Bottle brush-shaped amphiphilic block copolymer and preparation method and application thereof
阅读说明：本技术 一种瓶刷状两亲性嵌段共聚物及其制备方法与应用 (Bottle brush-shaped amphiphilic block copolymer and preparation method and application thereof ) 是由 王彦丹 朱健 潘向强 倪端颖 朱立俊 李坤 高鸣昶 于 2021-09-18 设计创作，主要内容包括：本发明涉及一种瓶刷状两亲性嵌段共聚物及其制备方法与应用,涉及聚合物制备技术领域。本发明所述的瓶刷状两亲性嵌段共聚物用于瓶刷状乳化剂；所述瓶刷状乳化剂由1-3质量份瓶刷状两亲性嵌段共聚物和1-5质量份复配乳化剂组成,利用瓶刷状大分子共聚物具有比小分子和常见钳段共聚物更低的迁移率,减缓和阻碍分散相的兼并,实现稳定性的提升,进而解决乳化墨水长期稳定及保存问题,制造一种可靠及性能优越的乳化墨水。(The invention relates to a bottle brush-shaped amphiphilic block copolymer, a preparation method and application thereof, and relates to the technical field of polymer preparation. The bottle brush-shaped amphiphilic block copolymer is used for a bottle brush-shaped emulsifier; the bottle-brush-shaped emulsifier is composed of 1-3 parts by mass of bottle-brush-shaped amphiphilic block copolymer and 1-5 parts by mass of compound emulsifier, and the bottle-brush-shaped macromolecular copolymer has lower mobility than small molecules and common clamp segment copolymers, so that the compatibility of dispersed phases is slowed down and hindered, the improvement of stability is realized, the problems of long-term stability and storage of the emulsion ink are solved, and the reliable emulsion ink with excellent performance is manufactured.)
1. A bottle brush-shaped amphiphilic block copolymer is characterized in that the structure is shown as the formula (I):
wherein M is1Is styrene, methyl acrylate, ethyl acrylate, polybutyl acrylate or random copolymer thereof; m2Is a vinyl ether; m3Is acrylic acid, hydroxyethyl acrylate, polyethylene glycol or random copolymer thereof;
n is an integer of 10 to 60; m is an integer of 10 to 100; o is an integer of 5 to 50.
2. The bottle brush amphiphilic block copolymer of claim 1, wherein the HLB value of the bottle brush amphiphilic block copolymer is in the range of 2 to 7.5.
3. The bottle brush amphiphilic block copolymer of claim 1, wherein the bottle brush amphiphilic block copolymer is selected from the group consisting of:
4. a preparation method of a bottle brush-shaped amphiphilic block copolymer is characterized by comprising the following steps:
dissolving a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) in a solvent, and performing an irradiation reaction under an ultraviolet light source to obtain the bottle brush-shaped amphiphilic block copolymer shown in the formula (I);
wherein the structural formulas of the formulas (I), (II) and (III) are shown as follows,
wherein M is1Is styrene, methyl acrylate, ethyl acrylate, polybutyl acrylate or random copolymer thereof; m2Is a vinyl ether; m3Is acrylic acid, hydroxyethyl acrylate, polyethylene glycol or random copolymer thereof;
n is an integer of 10 to 60; m is an integer of 10 to 100; o is an integer of 5 to 50.
5. The method for preparing a bottle brush-shaped amphiphilic block copolymer according to claim 4, wherein the molar ratio of the compound having the structure of formula (II) to the compound having the structure of formula (III) is 1: 0.8-1.2.
6. A bottle brush-shaped emulsifier is characterized in that: the bottle brush-shaped emulsifier consists of 1-3 parts by mass of the bottle brush-shaped amphiphilic block copolymer as claimed in any one of claims 1-3 and 1-5 parts by mass of a compound emulsifier.
7. The bottle-brush emulsifier according to claim 6, wherein the compound emulsifier is two or more selected from polyoxyethylene ether of nonylphenol, polyoxyethylene ether of octylphenol, span, glycerin fatty acid, and polyoxyethylene ether of fatty acid methyl ester.
8. The emulsified ink is characterized in that the emulsified ink comprises, by mass, 5.0-10.0 parts of pigment, 30.0-50.0 parts of organic solvent, 20-35 parts of water, 2.5-4.5 parts of aqueous polymer resin, 2.0-4.5 parts of oil-soluble polymer resin, 2.0-5.0 parts of bottle-brush-shaped emulsifier and 1.0-2.5 parts of auxiliary agent; wherein the bottle brush emulsifier is the bottle brush emulsifier of claim 6 or 7.
