WO2022134535A1 - 一种活性藏青至黑色染料组合物及染料制品 - Google Patents
一种活性藏青至黑色染料组合物及染料制品 Download PDFInfo
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- WO2022134535A1 WO2022134535A1 PCT/CN2021/104713 CN2021104713W WO2022134535A1 WO 2022134535 A1 WO2022134535 A1 WO 2022134535A1 CN 2021104713 W CN2021104713 W CN 2021104713W WO 2022134535 A1 WO2022134535 A1 WO 2022134535A1
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- sulfonic acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 60
- -1 alkali metal salts Chemical class 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 90
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 78
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 13
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 159000000000 sodium salts Chemical group 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 26
- 239000004744 fabric Substances 0.000 abstract description 17
- 238000005406 washing Methods 0.000 abstract description 15
- 239000002657 fibrous material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 5
- 239000000975 dye Substances 0.000 description 145
- 238000000034 method Methods 0.000 description 28
- 238000005859 coupling reaction Methods 0.000 description 21
- 239000007788 liquid Substances 0.000 description 18
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 18
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000985 reactive dye Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000010186 staining Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 235000010288 sodium nitrite Nutrition 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 8
- 210000002268 wool Anatomy 0.000 description 8
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- 238000006193 diazotization reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 238000009980 pad dyeing Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NMDKWAQVRNUKQH-UHFFFAOYSA-N 2-benzylnaphthalene-1-sulfonic acid formaldehyde Chemical compound C=O.C(C1=CC=CC=C1)C1=C(C2=CC=CC=C2C=C1)S(=O)(=O)O NMDKWAQVRNUKQH-UHFFFAOYSA-N 0.000 description 1
- FOINSAWEWXUXPQ-UHFFFAOYSA-N 4-acetamido-2-aminobenzenesulfonic acid Chemical compound CC(=O)NC1=CC=C(S(O)(=O)=O)C(N)=C1 FOINSAWEWXUXPQ-UHFFFAOYSA-N 0.000 description 1
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 description 1
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 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
- 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
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000005236 alkanoylamino group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- WQHQCQSAAOGHQP-UHFFFAOYSA-N formaldehyde;2-methylnaphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=CC2=C(S(O)(=O)=O)C(C)=CC=C21 WQHQCQSAAOGHQP-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- NTOLGSSKLPLTDW-UHFFFAOYSA-N hydrogen sulfate;phenylazanium Chemical compound OS(O)(=O)=O.NC1=CC=CC=C1 NTOLGSSKLPLTDW-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004045 reactive dyeing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UIEBGVDTKLYGTN-UHFFFAOYSA-J tetrasodium;7-[[2-(carbamoylamino)-4-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]phenyl]diazenyl]naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C=1C=C(N=NC=2C(=CC3=CC(=CC(=C3C=2)S([O-])(=O)=O)S([O-])(=O)=O)S([O-])(=O)=O)C(NC(=O)N)=CC=1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 UIEBGVDTKLYGTN-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B56/00—Azo dyes containing other chromophoric systems
- C09B56/04—Stilbene-azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
- C09B67/0055—Mixtures of two or more disazo dyes
- C09B67/0057—Mixtures of two or more reactive disazo dyes
- C09B67/0059—Mixtures of two or more reactive disazo dyes all the reactive groups are not directly attached to a heterocyclic system
-
- 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
- D06P1/384—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 reactive group not directly attached to heterocyclic group
-
- 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
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group
Definitions
- the present invention relates to a reactive dye composition and dye product, in particular to a reactive navy to black dye composition and dye product suitable for printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials.
- Reactive black KNB has become the most used type of black reactive dyes due to its low price, good fastness and easy washing.
- the existing reactive black dye color matching products still have problems such as poor lifting power and low washing fastness in the actual application process, such as patents CN100582168A, CN1730566A and so on.
- the object of the present invention is to provide a reactive navy to black dye composition and dye products, which have the characteristics of good washing fastness, high color fixing rate, good lifting power, etc., suitable for nitrogen-containing and/or containing Printing and dyeing of hydroxyl fiber materials and their blended fabrics.
