JP2024004469A - Method of producing cationic dye-dyeable fiber - Google Patents
Method of producing cationic dye-dyeable fiber Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 194
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229940126062 Compound A Drugs 0.000 claims abstract description 63
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000004043 dyeing Methods 0.000 claims abstract description 63
- 239000004744 fabric Substances 0.000 claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 230000002378 acidificating effect Effects 0.000 claims abstract description 28
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 22
- 230000005855 radiation Effects 0.000 claims abstract description 19
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 43
- 238000010559 graft polymerization reaction Methods 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- 125000001165 hydrophobic group Chemical group 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- 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 claims description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Chemical class 0.000 claims description 2
- 239000002184 metal Chemical class 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical class 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 abstract description 21
- 239000004745 nonwoven fabric Substances 0.000 abstract description 6
- 239000002759 woven fabric Substances 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 103
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 19
- 238000005406 washing Methods 0.000 description 19
- 238000010894 electron beam technology Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 229920002972 Acrylic fiber Polymers 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241001584775 Tunga penetrans Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 235000009120 camo Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 235000005607 chanvre indien Nutrition 0.000 description 2
- 235000013351 cheese Nutrition 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009975 hank dyeing Methods 0.000 description 2
- 239000011487 hemp Substances 0.000 description 2
- 238000009981 jet dyeing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000009974 package dyeing Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 239000000984 vat dye Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000009976 warp beam dyeing Methods 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000001263 FEMA 3042 Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical group CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Chemical group CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009971 piece dyeing Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000009970 yarn dyeing Methods 0.000 description 1
Abstract
Description
本発明は、カチオン染料可染性繊維の製造方法、前記カチオン染料可染性繊維を含む混紡品、及び前記カチオン染料可染性繊維または前記混紡品の染色方法に関する。 The present invention relates to a method for producing a fiber dyeable with cationic dyes, a blended product containing the fiber dyeable with cationic dyes, and a method for dyeing the fiber dyeable with cationic dyes or the blended fabric.
セルロース繊維は、木綿（コットン）、麻などの天然セルロース繊維と、レーヨンなどの再生繊維がある。従来からセルロース繊維は、直接染料、反応染料、硫化染料、ナフトール染料、スレン染料（建染染料、バット染料）などによって染色されている。ところが、このような染料を用いた染色方法では、濃色で鮮明な色調を出すことは困難であった。一方、鮮明な色調を出せる染料としてカチオン染料が知られている。カチオン染料はイオン結合により化学的に染色されるため発色性がよいが、この染料はアクリル系繊維、カチオン可染型ポリエステル繊維などに適用されている（非特許文献１）。非改質のセルロース繊維は、そのままでは染着座席はなく、カチオン染料には染まらない。 Cellulose fibers include natural cellulose fibers such as cotton and hemp, and recycled fibers such as rayon. Conventionally, cellulose fibers have been dyed with direct dyes, reactive dyes, sulfur dyes, naphthol dyes, thren dyes (vat dyes, vat dyes), and the like. However, with dyeing methods using such dyes, it has been difficult to produce deep and clear tones. On the other hand, cationic dyes are known as dyes that can produce vivid color tones. Cationic dyes have good coloring properties because they are chemically dyed by ionic bonds, and these dyes have been applied to acrylic fibers, cationically dyeable polyester fibers, etc. (Non-Patent Document 1). Unmodified cellulose fibers have no dyeing seat and cannot be dyed with cationic dyes.
特許文献１には、スルホン基、カルボキシル基、リン酸基などの酸性基をケミカルグラフト法によりセルロース繊維に導入することによりカチオン染料に対する染着性を改善し、さらにアセチル化することで洗濯堅牢度を向上させる染色性の改善方法が開示されている。特許文献２には、アルカリ剤と特定の化合物とを含む水溶液にセルロース繊維を浸漬させることでセルロース繊維に酸性基を導入し、酸性基導入セルロース繊維またはその繊維構造物を、カチオン染料にて染色した後、洗浄、タンニン酸処理、吐酒石酸処理、洗浄、乾燥を行う、酸性基導入セルロース繊維またはその繊維構造物の染色方法が開示されている。 Patent Document 1 discloses that acidic groups such as sulfone groups, carboxyl groups, and phosphoric acid groups are introduced into cellulose fibers by chemical grafting to improve dyeability with cationic dyes, and washing fastness is improved by acetylation. A method for improving stainability is disclosed. Patent Document 2 discloses that acidic groups are introduced into cellulose fibers by immersing the cellulose fibers in an aqueous solution containing an alkaline agent and a specific compound, and the acidic group-introduced cellulose fibers or their fiber structures are dyed with a cationic dye. Disclosed is a method for dyeing acidic group-introduced cellulose fibers or fiber structures thereof, which is then washed, treated with tannic acid, treated with tartaric acid, washed, and dried.
しかし、前記従来技術では、酸性基の導入がケミカルグラフト法によるため、連続式で行うことが困難である。また、酸性基の導入に際し、所定時間加熱を行うので、エネルギー使用量が多いという問題がある。 However, in the above-mentioned conventional technology, introduction of acidic groups is carried out by a chemical grafting method, and therefore it is difficult to carry out the introduction in a continuous manner. Furthermore, since heating is performed for a predetermined period of time when introducing acidic groups, there is a problem in that a large amount of energy is used.
本発明は、一態様において、少ないエネルギー量で且つ連続処理で酸性基を導入できる、カチオン染料可染性繊維の製造方法を提供する。また、本発明は、一態様において、当該カチオン染料可染性繊維を含む混紡品、及び当該カチオン染料可染性繊維を含む染色対象の染色方法を提供する。 In one aspect, the present invention provides a method for producing cationic dye-dyeable fibers that can introduce acidic groups with a small amount of energy and in a continuous process. Further, in one aspect, the present invention provides a blended product containing the cationic dye-dyeable fiber, and a method for dyeing an object to be dyed containing the cationic dye-dyeable fiber.
本発明は、一態様において、カチオン染料可染性繊維の製造方法であって、酸性基とエチレン性不飽和二重結合とを含む化合物Ａを繊維に接触させ、前記化合物Ａと前記繊維との接触の前又は同時に前記繊維に放射線を照射して、前記繊維に前記化合物Ａをグラフト重合させる工程を含む、カチオン染料可染性繊維の製造方法に関する。 In one embodiment, the present invention provides a method for producing a cationic dye-dyeable fiber, comprising: bringing a compound A containing an acidic group and an ethylenically unsaturated double bond into contact with the fiber; The present invention relates to a method for producing a cationic dye-dyeable fiber, which includes a step of graft polymerizing the compound A onto the fiber by irradiating the fiber with radiation before or at the same time as contacting the fiber.
本発明は、一態様において、前記カチオン染料可染性繊維の製造方法により製造されたカチオン染料可染性繊維と他の繊維とを含む混紡品に関する。 In one embodiment, the present invention relates to a blended product containing a cationic dye-dyeable fiber produced by the method for producing a cationic dye-dyeable fiber and another fiber.
本発明は、一態様において、前記カチオン染料可染性繊維の製造方法により製造されたカチオン染料可染性繊維又は前記混紡品の染色方法であって、
カチオン染料を含む染液を、前記カチオン染料可染性繊維又は前記混紡品に接触させる工程を含む、染色方法に関する。
In one embodiment, the present invention provides a method for dyeing a cationic dye-dyeable fiber or a blended fabric produced by the method for producing a cationic dye-dyeable fiber, comprising:
The present invention relates to a dyeing method including a step of bringing a dye solution containing a cationic dye into contact with the cationic dye-dyeable fiber or the blended fabric.
本発明によれば、少ないエネルギー量で且つ連続処理で酸性基を繊維に導入できるカチオン染料可染性繊維の製造方法、当該カチオン染料可染性繊維を含む混紡品、および染色品を提供できる。 According to the present invention, it is possible to provide a method for producing a cationic dye-dyeable fiber that can introduce acidic groups into the fiber in a continuous process with a small amount of energy, a blended product containing the cationic dye-dyeable fiber, and a dyed product.
（実施形態１）
本発明のカチオン染料可染性繊維の製造方法は、一態様において、以下の工程を含む。
（１）グラフト重合工程
一分子中に酸性基とエチレン性不飽和二重結合とを含む化合物Ａ（以下「化合物Ａ」と略称する場合もある。）を繊維に接触させ、前記接触の前又は同時に前記繊維に放射線を照射してラジカルを発生させ、前記繊維に前記化合物Ａをグラフト重合させる工程。
（２）洗浄工程
（３）乾燥工程
(Embodiment 1)
In one embodiment, the method for producing a cationic dye-dyeable fiber of the present invention includes the following steps.