9. The emulsion ink according to claim 8, wherein the aqueous polymer resin is one or more of a polyacrylic resin, a polyethylene glycol resin, a polyvinylpyrrolidone resin, and a polyvinylpyridine resin.
10. The emulsion ink according to claim 8, wherein the oil-soluble polymer resin is a polyethylene glycol butyral and/or an aldehyde ketone resin.
Technical Field
The invention relates to the technical field of polymer preparation, in particular to a bottle brush-shaped amphiphilic block copolymer and a preparation method and application thereof.
Background
Ink is a key product affecting writing performance. With the development of society, the modern society also puts higher and higher requirements on ink. The existing inks are mainly classified into aqueous inks and oil inks according to the solvents used in the inks. Compared with water-based inks, oil-based inks have a higher market share because of the use of dyes as colorants, which are more stable and have better writing properties than water-based inks using pigment colorants. Particularly in western countries, the market share of oil-based inks is as high as 80% or more due to writing habits and preferences. However, the conventional oily ink has a high viscosity (typically, about 8000 cps), which limits the smoothness of writing. Meanwhile, the oil-based ink uses an organic solvent such as benzyl alcohol, and thus has a certain problem of environmental pollution.
In order to solve the problems, emulsion ink with smoother writing performance appears in markets at home and abroad. The emulsion ink is formed by adding a part of water and an emulsifier to a conventional oil-based ink to form an emulsion system. On one hand, the cost is reduced and the environmental protection property of the ink is improved due to the addition of the water; on the other hand, through the construction of the aqueous emulsion system, the viscosity of the ink can be greatly reduced, and the writing smoothness is improved. The typical viscosity of the emulsified ink is less than 1000 centipoise. However, since the emulsification system is a thermodynamically unstable system. Improving the stability of emulsified inks has been a key in this field.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problem of low stability of the emulsion ink in the prior art.
In order to solve the technical problems, the invention provides a bottle brush-shaped amphiphilic block copolymer and a preparation method and application thereof. The bottle brush-shaped amphiphilic block copolymer is used for a bottle brush-shaped emulsifier, and the stability is improved by utilizing the special structure of the block copolymer. Further solves the problems of long-term stability and preservation of the emulsion ink, and produces the emulsion ink with reliability and excellent performance.
The first purpose of the invention is to provide a bottle brush-shaped amphiphilic block copolymer, which has a structure shown in a formula (I):
wherein M is1Is styrene, methyl acrylate, ethyl acrylate, polybutyl acrylate or random copolymer thereof; m2Is a vinyl ether; m3Is acrylic acid, hydroxyethyl acrylate, polyethylene glycol or random copolymer thereof;
n is an integer of 10 to 60; m is an integer of 10 to 100; o is an integer of 5 to 50.
Further, the HLB value of the bottle-brush amphiphilic block copolymer ranges from 2 to 7.5.
Further, the ratio of the degrees of polymerization of the hydrophilic chain segment and the lipophilic chain segment of the bottle-brush-shaped amphiphilic block copolymer is 5-10: 1, the polymerization degree of the hydrophilic side chain is 20-100.
Further, the hydrophilic side chain segment is one or more of polyethylene glycol, polyacrylic acid and polyhydroxyethyl acrylate; the lipophilic chain segment is one or more of polystyrene, polymethyl acrylate, polyethyl acrylate and polybutyl acrylate.
Further, the bottle-brush amphiphilic block copolymer is selected from the following compounds:
the second purpose of the invention is to provide a preparation method of the bottle brush-shaped amphiphilic block copolymer, which comprises the following steps:
dissolving a compound with a structure shown in a formula (II) and a compound with a structure shown in a formula (III) in a solvent, and performing an irradiation reaction under an ultraviolet light source to obtain the bottle brush-shaped amphiphilic block copolymer shown in the formula (I);
wherein the structural formulas of the formulas (I), (II) and (III) are shown as follows,
wherein M is1Is styrene, methyl acrylate, ethyl acrylate, polybutyl acrylate or random copolymer thereof; m2Is a vinyl ether; m3Is acrylic acid, hydroxyethyl acrylate, polyethylene glycol or random copolymer thereof;
n is an integer of 10 to 60; m is an integer of 10 to 100; o is an integer of 5 to 50.
