CN115109452A - Modified calcium carbonate, preparation method and application thereof in production of antibacterial powder coating - Google Patents
Modified calcium carbonate, preparation method and application thereof in production of antibacterial powder coating Download PDFInfo
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- CN115109452A CN115109452A CN202210867630.3A CN202210867630A CN115109452A CN 115109452 A CN115109452 A CN 115109452A CN 202210867630 A CN202210867630 A CN 202210867630A CN 115109452 A CN115109452 A CN 115109452A
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- calcium carbonate
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- powder coating
- modified calcium
- antibacterial
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 146
- 239000000843 powder Substances 0.000 title claims abstract description 113
- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 17
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000049 pigment Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 244000028419 Styrax benzoin Species 0.000 claims abstract description 7
- 235000000126 Styrax benzoin Nutrition 0.000 claims abstract description 7
- 235000008411 Sumatra benzointree Nutrition 0.000 claims abstract description 7
- 229960002130 benzoin Drugs 0.000 claims abstract description 7
- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 47
- 239000002131 composite material Substances 0.000 claims description 41
- 239000003607 modifier Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 18
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 claims description 17
- 229920001661 Chitosan Polymers 0.000 claims description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 17
- 235000019864 coconut oil Nutrition 0.000 claims description 17
- 239000003240 coconut oil Substances 0.000 claims description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- UZBQIPPOMKBLAS-UHFFFAOYSA-N diethylazanide Chemical compound CC[N-]CC UZBQIPPOMKBLAS-UHFFFAOYSA-N 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007873 sieving Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical group O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011363 dried mixture Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical group [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012986 modification Methods 0.000 description 16
- 230000004048 modification Effects 0.000 description 16
- 150000001408 amides Chemical group 0.000 description 8
- 239000000945 filler Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004668 long chain fatty acids Chemical group 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses modified calcium carbonate, a preparation method and application thereof in producing an antibacterial powder coating, wherein the antibacterial powder coating comprises the following raw materials in percentage by mass: 42.1 to 46.5 percent of modified calcium carbonate, 38.9 to 48.7 percent of epoxy resin, 2.8 to 4.2 percent of curing agent, 0.3 to 0.9 percent of benzoin, 0.7 to 1.1 percent of flatting agent, 0.3 to 0.6 percent of surfactant, 0.2 to 0.5 percent of defoaming agent, 0.1 to 0.4 percent of dispersing agent, 0.5 to 0.8 percent of brightener and 0.2 to 0.4 percent of pigment. The powder coating has the antibacterial rate of 99.01-99.32 percent, the impact resistance of 68.1-72.6kg/cm and low production cost, and can be widely applied to the fields of antibacterial products such as aluminum profiles, fitness equipment, medical appliances, household appliances, door industry and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of powder coating preparation, and particularly relates to modified calcium carbonate, a preparation method and application thereof in production of antibacterial powder coating.
[ background of the invention ]
Calcium carbonate is an important functional inorganic filler, has the advantages of low price, abundant reserves, stable performance, easy processing, no toxicity and the like, can obviously improve the processing performance and physical performance of materials, reduces the production cost and the like, is widely applied to the fields of coatings, plastics, rubbers, papermaking and the like, has the defects of insufficient compatibility with high polymers, poor dispersibility and the like in practical application because the calcium carbonate is a hydrophilic compound, cannot achieve a satisfactory filling reinforcing effect, and needs to be modified to improve the dispersibility and compatibility in the coatings so as to achieve the effect of improving the product performance.
Along with the continuous improvement of the living standard of people, the requirements of people on the living and sanitary quality are higher and higher, and the challenge of people on modern life is how to effectively resist bacteria and remove bacteria. The antibacterial coating industry is still in the development stage at present, and the application process of the antibacterial material in the coating is a common subject in the coating industry.
[ summary of the invention ]
The invention provides modified calcium carbonate, a preparation method and application thereof in producing an antibacterial powder coating, and aims to solve the problems of poor antibacterial performance, high production cost and the like of the antibacterial powder coating.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of modified calcium carbonate comprises the following steps:
(1) grinding calcium carbonate into powder, and sieving the powder through a 800-sand 1000-mesh sieve to obtain calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium, the addition amount of the composite modifier a is 2.9-3.6% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium is 1:2.4-4.3:1.4-3.2, and the mixture a is prepared by stirring at the microwave power of 300-400W, the temperature of 66-70 ℃ and the rotation speed of 200-400r/min for 0.7-1.1 h;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b consists of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the addition amount of the composite modifier b is 1.2-2% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.1-5, and the mixture b is prepared by stirring for 2.5-3.5h under the conditions that the microwave power is 200-300W, the temperature is 85-92 ℃, and the rotating speed is 300-500 r/min;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 65-72 ℃ until the water content is less than or equal to 1%, grinding the dried mixture into powder, and sieving the powder to obtain the modified calcium carbonate with the granularity of more than 600 meshes.
