CN111171220B - Preparation method of water-based pigment dispersion and water-based ink - Google Patents
Preparation method of water-based pigment dispersion and water-based ink Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/005—Carbon black
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
Abstract
The invention belongs to the technical field of water-based ink, and particularly relates to a preparation method of a water-based pigment dispersion and the water-based ink. The preparation method of the aqueous pigment dispersion is suitable for inorganic pigments and organic pigments, and the obtained aqueous pigment dispersion has the characteristics of small particle size and good storage stability.
Description
Technical Field
The invention belongs to the technical field of water-based ink, and relates to a preparation method of a water-based pigment dispersion and water-based ink.
Background
The ink is widely applied to various industries, along with the gradual enhancement of environmental protection consciousness, the water-based ink is more and more emphasized and is also more and more widely applied, wherein the water-based pigment dispersion has important influence on the performance of the water-based ink. The properties of the aqueous pigment dispersion are mainly reflected in two aspects: dispersion particle size and storage stability. Various methods have been used to increase the storage stability of aqueous pigment dispersions and to reduce the particle size of the dispersions. One of them is a method of coating pigment particles with a crosslinking compound. CN102675514B adopts a method of crosslinking coated pigment particles in an oil phase of a miniemulsion and then initiating an alkali soluble monomer in a water phase to obtain an aqueous pigment dispersion with a particle size of less than 100nm and a polydispersity of less than 0.1. Although the applicant claims that the initiator in the oil phase initiates the alkali-soluble monomer in the water phase to avoid the formation of polymer in the water phase to destroy the stability of the dispersion, there is a certain probability that the alkali-soluble monomer in the water phase will still enter the water phase after combining with free radicals to initiate the polymerization of the alkali-soluble monomer in the water phase, so that in practice it has been found that the formation of homopolymer of the alkali-soluble monomer in the water phase is unavoidable, resulting in a shortened storage time of the pigment dispersion.
Disclosure of Invention
An object of the present invention is to overcome the drawbacks of the prior art and to provide a method for preparing an aqueous pigment dispersion by preparing a structure of polymer-coated pigment particles by miniemulsion polymerization and then crosslinking the polymer to obtain an aqueous pigment dispersion of crosslinked polymer-coated pigment particles.
It is another object of the present invention to provide an aqueous ink.
The technical scheme of the invention is as follows:
a process for preparing an aqueous pigment dispersion comprising the steps of,
s1, mixing an emulsifier, an auxiliary emulsifier, a pigment, a monofunctional hydrophilic monomer, a monofunctional hydrophobic monomer and an oil-soluble initiator, and uniformly stirring and dispersing at a high speed to obtain an oil phase; the monofunctional hydrophilic monomer consists of a nonionic hydrophilic monomer and (meth) acrylic acid; the emulsifier is selected from the group consisting of nonionic emulsifiers and anionic emulsifiers, more preferably from the group consisting of OP-10 and sodium dodecylbenzenesulfonate; the auxiliary emulsifier is one of n-butyl alcohol, ethylene glycol, propylene glycol, glycerol and polyglycerol ester; the oil-soluble initiator is selected from azo free radical initiators, and specifically is at least one of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile and dimethyl azobisisobutyrate.
S2, gradually adding the oil phase obtained in the step S1 into high-speed stirred water to obtain transparent to semitransparent microemulsion; heating the microemulsion to 50-80 ℃ under low-speed stirring, reacting for 4-10 hours, cooling to below 50 ℃, adding a water-soluble cross-linking agent, stirring for 0.5-5 hours, adding ammonia water or triethanolamine, adjusting the pH value to 6.5-8, and filtering to obtain the aqueous pigment dispersion. The stirring speed of the high-speed stirring is 800-1500 rpm, and the stirring speed of the low-speed stirring is 150-300 rpm.
