CN117551382A - Coating material and preparation method thereof - Google Patents
Coating material and preparation method thereof Download PDFInfo
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- CN117551382A CN117551382A CN202410038009.5A CN202410038009A CN117551382A CN 117551382 A CN117551382 A CN 117551382A CN 202410038009 A CN202410038009 A CN 202410038009A CN 117551382 A CN117551382 A CN 117551382A
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- reaction kettle
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- 239000011248 coating agent Substances 0.000 title claims abstract description 122
- 238000000576 coating method Methods 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 66
- 229920001661 Chitosan Polymers 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000008367 deionised water Substances 0.000 claims abstract description 40
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 40
- 239000002270 dispersing agent Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 17
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001225 polyester resin Polymers 0.000 claims abstract description 17
- 239000004645 polyester resin Substances 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002216 antistatic agent Substances 0.000 claims abstract description 13
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims abstract description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 8
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 102
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 239000004005 microsphere Substances 0.000 claims description 58
- 239000002244 precipitate Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 36
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 30
- 230000010355 oscillation Effects 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 22
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 22
- 125000000129 anionic group Chemical group 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 229920002401 polyacrylamide Polymers 0.000 claims description 19
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- 230000006196 deacetylation Effects 0.000 claims description 15
- 238000003381 deacetylation reaction Methods 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 235000010413 sodium alginate Nutrition 0.000 claims description 10
- 229940005550 sodium alginate Drugs 0.000 claims description 10
- 239000000661 sodium alginate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000021523 carboxylation Effects 0.000 claims description 5
- 238000006473 carboxylation reaction Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000003889 chemical engineering Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 abstract description 67
- 239000000853 adhesive Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 6
- 239000002966 varnish Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007723 die pressing method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 cationic polysaccharide Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a coating material and a preparation method thereof, belonging to the technical field of coating materials, wherein the preparation method comprises the following steps: preparing coated particles, preparing a dispersing agent and mixing; mixing, namely mixing water-based acrylic resin, water-based acrylic modified polyester resin, coated particles, a dispersing agent, polyethylene glycol 200 and sodium dodecyl benzene sulfonate, stirring, adding carboxymethyl chitosan, an organosilicon defoamer, isopropanol, a water-based blocked isocyanate crosslinking agent, polyethyleneimine, polyethylene glycol 2000, a water-soluble antistatic agent and deionized water, and continuously stirring; the coating material can reduce the adhesive force of the UV gloss oil and the polyester film, avoid the coating material on the recycled polyester film, improve the smoothness of the back surface of the prepared plasticized-free UV label, avoid influencing the tensile strength, the elastic modulus and the thermal shrinkage rate of the polyester film, and also ensure that the surface of the coated polyester film is not cracked in transverse stretching.
Description
Technical Field
The invention relates to the technical field of coating materials, in particular to a coating material and a preparation method thereof.
Background
The application of Ultraviolet (UV) gloss oil to an optical film of a polyester film is generally related to the anti-reflection, anti-reflection and other optical property improvement of the optical film, and the polyester film is a common transparent plastic film and is widely applied to the production of optical devices, screen protection films, labels and packaging materials, particularly in the production of UV labels, the UV gloss oil and the polyester film are required to be compounded together, so that the purposes of anti-counterfeiting and attractive appearance are achieved.
However, when the UV varnish and the polyester film are compounded, the problem of poor adhesion between the UV varnish and the polyester film exists, and the surface of the polyester film needs to be coated and modified, so that the adhesion between the UV varnish and the polyester film is improved, and meanwhile, the influence of a coating liquid on the haze, the heat shrinkage, the high temperature resistance and the low temperature resistance of the polyester film needs to be avoided.
However, with increasing environmental pollution, the environmental protection requirement on the label is higher and higher, in order to protect the environment and reduce the use of plastics, more and more enterprises start to turn to the production of non-plasticizing UV labels, when the non-plasticizing UV labels are produced, UV varnish and a polyester film are first required to be compounded, and then after the UV varnish is solidified, the solidified UV varnish is peeled from the polyester film, so that new requirements are also provided for coating materials used on the polyester film: firstly, the adhesive force between the polyester film treated by the coating material and the UV gloss oil cannot be too large or too small, so that the uniform coating and the die pressing of the UV gloss oil can be realized, and the UV gloss oil can be easily peeled from the polyester film after being solidified; secondly, in the prior art, the coating material is coated on the surface of the polyester film and then transversely stretched, so that the surface of the polyester film treated by the coating material is not cracked after stretching, and the coating material cannot influence the tensile strength, the elastic modulus and the heat shrinkage rate of the polyester film; thirdly, in order to realize the recycling of the polyester film, the coating can be ensured to be completely combined with the back of the cured UV varnish during the peeling, so that the coating and the UV varnish can be completely peeled from the polyester film.