(1) Graft polymerization step Compound A containing an acidic group and an ethylenically unsaturated double bond in one molecule (hereinafter sometimes abbreviated as "compound A") is brought into contact with the fiber, and before the contact or A step of simultaneously irradiating the fiber with radiation to generate radicals and graft-polymerizing the compound A onto the fiber.
(2) Washing process (3) Drying process
［グラフト重合工程］
本発明において、繊維には、カチオン染料に対して染着座席を持たない、セルロース繊維、ポリエステル繊維などの非イオン性繊維（疎水性合成繊維）、ナイロン、ポリ乳酸繊維、アセテート繊維及びエチレンビニルアルコール繊維などが含まれる。セルロース繊維には、木綿（コットン）、麻などの天然セルロース繊維と、レーヨンなどの再生繊維が含まれる。セルロース繊維は、非改質では、カチオン染料で染めることはできない。本発明では、前記繊維に放射線を照射してラジカルを発生させ、前記化合物Ａを繊維にグラフト重合させる。これにより、セルロース繊維などの繊維は、カチオン染料で染色可能となる。カチオン染料で染色された染色物は、濃色で鮮明な色調であることは、アクリル系繊維、カチオン可染型ポリエステル繊維で実証されている。放射線は、単位時間当たりの放射線強度（線量率）が高い電子線が好ましい。
[Graft polymerization process]
In the present invention, the fibers include nonionic fibers (hydrophobic synthetic fibers) such as cellulose fibers and polyester fibers that do not have a dyeing seat for cationic dyes, nylon, polylactic acid fibers, acetate fibers, and ethylene vinyl alcohol. Includes fiber. Cellulose fibers include natural cellulose fibers such as cotton and linen, and recycled fibers such as rayon. Unmodified cellulose fibers cannot be dyed with cationic dyes. In the present invention, the fibers are irradiated with radiation to generate radicals, and the compound A is graft-polymerized onto the fibers. This allows fibers such as cellulose fibers to be dyed with cationic dyes. It has been demonstrated for acrylic fibers and cationic dyeable polyester fibers that dyed products dyed with cationic dyes have deep and vivid colors. The radiation is preferably an electron beam with high radiation intensity (dose rate) per unit time.
前記放射線が照射される前記繊維の状態は、綿（わた）状、スライバー状、糸状、織物状、編物状及び不織布状から選ばれる少なくとも一つの状態が好ましい。以下、前記状態をまとめて繊維基材と総称する。これらの中でも、グラフト重合の対象とされる繊維基材の状態は、好ましくは、グラフト重合する際の連続処理が可能なスライバー状、糸状、織物状、編物状又は不織布状であり、より好ましくは、スライバー状である。スライバー状の繊維にグラフト重合すると、他の繊維のスライバーと練条工程でスライバー混紡が行える。 The state of the fibers to which the radiation is irradiated is preferably at least one state selected from cotton, sliver, thread, woven, knitted, and nonwoven fabric. Hereinafter, the above state will be collectively referred to as a fiber base material. Among these, the state of the fiber base material to be subjected to graft polymerization is preferably in the form of a sliver, thread, woven fabric, knitted fabric, or nonwoven fabric, which can be continuously processed during graft polymerization, and more preferably , sliver-like. When graft polymerized to sliver-like fibers, the sliver can be blended with slivers of other fibers in the drawing process.
本態様において、前記化合物Ａのグラフト率は、強度保持と濃色染色との両立の観点から、好ましくは０．１～５０．０ｗｔ％、より好ましくは１．０～４５．０ｗｔ％、さらに好ましくは５．０～４０．０ｗｔ％であり、さらにより好ましくは１２．０～３６．０ｗｔ％である。前記繊維との接触に使用される前記化合物Ａの使用量は、グラフト率が上記範囲内の値となるような量であると好ましい。
なお、グラフト率は、グラフト加工前後の重量差より算出する重量の増加率（ｗｔ％）であり、その計算式は下記式（１）の通りである。下記式（１）中、Ｗ0はグラフト加工前の繊維の重量、Ｗgはグラフト加工後の繊維の重量である。重量測定される繊維の状態は、綿（わた）状、スライバー状、糸状、織物状、編物状及び不織布状のいずれであってもよい。
グラフト率(ｗｔ％)＝(Ｗg-Ｗ0)／Ｗ0×１００ （１）
In this embodiment, the grafting ratio of the compound A is preferably 0.1 to 50.0 wt%, more preferably 1.0 to 45.0 wt%, and even more preferably is 5.0 to 40.0 wt%, and even more preferably 12.0 to 36.0 wt%. The amount of the compound A used in contact with the fibers is preferably such that the grafting rate falls within the above range.
Incidentally, the graft ratio is the weight increase rate (wt%) calculated from the weight difference before and after the grafting process, and the calculation formula is as shown in the following formula (1). In the following formula (1), W 0 is the weight of the fiber before grafting, and W g is the weight of the fiber after grafting. The fibers to be weighed may be in the form of cotton, sliver, thread, woven fabric, knitted fabric, or nonwoven fabric.
Grafting rate (wt%) = (W g - W 0 )/W 0 ×100 (1)
前記酸性基はアニオン基とも言い、前記化合物Ａがグラフト結合された前記繊維において、カチオン染料の染着座席となる。前記酸性基は、好ましくはカルボキシル基（－ＣＯＯＨ）、リン酸基（－ＰＯ(ＯＨ)2）またはスルホン酸基（－ＳＯ3Ｈ）であり、より好ましくは弱酸性であるカルボキシル基である。また、前記酸性基は、金属塩などの塩の形態であってもよい。前記酸性基の塩としては、－ＣＯＯ-Ｎａ+基、－ＰＯ3 2-２Ｎａ+基又は－ＳＯ3 -Ｎａ+基などの、アルカリ金属塩、好ましくは、酸性基のナトリウム塩が挙げられる。前記酸性基は、化合物Ａにおいて、エチレン性不飽和二重結合に直接結合していてもよいが、分子鎖を介してエチレン性不飽和二重結合に結合していてもよい。前記化合物Ａは、具体的には、好ましくは、アクリル酸、メタクリル酸、２－メタクリロイルオキシエチルリン酸、ビニルスルホン酸ナトリウム、スチレンスルホン酸ナトリウム（Ｓスルホン酸Ｎａ）、および２－アクリルアミド－２－メチルプロパンスルホン酸（ＡＭＰＳ）から選ばれる少なくとも一つであり、より好ましくは、弱酸性である、アクリル酸、メタクリル酸、およびＳスルホン酸Ｎａから選ばれる少なくとも一つであり、更に好ましくは、アクリル酸およびメタクリル酸から選ばれる少なくとも一つである。前記化合物Ａの酸性基は、前記繊維との接触前に前記塩の形態としてもよいし、前記繊維との接触後、或いはグラフト重合後に、前記塩の形態となることもある。このようにして、前記化合物Ａがグラフト結合された繊維は、カチオン染料可染性繊維となる。 The acidic group is also called an anionic group, and serves as a dyeing site for the cationic dye in the fiber to which the compound A is grafted. The acidic group is preferably a carboxyl group (-COOH), a phosphoric acid group (-PO(OH) 2 ) or a sulfonic acid group (-SO 3 H), and more preferably a weakly acidic carboxyl group. Furthermore, the acidic group may be in the form of a salt such as a metal salt. Examples of the salts of the acidic group include alkali metal salts, preferably sodium salts of the acidic group, such as -COO - Na + group, -PO 3 2- 2Na + group or -SO 3 - Na + group. In compound A, the acidic group may be directly bonded to the ethylenically unsaturated double bond, or may be bonded to the ethylenically unsaturated double bond via a molecular chain. Specifically, the compound A is preferably acrylic acid, methacrylic acid, 2-methacryloyloxyethyl phosphoric acid, sodium vinylsulfonate, sodium styrenesulfonate (Na Ssulfonate), and 2-acrylamide-2- At least one selected from methylpropanesulfonic acid (AMPS), more preferably at least one selected from weakly acidic acrylic acid, methacrylic acid, and Na S sulfonate, still more preferably acrylic At least one selected from acid and methacrylic acid. The acidic group of the compound A may be in the form of the salt before contacting with the fiber, or may be in the form of the salt after contact with the fiber or after graft polymerization. In this way, the fiber to which the compound A is grafted becomes a cationic dye-dyeable fiber.
