CN106189514B - Black blue and white coloring material aqueous dispersing agent and preparation method and application for inkjet printing - Google Patents
Black blue and white coloring material aqueous dispersing agent and preparation method and application for inkjet printing Download PDFInfo
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- CN106189514B CN106189514B CN201610634411.5A CN201610634411A CN106189514B CN 106189514 B CN106189514 B CN 106189514B CN 201610634411 A CN201610634411 A CN 201610634411A CN 106189514 B CN106189514 B CN 106189514B
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 76
- 238000007641 inkjet printing Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000004040 coloring Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 title abstract 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960004502 levodopa Drugs 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- -1 polysiloxane backbone Polymers 0.000 claims abstract description 4
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 3
- 239000001055 blue pigment Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical group NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229960003638 dopamine Drugs 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000038 blue colorant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000578 graft copolymer Polymers 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 125000003827 glycol group Chemical group 0.000 claims 1
- 239000000049 pigment Substances 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 15
- 239000000919 ceramic Substances 0.000 abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 4
- 150000002505 iron Chemical class 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- 229920000570 polyether Polymers 0.000 abstract 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 abstract 1
- 230000005611 electricity Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 230000013011 mating Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 20
- 238000000498 ball milling Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000004873 anchoring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000012258 stirred mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
- C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Present invention relates particularly to a kind of black blue and white coloring material aqueous dispersing agent for inkjet printing and its preparation method and application modes.The dispersing agent contains polysiloxane backbone flexible, DOPA amine unit and primary amino group is contained on main chain, while there are also the polyether lateral chains containing carboxyl.DOPA amine unit and primary amino group can securely and manganese systems, iron series, chromium system oxide colour particle surface generate stable mating reaction；Polysiloxane backbone then can guarantee that dispersant molecule is attached to pigment granules surface as far as possible, and the surface tension of ceramic ink is enabled to be minimized；Polyether lateral chain containing carboxyl can disperse in water, while under the conditions of alkalescence, carboxyl ionization, generate negative electricity layer on pigment particle surface, further suppress the reunion sedimentation of pigment particle.
Description
Technical Field
The invention belongs to the technical field of organic/inorganic composite functional materials, and particularly relates to a black and blue pigment aqueous dispersant for ink-jet printing, a preparation method thereof and application thereof in the field of ink-jet printing.
Background
The ceramic digital ink-jet printing technology is a novel ceramic printing technology developed in nearly five years, has the advantages of vivid and fine printing effect and lower printing cost and breakage rate, and can realize the personalized design and manufacture of ceramic products. The preparation of ceramic ink is a key link of ink-jet printing technology. The pigment and the dispersant are two important components of the ceramic ink, and the quality of the pigment and the dispersant greatly determines the quality of the ceramic ink.
The dispersant is an amphiphilic high molecular polymer which can effectively reduce the interfacial energy between the pigment particles and the solvent, and the molecular structure of the dispersant is generally composed of more than two components, namely an anchoring component and a dispersing component. The anchoring component is generally more polar than the dispersing component and is capable of complexing or attracting the metal oxide ions on the surface of the colorant particles to cause the dispersant molecules to adsorb on the surface of the colorant particles. The dispersing components are generally of relatively weak polarity and are themselves well soluble in the solvent.
The dispersant may be classified into an oil-based dispersant and a water-based dispersant according to its solubility, and ceramic inks prepared therefrom may be classified into oil-based inks and water-based inks. The water is used as the solvent of the ceramic ink, has the unique advantage of environmental protection, and meanwhile, the production equipment of the water-based ink is convenient to clean and wash in the production process. However, the surface tension of water is higher than that of oil solvent, which is not favorable for fine ink-jet printing.
On the other hand, the molecular structure of the dispersant differs for different colorant types. The main components of the black and blue pigment in the ceramic ink are manganese oxide, iron oxide and chromium oxide. Compared with pigments of other colors, the performance of the dispersant matched with the black and blue pigments on the market at present still needs to be improved, and the solid content of the ink still needs to be enhanced. The reason is mainly that: 1) the anchoring effect of the dispersant anchoring component on manganese series, iron series and chromium series oxides is not ideal; 2) the anti-agglomeration effect of the dispersing component in the dispersant still needs to be improved.