The invention also provides an application of the modified calcium carbonate in producing an antibacterial powder coating, wherein the antibacterial powder coating comprises the following raw materials in percentage by mass: 42.1 to 46.5 percent of modified calcium carbonate, 38.9 to 48.7 percent of epoxy resin, 2.8 to 4.2 percent of curing agent, 0.3 to 0.9 percent of benzoin, 0.7 to 1.1 percent of flatting agent, 0.3 to 0.6 percent of surfactant, 0.2 to 0.5 percent of defoaming agent, 0.1 to 0.4 percent of dispersing agent, 0.5 to 0.8 percent of brightener and 0.2 to 0.4 percent of pigment;
the production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding the raw materials into a mixer, pre-crushing for 1-2min, and then mixing for 3-5min to obtain uniformly mixed raw materials;
B. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 104-112 ℃, the temperature in the area I is 104-107 ℃, and the temperature in the area II is 109-112 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
Further, the curing agent is a TGIC curing agent.
Further, the leveling agent is a leveling agent GLP 588.
Further, the surfactant is polyvinylpyrrolidone.
Further, the defoaming agent is TP-39 defoaming agent.
Further, the dispersant is dispersant NC.
Further, the brightener is brightener LD-608.
Further, the pigment is lead chrome yellow PY-34.
The invention has the following beneficial effects:
(1) the paint produced by the invention has excellent performance, and the appearance of the paint film is as follows: the product is smooth and has no air holes; the gloss (60 DEG mirror surface gloss) reaches more than 67.9 percent.
(2) The coconut oil fatty acid diethylamide, the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium are adopted to play a synergistic role in calcium carbonate modification, and the film gloss of the antibacterial powder coating is synergistically improved, which is probably because: the epoxy resin is non-polar, and the unmodified calcium carbonate is alkaline, and the powder coating prepared by filling the unmodified calcium carbonate into the epoxy resin has poor gloss. The calcium carbonate is subjected to surface modification by using coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, groups such as amide, long-chain fatty acid, sulfonic acid groups and the like can be introduced into the surfaces of calcium carbonate particles during first modification, the processing fluidity and the dispersibility of the modified calcium carbonate can be improved, the calcium carbonate is changed from hydrophilicity to lipophilicity, the modified calcium carbonate and other raw materials of the powder coating, such as epoxy resin, have better cohesiveness, wettability and compatibility, the interfacial cohesive force of the powder coating is improved, and the coating gloss of the powder coating is improved.
(3) The invention adopts the N-sulfofurfuryl chitosan and the 2-methyl-5-vinylpyridine to play a synergistic role in the modification of the calcium carbonate, and improves the antibacterial rate of the powder coating, which is probably because: after the calcium carbonate is modified for the first time, N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinylpyridine are adopted for carrying out secondary modification, amino and pyridyl antibacterial groups can be introduced to the surfaces of calcium carbonate particles during the secondary modification, under the mutual matching of the components, the antibacterial components are contacted with staphylococcus aureus and then adsorbed to the surfaces of bacteria, cell walls are penetrated, the composition of cell membranes is disturbed through the change of osmotic pressure and the decomposition of organic matters, the substances (RNA and DNA) in the cells are promoted to leak, the staphylococcus aureus is further effectively killed, and the antibacterial rate of the powder coating is further improved.
(4) The antibacterial rate of the powder coating is 99.01-99.32%, and the impact resistance is 68.1-72.6kg/cm, so that the powder coating has excellent performance and can be widely applied to the fields of antibacterial products such as aluminum profiles, fitness equipment, medical appliances, household appliances, door industry and the like.
(5) After the calcium carbonate is modified, the modified calcium carbonate is used as a filler to be filled into the prepared powder coating, the filling amount is high and reaches more than 42.1 percent (in the prior art, the resin content is generally not less than 50 percent, the filler dosage is generally not more than 40 percent, otherwise, the leveling property and other properties are not good), compared with the conventional fillers such as titanium dioxide, the modified calcium carbonate filler has good filling property and high filling amount, and the production cost of the modified calcium carbonate filler is far lower than that of the conventional filler titanium dioxide, so the cost for producing the antibacterial powder coating can be greatly reduced.
