WO2022110623A1 - 染色促进剂、其制备以及染色方法 - Google Patents
染色促进剂、其制备以及染色方法 Download PDFInfo
- Publication number
- WO2022110623A1 WO2022110623A1 PCT/CN2021/088991 CN2021088991W WO2022110623A1 WO 2022110623 A1 WO2022110623 A1 WO 2022110623A1 CN 2021088991 W CN2021088991 W CN 2021088991W WO 2022110623 A1 WO2022110623 A1 WO 2022110623A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dyeing
- group
- accelerator
- branched
- chain
- Prior art date
Links
- 238000004043 dyeing Methods 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 22
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical group CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 3
- 239000004744 fabric Substances 0.000 claims description 53
- 239000000975 dye Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 26
- 150000001412 amines Chemical class 0.000 claims description 20
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 17
- 239000000985 reactive dye Substances 0.000 claims description 15
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 14
- 229940097275 indigo Drugs 0.000 claims description 14
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000009990 desizing Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 150000003973 alkyl amines Chemical class 0.000 claims description 4
- 238000005576 amination reaction Methods 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 229920000742 Cotton Polymers 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000007774 anilox coating Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000004759 spandex Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000984 vat dye Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- HLHSUNWAPXINQU-GQCTYLIASA-N (E)-3-(3,4-dihydroxyphenyl)-N-prop-2-ynylprop-2-enamide Chemical compound OC=1C=C(C=CC=1O)/C=C/C(=O)NCC#C HLHSUNWAPXINQU-GQCTYLIASA-N 0.000 description 1
- VIFKLIUAPGUEBV-UHFFFAOYSA-N 2-(3-hydroxy-1h-indol-2-yl)-1h-indol-3-ol Chemical compound N1C2=CC=CC=C2C(O)=C1C1=C(O)C2=CC=CC=C2N1 VIFKLIUAPGUEBV-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VFKZECOCJCGZQK-UHFFFAOYSA-N Cl.C[N+](C)(C)CCCO Chemical compound Cl.C[N+](C)(C)CCCO VFKZECOCJCGZQK-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
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000035823 Non-specific autoimmune cerebellar ataxia without characteristic antibodies Diseases 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002993 phenylalanine derivatives Chemical class 0.000 description 1
- 229920000771 poly (alkylcyanoacrylate) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical class Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/655—Compounds containing ammonium groups
- D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
- D06P1/228—Indigo
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
Definitions
- the present application relates to the printing and dyeing technology of the textile industry, and more particularly to a new type of dyeing accelerator, its preparation method and dyeing method, especially the dyeing method for fiber fabrics such as denim grey fabrics.
- Fiber fabrics are widely used in the textile industry and clothing field.
- various natural fibers such as hemp, ramie, flax, silk, wool, etc. blended with cotton, regenerated fibers such as viscose, tencel, modal, etc., or synthetic fiber chemical fibers such as polyester, nylon , acrylic fiber, spandex, etc. have been widely used.
- the fiber fabrics need to be dyed with dyes.
- dyes include, for example, various reactive dyes or indigo.
- Reactive dyes are anionic dyes, also known as reactive dyes, which contain chemically active groups in their molecules and can react with cotton, wool and other fibers in aqueous solution to form co-bonded dyes. It is popular due to its good vividness, ease of use and good color fastness.
- reactive dyes and fibers are very easy to be hydrolyzed when covalently bonded, so there are problems of low dye uptake and fixation rate.
- Indigo is an ancient vat dye, which is also widely used in the dyeing of pure cotton fabrics.
- the process of indigo dyeing mainly includes: dye reduction, leuco dyeing, oxidation, washing, soaping and drying.
- Indigo dye is usually insoluble in water, has no affinity for fibers, and cannot be directly used for dyeing. It needs to be reduced by a strong reducing agent under alkaline conditions to become a leuco that is slightly soluble in water before it can be used for dyeing. But the reduction rate of indigo dye is slower. Compared with other vat dyes, the dyeing rate of indigo is slow and the dyeing rate is low, usually about 10%.
- indigo is also a low-alkali dyeing dye.
- CN110004742A attempts to solve some of the above technical problems, which provides a salt-free dyeing method for cationically modified cotton fabrics to improve levelness, color fastness, etc.
- CN107740295A provides a dyeing method based on a reactive dye cationic modifier for cotton fabrics, wherein the cotton fiber is modified, and the modified aqueous solution used is a glutamate aqueous solution or a phenylalanine salt aqueous solution.
- the inventor of the present application has developed a new type of dyeing accelerator, which can significantly improve the leuco color of indigo after pretreatment of fiber fabrics, especially cotton and blended fabrics such as denim grey fabrics.
- the affinity between bulk or reactive dyes and fibers can reduce the residual amount and COD pollution of indigo dyes or reactive dyes in the dyeing bath, improve dye utilization, stabilize dyeing quality, and improve fastness such as color fastness and rubbing fastness, etc. This reduces environmental pressure.
- a first aspect of the present application relates to a dyeing accelerator comprising a bi-active quaternary ammonium salt compound having an ethyl sulfone group and a monohalo-s-triazine group, the compound having the structural formula shown below ( i)
- M is H or an alkali metal ion, preferably Na or K;
- Y each independently represents H, halogen or straight-chain or branched C 1-12 alkyl, preferably H;
- X each independently represents a halogen, preferably Cl or F, more preferably Cl;
- R 1 and R 2 each represent a quaternary ammonium group, identically or differently, selected from:
- R 3 independently of one another represents a straight-chain or branched C 1-12 alkyl group, preferably methyl, ethyl or propyl,
- R 4 represents a straight-chain or branched C 1-12 alkylene group, preferably ethylene, propylene or butylene, and
- R 0 represents optionally one or more substituents such as 1, 2, 3 or 4 substituents on the benzene ring selected from halogen or C 1-8 alkyl.
- a second aspect of the present application relates to a process for the preparation of a compound of formula (I) as described above, comprising the steps of:
- the trialkylammonium salt of the trialkylammonium salt is subjected to ring-closure reaction under alkaline conditions to obtain its corresponding epoxy derivative;
- step (1) (2) subjecting the epoxy derivative obtained in step (1) to an amination reaction to obtain its corresponding amino derivative;
- step (3) Combine the amine derivative obtained in step (2) with 1,3,5-trihalo-s-triazine and p-( ⁇ -sulfate ethyl optionally substituted with one or more R 0 groups) sulfone) aniline reaction.