However, the adhesion between the polyester film treated by the existing coating material and the cured UV gloss oil is large, the separation of the UV gloss oil is difficult, other additives are required to be added into the coating material to reduce the adhesion, so that the adhesion between the coating material and the polyester film is reduced, the coating material is prevented from being carried on the peeled polyester film, but the addition of the additives can influence the film forming property of the aqueous resin in the coating material, so that the smoothness of the back surface of the prepared plasticized UV label is influenced, the cohesive force between the aqueous resin of the coating material is reduced, the surface of the polyester film is easy to crack in transverse stretching, and the tensile strength, the elastic modulus and the thermal shrinkage rate of the polyester film are influenced. Therefore, the development of the coating material can reduce the adhesive force between the UV gloss oil and the polyester film, avoid the coating material on the recycled polyester film, improve the smoothness of the back surface of the prepared plasticizing-free UV label, avoid influencing the tensile strength, the elastic modulus and the heat shrinkage rate of the polyester film, ensure that the surface of the coated polyester film is not cracked in transverse stretching, and have important significance for the development and production of plasticizing-free UV labels.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the coating material and the preparation method thereof, and the prepared coating material can reduce the adhesive force of UV gloss oil and a polyester film, avoid the coating material on the recovered polyester film, improve the smoothness of the back surface of the prepared plasticized-free UV label, avoid influencing the tensile strength, the elastic modulus and the thermal shrinkage rate of the polyester film, and also ensure that the surface of the coated polyester film is not cracked in transverse stretching.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a coating material comprises the following steps: preparing coated particles, preparing a dispersing agent and mixing;
the preparation of the coated particles consists of the following steps: preparing styrene-maleic anhydride copolymer microspheres, and coating for the first time and coating for the second time;
adding styrene, maleic anhydride and butyl formate into a closed reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 65-75 ℃, starting stirring, adding azodiisobutyronitrile, stirring for reaction, centrifuging, cleaning and drying a precipitate to obtain the styrene-maleic anhydride copolymer microsphere;
in the preparation of the styrene-maleic anhydride copolymer microsphere, the mass ratio of styrene to maleic anhydride to butyl formate to azodiisobutyronitrile is 15-16:14-14.5:330-350:0.25-0.3;
the primary coating is carried out by mixing styrene-maleic anhydride copolymer microspheres with deionized water, then carrying out ultrasonic oscillation, and obtaining microsphere dispersion after the ultrasonic oscillation is finished; adding chitosan acetic acid solution into a reaction kettle, controlling the temperature of the reaction kettle to 25-40 ℃, starting stirring, dropwise adding microsphere dispersion liquid into the reaction kettle, continuing stirring after the dropwise adding is finished, centrifuging, finishing the centrifugation, cleaning, and drying the precipitate to obtain microspheres coated once;
in the primary coating, the mass ratio of the styrene-maleic anhydride copolymer microspheres to the deionized water to the chitosan acetic acid solution is 5-5.5:230-250:500-550;
the dropping speed of the microsphere dispersion liquid is 8-10g/min;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8-2%, and the mass fraction of acetic acid is 1.5-1.6%;
the deacetylation degree of the chitosan is 80-85%;
the secondary coating is carried out, after the microspheres subjected to primary coating and deionized water are mixed, ultrasonic oscillation is carried out, and after the ultrasonic oscillation is finished, microsphere dispersion liquid subjected to primary coating is obtained; adding sodium alginate aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 25-40 ℃, starting stirring, dripping microsphere dispersion liquid coated once into the reaction kettle, continuing stirring after dripping, centrifuging, finishing centrifuging, cleaning precipitate, then placing the precipitate into a polyvinylamine aqueous solution, completely soaking the precipitate at 25-40 ℃, filtering, and drying filter residues to obtain coated particles;
in the secondary coating, the mass ratio of the microspheres, deionized water and sodium alginate aqueous solution after primary coating is 5.8-6:230-250:500-550;
the dropping speed of the microsphere dispersion liquid after primary coating is 6-8g/min;
the mass fraction of the sodium alginate aqueous solution is 2-3%;
the mass fraction of the polyvinyl amine aqueous solution is 0.5-0.6%;