[ description of the drawings ]
FIG. 1 is a diagram of an antimicrobial powder coating product of example 2 of the present invention.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
In an embodiment, the antibacterial powder coating comprises the following raw materials in percentage by mass: 42.1 to 46.5 percent of modified calcium carbonate, 38.9 to 48.7 percent of epoxy resin, 2.8 to 4.2 percent of curing agent, 0.3 to 0.9 percent of benzoin, 0.7 to 1.1 percent of flatting agent, 0.3 to 0.6 percent of surfactant, 0.2 to 0.5 percent of defoaming agent, 0.1 to 0.4 percent of dispersing agent, 0.5 to 0.8 percent of brightener and 0.2 to 0.4 percent of pigment.
The epoxy resin is epoxy resin E-12.
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The surfactant is polyvinylpyrrolidone.
The defoaming agent is TP-39 defoaming agent.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The pigment is lead chrome yellow PY-34.
The preparation method of the modified calcium carbonate comprises the following steps:
(1) grinding calcium carbonate into powder, and sieving the powder through 800-1000 meshes to prepare calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium, the addition amount of the composite modifier a is 2.9-3.6% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium is 1:2.4-4.3:1.4-3.2, and the mixture a is prepared by stirring at the microwave power of 300-400W, the temperature of 66-70 ℃ and the rotation speed of 200-400r/min for 0.7-1.1 h;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b consists of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the addition amount of the composite modifier b is 1.2-2% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.1-5, and the mixture b is prepared by stirring for 2.5-3.5h under the conditions that the microwave power is 200-300W, the temperature is 85-92 ℃, and the rotating speed is 300-500 r/min;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 65-72 ℃ until the water content is less than or equal to 1%, grinding the dried mixture into powder, and sieving the powder to obtain the modified calcium carbonate with the granularity of more than 600 meshes.
The production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding the raw materials into a mixer, pre-crushing for 1-2min, and then mixing for 3-5min to obtain uniformly mixed raw materials;
B. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheets, wherein the melt extrusion temperature is 104-112 ℃, the temperature of the zone I is 104-107 ℃, and the temperature of the zone II is 109-112 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
In order to further illustrate the present invention and make the disclosure more complete, more specific embodiments are described below.
EXAMPLE 1
An antibacterial powder coating comprises the following raw materials in percentage by mass: 45.4% of modified calcium carbonate, 48.2% of epoxy resin, 3.8% of curing agent, 0.4% of benzoin, 0.8% of flatting agent, 0.3% of surfactant, 0.2% of defoaming agent, 0.2% of dispersing agent, 0.5% of brightener and 0.2% of pigment.
The epoxy resin is epoxy resin E-12.
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The surfactant is polyvinylpyrrolidone.
The defoaming agent is TP-39 defoaming agent.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The pigment is lead chrome yellow PY-34.
The preparation method of the modified calcium carbonate comprises the following steps:
(1) grinding calcium carbonate into powder, and sieving the powder by a 800-mesh sieve to obtain calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanol amide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the composite modifier a is 3% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanol amide stearic acid monoglyceride to the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 1:2.7:1.5, and the mixture a is prepared by stirring for 1.1h at the microwave power of 300W, the temperature of 67 ℃ and the rotating speed of 200 r/min;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b is composed of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the adding amount of the composite modifier b is 1.3% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.3, and stirring is carried out for 3.5h at the microwave power of 200W, the temperature of 85 ℃ and the rotating speed of 300r/min to prepare a mixture b;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 66 ℃ until the water content is 1%, grinding the dried mixture into powder, and sieving the powder to obtain 800-mesh modified calcium carbonate.
The production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding the raw materials into a mixer, pre-crushing for 1min, and then mixing for 5min to obtain uniformly mixed raw materials;
B. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 104-110 ℃, the temperature in the area I is 104-106 ℃, and the temperature in the area II is 109-110 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
EXAMPLE 2
An antibacterial powder coating comprises the following raw materials in percentage by mass: 44.3 percent of modified calcium carbonate, 47.9 percent of epoxy resin, 4.1 percent of curing agent, 0.6 percent of benzoin, 1 percent of flatting agent, 0.5 percent of surfactant, 0.4 percent of defoaming agent, 0.3 percent of dispersing agent, 0.6 percent of brightener and 0.3 percent of pigment.