- the present invention provides a reactive navy blue to black dye composition, comprising component A and component B, wherein component A is selected from one or more dye compounds represented by formula (I) or their alkali metal salts, Component B is selected from one or more dye compounds represented by formula (II) or their alkali metal salts; based on said component A and component B, the mass percentage of component A is 5-50 %, the mass percentage of component B is 50-95%,
- D 1 and D 2 are each independently a group represented by the following formula (a) or (b):
- R 1 and R 2 are each independently hydrogen, oxygen, -COR 7 , C 1 -C 4 alkyl or C 1 -C 4 alkyl substituted by hydroxyl, sulfonic acid or carboxyl, wherein R 7 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl or -NH 2 ;
- R 3 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxyl or sulfonic acid group;
- R 4 -R 6 are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or sulfonic acid group;
- R 8 -R 11 are each independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or sulfonic acid group;
- the C 1 -C 4 alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; the C 1 -C 4 The alkoxy group can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
- D 1 and D 2 are preferably groups represented by formula (a) or (b) at the same time.
- D 1 and D 2 are preferably groups represented by formula (a) at the same time.
- R 1 and R 2 are each independently preferably hydrogen or -COR 7 , wherein R 7 is methyl or -NH 2 .
- R 3 is preferably hydrogen, methyl, methoxy, carboxyl or sulfonic acid.
- R 4 to R 6 are each independently preferably hydrogen, methyl, methoxy or sulfonic acid group.
- R 8 to R 11 are each independently preferably hydrogen, methyl, methoxy or sulfonic acid group.
- the reactive navy to black dye composition is composed of component A and component B.
- the reactive navy to black dye composition may also include component C, wherein the component C is selected from one or more of formulas (III) to (IV) The compound shown or its alkali metal salt, in the composition, the mass of component C accounts for 1-50% of the total mass of component A and component B, preferably 1-40%:
- R 12 -R 15 are each independently H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, carboxyl or sulfonic acid group, preferably H, methyl, methoxy, carboxyl or sulfonic acid group;
- a is 0 or 1
- b is 0 or 1;
- c and d are independently 0 or 1, preferably 1;
- Each of D 3 and D 4 is independently a substituted phenyl group, an unsubstituted phenyl group, a substituted naphthyl group or an unsubstituted naphthyl group, and the number of substituents of the substituted phenyl group and the substituted naphthyl group is respectively 1-3, each substituent is independently selected from amino group, sulfonic acid group, urea group, C 1 -C 4 alkanoylamino group, C 1 -C 4 alkoxy group or hydroxyl group, preferably the number of substituent groups is respectively is 1-2, and each substituent is independently selected from amino, sulfonic acid, ureido, acetamido, methoxy or hydroxyl;
- R 16 -R 19 are each independently H, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or sulfonic acid group, preferably H, methyl, methoxy or sulfonic acid group;
- the reactive navy to black dye composition of the present invention preferably comprises the following dye components:
- Component A selected from at least one dye compound of formula (I) or its alkali metal salt;
- Component B selected from at least one dye compound represented by formula (II) or its alkali metal salt;
- Component C selected from at least one dye compound represented by formula (III) and/or formula (IV) or its alkali metal salt, wherein a and b are both 0, or one of a and b is 0, and the other is 1, c is 1, and d is 0 or 1.
- the reactive navy blue to black dye composition is composed of component A, component B and component C.
- the reactive navy to black dye composition of the present invention preferably consists of the following dye components:
- Component A selected from at least one dye compound of formula (I) or its alkali metal salt;
- Component B selected from at least one dye compound represented by formula (II) or its alkali metal salt;
- Component C selected from at least one dye compound represented by formula (III) and/or formula (IV) or its alkali metal salt, wherein a and b are both 0, or one of a and b is 0, and the other is 1, c is 1, and d is 0 or 1.
- the dye composition further includes component D, and the component D is selected from one or more compounds represented by formulae (V) to (VII) or their bases Metal salt, in the composition, the mass of component D accounts for 1-50% of the total mass of component A and component B, preferably 1-40%:
- f, g and h are each independently 0-3, and each R 20 , R 21 , and R 22 are each independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy or sulfonic acid group, preferably methyl , methoxy or sulfonic acid group;
- X 3 is hydrogen or carboxyl
- D 5 and D 6 are each independently a group represented by the following formula (c) or (d) or (f):
- R 23 , R 24 , R 26 , R 27 , R 29 , and R 30 are each independently H, C 1 -C 4 alkyl, C 1 -C 4 Alkoxy or sulfonic acid group, preferably H, methyl, methoxy or sulfonic acid group;
- each R 25 is independently selected from a sulfonic acid group, a urea group or an alkanoylamino group of C 1 -C 4 , preferably a methyl group, a sulfonic acid group, a urea group or an acetamido group;
- each R 28 is independently selected from hydroxyl or sulfonic acid group
- each R 31 is independently selected from amino group, sulfonic acid group, urea group, C 1 -C 4 alkanoylamino group, C 1 -C 4 alkoxy group or hydroxyl group, preferably amino group, sulfonic acid group or acetamido;
- each R 32 is independently a C 1 -C 4 linear or branched chain alkyl group, a C 1 -C 4 alkoxy group or a sulfonic acid group, preferably a methyl group, a methoxy group or a sulfonic acid group base.
