CN115850565A - Water-based fluorine-containing acrylic acid copolymer emulsion for antibacterial ink and preparation method and application thereof - Google Patents
Water-based fluorine-containing acrylic acid copolymer emulsion for antibacterial ink and preparation method and application thereof Download PDFInfo
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- CN115850565A CN115850565A CN202211444393.6A CN202211444393A CN115850565A CN 115850565 A CN115850565 A CN 115850565A CN 202211444393 A CN202211444393 A CN 202211444393A CN 115850565 A CN115850565 A CN 115850565A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 73
- 239000011737 fluorine Substances 0.000 title claims abstract description 73
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000000839 emulsion Substances 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229920002126 Acrylic acid copolymer Polymers 0.000 title claims abstract description 23
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 74
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 238000000034 method Methods 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 11
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 229920006243 acrylic copolymer Polymers 0.000 claims description 9
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 claims description 8
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 7
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 5
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 239000001593 sorbitan monooleate Substances 0.000 claims description 4
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 4
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 4
- 244000005700 microbiome Species 0.000 abstract description 4
- 150000001253 acrylic acids Chemical class 0.000 abstract description 2
- 230000001580 bacterial effect Effects 0.000 abstract description 2
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- 239000011162 core material Substances 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 17
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 238000007790 scraping Methods 0.000 description 8
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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Abstract
The invention discloses an aqueous fluorine-containing acrylic acid copolymer emulsion for antibacterial ink, a preparation method and application thereof, wherein the emulsion is prepared from the following raw materials in parts by weight: 60-70 parts of functional monomer, 30-40 parts of acrylic monomer, 10-20 parts of fluorine-containing monomer, 1-2 parts of first nonionic emulsifier, 1-2 parts of second nonionic emulsifier, 1-2 parts of viscosity regulator, 0.5-1 part of initiator and 20-25 parts of water. The fluorine-containing monomer is a core material of the water-based antibacterial ink and is matched with various acrylic acids for use, the acrylic acid is coated on the fluorine-containing monomer in a microscopic manner through an emulsification process, the fluorine-containing monomer is attached to the surface of paper through acrylic esters, the oxidability of fluoride ions is high, and general bacterial microorganisms cannot move in a medium with strong oxidability, so that the antibacterial and bacteriostatic effects are achieved.
Description
Technical Field
The invention belongs to the technical field of water-based ink, and particularly relates to water-based fluorine-containing acrylic acid copolymer emulsion for antibacterial ink, and a preparation method and application thereof.
Background
The ink is an important substance for forming graphic and text information in the printing process, and is generally a uniform mixture with certain flowing property and adhesive property formed by mixing substances such as color bodies, binders, fillers, additives and the like through a certain process. The traditional ink is gradually eliminated due to the problems of harmful solvent content, overproof VOC, easy environmental pollution and the like, the traditional oil-based ink is gradually replaced by the water-based ink along with the enhancement of the environmental awareness of people, but various additives added in the water-based ink are not easy to resist and inhibit bacteria, bacteria and various microorganisms are easily generated after printing, and potential harm is brought to the health of a human body and the use environment. Therefore, water-based inks having antibacterial properties have been a focus of attention.
Currently, antibacterial agents used in antibacterial inks mainly include inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent mainly comprises metal ion components and an inorganic carrier, but the application of the inorganic antibacterial agent in the ink has some problems, such as poor compatibility of the antibacterial material and the ink components, uneven dispersion in an ink system, easy generation of precipitate and long-time flowing state; most of the organic antibacterial agents are insoluble in water, have poor compatibility with water-based ink, and are sensitive to light and temperature. Therefore, a water-based ink which has high-efficiency antibacterial performance, good dispersibility, difficult precipitation and migration and no toxic or side effect on a human body is needed.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a water-based fluorine-containing acrylic acid copolymer emulsion for antibacterial ink, and a preparation method and application thereof.