Preferably, the pigment in step S1 is selected from at least one of inorganic pigments and organic pigments. The inorganic pigment is selected from at least one of carbon black, titanium dioxide, iron oxide red, lead chrome yellow, zinc chrome yellow, cadmium yellow, iron yellow, chromium oxide green, lead chrome green, iron blue, cobalt blue, ultramarine, iron oxide brown, bright yellow and titanium nickel yellow. The organic pigment is selected from at least one of azo pigments, phthalocyanine pigments and triarylmethane pigments, the azo pigments can be selected from at least one of macromolecule orange 4R, macromolecule red R, permanent orange RN, aurora red and benzidine yellow G, and the phthalocyanine pigments can be selected from at least one of phthalocyanine blue, phthalocyanine red, phthalocyanine violet, pigment yellow 2GLT, permanent violet RL and permanent orange HSL.
Preferably, the hydrophobic monomer in step S1 is at least one selected from the group consisting of acrylate monomers and styrene monomers. The acrylate monomer is at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, isooctyl (meth) acrylate, and lauryl (meth) acrylate. The styrene monomer is at least one selected from styrene, alpha-methyl styrene, 4-methyl styrene, 2-methyl styrene and 3-methyl styrene.
Preferably, the non-ionic hydrophilic monomer in step S1 is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and polyether monoacrylate. The structural general formula of the polyether monoacrylate is CH2＝C(CH3)COO(CH2CH2O)n(CH2CHCH3O)mR, wherein n is more than or equal to 3 and less than or equal to 10, m is more than or equal to 0 and less than or equal to 5, n-m is more than or equal to 3, and R is independently selected from hydrogen radical, methyl or isobutyl.
Preferably, the weight ratio of the emulsifier, the co-emulsifier, the pigment, the monofunctional hydrophilic monomer, the monofunctional hydrophobic monomer and the oil-soluble initiator in the step S1 is 0.5: 0.05-0.2: 5-10: 0.5-2: 5-15: 0.2-1.
Preferably, the weight ratio of the non-ionic hydrophilic monomer to the (meth) acrylic acid in the monofunctional hydrophilic monomer in step S1 is 1:5 to 5: 1. More preferably, the weight ratio is 1:3 to 3: 1.
Preferably, the weight ratio of the oil phase to the water in the step S2 is 1: 1-10. More preferably, the weight ratio of the oil phase to the water is 1: 1-4.
Preferably, the water-soluble crosslinking agent in step S2 is selected from one of a water-soluble carbodiimide-based crosslinking agent, a water-soluble aziridine-based crosslinking agent, and a water-soluble epoxy silane-based crosslinking agent.
Preferably, the weight ratio of the (meth) acrylic acid to the water-soluble crosslinking agent in the oil phase in step S2 is 1:0.005 to 0.05. More preferably, the weight ratio of the (meth) acrylic acid to the water-soluble crosslinking agent in the oil phase is 1:0.008 to 0.02.
An aqueous ink comprising the aqueous pigment dispersion obtained by the production method according to any one of the above embodiments.
According to the invention, a monofunctional hydrophilic monomer and a monofunctional hydrophobic monomer are adopted in an oil phase, a microemulsion with a small emulsion particle size is formed after the oil phase is added into water, emulsion polymerization is carried out after the temperature is raised, the monomers in the oil phase are polymerized to form a polymer coated on the surface of a pigment, a hydrophilic chain segment formed by the hydrophilic monomer in the polymer has a large polarity and can extend to a water phase, carboxyl in the polymer reacts with a water-soluble carboxyl crosslinking agent added, and the polymer is crosslinked, so that a coated crosslinking polymer is formed on the surface of the pigment, and meanwhile, electrostatic repulsion and steric hindrance effects existing in the emulsifier and the hydrophilic chain segment can effectively stabilize the pigment dispersion.