Further, the molar ratio of the compound with the structure of formula (II) to the compound with the structure of formula (III) is 1: 0.8-1.2.
Further, the irradiation is carried out for 5-24h at 20-40 ℃.
Further, the solvent is benzene, toluene or tetrahydrofuran.
The third purpose of the invention is to provide a bottle brush-shaped emulsifier, which consists of 1-3 parts by mass of bottle brush-shaped amphiphilic block copolymer and 1-5 parts by mass of compound emulsifier.
Further, the compound emulsifier is two or more of polyoxyethylene ether of nonyl phenol, polyoxyethylene ether of octyl phenol, span, glycerin fatty acid and polyoxyethylene ether of fatty acid methyl ester.
The fourth purpose of the invention is to provide an emulsion ink, wherein the raw materials of the emulsion ink comprise, by mass, 5.0-10.0 parts of pigment, 30.0-50.0 parts of organic solvent, 20-35 parts of water, 2.5-4.5 parts of aqueous polymer resin, 2.0-4.5 parts of oil-soluble polymer resin, 2.0-5.0 parts of bottle brush-shaped emulsifier and 1.0-2.5 parts of auxiliary agent.
Further, the aqueous polymer resin is one or more of polyacrylic resin, polyethylene glycol resin, polyvinylpyrrolidone resin and polyvinylpyridine resin.
Further, the oil-soluble polymer resin is polyethylene glycol butyral and/or aldehyde ketone resin.
Further, the pigment is black, red or blue superfine nano pigment, the black nano pigment is selected from swn-w-80111 or C611, and the average particle size of the black nano pigment is less than 50 nm; the red nano pigment is selected from swn-w-31701, R-177SM, R-122SM or 5B-K, and the average particle size of the red nano pigment is less than 55 nm; the blue nano pigment is selected from swn-w-41531, 4G-K or 1513, and has an average particle size of less than 50 nm.
Further, the superfine nano pigment is milled for 24-48h by a mill.
Further, the organic solvent is one or more of alcohols, ethers and esters. Preferably, the organic solvent is one or more of phenethyl alcohol, ethylene glycol butyl ether and ethylene glycol phenyl ether.
Further, the molecular weight of the polyacrylic resin is 2-10 ten thousand.
Further, the polyethylene glycol resin has a molecular weight of 8000 to 2 ten thousand.
Further, the polyvinylpyrrolidone resin has a molecular weight of 2 to 8 ten thousand.
Further, the vinylpyridine resin has a molecular weight of 1.5 to 5 ten thousand.
Furthermore, the adjuvant is benzisothiazolinone.
The fifth purpose of the invention is to provide a preparation method of emulsified ink obtained by using a bottle brush-shaped emulsifier, which comprises the following steps: uniformly mixing a pigment and oil-soluble polymer resin dissolved in an organic solvent, and grinding until the granularity of the pigment reaches D50-30-80 nm to prepare an A phase; dissolving the bottle brush-shaped emulsifier in water, stirring uniformly, adding the aqueous high polymer resin, adding the auxiliary agent, and fully dissolving for more than 24 hours to prepare a phase B; and uniformly stirring and mixing the solution of the phase A and the solution of the phase B to obtain the emulsified ink.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the bottle-brush-shaped emulsifier solves the problem of thermodynamic instability of the traditional emulsifying system, most of the instability is due to the merger of dispersed phase particles dispersed by an emulsion under a storage condition, the merging process is directly related to the migration capacity of a surfactant (emulsifier) on the surface of a dispersed phase, and the merging process of the dispersed phase can be effectively slowed down by reducing the migration rate of the emulsifier. Therefore, the amphiphilic bottle brush-shaped block copolymer is designed to be used as an emulsifier for dispersing the emulsified ink. The bottle brush-shaped macromolecular copolymer has lower mobility than micromolecules and common clamp segment copolymers, and the aim of improving the stability of the ink is fulfilled by combining the slowing and the blocking of a dispersed phase.