According to one aspect of the invention, the invention provides a water-based fluorine-containing acrylic acid copolymer emulsion, which is prepared from the following raw materials in parts by weight: 60-70 parts of functional monomer, 30-40 parts of acrylic monomer, 10-20 parts of fluorine-containing monomer, 1-2 parts of first nonionic emulsifier, 1-2 parts of second nonionic emulsifier, 1-2 parts of viscosity regulator, 0.5-1 part of initiator and 20-25 parts of water;
the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene;
the fluorine-containing monomer comprises heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane;
the acrylic monomer includes methacrylic acid, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate.
In some embodiments of the present invention, the mass ratio of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate is (30-40): (25-35): (20-30): (15-20). Methacrylic acid is matched with methyl methacrylate and ethyl methacrylate to wrap a fluorine-containing monomer for reaction and then is subjected to a connecting action to form a fluorine-containing monomer-acrylate compound, and because a part of acrylate chemical bonds are opened, acrylic acid needs to be replenished again for connection to form a macromolecular group with a certain molecular weight. If the amount of the methacrylic acid is too small, a molecular group with a certain molecular weight cannot be effectively produced, the molecular weight of the fluorine-containing monomer, namely the acrylate compound, is reduced, the boiling point is reduced, and more waste liquid is generated; if the amount of the methacrylic acid is too much, the molecular weight of the fluorine-containing monomer, namely the acrylate compound is too large, so that molecular agglomeration is caused, large particles are easy to generate, and the product quality is reduced. If the acrylic ester is unreasonable in collocation, self-crosslinking is easy to occur, so that the fluorine-containing monomer cannot be well connected with an acrylic ester polymerization system, the crosslinking proportion with the fluorine-containing monomer is small, the material cannot be completely utilized, waste is caused, and therefore the proportion of the acrylic ester monomers is strictly controlled, the later reaction can be controlled, and an expected product can be obtained.
In some embodiments of the invention, the lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene are in a mass ratio of (30-40): (10-20): (10-20): (5-10): (2-5). Lauryl methacrylate can effectively provide a three-dimensional space frame structure after emulsion is solidified, meanwhile, lauryl methacrylate contains a long chain, the rigidity of acrylic monomers can be regulated, the toughness of ink is enhanced, frames formed by other acrylic ester connecting fluorine monomers are poorer in weather resistance than the space frames formed by lauryl methacrylate, however, if the dosage of lauryl methacrylate is too much, the rigidity can be enhanced, irregular crystals can be easily generated on a paperboard, if the dosage is too little, the formed space frames are less, the space frame structure cannot be effectively provided, or the generated structure is a loose structure, a large-area structure is not generated, and the performance of ink is further influenced. The dodecafluoroheptyl methacrylate is an oil-soluble surfactant, the surface tension of acrylic acid is mainly increased, and the effect of the dodecafluoroheptyl methacrylate is more obvious than that of a water-soluble surfactant.
In some embodiments of the invention, the mass ratio of heptadecafluorodecyltrimethoxysilane to heptadecafluorodecyltriethoxysilane is (65-75): (25-35).
In some embodiments of the invention, the viscosity modifier is selected from at least one of ethanol, isopropanol, or glycerol.
