CN111116842B - Dispersing agent, preparation method and application - Google Patents
Dispersing agent, preparation method and application Download PDFInfo
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- CN111116842B CN111116842B CN202010000393.1A CN202010000393A CN111116842B CN 111116842 B CN111116842 B CN 111116842B CN 202010000393 A CN202010000393 A CN 202010000393A CN 111116842 B CN111116842 B CN 111116842B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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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
- C09D11/322—Pigment inks
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention belongs to the field of printing consumables, and discloses a dispersant which consists of a main chain and a branched chain, wherein the main chain comprises a hydrophobic group structural unit represented by a formula (I), and the main chain also comprises an alkali-containing structural unit represented by a formula (II) or/and a carboxyl-containing structural unit represented by a formula (III); the branched chain comprises a structural unit containing a hydrophilic group represented by formula (IV) or formula (V), wherein x is 10-220, and y is 2-30; z is 3-60; the molecular weight of the dispersant is 5000-100000.
Description
Technical Field
The invention belongs to the field of printing consumables, and particularly relates to a dispersing agent, and a preparation method and application thereof.
Background
The water-based white digital printing ink has good shielding capability, can cover defects on a base material, and improves the contrast and the vividness of the color digital printing ink in a surface printing mode or a back printing mode. In the surface printing mode, the color image is attached to the coating of the white digital printing ink, so that the color image is highlighted in a white background; in the reverse printing mode, a color image is printed on a transparent base material, and then white digital printing ink is attached to the color image, and the final image is observed through the transparent base material. The higher the whiteness, the more brilliant the relative color contrast. In order to obtain high whiteness, the white color paste preferably adopts a pigment with high refractive index so as to achieve the purpose of high shading rate. Common high refractive index white pigments include zinc oxide, barium sulfate, calcium carbonate, titanium dioxide, and the like. However, the inorganic pigment particles have a specific gravity which is several times higher than that of the traditional organic pigment, and are easy to generate hard precipitation and agglomeration in color paste, which affects the redispersion stability of the color paste and causes the problems of blockage, inclined spraying, ink breaking and the like of a digital printing nozzle.
White pastes are prone to non-redispersible precipitates due to the excessively close packing of the white pigment particles. The traditional micromolecule dispersant or polymer dispersant is used, the anchoring group of the traditional micromolecule dispersant or polymer dispersant has too few adsorption points or weak adsorption capacity to white pigment, the solvation chain has the defects of being too short or too long, the affinity to a solvent is poor, and enough steric hindrance or electrostatic repulsion cannot be generated, so that the prepared white color paste is easy to generate hard precipitation and coarse particles.
Therefore, it is desired to provide a dispersant which has a strong adsorption ability to white pigments and a strong affinity to solvents and can disperse white pastes.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the dispersing agent which has strong adsorption capacity on white pigment and strong affinity with a solvent and can disperse white color paste.
The invention also provides the water-based white color paste.
A dispersant is composed of a main chain and a branch chain, wherein the main chain comprises a hydrophobic group structural unit represented by a formula (I), and the main chain comprises a base-containing structural unit represented by a formula (II) or/and a carboxyl-containing structural unit represented by a formula (III); the side chain comprises a structural unit containing a hydrophilic group represented by formula (IV) or formula (V), wherein x is 10-220, and y is 2-30; z is 3-60; the molecular weight of the dispersant is 5000-100000.
Preferably, the branched chain has a molecular weight of 500-10000; further preferably, the molecular weight of the branch is 1000-.
The main chain of the dispersant comprises a hydrophobic structural unit, a structural unit containing an alkali group and a structural unit containing a carboxyl group, and can be adsorbed and anchored on the surface of a white pigment molecule; and the branched chain comprises a water-soluble ion or water-soluble non-ion structural unit, and can generate the hydrophilicity of steric hindrance and electrostatic repulsion. The dispersant can generate sufficient repulsive force or steric hindrance between inorganic pigment particles, so that the inorganic pigment particles are not easy to flocculate or precipitate.
A preparation method of the dispersing agent comprises the following steps:
(1) mixing a main chain monomer and a branched chain monomer to obtain a premix;
(2) and (2) heating a solvent and an initiator under an inert atmosphere, dissolving, adding the premix prepared in the step (1), reacting, and detecting that the amount of the residual monomer is less than 5% to terminate the reaction, thus preparing the dispersing agent.