The epoxy resin is epoxy resin E-12.
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The surfactant is polyvinylpyrrolidone.
The defoaming agent is TP-39 defoaming agent.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The pigment is lead chrome yellow PY-34.
The preparation method of the modified calcium carbonate comprises the following steps:
(1) grinding calcium carbonate into powder, and sieving the powder by a 1000-mesh sieve to obtain calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanol amide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the composite modifier a is 3.2% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanol amide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 1:3.5:2.3, and the mixture a is prepared by stirring for 1h at the microwave power of 400W, the temperature of 68 ℃ and the rotating speed of 300 r/min;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b is composed of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the adding amount of the composite modifier b is 1.5% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.5, and stirring is carried out for 3 hours at the microwave power of 300W, the temperature of 88 ℃ and the rotating speed of 400r/min to prepare a mixture b;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 70 ℃ until the water content is 0.8%, grinding the dried mixture into powder, and sieving the powder to obtain the modified calcium carbonate of 1000 meshes.
The production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding the raw materials into a mixer, pre-crushing for 2min, and then mixing for 3min to obtain uniformly mixed raw materials;
B. melt extrusion: putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 105-112 ℃, the temperature in the area I is 105-107 ℃, and the temperature in the area II is 109-112 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
EXAMPLE 3
An antibacterial powder coating comprises the following raw materials in percentage by mass: 46.5 percent of modified calcium carbonate, 44.9 percent of epoxy resin, 4.2 percent of curing agent, 0.8 percent of benzoin, 1.1 percent of flatting agent, 0.6 percent of surfactant, 0.4 percent of defoaming agent, 0.4 percent of dispersing agent, 0.8 percent of brightener and 0.3 percent of pigment.
The epoxy resin is epoxy resin E-12.
The curing agent is TGIC curing agent.
The leveling agent is a leveling agent GLP 588.
The surfactant is polyvinylpyrrolidone.
The defoaming agent is TP-39 defoaming agent.
The dispersant is dispersant NC.
The brightener is brightener LD-608.
The pigment is lead chrome yellow PY-34.
The preparation method of the modified calcium carbonate comprises the following steps:
(1) grinding calcium carbonate into powder, and sieving with a 900-mesh sieve to obtain calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanol amide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, the addition amount of the composite modifier a is 3.5% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanol amide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium is 1:4:2.9, and the mixture a is prepared by stirring for 0.7h at the microwave power of 400W, the temperature of 70 ℃ and the rotating speed of 400 r/min;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b is composed of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the adding amount of the composite modifier b is 1.8% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.6, and stirring is carried out for 3.2 hours at the microwave power of 200W, the temperature of 90 ℃ and the rotating speed of 500r/min to prepare a mixture b;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 65-72 ℃ until the water content is less than or equal to 1%, grinding the dried mixture into powder, and sieving the powder to obtain the 900-mesh modified calcium carbonate.
The production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding the raw materials into a mixer, pre-crushing for 1min, and then mixing for 5min to obtain uniformly mixed raw materials;
B. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 104-111 ℃, the temperature in the area I is 104-107 ℃, and the temperature in the area II is 109-111 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
Comparative example 1
The production method of the powder coating was substantially the same as that of example 2, except that only the modification of step (3) was carried out in the preparation of the modified calcium carbonate, and the modification of step (2) was not carried out.
Comparative example 2
The powder coating was produced in essentially the same manner as in comparative example 1, except that the composite modifier a used in the preparation of the modified calcium carbonate increased coconut oil fatty acid diethylamide.
Comparative example 3
The production process of the powder coating was substantially the same as that of comparative example 1 except that the composite modifier a used in the preparation of the modified calcium carbonate was increased with diethanolamide stearic acid monoglyceride.
Comparative example 4
The powder coating was produced in substantially the same manner as in comparative example 1, except that the composite modifier a used in the preparation of the modified calcium carbonate was increased with ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium.
Comparative example 5
The production method of the powder coating was substantially the same as that of example 2, except that only the modification of step (2) was carried out in the preparation of the modified calcium carbonate, and the modification of step (3) was not carried out.
Comparative example 6
The powder coating was produced in substantially the same manner as in comparative example 5 except that the composite modifier b used in the preparation of the modified calcium carbonate was added with furfuryl chitosan N-sulfonate.