前記グラフト重合では、繊維への電子線（Ｅｌｅｃｔｒｏｎ Ｂｅａｍ）照射によりラジカルを発生させ、当該繊維と前記化合物Ａとの接触により、前記繊維に前記化合物Ａをグラフト重合させるのが好ましい。電子線照射は、易取扱い性、安全性、ラジカルを有効に発生させることができるなどの観点から、前記化合物Ａの前記繊維へのグラフト重合に好適である。また、電子線グラフト重合法などの放射線グラフト重合法によれば、連続加工が可能であり、エネルギーの使用量も少なく、薬剤を用いるケミカル法よりも工程数も少なく、廃液処理の問題、水使用量の増大を伴わないので、好ましい。 In the graft polymerization, it is preferable that radicals are generated by irradiating the fiber with an electron beam, and the compound A is graft-polymerized onto the fiber by contacting the fiber with the compound A. Electron beam irradiation is suitable for graft polymerization of the compound A to the fibers from the viewpoints of ease of handling, safety, and ability to effectively generate radicals. In addition, radiation graft polymerization methods such as electron beam graft polymerization methods allow continuous processing, use less energy, have fewer steps than chemical methods that use chemicals, and are free from waste liquid treatment problems and water usage. This is preferred because it does not involve an increase in quantity.
照射される電子線の線量は、通常、１～２００ｋＧｙであり、好ましくは５～１００ｋＧｙ、より好ましくは１０～５０ｋＧｙである。電子線の照射は、空気中でもよいが、窒素雰囲気下で照射を行うと好ましい。また、電子線の浸透力（透過能力）は、その加速電圧によって決まり、前記繊維基材の片側から照射するだけで、反対側に達するまで、電子線を浸透させることができる。電子線照射装置としては市販のものが使用可能であり、例えば、エレクトロカーテン型電子線照射装置としてＥＣ２５０／１５／１８０Ｌ（岩崎電気（株）製）、ＥＣ３００／１６５／８００（岩崎電気（株）製）、ＥＰＳ３００（（株）ＮＨＶコーポレーション製）などが使用できる。繊維と前記化合物Ａとの接触は、例えば、前記繊維基材を前記化合物Ａの水溶液に所定の浴比で浸漬させるか、又は前記水溶液を滴下することで行える。接触時間（反応時間）は、使用される化合物Ａの種類や接触方法などに応じて異なるが、通常、好ましくは１０～６０分、より好ましくは１０～３０分である。前記水溶液には、さらに浸透剤などが含まれていてもよい。 The dose of the irradiated electron beam is usually 1 to 200 kGy, preferably 5 to 100 kGy, and more preferably 10 to 50 kGy. Although the electron beam irradiation may be performed in air, it is preferable to perform the irradiation under a nitrogen atmosphere. Further, the penetrating power (penetration ability) of the electron beam is determined by its accelerating voltage, and by simply irradiating it from one side of the fiber base material, the electron beam can penetrate until it reaches the opposite side. Commercially available electron beam irradiators can be used, such as electrocurtain type electron beam irradiators such as EC250/15/180L (manufactured by Iwasaki Electric Co., Ltd.) and EC300/165/800 (manufactured by Iwasaki Electric Co., Ltd.). (manufactured by NHV Corporation), EPS300 (manufactured by NHV Corporation), etc. can be used. The contact between the fiber and the compound A can be carried out, for example, by immersing the fiber base material in an aqueous solution of the compound A at a predetermined bath ratio, or by dropping the aqueous solution. The contact time (reaction time) varies depending on the type of compound A used and the contact method, but is usually preferably 10 to 60 minutes, more preferably 10 to 30 minutes. The aqueous solution may further contain a penetrant or the like.
［洗浄工程］
前記洗浄工程では、グラフト反応終了後、水洗により未反応成分を除去する。未反応成分を除去することにより染めむらの発生を抑制できる。水洗は、好ましくは流水中で行い、水の温度は１５～６０℃であると好ましい。
[Washing process]
In the washing step, after the grafting reaction is completed, unreacted components are removed by washing with water. By removing unreacted components, uneven dyeing can be suppressed. Washing with water is preferably carried out under running water, and the temperature of the water is preferably 15 to 60°C.
［乾燥工程］
前記乾燥工程は、前記化合物Ａがグラフト重合された繊維基材を、例えば、乾燥温度１００℃、乾燥時間５分程度で行う。なお、２０～９０℃で０．５～２４時間乾燥してもよく、風乾してもよい。
[Drying process]
The drying step is performed on the fiber base material graft-polymerized with the compound A at a drying temperature of 100° C. and a drying time of about 5 minutes, for example. Note that drying may be performed at 20 to 90° C. for 0.5 to 24 hours, or air drying may be performed.
本発明のカチオン染料可染性繊維の製造方法により得られたカチオン染料可染性繊維は、放射線が照射される繊維の状態に応じて、綿（わた）状、スライバー状、糸状、織物状、編物状及び不織布状から選ばれる少なくとも一つの状態である。 The cationic dye-dyeable fiber obtained by the method for producing cationic dye-dyeable fiber of the present invention can be cotton-like, sliver-like, thread-like, woven-like, The state is at least one selected from knitted fabric-like and non-woven fabric-like.
（実施形態２）
本発明のカチオン染料可染性繊維の製造方法は、別の一態様において、以下の工程を含む。
（１）グラフト重合工程
前記化合物Ａを繊維に接触させ、前記化合物Ａと前記繊維との接触の前又は接触と同時に前記繊維に放射線を照射してラジカルを発生させ、前記繊維に前記化合物Ａをグラフト重合させ、下記化合物Ｂを繊維に接触させ、前記化合物Ｂと前記繊維との接触の前又は接触と同時に前記繊維に放射線を照射してラジカルを発生させ、前記繊維に前記化合物Ｂをグラフト重合させる工程。
（２）洗浄工程
（３）乾燥工程
(Embodiment 2)
In another embodiment, the method for producing a cationic dye-dyeable fiber of the present invention includes the following steps.
(1) Graft polymerization step The compound A is brought into contact with the fiber, and the fiber is irradiated with radiation before or simultaneously with the contact between the compound A and the fiber to generate radicals, and the compound A is brought into contact with the fiber. Graft polymerization, bringing the following compound B into contact with the fibers, irradiating the fibers with radiation before or simultaneously with the contact between the compound B and the fibers to generate radicals, and graft polymerizing the compound B onto the fibers. process.
(2) Washing process (3) Drying process
化合物Ｂは、一分子中に疎水性基とエチレン性不飽和二重結合を含む化合物であり、極性が小さい分子構造を有する。 Compound B is a compound containing a hydrophobic group and an ethylenically unsaturated double bond in one molecule, and has a molecular structure with low polarity.
［グラフト重合工程］
本態様におけるグラフト重合工程は、繊維に対して、化合物Ａに加えて化合物Ｂもグラフト結合させること以外は、（実施形態１）における［グラフト重合工程］と同じである。化合物Ｂのグラフト結合には、化合物Ｂが直接繊維に結合する場合、化合物Ｂが繊維にグラフト結合した化合物Ａに結合する場合、のいずれか一方または双方が含まれる。
木綿に代表されるセルロース繊維は、親水基である水酸基を分子内に多数有しているため、カチオン染料の疎水部分との相互作用が少ない。しかし、本態様では、疎水性基を有する化合物Ｂが、グラフト結合により繊維表面に導入されているので、当該疎水性基とカチオン染料の疎水部分との強い疎水性相互作用によって、カチオン染料が繊維表面または繊維表面近傍に強く引き寄せられる。そのため、グラフト結合されている化合物Ａの酸性基（染着座席）へのカチオン染料の染着が効果的に行われることとなり、カチオン染料の繊維に対する染着率が向上し、その結果、繊維をより濃色に染色することが可能となる。
[Graft polymerization process]
The graft polymerization step in this embodiment is the same as the [graft polymerization step] in (Embodiment 1) except that compound B is also grafted to the fiber in addition to compound A. Graft bonding of compound B includes either or both of the cases where compound B is directly bonded to the fiber, and the case where compound B is bonded to compound A graft bonded to the fiber.
Cellulose fibers, typified by cotton, have many hydroxyl groups, which are hydrophilic groups, in their molecules, so they have little interaction with the hydrophobic portion of cationic dyes. However, in this embodiment, compound B having a hydrophobic group is introduced onto the fiber surface through graft bonding, so the cationic dye is transferred to the fiber due to the strong hydrophobic interaction between the hydrophobic group and the hydrophobic part of the cationic dye. Strongly attracted to surfaces or near fiber surfaces. Therefore, the cationic dye is effectively dyed to the acidic group (dyeing seat) of the graft-bonded compound A, and the dyeing rate of the cationic dye to the fiber is improved.As a result, the dyeing of the fiber is improved. It becomes possible to dye darker colors.