The main chain monomer in the step (1) is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hydroxymethyl acrylamide, hydroxyethyl acrylamide, hydroxypropyl acrylamide, maleic acid and fumaric acid monomer; the branched chain monomer is sodium vinylsulfonate and methyl methacrylate monofunctional oligomer or polyethylene glycol methyl ether methacrylate;
preferably, the initiator in step (2) is an azo group-containing compound.
Preferably, the initiator in the step (2) is at least one of azobisisoheptonitrile, azobisisobutyronitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, azobisisobutyronitrile formamide or azobisdicyclohexyl carbonitrile.
Preferably, the solvent in step (2) is at least one of ethanol, propanol, isopropanol, butanone, methyl isobutyl ketone, ethyl acetate, isopropyl acetate, dichloromethane, acetone, dichloroethane, toluene, xylene, tetrahydrofuran or cyclohexanone; further preferably, the solvent is acetone, isopropanol, butanone or ethyl acetate. The amount of the solvent used in the present invention is not particularly limited, and the initiator can be sufficiently dissolved.
The reaction temperature in the step (2) is 50-100 ℃, and the reaction time is 4-7 hours.
The water-based color paste comprises the following components: pigment, auxiliary agent, water and the dispersant.
The water-based white color paste comprises the following components in parts by mass:
30-70 parts of white pigment
5-20 parts of dispersant
0-25 parts of assistant
30-70 parts of water.
Preferably, the white pigment includes at least one of zinc oxide, barium sulfate, calcium carbonate, or titanium dioxide; further preferably, the white pigment is titanium dioxide, such as U.S. DuPont titanium dioxide pigments R-706, R-900, R-902+, R-960, R-931, R-102, R-103, R-104, R-105, R-108, R-350, Allied Unititanium dioxide pigments TIONA595, R-CL 69; titanium dioxide pigment CR-90-2, CR-60-2, CR-57; teno titanium dioxide pigments CR-828, CR-826; saharley titanium dioxide pigment RDI-S, RODI, RED2, RDDI.
Preferably, the auxiliary agent comprises a cosolvent and/or a wetting agent; further preferably, the auxiliary agent consists of a cosolvent and a wetting agent, and the mass ratio of the cosolvent to the wetting agent is (3-10): 1.
Preferably, the co-solvent comprises one or more of a monohydric alcohol, a polyhydric alcohol, an ether, a ketone or an alcohol ether, such as methanol, ethanol, glycerol, ethylene glycol, propylene glycol, methyl ether, ethyl ether, 2-pyrrolidone, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, triethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether.
Preferably, the moisturizer comprises one or more of ByK154, ByK190, ByK306, ByK333, ByK346, ByK378 and ByK-DYNFET 800N, Evonik SURFYNOL104E, Evonik SURFYNOL420, Evonik SURFYNOL465 and Evonik DYNOL 604 or Evonik DYNOL 607.
A preparation method of water-based white color paste comprises the following steps:
(1) dissolving a dispersing agent, water and an auxiliary agent, adding a white pigment, and mixing to prepare a pre-dispersion liquid;
(2) and (2) grinding the pre-dispersion liquid prepared in the step (1), filtering, and taking filtrate to obtain the water-based white color paste.
Grinding to an average particle size of 200-300nm in the step (2), and filtering to remove colloid and large-particle-size particles.
The white ink comprises the aqueous white color paste.
Compared with the prior art, the invention has the following beneficial effects:
(1) the main chain of the dispersant has an anchoring structure which is strongly adsorbed with the surface of the white pigment, and can simultaneously carry out high-compatibility strong adsorption on the surface of the pigment; meanwhile, the solvation branched chain structure has good compatibility with water, so that a solvation chain can be smoothly spread to form three-dimensional space obstacle or electrostatic repulsion, and the dispersibility and stability of the color paste can be effectively improved.
(2) According to the invention, by selecting the dispersant and matching with the nano grinding process, the dispersant has a strong adsorption effect on the white pigment, is not easy to fall off and replace, and can effectively reduce the surface energy of the white pigment, the water-based white color paste prepared by using the dispersant has the advantages of no precipitation, good redispersibility, strong stability, no blockage of a spray head, and high whiteness and high shielding rate.