In some embodiments of the invention, the viscosity modifier is prepared from (45-50): (40-45): 10 of ethanol, isopropanol and glycerol. The ethanol has the effects of improving the leveling property and reducing the surface tension of the aqueous solution, and if the ethanol is used in too small amount, the leveling property is poor, the surface tension is too large, the surface cannot be completely spread when the paper is used, the agglomeration is easy to generate, and the use is not facilitated; if the amount of the ethanol is too much, the leveling property is strong, the surface tension is too small, the permeability is strong, the ethanol can easily permeate the bottom of paper, and other components staying on the surface are less, so that waste is caused. The isopropanol has the function of adjusting surface tension, and the problem that after part of ethanol is evaporated, the surface tension of the solution suddenly rises to cause that the diffusion speed suddenly drops during laying and leveling, so that the tail end of part of the solution is agglomerated can be avoided because the boiling point of the ethanol is lower than that of the isopropanol, the evaporation point is lower, and the boiling point of the isopropanol is higher; if the dosage of the isopropanol is too small, the solution cannot be effectively paved after part of ethanol is evaporated, and the diffusion speed is reduced; if the dosage of the isopropanol is too much, the solution permeability is stronger, the ink staying on the surface of the paper is less, and the waste is easily caused. The glycerol has the function of reducing the evaporation capacity of the solution in a certain area, so that water in the solution can be effectively paved on paper in a certain time, and the solution has a certain reaction time on the paper; if the consumption of the glycerol is too small, the evaporation amount of water in the solution is increased, and other materials on the paper have insufficient reaction time, so that the material waste is caused; if the consumption of the glycerol is too much, the evaporation capacity of water in the solution is reduced, the humidity on the paper is too high, the drying time of the paper is long, the drying energy consumption is high, and the production benefit is low.
In some embodiments of the invention, the first non-ionic emulsifier is selected from one or both of sorbitan monooleate or sucrose fatty acid ester.
In some preferred embodiments of the present invention, the first nonionic emulsifier is prepared by mixing, in mass ratio (40-50): (50-60) sorbitan monooleate and sucrose fatty acid ester. Sorbitan monooleate is used as a fluorine-containing monomer for primary emulsification in a solution with the compounding temperature of 45-50 ℃ and is used as a chemical bond linking emulsifying and wrapping emulsifier, and sucrose fatty acid ester is used as a fluorine-containing monomer for post-emulsification or partial incomplete emulsification for emulsifying and wrapping after the compounding temperature of 50-55 ℃. The two emulsifiers are used because a plurality of acrylic monomers are used and the emulsification efficiency is different at a specific temperature, and the use of the two emulsifiers can increase the emulsification efficiency.
In some embodiments of the present invention, the second nonionic emulsifier is selected from one or both of sodium lauryl sulfate or fatty alcohol polyoxyethylene ether.
In some embodiments of the invention, the second non-ionic emulsifier is prepared from (30-40): (60-70) sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether.
In some embodiments of the invention, the initiator is ammonium persulfate.
The invention also provides a preparation method of the aqueous fluorine-containing acrylic acid copolymer emulsion, which comprises the following steps:
s1: mixing and dispersing a functional monomer, a first nonionic emulsifier and a viscosity regulator to obtain a first pre-emulsion; mixing and dispersing an acrylic monomer, a fluorine-containing monomer, a second non-ionic emulsifier, an initiator and water to obtain a second pre-emulsion;
s2: and under the heating condition, dropwise adding the first pre-emulsion into the second pre-emulsion, carrying out heat preservation reaction after dropwise adding is finished, cooling after the reaction is finished, and then adjusting the alkalinity to 7.5-8.0 to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
In some embodiments of the present invention, in step S1, the temperature at which the functional monomer, the first nonionic emulsifier, and the viscosity modifier are mixed and dispersed is 45 to 55 ℃.
In some embodiments of the present invention, in step S1, the temperature at which the acrylic monomer, the fluorine-containing monomer, the second non-ionic emulsifier, the initiator and the water are mixed and dispersed is 35 to 45 ℃.
In some embodiments of the present invention, in step S2, an alkaline regulator is used for regulating the alkalinity, and the alkaline regulator is ammonia water with a mass concentration of 28% to 35%.
In some embodiments of the invention, the temperature of the heating in step S2 is 60 to 65 ℃.
In some embodiments of the present invention, in step S2, the dropping time is 1.5 to 2.0 hours.
In some embodiments of the invention, the aqueous fluoroacrylic copolymer emulsion has a viscosity of from 500 to 700mPa · s and a molecular weight of from 1000 to 1500.