- component D is selected from at least one dye represented by formula (VI).
- the reactive navy blue to black dye composition is composed of component A, component B and component D.
- the reactive navy to black dye composition of the present invention is composed of the following dye components:
- Component A selected from at least one dye compound of formula (I) or its alkali metal salt;
- Component B selected from at least one dye compound represented by formula (II) or its alkali metal salt;
- Component C selected from at least one dye compound represented by formula (VI) or an alkali metal salt thereof.
- the reactive navy to black dye composition may also include component C and component D, and component C is selected from one or more of formulae (III) to (IV) ) or an alkali metal salt thereof, in the composition, the mass of component C accounts for 1-50% of the total mass of component A and component B, preferably 1-40%; the component D Selected from one or more compounds represented by formulas (V) to (VII) or their alkali metal salts, in the composition, the mass of component D accounts for 1 to 1 of the total mass of component A and component B 50%, preferably 1 to 40%:
- the reactive navy to black dye composition is composed of component A, component B, component C and component D.
- component C is selected from at least one dye compound represented by formula (III) and/or formula (IV) or its alkali metal salt, wherein a and b are both 0, or one of a and b is 0, and the other a is 1, c is 1, and d is 0 or 1.
- component D is selected from at least one dye compound represented by formula (VI) or an alkali metal salt thereof.
- the reactive navy to black dye composition of the present invention comprises the following dye components:
- Component A selected from at least one dye compound of formula (I) or its alkali metal salt;
- Component B selected from at least one dye compound represented by formula (II) or its alkali metal salt;
- Component C selected from at least one dye compound represented by formula (III) and/or formula (IV) or its alkali metal salt, wherein a and b are both 0, or one of a and b is 0, and the other is 1, c is 1, and d is 0 or 1;
- Component D selected from at least one dye compound represented by formula (VI) or an alkali metal salt thereof.
- the reactive navy to black dye composition is composed of component A, component B, component C and component D, wherein:
- Component A selected from at least one dye compound of formula (I) or its alkali metal salt;
- Component B selected from at least one dye compound represented by formula (II) or its alkali metal salt;
- Component C selected from at least one dye compound represented by formula (III) and/or formula (IV) or its alkali metal salt, wherein a and b are both 0, or one of a and b is 0, and the other is 1, c is 1, and d is 0 or 1;
- Component D selected from at least one dye compound represented by formula (VI) or an alkali metal salt thereof.
- the reactive navy to black dye composition of the present invention in addition to the component A, the component B, the component C and the component D, may also contain conventional hueing dye components on the market, such as C.I. Reactive Yellow 145 , C.I. Reactive Red 194, C.I. Reactive Red 195 and C.I. Reactive Red 198, etc., the addition amount of conventional hueing dye components does not exceed 30% of the total weight of component A, component B, component C and component D.
- conventional hueing dye components on the market such as C.I. Reactive Yellow 145 , C.I. Reactive Red 194, C.I. Reactive Red 195 and C.I. Reactive Red 198, etc.
- the component A is preferably selected from at least one of the dye compounds represented by the following formulas (I-1) to (I-66) and their alkali metal salts:
- component A is preferably at least one of the compounds represented by formula (I-1) to formula (I-28), formula (I-48) to formula (I-55) and their alkali metal salts.
- component A is preferably the compounds shown in (I-1), (I-2), (I-4), (I-5), (I-6), (I-7) and their alkali metal salts at least one of them.
- the component B is preferably selected from at least one of the following compounds and their alkali metal salts:
- component B is preferably at least one of formula (II-1), formula (II-3) and their alkali metal salts.
- the component C is preferably selected from at least one of the following compounds and their alkali metal salts:
- component C is preferably at least one selected from the group consisting of formulae (III-1) to (III-33), (IV-1) to (IV-10) and their alkali metal salts. Furthermore, component C is preferably at least one selected from the group consisting of formulae (III-1), (III-2), (III-4), (IV-1), (IV-3) and their alkali metal salts.
- the component D is selected from at least one of the following compounds and their alkali metal salts:
- component D is preferably selected from formulae (VI-1), (VI-3), (VI-4), (VI-26), (VI-27), (VI-31), (VI-38), ( At least one of VI-41), (VI-42), (VI-45), (VI-54) and their alkali metal salts.