化合物Ｂは、染着性の向上の観点から、例えば、化合物Ａが、アクリル酸およびメタクリル酸から選ばれる少なくとも一つである場合、好ましくは、アクリル酸系エステルおよびメタクリル酸系エステルから選ばれる少なくとも一つである。疎水性基としては、例えば、アルキル基、またはアリール基等の炭化水素基が挙げられるが、カチオン染料の酸性基への染着の立体障害となりにくいという理由から、直鎖状または分岐状の炭化水素基が好ましく、直鎖状または分岐状のアルキル基がより好ましく、直鎖状のアルキル基がさらに好ましい。疎水性基の炭素鎖が長いほど、分子の極性が小さくなりカチオン染料の染着に有利であるが、炭素鎖が長いほど、グラフト加工用の水溶液の調整の際の水への化合物Ｂの分散が難しくなる。したがって、カチオン染料の染着性の向上とグラフト加工用の水溶液の調整の容易性の両立の観点から、前記炭化水素基の炭素数は、好ましくは１以上１８以下であり、より好ましくは１以上１２以下であり、さらに好ましくは１以上４以下である。なお、前記グラフト加工用の水溶液の調整の際に化合物Ｂを水に分散させるために、ポリオキシエチレンソルビタンモノラウレート等の界面活性剤を併用してもよく、炭化水素基の炭素鎖が長い場合は、界面活性剤で化合物Ｂを積極的に分散させてもよい。 From the viewpoint of improving dyeability, for example, when Compound A is at least one selected from acrylic acid and methacrylic acid, Compound B preferably contains at least one selected from acrylic esters and methacrylic esters. There is one. Examples of hydrophobic groups include hydrocarbon groups such as alkyl groups and aryl groups, but linear or branched carbonized groups are preferred because they are less likely to cause steric hindrance to the dyeing of cationic dyes to acidic groups. A hydrogen group is preferable, a linear or branched alkyl group is more preferable, and a linear alkyl group is even more preferable. The longer the carbon chain of the hydrophobic group, the smaller the polarity of the molecule, which is advantageous for dyeing with cationic dyes, but the longer the carbon chain, the more difficult it is to disperse compound B in water when preparing an aqueous solution for grafting. becomes difficult. Therefore, from the viewpoint of both improving the dyeability of the cationic dye and facilitating preparation of the aqueous solution for grafting, the number of carbon atoms in the hydrocarbon group is preferably 1 or more and 18 or less, more preferably 1 or more. It is 12 or less, more preferably 1 or more and 4 or less. In addition, in order to disperse Compound B in water when preparing the aqueous solution for grafting, a surfactant such as polyoxyethylene sorbitan monolaurate may be used in combination, and if the hydrocarbon group has a long carbon chain, In such cases, compound B may be actively dispersed with a surfactant.
化合物Ｂは、より具体的には、染着性の向上の観点から、好ましくはアクリル酸メチル、メタクリル酸メチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸ドデシル、メタクリル酸ドデシル、アクリル酸ステアリル、およびメタクリル酸ステアリルから選ばれる少なくとも１種のモノマーであり、より好ましくはアクリル酸メチル、メタクリル酸メチル、アクリル酸ブチル、およびメタクリル酸ブチルから選ばれる少なくとも１種のモノマーである。 More specifically, compound B is preferably methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, or methacrylate, from the viewpoint of improving dyeability. At least one monomer selected from propyl acid, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, and stearyl methacrylate, more preferably from methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate. At least one selected monomer.
また、化合物Ｂは、ビニル基を有する芳香族化合物であってもよい。具体的には、芳香族化合物の置換基にビニル基が含まれる化合物が挙げられ、より具体的には、スチレン、ビニルナフタレン等が挙げられる。化合物Ｂが、疎水性基として芳香族炭化水素を含む場合、当該疎水性基とカチオン染料分子との疎水性相互作用により、染料分子が繊維表面または繊維表面近傍に引き寄せられ、カチオン染料の染着が効果的に行われる。 Moreover, the compound B may be an aromatic compound having a vinyl group. Specifically, examples include compounds in which a vinyl group is included as a substituent of an aromatic compound, and more specifically, styrene, vinylnaphthalene, and the like. When compound B contains an aromatic hydrocarbon as a hydrophobic group, the hydrophobic interaction between the hydrophobic group and the cationic dye molecule causes the dye molecule to be attracted to the fiber surface or near the fiber surface, resulting in dyeing of the cationic dye. is carried out effectively.
このように２種のモノマーを繊維にグラフト結合させる方法として、好ましくは、２種のモノマーを同時に繊維に接触させる共グラフト重合法、または、一方のモノマーをグラフト結合させた後に他方のモノマーをグラフト結合させる二段グラフト重合法が挙げられるが、放射線の照射による繊維の劣化および生産効率の観点から、より好ましくは、共グラフト重合法が好ましい。
すなわち、本開示のカチオン染料可染性繊維の製造方法は、一態様において、より好ましくは、前記化合物Ａに加えて、疎水性基とエチレン性不飽和二重結合とを含む化合物Ｂを前記繊維に接触させ、前記化合物Ａおよび前記化合物Ｂと前記繊維との前記接触の前又は同時に前記繊維に放射線を照射して、前記繊維に前記化合物Ａおよび前記化合物Ｂをグラフト重合させることを含む。
As a method for grafting two types of monomers to fibers in this way, preferably, a cograft polymerization method in which two types of monomers are brought into contact with fibers at the same time, or a method in which one monomer is grafted and then the other monomer is grafted. Although a two-stage graft polymerization method for bonding may be mentioned, a co-graft polymerization method is more preferable from the viewpoint of fiber deterioration due to radiation irradiation and production efficiency.
That is, in one aspect of the method for producing a cationic dye-dyeable fiber of the present disclosure, more preferably, in addition to the compound A, a compound B containing a hydrophobic group and an ethylenically unsaturated double bond is added to the fiber. and irradiating the fiber with radiation before or simultaneously with the contact of the compound A and the compound B with the fiber to graft-polymerize the compound A and the compound B onto the fiber.
共グラフト重合法において、化合物Ａおよび化合物Ｂと繊維との接触は、例えば、化合物Ａ（酸性基含有モノマー）と化合物Ｂ（疎水性モノマー）を各々所定の濃度で含むグラフト加工用の水溶液に、繊維を浸漬させることで行える。当該水溶液には、化合物Ｂの疎水性基（炭化水素基）の炭素数に応じて、ポリオキシエチレンソルビタンモノラウレート等の界面活性剤が含まれていてもよい。 In the co-graft polymerization method, the contact of Compound A and Compound B with the fiber is carried out, for example, by adding an aqueous solution for grafting containing Compound A (acidic group-containing monomer) and Compound B (hydrophobic monomer) at predetermined concentrations, respectively. This can be done by soaking the fibers. The aqueous solution may contain a surfactant such as polyoxyethylene sorbitan monolaurate depending on the number of carbon atoms in the hydrophobic group (hydrocarbon group) of compound B.
本態様において、前記化合物Ａと前記化合物Ｂのグラフト率は、強度保持と濃色染色との両立の観点から、好ましくは１．０～５０．０ｗｔ％、より好ましくは２．０～４５．０ｗｔ％、さらに好ましくは３．０～４０．０ｗｔ％である。前記繊維との接触に使用される前記化合物Ａと前記化合物Ｂの使用量の合計は、グラフト率が上記範囲内の値となるような量であると好ましい。 In this embodiment, the grafting rate of the compound A and the compound B is preferably 1.0 to 50.0 wt%, more preferably 2.0 to 45.0 wt%, from the viewpoint of both strength retention and deep color dyeing. %, more preferably 3.0 to 40.0 wt%. The total amount of Compound A and Compound B used in contact with the fibers is preferably such that the grafting rate falls within the above range.
前記繊維との接触に使用される化合物Ａと化合物Ｂの量比は、染着率の向上の観点から、化合物Ａが有する酸性基に対する化合物Ｂが有する疎水性基のモル比（疎水性基／酸性基）が下記となるような量比であると好ましく、前記モル比（疎水性基／酸性基）は、好ましくは１．０～４０．０、より好ましくは１．５～１５．０、さらに好ましくは２．０～１０．０である。 The quantitative ratio of Compound A and Compound B used in contact with the fibers is determined by the molar ratio of the hydrophobic group of Compound B to the acidic group of Compound A (hydrophobic group/ The molar ratio (hydrophobic group/acidic group) is preferably 1.0 to 40.0, more preferably 1.5 to 15.0, More preferably, it is 2.0 to 10.0.
本態様において、好ましい放射線の種類、線量、照射雰囲気、浴比、化合物と繊維の接触時間等は、（実施形態１）におけるそれと同じでよい。 In this embodiment, preferable types of radiation, dose, irradiation atmosphere, bath ratio, contact time of the compound and fibers, etc. may be the same as those in (Embodiment 1).
本態様において、［洗浄工程］および［乾燥工程］についても（実施形態１）におけるそれと同じでよい。 In this embodiment, the [washing step] and the [drying step] may be the same as those in (Embodiment 1).
