CN115850565B - 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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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 57
- 239000011737 fluorine Substances 0.000 title claims abstract description 57
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000839 emulsion Substances 0.000 title claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229920002126 Acrylic acid copolymer Polymers 0.000 title claims abstract description 17
- 230000000844 anti-bacterial effect Effects 0.000 title abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 65
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 fluorine ions Chemical class 0.000 claims abstract description 21
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 20
- 239000012875 nonionic emulsifier Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000976 ink Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 229920006243 acrylic copolymer Polymers 0.000 claims description 14
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 13
- 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 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 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
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 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
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000001593 sorbitan monooleate Substances 0.000 claims description 8
- 229940035049 sorbitan monooleate Drugs 0.000 claims description 8
- 235000011069 sorbitan monooleate Nutrition 0.000 claims description 8
- 239000005720 sucrose Substances 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 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
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 10
- 238000004945 emulsification Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 230000001580 bacterial effect Effects 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
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- 239000000123 paper Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 238000007790 scraping Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
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- 238000009835 boiling Methods 0.000 description 2
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- 238000004132 cross linking Methods 0.000 description 2
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Abstract
The invention discloses an aqueous fluorine-containing acrylic acid copolymer emulsion for antibacterial ink, and a preparation method and application thereof, wherein the aqueous fluorine-containing acrylic acid copolymer 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 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 acid for use, the acrylic acid is coated on the fluorine-containing monomer in a microcosmic way through an emulsification process, the fluorine-containing monomer is attached to the surface of paper through acrylic esters, the oxidizing property of fluorine ions is high, and general bacterial microorganisms cannot move in a medium with strong oxidizing property, so that the antibacterial effect is achieved.
Description
Technical Field
The invention belongs to the technical field of water-based ink, and particularly relates to a 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 information in a printing process, and is generally a uniform mixture with certain flowability and adhesion property, wherein the uniform mixture is formed by mixing substances such as a color body, a binder, a filler, an additive and the like through a certain process. The traditional ink is gradually eliminated due to the problems of harmful solvents, exceeding VOC (volatile organic compounds), easy environmental pollution and the like, and along with the enhancement of environmental awareness of people, the water-based ink gradually replaces the traditional oily ink, but various auxiliary agents are added into the water-based ink, so that the water-based ink is not easy to be antibacterial and bacteriostatic, and can easily produce bacterial and various microbial pollution after printing, thereby bringing potential harm to human health and use environment. Therefore, water-based inks having antibacterial properties have become a focus of attention for research and development.
Currently, antibacterial agents used in antibacterial inks mainly include inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent mainly comprises a metal ion component and an inorganic carrier, but the inorganic antibacterial agent has some problems in the application of the inorganic antibacterial agent in the ink, such as poor compatibility of antibacterial materials and ink components, uneven dispersion in an ink system, easy generation of precipitation and long-time flowing; most of organic antibacterial agents are poorly soluble in water, have poor compatibility with water-based ink, and are sensitive to light and temperature. Therefore, a water-based ink with high-efficiency antibacterial performance, good dispersibility, difficult precipitation and migration and no toxic or side effect on human bodies is needed.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides an aqueous fluorine-containing acrylic acid copolymer emulsion for antibacterial ink, and a preparation method and application thereof.
According to one aspect of the invention, an aqueous fluorine-containing acrylic copolymer emulsion is provided, 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 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, tridecyl-n-octyl methacrylate and styrene;
The fluorine-containing monomer comprises heptadecafluorodecyl trimethoxysilane and heptadecafluorodecyl triethoxysilane;
The acrylic monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate.
In some embodiments of the 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 a large molecular group which is formed by connecting methyl methacrylate and ethyl methacrylate which are matched with each other to wrap a fluorine-containing monomer for reaction and then form a fluorine-containing monomer-acrylic ester compound, and the acrylic acid needs to be supplemented again for connection because part of acrylic ester chemical bonds are opened. If the using amount of methacrylic acid is too small, molecular groups with certain molecular weight cannot be effectively produced, the molecular weight of fluorine-containing monomers-acrylic ester compounds is reduced, the boiling point is reduced, and more waste liquid is caused; if the using amount of the methacrylic acid is too large, the molecular weight of the formed fluorine-containing monomer-acrylic ester compound is too large, so that molecular aggregation is caused, large particles are easy to generate, and the quality of the product is reduced. If the acrylic ester is unreasonably matched and self-crosslinking is easy to occur, the fluorine-containing monomer cannot be well connected with an acrylic ester polymerization system, and the crosslinking proportion of the fluorine-containing monomer is smaller, so that the material cannot be completely utilized to cause waste, and therefore, the follow-up reaction can be controlled by strictly controlling the proportion of the acrylic ester monomer, and the expected product is obtained.