- a third aspect of the present application relates to a method for dyeing fiber fabrics, comprising the steps of:
- the fiber fabric to which the dyeing accelerator is applied is dyed with reactive dyes or indigo dyes.
- alkali metal denotes a metal element of main group I of the periodic table, including Li, Na and K, etc., preferably Na or K.
- alkyl preferably denotes a straight-chain or branched alkyl group having 1-12, preferably 1-8 or 1-4 carbon atoms, and one or more H on the carbon atoms may be Substituted by halogen such as F, Cl or Br.
- the alkyl group represents an unsubstituted C 1-8 alkyl group, more preferably a C 1-4 alkyl group, such as methyl, ethyl, propyl or butyl.
- halogen preferably includes F, Cl and Br, more preferably means Cl.
- each benzene ring of formula (I) has no substituent R 0 , that is, the benzene ring is unsubstituted.
- M is Na or K
- Y represents H
- X represents Cl
- R 3 independently of each other represent straight-chain or branched C 1-8 alkyl, more preferably C 1-6 alkyl, particularly preferably methyl or ethyl;
- R 4 represents a straight-chain or branched C 1-8 alkylene group, more preferably a C 2-6 alkylene group, especially preferably a propylene group;
- the substituent R 0 is not included in the benzene ring.
- a second aspect of the present application relates to a process for preparing a compound of formula (I) as described above.
- step (1) of the method A ring-closure reaction is involved in step (1) of the method.
- the three kinds of trialkylammonium salts of m-phenylhydroxyalkyl trialkylammonium salt, p-phenylhydroxyalkyl trialkylammonium salt or hydroxyalkyl trialkylammonium salt correspond to R 1 and
- R2 There are three sources of R2, namely ammonium salts of substances having the following structure, wherein R3 and R4 are as defined above, and R5 represents a linear or branched C1-8 alkylene group, preferably a methylene group:
- ammonium salt may preferably be formed from a cationic structure as described above with an organic or inorganic acid, such as hydrochloric acid, nitric acid or sulfuric acid.
- organic or inorganic acid such as hydrochloric acid, nitric acid or sulfuric acid.
- all three ammonium salts are hydrochloride salts.
- an alkaline solution such as NaOH or KOH may be added to the trialkylammonium salt for the reaction.
- salts such as NaCl formed in the reaction are optionally filtered off, and then the pH value is adjusted to, for example, 6.0-7.5, especially 6.5-7, to obtain the epoxy derivative of the trialkylammonium salt.
- the pH adjusting agent may be selected from acidic compounds such as hydrochloric acid.
- the reaction temperature can be controlled at room temperature (eg, about 23°C).
- step (2) the epoxy derivative obtained in step (1) is subjected to an amination reaction to obtain its corresponding amine derivative.
- the amination reaction can be carried out by adding the resulting epoxy derivative to excess ammonia. Concentrated ammonia water can be used here. The reaction is kept for a period of time after the addition, eg 3-4h. The excess ammonia is then removed by increasing the temperature (eg, at 80°C) to give the amine derivative.
- step (3) the amino derivative obtained in step ( 2 ) is combined with 1,3,5-trihalo-s-triazine and p-( ⁇ - Sulfate ethyl sulfone) aniline reaction.
- the above-obtained amine derivatives can be combined with 1,3,5-trihalo-s-triazine and p-( ⁇ -sulfate ethylsulfone)aniline React in a molar ratio of 2:1:1.
- the reaction molar ratio of the three is 1:1:1:1.
- the reaction mixture containing 1,3,5-trihalo-s-triazine and p-( ⁇ -sulfate ethylsulfone)aniline is usually carried out at a low temperature such as 0-10°C, more preferably 0-5°C.
- the solution is mixed with the amine derivative obtained above.
- a suitable solvent for dissolving 1,3,5-trihalo-s-triazine and p-(beta-sulfate ethylsulfone)aniline is, for example, acetone.
- one amine derivative may first be combined with a mixture comprising 1,3,5-trihalo-s-triazine and p-(beta-sulfate ethyl sulfone)
- the solution of aniline is mixed and reacted, followed by raising the temperature (eg, to 25-50°C, preferably 35-40°C) and mixing with another amine derivative to obtain the desired accelerator compound.
- a pH adjusting agent can be preferably added to control the pH value of the reaction to be about 6-7, such as about 6.5.
- suitable pH regulators are, for example, Na 2 CO 3 .
- a third aspect of the present application relates to a method of dyeing a fibrous fabric.
- the dyeing accelerator according to the invention is particularly suitable for dyeing fibrous fabrics, especially for denim grey fabrics. Fibre fabrics that have been previously desized are advantageous. Desizing of fabrics is known per se to those skilled in the art. Taking denim grey fabrics as an example, the desizing treatment can be carried out as follows: padding in a desizing enzyme solution at a temperature of 50-60°C for 3-4 hours, and then using a temperature above 60°C (such as 90°C) It is washed with hot water, then washed with normal temperature water, and finally dried to obtain the denim grey fabric to be dyed.
- an accelerator solution comprising a dye accelerator of the compound of formula (I) as described above is applied to the fibrous facestock.
- This application can be by, for example, double-sided anilox coating or double-sided foam coating or padding to uniformly coat the dye accelerator solution on one or both sides of the fabric.
- the liquid-carrying rate of the fiber fabric preferably denim grey fabric is made to reach more than 20%, for example, 25%-50% or 25%-40%.
- the accelerator solution relates to a dye accelerator composition comprising (by weight percent):
- the balance of the dye accelerator composition may contain other suitable additives, regulators, salts, dispersants, solvents, and the like.
- the balance of the dyeing accelerator composition is a dispersant or a solvent, such as water.
- the vehicle itself is a component known to those skilled in the art and is usually used as a dispersion medium, which can adjust the rheology, viscosity, film-forming properties and coating properties of the system to a certain extent.
- binders may, for example, consist of vegetable oils, mineral oils, organic solvents, various natural and synthetic resins and small amounts of waxes.
- the binder is sodium alginate, or guar gum, or synthetic dragon gum, or cellulose and its derivatives, or starch and its derivatives, or acrylic acid, crotonic acid and its derivatives Derivatives of multipolymers, or mixtures thereof.
- the surfactant is polyvinylpyrrolidone, or polyoxyethylene alkylamine, or fatty alcohol polyoxyethylene ether, or polysilicon ether, or a mixture thereof.