- component D is preferably selected from at least one of formulae (VI-26), (VI-27), (VI-41), (VI-42) and their alkali metal salts.
- the particularly preferred dye composition of the present invention includes component A and component B:
- Component A at least one selected from the dye compounds represented by formula (I-1) to formula (I-28), formula (I-48) to formula (I-55) and their alkali metal salts, more particularly Preferably, at least one of the dye compounds represented by (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and their alkali metal salts ;
- Component B at least one selected from the dye compounds represented by formulas (II-1) and (II-3) and their alkali metal salts;
- the mass percentage of the component A is 5-50%, and the mass percentage of the component B is 50-95%.
- the dye composition comprises component A, component B and component C:
- Component A at least one selected from the dye compounds represented by formula (I-1) to formula (I-28), formula (I-48) to formula (I-55) and their alkali metal salts, more particularly Preferably, at least one of the dye compounds represented by (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and their alkali metal salts ;
- Component B at least one selected from the dye compounds represented by formulas (II-1) and (II-3) and their alkali metal salts;
- Component C at least one selected from the dye compounds represented by formulae (III-1), (III-2), (III-4), (IV-1), (IV-3) and their alkali metal salts ;
- the mass percentage of the component A is 5-50%
- the mass percentage of the component B is 50-95%
- the mass of the component C is the component A and the 1-50% of the total mass of component B.
- the dye composition comprises component A, component B and component D:
- Component A at least one selected from the dye compounds represented by formula (I-1) to formula (I-28), formula (I-48) to formula (I-55) and their alkali metal salts, more particularly Preferably, at least one of the dye compounds represented by (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and their alkali metal salts ;
- Component B at least one selected from the dye compounds represented by formulas (II-1) and (II-3) and their alkali metal salts;
- Component D at least one selected from the dye compounds represented by formulae (VI-26), (VI-27), (VI-41), (VI-42) and their alkali metal salts;
- the mass percentage of component A is 5-50%
- the mass percentage of component B is 50-95%
- the mass of component D is 1-50% of the total mass of component B.
- the dye composition comprises component A, component B, component C and component D:
- Component A at least one selected from the dye compounds represented by formula (I-1) to formula (I-28), formula (I-48) to formula (I-55) and their alkali metal salts, more particularly Preferably, at least one of the dye compounds represented by (I-1), (I-2), (I-4), (I-5), (I-6) and (I-7) and their alkali metal salts ;
- Component B at least one selected from the dye compounds represented by formulas (II-1) and (II-3) and their alkali metal salts;
- Component C at least one selected from the dye compounds represented by formulae (III-1), (III-2), (III-4), (IV-1), (IV-3) and their alkali metal salts ;
- Component D at least one selected from the dye compounds represented by formulae (VI-26), (VI-27), (VI-41), (VI-42) and their alkali metal salts;
- the mass percentage of the component A is 5-50%
- the mass percentage of the component B is 50-95%
- the mass of the component C is the component A and the 1-50% of the total mass of component B
- the mass of component D is 1-50% of the total mass of component A and component B.
- the used dye compounds (II) to (VII) are all known dyes, which can be synthesized by conventional methods, for example, by using suitable compounds well known to those skilled in the art. Divide and use necessary ratio to synthesize by means of usual diazotization reaction and coupling reaction, or prepare with reference to the method in patents CN101250334A, CN105176139A, CN 105524485A, CN1266869A, CN109971208A or similar methods.
- the reactive dye compound represented by the formula (I) can also be prepared according to the conventional diazo and coupling methods of reactive dyes, for example:
- each compound of formula (Ia), formula (Ib) or formula (Ic) to hydrochloric acid and sodium nitrite is 1:(1-3):(1-1.1), preferably 1:(1-1.8 ):(1-1.05);
- 3,5-diaminobenzoic acid is dissolved in water, the pH is controlled to be 8.0-12.0, and the temperature is 15-25°C.