In some embodiments of the invention, the weight ratio of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl-fluoro-n-octyl methacrylate, and styrene is (30-40): (10-20): (10-20): (5-10): (2-5). The lauryl methacrylate can effectively provide a three-dimensional space frame structure after emulsion is solidified, meanwhile, the lauryl methacrylate contains long chains, the rigidity of an acrylic monomer can be regulated, the toughness of the ink is enhanced, frames formed by other acrylic ester connecting fluorine monomers are poor in weather resistance compared with space frames formed by the lauryl methacrylate, but if the consumption of the lauryl methacrylate is excessive, the rigidity is enhanced, irregular crystals are easy to generate on a paperboard, if the consumption of the lauryl methacrylate is too small, 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 the ink is further influenced. The dodecafluoroheptyl methacrylate is an oil-soluble surfactant, mainly increases the surface tension of acrylic acid, and has more obvious effect than the water-soluble surfactant.
In some embodiments of the invention, the mass ratio of heptadecafluorodecyl trimethoxysilane to heptadecafluorodecyl triethoxysilane 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 consists of (45-50) by mass ratio: (40-45): 10, ethanol, isopropanol and glycerol. The ethanol has the effects of increasing leveling property and reducing the surface tension of the aqueous solution, if the consumption of the ethanol is too small, the leveling property is poor, the surface tension is too large, the surface can not be completely spread when the paper is used on paper, agglomeration is easy to generate, and the paper is unfavorable to use; if the ethanol is used too much, the leveling property is stronger, the surface tension is too small, the permeability is stronger, the paper is easy to permeate to the bottom of the paper, and other components remained on the surface are less, so that waste is caused. The isopropanol has the function of regulating the surface tension, and can avoid the problem that the diffusion speed is suddenly reduced when the solution is spread due to the sudden rise of the surface tension of part of the solution after the ethanol is evaporated, so that the tail ends of part of the solution are agglomerated because the boiling point of the ethanol is lower than that of the isopropanol and the evaporation point of the isopropanol is higher; if the dosage of isopropanol is too small, after part of ethanol is evaporated, the solution can not be effectively paved, and the diffusion speed is reduced; if the dosage of isopropanol is too much, the solution permeability is stronger, the ink remained on the surface of the paper is less, and waste is easy to cause. 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 glycerol consumption is too small, the evaporation amount of water in the solution can be increased, and other materials on the paper have insufficient reaction time, so that the materials are wasted; if the consumption of glycerol is too much, the evaporation capacity of water in the solution can be reduced, the humidity on paper is too high, the paper drying time is long, the drying energy consumption is higher, and the production benefit is low.
In some embodiments of the invention, the first nonionic 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 consists of (40-50) by mass ratio: (50-60) sorbitan monooleate and sucrose fatty acid ester. The sorbitan monooleate is prepared by pre-emulsifying fluorine-containing monomers in a solution with the compounding temperature of 45-50 ℃ to serve as a chemical bond linking emulsifying and coating emulsifier, and the sucrose fatty acid ester is prepared by post-emulsifying with the compounding temperature of 50-55 ℃ to serve as a post-emulsifying or partially incompletely emulsifying fluorine-containing monomer to carry out emulsifying and coating. 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 two emulsifiers can increase the emulsification efficiency.
In some embodiments of the invention, the second emulsifier is selected from one or both of sodium dodecyl sulfate or fatty alcohol-polyoxyethylene ether.
In some embodiments of the invention, the second emulsifier consists of (30-40) by mass ratio: (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 the functional monomer, the first nonionic emulsifier and the viscosity regulator to obtain a first pre-emulsion; mixing and dispersing an acrylic monomer, a fluorine-containing monomer, a second 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 the dropwise adding is finished, cooling after the reaction is finished, and regulating 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 45-55 ℃.
In some embodiments of the present invention, in step S1, the acrylic monomer, the fluoromonomer, the second emulsifier is a mixture of initiator and water dispersed at a temperature of 35-45 ℃.
In some embodiments of the present invention, in step S2, the alkalinity is adjusted by using an alkaline regulator, and the alkaline regulator is ammonia water with a mass concentration of 28% -35%.