adding chitosan acetic acid solution and nano calcium carbonate into a reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, stirring, centrifuging, cleaning the precipitate, then adding the cleaned precipitate and deionized water into the reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, starting stirring, dropwise adding anionic polyacrylamide solution into the reaction kettle, continuing stirring after the dropwise adding, centrifuging, cleaning and drying the precipitate to obtain the dispersing agent;
in the preparation of the dispersing agent, the mass ratio of the chitosan acetic acid solution to the nano calcium carbonate to the deionized water to the anionic polyacrylamide solution is 100-110:10-12:120-150:15-16;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8-2%, and the mass fraction of acetic acid is 1.5-1.6%;
the deacetylation degree of the chitosan is 80-85%;
the particle size of the nano calcium carbonate is 50-100nm;
the mass fraction of the anionic polyacrylamide solution is 0.8-1%;
the molecular weight of the anionic polyacrylamide is 1000-1200 ten thousand, the degree of hydrolysis is 23-27%, and the charge density is 20-30mol%;
the dropping speed of the anionic polyacrylamide solution is 2-2.5g/min;
adding water-based acrylic resin, water-based acrylic modified polyester resin, coated particles, a dispersing agent, polyethylene glycol 200 and sodium dodecyl benzene sulfonate into a reaction kettle, stirring, adding carboxymethyl chitosan, an organosilicon defoamer, isopropanol, water-based blocked isocyanate cross-linking agent, polyethyleneimine, polyethylene glycol 2000, water-soluble antistatic agent and deionized water, and continuously stirring to obtain a coating liquid;
in the mixing process, the mass ratio of the aqueous acrylic resin to the aqueous acrylic modified polyester resin to the coated particles to the dispersing agent to the polyethylene glycol 200 to the sodium dodecyl benzene sulfonate to the carboxymethyl chitosan to the silicone defoamer to the isopropanol to the aqueous blocked isocyanate crosslinking agent to the polyethyleneimine to the polyethylene glycol 2000 to the water soluble antistatic agent to the deionized water is 23-25:35-38:5-6:2-2.5:2-2.5:0.8-1:3-4:3-3.5:2.5-3:2-2.5:2-2.5:1.5-2:1-1.5:45-50;
the solid content of the aqueous acrylic resin is 40-50%, the glass transition temperature is 40-60 ℃, the acid value is 10-15KOH/g, and the hydroxyl value is 35-40KOH/g;
the solid content of the aqueous acrylic modified polyester resin is 50-55%, the glass transition temperature is 15-20 ℃, the acid value is 25-35KOH/g, and the hydroxyl value is 40-50KOH/g;
the deacetylation degree of the carboxymethyl chitosan is 80-85%, and the carboxylation degree is 80-90%;
the manufacturer of the water-soluble antistatic agent is the Mini chemical engineering (Shanghai) limited company, and the model is MI00-10T.
A coating material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the coating material is added with the coating particles and the dispersing agent in the preparation of the coating material, so that the influence of the coating material on the tensile strength, the elastic modulus and the thermal shrinkage rate of the polyester film can be avoided, the transverse tensile strength of the polyester film coated by the coating material is 248-250MPa, the longitudinal tensile strength of the polyester film is 220-221MPa, the transverse elastic modulus is 4831-4847MPa, the longitudinal elastic modulus is 4243-4249MPa, the transverse thermal shrinkage rate is-0.18-0.15%, and the longitudinal thermal shrinkage rate is 1.21-1.22%;
(2) According to the invention, the coated particles and the dispersing agent are added in the preparation of the coating material, so that the surface of the coated polyester film is prevented from cracking in transverse stretching;
(3) According to the invention, the coating particles and the dispersing agent are added in the preparation of the coating material, so that the adhesive force between the UV gloss oil and the polyester film can be reduced, and the adhesive force between the polyester film coated by the coating material and the cured UV gloss oil is 0.9-1.2N/mm;
(4) According to the invention, the coating particles and the dispersing agent are added in the preparation of the coating material, so that the smoothness of the back surface of the prepared plasticized-free UV label can be improved, the static friction coefficient of the back surface of the plasticized-free UV label prepared from the polyester film coated by the coating material is 0.52-0.54, and the dynamic friction coefficient is 0.47-0.48;
(5) According to the invention, the coating material is prevented from being carried on the recycled polyester film by adding the coating particles and the dispersing agent in the preparation of the coating material.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of a coating material specifically comprises the following steps:
1. preparing coated particles:
