α-olefin / maleic anhydride copolymer is a mixture of poly (meth) acrylic acid polymer and α-olefin / maleic anhydride copolymer. By applying a combined aqueous solution to the fibers, a mixed film in which the two are completely mixed is formed on the fibers. As another form, a film of a two-layer structure in which a film of a poly (meth) acrylic acid polymer is previously formed and an α-olefin-maleic anhydride copolymer film is formed thereon is exemplified. It is done.
繊維製品に対するポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の混合皮膜の付着量としては、繊維重量に対して０．５〜５０重量％とするのが好ましい。より好ましくは１〜１５重量％である。付着量が上記範囲未満であると、吸湿性、消臭性の効果が低くなる可能性があり、上記範囲を超えると、繊維製品に柔軟性がなくなり、風合いが非常に硬くなる可能性がある。 The adhesion amount of the mixed film of the poly (meth) acrylic acid polymer and the α-olefin-maleic anhydride copolymer to the fiber product is preferably 0.5 to 50% by weight based on the fiber weight. More preferably, it is 1 to 15% by weight. If the adhesion amount is less than the above range, the hygroscopic and deodorant effects may be reduced, and if it exceeds the above range, the textile product may lose flexibility and the texture may become very hard. .
混合皮膜中のポリアクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の重量比率は、１０：９０〜９０：１０であり、より好ましくは７５：２５〜２５：７５である。αオレフィン−無水マレイン酸系共重合体の比率が上記範囲未満であると高い洗濯耐久性を得ることが難しくなり、上記範囲を超えるとポリ（メタ）アクリル酸系共重合体の高い吸湿効果が低下する可能性がある。 The weight ratio of the polyacrylic acid polymer and the α-olefin-maleic anhydride copolymer in the mixed film is 10:90 to 90:10, more preferably 75:25 to 25:75. If the ratio of α-olefin-maleic anhydride copolymer is less than the above range, it becomes difficult to obtain high washing durability, and if it exceeds the above range, the poly (meth) acrylic acid copolymer has a high moisture absorption effect. May be reduced.
繊維製品にポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の混合皮膜を形成させる方法としては、繊維製品が布状の場合、ＤＩＰ−ＮＩＰ法が好適に用いられる。これは繊維製品を加工液に含浸してからマングル等を用いて絞ることで加工液の付着量をコントロールし、その後、乾燥・熱処理を行う方法である。これ以外にも印捺、グラビヤ加工、スプレー法等を用いることができる。繊維製品が衣料製品等の場合にはスプレー法、浸漬−遠心脱水等の方法が好ましく用いられる。繊維製品が糸条の場合は、糊付機等を用いて付与したり、カセやチーズ状で浸漬処理してもよい。中綿等ではスプレー法が好適であり、繊維製品の形態によって最適な方法を選択すればよい。 As a method for forming a mixed film of a poly (meth) acrylic acid polymer and an α-olefin / maleic anhydride copolymer on a fiber product, the DIP-NIP method is suitably used when the fiber product is in the form of a cloth. . This is a method of impregnating a textile product into a processing liquid and then squeezing it with a mangle or the like to control the amount of the processing liquid adhered, and then drying and heat treatment. In addition to this, printing, gravure processing, a spray method, etc. can be used. When the textile product is a clothing product or the like, a method such as spraying or dipping-centrifugal dehydration is preferably used. When the fiber product is a yarn, it may be applied using a gluing machine or may be dipped in a cake or cheese form. The spray method is suitable for batting and the like, and an optimal method may be selected depending on the form of the fiber product.
ＤＩＰ−ＮＩＰ法により混合皮膜を形成させる場合の具体的な方法の一例を以下に説明する。まず、α−オレフィン−無水マレイン酸系共重合体を中和してから水に溶解して水溶液を調製したものと、同じくポリ（メタ）アクリル酸系重合体を中和してから水に溶解した水溶液を調整したものを混合してそれぞれ特定の濃度の混合水溶液を作製する。このとき、水に溶かすのと中和の順番は逆にしても構わないが、個々に適切な中和剤を使って中和してから混合することがより好ましい。更に繊維製品をこの混合水溶液でパディングして混合液が特定付着量になるように絞り率を調整して絞ることで繊維製品に均一に付着させる。その後、熱処理等を行って乾燥することにより繊維製品（繊維）の表面に混合皮膜を形成することができる。さらに、繊維製品を所望の生地ｐＨに調整することにより希望の機能性を有する繊維製品が得られる。 An example of a specific method in the case of forming a mixed film by the DIP-NIP method will be described below. First, the α-olefin-maleic anhydride copolymer is neutralized and then dissolved in water to prepare an aqueous solution. Similarly, the poly (meth) acrylic acid polymer is neutralized and then dissolved in water. The prepared aqueous solutions are mixed to prepare mixed aqueous solutions having specific concentrations. At this time, the order of dissolution in water and neutralization may be reversed, but it is more preferable to mix them after neutralization using an appropriate neutralizing agent. Further, the fiber product is padded with this mixed aqueous solution, and the squeezing rate is adjusted so that the mixed solution becomes a specific adhesion amount, and the fiber product is uniformly attached to the fiber product. Thereafter, a mixed film can be formed on the surface of the fiber product (fiber) by performing heat treatment and drying. Furthermore, the fiber product which has desired functionality is obtained by adjusting a fiber product to desired fabric pH.