- the dissolved 3,5-diaminobenzoic acid solution is added to the diazo liquid of formula (Ia) obtained in the above step (1), and the pH is controlled to be 2.0-6.0 with liquid caustic soda or baking soda, and the temperature is 0-20 °C, carry out the first coupling reaction, test the diazonium with H acid test solution, the infiltration circle is colorless, that is, the diazonium has reacted completely to the end point, and the coupling product 1 is obtained;
- the diazo liquid of formula (Ib) or the diazo liquid of formula (Ic) obtained in step (1) is added to the coupling product 1, and the pH is controlled at 5.0-8.0 with liquid caustic soda or baking soda, and the temperature is controlled at 0- At 20°C, carry out the second coupling reaction, test the diazonium with H acid test solution, the infiltration circle is colorless, that is, the diazonium has reacted completely to the end point, and the coupling product 2 is obtained;
- the diazo liquid of formula (Ib) or the diazo liquid of formula (Ic) obtained in step (1) is added to the coupling product 2, and the pH is controlled at 5.0-8.0 with liquid caustic soda or baking soda, and the temperature is controlled at 0 -20°C, carry out the third coupling reaction, use H acid test solution to test the diazo, the infiltration circle is colorless, that is, the diazo has reacted completely to the end point, and the reactive dye compound of the formula (I) of the present invention can be obtained. ;
- the molar ratio of each coupling formula (Ia), formula (Ib) or formula (Ic) and 3,5-diaminobenzoic acid is (0.95-1.2):1, preferably (0.98-1.08):1.
- D 1 and D 2 are groups represented by formula (a) or (b) at the same time, the second coupling reaction and the third coupling reaction can be combined into one coupling reaction, that is, the second coupling reaction and the third coupling reaction can be combined.
- the third coupling reaction is changed to: then add the diazo liquid of formula (Ib) or the diazo liquid of formula (Ic) obtained in step (1) to the coupling product 1, and use liquid caustic soda or baking soda to control pH at 5.0- 8.0, the temperature is controlled to be 0-20 ° C, and the second coupling reaction is carried out, and the diazonium is tested with the H acid test solution, and the infiltration circle is colorless, that is, the diazonium has reacted completely to the end point, and the formula of the present invention can be obtained (
- the reactive dye compound of I), wherein the molar ratio of formula (Ib) or formula (Ic) to 3,5-diaminobenzoic acid is (1.9-2.4):1, preferably (1.96-2.16):1.
- the dye compound monomers coupled in the ortho-position of the phenolic hydroxyl group often exist in the stable state of quinone hydrazone, that is, the general formula (II),
- the dye of IV) essentially contains the quinone hydrazone structure represented by the following formulas (IIa) and (IVa)
- the dye of the general formula (VI) essentially contains the following formula (VIa) and/or formula (VIb) and/or (VIc) And/or the quinone hydrazone structure shown in (VId)
- the writing form of the azo body is still adopted in the Summary of the Invention and Examples, which does not affect the essence of the present invention:
- the component A can be the compound represented by the formula (I) or its alkali metal salt
- the component B can be the compound represented by the formula (II) or its Alkali metal salt
- component C can be the compound represented by formula (III) ⁇ (IV) or its alkali metal salt
- component D can be the compound represented by formula (V) ⁇ (VII) or its alkali metal salt, when it is In the case of an alkali metal salt, the carboxyl group and the sulfonic acid group in the formulae (I) to (VII) exist in the form of an alkali metal salt of carboxylic acid and an alkali metal salt of sulfonic acid.
- the alkali metal salt is a sodium salt or a potassium salt.
- dye compounds in the form of free acids and dye compounds in the form of alkali metal salts have substantially the same dyeing properties, and usually the structural formula of each monochromatic dye compound adopts free acid In the actual synthesis process, it is usually prepared and isolated in the form of its alkali metal salt (such as sodium or potassium salt), and also used for dyeing in the form of its salt, which is also known by those skilled in the art. well known.
- the preparation method of the reactive navy blue to black dye composition of the present invention includes mixing the dye components according to the aforementioned proportions, and the mixing can be carried out by conventional mechanical methods, such as in a grinder, a kneader or a homogenizer.
- a single dye compound can exist in the form of powder, granule, aqueous solution or synthetic solution.
- the composite reactive navy blue to black dye of the present invention is separated from the synthetic solution.
- compositions typically contain electrolyte salts (eg, sodium chloride, sodium sulfate, etc.) conventional in reactive dyes.
- the present invention also provides a reactive navy to black dye product, which contains the reactive navy to black dye composition.
- the reactive navy to black dye product contains the reactive navy to black dye composition and auxiliary.
- the weight of the adjuvant does not exceed 45% by weight of the reactive navy to black dye composition, preferably not more than 40%.
- auxiliary agent is preferably one or any combination of the following: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersing agent MF), diffusing agent CNF (benzylnaphthalenesulfonate) Formaldehyde condensate), Yuanming powder (industrial sodium sulfate), lignosulfonate, sodium acetate, sodium bicarbonate, sodium citrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, thickener, etc.
- the auxiliary agents are all commercially available conventional varieties.