The invention has the beneficial effects that:
(1) the pigment in the oil phase is well dispersed in the oil phase, even though microemulsion is formed, the surface of the pigment particle is relatively completely coated with the oil phase, namely, the polymerizable monomer consisting of the hydrophilic monomer and the hydrophobic monomer can relatively completely coat the pigment particle, so that the polymer formed after subsequent emulsion polymerization can also relatively completely coat the pigment particle, and the polymer can also relatively completely coat the pigment particle after being crosslinked. On the other hand, if the pigment is dispersed by using the pigment dispersant containing a carboxyl group, it is difficult to completely coat the pigment particles with the pigment dispersant, and even if the pigment dispersant is crosslinked, it is difficult to completely coat the pigment particles.
(2) The coated cross-linked polymer formed on the surface of the pigment can effectively prevent the movement of pigment particles and the pigment particles from separating from the polymer and entering a water phase, and the pigment particles have better stability in dispersion.
(3) The surface of the cross-linking type polymer has both the electrostatic repulsion of anions and the steric hindrance of a non-ionic hydrophilic chain segment, so that the cross-linking type polymer can stably exist in a water phase, and simultaneously can inhibit the thermal motion of the polymer, so that the polymer is prevented from being separated from the surface of pigment particles due to the thermal motion of the polymer at high temperature or in the long-term storage process, the dispersion effect is reduced, and the pigment particles are prevented from aggregating.
(4) By controlling the ratio of hydrophilic monomer to hydrophobic monomer in the oil phase, the hydrophilic monomer is prevented from entering the water phase. If the hydrophilic monomer enters the aqueous phase, this may lead to the initiation of the polymerization of the hydrophilic monomer entering the aqueous phase during the emulsion polymerization, which may lead to the formation of polymers in the aqueous phase, which may affect the stability of the dispersion.
(5) The hydrophilic monomer and the hydrophobic monomer in the oil phase are both monofunctional, and when emulsion polymerization is carried out, the polymer coated on the surface of the pigment particle is non-crosslinking, so that the hydrophilic chain segments (carboxyl and nonionic hydrophilic chain segments) can freely extend to the water phase, part of the carboxyl extending to the water phase can react with a water-soluble carboxyl crosslinking agent added later, and the rest of the carboxyl forms anions, and together with the nonionic hydrophilic chain segments, the dispersion can be stabilized.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Water-soluble as used herein means that it dissolves in water at room temperature to form a stable solution, or it disperses in water to form a stable dispersion, at a concentration of 3% by weight.
Unless otherwise specified, the parts in the following embodiments are parts by weight.
Example 1
4 parts of emulsifier consisting of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 2 parts of n-butyl alcohol, 50 parts of pigment carbon black, 5 parts of methacrylic acid and 15 parts of compound with a structural formula of CH2＝C(CH3)COO(CH2CH2O)5.5(CH2CHCH3O)1.2CH3Mixing the polyether monoacrylate, 50 parts of methyl methacrylate, 100 parts of butyl acrylate and 10 parts of azodiisobutyronitrile, and stirring at a high speed to uniformly disperse to obtain an oil phase;
the oil phase is gradually added into 320 parts of water stirred at high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for 10 hours of reaction, cooling to below 50 ℃, adding 0.05 part of water-soluble aziridine crosslinking agent, stirring for 4 hours, adding ammonia water for adjusting the pH value to 7.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-1.
Example 2
4 parts of emulsifier consisting of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1 part of glycol, 70 parts of iron oxide red, 5 parts of acrylic acid, 5 parts of hydroxypropyl methacrylate and 5 parts of emulsifier with a structural formula of CH2＝C(CH3)COO(CH2CH2O)6.7CH3Mixing the polyether monoacrylate, 100 parts of styrene and 5 parts of azodiisoheptanonitrile, and uniformly stirring and dispersing at a high speed to obtain an oil phase;
gradually adding the oil phase into 350 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 60 ℃ under low-speed stirring for reacting for 8 hours, cooling to below 50 ℃, adding 0.1 part of water-soluble carbodiimide cross-linking agent, stirring for 2 hours, adding ammonia water to adjust the pH value to 8.0, and filtering by a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-2.
