CN111116860A - Waterborne polyurethane dispersant and waterborne color paste containing same - Google Patents
Waterborne polyurethane dispersant and waterborne color paste containing same Download PDFInfo
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- CN111116860A CN111116860A CN202010001978.5A CN202010001978A CN111116860A CN 111116860 A CN111116860 A CN 111116860A CN 202010001978 A CN202010001978 A CN 202010001978A CN 111116860 A CN111116860 A CN 111116860A
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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
- 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
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- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
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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
- 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
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
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Abstract
The invention belongs to the field of materials, and discloses a water-based polyurethane dispersant which is mainly prepared by reacting raw materials of a polyglycol monomer, an isocyanate monomer, an emulsifier, a solvent, a catalyst and a blocking agent. The waterborne polyurethane dispersant has strong adsorbability on the surface of an organic pigment, is not easy to fall off and replace, can effectively reduce the surface energy of the pigment, and has strong dispersion stability.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a waterborne polyurethane dispersant and a waterborne color paste containing the same.
Background
Organic pigments are widely used in paints, inks, inkjet inks, and the like. The structure of common organic pigment toner is mostly polycyclic, such as azo, phthalocyanine, anthraquinone, indigo, quinacridone, dioxazine, and arylmethane. The organic pigments generally have lipophilic benzene ring or heterocyclic structure, and the surface of the organic pigments contains active amine groups, amide groups, carboxylic acid groups, ester groups, hydroxyl groups and the like. Because the intermolecular attraction is strong and easy to agglomerate and is difficult to disperse, the organic pigment is not easy to stably disperse in a solution phase, and toner is easy to separate out and aggregate to cause sedimentation, so that the organic pigment color paste is unstable and easy to layer or float.
In order to avoid aggregation of the toner in the solution and instability of the color paste, a dispersant needs to be added into the color paste to serve as a bridge between the toner and a dispersion medium, so that the toner can be stably dispersed in the solution. However, the prior dispersing agent still can not achieve good dispersing effect, and the color paste is easy to generate the phenomenon of layering or flooding.
Therefore, it is desirable to provide a dispersant having good dispersibility.
Disclosure of Invention
The present invention has been made to solve at least one of the above problems occurring in the prior art. Therefore, the invention provides the waterborne polyurethane dispersant which has good dispersibility.
The invention provides a water-based polyurethane dispersant which is mainly prepared by reacting raw materials of a polyglycol monomer, an isocyanate monomer, an emulsifier, a solvent, a catalyst and a blocking agent.
The waterborne polyurethane dispersant is mainly prepared from the following raw materials in parts by weight:
preferably, the waterborne polyurethane dispersant is mainly prepared from the following raw materials in parts by weight:
the polyglycol monomer includes polyether glycol and/or polyester glycol. Preferably, the polyester diol is a polycarbonate diol or a polycaprolactone diol.
Preferably, the isocyanate monomer is a diisocyanate monomer containing a benzene ring and/or a heterocyclic structure; more preferably, the diisocyanate monomer is a monomer containing a benzene ring structure; more preferably, the diisocyanate monomer is at least one of dicyclohexylmethane diisocyanate, xylylene diisocyanate, m-xylylene isocyanate, toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tetramethyl m-xylylene diisocyanate, or naphthalene diisocyanate. The monomer with a ring structure has stronger adsorbability to the toner.
The emulsifier is dimethylolpropionic acid and/or dimethylolbutyric acid.
The capping agent comprises at least one of diethylamine, triethylamine, bis (2-methoxyethyl) amine, or taurine.
The catalyst is at least one of organic tin, organic zinc, organic titanium, aliphatic amines, alicyclic amines, aromatic amines or alcohol amines. Wherein the organic tin is dibutyltin dilaurate or stannous octoate; the organic zinc is zinc isooctanoate; the organic titanium is tetrabutyl titanate; the aliphatic amine includes N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, N, N-dimethylbenzylamine; the alicyclic amine comprises solid amine, N-ethyl morpholine and N, N' -diethyl piperazine; alcohol amines include dimethylethanolamine; the aromatic amine is pyridine or N, N' -dimethylpyridine.