- the reactive navy to black dye product of the present invention is suitable for the printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials
- the nitrogen-containing and/or hydroxyl-containing fiber materials can be cellulose fibers, polyamide fibers and fabrics thereof, Among them, cellulose fibers are preferably cotton fibers or regenerated fibers, and of course other vegetable fibers, such as hemp fibers or fabrics; polyamide fibers preferably include animal fiber materials including skin, wool or silk, as well as synthetic fibers. Nylon 6, nylon 66 and other fiber materials.
- the reactive navy to black dye product of the present invention When using the reactive navy to black dye product of the present invention to print and dye the above-mentioned fiber material, it can be carried out according to the known reactive dye dyeing method, such as the commonly used reactive dyeing dyeing method and pad dyeing method.
- the method of immersing the fabric in the dye solution to gradually dye the fabric with the dye usually requires the processes of dyeing - fixing - washing - soaping - washing - dehydrating - drying.
- the said pad dyeing is a dyeing method in which the fabric is first immersed in the dye liquor, and then the fabric is passed through the rollers, the dye liquor is evenly rolled into the fabric, and then the dyeing method is processed by steaming or hot melting. Liquid-drying-(paddle fixing solution)-steaming or baking-washing-soap washing-washing-drying and other processes.
- the amount of dye used will also be different.
- the dyeing depth (owf) is generally 0.1% to 10% (dye accounts for the weight of the fabric), and the bath ratio is 1: 2 ⁇ 1:60 (weight ratio of fabric to dye liquor, preferably 1:10 ⁇ 1:30)
- initial dyeing temperature is controlled at 30 ⁇ 60°C
- dyeing time is 10 ⁇ 30 minutes
- soap cooking temperature is 85 ⁇ 95°C
- fixing temperature 60-100°C fixing time 10-50 minutes
- fixing pH 9-11 the padding rate of cellulose fibers is generally 60-80%
- the steaming temperature is 100-103°C
- the steaming time is 1-3 minutes.
- the cold pad stack dyeing method is more commonly used at present.
- the dyes and alkaline substances are introduced into the pad dyeing machine, and they are rolled and stacked at room temperature for 2 to 30 hours to fix the color, and then thoroughly rinsed. .
- the beneficial effects of the present invention are mainly reflected in: the reactive navy to black dye compositions and products of the present invention, when used in the printing and dyeing of nitrogen-containing and/or hydroxyl-containing fiber materials, have the advantages of good promotion, good compatibility, high color fixing rate, high color The fastness is excellent, especially the washing fastness is outstanding.
- FIG. 1 is a mass spectrum of compound (I-1) prepared in Example 1.
- FIG. 1 is a mass spectrum of compound (I-1) prepared in Example 1.
- FIG. 2 is a mass spectrum of the chromophore (A) prepared in Example 1.
- FIG. 2 is a mass spectrum of the chromophore (A) prepared in Example 1.
- the dye compounds used in the examples of the present invention are prepared and isolated in the form of their sodium salts in the actual synthesis process, and are also used for dyeing in the form of sodium salts, but for the convenience of writing, all the dye compounds in the examples are
- the chemical formula is embodied in the form of free acid, and its substantial dyeing properties are equivalent to the form of sodium salt.
- para-ester p- ⁇ -hydroxyethylsulfone sulfate aniline
- hydrochloric acid containing HCl 0.3mol
- sodium nitrite solution containing 0.208mol of sodium nitrite
- control pH 0.5-2.0
- formaldehyde detects the end point (that is, no discoloration within 5s). After the diazo end point is reached, the excess sodium nitrite is eliminated with sulfamic acid, and the obtained para-ester diazo liquid is stored for later use.
- Amino-2-aminobenzenesulfonic acid diazo liquid is added to the beaten 3,5-diaminobenzoic acid solution, the pH is controlled at 5-5.5 with 30% liquid alkali, the temperature is controlled at 5-10 °C, and the reaction is 0.5- In 2.5h, the free 3,5-diaminobenzoic acid was controlled by HPLC to reach the end point below 3%, and the chromophore represented by the following formula (A) was obtained, and the mass spectrum was shown in FIG. 2 .
- the mass spectrum of compound (I-1) is shown in Fig. 1 .
- the dye of formula (I-1), 75 parts of dye of formula (II-1) and 10 parts of Yuanming powder are mechanically mixed, and the obtained composite dye is dyed black by conventional dip dyeing method, and it is particularly resistant to washing and staining.
- It is nylon and wool with color fastness above grade 4 (refer to ISO 105 C10-2006), excellent lifting force and color fixation rate (refer to GB/T21875-2016 and GB/T2391-2014).