(1) Preparation of styrene-maleic anhydride copolymer microspheres: adding 15g of styrene, 14g of maleic anhydride and 330g of butyl formate into a closed reaction kettle, sealing the reaction kettle, replacing air in the reaction kettle by using nitrogen, controlling the temperature of the reaction kettle to 65 ℃, controlling the stirring speed to 100rpm, then adding 0.25g of azodiisobutyronitrile, stirring and reacting for 5 hours, centrifuging, controlling the centrifuging speed to 7000rpm, centrifuging for 6 minutes, cleaning a precipitate by using butyl formate for 2 times after centrifuging, and drying at 50 ℃ to obtain styrene-maleic anhydride copolymer microspheres;
(2) Primary coating: mixing 5g of styrene-maleic anhydride copolymer microspheres and 230g of deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20kHz and the time to be 15min, and obtaining microsphere dispersion after the ultrasonic oscillation is finished; adding 500g of chitosan acetic acid solution into a reaction kettle, controlling the temperature of the reaction kettle to 25 ℃, controlling the stirring speed to 100rpm, dropwise adding microsphere dispersion liquid into the reaction kettle, controlling the dripping speed to 8g/min, continuously stirring for 1.5h after the dripping is finished, centrifuging, controlling the centrifuging speed to 7000rpm, controlling the centrifuging time to 6min, cleaning a precipitate by deionized water for 2 times after the centrifuging is finished, and drying at 50 ℃ to obtain microspheres coated once;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8%, and the mass fraction of acetic acid is 1.5%;
the deacetylation degree of the chitosan is 80%;
(3) And (3) secondary coating: mixing 5.8g of microspheres subjected to primary coating and 230g of deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 20kHz and the time to be 15min, and obtaining a microsphere dispersion after primary coating after ultrasonic oscillation is finished; adding 500g of sodium alginate aqueous solution with the mass fraction of 2% into a reaction kettle, controlling the temperature of the reaction kettle to 25 ℃, controlling the stirring speed to 100rpm, dripping the coated microsphere dispersion liquid into the reaction kettle once, controlling the dripping speed to 6g/min, continuing stirring for 1.5h after dripping, centrifuging, controlling the centrifuging speed to 7000rpm, centrifuging for 8min, cleaning the precipitate with deionized water for 2 times after centrifuging, then placing the precipitate into a polyvinylamine aqueous solution with the mass fraction of 0.5%, completely soaking the precipitate for 1h at 25 ℃, filtering, and drying filter residues at 50 ℃ to obtain coated particles;
2. preparing a dispersing agent: adding 100g of chitosan acetic acid solution and 10g of nano calcium carbonate into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 100rpm, stirring for 2 hours, centrifuging, controlling the centrifuging speed to 7000rpm, centrifuging for 10 minutes, cleaning the precipitate by using deionized water for 2 times, adding the cleaned precipitate and 120g of deionized water into the reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 100rpm, dropwise adding 15g of 0.8% anionic polyacrylamide solution into the reaction kettle, controlling the dropwise adding speed to 2g/min, continuing stirring for 1.5 hours after the dropwise adding, centrifuging, controlling the centrifuging speed to 7000rpm, centrifuging for 10 minutes, cleaning the precipitate by using deionized water for 2 times, and drying at 80 ℃ to obtain a dispersing agent;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8%, and the mass fraction of acetic acid is 1.5%;
the deacetylation degree of the chitosan is 80%;
the particle size of the nano calcium carbonate is 50nm;
the molecular weight of the anionic polyacrylamide is 1000 ten thousand, the degree of hydrolysis is 23%, and the charge density is 20mol%;
3. mixing: adding 23g of aqueous acrylic resin, 35g of aqueous acrylic modified polyester resin, 5g of coated particles, 2g of dispersing agent, 2g of polyethylene glycol 200 and 0.8g of sodium dodecyl benzene sulfonate into a reaction kettle, starting stirring and controlling the stirring speed to 500rpm, stirring for 30min, adding 3g of carboxymethyl chitosan, 3g of organosilicon defoamer, 2.5g of isopropanol, 2g of aqueous closed isocyanate crosslinking agent, 2g of polyethyleneimine, 1.5g of polyethylene glycol 2000, 1g of water-soluble antistatic agent and 45g of deionized water, and continuously stirring for 50min to obtain a coating liquid;
the solid content of the aqueous acrylic resin is 40%, the glass transition temperature is 40 ℃, the acid value is 10KOH/g, and the hydroxyl value is 35KOH/g;
the solid content of the aqueous acrylic modified polyester resin is 50%, the glass transition temperature is 15 ℃, the acid value is 25KOH/g, and the hydroxyl value is 40KOH/g;
the deacetylation degree of the carboxymethyl chitosan is 80%, and the carboxylation degree is 80%;
the manufacturer of the water-soluble antistatic agent is the Mini chemical engineering (Shanghai) limited company, and the model is MI00-10T.