繊維製品に上記混合水溶液を付着させた後、強固な混合皮膜を形成させるために、乾熱熱処理、蒸熱処理、電磁波処理等を行ってもよい。特に架橋剤や三次元架橋させ得る官能基がある場合には好適に処理できる。例えば乾熱処理する場合には１２０℃〜２２０℃で０．５〜２分程度処理すると効果的である。蒸熱処理の場合は飽和水蒸気で１〜３０分処理するとよい。勿論これらの処理を併用してもよい。 After the mixed aqueous solution is adhered to the textile product, dry heat treatment, steam heat treatment, electromagnetic wave treatment, or the like may be performed in order to form a strong mixed film. In particular, when there is a cross-linking agent or a functional group capable of three-dimensional cross-linking, it can be suitably treated. For example, in the case of dry heat treatment, it is effective to treat at 120 ° C. to 220 ° C. for about 0.5 to 2 minutes. In the case of steaming heat treatment, it may be treated with saturated steam for 1 to 30 minutes. Of course, these treatments may be used in combination.
本発明において、加工上がりの繊維製品の生地ｐＨは、機能性の性能を十分に発揮させるために重要である。繊維製品の生地ｐＨは４〜１１が好ましく、より好ましくは５〜１０である。繊維製品の生地ｐＨが上記範囲未満になると吸湿性が殆ど向上しなくなり、上記範囲を超えると洗濯耐久性が低下したり黄変が起こりやすくなる。本発明ではｐＨ４〜１１の間で所望の機能性をコントロールすることが可能である。吸湿性を重視する場合はｐＨ５．５〜１１とすると繊維製品の吸湿性を高めることができ、酢酸やイソ吉草酸の消臭性能が高まる。ｐＨを４〜８とすることでアンモニア等の塩基性の臭いの消臭性を高めることができる。吸湿性と各種臭いの消臭性にバランス良く性能を引き出すにはｐＨ５〜１０が好ましい。繊維製品のｐＨを調整する方法としては、ポリ（メタ）アクリル酸系重合体とαオレフィン−無水マレイン酸系共重合体の混合液のｐＨを予め調整してから繊維製品に付与する方法でもよいし、繊維製品に混合皮膜を形成した後に、所望のｐＨ液で洗浄したり、或いは工程最後にｐＨ調整液に含浸したり、スプレーなどで付与することで繊維製品のｐＨを調整することができる。 In the present invention, the fabric pH of the finished textile product is important in order to sufficiently exhibit functional performance. The fabric pH of the textile product is preferably 4-11, more preferably 5-10. When the fabric pH of the textile product is less than the above range, the hygroscopicity is hardly improved, and when it exceeds the above range, the washing durability is lowered or yellowing easily occurs. In the present invention, desired functionality can be controlled between pH 4-11. When placing importance on hygroscopicity, the pH of the fiber product can be increased to 5.5-11, and the deodorizing performance of acetic acid and isovaleric acid is enhanced. By adjusting the pH to 4 to 8, the deodorizing property of a basic odor such as ammonia can be enhanced. A pH of 5 to 10 is preferred to bring out the performance in a good balance between hygroscopicity and deodorization of various odors. As a method for adjusting the pH of the textile product, a method of preliminarily adjusting the pH of the mixed liquid of the poly (meth) acrylic acid polymer and the α-olefin-maleic anhydride copolymer may be applied to the textile product. Then, after forming a mixed film on the fiber product, the pH of the fiber product can be adjusted by washing with a desired pH solution, or impregnating with a pH adjusting solution at the end of the process, or applying by spraying or the like. .
ポリ（メタ）アクリル酸の付与量は、吸湿性、アンモニア等の消臭性の性能に影響する。これらの機能を十分に発揮させるためには繊維製品の重量に対する付与量を１〜２０重量％とすることが好適であり、より好ましくは２〜１５重量％である。付与量が上記範囲未満では吸湿性を達成することが困難となり、上記範囲を超えると風合が硬くなり、繊維製品としては好適ではなくなる。 The application amount of poly (meth) acrylic acid affects hygroscopicity and deodorant performance such as ammonia. In order to sufficiently exhibit these functions, it is preferable that the applied amount with respect to the weight of the fiber product is 1 to 20% by weight, and more preferably 2 to 15% by weight. If the applied amount is less than the above range, it becomes difficult to achieve hygroscopicity, and if it exceeds the above range, the texture becomes hard and it is not suitable as a textile product.
本発明の繊維製品の形態は、特に制約はなく、織物、編物、不織布、糸、ワタ等のいずれの形態であってもよいし、衣料品やインテリア、寝装品等の最終製品の形態でも構わない。繊維製品を構成する繊維素材としても特に制限されないが、例えば、綿、絹、ウール等の天然繊維；ポリアミド系繊維、ポリウレタン系繊維、ポリエステル系繊維、ポリエチレン系繊維、ポリプロピレン系繊維、ポリ塩化ビニリデン系繊維等の合成繊維；アセテート等の半合成繊維；レーヨン等の再生繊維；綿／ポリエステル、ナイロン／スパンデックス等の複合繊維；混紡繊維を挙げることができる。 The form of the textile product of the present invention is not particularly limited, and may be any form such as a woven fabric, a knitted fabric, a nonwoven fabric, a thread, a cotton, or the like, and may be a finished product such as clothing, interior, and bedding. . The fiber material constituting the fiber product is not particularly limited. For example, natural fibers such as cotton, silk, and wool; polyamide fibers, polyurethane fibers, polyester fibers, polyethylene fibers, polypropylene fibers, and polyvinylidene chloride Examples thereof include synthetic fibers such as fibers; semi-synthetic fibers such as acetate; recycled fibers such as rayon; composite fibers such as cotton / polyester and nylon / spandex; and blended fibers.