- the leveling agent is an alkali metal alkyl sulfonate such as sodium alkyl sulfonate, or an alkali metal aliphatic alcohol sulfate such as sodium higher aliphatic alcohol sulfate, or aliphatic alcohol polyoxyethylene Or polyoxypropylene or their mixtures.
- the alkali agent may be an amine compound or an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide.
- the dye accelerator-applied fibrous facestock is dyed with reactive dyes (eg type B reactive dyes) or indigo dyes.
- reactive dyes eg type B reactive dyes
- indigo dyes Such dyeing or printing processes are known.
- the thus dyed fabric such as denim can be dried, fixed, washed and shaped to obtain a finished product.
- the bi-active quaternary ammonium salt having both monohalo-s-triazine and ethyl sulfone groups not only has excellent anchoring reaction characteristics for fibers in fiber fabrics such as cotton fibers, but also when used as a Dyeing accelerators modify fabrics, especially denim grey fabrics, and then dye them, which has significant ecological advantages compared to traditional indigo dyeing methods.
- using the compound of formula (I) of the present invention as a dyeing accelerator can greatly reduce or even completely eliminate the need for traditional salts as dyeing accelerators while maintaining or even improving the dyeability of fiber fabrics.
- the expense, handling difficulties and disposal problems associated with adding salt can be eliminated.
- the dyes after being treated by the dyeing accelerator of the present invention, can be completely combined with the fibrous tissue to achieve a high apparent color yield, thereby maximizing the utilization of the dyes and significantly reducing the use of the dyes.
- the resulting textiles can be dyed uniformly and have good color fastness, thereby also reducing the need for color-fixing alkalis.
- preferred dye accelerator compositions may also contain other suitable salts such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
- the use can be reduced (for example, less than 5%, 2% by weight of the accelerator composition) %, 1% or even 0.5%) and even do not use those alkaline agents that are prone to pollution such as alkali metal hydroxides, especially those selected from amine compounds, such as alkylamines including triethylamine and the like. and/or no other organic ammonium salt other than the quaternary ammonium salt compound of formula (I) is used.
- FIG. 1a is the nuclear magnetic resonance (1H-NMR) spectrum of the dyeing accelerator synthesized in Example 1.
- FIG. 1a is the nuclear magnetic resonance (1H-NMR) spectrum of the dyeing accelerator synthesized in Example 1.
- Figure 1b is the infrared spectrum of the dyeing accelerator synthesized in Example 1.
- FIG. 2a is the nuclear magnetic resonance (1H-NMR) spectrum of the dyeing accelerator synthesized in Example 2.
- the fixation rate test described in the following examples is carried out according to the GB/T 2391-2014 "Determination of the Fixation Rate of Reactive Dyes”.
- Dry rubbing fastness and wet rubbing fastness test are carried out according to GB/T 3920-2008 "Textiles. Color fastness test. Color fastness to rubbing".
- Width 58-60 inches
- Composition 100% Cotton.
- the reaction system containing preliminary product is warmed up to 35-40 °C, and the amino derivative of hydroxypropyltrimethylammonium hydrochloride is added dropwise with stirring, wherein still with Na 2 CO
- the pH value of the control reaction is adjusted to 6.5, until After the reaction, the denim fabric dyeing accelerator is obtained. At this point, no further addition of aqueous Na2CO3 was added and the pH of the solution remained at 6.5.
- the obtained dyeing accelerator has the following molecular formula and its NMR and IR spectra are shown in Figures 1a and 1b:
- X is Cl
- R 1 and R 2 are respectively
- a dye accelerator solution comprising the following components is first formulated based on the dye accelerator compound prepared above:
- the fabric samples prepared in this example have a printing fixation rate of 93% with reactive dyes, and the obtained elastic cotton denim dyed fabric has a dry rubbing fastness of 4-5, and a wet rubbing fastness of 3.5-4.
- the fastness is grade 5, and the color fastness to soaping is grade 4-5.
- Width 50-52 inches
- Composition 97% Cotton + 3% Stretch Spandex.
- the synthetic method of denim fabric dyeing accelerator is as follows:
- reaction kettles containing the epoxy derivatives were respectively added dropwise to excess concentrated ammonia water with a concentration of 32%. After the dropwise addition, the reaction was continued for 3-4h. The excess ammonia was then removed in vacuo at 80°C to yield two identical amine derivatives of p-phenylhydroxymethyltrimethylammonium hydrochloride.
- the reaction system containing the preliminary product is heated to 35-40° C., and the second portion of the obtained amino derivative is added dropwise under stirring, wherein the pH value of the reaction is still adjusted and controlled at 6.5 with an aqueous Na 2 CO 3 solution until the reaction ends, to obtain Dyeing accelerator. At this time, the aqueous Na 2 CO 3 solution was no longer added, and the pH value of the solution remained at 6.5.
- the prepared dyeing accelerator compound has the following structural formula and its nuclear magnetic resonance spectrum and infrared spectrum are shown in Figures 2a and 2b:
- R1 and R2 are both and
- a dye accelerator solution comprising the following components is first formulated based on the dye accelerator compound prepared above:
- the denim grey fabric is paddled in the desizing enzyme solution at 50-60°C and stacked for 3-4 hours, then washed with hot water at 90°C, then washed with normal temperature water, dried and ready to be printed. Then, the prepared dyeing accelerator solution is coated on the front and back sides of the denim grey fabric by double-sided anilox roller coating.
- use indigo dye to use the dip dyeing method known to professionals in the field (such as review literature: Yang Guili, Peng Cheng. Denim Dyeing and Quality Control [J]. Tianjin Textile Science and Technology, 2011, (3): 7-9 described in method) to carry out printing and dyeing operations to obtain elastic cotton denim dyed cloth.
- the fabric sample prepared in this example has a dyeing fixation rate of indigo dye of 90%, and the obtained elastic cotton denim dyed fabric has a dry rubbing fastness of 4-5 grade and a wet rubbing fastness of 3.5-4 grade.