Example 2
A preparation method of a coating material specifically comprises the following steps:
1. preparing coated particles:
(1) Preparation of styrene-maleic anhydride copolymer microspheres: 15.5g of styrene, 14.2g of maleic anhydride and 340g of butyl formate are added into a closed reaction kettle, after the reaction kettle is closed, nitrogen is used for replacing air in the reaction kettle, the temperature of the reaction kettle is controlled to 70 ℃, the stirring speed is controlled to 100rpm, then 0.28g of azodiisobutyronitrile is added, after stirring for 5.2h, the reaction kettle is centrifuged, the centrifugation speed is controlled to 8000rpm, the centrifugation time is 7min, after the centrifugation is finished, butyl formate is used for cleaning sediment for 2 times, and the sediment is dried at 55 ℃ to obtain styrene-maleic anhydride copolymer microspheres;
(2) Primary coating: mixing 5.2g of styrene-maleic anhydride copolymer microspheres and 240g of deionized water, and performing ultrasonic oscillation, wherein the frequency of ultrasonic oscillation is controlled to be 30kHz, the time is controlled to be 20min, and microsphere dispersion liquid is obtained after the ultrasonic oscillation is finished; adding 520g of chitosan acetic acid solution into a reaction kettle, controlling the temperature of the reaction kettle to 35 ℃, controlling the stirring speed to 200rpm, dropwise adding microsphere dispersion liquid into the reaction kettle, controlling the dripping speed to 9g/min, continuously stirring for 1.8h after the dripping is finished, centrifuging, controlling the centrifuging speed to 8000rpm, controlling the centrifuging time to 7min, cleaning a precipitate 3 times after centrifuging, and drying at 55 ℃ to obtain microspheres coated once;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.9%, and the mass fraction of acetic acid is 1.5%;
the deacetylation degree of the chitosan is 85%;
(3) And (3) secondary coating: mixing 5.9g of microspheres subjected to primary coating and 240g of deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 25kHz and the time to be 20min, and obtaining microsphere dispersion after primary coating after ultrasonic oscillation is finished; adding 520g of sodium alginate aqueous solution with the mass fraction of 2.5% into a reaction kettle, controlling the temperature of the reaction kettle to 35 ℃, controlling the stirring speed to 200rpm, dripping the coated microsphere dispersion liquid into the reaction kettle once, controlling the dripping speed to 7g/min, continuing stirring for 1.8h after dripping, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 9min, cleaning the precipitate with deionized water for 3 times after centrifuging, then placing the precipitate into a polyvinylamine aqueous solution with the mass fraction of 0.5%, completely soaking for 1.2h at 35 ℃, filtering, and drying filter residues at 55 ℃ to obtain coated particles;
2. preparing a dispersing agent: adding 105g of chitosan acetic acid solution and 11g of nano calcium carbonate into a reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, stirring for 2.2 hours, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 11 minutes, cleaning the precipitate by using deionized water for 2-3 times, adding the cleaned precipitate and 130g of deionized water into the reaction kettle, controlling the temperature of the reaction kettle to 50 ℃, controlling the stirring speed to 200rpm, dropwise adding 15.5g of 0.9% mass fraction anionic polyacrylamide solution into the reaction kettle, controlling the dropwise adding speed to 2.2g/min, continuing stirring for 1.8 hours after the dropwise adding is finished, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 11 minutes, cleaning the precipitate by using deionized water for 3 times, and drying at 85 ℃ to obtain a dispersing agent;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.9%, and the mass fraction of acetic acid is 1.5%;
the deacetylation degree of the chitosan is 85%;
the particle size of the nano calcium carbonate is 80nm;
the molecular weight of the anionic polyacrylamide is 1100 ten thousand, the degree of hydrolysis is 25%, and the charge density is 25mol%;
3. mixing: adding 24g of aqueous acrylic resin, 36g of aqueous acrylic modified polyester resin, 5.5g of coated particles, 2.2g of dispersing agent, 2.2g of polyethylene glycol 200 and 0.9g of sodium dodecyl benzene sulfonate into a reaction kettle, starting stirring, controlling the stirring speed to 600rpm, stirring for 35min, adding 3.5g of carboxymethyl chitosan, 3.2g of organosilicon defoamer, 2.8g of isopropanol, 2.2g of aqueous closed isocyanate crosslinking agent, 2.2g of polyethyleneimine, 1.8g of polyethylene glycol 2000, 1.2g of water-soluble antistatic agent and 48g of deionized water, and continuously stirring for 55min to obtain a coating liquid;
the solid content of the aqueous acrylic resin is 50%, the glass transition temperature is 60 ℃, the acid value is 15KOH/g, and the hydroxyl value is 40KOH/g;
the solid content of the aqueous acrylic modified polyester resin is 55%, the glass transition temperature is 20 ℃, the acid value is 35KOH/g, and the hydroxyl value is 50KOH/g;
the deacetylation degree of the carboxymethyl chitosan is 85%, and the carboxylation degree is 90%;
the manufacturer of the water-soluble antistatic agent is the Mini chemical engineering (Shanghai) limited company, and the model is MI00-10T.