- the dyed cotton is dark black, and it is resistant to washing and staining, especially nylon and wool with a color fastness of 4 or higher (refer to ISO 105 C10-2006), excellent lifting force and color fixation rate (refer to GB/T21875-2016 and GB/T2391). -2014).
- the obtained composite dye-dyed cotton is dark black, and it is resistant to washing and staining, especially nylon and wool.
- the staining fastness is above grade 4 (refer to ISO 105 C10-2006). 2016 and GB/T2391-2014).
- the dyed cotton is navy blue to black, and it is resistant to washing and staining, especially nylon and wool staining.
- the fastness is above grade 4 (refer to ISO 105 C10-2006), the lifting force is excellent (refer to the standard GB/T 21875-2016), and the lifting force and color fixing rate are excellent (refer to GB/T 21875-2016 and GB/T2391-2014). ).
- Comparative Example 1 According to Example 1 in Patent CN100582168A, the following two-component reactive black dyes were prepared:
- the reactive dyes prepared in the representative examples 67-72 of the present invention and comparative examples 1 and 2 were tested for their lifting power according to the method specified in the standard GB/T 21875-2016, and it was found that examples 67-72 The reactive dyes of 1 to 2 have significantly better lifting power than those of Comparative Examples 1 to 2. Under the same dyeing conditions, the consumption of dyes can be saved by 5 to 15%, and the economy is remarkable.
- Example Example 67 Example 68 Example 69 Example 70 Example 71 Example 72 Comparative Example 1 Comparative Example 2 Fixation rate 81.1% 80.9% 81.5% 82.0% 81.8% 80.5% 72.3% 70.5%
- the dyes of the present invention are obviously better than the comparative examples, and for the industry, they have significant improvements in color fastness, lifting force and color fixation rate.
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Abstract
Description
实施例 | 实施例67 | 实施例68 | 实施例69 | 实施例70 | 实施例71 | 实施例72 | 对比例1 | 对比例2 |
固色率 | 81.1% | 80.9% | 81.5% | 82.0% | 81.8% | 80.5% | 72.3% | 70.5% |
Claims (14)
- 一种活性藏青至黑色染料组合物,包括组分A和组分B,其中组分A选自一种或多种如式(Ⅰ)所示的染料化合物或其碱金属盐,组分B选自一种或多种如式(Ⅱ)所示的染料化合物或其碱金属盐;基于所述的组分A和组分B,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%,式(Ⅰ)中:D 1、D 2各自独立为下式(a)或(b)所示的基团:上式(Ⅰ)、式(a)和(b)中:R 1、R 2各自独立为氢、氧、-COR 7、C 1~C 4烷基或被羟基、磺酸基或羧基取代的C 1~C 4烷基,其中R 7为C 1~C 4烷基、C 2~C 4烯基或-NH 2;R 3为氢、C 1~C 4烷基、C 1~C 4烷氧基、羧基或磺酸基;R 4~R 6各自独立为氢、C 1~C 4烷基、C 1~C 4烷氧基或磺酸基;X 1、X 2各自独立为-SO 2Y 1、-NHCO(CH 2) pSO 2Y 2或-CONH(CH 2) qSO 2Y 3,其中Y 1~Y 3各自独立为-CH=CH 2、-CH 2CH 2OSO 3H或-CH 2CH 2Cl,p=1-3,q=1-3;式(Ⅱ)中:R 8~R 11各自独立为氢、C 1~C 4烷基、C 1~C 4烷氧基或磺酸基;Y 4、Y 5各自独立为-CH=CH 2、-CH 2CH 2OSO 3H或-CH 2CH 2Cl。
