CN111205672B - 液体染料、液体染料的制备方法和用途、以及热塑性树脂 - Google Patents
液体染料、液体染料的制备方法和用途、以及热塑性树脂 Download PDFInfo
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- CN111205672B CN111205672B CN202010115928.XA CN202010115928A CN111205672B CN 111205672 B CN111205672 B CN 111205672B CN 202010115928 A CN202010115928 A CN 202010115928A CN 111205672 B CN111205672 B CN 111205672B
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- 239000007788 liquid Substances 0.000 title claims abstract description 62
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 13
- -1 tertiary amine compound Chemical class 0.000 claims abstract description 43
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 29
- 229940126062 Compound A Drugs 0.000 claims abstract description 25
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- 238000004043 dyeing Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000013076 target substance Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 20
- 239000002994 raw material Substances 0.000 abstract description 11
- 125000001424 substituent group Chemical group 0.000 abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract description 5
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 5
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000012815 thermoplastic material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000000975 dye Substances 0.000 description 54
- 239000000047 product Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 150000003512 tertiary amines Chemical group 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 229920005830 Polyurethane Foam Polymers 0.000 description 10
- 239000000049 pigment Substances 0.000 description 9
- 239000011496 polyurethane foam Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
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- 238000000605 extraction Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HMEKVHWROSNWPD-UHFFFAOYSA-N Erioglaucine A Chemical compound [NH4+].[NH4+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 HMEKVHWROSNWPD-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- WXLFIFHRGFOVCD-UHFFFAOYSA-L azophloxine Chemical compound [Na+].[Na+].OC1=C2C(NC(=O)C)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 WXLFIFHRGFOVCD-UHFFFAOYSA-L 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RRETZLLHOMHNNB-UHFFFAOYSA-M sodium;1-amino-9,10-dioxo-4-(2,4,6-trimethylanilino)anthracene-2-sulfonate Chemical compound [Na+].CC1=CC(C)=CC(C)=C1NC1=CC(S([O-])(=O)=O)=C(N)C2=C1C(=O)C1=CC=CC=C1C2=O RRETZLLHOMHNNB-UHFFFAOYSA-M 0.000 description 1
- UDTJJVCMRRCRDB-UHFFFAOYSA-M sodium;4-(3-methyl-5-oxo-4-phenyldiazenyl-4h-pyrazol-1-yl)benzenesulfonate Chemical compound [Na+].CC1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=CC=C1 UDTJJVCMRRCRDB-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- 230000007704 transition Effects 0.000 description 1
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
- C09B43/00—Preparation of azo dyes from other azo compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/48—Anthrimides
-
- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/514—N-aryl derivatives
-
- 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
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- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Abstract
本申请公开了一种液体染料、液体染料的制备方法和用途、以及热塑性树脂,所述液体染料由含有磺酸基及发色团部分的化合物A与含有以羟基结尾的聚醚结构的叔胺化合物B通过酸碱中和得到。液体染料的结构通式中,D代表发色团部分;R1、R2和R3各自独立选自芳基、烷基、烷氧基、聚醚结构取代基中的一种,且R1、R2和R3中至少有一个取代基为聚醚结构取代基;所述聚醚结构为以聚氧乙烯醚、聚氧丙烯醚、聚氧丁烯醚中的一种或多种为反应原料得到的共聚物,且以羟基为末端;m为正整数且m≤4;n为正整数且n≤4;且n≤m。本申请提供的液体染料,该液体染料在常温下为液体,着色力较强,与热塑性材料具有良好的相容性。
Description
技术领域
本申请涉及液体染料技术领域,特别是涉及液体染料、液体染料的制备方法和用途、以及热塑性树脂。
背景技术
在聚氨酯树脂或泡沫等材料的使用过程中,经常需要赋予材料各种颜色,以提高材料的某些性能和美感。目前最常用的着色材料为各种颜料制品,即所谓色膏或色浆。由于色膏或色浆为非溶性化合物,其在着色过程中需要将颜料碾磨,并依靠分散剂分散于着色体系中,这导致颜料制品在制造及使用过程中带来诸多不便,如稳定性差,在长时间存储过程中容易分层;使用不方便,着色剂多为粉状货粘稠膏状,不便于计量;着色力低,无法赋予材料较深的颜色;迁移性差,制成品的色牢度较差;同时由于颜料与着色体系不相容,经常会影响合成材料自身的性能。
随着颜料技术的发展,颜料产品已能满足多种方面的需求,但在某些场合的某些性能仍存在较大的提升空间。
发明内容
为了解决现有技术存在的问题,本申请提供了一种液体染料,该液体染料在常温下为液体,着色力较强,与热塑性材料具有良好的相容性。
本申请提供一种液体染料,具有如下结构通式:
其中,D代表发色团部分;