- the fastness is grade 5
- the color fastness to soaping is grade 4-5.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
本发明涉及一种染色促进剂,其包含具有乙基砜基团和一卤均三嗪基团的双活性基季铵盐化合物,所述化合物具有如下所示的结构式(I) 其中 M为H或碱金属离子,优选Na或K; Y各自独立地表示H、卤素或者直链或支化的C 1-12的烷基,优选H; X各自独立地表示卤素,优选Cl或F;和 R 1和R 2各自表示相同或不同地选自以下的季铵基团:或(R 3) 3N +-R 4-, 其中R 3彼此独立地表示直链或支化的C 1-12的烷基,优选甲基、乙基或丙基, R 4表示直链或支化的C 1-12的亚烷基,优选亚乙基、亚丙基或亚丁基,和 R 0表示任选的位于苯环上的一个或多个选自卤素或C 1-8的烷基的取代基。此外,本发明还涉及制备该化合物的方法,包含该化合物的染色促进剂组合物以及染色的方法,特别是对牛仔坯布进行染色。
Description
本申请涉及纺织工业的印染技术,更具体是涉及一种新型的染色促进剂、其制备方法以及染色方法,特别是对纤维面料如牛仔坯布的染色方法。
纤维面料在纺织工业和服装领域中广泛使用。除了传统而常见的棉纤维之外,各种天然纤维如大麻、苎麻、亚麻、蚕丝、羊毛等与棉混纺,粘胶、天丝、莫代尔等的再生纤维,或者合成纤维化学纤维如涤纶、锦纶、腈纶、氨纶等均已经广泛使用。
为了提供服装和织物的丰富色彩和美感,需要采用染料对纤维面料进行染色。这些染料包括例如各种活性染料或靛蓝。活性染料是一种阴离子型染料,又称反应性染料,其分子中含有化学性活泼的基团,能在水溶液中与棉、毛等纤维反应形成共键的染料。由于其鲜艳度好、使用方便和色牢度佳等特点而广受欢迎。然而,活性染料与纤维在发生共价键合的同时非常容易发生水解,从而存在着染料上染率和固色率低的问题。在传统染色工艺中通常需要加入大量无机盐以屏蔽纤维表面负电荷聚集,提高染料吸附性能。但是这样做会产生高盐含量的废水从而影响环境或造成废水处理问题。
靛蓝是一种古老的还原染料,也广泛应用于纯棉织物的染色。靛蓝染色的过程主要包括:染料还原,浸染隐色体,氧化,水洗,皂洗和干燥。靛蓝染料通常不溶于水,对纤维没有亲和力,不能直接用来染色,而需在碱性条件下经强还原剂还原,成为微溶于水的隐色体才能够用来染色。但靛蓝染料的还原速率较慢。靛蓝染色速率与其他还原染料相比,染色速率慢而且上染率低,通常为10%左右。这被认为是由于靛蓝隐色体分子平面性差,对纤维亲和力小。靛蓝属于低温染色型染料,一般常温条件下染色,温度越高得色率相反会下降;同时靛蓝也属于低碱度染色染料,碱度愈高,得色率也会下降。
因此,在纺织工业,在纤维面料例如在牛仔坯布染色过程中会产生大量的染色废水且处理起来困难,同时使用过多的染化料如还原剂和碱剂氢氧化钠等,从而产生大量的无机盐和废弃染料,增加了污水的COD。另外,加工稳定性不好,染色受到季节,环境的影响很大,重现性差,条件稍微有所变化就会引起色泽和色调的变化。特别的,对于常用的商品靛蓝,难以染得深浓色和鲜艳色光并且当用靛蓝染色牛仔布时色牢度不好,尤其是摩擦色牢度及水洗色牢度,并且在洗用过程中很容易沾染其他织物。
在CN110004742A中试图解决以上部分技术问题,其提供了一种阳离子改性棉织物的无盐染色方法以改善匀染性、色牢度等,其中特别使用了包含选自N-羟甲基丙烯酰胺NMA、N-二甲基氮杂环丁烷氯化物DMAC和聚氨基羧酸PACA之一的改性剂的改性处理液。
另外,CN107740295A提供了一种基于棉织物活性染料阳离子改性剂的染色方法,其中对棉纤维进行了改性处理,而所用改性水溶液为谷氨酸盐水溶液或苯丙氨酸盐水溶液。
然而,对于上述那些技术问题仍然存在着改进的空间,并且也需要进一步探索适用的改善染色工艺的促进剂。
发明内容
鉴于以上技术问题,本申请的发明人开发了一种新型的染色促进剂,采用该染色促进剂对纤维面料,特别是棉及混纺的面料如牛仔坯布进行预处理后,能够显著提升靛蓝隐色体或活性染料与纤维之间的亲和力,减少染浴中靛蓝染料或活性染料的残余量和COD污染,提高染料利用率、稳定染色品质以及改善牢度如色牢度和摩擦牢度等,并由此减轻了环境压力。
因此,本申请的第一方面涉及一种染色促进剂,其包含具有乙基砜基团和一卤均三嗪基团的双活性基季铵盐化合物,所述化合物具有如下所示的结构式(I)
其中
M为H或碱金属离子,优选Na或K;
Y各自独立地表示H、卤素或者直链或支化的C
1-12的烷基,优选H;
X各自独立地表示卤素,优选Cl或F,更优选Cl;和
R
1和R
2各自表示相同或不同地选自以下的季铵基团:
其中R
3彼此独立地表示直链或支化的C
1-12的烷基,优选甲基、乙基或丙基,
R
4表示直链或支化的C
1-12的亚烷基,优选亚乙基、亚丙基或亚丁基,和
R
0表示任选的位于苯环上的一个或多个如1、2、3或4个选自卤素或C
1-8的烷基的取代基。
本申请的第二个方面涉及制备如上所述的式(I)化合物的方法,包括如下步骤:
(1)将一种或多种选自任选地被一个或多个R
0基团取代的间苯羟烷基三烷基铵盐、对苯羟烷基三烷基铵盐或羟烷基三烷基铵盐的三烷基铵盐在碱性条件下闭环反应,得到其对应环氧衍生物;
(2)使步骤(1)中获得的环氧衍生物发生氨化反应,得到其对应的胺基衍生物;和
(3)使步骤(2)中所得的胺基衍生物与1,3,5-三卤均三嗪和任选地被一个或多个R
0基团取代的对(β-硫酸酯乙基砜)苯胺反应。
本申请的第三个方面涉及一种对纤维面料进行染色的方法,包括如下步骤:
(1)提供任选地经退浆处理的纤维面料;
(2)将如上所述的包含式(I)化合物的染色促进剂溶液施加在该 纤维面料上;和
(3)用活性染料或靛蓝染料对施加了染色促进剂的纤维面料进行染色。
在本申请的上下文中,术语“碱金属”表示元素周期表中第I主族的金属元素,包括Li、Na和K等,优选Na或K。
在本申请上下文中,术语“烷基”优选表示具有1-12、优选1-8或1-4个碳原子的直链或支化的烷基,并且碳原子上的一个或多个H可以被卤素如F、Cl或Br取代。在一个优选的实施方式,所述烷基表示未取代的C
1-8的烷基,更优选C
1-4的烷基,如甲基、乙基、丙基或丁基。