The solvent is dimethyl sulfoxide and/or sulfolane, and is used for dissolving the monomer, the catalyst and the prepolymer after polymerization, so that the components can quickly react in a homogeneous phase. The solvent has high polarity, high thermal stability, stability to acid and alkali, mutual solubility with water and no corrosiveness.
A preparation method of the water-based polyurethane dispersant comprises the following steps:
in an inert atmosphere, mixing a solvent, a polyglycol monomer, an emulsifier and a catalyst, heating, adding an isocyanate monomer, reacting, heating, adding a blocking agent, and stirring to obtain the waterborne polyurethane dispersant.
Preferably, the reaction time is 60-90min, and the reaction temperature is 50-70 ℃.
Preferably, the temperature is raised from the reaction temperature to 100-110 ℃.
Preferably, the stirring temperature is 50-70 ℃, and the stirring time is 30-90 min.
Preferably, the rotation speed of the stirring is 1000-1800rpm, the stirring temperature is 50-70 ℃, and the stirring time is 30-90 min.
Preferably, after the aqueous polyurethane dispersant is prepared, the method further comprises the following subsequent treatment steps: and adding a neutralizing agent and water into the prepared waterborne polyurethane dispersant, stirring, filtering, and taking a filtrate.
The neutralizing agent is potassium hydroxide solution or/and sodium hydroxide solution.
Preferably, the mass of the water is 10-40% of that of the aqueous polyurethane dispersant; the mass of the neutralizing agent is 10-40% of that of the aqueous polyurethane dispersing agent.
Adding a neutralizing agent and water in the subsequent steps, stirring, and dispersing the aqueous polyurethane dispersant in deionized water through strong shearing action, so that the prepared aqueous polyurethane dispersant is more stable, has longer storage time and is not easy to generate precipitates; meanwhile, the addition of the neutralizer and the water enables the dispersant to be easily combined with pigment molecules, and the subsequent color paste preparation is easy.
The aqueous color paste comprises organic pigment, the aqueous polyurethane dispersant, surfactant and water.
The mass ratio (P/D) of the mass of the organic pigment to the mass of the effective components of the aqueous polyurethane dispersant is (1.5-3): preferably, the mass ratio (P/D) of the mass of the organic pigment to the mass of the active ingredients of the aqueous polyurethane dispersant is (2-3): 1. the mass of the effective components of the aqueous polyurethane dispersant is the sum of the mass of a polyglycol monomer, an emulsifier, an isocyanate monomer and a blocking agent. When P/D is (1.5-3): 1, the prepared color paste has the lowest viscosity, reaches the color paste particle size standard and has the shortest grinding time; when the P/D value is not in the proportion range, the viscosity of the color paste is high, and the grinding time is prolonged.
The organic pigment is a common organic pigment, such as black PB1, PB7 and the like; blue PB15, PB15:3, PB15:4, and the like; red PV19, PR122, PR202, PR207, PR209, etc.; yellow PY74, PY128, PY150, PY155, PY181, etc.