The invention also provides application of the water-based fluorine-containing acrylic acid copolymer emulsion in printing ink.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
in the aqueous fluorine-containing acrylic acid copolymer emulsion, water is a disperse phase, the fluorine-containing monomer is a core material of the aqueous antibacterial ink and is used as a main medium for resisting and inhibiting bacteria, various acrylic acids are matched for use, the acrylic acid is coated on the surface of paper microscopically through an emulsification process, the fluorine-containing monomer is attached to the surface of the paper through acrylate, the oxidizing property of fluorine ions is high, and common bacterial microorganisms cannot move in a medium with strong oxidizing property, so that the effects of resisting and inhibiting bacteria are achieved. The surface area of the antibacterial ink is increased during production and use, the antibacterial and bacteriostatic area of the antibacterial ink can be enlarged, and the problem of instability of an emulsion system caused by evaporation of water in a solution can be effectively solved by adding the alcohol viscosity regulator, and the problem of uneven solidification caused by sudden increase of the tiled surface area can be reduced.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic drawing of a draw down test.
Reference numerals: 1. scraping sample paper; 2. printing ink to be detected; 3. standard ink; 4. black cross-road; 5. a thick ink layer.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares the water-based fluorine-containing acrylic acid copolymer emulsion by the following specific processes:
(1) Adding 65 parts by weight of functional monomer and 1.5 parts by weight of first nonionic emulsifier into a reaction kettle for preliminary emulsification, adding 2 parts by weight of viscosity regulator, mixing, heating, sealing and dispersing at 45-55 ℃ for 1 hour to prepare a first pre-emulsion; wherein the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene in a mass ratio of 35 to 15;
(2) Adding 1.5 parts by weight of a second nonionic emulsifier, 35 parts by weight of an acrylic monomer, 15 parts by weight of a fluorine-containing monomer and 0.5 part by weight of ammonium persulfate into a reaction kettle, mixing and dispersing at 35-45 ℃ for 1 hour to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersion to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate in a mass ratio of 7: 1, the fluorine-containing monomer consists of heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane in a mass ratio of 7:3;
(3) Preparation of aqueous fluorine-containing acrylic copolymer emulsion: heating to 60-65 ℃ under the stirring state of the reaction kettle in the step (2), slowly adding the first pre-emulsion, wherein the dropwise adding time is 1.5-2h, after the dropwise adding is finished, keeping the temperature for reaction for 1 h, and simultaneously reducing the air pressure to 0.5MPa (the air pressure reduction can reduce bubbles generated during the stirring of the emulsion reaction and partial bubbles generated during the acrylic polymerization reaction, the air pressure is reduced to 0.5MPa, and the heat preservation mainly controls the molecular chain length structure of the acrylic polymerization reaction, if the molecular chain is too long, fluorine-containing monomers are easily and completely wrapped, the antibacterial performance is influenced, the molecular chain structure is too short, the surface area of a molecular net after the reaction can be reduced, the generated space structure is not firm), after the reaction is finished, keeping the air pressure at 0.5MPa, cooling to 45 ℃, adjusting the pH value to 7.7 by using ammonia water, and discharging to obtain the aqueous fluorine-containing acrylic copolymer emulsion.