在本申请上下文中,术语“卤素”优选包括F、Cl和Br,更优选表示Cl。
基团R
0表示任选的位于苯环上的一个或多个选自卤素或C
1-8的烷基的取代基。在根据本发明的一个优选的实施方式中,式(I)的各个苯环中不具有取代基R
0,即苯环是未取代的。
根据本发明,在优选的式(I)的化合物中:
M为Na或K;
Y表示H;
X表示Cl;
R
3彼此独立地表示直链或支化的C
1-8的烷基,更优选C
1-6的烷基,特别优选甲基或乙基;
R
4表示直链或支化的C
1-8的亚烷基,更优选C
2-6的亚烷基,尤其优选亚丙基;和/或
苯环中不包含取代基R
0。
本申请的第二个方面涉及如上所述的制备式(I)化合物的方法。
在该方法的第(1)步骤中涉及闭环反应。显然的,所述的间苯羟烷基三烷基铵盐、对苯羟烷基三烷基铵盐或羟烷基三烷基铵盐的三种三烷基铵盐分别对应于R
1和R
2的三类来源,即具有如下结构的物质的铵盐,其中R
3和R
4如上定义,而R
5表示直链或支化的C
1-8的亚烷基,优选亚甲基:
(R
3)
3N
+-R
4-OH。
此外,所述铵盐可以优选由如上所述的阳离子结构与有机或无机酸形成,例如盐酸、硝酸或硫酸。优选的,三种铵盐都是盐酸盐。
在该闭环反应的例示性的实施方式中,可以向所述三烷基铵盐中加入诸如NaOH或KOH的碱性溶液进行反应。反应一段时间后任选地滤去反应中生成的盐如NaCl,随后将pH值调节至例如6.0-7.5,特别是6.5-7,得到三烷基铵盐的环氧衍生物。pH值调节剂可以选自酸性化合物,如盐酸。反应温度可以控制在室温(例如约23℃)。
第(2)步中,使步骤(1)中获得的环氧衍生物发生氨化反应,得到其对应的胺基衍生物。氨化反应可以通过将所得的环氧衍生物加入到过量的氨中而进行。这里可以采用浓氨水。在加料之后保持反应一段时间,如3-4h。然后升高温度(例如在80℃下)脱除多余的氨,得到胺基衍生物。
第(3)步中,使步骤(2)中所得的胺基衍生物与1,3,5-三卤均三嗪和任选地被一个或多个R
0基团取代的对(β-硫酸酯乙基砜)苯胺反应。
根据所期望获得的具体的式(I)化合物的化学计量比,可以使上述得到的胺基衍生物与1,3,5-三卤均三嗪和对(β-硫酸酯乙基砜)苯胺按照2:1:1的摩尔比反应。例如,显然的,如果采用两种不同的胺基衍生物,则三者的反应摩尔比为1:1:1:1。
在该反应步骤中,通常在低温如0-10℃、更优选0-5℃的温度下使包含1,3,5-三卤均三嗪和对(β-硫酸酯乙基砜)苯胺的溶液与上述获得的胺基衍生物混合。适合溶解1,3,5-三卤均三嗪和对(β-硫酸酯乙基砜)苯胺的溶剂为例如丙酮。在采用两种胺基衍生物的一种例示性实施方式中,可以首先使一种胺基衍生物与包含1,3,5-三卤均三嗪和对(β-硫酸酯乙基砜)苯胺的溶液混合并反应,随后升高温 度(如升高到25-50℃,优选35-40℃)再混合另一种胺基衍生物,从而得到所期望的促进剂化合物。在该步的反应过程中,可以优选加入pH调节剂以控制反应的pH值在6-7,如6.5左右。在此,合适的pH调节剂例如Na
2CO
3。
本申请的第三个方面涉及一种对纤维面料进行染色的方法。
根据本发明的染色促进剂特别适用于纤维面料的染色,尤其是针对牛仔坯布。事先经退浆处理的纤维面料是有利的。面料的退浆处理本身是本领域技术人员已知的。以牛仔坯布为例,该退浆处理例如可以如下进行:在50-60℃的温度下于退浆酶液中浸轧后堆置3-4小时,随后用60℃以上(如90℃)的热水水洗,再用常温水洗,最后烘干得到待染色的牛仔坯布。
随后,将如上所述的包含式(I)化合物的染色促进剂的促进剂溶液施加在该纤维面料上。这种施加可以通过例如双面网纹辊涂或双面泡沫涂布或浸轧的方式而将染色促进剂溶液均匀涂覆在面料的一面或两面上。优选的,使得纤维面料(优选牛仔坯布)的带液率达到20%以上,例如25%-50%或25%-40%。
在一个示例性实施方式中,所述促进剂溶液涉及这样的染色促进剂组合物,其包含(按重量百分比计):
3-5%的如上所述的染色促进剂,
2-5%的连接料,
1-3%的表面活性剂,
0-12%的碱剂
0.5-2%的匀染剂。
所述染色促进剂组合物的余量可以包含其他一些适用的添加剂、调节剂、盐、分散剂和溶剂等。这里,优选的,所述染色促进剂组合物的余量为分散剂或溶剂,如水。
连接料本身是本领域技术人员已知的组分,通常用作分散介质,其可以在一定程度上调节体系的流变性、黏度、成膜性以及涂布性能。这样的连接料可以例如由植物油、矿物油、有机溶剂、各种天然和合成树脂及少量蜡质构成。在一个优选的实施方式中,所述连接料为海 藻酸钠,或瓜尔胶,或合成龙胶,或纤维素及其衍生物,或淀粉及其衍生物,或丙烯酸、丁烯酸及其衍生物的多元聚合物,或它们的混合物。
在一个优选的实施方式中,所述表面活性剂为聚乙烯吡咯烷酮,或聚氧乙烯烷基胺,或脂肪醇聚氧乙烯醚,或聚硅醚,或它们的混合物。
在一个优选的实施方式中,所述匀染剂为碱金属的烷基磺酸盐如烷基磺酸钠,或碱金属的脂肪醇硫酸盐如高级脂肪醇硫酸钠,或脂肪醇聚氧乙烯或聚氧丙烯或它们的混合物。
在一个优选的实施方式中,所述碱剂可以为胺类化合物或碱金属的氢氧化物,如氢氧化钠或氢氧化钾等。
在用染色促进剂溶液进行处理之后,用活性染料(如B型活性染料)或靛蓝染料对施加了染色促进剂的纤维面料进行染色。这样的染色或印染过程是已知的。
最后,可以将经如此染色之后的面料如牛仔布烘干,经固色处理,水洗和定型,得到成品。
本申请的发明人发现,同时具有一卤均三嗪和乙基砜基团的双活性基季铵盐不仅对纤维面料中的纤维如棉纤维具有极好的固着反应特性,而且当用其作为染色促进剂对面料,特别是牛仔坯布进行改性后再进行染色,具有相比于传统靛蓝染色方法显著的生态优势。例如,采用了本发明的式(I)的化合物作为染色促进剂之后,可以大幅减少甚至完全不需要传统的盐作为染色促进剂而同时又能保持甚至提高纤维面料的可染性。因此,可以消除与添加盐有关的费用、处理困难和处置问题。此外,经过本发明的染色促进剂处理之后,染料可以完全结合到纤维组织上实现高的表观得色量,从而最大限度地利用染料,显著减少染料的使用。此外,所得纺织品可以均匀染色并且具有良好的染色牢度,从而也减少了对固色碱剂的需要。
因此,在根据本发明的优选实施方式中,优选的染色促进剂组合物还可以包含其他一些适用的盐如碳酸钠、碳酸氢钠、碳酸钾和碳酸氢钾。