It is known from the law of thermodynamics that a substance tends to spontaneously go to the lowest energy. Therefore, the organic pigment spontaneously aggregates into large particles to reduce its surface energy. To overcome this phenomenon, the surface energy of the organic pigment particles must be reduced. When the polyurethane is synthesized, the polyurethane contains a hydrophilic end-capping agent and the like, so that the polyurethane molecule has an oleophilic chain segment and a hydrophilic chain segment simultaneously. Therefore, the polyurethane dispersant has a function of reducing the surface energy of the toner and has the ability of stabilizing the toner. The structure of the polyurethane dispersant is composed of two parts, one part is a hydrophilic polar group, and the other part is a lipophilic non-polar group. When the dispersion medium is a polar solvent, such as water, it is difficult for the lipophilic organic pigment to mix with water. In this case, the lipophilic end of the dispersant can be adsorbed onto the surface of the organic pigment, and the surface of the organic pigment is coated with a layer of dispersant having a hydrophilic group by the adsorption of the dispersant, so that the organic pigment becomes hydrophilic and can be mixed into water.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waterborne polyurethane dispersant has strong adsorption force on the surface of the organic pigment, is not easy to fall off and replace, can effectively reduce the surface energy of the pigment, and has strong dispersion stability.
(2) The aqueous polyurethane dispersant has good stability, and the viscosity change rate is less than 4 percent and the average particle size change rate is less than 4 percent when the aqueous polyurethane dispersant is stored for 14 days at 60 ℃; the product can be stored at 0-5 deg.C for 14 days without layering and precipitation.
(3) The waterborne polyurethane dispersant has strong dispersing ability, and the waterborne color paste prepared by the waterborne polyurethane dispersant has good stability. The color paste is stored for 14 days at the temperature of 60 ℃ without precipitation, flocculation or layering, the viscosity change rate is less than 4 percent, the average particle size change rate is less than 4.4 percent, the color paste absorption wavelength change difference value is less than 1.2nm, and the color paste ultraviolet absorption value change rate is less than 2 percent; the color paste is stored for 14 days at the temperature of 18 ℃ below zero for no precipitation, no flocculation and no delamination, the viscosity change rate is less than 1.7 percent, the average particle diameter change rate is less than 1 percent, the color paste absorption wavelength change difference value is less than 0.6nm, and the color paste ultraviolet absorption value change rate is less than 0.5 percent.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
In the examples, polycarbonate diol UH-50, polycarbonate diol UH-100, polytetramethylene ether glycol TETRATHANE 650, polytetramethylene ether glycol TETRATHANE 250 were purchased from Jining HuaKai resin Co., Ltd; organic pigments yellow PY74, red PR122, blue PB15:3 and black PK7 were purchased from Jiangsu Maxam pigment chemical Co., Ltd; the surfactant 420 is purchased from air chemical products, ltd.
Examples 1 to 4 are examples of preparing an aqueous polyurethane dispersant.
Example 1
A dry, clean four-neck flask equipped with a stirring and condensing reflux unit was purged with nitrogen, and 200g of sulfolane, UH-50148 g of polycarbonate diol, 96g of 2, 2-dimethylolpropionic acid (DMPA), and 10g of tetrabutyl titanate were poured into a reactor in this order, stirred uniformly and heated, and the temperature was controlled at 60 ℃. Then adding tetramethyl m-xylylene diisocyanate TMXDI262g into a reaction bottle for reaction, and slowly and uniformly adding the mixture by using a peristaltic pump in a slow dropwise adding mode for 90min at the reaction temperature of 60 ℃; after the addition, the temperature is raised to 100 ℃, the mixture is uniformly stirred until the concentration of the isocyanate group (% NCO) is lower than 1.5 percent, and the temperature is reduced to 60 ℃. And then adding 30g of triethylamine TEA slowly into the reaction bottle, adding the triethylamine TEA for 5min, and uniformly stirring the triethylamine TEA for 1h at the temperature of 60 ℃ to obtain a dispersant prepolymer. And finally, 133.2g of 3% potassium hydroxide aqueous solution is added into the dispersion prepolymer for 10min, 121g of deionized water is added, the stirring speed is increased, the stirring speed is high-speed stirred, the stirring speed is 1000 plus 1800rpm, the mixture is stirred at a high speed at 60 ℃ for reaction for 1h, the reaction temperature is cooled to room temperature, a PVDF membrane with the diameter of 1.0 mu m is used for filtration, and filter residues are removed, so that the waterborne polyurethane dispersant A is obtained.