［カチオン染料可染性繊維を含む繊維構造物］
前記カチオン染料可染性繊維を含む繊維構造物は、本発明の製造方法により製造されたカチオン染料可染性繊維（Ａ）１００％使いでもよいし、他の繊維（Ｂ）と混紡されてもよい。また、前記繊維構造物は、本発明の製造方法により製造されたカチオン染料可染性セルロース繊維１００％使いでもよいし、当該カチオン染料可染性セルロース繊維と他の繊維（Ｂ）との混紡品であってもよい。前記カチオン染料可染性繊維（Ａ）が他の繊維（Ｂ）と混紡されることにより、繊維構造物の色調、風合い、物理的特性などを制御できる。前記他の繊維としては、天然繊維、再生繊維、合成繊維など任意の繊維を採用できる。前記他の繊維としては、例えば、本発明の製造方法により製造された前記カチオン染料可染性セルロース繊維以外のセルロース繊維（コットン、麻、レーヨン、アセテート、キュプラなど）、ウール、シルク、ポリエステル、ナイロン、アクリル系などの繊維を使用できる。
[Fiber structure containing cationic dye-dyeable fiber]
The fiber structure containing the cationic dye-dyeable fiber may be made of 100% cationic dye-dyeable fiber (A) produced by the production method of the present invention, or may be blended with other fibers (B). good. Further, the fiber structure may be made of 100% cationic dye-dyeable cellulose fibers produced by the production method of the present invention, or may be a blended product of the cationic dye-dyeable cellulose fibers and other fibers (B). It may be. By blending the cationic dye-dyeable fiber (A) with other fibers (B), the color tone, texture, physical properties, etc. of the fiber structure can be controlled. As the other fibers, any fibers such as natural fibers, regenerated fibers, and synthetic fibers can be used. Examples of the other fibers include cellulose fibers (cotton, hemp, rayon, acetate, cupro, etc.) other than the cationic dye-dyeable cellulose fibers produced by the production method of the present invention, wool, silk, polyester, and nylon. , acrylic fibers can be used.
前記カチオン染料可染性繊維（Ａ）と他の繊維（Ｂ）との好ましい混紡割合（Ａ：Ｂ）は、強度の観点から、質量割合で、好ましくは１０：９０～９０：１０であり、より好ましくは２０：８０～８０：２０であり、更に好ましくは３０：７０～７０：３０である。 From the viewpoint of strength, the preferred blending ratio (A:B) of the cationic dye-dyeable fiber (A) and other fibers (B) is preferably 10:90 to 90:10 in terms of mass ratio, More preferably 20:80 to 80:20, still more preferably 30:70 to 70:30.
前記他の繊維（Ｂ）は、カチオン染料可染性合成繊維であるのが好ましく、例えば、アクリル繊維、カチオン染料可染型ポリエステル繊維などが挙げられる。本発明のカチオン染料可染性繊維と前記他の繊維（Ｂ）として本発明のカチオン染料可染性繊維以外のカチオン染料可染性合成繊維とを混紡すると、一浴染めができ、その結果、水の使用量および電力使用量を大幅に低減できる。 The other fibers (B) are preferably synthetic fibers dyeable with cationic dyes, such as acrylic fibers and polyester fibers dyeable with cationic dyes. When the cationic dye dyeable fiber of the present invention is blended with a cationic dye dyeable synthetic fiber other than the cationic dye dyeable fiber of the present invention as the other fiber (B), one-bath dyeing is possible, and as a result, Water and electricity consumption can be significantly reduced.
また、本発明は、一態様において、カチオン染料可染性繊維（Ａ）と他の繊維（Ｂ）とを含む混紡品の製造方法に関する。当該混紡品の製造方法は、前記化合物Ａをスライバー状の繊維に接触させ、前記化合物Ａと前記繊維との接触の前又は同時に前記繊維に放射線を照射して、前記繊維に前記化合物Ａをグラフト重合させること、グラフト反応終了後に前記繊維を洗浄し次いで乾燥してカチオン染料可染性繊維（Ａ）を得ること、前記カチオン染料可染性繊維（Ａ）とスライバー状の他の繊維（Ｂ）とを混紡すること、を含む。
また、本発明は、別の一態様において、前記化合物Ａおよび前記化合物Ｂをスライバー状の繊維に接触させ、前記化合物Ａおよび前記化合物Ｂと前記繊維との接触の前又は同時に前記繊維に放射線を照射して、前記繊維に前記化合物Ａおよび前記化合物Ｂをグラフト重合させること、グラフト反応終了後に前記繊維を洗浄し次いで乾燥してカチオン染料可染性繊維（Ａ）を得ること、前記カチオン染料可染性繊維（Ａ）とスライバー状の他の繊維（Ｂ）とを混紡すること、を含む、カチオン染料可染性繊維（Ａ）と他の繊維（Ｂ）とを含む混紡品の製造方法に関する。
In one aspect, the present invention also relates to a method for producing a blended product containing a cationic dye-dyeable fiber (A) and another fiber (B). The method for producing the blended product includes bringing the compound A into contact with sliver-like fibers, and irradiating the fibers with radiation before or at the same time as the contact between the compound A and the fibers to graft the compound A onto the fibers. polymerization; washing and drying the fibers after the grafting reaction to obtain cationic dye-dyeable fibers (A); and cationic dye-dyeable fibers (A) and other sliver-like fibers (B). Including blending with.
Further, in another aspect of the present invention, the compound A and the compound B are brought into contact with a sliver-like fiber, and the fiber is exposed to radiation before or at the same time as the compound A and the compound B contact with the fiber. irradiation to graft-polymerize the compound A and the compound B onto the fiber; washing and drying the fiber after the grafting reaction to obtain a cationic dye-dyeable fiber (A); A method for producing a blended product containing a cationic dye-dyeable fiber (A) and another fiber (B), including blending the dyeable fiber (A) and another fiber in the form of a sliver (B). .
［染色方法］
本発明の製造方法により製造されたカチオン染料可染性繊維又は前記混紡品（以下、これらをまとめて「染色対象」と呼ぶ場合がある。）の染色方法は、一態様において、カチオン染料を含む染液を、（ａ）浸漬法、（ｂ）パッド法又は（ｃ）インクジェット法などにより、前記カチオン染料可染性繊維又は前記混紡品に接触させ、加熱により染色固定させ、その後、洗浄および乾燥するのが好ましい。本発明の染色方法による染色は、染色対象の態様に応じて、先染め、後染めのいずれであってもよい。本発明の染色方法によれば、染料としてカチオン染料を用いるので、濃色で鮮明な色調の染色品を得ることができる。混紡品の態様は、織物状、編物状または不織布状等の生地または糸である。染色対象の態様は、織物状、編物状または不織布状等の生地、綿（わた）、スライバー、または糸が挙げられる。
[Staining method]
In one embodiment, the method for dyeing the cationic dye-dyeable fiber or the blended fabric (hereinafter, these may be collectively referred to as "dying target") produced by the production method of the present invention includes a cationic dye. The dye solution is brought into contact with the cationic dye-dyeable fiber or the blended product by (a) dipping method, (b) pad method, or (c) inkjet method, dyeing and fixing by heating, followed by washing and drying. It is preferable to do so. Dyeing by the dyeing method of the present invention may be either pre-dyed or piece-dyed depending on the aspect of the object to be dyed. According to the dyeing method of the present invention, since a cationic dye is used as the dye, it is possible to obtain a dyed product with a deep and clear tone. The blended product may be a fabric or yarn in the form of a woven fabric, knitted fabric, or non-woven fabric. Examples of objects to be dyed include fabrics such as woven, knitted or non-woven fabrics, cotton, slivers, and threads.