R1、R2和R3各自独立选自芳基、烷基、烷氧基、聚醚结构取代基中的一种,且R1、R2和R3中至少有一个取代基为聚醚结构取代基;
所述聚醚结构为以聚氧乙烯醚、聚氧丙烯醚、聚氧丁烯醚中的一种或多种为反应原料得到的共聚物,且以羟基为末端;
m为正整数且m≤4;n为正整数且n≤4;且n≤m。
可选的,所述发色团部分选自偶氮、蒽醌、氧杂蒽、三芳甲烷中的一种。
可选的,所述m≤3。
本申请还提供一种液体染料的制备方法,由含有磺酸基及发色团部分的化合物A与含有以羟基结尾的聚醚结构的叔胺化合物B通过酸碱中和得到。
可选的,包括如下步骤:化合物A与叔胺化合物B在pH值为2~6的水相体系中于60~95℃下反应,得到目标物粗品;然后将目标物粗品进行纯化,得到所述液体染料。
可选的,所述化合物A与所述叔胺化合物B的摩尔比为1:1~4。
可选的,所述化合物A与所述叔胺化合物B的摩尔比为1:1~3。
可选的,所述反应的温度为70~80℃,反应的时间为30~60min。
可选的,所述纯化的具体步骤为:在温度为25~30℃下,用有机溶剂进行液-液萃取,然后洗涤至中性并蒸除有机溶剂。
本申请还提供一种液体染料的用途,液体染料用于热塑性树脂的染色。
本申请还提供一种热塑性树脂,包含染色组分,所述染色组分采用本申请所述的液体染料。本申请的液体染料至少具有以下技术效果之一:本申请的液体染料在常温下为液体,具有良好的流动性;着色力强,耐迁移性好;与热塑性树脂相容性较好,特别是聚氨酯材料,能与聚氨酯材料完全相容,且是在聚氨酯材料制备过程中加入,能与聚氨酯发生化学反应形成有机化合物,可以解决传统颜料产品在着色过程中存在的各种问题。
具体实施方式
下面结合具体实施例对本申请作进一步阐述。
本申请提供一种液体染料,具有如下结构通式:
其中,D代表发色团部分;
R1、R2和R3各自独立选自芳基、烷基、烷氧基、聚醚结构取代基中的一种,且R1、R2和R3中至少有一个取代基为聚醚结构取代基;
聚醚结构为以聚氧乙烯醚、聚氧丙烯醚、聚氧丁烯醚中的一种或多种为反应原料得到的共聚物,且以羟基为末端;
m为正整数且m≤4;n为正整数且n≤4;且n≤m。本实施例中的D代表发色团部分,能够对光发生不同的选择吸收,呈现各种颜色。D并不表示液体染料分子中仅含有一个发色团,可以表示含有两个或两个以上的发色团,D表示发色团部分。
上述中的芳基是指任何从简单芳香环衍生出的官能团或取代基。例如苯基、邻甲苯基、1-萘基、2-萘基等。
上述中的烷基是指具有直链或支链的烷基。例如:甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、仲丁基、戊基、新戊基、己基、庚基、辛基、十二烷基等。优选具有1~4个碳原子的支链或者支链的烷基。
上述中的烷氧基是指具有支链或支链的烷氧基。例如:甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、异丁氧基、丁氧基、异丁氧基、叔丁氧基、仲丁氧基、戊氧基、新戊氧基、已氧基等。优选具有1~4个碳原子的直链或支链的烷氧基,特别优选乙氧基、丙氧基或丁氧基。
聚醚结构可以选择聚氧乙烯醚、聚氧丙烯醚或者聚氧丁烯醚;也可以选择聚氧乙烯醚、聚氧丙烯醚、聚氧丁烯醚中的两种或三种的共聚物,包括有规共聚物和无规共聚物。另一实施例中,发色团部分选自偶氮、蒽醌、氧杂蒽、三芳甲烷中的一种。
另一实施例中,m为正整数且m≤3;n为正整数且n≤3;且n≤m。
进一步的,m优选取值为1或者2;n优选取值为1。
本申请还提供一种液体染料的制备方法,由含有磺酸基及发色团部分的化合物A与含有以羟基结尾的聚醚结构的叔胺化合物B通过酸碱中和得到。具体的反应方程式如下所示:
含有发色团部分的化合物A经含有聚醚结构的叔胺化合物B改性后,聚醚结构使得原本没有水溶性的化合物A在常温下具有了水溶性,得到的液体染料可以应用到水性配方体系中。另一实施例中,液体染料的制备方法包括如下步骤:
化合物A与叔胺化合物B在pH值为2~6的水相体系中于60~95℃下反应,得到目标物粗品;然后将目标物粗品进行纯化,得到液体染料。
首先,化合物A具有发色团结构,可以对光辐射产生吸收、具有跃迁的不饱和基团及其相关的化学键。化合物A中存在含有不饱和键的基团,能够在紫外及可见光区域内产生吸收,且吸收具有波长选择性,吸收某种颜色的光,而不吸收另外波长的光,使物质显示不同的颜色。
在pH在2~6的水相体系中,化合物A中的磺酸基发生电离。若分子中含有的是D-SO3H,那么D-SO3HD-SO3 -+H+,由于H+的存在,会促进电离平衡逆向移动;若分子中含有的是D-SO3M(M表示金属元素),那么D-SO3MD-SO3 -+M+,D-SO3 -+H+ D-SO3H,由于H+的存在,会促进电离平衡正向移动,这样反应体系中存在更多的D-SO3H分子。