Disclosure of Invention
The invention aims to provide a novel graft copolymer as a dispersant, which is effective in improving the effect of dispersing black and blue pigment particles in an aqueous solvent and which can reduce the surface tension of black and blue ink to a certain extent.
Another object of the present invention is to provide a method for preparing the aqueous dispersant for a blackish blue colorant;
the invention further aims to provide an application method of the aqueous black and blue pigment dispersant in the field of ink-jet printing.
A black and blue pigment aqueous dispersant for ink-jet printing, the structure of which has the structural characteristics of a graft copolymer as shown in the following:
PHMS-g-(DOPA-r-EDA-r-PEGDMA)
wherein g represents grafting and r represents random distribution; PHMS represents a hydrogenpolysiloxane polymer chain; DOPA represents a dopamine unit; EDA represents ethylenediamine; PEGDMA represents dicarboxylic acid polyethylene glycol with molecular weight of 2000-20000 Da.
Further, the mass molar ratio of DOPA to EDA is 1.0: 1.0-1.0: 5.0, and the mass molar ratio of DOPA to PEGDMA is 1.0: 0.1-1.0: 2.0.
A black and blue pigment aqueous dispersant for ink-jet printing is prepared by the following method:
(1) dissolving PHMS and Glycidyl Methacrylate (GMA) in a solvent A, wherein the mass ratio of PHMS to GMA is 1: 1-1: 15, adding a platinum catalyst, wherein the relative mass fraction of the catalyst to an epoxy unit is 0.01-0.1%, then carrying out oxygen removal by bubbling with an inert gas for 10-60 minutes, heating and refluxing for 2-12 hours at 40-100 ℃, after the reaction is finished, pouring 0.5-5 times of solvent B for washing, then standing for liquid separation for 5-30 minutes, collecting lower-layer liquid, and carrying out vacuum drying at room temperature to obtain epoxy functionalized PHMS;
(2) dissolving a certain amount of epoxy-functionalized PHMS in a solvent C, wherein the mass concentration of the dissolved PHMS is 10-40%, adding 1-10 times of dicarboxyl polyethylene glycol of the mass of the epoxy-functionalized PHMS, adding 0.05-0.5 times of dopamine hydrochloride of the mass of the epoxy-functionalized PHMS, finally adding 0.1-2.0% of NaOH solution relative to the mass of the epoxy-functionalized PHMS, heating and refluxing for 0.5-6 hours at 40-80 ℃, adding 0.01-0.2 times of ethylenediamine of the mass of the epoxy-functionalized PHMS, continuously heating and refluxing for 0.5-6 hours at 40-80 ℃, concentrating all solutions to 1/10-1/2 of the original volume through rotary evaporation after the reaction is finished, and obtaining the black and blue pigment aqueous dispersant for ink-jet printing.
Wherein the molecular weight of the PHMS in the step (1) is 500-10000 Da, and the hydrogen substitution degree is 40-80%; the solvent A is one of xylene, toluene and benzene; the solvent B is one of methanol, ethanol, isopropanol and n-hexane;
the solvent C in the step (2) is one of dimethylformamide, dimethylacetamide, benzene, toluene, dichloromethane and chloroform; the molecular weight of the dicarboxy polyethylene glycol is 2000-20000 Da.
The black and blue pigment aqueous dispersant for ink-jet printing can be applied to preparing black and blue ink, and the black and blue ink is realized by the following technical means:
a. adding a dispersing agent into the black and blue pigment, wherein the dispersing agent accounts for 10-20% of the pigment in mass fraction, adding distilled water, wherein the total mass of the pigment and the dispersing agent accounts for 30-50% of the system in mass fraction, setting the rotating speed of a stirrer to be 60-240 revolutions per minute, and carrying out pre-stirring operation for 15-120 minutes.
b. And adding the pre-stirred mixture into a ball mill, setting the rotating speed to be 6000-12000 r/min, carrying out ball milling for 30-150 min, and continuously and slowly adjusting the pH value of the mixture to 7.0-9.0 by using dilute alkali liquor in the ball milling process to obtain the black and blue ink for ink-jet printing.