本発明の繊維製品には、上述の混合皮膜による機能性付与以外に他の機能加工を施してもよい。例えば防汚加工、ＵＶカット加工、スキンケア加工、抗菌防臭、制菌、抗ウイルス、制電加工などの機能加工を併用することができる。本発明において好ましく併用される機能加工としては、抗菌防臭や制菌加工がある。これらの抗菌処理には、銀、銅あるいは亜鉛などの無機系抗菌剤や、第四級アンモニウム塩などの有機系抗菌剤が好ましく用いられる。これらの加工は染色加工中で行うのが好ましい。ポリアクリル酸の加工と同時に行ってもよいし、前後の工程で別々に行ってもよい。加工方法としては、染色機等の液中で吸尽加工する方法、スプレー処理して付与する方法、あるいはパディング処理して付与する方法等が用いられる。好ましくは、本発明の混合皮膜を形成した後に加工する二段法で加工するのが好ましい。 The fiber product of the present invention may be subjected to other functional processing in addition to the functional addition by the mixed film. For example, functional processing such as antifouling processing, UV cut processing, skin care processing, antibacterial deodorization, antibacterial, antiviral and antistatic processing can be used in combination. The functional processing preferably used in the present invention includes antibacterial deodorization and antibacterial processing. For these antibacterial treatments, inorganic antibacterial agents such as silver, copper or zinc and organic antibacterial agents such as quaternary ammonium salts are preferably used. These processes are preferably performed during the dyeing process. It may be performed simultaneously with the processing of polyacrylic acid, or may be performed separately in the preceding and following steps. As a processing method, a method of exhausting in a liquid such as a dyeing machine, a method of applying by spraying, or a method of applying by padding is used. Preferably, it is preferable to process by the two-stage method of processing after forming the mixed film of the present invention.
繊維製品の吸湿性に関して、２０℃、６５％ＲＨの標準状態における生地、例えばポリエステル繊維の水分率は０．３〜０．４％であるが、本発明のような皮膜を表面に形成すると水分率を０．７％以上、５％以下程度に向上させることができる。すなわち、本発明の混合皮膜が寄与する水分率増加は０．４〜４．６％程度である。但し衣料品等の場合、風合いとの兼ね合いから０．３〜２．０％程度の生地水分率とするのが好ましい。なお、２０℃、９５％ＲＨの高湿度の環境では従来のポリエステル繊維の水分率は０．６％程度であるが、本発明の繊維製品は１．０〜１０％程度で水分率を保持することができ、高湿度下でも蒸れにくい繊維製品にすることができる。 Regarding the hygroscopicity of the textile product, the moisture content of the fabric in the standard state of 20 ° C. and 65% RH, for example, the polyester fiber is 0.3 to 0.4%. The rate can be improved to about 0.7% or more and 5% or less. That is, the increase in moisture content contributed by the mixed film of the present invention is about 0.4 to 4.6%. However, in the case of clothing and the like, it is preferable that the moisture content of the cloth is about 0.3 to 2.0% in consideration of the texture. The moisture content of the conventional polyester fiber is about 0.6% in a high humidity environment of 20 ° C. and 95% RH, but the fiber product of the present invention maintains the moisture content at about 1.0 to 10%. It can be made into a textile product that is not easily stuffy even under high humidity.
従来の技術で付与された吸湿性の繊維製品であればＪＩＳ−Ｌ−１０９６Ｆ２法の高温洗濯５０回後では吸湿効果は殆どなくなってしまうが、本発明では、かかる場合でも吸湿効果を効果的に持続することができる。高温洗濯５０回後でも混合皮膜による生地水分率は０．６％以上、増加水分率は０．２〜２．０％に維持することができる。 In the case of a hygroscopic textile product provided by the conventional technique, the hygroscopic effect is almost lost after 50 times of high temperature washing by the JIS-L-1096F2 method. However, in the present invention, the hygroscopic effect is effectively obtained even in such a case. Can last. Even after 50 high temperature washings, the moisture content of the dough by the mixed film can be maintained at 0.6% or more, and the increased moisture content can be maintained at 0.2-2.0%.
本発明の繊維製品は、酢酸、イソ吉草酸等の酸性臭にも、アンモニア等の塩基臭にも高い消臭性があり、最適なｐＨに調整した繊維製品であれば、酢酸は９５％以上、イソ吉草酸は８５％以上、アンモニアは９０％以上消臭することができる。また、ＪＩＳ−Ｌ−１０９６Ｆ２法の高温洗濯５０回後でもそれぞれ８０％以上の高い消臭性を維持することができる。 The fiber product of the present invention has a high deodorizing property in both an acidic odor such as acetic acid and isovaleric acid, and a basic odor such as ammonia. If the fiber product is adjusted to an optimum pH, acetic acid is 95% or more. Isovaleric acid can be deodorized by 85% or more, and ammonia can be deodorized by 90% or more. Moreover, the high deodorizing property of 80% or more can be maintained even after 50 times of high-temperature washing according to JIS-L-1096F2.