Comparative example 1
The comparative example prepares a water-based fluorine-containing acrylic acid copolymer emulsion, and is different from the example 1 in that heptadecafluorodecyltriethoxysilane is not added into a fluorine-containing monomer, and the specific process comprises the following steps:
(1) Adding 65 parts by weight of functional monomer and 1.5 parts by weight of first nonionic emulsifier into a reaction kettle for preliminary emulsification, adding 2 parts by weight of viscosity regulator, mixing, heating, sealing and dispersing at 45-55 ℃ for 1 hour to prepare a first pre-emulsion; wherein the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene in a mass ratio of 35 to 15;
(2) Adding 1.5 parts by weight of second non-ionic emulsifier, 35 parts by weight of acrylic monomer, 15 parts by weight of fluorine-containing monomer and 0.5 part by weight of ammonium persulfate into a reaction kettle, mixing and dispersing at 35-45 ℃ for 1 hour to obtain white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersion to prepare second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate in a mass ratio of 7: 1, the fluorine-containing monomer is heptadecafluorodecyltrimethoxysilane;
(3) Preparation of aqueous fluorine-containing acrylic copolymer emulsion: heating to 60-65 ℃ under the stirring state of the reaction kettle in the step (2), slowly adding the first pre-emulsion, wherein the dropwise adding time is 1.5-2h, after the dropwise adding is finished, keeping the temperature for reaction for 1 h, simultaneously reducing the air pressure to 0.5MPa, after the reaction is finished, keeping the air pressure to 0.5MPa, cooling to 45 ℃, adjusting the pH value to 7.7 by using ammonia water, and discharging to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
Comparative example 2
The comparative example prepares a water-based fluorine-containing acrylic acid copolymer emulsion, and is different from the example 1 in that heptadecafluorodecyltrimethoxysilane is not added into a fluorine-containing monomer, and the specific process is as follows:
(1) Adding 65 parts by weight of functional monomer and 1.5 parts by weight of first nonionic emulsifier into a reaction kettle for preliminary emulsification, adding 2 parts by weight of viscosity regulator, mixing, heating, sealing and dispersing at 45-55 ℃ for 1 hour to prepare a first pre-emulsion; wherein the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene in a mass ratio of 35 to 15;
(2) Adding 1.5 parts by weight of a second nonionic emulsifier, 35 parts by weight of an acrylic monomer, 15 parts by weight of a fluorine-containing monomer and 0.5 part by weight of ammonium persulfate into a reaction kettle, mixing and dispersing at 35-45 ℃ for 1 hour to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersion to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate in a mass ratio of 7: 1, wherein the fluorine-containing monomer is heptadecafluorodecyltriethoxysilane;
(3) Preparation of water-based fluorine-containing acrylic acid copolymer emulsion: heating to 60-65 ℃ under the stirring state of the reaction kettle in the step (2), slowly adding the first pre-emulsion, wherein the dropwise adding time is 1.5-2h, after the dropwise adding is finished, keeping the temperature for reaction for 1 h, simultaneously reducing the air pressure to 0.5MPa, after the reaction is finished, keeping the air pressure to 0.5MPa, cooling to 45 ℃, adjusting the pH value to 7.7 by using ammonia water, and discharging to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
Comparative example 3
The comparative example prepares a water-based fluorine-containing acrylic acid copolymer emulsion, and is different from the example 1 in that no fluorine-containing monomer is added, and the specific process comprises the following steps:
(1) Adding 65 parts by weight of functional monomer and 1.5 parts by weight of first nonionic emulsifier into a reaction kettle for preliminary emulsification, adding 2 parts by weight of viscosity regulator, mixing, heating, sealing and dispersing at 45-55 ℃ for 1 hour to prepare a first pre-emulsion; wherein the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene in a mass ratio of 35 to 15;
(2) Adding 1.5 parts by weight of a second nonionic emulsifier, 35 parts by weight of an acrylic monomer and 0.5 part by weight of ammonium persulfate into a reaction kettle, mixing and dispersing at 35-45 ℃ for 1 hour to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersion to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate in a mass ratio of 7: 1, sodium dodecyl sulfate and fatty alcohol-polyoxyethylene ether;
(3) Preparation of aqueous fluorine-containing acrylic copolymer emulsion: heating to 60-65 ℃ under the stirring state of the reaction kettle in the step (2), slowly adding the first pre-emulsion, wherein the dropwise adding time is 1.5-2h, after the dropwise adding is finished, keeping the temperature for reaction for 1 h, simultaneously reducing the air pressure to 0.5MPa, after the reaction is finished, keeping the air pressure to 0.5MPa, cooling to 45 ℃, adjusting the pH value to 7.7 by using ammonia water, and discharging to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
Test example 1
The sample paper is coated with the example 1 and the comparative examples 1 to 3 respectively, the sample paper is placed in a heating oven to evaporate the moisture and accelerate the curing, then the sample paper is placed in a shady and cool sunlight-free irradiation room, a shady and cool sunlight-irradiation outdoor and constant-temperature and constant-humidity equipment respectively for 15 days, 30 days and 120 days according to GB/T21866-2008, and the microbial growth condition of the sample paper is detected, and the results are shown in Table 1.