但是,作为本发明的有益效果之一,在根据本发明的染色方法或染色促进剂组合物的优选实施方式中,可以减少使用(例如以所述促进剂组合物重量计低于5%、2%、1%或甚至0.5%)甚至不使用容易造成污染的那些碱剂如碱金属氢氧化物,特别还有选自胺类化合物的碱剂,如包括三乙胺之类的烷基胺在内的有机胺;和/或不使用除了式(I)的季铵盐化合物之外的其他有机铵盐。
图1a为实施例1合成的染色促进剂核磁共振(1H-NMR)谱。
图1b为实施例1合成的染色促进剂红外光谱。
图2a为实施例2中合成的染色促进剂核磁共振(1H-NMR)谱。
图2b实施例2中合成的染色促进剂红外光谱。
以下实施例意图展示本发明的各种实施方案,但不应解释为以任何方式限制本发明。
虽然以上已为了说明的目的描述了本发明特定的实施方案,但对本领域技术人员明显的是,可作出本发明细节的多种变体,但不会背离所附权利要求中限定的本发明的范围。
测试方法
下述实施例中所述固色率测试依据GB/T 2391-2014《反应染料固色率的测定》测定方法进行。
干摩擦牢度和湿摩擦牢度测试依据GB/T 3920-2008《纺织品.色牢度试验.耐摩擦色牢度》进行。
日晒牢度和耐皂洗色牢度测试依据GB/T 14575-2009《纺织品 色牢度试验 综合色牢度》进行。
实施例1
纯棉人字斜牛仔面料活性染料以印代染染色
(1)、牛仔坯布面料准备:
规格:10×10/72×44;
重量:10OZ;
幅宽:58-60英寸;
成份:100%棉。
(2)、染色促进剂的合成:
在室温搅拌的条件下分别向置于反应釜中的1摩尔质量份间苯羟甲基三甲铵盐酸盐(购自Sigma-Aldrich,分析纯)和1摩尔质量份羟丙基三甲铵盐酸盐(购自Sigma-Aldrich,分析纯)这两种三甲铵盐酸盐中分别滴加浓度40%的NaOH水溶液1摩尔质量份。滴加完成后,继续反应30~60分钟。滤去反应中生成的NaCl,用盐酸调节溶液pH值6.5~7,由此分别制得对应的环氧衍生物。
然后分别向两个上述装有新制环氧衍生物的反应釜中滴加过量的32%浓度的浓氨水。滴加完成后,继续反应3—4h。然后于80℃真空脱除多余的氨,得到对应的两种胺基衍生物,产率约85%以上。
随后,在0~5℃的条件下,在均匀搅拌环境中,将溶有1,3,5-一氯均三嗪和对(β-硫酸酯乙基砜)苯胺的丙酮溶液缓缓滴加到上述间苯羟甲基三甲铵盐酸的胺基衍生物中,其中随时用Na
2CO
3水溶液调节控制反应pH值为6.5,直到反应结束得到初步产物。此时,不再加入Na
2CO
3水溶液,溶液的pH值仍保持在6.5不变为止。将含有初步产物的反应体系升温至35-40℃,搅拌下滴加羟丙基三甲铵盐酸盐的胺基衍生物,其中仍用Na
2CO
3水溶液调节控制反应的pH值为6.5,直到反应结束,得到所述牛仔面料染色促进剂。此时不再加Na
2CO
3水溶液而溶液的pH值仍保持在6.5。
得到的染色促进剂具有如下的分子式且其核磁共振谱和红外光谱如图1a和1b所示:
其中
X为Cl;和
(3)染色过程
首先基于如上所制得的染色促进剂化合物配制包含如下组分的染色促进剂溶液:
将准备的牛仔胚布面料在50-60℃的退浆酶液中浸轧后堆置3-4小时,然后用90℃热水水洗,再用常温水洗,烘干后待印。随后通过双面网纹辊涂布将制备的染色促进剂溶液涂覆在牛仔坯布的正反两面。最后,应用B型双活性基活性染料(浙江闰土化工有限公司生产)采用中国专利CN201710048417.9中所述的转移染色的方法进行印染作业,即得到纯棉人字斜牛仔印染布。
本实施例所制布样,其活性染料的印花固色率为93%,制得的弹力棉牛仔染色布干摩擦牢度为4-5级,湿摩擦牢度为3.5-4级,日晒牢度5级,耐皂洗色牢度为4-5级。
实施例2:
弹力棉牛仔面料浸染
(1)、牛仔坯布面料准备:
规格:7×16/70D;
幅宽:50-52英寸;
重量:11.5OZ;
成份:97%棉+3%弹力氨纶。
牛仔面料染色促进剂的合成方法如下:
(2)、染色促进剂的合成:
室温搅拌下分别向置于两个反应釜中的各1摩尔质量份的对苯羟甲基三甲铵盐酸盐(购自Sigma-Aldrich,分析纯)中滴加浓度40%的NaOH水溶液1摩尔质量份。在滴加完成后继续反应30~60分钟。滤去反应中生成的NaCl,用盐酸调节溶液pH值6.5~7,得到2份相同的环氧衍生物。
然后在室温搅拌下分别向装有该环氧衍生物的反应釜滴加到过量的32%浓度的浓氨水中。滴加完毕后,继续反应3—4h。然后于80℃真空脱除多余的氨,得到两份相同的对苯羟甲基三甲铵盐酸盐的胺基衍生物。
随后,在0~5摄氏度条件下,在均匀搅拌环境中,将溶有摩尔比为1:1的1,3,5-一氯均三嗪和对(β-硫酸酯乙基砜)苯胺的丙酮溶液缓缓滴加到上述一份所得的胺基衍生物中,其中随时用Na
2CO
3水溶液调节控制反应pH值在6.5,直到反应结束,得到初步产物。此时,不再加入Na
2CO
3水溶液,溶液pH值仍保持在6.5不变。将包含初步产物的反应体系升温至35-40℃,于搅拌下滴加第二份的所得的胺基衍生物,其中仍用Na
2CO
3水溶液调节控制反应pH值在6.5直到反应结束,得到染色促进剂。此时不再加Na
2CO
3水溶液,溶液pH值仍保持在6.5。
制得的染色促进剂化合物具有如下结构式且其核磁共振谱和红外光谱如图2a和2b所示:
其中
X为Cl。
(3)染色过程
首先基于如上所制得的染色促进剂化合物配制包含如下组分的染色促进剂溶液:
将牛仔坯布在50-60℃的退浆酶液中浸轧后堆置3-4小时,然后用90℃热水水洗,再用常温水洗,烘干后待印。随后将配制好的染色促进剂溶液通过双面网纹辊涂布涂覆在牛仔坯布正反两面。最后,应用靛蓝染料采用本领域专业人员熟知的浸染方法(如综述文献:杨桂莉,彭诚.牛仔布染色及质量控制[J].天津纺织科技,2011,(3):7-9中所述方法)进行印染作业,得到弹力棉牛仔染色布。
本实施例所制布样,其靛蓝染料的染色固色率为90%,制得的弹力棉牛仔染色布干摩擦牢度为4-5级,湿摩擦牢度为3.5-4级,日晒牢度5级,耐皂洗色牢度为4-5级。
Claims (13)