以下に実施例により本発明の効果を示すが、本発明は、これらに何ら限定されるものではない。本実施例における特性値の評価は以下の方法で行った。 Examples The effects of the present invention will be described below with reference to examples, but the present invention is not limited to these examples. The characteristic values in this example were evaluated by the following method.
（繊維製品の吸湿率）
（１）絶乾重量
試料を１２０℃×３時間乾燥して絶乾した後、シリカゲル入りデシケータに入れ、２０℃、６５％ＲＨの環境試験室で調温調湿後、重量測定を行った。
（２）吸湿重量
秤量ビンの蓋を開け恒温恒湿器で２０℃、６５％ＲＨ（又は２０℃、９０％ＲＨ）で１２時間調温調湿後、蓋をして密閉してから恒温恒湿器から取り出し、秤量瓶ごと重量測定を行い、後で秤量瓶単体の重量を引いて試料のみの吸湿重量を求めた。
吸湿率（％）＝｛（吸湿重量−絶乾重量）／絶乾重量｝×１００
(Hygroscopic rate of textile products)
(1) Absolutely dry weight The sample was dried at 120 ° C. for 3 hours and completely dried, and then placed in a desiccator containing silica gel, and the temperature was adjusted in an environmental test chamber at 20 ° C. and 65% RH, and then the weight was measured.
(2) Moisture absorption weight The lid of the weighing bottle is opened and the temperature and humidity controlled at 20 ° C. and 65% RH (or 20 ° C., 90% RH) for 12 hours with a thermo-hygrostat. The sample was taken out from the humidifier and weighed together with the weighing bottle. Thereafter, the weight of the weighing bottle alone was subtracted to obtain the moisture absorption weight of only the sample.
Moisture absorption rate (%) = {(hygroscopic weight−absolute dry weight) / absolute dry weight} × 100
（繊維製品の消臭性）
繊維製品の各臭気成分の減少率は、以下の方法で測定した。なお、繊維製品が生地の場合は１０ｃｍ×１０ｃｍの面積の大きさに採取し（生地でない形態の場合は試料を１．０ｇ採取）、５０℃×２時間、絶乾処理した後、６５％×２０℃×２４時間以上、調湿した。
(Deodorization of textile products)
The reduction rate of each odor component of the textile product was measured by the following method. In addition, when the textile product is a fabric, it is sampled to a size of 10 cm × 10 cm (1.0 g sample is collected in the case of a non-fabric form), and after drying at 50 ° C. for 2 hours, 65% × The humidity was adjusted at 20 ° C. for 24 hours or more.
（１）アンモニア臭気減少率、酢酸臭気減少率
試料をガス３Ｌ（濃度：アンモニア１００ｐｐｍ、酢酸３０ｐｐｍ）中、２時間放置した後、検知管で残留ガス濃度を測定した。
(1) Ammonia odor reduction rate, acetic acid odor reduction rate The sample was left in gas 3 L (concentration: ammonia 100 ppm, acetic acid 30 ppm) for 2 hours, and then the residual gas concentration was measured with a detector tube.
（２）イソ吉草酸臭気減少率
試料をガス３Ｌ（濃度：イソ吉草酸３８ｐｐｍ）中、２時間放置した後、ガスクロマトグラフィーで残留ガス濃度を測定した。
(2) Isovaleric acid odor reduction rate The sample was left in gas 3 L (concentration: isovaleric acid 38 ppm) for 2 hours, and then the residual gas concentration was measured by gas chromatography.
臭気減少率は、上記の残留ガス濃度測定値から以下の式を用いて求めた。
臭気減少率（％）＝（（空試験の平均値−測定値の平均値）／空試験の平均値）×１００
一般社団法人繊維評価技術協議会の消臭性繊維製品の認証基準（平成２７年４月１日改定）に準じて、以下の全てを同時に満足した場合、消臭性判定を「良好」と判断した。
・アンモニア臭気減少率（％）：７０％以上
・酢酸臭気減少率（％） ：７０％以上
・イソ吉草酸臭気減少率（％）：８５％以上
The odor reduction rate was determined from the above residual gas concentration measurement value using the following formula.
Odor reduction rate (%) = ((average value of blank test−average value of measured value) / average value of blank test) × 100
In accordance with the certification standards (revised on April 1, 2015) for deodorant fiber products of the Japan Fiber Evaluation Technology Council, if all of the following are satisfied at the same time, the deodorant determination is judged as “good” did.
・ Ammonia odor reduction rate (%): 70% or more ・ Acetic acid odor reduction rate (%): 70% or more ・ Isovaleric acid odor reduction rate (%): 85% or more
（制菌性）
ＪＩＳ−Ｌ１９０２繊維製品の抗菌性試験方法及び抗菌効果に準拠して測定した。試料０．４ｇをバイアル瓶に入れ、試験菌液０．２ｍｌを接種し、３７±２℃で１８±１時間培養した。非イオン界面活性剤を０．２重量％含む生理食塩水２０ｍｌを加えて試料から菌を洗い出し、洗い出し液中の菌数を混釈平板培養法（コロニー法）により測定し、下記の式に従い殺菌活性値を算出した。試験菌種は黄色ぶどう球菌Ｓｔａｐｈ−ｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＡＴＣＣ ６５３８Ｐ）とし、殺菌活性値≧０の場合に制菌性が良好と判断した。
殺菌活性値＝ｌｏｇ（標準布・接種直後生菌数）−ｌｏｇ（加工試料・培養後生菌数）
(Antibacterial)
It measured based on the antibacterial test method and antibacterial effect of JIS-L1902 textiles. 0.4 g of a sample was put in a vial, inoculated with 0.2 ml of a test bacterial solution, and cultured at 37 ± 2 ° C. for 18 ± 1 hour. 20 ml of physiological saline containing 0.2% by weight of a nonionic surfactant is added to wash out bacteria from the sample, the number of bacteria in the washing solution is measured by the pour plate culture method (colony method), and sterilized according to the following formula Activity values were calculated. The test bacterial species was Staphylococcus aureus Staph-ylococcus aureus ATCC 6538P), and the bactericidal activity was judged to be good when the bactericidal activity value ≧ 0.