In some embodiments of the invention, in step S2, the heating temperature is 60-65 ℃.
In some embodiments of the invention, in step S2, the time of the dropping is 1.5-2.0h.
In some embodiments of the invention, the aqueous fluorinated acrylic copolymer emulsion has a viscosity of 500 to 700 mPas and a molecular weight of 1000 to 1500.
The invention also provides application of the aqueous fluorine-containing acrylic acid copolymer emulsion in printing ink.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
In the aqueous fluorine-containing acrylic acid copolymer emulsion, water is a disperse phase, a fluorine-containing monomer is a core material of 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 fluorine-containing monomer on the surface of paper in a microcosmic way through an emulsification process, the fluorine-containing monomer is attached to the surface of the paper through acrylic esters, the oxidizing property of fluorine ions is higher, and general 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 in addition, the problem of unstable emulsion system caused by evaporation of water in the solution can be effectively avoided by adding the alcohol viscosity regulator, and meanwhile, the problem of uneven solidification caused by suddenly increased tiling surface area can be reduced.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic illustration of a scratch paper test.
Reference numerals: 1. scraping sample paper; 2. ink to be measured; 3. standard ink; 4. black crossroad; 5. a thick ink layer.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares the aqueous fluorine-containing acrylic acid copolymer emulsion, which comprises 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 modifier, mixing, heating, sealing and dispersing for 1 hour at 45-55 ℃ to prepare first pre-emulsion; the functional monomer consists of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl fluoride-n-octyl methacrylate and styrene in a mass ratio of 35:14:15:7:4, the first nonionic emulsifier consists of sorbitan monooleate and sucrose fatty acid ester in a mass ratio of 1:1, and the viscosity modifier consists of ethanol, isopropanol and glycerol in a mass ratio of 5:4:1;
(2) Adding 1.5 parts by weight of a second 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 for 1 hour at 35-45 ℃ to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersing to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethylacrylate with the mass ratio of 7:5:4:3, and the second emulsifier consists of the following components with the mass ratio of 0.5:1, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether, wherein the fluorine-containing monomer consists of heptadecafluorodecyl trimethoxy silane and heptadecafluorodecyl triethoxy silane with the mass ratio of 7:3;
(3) Preparing an 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 for 1.5-2h, keeping the temperature for reaction for 1h after the dripping is finished, simultaneously reducing the air pressure to 0.5MPa (the air pressure can reduce the air bubbles generated during the stirring of the emulsification reaction and the air bubbles generated during the polymerization reaction of partial acrylic acid, the air pressure is reduced to 0.5MPa, the heat preservation mainly controls the molecular chain length structure of the acrylic acid polymerization reaction, if the molecular chain is too long, the fluorine-containing monomer is easy to completely wrap, the antibacterial performance is influenced, the molecular chain structure is too short, the area of the molecular net list after the reaction is reduced, the generated space structure is unstable), keeping the air pressure to 0.5MPa after the reaction is finished, cooling to 45 ℃, and then using ammonia water to adjust the pH value to 7.7, so that the water-based fluorine-containing acrylic acid copolymer emulsion can be obtained after discharging.