The principle of the invention is as follows:
a black and blue pigment water-based dispersant for ink-jet printing is synthesized by a hydrosilylation reaction and an epoxy ring-opening reaction. In the ball milling process, a dopamine anchoring group and a primary amino group contained in a main chain of the dispersing agent are used for being matched with a soft siloxane main chain to generate stable multi-point synergistic adsorption on the surfaces of the black and blue pigment particles, so that the dispersing agent is firmly fixed on the surfaces of the black and blue pigment particles. The carboxyl group contained in the dispersing agent dispersion chain is in a negative ion state under a slightly alkaline condition, and can form an electrostatic layer on the surface of the pigment particles, enhance the repulsion effect among the pigment particles and prevent the aggregation and sedimentation of the pigment. On the other hand, the introduction of the siloxane main chain can also reduce the surface tension of the ceramic ink product to a certain extent.
Compared with the prior art, the invention has the following advantages and effects:
(1) the main chain of the dispersing agent is polysiloxane, so that the dispersing agent has excellent flexibility, molecules of the dispersing agent can be fully contacted with the surfaces of pigment particles, the adsorption probability is enhanced, and the surface tension of the ceramic ink is reduced;
(2) dopamine and primary amino in the dispersing agent have excellent anchoring effect on manganese series, iron series and chromium series oxide particles, so that the adsorption of the dispersing agent has long-term stability;
(3) the main chain of the dispersant contains a plurality of dopamine and primary amine units, so that the synergistic adsorption on the surfaces of the pigment particles can be effectively realized, and the adsorption effect of the dispersant is enhanced;
(4) the dispersing agent has carboxyl functional group at the end of dispersing chain, and is ionized under slightly alkaline condition to form negative electric layer and prevent the collision and aggregation of pigment particles.
Drawings
FIG. 1 is a schematic diagram of a synthetic route for an aqueous dispersant of a cyan colorant for ink-jet printing;
FIG. 2 preparation of aqueous dispersant of cyan colorant for inkjet printing prepared in example 41H NMR spectrum.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The raw materials used in the examples were as follows:
example 1
A black and blue pigment aqueous dispersant for ink-jet printing is prepared by the following method:
(1) dissolving PHMS (molecular weight is 500Da, hydrogen substitution degree is 40%) and GMA in xylene, wherein the mass ratio of PHMS to GMA is 1:15, adding a platinum catalyst, wherein the relative mass fraction of the catalyst and an epoxy unit is 0.01%, then carrying out oxygen removal by bubbling inert gas for 10 minutes, heating and refluxing for 12 hours at 40 ℃, pouring 0.5-time volume of methanol for washing after the reaction is finished, then standing and separating for 30 minutes, collecting lower layer liquid, and carrying out vacuum drying at room temperature to obtain the epoxy functionalized PHMS.
(2) Dissolving a certain amount of epoxy-functionalized PHMS in dimethylformamide, wherein the mass concentration of the dissolved epoxy-functionalized PHMS is 10%, adding 1 time of dicarboxy polyethylene glycol of the mass of the epoxy-functionalized PHMS, adding 0.05 time of dopamine hydrochloride of the mass of the epoxy-functionalized PHMS, finally adding 0.1% of NaOH solution relative to the mass of the epoxy-functionalized PHMS, heating and refluxing for 6 hours at 40 ℃, adding 0.01 time of ethylenediamine of the mass of the epoxy-functionalized PHMS, continuously heating and refluxing for 6 hours at 40 ℃, concentrating the whole solution to 1/10 of the original volume by rotary evaporation after the reaction is finished, and obtaining the black and blue pigment aqueous dispersant for ink-jet printing.
The dispersing agent prepared by the method has the molar ratio of DOPA to EDA of 1.0:1.4 and the molar ratio of DOPA to PEGDMA of 1.0: 0.16-1.0: 2.0.
Example 2
A black and blue pigment aqueous dispersant for ink-jet printing is prepared by the following method:
(1) dissolving PHMS (molecular weight of 2000Da, hydrogen substitution degree of 60%) and GMA in toluene, wherein the mass ratio of PHMS to GMA is 1:10, adding a platinum catalyst, wherein the relative mass fraction of the catalyst and an epoxy unit is 0.03%, then carrying out oxygen removal by bubbling inert gas for 20 minutes, heating and refluxing for 6 hours at 60 ℃, after the reaction is finished, pouring 2 times of volume of ethanol for washing, then standing and separating for 20 minutes, collecting lower layer liquid, and carrying out vacuum drying at room temperature to obtain the epoxy functionalized PHMS.