（Ａ）浸漬法
浸漬法は、カチオン染料を含む染液浴に染色対象を浸漬し、染液の温度を徐々に上げ、一例として、９０～１１０℃で１５～６０分間加熱して、染料を繊維に固定させる。次いで、染液の温度を徐々に下げ、繊維表面に残留した余分な染料を湯洗により洗い落とし、その後乾燥する。染液には、カチオン染料の他に、助剤として、酢酸、濃染剤が含まれていてもよい。先染めの場合、例えば、チーズ染色、綛染め染色、パッケージ型染色等の染色方法が挙げられる。チーズ染色では、穴の開いた染色専用のボビンに巻かれた糸を染色釜（染色浴）に入れ、加圧しながら均一に染まるようにポンプで染液を循環させる。綛染め染色では、糸をかせの状態で吊り下げながら染色する。パッケージ型染色では、孔を開けた容器に繊維や糸を詰め込み、そこへ染料を含む染色液を循環させて染色する。後染め（生地染め）の場合、ウインス染色、液流染色、ジッガー染色、ビーム染色などの染色方法が挙げられる。ウインス染色では、一定の長さの織物の反末同士を縫い合わせループ状とし、これを染料液の中に繰り返し通しながら染色する。液流染色では、生地をロープ状につなげて染液の水流に乗せて、染液が入った管内を循環させながら高温高圧下で染色する。ビーム染色では、パンチング孔のあるビーム管に生地を巻きつけ、生地を固定し、それを高温高圧下で染料液に浸すことで染める。ジッガー染色では、大きな２本のロールに生地を巻き付け、生地をロール間で行ったり来たりさせながら染液に浸して染色する。
(A) Dipping method In the dipping method, the object to be dyed is immersed in a dye bath containing a cationic dye, the temperature of the dye bath is gradually raised, and the dye is heated for 15 to 60 minutes at 90 to 110°C. Fix it to the fibers. Next, the temperature of the dye liquor is gradually lowered, excess dye remaining on the fiber surface is washed off with hot water, and then dried. In addition to the cationic dye, the dye liquor may contain acetic acid and a strong dyeing agent as auxiliary agents. In the case of yarn dyeing, examples include dyeing methods such as cheese dyeing, skein dyeing, and package dyeing. In cheese dyeing, thread wound around a perforated bobbin is placed in a dyeing pot (dye bath), and a pump is used to circulate the dye solution while applying pressure to ensure uniform dyeing. In skein dyeing, the thread is hung in a skein while being dyed. In package dyeing, fibers and threads are packed into a container with holes, and a dye solution containing the dye is circulated through the container. In the case of piece dyeing (fabric dyeing), there are dyeing methods such as wince dyeing, jet dyeing, jigger dyeing, and beam dyeing. In wince dyeing, the ends of a certain length of fabric are sewn together to form a loop, which is repeatedly passed through a dye solution for dyeing. In jet dyeing, the fabric is tied into a rope and placed in a stream of dye liquid, and the dye is dyed under high temperature and pressure as it circulates through the tube containing the dye liquid. In beam dyeing, the fabric is wrapped around a beam tube with perforated holes, the fabric is fixed, and the fabric is immersed in a dye solution under high temperature and pressure. In jigger dyeing, the fabric is wrapped around two large rolls and dipped in a dye solution while being passed back and forth between the rolls.
（Ｂ）パッド法
パッド法は、繊維基材（染色対象）にカチオン染料を含む染液をパッドにより付着させ、その後９０～１１０℃で２０～４０分間スチームの熱などにより加熱して、染料を繊維に固定させる。次いで、湯水洗し、その後乾燥する。
(B) Pad method In the pad method, a dye solution containing a cationic dye is applied to the fiber base material (to be dyed) using a pad, and then heated with steam heat for 20 to 40 minutes at 90 to 110°C to remove the dye. Fix it to the fibers. Next, it is washed with hot water and then dried.
（Ｃ）インクジェット法
インクジェット法は、インクジェットにより、繊維基材（染色対象）にカチオン染料を含む染液を印刷し、その後１００～１３０℃で１０～３０分間スチーム加熱し、湯洗し、その後乾燥する。
(C) Inkjet method In the inkjet method, a dye solution containing a cationic dye is printed on the fiber base material (to be dyed) using an inkjet, followed by steam heating at 100 to 130°C for 10 to 30 minutes, washing with hot water, and then drying. do.
本発明のカチオン染料可染性繊維又は混紡品の染色方法で用いられるカチオン染料としては、アクリル繊維の染色に使用されている従来から公知のカチオン染料が使用でき、例えば、アントラキノン系、アザメチン系、アゾ系、ポリメチン系などが挙げられる。市販品としては、例えば、Ｋａｙａｃｒｙｌ（日本化薬（株）製）などが挙げられる。上記染色方法では、カチオン染料を用いて染色対象を染色するので、他の種属の染料では得られない鮮明色の染色品を得ることができる。前記染液には、常法に従い、カチオン染料以外に、染色助剤として、均染剤、緩染剤、分散剤、浸透剤、ｐＨ調整剤などが含まれていてもよい。 As the cationic dye used in the method for dyeing cationic dye-dyeable fibers or blended products of the present invention, conventionally known cationic dyes used for dyeing acrylic fibers can be used, such as anthraquinone-based, azamethine-based, Examples include azo type and polymethine type. Examples of commercially available products include Kayacryl (manufactured by Nippon Kayaku Co., Ltd.). In the above dyeing method, since the object to be dyed is dyed using a cationic dye, it is possible to obtain a dyed product with vivid colors that cannot be obtained with dyes of other species. In addition to the cationic dye, the dye liquor may contain dyeing aids such as a leveling agent, a slowing dye, a dispersing agent, a penetrating agent, and a pH adjusting agent, according to a conventional method.
以下、実施例により、本発明をさらに具体的に説明する。なお本発明は下記の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the present invention is not limited to the following examples.
（実施例１～４）
＜使用生地＞
木綿１００％晒上がりの織物（平織物、経糸（紡績糸）及び緯糸（紡績糸）はともに４０番手（綿番手）単糸、単位面積当たりの質量（目付）１２２．５ｇ／ｍ2）
(Examples 1 to 4)
<Fabric used>
100% cotton bleached fabric (plain weave, warp (spun yarn) and weft (spun yarn) are both 40 count (cotton count) single yarn, mass per unit area (fabric weight) 122.5 g/m 2 )
［グラフト重合］
（１）化合物Ａ
・アクリル酸
・メタクリル酸
・スチレンスルホン酸ナトリウム：Ｓスルホン酸Ｎａ
・２－アクリルアミド－２－メチルプロパンスルホン酸：ＡＭＰＳ
[Graft polymerization]
(1) Compound A
・Acrylic acid ・Methacrylic acid ・Sodium styrene sulfonate: Sodium S sulfonate
・2-acrylamido-2-methylpropanesulfonic acid: AMPS
（２）グラフト重合条件
上記使用生地からサンプルとしてタテ７０ｍｍ×ヨコ２８０ｍｍの生地（約２．３ｇ）を採取した。これに、エレクトロカーテン型電子線照射装置（岩崎電気（株）製、ＥＣ２５０／３０／９０Ｌ）を使用して、窒素ガス雰囲気下で、加速電圧２００ｋＶ、照射線量４０ｋＧｙの条件で電子線を照射した。その後、容器に入れ、上記化合物Ａを含む水溶液に浴比１：２０で２０分間浸漬して反応させた後、容器から生地を取り出して水洗し、風乾させた。
(2) Graft polymerization conditions A fabric (approximately 2.3 g) measuring 70 mm in length x 280 mm in width was taken as a sample from the fabric used above. This was irradiated with an electron beam using an electrocurtain type electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd., EC250/30/90L) under conditions of an acceleration voltage of 200 kV and an irradiation dose of 40 kGy in a nitrogen gas atmosphere. . Thereafter, the fabric was placed in a container and immersed in an aqueous solution containing the above compound A at a bath ratio of 1:20 for 20 minutes to react, and then the fabric was taken out from the container, washed with water, and air-dried.
［染色処理］
（１）染液調製
下記＜染色レサイプ＞にしたがって染液を調製した。
＜染色レサイプ＞
・カチオン染料、日本化薬（株）製、Kayacryl Yellow 3RL:0.124%owf(owfはon the weight of fiber)
・カチオン染料、日本化薬（株）製、Kayacryl Red GRL:0.045%owf
・カチオン染料、日本化薬（株）製、Kayacryl Blue GRL:0.028%owf
・ｐＨ調整剤(染液をｐＨ（２５℃）＝４程度に調整用)
・残部は水
[Staining treatment]
(1) Preparation of Dyeing Solution A dyeing solution was prepared according to the following <Dyeing Recipe>.
<Dyeing recipe>
・Cationic dye, manufactured by Nippon Kayaku Co., Ltd., Kayacryl Yellow 3RL:0.124%owf (owf is on the weight of fiber)
・Cationic dye, manufactured by Nippon Kayaku Co., Ltd., Kayacryl Red GRL:0.045%owf
・Cationic dye, manufactured by Nippon Kayaku Co., Ltd., Kayacryl Blue GRL:0.028%owf
・pH adjuster (for adjusting the dye liquor to pH (25℃) = around 4)
・The rest is water
（２）染色方法
浴比１：２０でサンプルを染液に浸漬し、１００℃で４５分間染色処理した。次いで、染液を廃棄した後に、染色されたサンプルを５０℃程度の湯で洗浄し、風乾して、染色品を得た。
(2) Dyeing method The sample was immersed in a dye solution at a bath ratio of 1:20, and dyed at 100° C. for 45 minutes. Next, after discarding the dye solution, the dyed sample was washed with hot water at about 50° C. and air-dried to obtain a dyed product.
（比較例１）
電子線照射およびグラフト重合しない以外は実施例１と同様に染色処理した。
(Comparative example 1)
The dyeing treatment was carried out in the same manner as in Example 1 except that electron beam irradiation and graft polymerization were not performed.