Example 3
Mixing an emulsifier consisting of 3.8 parts of OP-10 and 1.2 parts of sodium dodecyl benzene sulfonate, 0.5 part of propylene glycol, 50 parts of ultramarine, 1 part of acrylic acid, 4.5 parts of hydroxypropyl methacrylate, 10 parts of styrene, 40 parts of butyl acrylate and 2 parts of azodiisobutyronitrile, and stirring at a high speed to disperse uniformly to obtain an oil phase;
the oil phase is gradually added into 120 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for reacting for 8 hours, cooling to below 50 ℃, adding 0.015 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 6.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-3.
Example 4
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1.5 parts of n-butyl alcohol, 100 parts of lead chrome yellow, 10 parts of methacrylic acid and 10 parts of emulsifier with a structural formula of CH2＝C(CH3)COO(CH2CH2O)8.1C4H9Mixing the polyether monoacrylate, 50 parts of isopropyl methacrylate, 100 parts of butyl methacrylate and 6 parts of azobisisoheptonitrile, stirring at a high speed and dispersing uniformly to obtain an oil phase;
gradually adding the oil phase into 550 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 65 ℃ under low-speed stirring for 5 hours of reaction, cooling to below 50 ℃, adding 0.2 part of 3-glycidyl ether oxypropyltriethoxysilane, stirring for 1 hour, adding ammonia water to adjust the pH value to 8.0, and filtering with a 80-mesh filter screen to obtain an aqueous pigment dispersion, which is marked as D-4.
Example 5
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1.2 parts of n-butyl alcohol, 70 parts of macromolecule orange 4R, 10 parts of methacrylic acid and 6 parts of emulsifier with a structural formula of CH2＝C(CH3)COO(CH2CH2O)8.1C4H9Mixing the polyether monoacrylate, 30 parts of methyl methacrylate, 90 parts of butyl acrylate and 5 parts of azodiisobutyronitrile, and stirring at a high speed to uniformly disperse to obtain an oil phase;
gradually adding the oil phase into 800 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for reaction for 7 hours, cooling to below 50 ℃, adding 0.1 part of water-soluble aziridine crosslinking agent, stirring for 4 hours, adding ammonia water for adjusting the pH value to 7.0, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-5.
Example 6
Emulsifier composed of 4.1 parts of OP-10 and 0.9 part of sodium dodecyl benzene sulfonate, 0.7 part of glycerol, 80 parts of aurora red, 11 parts of methacrylic acid, 1 part of hydroxypropyl methacrylate and 3 parts of compound with a structural formula of CH2＝C(CH3)COO(CH2CH2O)4.7Mixing the polyether monoacrylate of H, 30 parts of methyl methacrylate, 70 parts of butyl methacrylate and 4 parts of azobisisoheptonitrile, and stirring at a high speed to disperse uniformly to obtain an oil phase;
gradually adding the oil phase into 600 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 65 ℃ under low-speed stirring for reacting for 6 hours, cooling to below 50 ℃, adding 0.2 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 7.5, and filtering by a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-6.
Example 7
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1 part of n-butyl alcohol, 50 parts of phthalocyanine blue, 6 parts of acrylic acid and 14 parts of compound with a structural formula of CH2＝C(CH3)COO(CH2CH2O)4.7Mixing the polyether monoacrylate of H, 10 parts of methyl methacrylate, 40 parts of isooctyl methacrylate and 3 parts of azobisisobutyronitrile, and stirring at a high speed to disperse uniformly to obtain an oil phase;
gradually adding the oil phase into 200 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for 10 hours of reaction, cooling to below 50 ℃, adding 0.1 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 6.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-7.
Comparative example 1
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1N-butanol, 50 phthalocyanine blue, 10 acrylic acid and 14 portions of compound with a structural formula of CH2＝C(CH3)COO(CH2CH2O)4.7H, 10 parts of polyether monoacrylate to obtain an oil phase;
gradually adding the oil phase into 200 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for 10 hours of reaction, cooling to below 50 ℃, adding 0.1 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 6.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-8.