- 染色促进剂,其包含具有乙基砜基团和一卤均三嗪基团的双活性基季铵盐化合物,所述化合物具有如下所示的结构式(I)其中M为H或碱金属离子,优选Na或K;Y各自独立地表示H、卤素或者直链或支化的C 1-12的烷基,优选H;X各自独立地表示卤素,优选Cl或F,更优选Cl;和R 1和R 2各自表示相同或不同地选自以下的季铵基团:其中R 3彼此独立地表示直链或支化的C 1-12的烷基,优选甲基、乙基或丙基,R 4表示直链或支化的C 1-12的亚烷基,优选亚乙基、亚丙基或亚丁基,和R 0表示任选存在的位于苯环上的一个或多个选自卤素或C 1-8的烷基的取代基。
- 根据权利要求1所述的染色促进剂,其特征在于,在所述结构式(I)中:M为Na或K;Y表示H;X表示Cl;R 3彼此独立地表示直链或支化的C 1-8的烷基,更优选C 1-6的烷基,特别优选甲基或乙基;R 4表示直链或支化的C 1-8的亚烷基,更优选C 2-6的亚烷基,尤其 优选亚丙基;和/或苯环中不包含取代基R 0。
- 制备如权利要求1-2中任一项所述的染色促进剂的方法,包括如下步骤:(1)将一种或多种选自任选地被一个或多个R 0基团取代的间苯羟烷基三烷基铵盐、对苯羟烷基三烷基铵盐或羟烷基三烷基铵盐的三烷基铵盐在碱性条件下闭环反应,得到其对应环氧衍生物;(2)使步骤(1)中获得的环氧衍生物发生氨化反应,得到其对应的胺基衍生物;和(3)使步骤(2)中所得的胺基衍生物与1,3,5-三卤均三嗪和任选地被一个或多个R 0基团取代的对(β-硫酸酯乙基砜)苯胺反应。
- 根据权利要求3所述的方法,其特征在于,在第(3)步中加入pH调节剂以控制反应的pH值在6-7,如6.5左右。
- 对纤维面料进行染色的方法,包括如下步骤:(1)提供任选地经退浆处理的纤维面料;(2)将包含如权利要求1-2中任一项所述的式(I)化合物的染色促进剂溶液施加在该纤维面料上;和(3)用活性染料或靛蓝染料对施加了染色促进剂的纤维面料进行染色。
- 根据权利要求5所述的方法,其特征在于,所述纤维面料是牛仔坯布。
- 根据权利要求5或6所述的方法,其特征在于,所述方法中不使用选自胺类化合物,如包括三乙胺之类的烷基胺在内的有机胺;和/或不使用除了式(I)的季铵盐化合物之外的其他有机铵盐。
- 根据权利要求5至7任一项所述的方法,其特征在于,用靛蓝染料对牛仔坯布进行染色。
- 染色促进剂组合物,其按组合物的总重量计包含:3-5%的如权利要求1-2任一项所述的染色促进剂,2-5%的连接料,1-3%的表面活性剂,0-12%的碱剂,和0.5-2%的匀染剂。
- 根据权利要求9的染色促进剂组合物,其特征在于,余量为水。
- 根据权利要求9或10的染色促进剂组合物,其特征在于,所述连接料为海藻酸钠,或瓜尔胶,或合成龙胶,或纤维素及其衍生物,或淀粉及其衍生物,或丙烯酸、丁烯酸及其衍生物的多元聚合物,或它们的混合物。
- 根据权利要求9至11任一项的染色促进剂组合物,其特征在于,所述表面活性剂为聚乙烯吡咯烷酮,或聚氧乙烯烷基胺,或脂肪醇聚氧乙烯醚,或聚硅醚,或它们的混合物。
- 根据权利要求9至12任一项的染色促进剂组合物,其特征在于,所述匀染剂为碱金属的烷基磺酸盐如烷基磺酸钠,或碱金属的脂肪醇硫酸盐如高级脂肪醇硫酸钠,或脂肪醇聚氧乙烯或聚氧丙烯或它们的混合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011328829.6A CN112647323B (zh) | 2020-11-24 | 2020-11-24 | 染色促进剂、其制备以及染色方法 |
CN202011328829.6 | 2020-11-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022110623A1 true WO2022110623A1 (zh) | 2022-06-02 |
Family
ID=75349330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/088991 WO2022110623A1 (zh) | 2020-11-24 | 2021-04-22 | 染色促进剂、其制备以及染色方法 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN112647323B (zh) |
WO (1) | WO2022110623A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116163138A (zh) * | 2022-12-30 | 2023-05-26 | 福建省联丰盛漂染植绒有限公司 | 一种上染率高的强力超细纯棉平布加工工艺 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112647323B (zh) * | 2020-11-24 | 2022-01-21 | 长胜纺织科技发展(上海)有限公司 | 染色促进剂、其制备以及染色方法 |
CN112832042A (zh) * | 2020-12-30 | 2021-05-25 | 长胜纺织科技发展(上海)有限公司 | 一种用于牛仔布的悬浮体染料转移染色的方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103333332A (zh) * | 2013-07-01 | 2013-10-02 | 达利(中国)有限公司 | 一种染色促进剂的制备方法及其应用 |
CN108486930A (zh) * | 2018-05-10 | 2018-09-04 | 东华大学 | 一浴法阳离子改性活性染料染色的整理方法 |
CN110382775A (zh) * | 2017-04-14 | 2019-10-25 | 日东纺绩株式会社 | 纤维素系纤维用湿摩擦坚牢度提高剂、使用了该提高剂的染色纤维素纤维的制造方法及其用途 |
US20200317943A1 (en) * | 2018-05-10 | 2020-10-08 | Donghua University | Finishing method for reactive dye inkjet printing based on the cationic modifier ink |
CN112301763A (zh) * | 2019-07-23 | 2021-02-02 | 广东溢达纺织有限公司 | 一种纯棉织物及其染色方法 |