TABLE 1
As can be seen from the above table, example 1 has excellent antimicrobial properties in indoor, outdoor and equipment compared to comparative examples 1 to 3. Wherein, the comparative example 1 and the comparative example 2 are the antibacterial cases of the single fluorine-containing monomer, the antibacterial performance is still not as good as that of the mixed fluorine-containing monomer in the example 1, and the mixed fluorine-containing monomer has better antimicrobial performance than the single fluorine-containing monomer. Comparative example 3 has a certain antibacterial property at the beginning due to the small amount of the antimicrobial property contained in the other component materials, but the antibacterial property is remarkably reduced after being left for a long time. It should be noted that the fluorine-containing monomers of the examples and comparative examples are relatively stable for a period of time in the weakly alkaline liquid of the formulation after being encapsulated and emulsified by the acrylic, and the acrylic after curing is just used as an encapsulation frame to cover the surface of the paper and disperse the fluorine-containing monomers, and microscopically the fluorine-containing monomers are embedded in the frame linked by each acrylic.
Test example 2
Example 1, comparative example 2 and comparative example 3 were compared by using a yellow ink as a standard ink in consideration of the antibacterial property of the ink according to GB/T13217.1-2020 ink color and tinting strength test method.
And (4) diluting the ink to be detected and the standard sample ink respectively by using quantitative standard yellow ink.
1. 2 g of standard yellow ink and 20 g of ink to be measured are weighed by a weighing bottle on an analytical balance, the example 1, the comparative example 2 and the comparative example 3 are weighed by the same method, and the materials are respectively and fully stirred uniformly by an ink adjusting knife.
2. Referring to fig. 1, about 0.5 g of the standard ink is applied to the upper left of the paper, and about 0.5 g of the ink to be tested is applied to the upper right of the paper, which are adjacent but not connected.
3. And (3) placing a scraping blade above the coated ink sample, enabling the main body part of the scraping blade to form a 90-degree angle with the sample scraping paper, scraping the ink on the sample scraping paper into a thin layer from top to bottom with force, and reducing the force when the ink is scraped to 2/3 of the black cross road to enable the inner side angle of the scraping blade to be approximate to a 25-degree angle, so that the ink is coated on the paper into a thicker ink layer.
And observing whether the surface color and the ink color of the ink to be detected are consistent with those of the standard sample ink, and if not, changing the using amount of the standard ink until the surface color and the ink color of the ink to be detected are consistent with those of the standard sample ink.
And (3) after scraping, using a heating oven to cure the printing ink, drying for 20 seconds at 120 ℃, after the coating is cured, soaking tap water, respectively placing the coating indoors, observing whether the coating generates white points or black point mildew points (the black mildew points are generated after part of the antibacterial printing ink is separated from the paper due to insufficient adhesive force and the paper has no antibacterial property) outdoors and equipment.
TABLE 2
As can be seen from the above table, example 1 has superior adhesion performance in indoor, outdoor and equipment, compared to comparative examples 1-3. According to the specific embodiment 1, a certain amount of space structures are formed after various acrylates are cured, under the condition that the same amount of acrylates are used, the antibacterial performance of the whole formula is reduced due to inconsistent use amount and proportion of fluorine-containing monomers, and the adhesion force of the acrylates on paper is damaged by the propagation of microorganisms on the paper, so that a certain amount of ink adhesion force is reduced, and the paper falls off to form white spots.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The water-based fluorine-containing acrylic acid copolymer emulsion is characterized by being prepared from the following raw materials in parts by weight: 60-70 parts of functional monomer, 30-40 parts of acrylic monomer, 10-20 parts of fluorine-containing monomer, 1-2 parts of first nonionic emulsifier, 1-2 parts of second nonionic emulsifier, 1-2 parts of viscosity regulator, 0.5-1 part of initiator and 20-25 parts of water;
the functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoro heptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene;
the fluorine-containing monomer comprises heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane;
the acrylic monomer includes methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate.