Example 2
A clean four-neck flask bottle which is provided with a stirring and condensing reflux device is dried is filled with nitrogen, and 150g of dimethyl sulfoxide, UH-10068 g of polycarbonate diol, 52g of dimethylolbutyric acid (DMBA) and 0.01g of dibutyltin dilaurate are poured into a reactor in sequence, stirred uniformly and heated, and the temperature is controlled at 60 ℃. Then adding 126g of dicyclohexylmethane diisocyanate (HMDI) into a reaction bottle for reaction, and slowly and uniformly adding the HMDI by using a peristaltic pump in a slow dropwise adding mode for 60min at the reaction temperature of 60 ℃; after the addition, the temperature is raised to 100 ℃, the mixture is uniformly stirred until the concentration of the isocyanate group (% NCO) is lower than 1.5 percent, and the temperature is reduced to 60 ℃. Then 16.7g of diethylamine DEA is added into a reaction bottle, the addition is finished for 5min, and the mixture is uniformly stirred for 1h at the temperature of 60 ℃ to obtain a dispersant prepolymer. And finally, adding 187.3g of 3% sodium hydroxide aqueous solution into the dispersion prepolymer for 10min, then adding 400g of deionized water, simultaneously increasing the stirring speed, stirring at a high speed of 1800rpm, stirring at a high speed of 60 ℃ for reaction for 1h, cooling the reaction temperature to room temperature, filtering with a 1.0 mu m PVDF membrane, and removing filter residues to obtain the waterborne polyurethane dispersant B.
Example 3
Introducing nitrogen into a clean four-neck flask bottle which is provided with a stirring and condensing reflux device, pouring 100g of dimethyl sulfoxide, TETRATHANE 650102 g of polytetramethylene ether glycol, 86.9g of 2, 2-dimethylolpropionic acid (DMPA) and 1g of stannous octoate into a reactor in sequence, uniformly stirring and heating, controlling the temperature to be 60 ℃, then adding 152g of m-xylylene isocyanate MXDI into the reaction bottle for reaction, and slowly and uniformly adding the m-xylylene isocyanate MXDI into the reaction bottle by using a peristaltic pump in a slow dripping manner for 70min at the reaction temperature of 60 ℃; after the addition was completed, the temperature was raised to 100 ℃ and the mixture was stirred until the isocyanate group (% NCO) concentration was less than 1.5%. The temperature is reduced to 60 ℃. Then 6.8g of bis (2-methoxyethyl) amine BMEA is added into a reaction bottle, the addition is finished for 5min, and the mixture is uniformly stirred for 1h at 60 ℃ to obtain a dispersant prepolymer. And finally, adding 150g of 3% potassium hydroxide aqueous solution and 200g of 3% sodium hydroxide aqueous solution into the dispersant prepolymer for 10min, then adding 201.3g of deionized water, simultaneously increasing the stirring speed, stirring at a high speed of 1800rpm, stirring at a high speed of 60 ℃ for 1h, cooling the reaction temperature to room temperature, filtering with a 1.0 mu m PVDF membrane, and removing filter residues to obtain the waterborne polyurethane dispersant C.