CN112647323A (zh) * | 2020-11-24 | 2021-04-13 | 长胜纺织科技发展(上海)有限公司 | 染色促进剂、其制备以及染色方法 |
CN112647320A (zh) * | 2020-12-17 | 2021-04-13 | 长胜纺织科技发展(上海)有限公司 | 一种用于牛仔布的活性染料转移染色方法 |
-
2020
- 2020-11-24 CN CN202011328829.6A patent/CN112647323B/zh active Active
-
2021
- 2021-04-22 WO PCT/CN2021/088991 patent/WO2022110623A1/zh active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103333332A (zh) * | 2013-07-01 | 2013-10-02 | 达利(中国)有限公司 | 一种染色促进剂的制备方法及其应用 |
CN110382775A (zh) * | 2017-04-14 | 2019-10-25 | 日东纺绩株式会社 | 纤维素系纤维用湿摩擦坚牢度提高剂、使用了该提高剂的染色纤维素纤维的制造方法及其用途 |
CN108486930A (zh) * | 2018-05-10 | 2018-09-04 | 东华大学 | 一浴法阳离子改性活性染料染色的整理方法 |
US20200317943A1 (en) * | 2018-05-10 | 2020-10-08 | Donghua University | Finishing method for reactive dye inkjet printing based on the cationic modifier ink |
CN112301763A (zh) * | 2019-07-23 | 2021-02-02 | 广东溢达纺织有限公司 | 一种纯棉织物及其染色方法 |
CN112647323A (zh) * | 2020-11-24 | 2021-04-13 | 长胜纺织科技发展(上海)有限公司 | 染色促进剂、其制备以及染色方法 |
CN112647320A (zh) * | 2020-12-17 | 2021-04-13 | 长胜纺织科技发展(上海)有限公司 | 一种用于牛仔布的活性染料转移染色方法 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116163138A (zh) * | 2022-12-30 | 2023-05-26 | 福建省联丰盛漂染植绒有限公司 | 一种上染率高的强力超细纯棉平布加工工艺 |
Also Published As
Publication number | Publication date |
---|---|
CN112647323A (zh) | 2021-04-13 |
CN112647323B (zh) | 2022-01-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022110623A1 (zh) | 染色促进剂、其制备以及染色方法 | |
KR100533181B1 (ko) | 반응성염료혼합물및이를사용하여염색또는날염하는방법 | |
KR840001760B1 (ko) | 수용성 아조 화합물의 제조방법 | |
CN112647320B (zh) | 一种用于牛仔布的活性染料转移染色方法 | |
KR950009540B1 (ko) | 섬유 반응성 적색염료 조성물 | |
WO2022110622A1 (zh) | 转移染色活性染料墨水及其应用 | |
CN106833012B (zh) | 一种活性黄染料及其制备和应用 | |
CN1379065A (zh) | 活性染料以及其制备方法和用途 | |
KR880002250B1 (ko) | 수용성 디스아조 화합물의 제조방법 | |
EP2000511A2 (en) | Trisazo reactive dyestuff compound | |
CN105176139B (zh) | 一种多偶氮棕色活性染料化合物及其制备方法和应用 | |
JPS62164765A (ja) | モノアゾ化合物およびそれを用いて繊維材料を染色または捺染する方法 | |
US20150232668A1 (en) | Yellow Reactive Dye Compound | |
CN101880475B (zh) | 一种活性大红染料组合物 | |
JPH09176505A (ja) | 反応性染料及びそれらを製造する方法 | |
JPH07268231A (ja) | 反応性染料、その製造方法及びその用途 | |
CN103773072A (zh) | 一种活性黄染料化合物 | |
CN116023796B (zh) | 一种水溶性染料化合物及制备方法和应用 | |
JPS63101458A (ja) | 水溶性モノアゾ化合物及びそれを用いる繊維材料の染色又は捺染方法 | |
CN113150576B (zh) | 一种喷墨印花活性红色染料及其制备方法和应用 | |
CN115397924B (zh) | 反应性染料的混合物及其用于纺织纤维材料的染色或印花的用途 | |
TR2022009345T2 (tr) | Boyama promotörü ve hazirlanmasi ve yöntemi̇ | |
CN108504137B (zh) | 一类基于间脲基苯胺系绿色活性染料及其制备方法和应用 | |
CN109403083B (zh) | 一种活性喷墨印花染料混合物及其应用 | |
CN108530941A (zh) | 一种藏青色活性染料及其用途 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21896138 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21896138 Country of ref document: EP Kind code of ref document: A1 |