(2) Dissolving a certain amount of epoxy-functionalized PHMS in dimethylacetamide, wherein the mass concentration after dissolution is 20%, adding dicarboxy polyethylene glycol with the mass 4 times that of the epoxy-functionalized PHMS, adding dopamine hydrochloride with the mass 0.1 times that of the epoxy-functionalized PHMS, finally adding NaOH solution with the mass 0.5% relative to the mass of the epoxy-functionalized PHMS, heating and refluxing for 4 hours at 60 ℃, adding ethylenediamine with the mass 0.05 times that of the epoxy-functionalized PHMS, continuously heating and refluxing for 4 hours at 60 ℃, concentrating the whole solution to 1/5 of the original volume through rotary evaporation after the reaction is finished, and obtaining the black and blue pigment aqueous dispersant for ink-jet printing.
The dispersant thus prepared had a molar ratio of DOPA to EDA of 1.0:2.9 and a molar ratio of DOPA to PEGDMA of 1.0: 0.52.
Example 3
A black and blue pigment aqueous dispersant for ink-jet printing is prepared by the following method:
(1) dissolving PHMS (molecular weight is 5000Da, and hydrogen substitution degree is 80%) and GMA in toluene, wherein the mass ratio of PHMS to GMA is 1:5, adding a platinum catalyst, wherein the relative mass fraction of the catalyst to an epoxy unit is 0.06%, then carrying out oxygen removal by bubbling inert gas for 40 minutes, heating and refluxing for 4 hours at 80 ℃, after the reaction is finished, pouring isopropanol with volume of 0.5-5 times of that of the mixture for washing, then standing and separating for 10 minutes, collecting lower layer liquid, and carrying out vacuum drying at room temperature to obtain the epoxy functionalized PHMS.
(2) Dissolving a certain amount of epoxy-functionalized PHMS in dichloromethane, wherein the mass concentration after dissolution is 30%, adding dicarboxy polyethylene glycol 8 times the mass of the epoxy-functionalized PHMS, adding dopamine hydrochloride 0.3 times the mass of the epoxy-functionalized PHMS, finally adding NaOH solution 1.0% relative to the mass of the epoxy-functionalized PHMS, heating and refluxing for 2 hours at 80 ℃, adding ethylenediamine 0.1 times the mass of the epoxy-functionalized PHMS, continuously heating and refluxing for 2 hours at 80 ℃, concentrating the whole solution to 2/5 of the original volume through rotary evaporation after the reaction is finished, and obtaining the black and blue pigment water-based dispersant for ink-jet printing.
The dispersant thus prepared had a molar ratio of DOPA to EDA of 1.0:3.6 and a molar ratio of DOPA to PEGDMA of 1.0: 1.2.
Example 4
A black and blue pigment aqueous dispersant for ink-jet printing is prepared by the following method:
(1) dissolving PHMS (molecular weight is 10000Da, hydrogen substitution degree is 80%) and GMA in benzene, wherein the mass ratio of PHMS to GMA is 1:1, adding a platinum catalyst, wherein the relative mass fraction of the catalyst and an epoxy unit is 0.1%, then carrying out oxygen removal by bubbling inert gas for 60 minutes, heating and refluxing for 2 hours at 100 ℃, after the reaction is finished, pouring n-hexane with 5 times volume for washing, then standing and separating for 5 minutes, collecting lower layer liquid, and carrying out vacuum drying at room temperature to obtain the epoxy functionalized PHMS.
(2) Dissolving a certain amount of epoxy-functionalized PHMS in chloroform, wherein the mass concentration of the dissolved epoxy-functionalized PHMS is 40%, adding 10 times of dicarboxy polyethylene glycol of the mass of the epoxy-functionalized PHMS, adding 0.5 time of dopamine hydrochloride of the mass of the epoxy-functionalized PHMS, finally adding 2.0% NaOH solution relative to the mass of the epoxy-functionalized PHMS, heating and refluxing for 0.5 hour at 80 ℃, adding 0.2 time of ethylenediamine of the mass of the epoxy-functionalized PHMS, continuously heating and refluxing for 0.5 hour at 80 ℃, concentrating the whole solution to 1/2 of the original volume by rotary evaporation after the reaction is finished, and obtaining the black and blue pigment aqueous dispersant for ink-jet printing.