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.
Example 1
Introducing nitrogen into a reaction bottle provided with a condensing reflux device, adding 290g of butanone and 140g of isopropanol serving as solvents, and heating to 70-80 ℃; then, 52g of methyl acrylate, 78g of butyl acrylate, 70g of hydroxyethyl acrylamide and 300g of polyethylene glycol methyl ether methacrylate (M is 2000) serving as a branched macromonomer are mixed to obtain a premixed solution A; then, 60g of butanone and 10g of azobisisobutyronitrile are mixed and stirred until the mixture is dissolved, so as to obtain a premixed solution B; then slowly adding the premixed liquid A and the premixed liquid B into a reaction bottle for reaction; after about 4-7 hours of reaction, the reaction was terminated by detecting that the amount of residual monomer was less than 5%; then 490g of 2-pyrrolidone is added and mixed evenly, butanone and isopropanol are removed after heating to 100 ℃, cooling to room temperature is carried out, deionized water is added until the total mass is 1250g, and SA1 dispersing agent solution with solid content of 40% is obtained; wherein the SA1 dispersant has a molecular weight of about 30000 and comprises the following structural units:
example 2
Introducing nitrogen into a reaction bottle provided with a condensing reflux device, adding 304g of ethyl acetate and 140g of isopropanol serving as solvents, and heating to 70-80 ℃; then, 26g of methyl acrylate, 39g of butyl acrylate, 35g of fumaric acid as a main chain monomer, and 400g of sodium vinylsulfonate as a branched macromonomer and a monofunctional oligomer (M ═ 4000) of methyl methacrylate were mixed to obtain a premix A; then, 48g of ethyl acetate and 8g of azobisisoheptonitrile are mixed and stirred until dissolved, so as to obtain a premixed solution B; then slowly adding the premixed liquid A and the premixed liquid B into a reaction bottle for reaction; after about 4-7 hours of reaction, the reaction was terminated by detecting that the amount of residual monomer was less than 5%; then adding 484g of 2-pyrrolidone, uniformly mixing, heating to 100 ℃ to remove ethyl acetate and isopropanol, cooling to room temperature, adjusting the pH value to 9, and adding deionized water until the total mass is 1250g to obtain an SA2 dispersing agent solution with the solid content of 40%; wherein the SA2 dispersant has a molecular weight of about 15000 and comprises the following structural units:
example 3
Taking a dispersing agent SA 11000 g, adding 490g of 2-pyrrolidone, uniformly mixing, heating to 100 ℃ to remove butanone and isopropanol, cooling to room temperature, and then adding deionized water until the total mass is 1250g to obtain a dispersing agent solution with the solid content of 40%; mixing 180g of dispersant solution with 320g of deionized water, and stirring until the dispersant solution is completely dissolved to obtain an aqueous pre-solution; then mixing 500g of white pigment R-706 with the aqueous pre-solution, and stirring to completely wet the white pigment to obtain an aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove colloid and large-particle-size particles to obtain the stably dispersed water-based white color paste.
Example 4
Adding 484g of 2-pyrrolidone into a dispersing agent SA 21000 g, uniformly mixing, heating to 100 ℃ to remove ethyl acetate and isopropanol, cooling to room temperature, adding deionized water until the total mass is 1250g, and adjusting the pH value to 9 to obtain a dispersing agent solution with the solid content of 40%; mixing 150g of dispersant solution with 350g of deionized water, and stirring until the dispersant solution is completely dissolved to obtain an aqueous pre-solution; then 500g of white pigment CR-60-2 is mixed with the aqueous pre-solution, and the mixture is stirred to completely wet the white pigment to obtain aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove colloid and large-particle-size particles to obtain the stably dispersed water-based white color paste.
Example 5
Taking the dispersing agents SA 1400 g and SA 2600 g prepared in the examples 1 and 2, adding 486g of 2-pyrrolidone, uniformly mixing, heating to 100 ℃ to remove ethyl acetate, butanone and isopropanol, cooling to room temperature, then adding deionized water until the total mass is 1250g, and adjusting the pH value to 9 to obtain a dispersing agent solution with the solid content of 40%; mixing 150g of the dispersant solution with 320g of deionized water, and stirring until the dispersant solution is completely dissolved to obtain an aqueous pre-solution; then mixing 500g of white pigment RODI with the aqueous pre-solution, and stirring to completely wet the white pigment to obtain an aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove colloid and large-particle-size particles to obtain the stably dispersed water-based white color paste.