Example 3
A preparation method of a coating material specifically comprises the following steps:
1. preparing coated particles:
(1) Preparation of styrene-maleic anhydride copolymer microspheres: adding 16g of styrene, 14.5g of maleic anhydride and 350g of butyl formate into a closed reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 75 ℃, controlling the stirring speed to 200rpm, then adding 0.3g of azodiisobutyronitrile, stirring for 5.5h, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 8min, cleaning a precipitate 3 times after centrifuging, and drying at 60 ℃ to obtain styrene-maleic anhydride copolymer microspheres;
(2) Primary coating: mixing 5.5g of styrene-maleic anhydride copolymer microspheres and 250g of deionized water, and performing ultrasonic oscillation, wherein the frequency of ultrasonic oscillation is controlled to be 30kHz, the time is 25min, and microsphere dispersion liquid is obtained after the ultrasonic oscillation is finished; adding 550g of chitosan acetic acid solution into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 200rpm, dropwise adding microsphere dispersion liquid into the reaction kettle, controlling the dripping speed to 10g/min, continuously stirring for 2 hours after dripping, centrifuging, controlling the centrifuging speed to 8000rpm, controlling the centrifuging time to 8min, cleaning a precipitate by using deionized water after centrifuging, drying at 60 ℃ to obtain microspheres coated once;
the mass fraction of chitosan in the chitosan acetic acid solution is 2%, and the mass fraction of acetic acid is 1.6%;
the deacetylation degree of the chitosan is 85%;
(3) And (3) secondary coating: mixing 6g of microspheres subjected to primary coating and 250g of deionized water, performing ultrasonic oscillation, controlling the frequency of ultrasonic oscillation to be 30kHz and the time to be 25 minutes, and obtaining microsphere dispersion after primary coating after ultrasonic oscillation is finished; adding 550g of sodium alginate aqueous solution with the mass fraction of 3% into a reaction kettle, controlling the temperature of the reaction kettle to 40 ℃, controlling the stirring speed to 200rpm, dripping the coated microsphere dispersion liquid into the reaction kettle for one time, controlling the dripping speed to 8g/min, continuing stirring for 2 hours after dripping, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 10 minutes, cleaning the precipitate with deionized water for 3 times after centrifuging, then placing the precipitate into a polyvinylamine aqueous solution with the mass fraction of 0.6%, completely soaking for 1.5 hours at 40 ℃, filtering, and drying filter residues at 60 ℃ to obtain coated particles;
2. preparing a dispersing agent: adding 110g of chitosan acetic acid solution and 12g of nano calcium carbonate into a reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 300rpm, stirring for 2.5h, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 12min, cleaning the precipitate by using deionized water for 2-3 times, adding the cleaned precipitate and 150g of deionized water into the reaction kettle, controlling the temperature of the reaction kettle to 60 ℃, controlling the stirring speed to 300rpm, dripping 16g of anionic polyacrylamide solution with the mass fraction of 1% into the reaction kettle, controlling the dripping speed to 2.5g/min, continuing stirring for 2h after the dripping is finished, centrifuging, controlling the centrifuging speed to 8000rpm, centrifuging for 12min, cleaning the precipitate by using deionized water for 3 times, and drying at 90 ℃ to obtain a dispersing agent;
the mass fraction of chitosan in the chitosan acetic acid solution is 2%, and the mass fraction of acetic acid is 1.6%;
the deacetylation degree of the chitosan is 85%;
the particle size of the nano calcium carbonate is 100nm;
the molecular weight of the anionic polyacrylamide is 1200 ten thousand, the degree of hydrolysis is 27%, and the charge density is 30mol%;
3. mixing: adding 25g of aqueous acrylic resin, 38g of aqueous acrylic modified polyester resin, 6g of coated particles, 2.5g of dispersing agent, 2.5g of polyethylene glycol 200 and 1g of sodium dodecyl benzene sulfonate into a reaction kettle, starting stirring, controlling the stirring speed to 700rpm, stirring for 40min, adding 4g of carboxymethyl chitosan, 3.5g of organosilicon antifoaming agent, 3g of isopropanol, 2.5g of aqueous closed isocyanate crosslinking agent, 2.5g of polyethyleneimine, 2g of polyethylene glycol 2000, 1.5g of water-soluble antistatic agent and 50g of deionized water, and continuously stirring for 60min to obtain a coating liquid;
the solid content of the aqueous acrylic resin is 50%, the glass transition temperature is 60 ℃, the acid value is 15KOH/g, and the hydroxyl value is 40KOH/g;
the solid content of the aqueous acrylic modified polyester resin is 55%, the glass transition temperature is 20 ℃, the acid value is 35KOH/g, and the hydroxyl value is 50KOH/g;
the deacetylation degree of the carboxymethyl chitosan is 85%, and the carboxylation degree is 90%;
the manufacturer of the water-soluble antistatic agent is the Mini chemical engineering (Shanghai) limited company, and the model is MI00-10T.
Comparative example 1
The preparation method of the coating material described in the embodiment 2 is different in that: the step of preparing coated particles in step 1 is omitted, and the addition of coated particles is omitted in the step of mixing in step 3.
Comparative example 2
The preparation method of the coating material described in the embodiment 2 is different in that: the step of preparing the dispersant in step 2 is omitted, and the addition of the dispersant is omitted in the step of mixing in step 3.
Test example 1
The coating materials prepared in examples 1-3 and comparative examples 1-2 were used in the production of plasticized-free UV labels, respectively, by the following method:
1. melt extrusion: putting the raw materials of the polyester film into a double-screw extruder for melt extrusion to obtain a polyester thick sheet;
2. stretching in the longitudinal direction: longitudinally stretching the polyester thick sheet, controlling the temperature at 120 ℃ during longitudinal stretching, and controlling the multiplying power to be 4.5:1 to obtain a longitudinally stretched polyester film;
3. coating: coating the polyester film after longitudinal stretching by using coating materials, and controlling the coatingThe amount of the coating material used was 0.5g/m 2 Obtaining a coated polyester film;
4. and (3) transversely stretching: transversely stretching the coated polyester film, controlling the temperature at 130 ℃ during transverse stretching, and controlling the multiplying power to be 4:1 to obtain the transversely stretched polyester film;
5. and (3) coating: pouring UV varnish on the surface of the transversely stretched polyester film, uniformly coating by using a coating rod, and controlling the use amount of the UV varnish to be 6g/cm 2 Obtaining a coated polyester film;
6. and (3) mould pressing: pasting the coated polyester film on a laser plate, flattening, enabling the film surface to face upwards, and irradiating for 10s under a 250W UV lamp to enable UV gloss oil to be solidified, so as to obtain the polyester film after die pressing;
7. stripping: and stripping the cured UV gloss oil from the polyester film to obtain the non-plasticizing UV label.