The dispersant thus prepared had a molar ratio of DOPA to EDA of 1.0:4.7 and a molar ratio of DOPA to PEGDMA of 1.0: 1.8.
Example 5
An application method of a black and blue pigment aqueous dispersant for ink-jet printing is realized by the following technical means:
(1) adding a dispersing agent into the black and blue pigment, wherein the mass fraction of the dispersing agent in the pigment is 10%, adding distilled water, the mass fraction of the total mass of the pigment and the dispersing agent in the system is 30%, setting the rotating speed of a stirrer to be 60 revolutions per minute, and carrying out pre-stirring operation for 15 minutes.
(2) And adding the pre-stirred mixture into a ball mill, setting the rotating speed to be 6000 rpm, carrying out ball milling for 150 minutes, and continuously and slowly adjusting the pH value of the mixture to 7.0 by using dilute alkali liquor in the ball milling process to obtain the black and blue ink for ink-jet printing.
Example 6
An application method of a black and blue pigment aqueous dispersant for ink-jet printing is realized by the following technical means:
(1) adding a dispersing agent into the black and blue pigment, wherein the mass fraction of the dispersing agent in the pigment is 15%, adding distilled water, wherein the mass fraction of the total mass of the pigment and the dispersing agent in the system is 40%, setting the rotating speed of a stirrer to be 120 r/min, and carrying out pre-stirring operation for 60 min.
(2) And adding the pre-stirred mixture into a ball mill, setting the rotating speed to 8000 revolutions per minute, carrying out ball milling for 90 minutes, and continuously and slowly adjusting the pH value of the mixture to 7.0 by using dilute alkali liquor in the ball milling process to obtain the black and blue ink for ink-jet printing.
Example 7
An application method of a black and blue pigment aqueous dispersant for ink-jet printing is realized by the following technical means:
(1) adding a dispersing agent into the black and blue pigment, wherein the mass fraction of the dispersing agent in the pigment is 20%, adding distilled water, the mass fraction of the total mass of the pigment and the dispersing agent in the system is 40%, setting the rotating speed of a stirrer to be 180 r/min, and carrying out pre-stirring operation for 90 min.
(2) And adding the pre-stirred mixture into a ball mill, setting the rotating speed to 10000 r/min, performing ball milling for 60 min, and continuously and slowly adjusting the pH value of the mixture to 8.0 by using dilute alkali liquor in the ball milling process to obtain the black and blue ink for ink-jet printing.
Example 8
An application method of a black and blue pigment aqueous dispersant for ink-jet printing is realized by the following technical means:
(1) adding a dispersing agent into the black and blue pigment, wherein the mass fraction of the dispersing agent in the pigment is 20%, adding distilled water, wherein the mass fraction of the total mass of the pigment and the dispersing agent in the system is 50%, setting the rotating speed of a stirrer to be 240 r/min, and carrying out pre-stirring operation for 120 min.
(2) And adding the pre-stirred mixture into a ball mill, setting the rotating speed to be 12000 r/min, carrying out ball milling for 30 min, and continuously and slowly adjusting the pH value of the mixture to 9.0 by using dilute alkali liquor in the ball milling process to obtain the black and blue ink for ink-jet printing.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The black and blue pigment water dispersant for ink-jet printing is characterized in that the structure of the graft copolymer is shown as PHMS-g-(DOPA-r-EDA-r-PEGDMA); the method specifically comprises the following steps:
wherein,grepresents the grafting of the graft,rrepresenting a random distribution, PHMS representing units made from hydrogenpolysiloxane and glycidyl methacrylate, DOPA representing dopamine units, EDA representing ethylenediamine units, PEGDMA representing dicarboxylic acid polyethylene glycol units, having a weight average molecular weight of 2000 ~ 20000 Da.
2. The aqueous black and blue colorant dispersant for inkjet printing according to claim 1, wherein the molar ratio of DOPA and EDA is 1.0:1.0 ~ 1.0.0: 5.0, and the molar ratio of DOPA and PEGDMA is 1.0:0.1 ~ 1.0.0: 2.0.