(2) The emulsified ink disclosed by the invention is green and nontoxic in raw materials and environment-friendly in process. The produced emulsified ink conforms to GB/T6678-. The emulsified ink of the invention is stable for a long time (the stability is more than 36 months), the finished product of the pen core is marked with a line of more than 300m, the stitch has no obvious phenomena of line breakage and light fading, the water resistance is more than or equal to 3 hours, the light resistance is more than or equal to 72 hours, and the stitch can be kept visible.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a nuclear magnetic representation of PS-b-PVEA and PS-b-PVEA-g-PAA prepared in example 1 of the present invention.
FIG. 2 is a GPC outflow graph of PS-b-PVEA and PS-b-PVEA-g-PAA prepared in example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
A bottle brush-shaped amphiphilic block copolymer and a preparation method thereof comprise the following specific steps:
step 1: preparation of hydrophilic side chains
10.0g of acrylic acid (distilled under reduced pressure before use), 0.2g of isobutyronitrile dithiobenzoate (CPDB) and 0.1g of azobisisobutyronitrile (AIBN, recrystallized from ethanol before use and then dried) were mixed in a reaction flask. Argon was passed through the solution to evacuate oxygen for 20min, and then the reaction flask was closed with a rubber stopper with an inverted mouth. The reaction bottle is put into a constant-temperature bath with constant temperature of 60 ℃ in advance for reaction for 10 h. Subsequently, 10mL of dioxane was added to the reaction mixture, and the mixture was thoroughly and uniformly mixed. 5.0 n-hexylamine is added dropwise into the mixture and stirred for 24h at room temperature. The reaction solution was dropped dropwise into 500mL of petroleum ether. The precipitate was collected by filtration and dried to give a mercapto group-containing polyacrylic acid whose degree of polymerization was measured by gel chromatography to be 48 (using narrow-distribution polystyrene as a standard).
Step 2: preparation of lipophilic chain segment
10.0g of styrene (S), 1.5g of copper bromide (CuBr)2) 1.4g Pentamethyldivinylpentamine (PMDETA), 2.2g vitamin C (VCNa) and 2.2g bromo-amineAdding 2-ethyl propionate (EBiB) into a reaction bottle, mixing uniformly, and introducing argon for 20min to discharge oxygen. The reaction flask was then sealed with a rubber stopper and reacted at 80 ℃ for 24 h. The rubber stopper is opened, 10mL of toluene solvent is added and mixed evenly. The mixed solution was added dropwise to 500mL of methanol, followed by suction filtration and drying to obtain 8.2g of polystyrene (PS-Br), the degree of polymerization of which was determined by gel chromatography to be 20.
5.0g of PS-Br was dissolved in 10mL of dimethyl sulfoxide (DMSO), followed by addition of 2.0g of sodium diselenide and stirring at room temperature for 24 hours. Precipitating in 500mL of methanol, filtering and drying to obtain 5.1g of diselenide functionalized polystyrene PS-Se.
5.0g of PS-Se was dissolved in 10mL of dimethyl sulfoxide (DMSO), and then 2.5g of thionyl chloride (SOCl2) was added thereto, and stirred at room temperature for 12 hours. Precipitating in 500mL of methanol, filtering and drying to obtain 4.9g of chlorine selenium functionalized polystyrene PS-SeCl.
2.5g of PS-SeCl was dissolved in 2.5mL of toluene, and 20.0g of Vinyl Ether Acrylate (VEA) and 1.2g of manganese bromide were added thereto, followed by stirring and reacting at room temperature for 12 hours. The resulting reaction solution was dissolved in 10mL of ethyl acetate and then precipitated in 800mL of methanol to obtain 18g of a block copolymer PS-b-PVEA, the polymerization degree of which was determined by gel chromatography to be 100.
Step 3: preparation of bottle brush-like amphiphilic copolymer
2.0g of the block copolymer PS-b-PVEA was dissolved in 10mL of toluene, and 8.0g of polyacrylic acid prepared in Step1 was added thereto, followed by stirring and irradiation with a high-pressure mercury lamp at room temperature for 12 hours. Precipitating in toluene, collecting the copolymer, and drying to obtain bottle brush-shaped amphiphilic block copolymer PS-b-PVEA-g-PAA 8.9 g.