Example 4
A dry, clean four-neck flask equipped with a stirring and condensing reflux unit was purged with nitrogen, and 160g of sulfolane, TETRATHANE 25085.2 g of polytetramethylene ether glycol, 130g of dimethylolbutanoic acid (DMBA), and 5g of zinc isooctanoate were poured into a reactor in this order, stirred uniformly and heated, and the temperature was controlled at 60 ℃. Then adding 201g of toluene diisocyanate TDI into a reaction bottle for reaction, and slowly and uniformly adding the toluene diisocyanate TDI by using a peristaltic pump in a slow dropwise adding mode, wherein the adding time is 80min, and the reaction temperature is 60 ℃; after the addition was completed, the temperature was raised to 100 ℃ and the mixture was stirred until the isocyanate group (% NCO) concentration was less than 1.5%. The temperature is reduced to 60 ℃. And then adding 12g of diethylamine DEA and 36g of taurine into a reaction bottle, adding for 5min, and uniformly stirring for 1h at 60 ℃ to obtain a dispersant prepolymer. And finally, adding 160.8g of 3% potassium hydroxide aqueous solution and 100g of 3% sodium hydroxide aqueous solution into the dispersion prepolymer for 10min, then adding 110g of deionized water, simultaneously increasing the stirring speed, stirring at a high speed of 1800rpm, stirring at a high speed of 60 ℃ for 1h, cooling the reaction temperature to room temperature, filtering with a 1.0 mu m PVDF membrane, and removing filter residues to obtain the waterborne polyurethane dispersant D.
The water-based polyurethane dispersants prepared in examples 1 to 4 were subjected to physical and chemical properties and storage stability tests, and the test results are shown in table 1.
TABLE 1 physical and chemical Properties and storage stability results of aqueous polyurethane dispersants
As can be seen from Table 1, the aqueous polyurethane dispersant meets the requirement of stability determination, the phenomena of layering and precipitation do not occur in hot storage (60 +/-1 ℃, 14 days) and cold storage (0-5 ℃, 14 days), and the change rate of the particle size is less than or equal to 5 percent. Is stable when stored for 2 years at normal temperature.
Examples 5-8 are examples of the preparation of aqueous color pastes.
The amount of the organic pigment and the dispersant in the color paste is measured by the mass ratio (marked as P/D) of the organic pigment and the effective components of the dispersant in the color paste. As the amount of the dispersant is increased, the value of P/D becomes smaller, and the value of P/D and the amount of the dispersant added are in an inverse relationship. In the color paste formula, the content of the organic pigment is 15 percent as an example, the dispersing agent A, the dispersing agent B, the dispersing agent C and the dispersing agent D are respectively taken as the dispersing agent A, the dispersing agent B, the dispersing agent C and the dispersing agent D, and the P/D ratio is respectively 1.5, 2.0, 2.5 and 3.0. In examples 5 to 8, the color pastes prepared by weighing the organic pigments yellow PY74, red PR122, blue PB15:3 and black PK7 according to the formula shown in Table 2, mixing and grinding for 480min are respectively adopted.
TABLE 2 color paste formula
| Color paste composition | 1 | 2 | 3 | 4 |
| Deionized water% | 66.1 | 56.3 | 67.5 | 74.0 |
| Organic pigment% | 15.0 | 15.0 | 15.0 | 15.0 |
| Dispersant A% | 18.7 | 0 | / | / |
| Dispersant B% | / | 28.5 | / | / |
| Dispersant C% | / | / | 17.3 | / |
| Dispersant D% | / | / | / | 10.8 |
| 420% of surfactant | 0.2 | 0.2 | 0.2 | 0.2 |
| The effective components of the dispersing agent in the color paste are as follows | 10.0 | 7.5 | 6.0 | 5.0 |
| P/D | 1.5 | 2.0 | 2.5 | 3.0 |
Example 5
According to the formula shown in Table 2, an organic pigment yellow PY74 is taken, and color pastes are prepared according to the mass ratios of the organic pigment to the effective components of the dispersing agent of 1.5, 2, 2.5 and 3, wherein the prepared color pastes are PY74-1, PY74-2, PY74-3 and PY74-4 respectively.
The prepared color pastes PY74-1, PY74-2, PY74-3 and PY74-4 are tested for viscosity and particle size. The test results are shown in Table 3.
TABLE 3 test results of color pastes made with the organic pigment yellow PY74
Example 6
According to the formula shown in Table 2, an organic pigment red PR122 is taken, and color pastes are prepared according to the mass ratios of the organic pigment to the effective components of the dispersing agent of 1.5, 2, 2.5 and 3, wherein the prepared color pastes are PR122-1, PR122-2, PR122-3 and PR122-4 respectively.