［測色評価］
（１）測色試験
ＪＩＳ Ｚ ８７３０：２００９に準じて、国際照明委員会の規定するＣＩＥ色差式を用いて、Ｌ*値、ａ*値、及びｂ*値を求めた。なお、Ｌ*値は、色の明度を０～１００の値で表し、０に近いほど暗く、１００に近いほど明るいことを示している。ａ*値は、色の赤緑位置を表し、正の数値は赤寄りの色を、負の数値は緑寄りの色を示している。ｂ*値は、色の黄青位置を表し、正の数値は黄寄りの色を、負の数値は青寄りの色を示している。
また、測定基準白布（未加工未染色生地）との差ΔＬ*値、Δａ*値、及びΔｂ*値を求めた。下記表２中、Ｄ６５はＣＩＥ標準光源のことである。ΔＥ*ａｂ値は測定基準白布との色差のことである。
[Colorometric evaluation]
(1) Colorimetric test According to JIS Z 8730:2009, the L * value, a * value, and b * value were determined using the CIE color difference formula prescribed by the International Commission on Illumination. Note that the L * value represents the lightness of a color as a value from 0 to 100, with the closer it is to 0, the darker it is, and the closer it is to 100, it is brighter. The a * value represents the red-green position of a color, with positive numbers indicating a color closer to red and negative numbers indicating a color closer to green. The b * value represents the yellow-blue position of a color, with positive numbers indicating a yellow-leaning color and negative numbers indicating a blue-biasing color.
In addition, the difference ΔL * value, Δa * value, and Δb * value from the measurement reference white cloth (unprocessed undyed fabric) were determined. In Table 2 below, D65 is a CIE standard light source. The ΔE * ab value is the color difference from the measurement reference white cloth.
（２）測定機器
Ｌ*ａ*ｂ*の測定にはコニカミノルタ（株）製、分光測色計、ＣＭ－６００ｄを用いた。測定数は３とし、その平均値を下記表２に示した。
(2) Measuring equipment A spectrophotometer, CM-600d, manufactured by Konica Minolta, Inc., was used to measure L * a * b * . The number of measurements was 3, and the average value is shown in Table 2 below.
表２から明らかなとおり、実施例１～４の染色品は、比較例１よりもΔＬ*値が低く、カチオン染料により濃色に染色されていた。とくに実施例１～３の染色品は濃色であった。また目視観察では、実施例１～４の染色品は鮮明に染色されていた。 As is clear from Table 2, the dyed products of Examples 1 to 4 had lower ΔL * values than Comparative Example 1, and were dyed in deep colors with the cationic dye. In particular, the dyed products of Examples 1 to 3 had deep colors. Visual observation revealed that the dyed products of Examples 1 to 4 were clearly dyed.
（実施例５）
＜スライバーの処理＞
コットンスライバー（単位長さあたりの質量、単位ゲレン：２５．０ｇ／６ｙｄ（４．６ｇ／ｍ））に対し、エレクトロカーテン型電子線照射装置ＥＣ２５０／３０／９０Ｌ（岩崎電気（株）製）により、窒素雰囲気下で、電子線を、加速電圧２００ｋＶ、照射線量４０ｋＧｙで照射した。電子線が照射されたスライバーをその直後に０．５質量％の浸透剤ＣＴ－２４Ｔ（京浜化成（株）製）を含有するアクリル酸（ナカライテスク（株）製）の５質量％水溶液に浸漬し（浴比１：８）、室温で２０分間反応させ、マングルでスライバー重量に対して約１００質量％のピックアップ率となるように絞った。次に、連続して未反応のアクリル酸を水洗して除去し、乾燥し、グラフト率１７．０％のアクリル酸グラフトコットンを得た。
(Example 5)
<Sliver processing>
Cotton sliver (mass per unit length, unit gel: 25.0 g/6 yd (4.6 g/m)) was irradiated with an electrocurtain type electron beam irradiation device EC250/30/90L (manufactured by Iwasaki Electric Co., Ltd.). , an electron beam was irradiated at an acceleration voltage of 200 kV and an irradiation dose of 40 kGy under a nitrogen atmosphere. The sliver irradiated with the electron beam was immediately immersed in a 5% by mass aqueous solution of acrylic acid (manufactured by Nacalai Tesque Co., Ltd.) containing 0.5% by mass of penetrant CT-24T (manufactured by Keihin Kasei Co., Ltd.). (bath ratio 1:8), reacted at room temperature for 20 minutes, and squeezed with a mangle to give a pickup rate of about 100% by mass based on the weight of the sliver. Next, unreacted acrylic acid was continuously removed by washing with water and dried to obtain acrylic acid grafted cotton with a grafting ratio of 17.0%.
＜紡績糸の製造＞
前記アクリル酸グラフトコットンと未処理コットンとを混打綿工程で混紡し、綿番手４０番の糸を紡績した。混紡糸中のアクリル酸グラフトコットンの割合は２５質量％となるようにした。
<Manufacture of spun yarn>
The acrylic acid grafted cotton and untreated cotton were blended in a blending process and spun into yarn with a cotton count of 40. The proportion of acrylic acid grafted cotton in the blended yarn was set to 25% by mass.
＜編地の作製＞
前記混紡糸を用い筒編み機で編地を編成し、アクリル酸グラフトコットン含有生地を得た。
<Production of knitted fabric>
A knitted fabric was knitted using a tube knitting machine using the blended yarn to obtain a fabric containing acrylic acid grafted cotton.
＜晒＞
得られたアクリル酸グラフトコットン含有生地を常法で晒処理した。
<Exposure>
The resulting acrylic acid grafted cotton-containing fabric was bleached in a conventional manner.
＜染色＞
上記（実施例１～４）の[染色処理]と同様の方法で染色処理を行い、染色されたアクリル酸グラフトコットン含有生地（染色品）を得た。ただし、染料はKayacryl Blue GRLのみを使用し、ｏｗｆは、２．０％ｏｗｆとした。
<Dyeing>
A dyeing treatment was performed in the same manner as [Dyeing treatment] in Examples 1 to 4 above to obtain a dyed fabric (dyed product) containing acrylic acid grafted cotton. However, only Kayacryl Blue GRL was used as the dye, and the owf was 2.0% owf.
実施例５の染色品について、測色評価を実施例１～４と同様に行い、結果を表３に示した。 The dyed product of Example 5 was subjected to colorimetric evaluation in the same manner as Examples 1 to 4, and the results are shown in Table 3.
表３から明らかなとおり、実施例５の染色品も、ΔＬ*値が低く、カチオン染料により濃色に染色されていた。また目視観察でも、実施例５の染色品は鮮明に染色されていた。 As is clear from Table 3, the dyed product of Example 5 also had a low ΔL * value and was dyed in a deep color with the cationic dye. Visual observation also showed that the dyed product of Example 5 was clearly dyed.
（実施例６～１６）
＜使用生地＞
木綿１００％晒上がりの織物（平織物、経糸（紡績糸）及び緯糸（紡績糸）はともに４０番手（綿番手）単糸、単位面積当たりの質量（目付）１２２．５ｇ／ｍ2）
(Examples 6 to 16)
<Fabric used>
100% cotton bleached fabric (plain weave, warp (spun yarn) and weft (spun yarn) are both 40 count (cotton count) single yarn, mass per unit area (fabric weight) 122.5 g/m 2 )
［グラフト重合］
（１）化合物
化合物Ａ：アクリル酸
化合物Ｂ：アクリル酸メチル、メタクリル酸メチル、アクリル酸ブチル、メタクリル酸ブチル
化合物Ａと化合物Ｂを各々所定の濃度で含む水溶液（グラフト加工用の水溶液）を調製した。当該水溶液における化合物Ａおよび化合物Ｂの各濃度、組み合わせは下記表４に記載した通りである。
[Graft polymerization]
(1) Compound Compound A: Acrylic acid Compound B: Methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate An aqueous solution (aqueous solution for grafting) containing each of Compound A and Compound B at predetermined concentrations was prepared. . The respective concentrations and combinations of Compound A and Compound B in the aqueous solution are as listed in Table 4 below.
（２）グラフト重合条件
上記使用生地からサンプルとしてタテ７０ｍｍ×ヨコ２８０ｍｍの生地（約２．３ｇ）を採取した。これに、エレクトロカーテン型電子線照射装置（岩崎電気（株）製、ＥＣ２５０／３０／９０Ｌ）を使用して、窒素ガス雰囲気下で、加速電圧２００ｋＶ、照射線量４０ｋＧｙの条件で電子線を照射した。その後、容器に入れ、グラフト加工用の水溶液に浴比１：２０で２０分間浸漬して反応させた後、容器から生地を取り出して水洗し、風乾させた。
(2) Graft polymerization conditions A fabric (approximately 2.3 g) measuring 70 mm in length x 280 mm in width was taken as a sample from the fabric used above. This was irradiated with an electron beam using an electrocurtain type electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd., EC250/30/90L) under conditions of an acceleration voltage of 200 kV and an irradiation dose of 40 kGy in a nitrogen gas atmosphere. . Thereafter, the fabric was placed in a container and immersed in an aqueous solution for grafting at a bath ratio of 1:20 for 20 minutes to react, and then the fabric was taken out of the container, washed with water, and air-dried.