Example 2
By a method similar to that in example 1, the bottle-brush-like amphiphilic block copolymer PS-b-PVEA-gpheea was prepared by replacing the acrylic monomer with hydroxyethyl acrylate, and its structural formula was as follows:
example 3
By using a method similar to that in example 1, the bottle-brush-like amphiphilic block copolymer PMA-b-PVEA-gpheea was prepared by replacing styrene monomer with methyl acrylate and acrylic monomer with hydroxyethyl acrylate, and its structural formula was as follows:
application example 1
Use of the bottle brush amphiphilic block copolymer prepared in example 1 in an emulsion ink:
7.0g of black nanopigment swn-w-80111, 45.0g of ethylene glycol phenyl ether, 30.0g of water, 4.0g of aqueous polyacrylic resin (molecular weight 5 ten thousand), 4.5g of aldehyde ketone resin (molecular weight 8000), 4.5g of bottle brush type emulsifier (bottle brush type amphiphilic block copolymer 2g, fatty acid methyl ester polyoxyethylene ether 0.5g, polyoxyethylene ether of nonylphenol 2g), 1.5g of auxiliary agent benzisothiazolinone, and the preparation method is as follows:
firstly, 45.0g of ethylene glycol phenyl ether is added into a dispersion pot, 4.5g of aldehyde ketone resin is added while stirring, the stirring speed is controlled to be 200r/min and is about 0.5h, so that the aldehyde ketone resin is fully dissolved, finally, 7.0g of black nano pigment swn-w-80111 is added, and the mixture is fully stirred and mixed for 1.5 h. Then carrying out superfine grinding, adjusting the rotating speed to 1000r/min, and grinding for 35h until the size of the pigment particle size reaches D50-60 nm, and stopping grinding to obtain the A-phase solution. And adding water of 30.0g into water-based polyacrylic resin of 4.0g, stirring for dissolving, adding bottle brush-shaped emulsifier of 4.5g and benzisothiazolinone of 1.5g as an auxiliary, continuously stirring for 24h, and uniformly mixing to obtain phase B.
And adding the phase B solution into the phase A, fully stirring and discharging to obtain the black emulsified ink.
Application example 2
Use of the bottle brush amphiphilic block copolymer prepared in example 1 in an emulsion ink:
9.0g of red nanopigment swn-w-31701, 45.0g of benzyl alcohol, 30.0g of water, 4.0g of aqueous polyethylene glycol resin (molecular weight 4 ten thousand), 4.5g of aldehyde ketone resin (molecular weight 6000), 5.0g of bottle brush-like emulsifier (bottle brush-like amphiphilic block copolymer 2.5g, glycerin fatty acid 1.5g, polyoxyethylene ether of nonylphenol 1g), 1.5g of auxiliary agent benzisothiazolinone, and the preparation method is as follows:
firstly, 45.0g of benzyl alcohol is added into a dispersion pot, 4.5g of aldehyde ketone resin is added while stirring, the stirring speed is controlled to be 200r/min and is about 0.5 hour, so that the aldehyde ketone resin is fully dissolved, and finally 7.0g of red nano pigment swn-w-31701 is added, and the mixture is fully stirred and mixed for 1.5 hours. Then carrying out superfine grinding, adjusting the rotating speed to 1000r/min, and grinding for 35h until the size of the pigment particle size reaches D50-50 nm, and stopping grinding to obtain the A-phase solution. And adding water of 30.0g into water-based polyethylene glycol resin of 4.0g, stirring for dissolving, adding bottle brush-shaped emulsifier of 5.0g and benzisothiazolinone of 1.5g as an auxiliary, continuously stirring for 24h, and uniformly mixing to obtain phase B.
And adding the phase B solution into the phase A, fully stirring and discharging to obtain the red emulsified ink.
Application example 3
Use of the bottle brush amphiphilic block copolymer prepared in example 1 in an emulsion ink:
10g of blue nano pigment swn-w-41531, 45.0g of ethylene glycol phenyl ether, 30.0g of water, 3.5g of water-based polyvinyl pyridine resin (molecular weight is 4.8 ten thousand), 4.5g of polyethylene glycol butyral (molecular weight is 6 ten thousand, acetalization degree is 85%), 4.5g of bottle brush-shaped emulsifier (bottle brush-shaped amphiphilic block copolymer 1g, glycerol fatty acid 2g and span 1.5g) and 1g of benzisothiazolinone, and the preparation method is as follows:
firstly, 45.0g of ethylene glycol phenyl ether is added into a dispersion pot, 4.5g of polyethylene glycol butyral is added while stirring, the stirring speed is controlled to be 200r/min and is about 0.5 hour, so that the polyethylene glycol phenyl ether is fully dissolved, and finally 10.0g of blue nano pigment swn-w-41531 is added, and the mixture is fully stirred and mixed for 1.5 hours. And then carrying out superfine grinding, adjusting the rotating speed to 1000r/min, and grinding for 35h until the size of the pigment particle size reaches D50-50 nm, and stopping grinding to obtain the A-phase solution. And adding water 30.0g into water-based polyvinyl pyridine resin 3.5g, stirring for dissolving, adding bottle brush-shaped emulsifier 4.5g and benzisothiazolinone 1.0g as adjuvant, stirring for 24h, and mixing to obtain phase B.