The prepared color paste PR122-1, PR122-2, PR122-3 and PR122-4 are tested for viscosity and particle size. The test results are shown in Table 4.
TABLE 4 test results of color pastes made with organic pigment Red PR122
| Color paste name | PR122-1 | PR122-2 | PR122-3 | PR122-4 |
| P/D | 1.5 | 2 | 2.5 | 3 |
| Viscosity, mP.s (@25 ℃ C.) | 40.52 | 12.88 | 5.51 | 17.22 |
| Average particle diameter, nm | 193.3 | 144.2 | 125.4 | 172.5 |
| D10，nm | 129 | 92.8 | 91.1 | 108 |
| D50，nm | 211 | 163 | 139 | 189 |
| D90，nm | 370 | 287 | 255 | 334 |
| D99，nm | 510 | 415 | 382 | 478 |
| D100，nm | 631 | 563 | 459 | 657 |
Example 7
According to the formula shown in Table 2, color pastes are prepared from organic pigment blue PB15:3 and organic pigment and dispersing agents according to the mass ratio of 1.5, 2, 2.5 and 3, wherein the prepared color pastes are PB15:3-1, PB15:3-2, PB15:3-3 and PB15:3-4 respectively.
The prepared color paste PB15:3-1, PB15:3-2, PB15:3-3 and PB15:3-4 are subjected to viscosity and particle size tests. The test results are shown in Table 5.
TABLE 5 test results of color pastes made of blue organic pigments PB15:3
| Color paste name | PB15:3-1 | PB15:3-2 | PB15:3-3 | PB15:3-4 |
| P/D | 1.5 | 2 | 2.5 | 3 |
| Viscosity, mP.s (@25 ℃ C.) | 16.59 | 5.29 | 10.98 | 17.38 |
| Average particle diameter, nm | 136.1 | 117.2 | 162.3 | 170.1 |
| D10，nm | 95.2 | 89.2 | 109 | 95.8 |
| D50，nm | 159 | 123 | 191 | 202 |
| D90，nm | 27 | 255 | 333 | 411 |
| D99，nm | 386 | 382 | 471 | 630 |
| D100，nm | 531 | 459 | 615 | 955 |
Example 8
According to the formula shown in Table 2, color pastes are prepared from organic pigment black PK7 according to the mass ratio of the organic pigment to the effective components of the dispersing agent of 1.5, 2, 2.5 and 3, wherein the prepared color pastes are PK7-1, PK7-2, PK7-3 and PK7-4 respectively.
The prepared color pastes PK7-1, PK7-2, PK7-3 and PK7-4 are subjected to viscosity and particle size tests. The test results are shown in Table 6.
TABLE 6 test results of color pastes made with organic pigment Black PK7
| Color paste name | PK7-1 | PK7-2 | PK7-3 | PK7-4 |
| P/D | 1.5 | 2 | 2.5 | 3 |
| Viscosity, mP.s (@25 ℃ C.) | 21.48 | 4.16 | 7.22 | 17.11 |
| Average particle diameter, nm | 145.6 | 101.2 | 142.8 | 152.4 |
| D10，nm | 97.6 | 86.9 | 88 | 94.8 |
| D50，nm | 178 | 113 | 157 | 188.8 |
| D90，nm | 356 | 255 | 288 | 389 |
| D99，nm | 468 | 382 | 430 | 415 |
| D100，nm | 573 | 459 | 615 | 531 |
From the examples 5-8, it can be seen that the P/D value becomes smaller with the increase of the amount of the dispersant, and when the P/D is 1.5-3, the viscosity of the prepared color paste is smaller and the particle size is smaller; when the P/D is 2-2.5, the viscosity of the prepared color paste is the lowest, and the particle size of the color paste is the smallest in the same grinding time, namely the grinding time required for reaching the standard particle size of the color paste is the shortest.