Example 6
Adding 484g of 2-pyrrolidone into a dispersing agent SA 21000 g, uniformly mixing, heating to 100 ℃ to remove ethyl acetate and isopropanol, cooling to room temperature, adding deionized water until the total mass is 1250g, and adjusting the pH value to 9 to obtain a dispersing agent solution with the solid content of 40%; mixing 500g of dispersant solution with 700g of deionized water, and stirring until the dispersant solution is completely dissolved to obtain an aqueous pre-solution; then 700g of white pigment CR-60-2 is mixed with the aqueous pre-solution, and the mixture is stirred to completely wet the white pigment to obtain aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove colloid and large-particle-size particles to obtain the stably dispersed water-based white color paste.
Example 7
Adding 484g of 2-pyrrolidone into a dispersing agent SA 21000 g, uniformly mixing, heating to 100 ℃ to remove ethyl acetate and isopropanol, cooling to room temperature, adding deionized water until the total mass is 1250g, and adjusting the pH value to 9 to obtain a dispersing agent solution with the solid content of 40%; mixing 150g of dispersant solution with 400g of deionized water, and stirring until the dispersant solution is completely dissolved to obtain an aqueous pre-solution; then mixing 250g of white pigment CR-60-2 with the aqueous pre-solution, and stirring to completely wet the white pigment to obtain an aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove colloid and large-particle-size particles to obtain the stably dispersed water-based white color paste.
Comparative example 1
Mixing 100g of nonylphenol polyoxyethylene ether dispersant with the molecular weight Mw of 800 and 400g of deionized water, and stirring until the mixture is completely dissolved to obtain an aqueous pre-solution; then mixing 500g of white pigment R-706 with the aqueous pre-solution, and stirring to completely wet the white pigment to obtain an aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove the colloid and the large-particle-size particles, and preparing the water-based white color paste.
Comparative example 2
Mixing 72g of nonylphenol polyoxyethylene ether dispersant with the molecular weight Mw of 800 and 320g of deionized water, and stirring until the mixture is completely dissolved to obtain an aqueous pre-solution; then mixing 500g of white pigment R-706 with the aqueous pre-solution, and stirring to completely wet the white pigment to obtain an aqueous pre-dispersion liquid; introducing the aqueous pre-dispersion liquid into a sand mill for grinding until the average particle size is 200-300 nm; filtering to remove the colloid and the large-particle-size particles, and preparing the water-based white color paste.
Product effectiveness testing
Preparing white ink: the aqueous white color pastes prepared in examples 3-5 and comparative examples 1-2 were diluted 5 times with 15% glycerol aqueous solution to obtain white ink.
And (3) performance testing: particle size, viscosity, surface tension, filterability and aging tests were performed on the white ink.
(1) Particle size was measured using a Marvin (Malvern) Nano S90 nanosize particle sizer in British.
(2) Viscosity was measured using a Wells cone and plate viscometer, Bohler fly (Brookfield).
(3) Surface tension test, using a Japanese synergy (KYOWA) CBVP type surface tension meter.
(4) And (4) testing the filterability, namely filtering by adopting a glass fiber filter membrane with the aperture of 1.0 mu m and a PP filter membrane with the aperture of 0.45 mu m.
(5) And (4) testing the stability, namely aging for 7 days at the high temperature of 60 ℃, and testing the particle size, viscosity and filterability after aging.
The test results are shown in table 1, wherein the QC evaluation criteria: the average particle size is 200-300nm, the viscosity is 2-6cp, the surface tension is 35-45dyn/cm, and the filtering property is less than 15 min/kg; and (3) aging for 7 days at the high temperature of 60 ℃ in a stability test, wherein the particle size change is less than 10%, the surface tension change is less than 5%, the viscosity change is less than 10%, the filterability is less than 15min/kg, and the product is qualified, otherwise, the product is unqualified.
TABLE 1 stability of white inks obtained in examples 3 to 7 and comparative example 1
As can be seen from the test results in Table 1: the dispersing agent provided by the invention has strong dispersing effect, and the white color paste and the white ink prepared by using the dispersing agent have good stability, and the particle size, viscosity, surface tension and filterability are still good in stability after aging for 7 days.