Comparative example 2
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1 part of n-butyl alcohol, 50 parts of phthalocyanine blue, 6 parts of acrylic acid and 18 parts of compound with a structural formula of CH2＝C(CH3)COO(CH2CH2O)4.7Mixing the polyether monoacrylate of H, 10 parts of methyl methacrylate, 40 parts of isooctyl methacrylate and 3 parts of azobisisobutyronitrile, and stirring at a high speed to disperse uniformly to obtain an oil phase;
gradually adding the oil phase into 200 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for 10 hours of reaction, cooling to below 50 ℃, adding 0.1 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 6.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-9.
Comparative example 3
Emulsifier composed of 4 parts of OP-10 and 1 part of sodium dodecyl benzene sulfonate, 1 part of n-butyl alcohol, 50 parts of macromolecule orange 4R, 9 parts of acrylic acid and 14 parts of emulsifier with a structural formula of CH2＝C(CH3)COO(CH2CH2O)4.7Mixing the polyether monoacrylate of H, 10 parts of methyl methacrylate, 40 parts of isooctyl methacrylate and 3 parts of azobisisobutyronitrile, and stirring at a high speed to disperse uniformly to obtain an oil phase;
gradually adding the oil phase into 200 parts of water stirred at a high speed to obtain transparent to semitransparent microemulsion; heating the microemulsion to 80 ℃ under low-speed stirring for 10 hours of reaction, cooling to below 50 ℃, adding 0.1 part of water-soluble aziridine crosslinking agent, stirring for 3 hours, adding ammonia water for adjusting the pH value to 6.5, and filtering by using a 80-mesh filter screen to obtain the aqueous pigment dispersion, which is marked as D-10.
Comparative example 4
30 parts of styrene with polymerization inhibitor removed by distillation, 10 parts of n-butyl acrylate, 5 parts of methyl methacrylate, 1.3 parts of 1, 6-hexanediol diacrylate, 1.7 parts of dipropylene glycol diacrylate, 1 part of hexadecanol and 0.5 part of benzoyl peroxide are mixed to form a mixture, and then 1.8 parts of organic pigment phthalocyanine blue is dissolved in the mixture to form an oil phase solution after complete dissolution.
3 parts of sodium dodecyl sulfate and 2.2 parts of NaHCO3And dissolved in 120 parts of deionized water to form an aqueous solution.
Mixing the oil phase solution and the water phase solution, stirring at 800rpm for 15min, and ultrasonic homogenizing in an ultrasonic homogenizer to form miniemulsion. And (3) transferring the miniemulsion into a reactor, introducing nitrogen, heating to 80 ℃, initiating a polymerization reaction, adding 4 parts of methacrylic acid and 2 parts of hydroxyethyl methacrylate after the reaction is carried out for 12min, continuing the reaction for 3h, cooling to room temperature, adjusting the pH of the obtained solution to 9 by using ammonia water, filtering and discharging to obtain the aqueous pigment dispersion liquid, wherein the D-11 is recorded.
Test and results
(1) Storage stability: the aqueous pigment dispersions D-1 to D-11 were allowed to stand still at 60 ℃ for 1 week and at 45 ℃ for 30 days, respectively, and the presence or absence of precipitation and delamination was observed, and the results are shown in Table 1.
(2) Cold-hot cycle stability: the aqueous pigment dispersions D-1 to D-11 are respectively kept stand at 70 ℃ for 4 hours, then are kept stand at-20 ℃ for 4 hours, then are kept stand at 70 ℃ for 4 hours, then are kept stand at-20 ℃ for 4 hours, and are circulated for 4 times. The change in particle size of the pigment particles before and after storage was measured using a laser particle sizer and the results are shown in table 1.
(3) Compatibility: the aqueous pigment dispersions D-1 to D-11 are respectively and uniformly mixed with the single-component polyurethane white surface slurry according to the weight ratio of 3:100, and after film coating and drying, whether the film has floating color, flocculation or surface defects is observed, and the result is shown in Table 1.
Table 1 results of performance testing
Thus, the aqueous pigment dispersions prepared by the process of the present invention have better storage stability, with less increase in particle size after cold and heat shock testing, indicating better stability.