The color pastes PY74-2, PR122-3, PB15:3-2 and PK7-2 prepared in examples 5-8 were subjected to storage stability evaluation. The method utilizes the temperature-time linear function relationship and the reaction speed theoretical formula to predict that the storage stability of the organic pigment color paste at high temperature (60 +/-1 ℃ for 14 days) and the storage stability at low temperature (18 ℃ for 14 days) is equivalent to the storage result at normal temperature for two years.
(1) High temperature storage stability test: respectively putting 1kg of 4-color paste into a 60 ℃ oven, taking out after 14 days without shaking, observing the appearance after recovering the normal temperature, judging whether the phenomena of layering, flocculation and the like exist, testing related parameters, and judging whether the product is qualified.
(2) Low-temperature storage stability test: respectively putting 1kg of 4-color paste into a freezer at the temperature of-18 ℃, taking out after 14 days without shaking, observing the appearance after the room temperature is recovered, and judging whether the color paste is qualified or not by detecting relevant parameters, wherein the phenomena of layering, powder precipitation, precipitation and the like exist.
TABLE 7 color paste high-temperature storage stability test results
As can be seen from Table 7, the 4-color paste has a satisfactory high-temperature storage stability.
TABLE 8 color paste low-temperature storage stability test results
As can be seen from Table 8, the 4-color paste has a good low-temperature freeze-thaw storage stability.
In conclusion, the waterborne polyurethane dispersant disclosed by the invention is good in stability and strong in dispersing capacity, and is applied to color pastes, so that the prepared color pastes are good in storage stability.
Claims (10)
1. The water-based polyurethane dispersant is characterized by being prepared by reacting raw materials of a polyglycol monomer, an isocyanate monomer, an emulsifier, a solvent, a catalyst and a blocking agent.
2. The aqueous polyurethane dispersant of claim 1, which is mainly prepared from the following raw materials in parts by weight:
3. the aqueous polyurethane dispersant of claim 1 or 2, wherein said polyglycol-based monomer comprises a polyether diol or/and a polyester diol.
4. The aqueous polyurethane dispersant of claim 1 or 2, wherein the isocyanate monomer is a diisocyanate monomer containing a benzene ring and/or a heterocyclic ring structure.
5. The aqueous polyurethane dispersant of claim 1 or 2, characterized in that the end-capping agent is at least one of diethylamine, triethylamine, bis (2-methoxyethyl) amine or taurine.
6. The aqueous polyurethane dispersant of claim 1 or 2, wherein said catalyst is at least one of organotin, organozinc, organotitanium, aliphatic amine, alicyclic amine, aromatic amine, or alcohol amine.
7. The aqueous polyurethane dispersant according to claim 1 or 2, characterized in that said solvent is dimethyl sulfoxide and/or sulfolane.
8. A preparation method of the water-based polyurethane dispersant is characterized by comprising the following steps:
mixing a solvent, a polyglycol monomer, an emulsifier and a catalyst in an inert atmosphere, heating, adding an isocyanate monomer, reacting, heating, adding a blocking agent, and stirring to obtain the aqueous polyurethane dispersant of any one of claims 1 to 7.
9. An aqueous color paste characterized by mainly comprising an organic pigment, a surfactant, water and the aqueous polyurethane dispersant of any one of claims 1 to 7.
10. The aqueous color paste according to claim 9, wherein the mass ratio of the organic pigment to the effective components of the aqueous polyurethane dispersant is (1.5-3): 1; the mass of the effective components of the aqueous polyurethane dispersant is the sum of the mass of a polyglycol monomer, an emulsifier, an isocyanate monomer and a blocking agent.
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| CN113501932A (en) * | 2021-07-30 | 2021-10-15 | 杰印数码科技(珠海)有限公司 | Active pigment dispersant |
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