Claims (9)
1. The water-based white color paste is characterized by comprising the following components: a white pigment, water and a dispersant; the dispersant consists of a main chain and a branch chain, wherein the main chain comprises a hydrophobic group structural unit represented by a formula (I), and the main chain also comprises a base-containing structural unit represented by a formula (II) or/and a carboxyl-containing structural unit represented by a formula (III); the side chain comprises a structural unit containing a hydrophilic group represented by formula (IV) or formula (V), wherein x is 10-220, and y is 2-30; z is 3-60; the molecular weight of the dispersant is 5000-100000;
2. the aqueous white paste according to claim 1, wherein the molecular weight of the branched chain of the dispersant is 500-10000.
3. The aqueous white paste according to claim 1, wherein the preparation method of the dispersant comprises the following steps:
(1) mixing a main chain monomer and a branched chain monomer to obtain a premix;
(2) heating a solvent and an initiator under an inert atmosphere, dissolving, adding the premix prepared in the step (1), and reacting to obtain the dispersing agent;
the main chain monomer in the step (1) is at least one selected from methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hydroxymethyl acrylamide, hydroxyethyl acrylamide, hydroxypropyl acrylamide, maleic acid and fumaric acid; the branched monomer is selected from at least one of sodium vinyl sulfonate and methyl methacrylate monofunctional oligomer or polyethylene glycol methyl ether methacrylate;
in the step (1), the initiator is an azo-containing compound.
4. The water-based white paste according to claim 3, wherein the reaction temperature in the step (2) is 50-100 ℃ and the reaction time is 4-7 hours.
5. The aqueous white color paste according to any one of claims 1 to 4, wherein the aqueous white color paste further comprises an auxiliary agent, and the auxiliary agent comprises the following components in parts by weight:
6. the aqueous white paste according to claim 5, wherein the white pigment comprises at least one of zinc oxide, barium sulfate, calcium carbonate or titanium dioxide.
7. The aqueous white paste according to claim 5, wherein the auxiliary agent comprises a co-solvent and/or a wetting agent.
8. The water-based white paste according to claim 7, wherein the auxiliary agent comprises a cosolvent and a wetting agent, and the mass ratio of the cosolvent to the wetting agent is (3-10): 1.
9. A white ink comprising the aqueous white paste according to any one of claims 1 to 8.
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| CN100439408C (en) * | 2005-12-31 | 2008-12-03 | 浙江大学 | Nano grade polymer micro-emulsion for ink-jet printing and method for preparing the same |
| US20090192261A1 (en) * | 2008-01-25 | 2009-07-30 | Waifong Liew Anton | Ink jet inks having improved corrosion resistance |
| CN101812163B (en) * | 2010-04-19 | 2011-09-14 | 河北铁园科技发展有限公司 | Method for preparing polycarboxylic acid retarding water reducer |
| CN102558935B (en) * | 2011-12-15 | 2013-10-09 | 洛阳理工学院 | Stabilizing agent for lime colloid paint |
| WO2014091923A1 (en) * | 2012-12-11 | 2014-06-19 | 大日精化工業株式会社 | Pigment dispersant, production method for pigment dispersant, and pigment dispersion liquid |
| CN103045002B (en) * | 2013-01-17 | 2014-04-09 | 长沙华润涂料有限公司 | Method for preparing environment-friendly and efficient water-borne coating dispersing agent |
| CN103406067B (en) * | 2013-07-31 | 2016-03-16 | 中科院广州化学有限公司 | -kind of polycarboxylate dispersant and preparation method thereof and application |
| CN104005240B (en) * | 2014-05-21 | 2016-08-17 | 浙江理工大学 | A kind of white concentrator and its production and use |
| FR3030530B1 (en) * | 2014-12-23 | 2017-01-27 | Arkema France | COPOLYMER DIBLOC WATER SOLUBLE |
| TWI691558B (en) * | 2018-05-08 | 2020-04-21 | 臺灣永光化學工業股份有限公司 | Ultra-high whiteness aqueous white color paste for digital textile printing ink and an ink composition using the same |
| CN109930403B (en) * | 2019-03-19 | 2022-01-04 | 上海贝通色彩科技有限公司 | Printing paste composition for textiles |
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