Bactericidal activity value = log (standard cloth / viable count immediately after inoculation) -log (processed sample / viable count after culture)
（洗濯方法）
ＪＩＳ−Ｌ１０９６Ｆ２法に基づいて洗濯を実施した。但し、洗い時の初期洗液温度を８０℃にして行った。洗濯は連続して５０回行い、最後にライン乾燥した。乾燥後の試料は２０℃及び６５％ＲＨの条件下に２４時間放置してから各評価に供した。
(Washing method)
Washing was performed based on the JIS-L1096F2 method. However, the initial washing temperature during washing was set to 80 ° C. Laundry was performed 50 times in a row and finally line dried. The dried sample was allowed to stand for 24 hours under the conditions of 20 ° C. and 65% RH, and then subjected to each evaluation.
（生地ｐＨ）
ＪＩＳ−Ｌ１０９６Ａ法に準拠して測定した。
(Dough pH)
It measured based on JIS-L1096A method.
（摩擦堅牢度）
ＪＩＳ−Ｌ０８４９Ａ法（ＩＩ型）に準拠して測定した。乾燥４級、及び湿潤３級以上のものを良好と判断した。
(Friction fastness)
It measured based on JIS-L0849A method (II type). Dry grade 4 and wet grade 3 or higher were judged good.
（風合）
繊維製品の風合は、３人のモニターで比較評価した。機能性樹脂皮膜の加工する直前のセット上がり繊維製品の風合の柔らかさを“◎”とした。また、実施例、比較例の中で最も風合いが硬くなった比較例２の処方で加工した繊維製品（経編，丸編，織物）を“×”として、“◎、○、△、×”の４段階の比較評価を行った。尚、織編の違う素材同士では比較せず、比較例２の処方で加工した織物、丸編、経編それぞれに“×”サンプルを作り、比較例２、未加工品と各実施例の３者で比較して評価した。
(Feel)
The texture of the textile product was comparatively evaluated by three monitors. The softness of the texture of the set-up fiber product immediately before processing the functional resin film was designated as “◎”. In addition, the fiber product (warp knitting, circular knitting, woven fabric) processed with the formulation of Comparative Example 2 having the hardest texture in Examples and Comparative Examples is “×”, “◎, ○, Δ, ×” A four-stage comparative evaluation was performed. It should be noted that materials of different weaving and knitting are not compared with each other, and “×” samples are made for each of the woven fabric, the circular knitting and the warp knitting processed according to the prescription of Comparative Example 2, and Comparative Example 2, unprocessed product and each of Examples 3 Evaluation was made by comparison.
本実施例で用いた基布として経編、丸編、織物の製造は以下の方法で行った。 As a base fabric used in this example, warp knitting, circular knitting, and woven fabric were produced by the following method.
（１）丸編：編物に用いる糸として、次の加工糸Ａ、Ｂ、Ｃ、紡績糸Ｄ、制電糸Ｅを用意した。加工糸Ａとして、ＴｉＯ２を１．５重量％含有する８４ｄｔｅｘ、４８フィラメントの丸断面のポリエステル仮撚加工糸を用いた。加工糸Ｂとして、ＴｉＯ２を０．５重量％含有する１１０ｄｔｅｘ、３６フィラメントの丸断面のポリエステル仮撚加工糸を用いた。加工糸Ｃとして、ＴｉＯ２を１．５重量％含有する１６７ｄｔｅｘ４８フィラメントの丸断面のポリエステル仮撚加工糸を用いた。紡績糸Ｄとして、綿１００％のリング紡績糸 英式番手５０／１を用いた。制電糸Ｅとして、ＫＢセーレン製ベルトロン（登録商標）２２ｄｔｅｘ３フィラメント（Ｂ６８タイプ）を用いた。 (1) Circular knitting: The following processed yarns A, B, C, spun yarn D, and antistatic yarn E were prepared as yarns used in the knitted fabric. As the processed yarn A, a polyester false twisted yarn having a round section of 84 dtex and 48 filaments containing 1.5% by weight of TiO 2 was used. As the processed yarn B, a 110 dtex, 36 filament round cross-section polyester false twisted yarn containing 0.5% by weight of TiO 2 was used. As the processed yarn C, a polyester false twisted yarn having a round cross section of 167 dtex 48 filaments containing 1.5% by weight of TiO 2 was used. As the spun yarn D, 100% cotton ring spun yarn English count 50/1 was used. As the antistatic yarn E, Beltron (registered trademark) 22 dtex3 filament (B68 type) manufactured by KB Seiren was used.