Comparative example 1
This comparative example produced an aqueous fluorinated acrylic copolymer emulsion differing from example 1 in that heptadecafluorodecyl triethoxysilane was not added to the fluorinated monomer, and the specific procedure was:
(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 modifier, mixing, heating, sealing and dispersing for 1 hour at 45-55 ℃ to prepare first pre-emulsion; the functional monomer consists of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl fluoride-n-octyl methacrylate and styrene in a mass ratio of 35:14:15:7:4, the first nonionic emulsifier consists of sorbitan monooleate and sucrose fatty acid ester in a mass ratio of 1:1, and the viscosity modifier consists of ethanol, isopropanol and glycerol in a mass ratio of 5:4:1;
(2) Adding 1.5 parts by weight of a second 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 for 1 hour at 35-45 ℃ to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersing to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethylacrylate with the mass ratio of 7:5:4:3, and the second emulsifier consists of the following components with the mass ratio of 0.5:1, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether, wherein the fluorine-containing monomer is heptadecafluorodecyl trimethoxy silane;
(3) Preparing an 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 for 1.5-2h, keeping the temperature for 1h after the dripping is finished, simultaneously reducing the pressure to 0.5MPa, keeping the pressure to 0.5MPa after the reaction is finished, cooling to 45 ℃, regulating 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 prepared an aqueous fluorinated acrylic copolymer emulsion, differing from example 1 in that heptadecafluorodecyl trimethoxysilane was not added to the fluorinated monomer, comprising 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 modifier, mixing, heating, sealing and dispersing for 1 hour at 45-55 ℃ to prepare first pre-emulsion; the functional monomer consists of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl fluoride-n-octyl methacrylate and styrene in a mass ratio of 35:14:15:7:4, the first nonionic emulsifier consists of sorbitan monooleate and sucrose fatty acid ester in a mass ratio of 1:1, and the viscosity modifier consists of ethanol, isopropanol and glycerol in a mass ratio of 5:4:1;
(2) Adding 1.5 parts by weight of a second 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 for 1 hour at 35-45 ℃ to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersing to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethylacrylate with the mass ratio of 7:5:4:3, and the second emulsifier consists of the following components with the mass ratio of 0.5:1, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether, wherein the fluorine-containing monomer is heptadecafluorodecyl triethoxysilane;
(3) Preparing an 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 for 1.5-2h, keeping the temperature for 1h after the dripping is finished, simultaneously reducing the pressure to 0.5MPa, keeping the pressure to 0.5MPa after the reaction is finished, cooling to 45 ℃, regulating 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
This comparative example produced an aqueous fluorinated acrylic copolymer emulsion differing from example 1 in that no fluorinated monomer was added, the specific procedure being:
(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 modifier, mixing, heating, sealing and dispersing for 1 hour at 45-55 ℃ to prepare first pre-emulsion; the functional monomer consists of lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl fluoride-n-octyl methacrylate and styrene in a mass ratio of 35:14:15:7:4, the first nonionic emulsifier consists of sorbitan monooleate and sucrose fatty acid ester in a mass ratio of 1:1, and the viscosity modifier consists of ethanol, isopropanol and glycerol in a mass ratio of 5:4:1;
(2) Adding 1.5 parts by weight of a second 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 for 1 hour at the temperature of 35-45 ℃ to obtain a white emulsified viscous opaque liquid, and adding 22 parts by weight of deionized water for dispersing to prepare a second pre-emulsion; wherein the acrylic monomer consists of methacrylic acid, methyl methacrylate, ethyl methacrylate and ethyl ethylacrylate with the mass ratio of 7:5:4:3, and the second emulsifier consists of the following components with the mass ratio of 0.5:1, sodium dodecyl sulfate and fatty alcohol polyoxyethylene ether;
(3) Preparing an 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 for 1.5-2h, keeping the temperature for 1h after the dripping is finished, simultaneously reducing the pressure to 0.5MPa, keeping the pressure to 0.5MPa after the reaction is finished, cooling to 45 ℃, regulating 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
Sample paper was coated with example 1 and comparative examples 1 to 3, and the sample paper was placed in a heating oven to evaporate water and accelerate curing, and then placed in a cool non-sunlight irradiation room, a cool sunlight irradiation room and a constant temperature and humidity apparatus, respectively, and placed for 15 days, 30 days, 120 days with reference to GB/T21866 to 2008, and the microbial growth of the sample paper was 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 the indoor, outdoor and equipment as compared to comparative examples 1-3. Wherein comparative example 1 and comparative example 2 are antibacterial cases where fluoromonomers are used alone, the antibacterial properties thereof are still not as good as those of the case where fluoromonomers are used in combination in example 1, indicating that the use of fluoromonomers in combination has better antibacterial properties than that of fluoromonomers alone. Comparative example 3 has a certain antibacterial property initially due to the small amount of the antimicrobial property material contained in the other component materials, but the decrease in antibacterial property is remarkable after a long-term standing. After the fluoromonomer of each example and comparative example is wrapped and emulsified by acrylic acid, the fluoromonomer is relatively stable for a period of time in the liquid with weak alkalinity, and the acrylic acid after curing is only used as a wrapping frame, covers the surface of paper and disperses the fluoromonomer, and the microscopic fluoromonomer is inlaid in each acrylic acid linked frame.
Test example 2
Example 1, comparative example 2 and comparative example 3 were tested according to the ink color and tinting strength test method of GB/T13217.1-2020, but yellow ink was used as a standard ink for comparison in view of the antibacterial properties of the ink.
And respectively diluting the ink to be measured and the standard sample ink by using quantitative standard yellow ink.