And adding the phase B solution into the phase A, fully stirring and discharging to obtain the blue emulsified ink.
Application comparative example 1
An emulsion ink comprises the following components in parts by weight:
7.0g of carbon black color paste, 45.0g of ethylene glycol phenyl ether, 30.0g of water, 4.0g of water-based polyacrylic resin (molecular weight is 5 ten thousand), 4.5g of aldehyde ketone resin (molecular weight is 8000), 8.5g of emulsifier span and 0.5g of auxiliary agent benzisothiazolinone. The preparation method comprises the following steps:
firstly, 45.0g of ethylene glycol phenyl ether is added into a dispersion pot, 4.5g of aldehyde ketone resin is added while stirring, the stirring speed is controlled to be 200r/min and is about 0.5 hour, so that the aldehyde ketone resin is fully dissolved, and finally 7.0g of carbon black color paste is added, and the mixture is fully stirred and mixed for 1.5 hours. To obtain A phase solution. And adding water of 30.0g into water-based polyacrylic resin of 4.0g, stirring for dissolving, adding emulsifier span of 8.5g and benzisothiazolinone of 0.5g as an auxiliary agent, continuously stirring for 24h, and uniformly mixing to obtain a phase B.
And adding the phase B solution into the phase A, fully stirring and discharging to obtain the black emulsified ink.
Test example 1
The PS-b-PVEA prepared at Step2 of example 1 and the PS-b-PVEA-g-PAA material prepared at Step3 were subjected to the nuclear magnetic characterization and GPC outflow curve tests.
The nuclear magnetic characterization results are shown in FIG. 1, and the nuclear magnetic spectrum of the block copolymer before grafting the acrylic copolymer has a signal peak corresponding to the proton on the double bond in the range of 5.5-6.5 ppm. The signal peak in this range disappeared after grafting, indicating that upon grafting, the double bond in the precursor and the thiol group at the end of the polyacrylic acid underwent an addition reaction, and the polyacrylic acid was successfully grafted into the precursor.
GPC outflow curves As shown in FIG. 2, the molecular weight of the copolymer increased significantly by the grafting reaction, from 13100g/mol to 82200g/mol prior to grafting. The GPC outflow curve of the post-grafting sample showed no responsive signal peaks at the pre-grafting copolymer precursor position, indicating success and efficiency of the grafting process.
Test example 2
The emulsified inks prepared in application examples 1 to 3 and the marking ink prepared in application comparative example 1 were subjected to corresponding performance tests according to the ink industry standards, respectively. Adhesion strength with reference to the national standard QB/T2777-2015 aqueous marking ink adhesion test method, "1" represents not erased, "2" represents one-fourth erased, "3" represents half erased, "4" represents three-quarters erased, and "5" represents full erase.
The stability test environment is respectively selected to be high temperature (50 ℃), normal temperature (25 ℃) and low temperature (0 ℃) for carrying out particle size distribution test and D50 distribution test, the test time is 5 days, and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the emulsion inks of application examples 1 to 3 have stable performance after corresponding tests, and after the emulsion inks are stored for 5 days at 0 to 50 ℃, the particle size distribution and the D50 distribution of the pigments in the inks do not change obviously, which indicates that the pigments do not agglomerate under the above conditions, and the emulsion inks of the invention have stable properties. The emulsion ink prepared by the application example of the invention is fine and smooth in writing, green and environment-friendly, and is a high-stability emulsion ink with good performance. After the emulsified ink of the comparative example 1 is stored for 5 days at 0-50 ℃, the particle size distribution and the D50 distribution of the pigment in the ink are obviously changed, the change range of the particle size distribution and the D50 distribution is more than 60%, and the viscosity is also obviously changed, wherein the change range exceeds 17%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.