福原精機製ダブル丸編機（Ｖ−４ＡＬ）を用いて、口径３３ｉｎｃｈ、２８ゲージ／ｉｎｃｈ、針本数２９１６本で図１に示す組織でコードリバースを編み上げた。できあがった編地の混率は、ポリエステル９５％、綿５％であった。この生機を常法にて精練・過酸化漂白を行ったのち、開反してテンターで１８０℃×１分プレセットを行った。 Using a Fukuhara Seiki double circular knitting machine (V-4AL), a cord reverse was knitted with the structure shown in FIG. 1 with a caliber of 33 inch, 28 gauge / inch, and 2916 needles. The blend ratio of the finished knitted fabric was 95% polyester and 5% cotton. This raw machine was scoured and peroxygen bleached in a conventional manner, then opened and pre-set with a tenter at 180 ° C. for 1 minute.
（２）経編：経編に用いる糸として、加工糸Ａ、加工糸Ｆ、合撚糸Ｇを用意した。加工糸Ｆとして、ＴｉＯ２を０．５重量％含有する１６７ｄｔｅｘ４８フィラメントの丸断面のポリエステル仮撚加工糸を用いた。合撚糸Ｇとして、制電糸（２２ｄｔｅｘ３フィラメント ケービーセーレン製ベルトロン（登録商標））と加工糸ＡをＺ撚４００Ｔ／ｍで合撚した糸を用いた。 (2) Warp knitting: As yarns used for warp knitting, processed yarn A, processed yarn F, and twisted yarn G were prepared. As the processed yarn F, a polyester false twisted yarn having a round cross section of 167 dtex 48 filaments containing 0.5% by weight of TiO 2 was used. As the twisted yarn G, a yarn obtained by twisting an antistatic yarn (22 dtex3 filament, CB Selen Beltron (registered trademark)) and a processed yarn A at a Z twist of 400 T / m was used.
カールマイヤー製トリコット編機を用いて、第一筬（フロント）に加工糸Ａを、第二、第三筬に加工糸Ｆと合撚糸Ｇを２９本毎に１本の割合で配列した。そして、第四筬に加工糸Ａを使用して、フロント１０／１２、ミドル１１／００、バック２３／１０として筬番手２８ゲージ／ｉｎｃｈとしてトリコットハーフを作製した。この生機をプレウェットした後、精練を行い、テンターにて１８０℃×１分プレセットを行った。 Using a KARL MAYER tricot knitting machine, the processed yarn A was arranged on the first heel (front), and the processed yarn F and the twisted yarn G were arranged on the second and third ridges at a rate of one for every 29 pieces. Then, using the processed yarn A for the fourth kite, a tricot half was produced with a front count of 10/12, a middle of 11/00, and a back size of 23/10 with a count of 28 gauge / inch. After this wet machine was pre-wetted, scouring was performed, and a tenter was pre-set at 180 ° C. for 1 minute.
（３）織物：織物に用いる糸として、次の加工糸Ａ、合撚糸Ｈ、合撚糸Ｉを用意した。加工糸Ａは、甘撚（Ｓ撚４００Ｔ／ｍ）とした。合撚糸Ｈは、制電糸Ｅと加工糸ＡをＳ撚４００Ｔ／ｍで合撚した。合撚糸Ｉは、ＴｉＯ２を１．５重量％含有するＹ字型断面（異形度２．５）の８４ｄｔｅｘ、４８フィラメントのポリエステル仮撚加工と加工糸ＡをＺ撚で４００Ｔ／ｍにて合撚して１６７ｄｔｅｘとした。 (3) Fabric: The following processed yarn A, twisted yarn H, and twisted yarn I were prepared as yarns used for the fabric. The processed yarn A was a sweet twist (S twist 400 T / m). For the twisted yarn H, the antistatic yarn E and the processed yarn A were twisted at S twist of 400 T / m. Synthetic twisted yarn I is a Y-shaped cross section containing 1.5% by weight of TiO 2 (an irregularity of 2.5), 84 dtex, 48 filament polyester false twist processing and processed yarn A are combined with Z twist at 400 T / m. Twisted to 167 dtex.
経糸として、加工糸Ａ７１本毎に合撚糸Ｈを１本を配列して整経・糊付して経糸総数５７６８本の織機ビームを作製した。緯糸に合撚糸Ｉを用いてウォータージェットルームにて、筬番手 鯨寸６２番手、引込２本として、織上密度 経９０本／ｉｎｃｈ、緯糸６８本／ｉｎｃｈの平織（平織）を織り上げた。できあがった生機は、連続精練機にて糊抜き・精練を実施したのち、テンターにて１８０℃×１分プレセットを行った。 As warp yarns, one twisted yarn H was arranged for every 71 processed yarns A and warped and glued to produce a loom beam having a total of 5768 warp yarns. In the water jet loom, weaved a plain weave (plain weave) with a weaving density of 90 pieces / inch and weft density of 68 pieces / inch and weft 68 pieces / inch in a water jet loom by using the twisted yarn I as the weft. The finished machine was desizing and scouring with a continuous scourer, and then pre-set with a tenter at 180 ° C. for 1 minute.
実施例１
日本触媒製のアクアリック（登録商標）ＨＬ４１５（ポリアクリル酸水溶液 固形分３５重量％、重量平均分子量１００００）をモノエタノールアミン（ＧＲ）でｐＨ７に中和して用いた。
Example 1
AQUALIC (registered trademark) HL415 (polyacrylic acid aqueous solution, solid content 35% by weight, weight average molecular weight 10,000) manufactured by Nippon Shokubai was neutralized to pH 7 with monoethanolamine (GR) and used.