3. A method for producing an aqueous black and blue colorant dispersant for inkjet printing according to any one of claims 1 ~ 2, comprising the steps of:
(1) dissolving hydrogenpolysiloxane and glycidyl methacrylate in a solvent A, wherein the mass ratio of the hydrogenpolysiloxane to the glycidyl methacrylate is 1:1 ~ 1:15, adding a platinum catalyst, wherein the relative mass fraction of the platinum catalyst and an epoxy unit is 0.01% to ~ 0.1.1%, and then removing oxygen by bubbling inert gas for 10 ~ 60 minutes at 40 ~ 100oHeating and refluxing for 2 ~ 12 hours at C, pouring 0.5-0.5 ~ 5 times volume of solvent B for washing after the reaction is finished, standing and separating for 5 ~ 30 minutes, collecting lower layer liquid, and drying in vacuum at room temperature to obtain epoxy functionalized hydrogenous polysiloxane;
(2) by taking a certain amount of epoxy-functionalHydrogenpolysiloxane dissolved in solvent C to a mass concentration of 10% ~ 40%, 1 ~ 10 times the mass of dicarboxylic acid polyethylene glycol of the epoxy-functionalized hydrogenpolysiloxane, 0.05 ~ 0.5 times the mass of dopamine hydrochloride of the epoxy-functionalized hydrogenpolysiloxane, 0.1% ~ 2.0.0% of NaOH solution relative to the mass of epoxy-functionalized hydrogenpolysiloxane, and 40 ~ 80% of NaOH solutionoHeating and refluxing for 0.5 ~ 6 hr at C, adding 0.01 ~ 0.2.2 times of ethylene diamine (mass of epoxy-functionalized hydrogenpolysiloxane) at 40 ~ 80oAnd C, continuously heating and refluxing for 0.5 ~ 6 hours, and concentrating the whole solution to 1/10 ~ 1/2 of the original volume by rotary evaporation after the reaction is finished to obtain the black and blue pigment aqueous dispersant for ink-jet printing.
4. The method of producing an aqueous dispersant for a black and blue colorant for inkjet printing according to claim 3, wherein the hydrogenpolysiloxane in the step (1) has a molecular weight of 500 ~ 10000Da and a hydrogen substitution degree of 40% ~ 80%.
5. The method of claim 3, wherein the solvent A is one of xylene, toluene and benzene.
6. The method of claim 3, wherein the solvent B is one of methanol, ethanol, isopropanol and n-hexane.
7. The method of preparing an aqueous dispersant for a black and white colorant for inkjet printing according to claim 3, wherein said solvent C in step (2) is one of dimethylformamide, dimethylacetamide, benzene, toluene, xylene, dichloromethane, and chloroform.
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| CN1646606A (en) * | 2002-04-22 | 2005-07-27 | 宝洁公司 | Silicones |
| DE102004060543A1 (en) * | 2004-12-16 | 2006-06-29 | Ge Bayer Silicones Gmbh & Co. Kg | New aminosiloxane compounds useful in detergent formulation for treating hard surfaces such as glass-, ceramic-, metal-, polymer coated-, varnished- or plastic-surfaces (e.g. dishes, windows and tiles) |
| CN102802778A (en) * | 2009-06-22 | 2012-11-28 | 联合利华有限公司 | Branched Polymer Dispersants |
| CN103666109A (en) * | 2012-08-29 | 2014-03-26 | 株式会社理光 | Yellow ink composition for inkjet recording, and inkjet recording method and inkjet recorded material |
| CN103804993A (en) * | 2013-11-27 | 2014-05-21 | 佛山市明朝科技开发有限公司 | Extra-white aqueous ceramic ink-jet ink and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1646606A (en) * | 2002-04-22 | 2005-07-27 | 宝洁公司 | Silicones |
| DE102004060543A1 (en) * | 2004-12-16 | 2006-06-29 | Ge Bayer Silicones Gmbh & Co. Kg | New aminosiloxane compounds useful in detergent formulation for treating hard surfaces such as glass-, ceramic-, metal-, polymer coated-, varnished- or plastic-surfaces (e.g. dishes, windows and tiles) |
| CN102802778A (en) * | 2009-06-22 | 2012-11-28 | 联合利华有限公司 | Branched Polymer Dispersants |
| CN103666109A (en) * | 2012-08-29 | 2014-03-26 | 株式会社理光 | Yellow ink composition for inkjet recording, and inkjet recording method and inkjet recorded material |
| CN103804993A (en) * | 2013-11-27 | 2014-05-21 | 佛山市明朝科技开发有限公司 | Extra-white aqueous ceramic ink-jet ink and preparation method thereof |
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