- 如权利要求1所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物,由组分A和组分B组成。
- 如权利要求1所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物还包括组分C和组分D;所述组分C选自一种或多种如式(Ⅲ)~(IV)所示的化合物或其碱金属盐,组分C的质量占组分A和组分B总质量的1~50%,优选为1~40%;所述组分D选自一种或多种如式(V)~(VII)所示的化合物或其碱金属盐,组分D的质量占组分A和组分B总质量的1~50%,优选为1~40%;式(Ⅲ)中:R 12~R 15各自独立为H、C 1~C 4烷基、C 1~C 4烷氧基、羧基或磺酸基,优选为H、甲基、甲氧基、羧基或磺酸基;Y 6、Y 7各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;a为0或1;b为0或1;c、d彼此独立为0或1,优选为1;每个D 3、D 4彼此独立为取代的苯基、未取代的苯基、取代的萘基或未取代的萘基,所述的取代的苯基和取代的萘基的取代基个数分别为1-3个,每个取代基各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基,优选取代基个数分别为1-2个,每个取代基各自独立选自氨基、磺酸基、脲基、乙酰氨基、甲氧基或羟基;式(Ⅳ)中:R 16~R 19各自独立为H、C 1~C 4烷基、C 1~C 4烷氧基或磺酸基,优选为H、甲基、甲氧基或磺酸基;e=0-1;Y 8、Y 9各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;式(Ⅴ)中:f、g、h各自独立为0-3,每个R 20、R 21、R 22各自独立为C 1~C 4烷基、C 1~C 4烷氧基或磺酸基,优选为甲基、甲氧基或磺酸基;X 3为氢或羧基;Y 10、Y 11各自独立为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;式(Ⅵ)中:D 5、D 6各自独立为下式(c)或(d)或(f)所示的基团:上式(c)、(d)、(f)中:R 23、R 24、R 26、R 27、R 29、R 30各自独立为H、C 1~C 4烷基、C 1~C 4烷氧基或磺酸基,优选为H、甲基、甲氧基或磺酸基;i=0-3,每个R 25各自独立选自C 1~C 4烷基、磺酸基、脲基或C 1~C 4的烷酰氨基,优选为甲基、磺酸基、脲基或乙酰氨基;j=0-3,每个R 28各自独立选自羟基或磺酸基;X 4、X 5、X 6各自独立为-SO 2Y 13、-NHCO(CH 2) rSO 2Y 14或-CONH(CH 2) sSO 2Y 15,其中r、s为整数,r=1-3,s=1-3,Y 13~Y 15各自独立为-CH=CH 2、-C 2H 4OSO 3H或-CH 2CH 2Cl,其中,X 4、X 5、X 6各自独立优选为-SO 2Y 13;式(Ⅶ)中:m=1-3,每个R 31各自独立选自氨基、磺酸基、脲基、C 1~C 4的烷酰氨基、C 1~C 4烷氧基或羟基,优选氨基、磺酸基或乙酰氨基;Y 12为-CH=CH 2、-C 2H 4OSO 3H或-C 2H 4Cl;n=0-2,每个R 32各自独立为C 1~C 4直链或支链烷基、C 1~C 4烷氧基或磺酸基,优选为甲基、甲氧基或磺酸基。
- 如权利要求3所述的活性藏青至黑色染料组合物,其特征在于:所述的活性藏青至黑色染料组合物由组分A、组分B、组分C和组分D组成。
- 如权利要求1-4之一所述的活性藏青至黑色染料组合物,其特征在于:D 1、D 2同时为式(a)或(b)所示的基团;优选D 1、D 2同时为式(a)所示的基团。
- 如权利要求3或4所述的活性藏青至黑色染料组合物,其特征在于:组分C选自至少一种式(Ⅲ)和/或式(Ⅳ)所示的染料化合物或其碱金属盐,其中a、b同为0,或a、b之一为0,另一为1,c为1,d为0或1。
- 如权利要求1-4之一所述的活性藏青至黑色染料组合物,其特征在于:所述的染料组合物中,组分A:选自式(Ⅰ-1)~式(Ⅰ-28)、式(Ⅰ-48)~式(Ⅰ-55)所示染料化合物及其碱金属盐中的至少一种,更特别优选(Ⅰ-1)、(Ⅰ-2)、(Ⅰ-4)、(Ⅰ-5)、(Ⅰ-6)、(Ⅰ-7)所示染料化合物及其碱金属盐中的至少一种;组分B:选自式(Ⅱ-1)、(Ⅱ-3)所示染料化合物及其碱金属盐中的至少一种;组分C:选自式(Ⅲ-1)、(Ⅲ-2)、(Ⅲ-4)、(Ⅳ-1)、(Ⅳ-3)所示染料化合物及其碱金属盐中的至少一种;组分D:选自式(Ⅵ-26)、(Ⅵ-27)、(Ⅵ-41)、(Ⅵ-42)所示染料化合物及其碱金属盐中的至少一种;基于所述组分A~B质量之和,组分A的质量百分含量为5~50%,组分B的质量百分含量为50~95%,组分C的质量为组分A和组分B总质量的1~50%,组分D的质量为组分A和组分B总质量的1~50%。
- 如权利要求1-11之一所述的活性藏青至黑色染料组合物,其特征在于:所述的碱金属盐为钠盐或钾盐,优选为钠盐。
- 一种活性藏青至黑色染料制品,其含有权利要求1-4之一所述的活性藏青至黑色染料组合物。
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