由于叔胺化合物B中含有叔胺基团,在反应条件为60~95℃时,叔胺基团可以与D-SO3H分子中的磺酸基发生酸碱成盐反应,生成电中性的液体染料分子。同时,由于叔胺中含有聚醚结构,根据相似相溶的原理,生成具有聚醚结构的染料分子与具有聚醚体系的树脂完全相溶,会使着色能力更强,耐迁移性更好。
若染料发色体中含有活泼基团,例如羟基,那么生成的液体染料分子中具有端羟基结构,可以与异氰酸酯发生化学反应,形成有机结合,使其在聚氨酯树脂材料中着力力强;在应用不同的颜色进行染色时,不同颜色的染料之间相容性好,能有良好的配伍性,配色方便。
本申请中的反应条件均指常温常压下,即温度为25℃,压强为101.325kP。
另一实施例中,化合物A与叔胺化合物B的摩尔比为1:1~4。
叔胺化合物B可以选择自主合成,在合成时以伯胺、仲胺或者叔胺为原料,通过接枝聚醚链合成得到。也可以选择现有的叔胺商品。
聚醚链的接入,可以选择丁氧基,乙氧基,丙氧基,根据比例按先后顺序连接,也可以按照比例同时加入,即可得到无规共聚产物。例如表1中(以下为摩尔份数):
叔胺A-5为1份十二胺与10份环氧丙烷反应产物;
叔胺A-7为1份十二胺与10份环氧丙烷反应,再与6份环氧乙烷反应的产物。
在实际生产应用中,化合物A中含有磺酸基,叔胺化合物B中含有叔胺基,磺酸基与叔胺基发生反应,可以按照化合物A中含有的磺酸基的个数与叔胺化合物B中含有的叔胺基的个数一一对应的关系来进行摩尔比的选择。列举的化合物A的结构式与叔胺化合物B的结构式如表1所示。
进一步的,化合物A与叔胺化合物B的摩尔比为1:1~3。另一实施例中,反应的温度为70~80℃,反应的时间为30~60min。
反应通常是在加热条件下进行,反应温度优选在70~80℃条件下进行,在上述限定条件下,反应至完全大约30~60min的时间。在化合物A与叔胺化合物B反应过程中,pH的调节选用醋酸、盐酸中的一种或多种。
另一实施例中,纯化的具体步骤为:在温度为25~30℃下,用有机溶剂进行液-液萃取,然后洗涤至中性并蒸除有机溶剂。
在得到目标物粗品后,可以采用现有常规的纯化方法对其进行纯化,以得到纯净的液体染料。可以采用萃取来进行纯化,具体步骤为:选用二氯甲烷或者二氯乙烷为有机溶剂,将所制得的目标物粗品在二氯甲烷中萃取,然后有机相用去离子水洗涤两次,直至为中性,最后再蒸馏出去溶剂二氯甲烷,得到目标产物。
选用二氯甲烷或者二氯乙烷作为溶剂,是因为二氯甲烷或者二氯乙烷不仅有较高的分离效率,而且沸点较低,在蒸除有机溶剂的过程中,便于除去。
本申请通过化合物A与叔胺化合物B的反应,在发色体部分D上引入聚醚结构,提供了液体染料与热塑性树脂的相容性,并且通过聚醚结构的羟基与热塑性树脂原料的化学反应,使得液体染料与树脂牢固的结合。
热塑性树脂具有受热软化、冷却硬化的性能,而且不起化学反应,无论加热和冷却重复进行多少次,均能保持这种性能。在进行染色时,可以在受热条件下进行,热塑性树脂经加压加热即软化和流动,可以与液体染料相容,应用方便。
本申请的液体染料通过含有磺酸基及发色体部分的化合物A与含有以羟基结尾的聚醚结构的叔胺化合物B进行酸碱中合形成季铵盐而制得,叔胺结构连接环氧乙烷和(或)环氧丙烷结构组成的聚醚结构,并且叔胺连接的聚醚结构以羟基为末端,该羟基即为与组成热塑性树脂的原料(如异氰酸酯基、环氧基等)发生反应的活性基团。同时,本申请提供的液状染料可以做到水性树脂和油性树脂通用,与热塑性树脂材料及其原料完全相容,且在材料制作过程中加入,与形成热塑性树脂的一种或多种原料发生化学反应形成与热塑性树脂完全相溶的有机化合物,使得热塑性树脂本身具有颜色。
本申请的液体染料在常温下为液状,具有良好的流动性,其着色力强,耐迁移性好,不存在色浆或色浆等传统着色剂的高能耗,高VOC污染,潜在的重金属污染等问题,可以完美地解决上述颜料产品在着色过程中存在的各种问题。
本申请还提供一种液体染料的用途,液体染料用于热塑性树脂的染色。
在实际应用中,液体染料必须与生成热塑性树脂的组分发生反应,液体染料接枝到树脂上。这样得到的热塑性树脂耐干摩擦、耐湿摩擦以及耐溶剂性能好,展色性好,不会出现掉色的情况;染料与热塑性树脂的相容性好,染料在树脂上分散均匀,与树脂成为一个整体,且成膜性良好。
同时,经液体染料染色的热塑性树脂,例如聚氨酯树脂,可以作为高分子染料加到其他树脂(例如醇酸树脂/环氧树脂等)体系中为其他树脂染色。
本申请还提供一种热塑性树脂,包含染色组分,染色组分采用本申请提供的液体染料。
其中,液体染料的用量为热塑性树脂总质量的0.2%~5%。
列举的化合物A和叔胺化合物B的结构式如表1所示。
表1
上述表格中,BO为丁氧基,EO为乙氧基,PO为丙氧基,BO,EO,PO的单元数为其平均值。
实施例1