前記経編生地に、前記の中和したポリアクリル酸と、クラレ製イソバン（登録商標）１０４（イソブチレン−無水マレイン酸共重合ポリマーをアンモニア変性した（アンモニアで中和された）タイプ（重量平均分子量５５０００〜６５０００））を混合して下記の濃度になるように水で希釈して処方液１を作製した。
処方液１
・ポリアクリル酸固形分濃度として所定濃度５％ｓｏｌｕｔｉｏｎ（ｓｏｌｎ．）
（水１００ｍｌ中に５ｇ含む）
・イソバン１０４ ５％ｓｏｌｎ．
処方液１をパッド−ドライ−キュア法にて加工した。パディング時の処方液の生地付着率（液付着量／生地重量×１００）は１００％であった。このときのポリアクリル酸、イソバンの理論付着量は５％ｓｏｌｎ．×１００／１００＝５％ｏｗｆ（ｏｎ ｔｈｅ ｗｅｉｇｈｔ ｏｆ ｆｉｂｅｒ）である。また、乾燥は１２０℃、キュアは１５０℃×１分で行った。キュア後は水洗して蓚酸にてｐＨを調整した。ｐＨ調整後の生地ｐＨは５．０であった。実施例１の加工の詳細と評価結果を表１に示す。
On the warp knitted fabric, the neutralized polyacrylic acid and Kuraray Isoban (registered trademark) 104 (isobutylene-maleic anhydride copolymer modified with ammonia (neutralized with ammonia) type (weight average molecular weight) 55000-65000)) were mixed and diluted with water to the following concentration to prepare
-As a polyacrylic acid solid content concentration, a predetermined concentration of 5% solution (soln.)
(Includes 5g in 100ml water)
Isoban 104 5% soln.
実施例２
実施例１の処方液１の各薬剤濃度を二倍に変更（ポリアクリル酸を１０％ｓｏｌｎ．イソバン１０４を１０％ｓｏｌｎ．に変更）した以外は、実施例１と同様に加工した。実施例２の加工の詳細と評価結果を表１に示す。
Example 2
The processing was carried out in the same manner as in Example 1 except that the concentration of each drug in the
実施例３
生地は前記織物を用いて、ポリアクリル酸（アクアリックＨＬ４１５、重量平均分子量１００００）４．２％ｓｏｌｎ．及びイソバン１０４ ４．２％ｓｏｌｎ．の処方液２（加工剤濃度７０重量％）で加工した。このとき加工液の絞り率は６０％（ウェットピックアップ率Ｗ．Ｐ．Ｕ＝６０％）であった。この生地への薬剤固形分の理論付着量はポリアクリル酸 約２．５％ｏｗｆであり、イソバン１０４も２．５％ｏｗｆであった。実施例３の加工の詳細と評価結果を表１に示す。
Example 3
The fabric was made of the above-mentioned woven fabric, and polyacrylic acid (Aquaric HL415, weight average molecular weight 10,000) 4.2% soln. And isoban 104 4.2% soln. Was processed with the formulation liquid 2 (processing agent concentration 70% by weight). At this time, the drawing rate of the working fluid was 60% (wet pickup rate WPU = 60%). The theoretical adhesion amount of the drug solid content to the dough was about 2.5% owf of polyacrylic acid, and isoban 104 was also 2.5% owf. Table 1 shows details of processing and evaluation results of Example 3.
実施例４
実施例１の処方液１のポリアクリル酸濃度を二倍に変更（ポリアクリル酸を１０％ｓｏｌｎ．に変更）した以外は、実施例１と同様に加工した。実施例４の加工の詳細と評価結果を表１に示す。
Example 4
It processed like Example 1 except having changed polyacrylic acid concentration of
実施例５
実施例１の処方液１のイソバン１０４の濃度を二倍に変更（イソバン１０４を１０％ｓｏｌｎ．に変更）した以外は、実施例１と同様に加工した。実施例５の加工の詳細と評価結果を表１に示す。
Example 5
Processing was performed in the same manner as in Example 1 except that the concentration of isoban 104 in the
実施例６
実施例３において処方液２のポリアクリル酸（アクアリックＨＬ４１５、重量平均分子量１００００）に加えて重量平均分子量２２００００の日本触媒製アクアリックＨＬ３２１を０．６％ｓｏｌｎ．用いた（総ポリアクリル酸濃度４．８％ｓｏｌｎ．）。この際、処方液の粘度が上がりすぎるのを防ぐため、ポリアクリル酸は中和せずにそのまま使用して、キュア後の水洗にて中和を兼ねてｐＨを調整した。実施例６の加工の詳細と評価結果を表１に示す。
Example 6
In Example 3, in addition to the polyacrylic acid of formulation liquid 2 (Aquaric HL415, weight average molecular weight 10000), aqua catalyst HL321 made by Nippon Shokubai having a weight average molecular weight of 220,000 was 0.6% soln. Used (total polyacrylic acid concentration 4.8% soln.). At this time, in order to prevent the viscosity of the prescription solution from being increased too much, the polyacrylic acid was used as it was without being neutralized, and the pH was adjusted by washing with water after curing. Table 1 shows details of processing and evaluation results of Example 6.