2. The aqueous fluorine-containing acrylic copolymer emulsion according to claim 1, wherein the mass ratio of the methacrylic acid to the methyl methacrylate to the ethyl ethacrylate is (30-40): (25-35): (20-30): (15-20).
3. The aqueous fluorine-containing acrylic copolymer emulsion according to claim 1, wherein the mass ratio of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluoro-n-octyl methacrylate and styrene is (30-40): (10-20): (10-20): (5-10): (2-5).
4. The aqueous fluorine-containing acrylic copolymer emulsion according to claim 1, wherein the mass ratio of heptadecafluorodecyltrimethoxysilane to heptadecafluorodecyltriethoxysilane is (65-75): (25-35).
5. The aqueous fluorine-containing acrylic copolymer emulsion according to claim 1, wherein the viscosity modifier is at least one selected from the group consisting of ethanol, isopropanol and glycerol.
6. The aqueous fluorine-containing acrylic acid copolymer emulsion according to claim 5, wherein the viscosity modifier is prepared by mixing (45-50): (40-45): 10 of ethanol, isopropanol and glycerol.
7. The aqueous fluorine-containing acrylic acid copolymer emulsion according to claim 1, wherein the first nonionic emulsifier is one or two selected from sorbitan monooleate or sucrose fatty acid ester.
8. The aqueous fluorine-containing acrylic copolymer emulsion of claim 1, wherein the second non-ionic emulsifier is one or two selected from sodium lauryl sulfate and fatty alcohol-polyoxyethylene ether.
9. The method for preparing the aqueous fluorine-containing acrylic acid copolymer emulsion according to any one of claims 1 to 8, comprising the steps of:
s1: mixing and dispersing a functional monomer, a first nonionic emulsifier and a viscosity regulator to obtain a first pre-emulsion; mixing and dispersing an acrylic monomer, a fluorine-containing monomer, a second non-ionic emulsifier, an initiator and water to obtain a second pre-emulsion;
s2: and (3) under the heating condition, dropwise adding the first pre-emulsion into the second pre-emulsion, carrying out heat preservation reaction after dropwise adding is finished, cooling after the reaction is finished, and then adjusting the alkalinity to 7.5-8.0 to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
10. Use of the aqueous fluoroacrylic acid copolymer emulsion of any one of claims 1 to 8 in inks.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896113A (en) * | 2006-06-15 | 2007-01-17 | 南开大学 | Printing fluorinated acrylic ester self-crosslinked emulsion and its preparation |
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN103626911A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | Hydrophobic organic and inorganic acrylate polymer emulsion with high silicon content and preparation method and application thereof |
| CN105949374A (en) * | 2016-07-02 | 2016-09-21 | 安徽中恩化工有限公司 | Preparation method of modified silicone-acrylic water-in-water emulsion for multicolor paint |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896113A (en) * | 2006-06-15 | 2007-01-17 | 南开大学 | Printing fluorinated acrylic ester self-crosslinked emulsion and its preparation |
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN103626911A (en) * | 2013-10-14 | 2014-03-12 | 杭州师范大学 | Hydrophobic organic and inorganic acrylate polymer emulsion with high silicon content and preparation method and application thereof |
| CN105949374A (en) * | 2016-07-02 | 2016-09-21 | 安徽中恩化工有限公司 | Preparation method of modified silicone-acrylic water-in-water emulsion for multicolor paint |
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