The foregoing has shown and described the fundamental principles, principal features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for producing an aqueous pigment dispersion, comprising the steps of,
s1, mixing an emulsifier, an auxiliary emulsifier, a pigment, a monofunctional hydrophilic monomer, a monofunctional hydrophobic monomer and an oil-soluble initiator, and uniformly stirring and dispersing at a high speed to obtain an oil phase; the monofunctional hydrophilic monomer consists of a nonionic hydrophilic monomer and (meth) acrylic acid; the weight ratio of the emulsifier to the co-emulsifier to the pigment to the mono-functionality hydrophilic monomer to the mono-functionality hydrophobic monomer to the oil-soluble initiator is 0.5: 0.05-0.2: 5-10: 0.5-2: 5-15: 0.2-1;
s2, gradually adding the oil phase obtained in the step S1 into high-speed stirred water to obtain transparent to semitransparent microemulsion; heating the microemulsion to 50-80 ℃ under low-speed stirring, reacting for 4-10 hours, cooling to below 50 ℃, adding a water-soluble cross-linking agent, stirring for 0.5-5 hours, adding ammonia water or triethanolamine, adjusting the pH value to 6.5-8, and filtering to obtain the aqueous pigment dispersion;
in the step S1, the hydrophobic monomer is selected from at least one of acrylate monomers and styrene monomers;
in step S1, the non-ionic hydrophilic monomer is at least one selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and polyether monoacrylate, and the structural formula of the polyether monoacrylate is CH2＝C(CH3)COO(CH2CH2O)n(CH2CHCH3O)mR, wherein n is more than or equal to 3 and less than or equal to 10, m is more than or equal to 0 and less than or equal to 5, n-m is more than or equal to 3, and R is independently selected from hydrogen radical, methyl or isobutyl;
in the step S1, the weight ratio of the non-ionic hydrophilic monomer to the (meth) acrylic acid in the monofunctional hydrophilic monomer is 1: 5-5: 1;
the water-soluble cross-linking agent in the step S2 is selected from one of a water-soluble carbodiimide cross-linking agent, a water-soluble aziridine cross-linking agent and a water-soluble epoxy silane cross-linking agent;
in the step S2, the weight ratio of the (meth) acrylic acid to the water-soluble crosslinking agent in the oil phase is 1: 0.01-0.2.
2. The method according to claim 1, wherein the pigment in step S1 is at least one selected from the group consisting of inorganic pigments and organic pigments.
3. The method according to claim 1, wherein the weight ratio of the oil phase to the water in step S2 is 1:1 to 10.
4. An aqueous ink comprising the aqueous pigment dispersion obtained by the production method according to any one of claims 1 to 3.
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| CN101486845A (en) * | 2008-01-14 | 2009-07-22 | 深圳市海川实业股份有限公司 | Method for preparing nano colouring matter aqueous dispersions |
| CN101845122A (en) * | 2010-06-11 | 2010-09-29 | 成都达威化工科技有限公司 | Water-based polymer pigment dispersant and leather cationic pigment paste prepared from same |
| WO2018074372A1 (en) * | 2016-10-17 | 2018-04-26 | 花王株式会社 | Aqueous pigment dispersion |
| CN109563367A (en) * | 2016-08-12 | 2019-04-02 | 花王株式会社 | Aqueous pigment dispersions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101486845A (en) * | 2008-01-14 | 2009-07-22 | 深圳市海川实业股份有限公司 | Method for preparing nano colouring matter aqueous dispersions |
| CN101845122A (en) * | 2010-06-11 | 2010-09-29 | 成都达威化工科技有限公司 | Water-based polymer pigment dispersant and leather cationic pigment paste prepared from same |
| CN109563367A (en) * | 2016-08-12 | 2019-04-02 | 花王株式会社 | Aqueous pigment dispersions |
| WO2018074372A1 (en) * | 2016-10-17 | 2018-04-26 | 花王株式会社 | Aqueous pigment dispersion |
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