将38gA-1(C.I.酸性黄11)所示的染料加入200ml水中,升温至80℃,搅拌溶解,再加入6g醋酸(质量浓度为99%),搅拌均匀后加入86gB-5所示的聚醚胺,在80℃下搅拌至染料完全溶解,搅拌时间为30min;然后降温至25℃,加入200ml二氯甲烷进行萃取,静置分层,取下层二氯甲烷溶液使用100ml水洗涤两次,然后将二氯甲烷蒸馏除去,得到实施例1的目标产物。
该目标产物在常温下为流动性液体,溶于水为艳绿光黄色,λmax=390nm。
实施例2
将50.9gA-7(C.I.酸性红1)所示的染料加入400ml水中,升温至80℃,搅拌溶解,再加入12g醋酸(质量浓度为99%),搅拌均匀后加入125gB-6所示的聚醚胺,在80℃下搅拌至染料完全溶解,搅拌时间为40min;然后降温至25℃,加入400ml二氯甲烷进行萃取,静置分层,取下层二氯甲烷溶液使用100ml水洗涤两次,然后将二氯甲烷蒸馏除去,得到实施例2的目标产物。
该目标产物在常温下为流动性液体,溶于水为鲜艳的红色,λmax=510nm。
实施例3
将41.6g A-6(C.I.酸性蓝129)所示的染料加入200ml水中,升温至80℃,搅拌溶解,再加入12g盐酸(质量浓度为31%),搅拌均匀后加入113.2gB-1所示的聚醚胺,升温至80℃,搅拌至染料完全溶解,搅拌反应为30min;然后降温至25℃,加入400ml二氯甲烷进行萃取,静置分层,取下层二氯甲烷溶液使用100ml水洗涤两次至中性,然后将二氯甲烷蒸馏除去,得到实施例3的目标产物。
该目标产物在常温下为流动性液体,溶于水为鲜艳的蓝色,λmax=610nm。
实施例4
将17.2g A-1(C.I.酸性蓝9)所示的染料加入250ml水中,升温至80℃,搅拌溶解,再加入20g醋酸(质量浓度为99%),搅拌均匀后加入321gB-7所示的聚醚胺,升温至80℃,搅拌至染料完全溶解,搅拌反应为60min;然后降温至25℃,加入600ml二氯甲烷进行萃取,静置分层,取下层二氯甲烷溶液使用100ml水洗涤两次至中性,然后将二氯甲烷蒸馏除去,得到实施例4的目标产物。
该目标产物在常温下为流动性液体,溶于水为鲜艳绿光蓝色,λmax=635nm。
实施例5~10
实施例序号 | 化合物A | 叔胺化合物B | 液体染料的颜色 |
实施例5 | A-8 | B-13 | 橙色 |
实施例6 | A-9 | B-14 | 大红色 |
实施例7 | A-10 | B-15 | 玫红色 |
实施例8 | A-3 | B-16 | 荧光红 |
实施例9 | A-11 | B-16 | 紫色 |
实施例10 | A-7 | B-16 | 艳兰 |
实施例5~10采用制备例1的制备方法,采用如上表格中的原料,得到相应的实施例的目标产物。
应用例
将上述实施例1-4所得液体染料分别应用于聚氨酯泡沫的制备,按聚氨酯泡沫的重量比2%加入聚氨酯泡沫用聚醚原料中,分别加入水和催化剂,搅拌30s,混合均匀,再加入TDI,搅拌5-8s,倒入模具进行发泡,得到聚氨酯泡沫.。
所得聚氨酯泡沫泡孔细腻均匀,色泽饱满均一,用二氯甲烷萃取不掉色,耐热迁移性和耐晒牢度优异。
同样,将上述实施例5-6所得液体染料,分别按聚氨酯泡沫的质量比为0.2%、3%加入聚氨酯泡沫用聚醚原料中,采用常见的聚氨酯泡沫发泡程序进行发泡。
所得聚氨酯泡沫颜色各异,具有优异的色牢度。
将上述实施例7~10得到的液体染料分别应用于聚氨酯树脂的制备,制备步骤如下:
在带有搅拌、温度计和冷凝器的烧瓶(500ml)中加入液体染料40g,PTMG2000多元醇40g,DMF75g,BHT抗氧化剂0.1g以及乙二醇3.5g,搅拌均匀,缓慢加入25.5gMDI,升温至75℃,然后加入0.1g有机铋催化剂,反应1h,补加3.5gMDI,继续反应至粘度到达10000Mpas,加入95gDMF并加入0.2g甲醇,然后终止反应。
将所制得的聚氨酯树脂在离型纸上刮膜,并在120℃烘箱烘干,所得皮膜进行干、湿擦测试5000次,均没有掉色情况出现。
Claims (6)
2.根据权利要求1所述的液体染料的制备方法,其特征在于,包括如下步骤:
化合物A与叔胺化合物B在pH值为2~6的水相体系中于60~95℃下反应,得到目标物粗品;然后将目标物粗品进行纯化,得到所述液体染料。
3.根据权利要求2所述的液体染料的制备方法,其特征在于,所述反应的温度为70~80℃,反应的时间为30~60min。
4.根据权利要求2所述的液体染料的制备方法,其特征在于,所述纯化的具体步骤为:在温度为25~30℃下,用有机溶剂进行液-液萃取,然后洗涤至中性并蒸除有机溶剂。
5.如权利要求1所述的液体染料的用途,其特征在于,所述液体染料用于热塑性树脂的染色。
6.热塑性树脂,包含染色组分,其特征在于,所述染色组分采用如权利要求1~3任一项所述的液体染料。
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