After the 4 th step of transverse stretching, testing the tensile strength, the elastic modulus and the thermal shrinkage rate of the transversely stretched polyester film, for comparison, obtaining the longitudinally stretched polyester film according to the 1 st step of melt extrusion and the 2 nd step of longitudinal stretching, omitting the coating step, directly carrying out transverse stretching to obtain a blank polyester film, and testing the tensile strength, the elastic modulus and the thermal shrinkage rate of the blank polyester film:
and observing whether the surface of the polyester film has cracking phenomenon or not in transverse stretching, wherein the observation results are as follows:
in the step 7, the adhesion of the cured UV varnish on the polyester film was tested as follows:
and (3) testing the static friction coefficient and the dynamic friction coefficient of the back surface of the non-plasticizing UV label obtained after the stripping step 7, and observing whether coating materials remain on the surface of the stripped polyester film, wherein the observation results are as follows:
from the above results, it can be seen that by adding the coating particles and the dispersing agent in the mixing step, the effect of the coating on the tensile strength, the elastic modulus and the thermal shrinkage rate of the polyester film can be avoided, the surface of the coated polyester film is ensured not to crack in the transverse stretching process, the adhesion force between the UV gloss oil and the polyester film is reduced, the smoothness of the back surface of the prepared plasticized-free UV label is improved, and the coating on the recycled polyester film is avoided; the coated particles and the dispersing agent play a synergistic role;
the coated particles are coated particles obtained by coating styrene-maleic anhydride copolymer microspheres twice, wherein the first coating is coating by chitosan, the second coating is coating by sodium alginate and polyvinyl amine, and the polyvinyl amine is a high-cation polymer, so that the water solubility and stability of the styrene-maleic anhydride copolymer microspheres can be improved, and the crosslinking density between the styrene-maleic anhydride copolymer microspheres and the aqueous acrylic resin and the aqueous acrylic modified polyester resin, namely the crosslinking density in the coating material, can be improved, so that the film forming property of the coating material can be improved, and the viscosity of the aqueous acrylic resin and the aqueous acrylic modified polyester resin and the polyester film can be reduced;
the dispersing agent is coated by using an anionic polyacrylamide solution after coating chitosan on the surface of nano calcium carbonate, and is also subjected to two-layer coating treatment, wherein the chitosan is used as cationic polysaccharide, the chitosan can be compounded with the anionic polyacrylamide, so that the anionic charge on the surface of the anionic polyacrylamide is neutralized, a multi-layer cross-linked structure can be formed on the surface of the nano calcium carbonate after compounding, the film forming property of a coating material can be improved after the nano calcium carbonate is mixed with water-based acrylic resin and water-based acrylic modified polyester resin, the viscosity of the water-based acrylic resin and the water-based acrylic modified polyester resin and a polyester film is reduced, meanwhile, a certain cross-linking effect can be realized between coating particles and the dispersing agent, the coating particles and the dispersing agent can also play a role of stabilizing each other in the coating material, and the coating particles and the dispersing agent are prevented from sedimentation in the coating material.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for preparing a coating, comprising the steps of: preparing coated particles, preparing a dispersing agent and mixing;
the preparation of the coated particles consists of the following steps: preparing styrene-maleic anhydride copolymer microspheres, and coating for the first time and coating for the second time;
adding styrene, maleic anhydride and butyl formate into a closed reaction kettle, sealing the reaction kettle, using nitrogen to replace air in the reaction kettle, controlling the temperature of the reaction kettle to 65-75 ℃, starting stirring, adding azodiisobutyronitrile, stirring for reaction, centrifuging, cleaning and drying a precipitate to obtain the styrene-maleic anhydride copolymer microsphere;
the primary coating is carried out by mixing styrene-maleic anhydride copolymer microspheres with deionized water, then carrying out ultrasonic oscillation, and obtaining microsphere dispersion after the ultrasonic oscillation is finished; adding chitosan acetic acid solution into a reaction kettle, controlling the temperature of the reaction kettle to 25-40 ℃, starting stirring, dropwise adding microsphere dispersion liquid into the reaction kettle, continuing stirring after the dropwise adding is finished, centrifuging, finishing the centrifugation, cleaning, and drying the precipitate to obtain microspheres coated once;