［染色処理］
（１）染液調製
下記＜染色レサイプ＞にしたがって染液を調製した。
＜染色レサイプ＞
・カチオン染料、日本化薬（株）製、Kayacryl Blue GRL : 1.0%owf
・ｐＨ調整剤(染液をｐＨ（２５℃）＝４程度に調整用)
・残部は水
[Staining treatment]
(1) Preparation of Dyeing Solution A dyeing solution was prepared according to the following <Dyeing Recipe>.
<Dyeing recipe>
・Cationic dye, manufactured by Nippon Kayaku Co., Ltd., Kayacryl Blue GRL: 1.0%owf
・pH adjuster (for adjusting the dye liquor to pH (25℃) = around 4)
・The rest is water
（２）染色方法
浴比１：２０でサンプルを染液に浸漬し、１００℃で４５分間染色処理した。次いで、染液を廃棄した後に、染色されたサンプルを５０℃程度の湯で洗浄し、風乾して、染色品を得た。
(2) Dyeing method The sample was immersed in a dye solution at a bath ratio of 1:20, and dyed at 100° C. for 45 minutes. Next, after discarding the dye solution, the dyed sample was washed with hot water at about 50° C. and air-dried to obtain a dyed product.
実施例１～４と同様にして、実施例６～１６のグラフト率を算出しその結果を上記表４に示した。 The graft ratios of Examples 6 to 16 were calculated in the same manner as Examples 1 to 4, and the results are shown in Table 4 above.
［染着率］
下記式より、実施例６～１６の染色品について、下記式（２）を用いて染着率を算出しその結果を上記表４に示した。下記式（２）中、Ｃ0は初期染液の染料濃度、Ｃaは染色後染液の染料濃度、ＣW1は1回目の水洗に使用した当該水中の染料濃度、ＣW2は２回目の水洗に使用した当該水中の染料濃度、ＣW3は３回目の水洗に使用した当該水中の染料濃度である。１～３回目の水洗は、各々９０℃のイオン交換水に、浴比１：２０で浸漬し、１０分間容器を攪拌することにより行った。
染着率＝(Ｃ0－Ｃa-ＣW1-ＣW2-ＣW3)／Ｃ0×１００ （２）
[Dyeing rate]
From the following formula, the dyeing rate was calculated for the dyed products of Examples 6 to 16 using the following formula (2), and the results are shown in Table 4 above. In the following formula (2), C 0 is the dye concentration of the initial dye solution, C a is the dye concentration of the dye solution after dyeing, C W1 is the dye concentration in the water used for the first washing, and C W2 is the dye concentration of the second washing. The dye concentration in the water used for washing, C W3 , is the dye concentration in the water used for the third washing. The first to third water washings were performed by immersing each container in 90° C. ion exchange water at a bath ratio of 1:20 and stirring the container for 10 minutes.
Dyeing rate = (C 0 −C a −C W1 −C W2 −C W3 )/C 0 ×100 (2)
Ｃ0、Ｃa、ＣW1、ＣW2、ＣW3の染料濃度の算出は、各々、既知の染料濃度Ｃ（ｗｔ％)の吸光度(Ａ)をあらかじめ測定して染料濃度Ｃと吸光度(Ａ)の関係式を作成しておき、これを利用した。染料濃度を知りたい液体の吸光度(Ａ')を染料濃度Ｃと吸光度(Ａ)の関係式にあてはめ、逆算することで、当該液体における染料濃度(Ｃ’ｗｔ%)を算出した。
より具体的には、カチオン染料の濃度を０．０００５ｗｔ％から０．０１ｗｔ％まで段階的にイオン交換水で希釈し、紫外可視近赤外分光光度計ＵＨ５７００（（株）日立ハイテクサイエンス製）を用いて吸光度を測定した結果をもとに染料濃度Ｃと吸光度(Ａ)の関係式を作成した。
The dye concentrations of C 0 , C a , C W1 , C W2 , and C W3 are calculated by measuring the absorbance (A) of each known dye concentration C (wt%) in advance and calculating the dye concentration C and the absorbance (A). I created a relational expression and used this. The dye concentration (C'wt%) in the liquid was calculated by applying the absorbance (A') of the liquid whose dye concentration was desired to the relational expression between the dye concentration C and the absorbance (A) and calculating backwards.
More specifically, the concentration of the cationic dye was diluted stepwise with ion-exchanged water from 0.0005 wt% to 0.01 wt%, and an ultraviolet-visible near-infrared spectrophotometer UH5700 (manufactured by Hitachi High-Tech Science Co., Ltd.) was used. A relational expression between dye concentration C and absorbance (A) was created based on the results of measuring absorbance using the dye.
表４中の実施例６と実施例７との比較から、化合物Ａの単独使用よりも、化合物Ａと化合物Ｂとを共グラフト結合させた方が、染着率が顕著に向上することが確認できた。 From the comparison between Example 6 and Example 7 in Table 4, it was confirmed that the dyeing rate was significantly improved by co-grafting Compound A and Compound B than by using Compound A alone. did it.
３回水洗後の実施例６～１６の染色品について、実施例１～４と同様にして、上記［測色評価］に記載の方法に従って、Ｌ*値、ａ*値、ｂ*値、測定基準白布（未加工未染色生地）との差ΔＬ*値、Δａ*値、Δｂ*値、およびΔＥ*ａｂ値を求めた。測定数は３とし、その平均値を下記表５に示した。 For the dyed products of Examples 6 to 16 after washing with water three times, the L * value, a * value, b * value, and the like were measured in the same manner as in Examples 1 to 4, according to the method described in [Colorimetric evaluation] above. The difference ΔL * value, Δa * value, Δb * value, and ΔE * ab value from the reference white cloth (unprocessed undyed fabric) were determined. The number of measurements was three, and the average value is shown in Table 5 below.
表５中の実施例６と実施例７との比較から、化合物Ａの単独使用よりも、化合物Ａと化合物Ｂとを共グラフト結合させた方が、ΔＬ*値が低く、より濃色に染色されていることが確認できた。 From the comparison between Example 6 and Example 7 in Table 5, the ΔL * value is lower and the color is dyed darker when Compound A and Compound B are co-grafted than when Compound A is used alone. It was confirmed that this was done.
本発明のカチオン染料可染性繊維を含む布帛は、下着、中着、外着、上衣、下衣、靴下、手袋、マフラー、スカーフ、帽子などの衣類、シーツ、布団カバー、枕カバー、テーブルクロス、カーペットなどの様々な分野に有用である。特に、本発明のカチオン染料可染性セルロース繊維を含む布帛、上記衣類の材料として好適である。 The fabric containing the cationic dye dyeable fiber of the present invention can be used for clothing such as underwear, innerwear, outerwear, upper clothing, lower clothing, socks, gloves, mufflers, scarves, and hats, sheets, duvet covers, pillowcases, and tablecloths. , useful in various fields such as carpets. In particular, the fabric containing the cationic dye-dyeable cellulose fiber of the present invention is suitable as a material for the above-mentioned clothing.
Claims (14)
酸性基とエチレン性不飽和二重結合とを含む化合物Ａを繊維に接触させ、前記化合物Ａと前記繊維との接触の前又は同時に前記繊維に放射線を照射して、前記繊維に前記化合物Ａをグラフト重合させる工程を含む、カチオン染料可染性繊維の製造方法。 A method for producing a cationic dye-dyeable fiber, the method comprising:
A compound A containing an acidic group and an ethylenically unsaturated double bond is brought into contact with a fiber, and the fiber is irradiated with radiation before or at the same time as the contact of the compound A with the fiber, thereby imparting the compound A to the fiber. A method for producing a cationic dye-dyeable fiber, including a step of graft polymerization.
カチオン染料を含む染液を、前記カチオン染料可染性繊維に接触させる工程を含む、染色方法。 A method for dyeing a cationic dye-dyeable fiber produced by the method for producing a cationic dye-dyeable fiber according to any one of claims 1 to 9, comprising:
A dyeing method comprising the step of bringing a dye solution containing a cationic dye into contact with the cationic dye-dyeable fiber.
前記混紡品に含まれる前記カチオン染料可染性繊維（Ａ）および前記カチオン染料可染性繊維（Ｂ）を一浴で染色する、請求項１３に記載の染色方法。 The other fibers contained in the blended product are cationic dye dyeable fibers (B),
The dyeing method according to claim 13, wherein the cationic dye-dyeable fiber (A) and the cationic dye-dyable fiber (B) contained in the blended fabric are dyed in one bath.
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