実施例７
アクアリックＨＬ４１５の代わりに、アクアリックＤＬ３６５（ポリアクリル酸ナトリウム、重量平均分子量５５００）を用いた以外は、実施例１と同様に実施した。実施例７の加工の詳細と評価結果を表１に示す。
Example 7
It implemented similarly to Example 1 except having used Aqualic DL365 (sodium polyacrylate, the weight average molecular weight 5500) instead of Aqualic HL415. Table 1 shows details of processing and evaluation results of Example 7.
実施例８
生地は前記丸編を用いて、架橋剤として、エチレンジアミン０．５％ｓｏｌｎ．を処方液１に追加して加工した以外は、実施例１と同様に実施した。実施例８の加工の詳細と評価結果を表１に示す。
Example 8
The fabric used was the above circular knitting, and ethylenediamine 0.5% soln. Was carried out in the same manner as in Example 1, except that it was added to the
実施例９
アクアリックＨＬ４１５の代わりにナカライテスク社製ポリアクリル酸ナトリウム（ポリマー）（重量平均分子量３００００〜４００００）を水に溶かして用い、イソバン１０４の代わりにイソバン１１０（イソブチレン−無水マレイン酸共重合ポリマーをアンモニア変性した（アンモニアで中和された）タイプ（重量平均分子量１６５０００））を用いた以外は、実施例１と同様に実施した。実施例９の加工の詳細と評価結果を表１に示す。
Example 9
Instead of Aqualic HL415, sodium polyacrylate (polymer) (weight average molecular weight: 30,000 to 40,000) manufactured by Nacalai Tesque is used by dissolving in water, and isoban 110 (isobutylene-maleic anhydride copolymer) is used instead of isoban 104 as ammonia. This was carried out in the same manner as in Example 1 except that a modified type (neutralized with ammonia) (weight average molecular weight 165000) was used. Table 1 shows details of processing and evaluation results of Example 9.
実施例１０
キュア後の水洗工程にて苛性ソーダを用いて生地ｐＨを１０．２に調整した以外は、実施例１と同様に実施した。実施例１０の加工の詳細と評価結果を表１に示す。
Example 10
The same procedure as in Example 1 was performed except that the dough pH was adjusted to 10.2 using caustic soda in the water washing step after curing. Table 1 shows details of processing and evaluation results of Example 10.
実施例１１
実施例１の処方液１の加工後に２段目処理として、更に日華化学製ニッカノン（登録商標）ＮＳ−３０（第四級アンモニウム塩系抗菌剤 不揮発分４０重量％）２％ｓｏｌｎ．でＷ．Ｐ．Ｕ＝６０％にて抗菌加工を実施した。実施例１１の加工の詳細と評価結果を表１に示す。
Example 11
Nikkanon (registered trademark) NS-30 (quaternary ammonium salt antibacterial agent non-volatile content: 40% by weight) 2% soln. W. P. Antibacterial processing was performed at U = 60%. Table 1 shows details of processing and evaluation results of Example 11.
比較例１
前記丸編を用いて、日本エクスラン工業製の高吸湿性アクリレート微粒子分散液タフチック（登録商標）ＨＵ７０７Ｅ（固形分１５〜２０重量％）、及び日本触媒製のエポクロス（登録商標）ＷＳ７００（オキサゾリン系バインダー固形分２５重量％）をＨＵ７０７Ｅ ５％ｓｏｌｎ．及びエポクロスＷＳ−７００ ３％ｓｏｌｎ．になるようにしてＷ．Ｐ．Ｕ＝１００％で加工した。比較例１の加工の詳細と評価結果を表１に示す。
Comparative Example 1
Using the circular knitting, highly hygroscopic acrylate fine particle dispersion Tuftic (registered trademark) HU707E (solid content 15-20% by weight) manufactured by Nippon Exlan Industry, and Epocros (registered trademark) WS700 (oxazoline binder) manufactured by Nippon Shokubai Co., Ltd. HU707E 5% soln. And Epocros WS-700 3% soln. W. P. Processed at U = 100%. Table 1 shows details of processing and evaluation results of Comparative Example 1.
比較例２
前記丸編を用いて、イソバン１０４の代わりに、大和化学工業製のバインダーＵ−３０ＮＰ（ポリウレタン系バインダー）を同量５％ｓｏｌｎ．使用した以外は、実施例１と同様に実施した。比較例２の加工の詳細と評価結果を表１に示す。
Comparative Example 2
Using the circular knitting, instead of isoban 104, a binder U-30NP (polyurethane binder) manufactured by Daiwa Chemical Industry Co., Ltd. was used in the same amount of 5% soln. The same operation as in Example 1 was carried out except that it was used. Table 1 shows details of processing and evaluation results of Comparative Example 2.
比較例３
前記丸編の染色１８０℃×１分中間セット上がりをそのまま評価した。比較例３の加工の詳細と評価結果を表１に示す。
Comparative Example 3
The dyeing of the circular knitting at 180 ° C. × 1 minute was evaluated as it was. Table 1 shows details of processing and evaluation results of Comparative Example 3.
本発明によれば、消臭性や吸湿性に優れるポリ（メタ）アクリル酸系重合体を、洗濯耐久性良く、風合いも硬くならずに繊維に固着させた機能性繊維製品を提供することができる。 According to the present invention, it is possible to provide a functional fiber product in which a poly (meth) acrylic acid polymer having excellent deodorizing properties and hygroscopicity is fixed to a fiber with good washing durability and without feeling hard. it can.
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