1. On an analytical balance, 2 g of standard yellow ink and 20 g of ink to be measured are weighed by a weighing bottle, example 1, comparative example 2 and comparative example 3 are weighed by the same method, and are respectively and fully and uniformly stirred by an ink regulating knife.
2. Referring to fig. 1, about 0.5 g of the standard ink is coated on the upper left of the scratch paper, and about 0.5 g of the ink to be measured is coated on the upper right of the scratch paper, and the two ink are adjacent but not connected.
3. The doctor blade is arranged above the coated ink sample, so that the main body part of the doctor blade forms an angle of 90 degrees with the sample scraping paper, the ink is scraped into a thin layer on the sample scraping paper from top to bottom by force, and when the ink is scraped to 2/3 of a black transverse path, the force is reduced, the angle of the inner side of the doctor blade is approximately 25 degrees, and the ink is coated into a thicker ink layer on the paper.
Observing whether the surface colors of the ink to be measured and the standard ink are consistent, and if not, changing the dosage of the standard ink until the two scratch samples are consistent.
After sample scraping, the printing ink is cured by using a heating oven, the printing ink is dried for 20 seconds at 120 ℃, after the coating is cured, tap water is soaked, the coating is respectively placed indoors, the coating is observed whether white spots and fading or black spots and mildew spots are generated on the coating by outdoor equipment (the black mildew spots are generated after the part of antibacterial printing ink is separated from paper due to insufficient adhesive force), and the antibacterial property is not generated on the paper).
TABLE 2
As can be seen from the above table, example 1 has excellent adhesion properties in both indoor, outdoor and equipment, as compared to comparative examples 1-3. According to the specific embodiment 1, a certain amount of space structure is formed after the various acrylic esters are solidified, under the condition that the same amount of acrylic esters are used, the antibacterial performance of the whole formula is reduced due to inconsistent dosage and proportion of fluorine-containing monomers, and microorganisms damage the adhesive force of the acrylic esters on paper by propagating on the paper, so that the adhesive force of a certain amount of printing ink 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 one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (6)
1. The aqueous 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 emulsifier, 1-2 parts of viscosity regulator, 0.5-1 part of initiator and 20-25 parts of water; the first nonionic emulsifier is one or two of sorbitan monooleate or sucrose fatty acid ester; the second emulsifier is selected from one or two of sodium dodecyl sulfate or fatty alcohol polyoxyethylene ether;
The functional monomer comprises lauryl methacrylate, glycidyl methacrylate, dodecafluoroheptyl methacrylate, tridecyl methacrylate and styrene, wherein the mass ratio of the lauryl methacrylate to the glycidyl methacrylate to the dodecafluoroheptyl methacrylate to the tridecyl methacrylate to the styrene is (30-40): (10-20): (10-20): (5-10): (2-5);
The fluorine-containing monomer comprises heptadecafluorodecyl trimethoxysilane and heptadecafluorodecyl triethoxysilane;
The acrylic monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; the mass ratio of the methacrylic acid to the methyl methacrylate to the ethyl ethylacrylate is (30-40): (25-35): (20-30): (15-20).
2. The aqueous fluorine-containing acrylic copolymer emulsion according to claim 1, wherein the mass ratio of heptadecafluorodecyl trimethoxysilane to heptadecafluorodecyl triethoxysilane is (65-75): (25-35).
3. The aqueous fluorinated acrylic copolymer emulsion of claim 1, wherein the viscosity modifier is selected from at least one of ethanol, isopropanol, or glycerol.
4. The aqueous fluorinated acrylic copolymer emulsion according to claim 3, wherein the viscosity modifier consists of (45 to 50) by mass: (40-45): 10, ethanol, isopropanol and glycerol.
5. The method for producing an aqueous fluorine-containing acrylic copolymer emulsion according to any one of claims 1 to 4, comprising the steps of:
s1: mixing and dispersing the functional monomer, the first nonionic emulsifier and the viscosity regulator to obtain a first pre-emulsion; mixing and dispersing an acrylic monomer, a fluorine-containing monomer, a second 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 the dropwise adding is finished, cooling after the reaction is finished, and regulating the alkalinity to 7.5-8.0 to obtain the aqueous fluorine-containing acrylic acid copolymer emulsion.
6. Use of the aqueous fluorine-containing acrylic copolymer emulsion according to any one of claims 1 to 4 in inks.
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| 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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| 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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