the secondary coating is carried out, after the microspheres subjected to primary coating and deionized water are mixed, ultrasonic oscillation is carried out, and after the ultrasonic oscillation is finished, microsphere dispersion liquid subjected to primary coating is obtained; adding sodium alginate aqueous solution into a reaction kettle, controlling the temperature of the reaction kettle to 25-40 ℃, starting stirring, dripping microsphere dispersion liquid coated once into the reaction kettle, continuing stirring after dripping, centrifuging, finishing centrifuging, cleaning precipitate, then placing the precipitate into a polyvinylamine aqueous solution, completely soaking the precipitate at 25-40 ℃, filtering, and drying filter residues to obtain coated particles;
adding chitosan acetic acid solution and nano calcium carbonate into a reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, stirring, centrifuging, cleaning the precipitate, then adding the cleaned precipitate and deionized water into the reaction kettle, controlling the temperature of the reaction kettle to 40-60 ℃, starting stirring, dropwise adding anionic polyacrylamide solution into the reaction kettle, continuing stirring after the dropwise adding, centrifuging, cleaning and drying the precipitate to obtain the dispersing agent;
mixing, namely adding the aqueous acrylic resin, the aqueous acrylic modified polyester resin, the coated particles, the dispersing agent, the polyethylene glycol 200 and the sodium dodecyl benzene sulfonate into a reaction kettle, stirring, adding carboxymethyl chitosan, an organosilicon defoamer, isopropanol, the aqueous blocked isocyanate cross-linking agent, polyethylenimine, polyethylene glycol 2000, a water-soluble antistatic agent and deionized water, and continuously stirring to obtain a coating liquid.
2. The method for preparing the coating material according to claim 1, wherein in the preparation of the styrene-maleic anhydride copolymer microsphere, the mass ratio of styrene, maleic anhydride, butyl formate and azodiisobutyronitrile is 15-16:14-14.5:330-350:0.25-0.3.
3. The method for preparing the coating according to claim 1, wherein in the primary coating, the mass ratio of the styrene-maleic anhydride copolymer microspheres, deionized water and chitosan acetic acid solution is 5-5.5:230-250:500-550;
the dropping speed of the microsphere dispersion liquid is 8-10g/min;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8-2%, and the mass fraction of acetic acid is 1.5-1.6%;
the deacetylation degree of the chitosan is 80-85%.
4. The method for preparing the coating material according to claim 1, wherein in the secondary coating, the mass ratio of the microspheres, deionized water and sodium alginate aqueous solution after primary coating is 5.8-6:230-250:500-550;
the dropping speed of the microsphere dispersion liquid after primary coating is 6-8g/min;
the mass fraction of the sodium alginate aqueous solution is 2-3%;
the mass fraction of the polyvinyl amine aqueous solution is 0.5-0.6%.
5. The method for preparing the coating according to claim 1, wherein in the preparation of the dispersing agent, the mass ratio of the chitosan acetic acid solution, the nano calcium carbonate, the deionized water and the anionic polyacrylamide solution is 100-110:10-12:120-150:15-16;
the mass fraction of chitosan in the chitosan acetic acid solution is 1.8-2%, and the mass fraction of acetic acid is 1.5-1.6%;
the deacetylation degree of the chitosan is 80-85%;
the particle size of the nano calcium carbonate is 50-100nm;
the mass fraction of the anionic polyacrylamide solution is 0.8-1%;
the molecular weight of the anionic polyacrylamide is 1000-1200 ten thousand, the degree of hydrolysis is 23-27%, and the charge density is 20-30mol%;
the dropping speed of the anionic polyacrylamide solution is 2-2.5g/min.
6. The method for preparing the coating according to claim 1, wherein in the mixing, the mass ratio of the aqueous acrylic resin, the aqueous acrylic modified polyester resin, the coated particles, the dispersing agent, the polyethylene glycol 200, the sodium dodecyl benzene sulfonate, the carboxymethyl chitosan, the silicone defoamer, the isopropanol, the aqueous blocked isocyanate crosslinking agent, the polyethyleneimine, the polyethylene glycol 2000, the water-soluble antistatic agent and the deionized water is 23-25:35-38:5-6:2-2.5:2-2.5:0.8-1:3-4:3-3.5:2.5-3:2-2.5:2-2.5:1.5-1.5:45-50;
the solid content of the aqueous acrylic resin is 40-50%, the glass transition temperature is 40-60 ℃, the acid value is 10-15KOH/g, and the hydroxyl value is 35-40KOH/g;
the solid content of the aqueous acrylic modified polyester resin is 50-55%, the glass transition temperature is 15-20 ℃, the acid value is 25-35KOH/g, and the hydroxyl value is 40-50KOH/g;
the deacetylation degree of the carboxymethyl chitosan is 80-85%, and the carboxylation degree is 80-90%;
the manufacturer of the water-soluble antistatic agent is the Mini chemical engineering (Shanghai) limited company, and the model is MI00-10T.
7. A coating material, characterized by being produced by the production method according to any one of claims 1 to 6.
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