Comparative example 7
The powder coating was produced in substantially the same manner as in comparative example 5, except that the composite modifier b used in the preparation of the modified calcium carbonate was supplemented with 2-methyl-5-vinylpyridine.
And (3) performance detection:
preparing a coating layer: the powder coatings of examples 1-3 and comparative examples 1-4 were sprayed on the surface-treated cold-rolled steel sheets using an electrostatic spray gun, the thicknesses of the coating films were substantially uniform, and cured at 200 deg.C/10 min to give coating layers corresponding to examples 1-3 and comparative examples 1-4, the gloss being measured using GB/T1743-1979.
The coating test results of examples 1 to 3 and comparative examples 1 to 4 are shown in table 1.
TABLE 1 coating test results of examples 1-3 and comparative examples 1-4
As can be seen from Table 1: (1) as can be seen from the film appearance and gloss data of examples 1-3, the film appearance: the product is smooth and has no air holes; the gloss (60 DEG mirror gloss) reaches more than 67.9 percent, which shows that the coating has excellent performance.
(2) As can be seen from the gloss data of example 2 and comparative examples 1-4, coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride, and sodium ethylene-bis (N-ethanesulfonic acid-dodecanoamide) provided a synergistic effect in calcium carbonate modification, which synergistically improved the film gloss of the powder coating, probably because: the epoxy resin is non-polar, and the unmodified calcium carbonate is alkaline, and the powder coating prepared by filling the unmodified calcium carbonate into the epoxy resin has poor gloss. The calcium carbonate is subjected to surface modification by using coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanamide) sodium, groups such as amide, long-chain fatty acid, sulfonic acid groups and the like can be introduced into the surfaces of calcium carbonate particles during first modification, the processing fluidity and the dispersibility of the modified calcium carbonate can be improved, the calcium carbonate is changed from hydrophilicity to lipophilicity, the modified calcium carbonate and other raw materials of the powder coating, such as epoxy resin, have better cohesiveness, wettability and compatibility, the interfacial cohesive force of the powder coating is improved, and the coating gloss of the powder coating is improved.
The powder coatings obtained in examples 1 to 3 and comparative examples 5 to 7 were tested for antibacterial ratio and impact resistance, wherein the antibacterial ratio was measured in GB/T21866-2008 and the impact resistance was measured in GB/T1732-1993ISO6272, and the results are shown in Table 2 below.
TABLE 2 tables of results of performance tests of the powder coatings obtained in examples 1 to 3 and comparative examples 5 to 7
| Experimental project | Antibacterial ratio (%) | Impact resistance (kg/cm) |
| Example 1 | 99.01 | 68.1 |
| Example 2 | 99.32 | 72.6 |
| Example 3 | 99.14 | 70.9 |
| Comparative example 5 | 41.82 | - |
| Comparative example 6 | 70.15 | - |
| Comparative example 7 | 63.19 | - |
In Table 2, "-" indicates no detection.
As can be seen from Table 2: (1) as can be seen from the data of examples 1 to 3, the powder coating of the present invention has an antibacterial ratio of 99.01% to 99.32% and an impact resistance of 68.1 to 72.6kg/cm, and is excellent in performance, of which example 2 is the most preferable example, and the product diagram is shown in FIG. 1.
(2) From the data of example 2 and comparative examples 5-7, it can be seen that the N-sulfonic acid furfuryl chitosan, 2-methyl-5-vinylpyridine, in the modification of calcium carbonate, act synergistically, increasing the antibacterial rate of the powder coating, probably because: after the calcium carbonate is modified for the first time, N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinylpyridine are adopted for carrying out secondary modification, amino and pyridyl antibacterial groups can be introduced to the surfaces of calcium carbonate particles during the secondary modification, under the mutual matching of the components, the antibacterial components are contacted with staphylococcus aureus and then adsorbed to the surfaces of bacteria, cell walls are penetrated, the composition of cell membranes is disturbed through the change of osmotic pressure and the decomposition of organic matters, the substances (RNA and DNA) in the cells are promoted to leak, the staphylococcus aureus is further effectively killed, and the antibacterial rate of the powder coating is further improved.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (10)
1. The preparation method of the modified calcium carbonate is characterized by comprising the following steps:
(1) grinding calcium carbonate into powder, and sieving the powder through a 800-sand 1000-mesh sieve to obtain calcium carbonate powder;
(2) adding a composite modifier a into the calcium carbonate powder prepared in the step (1), wherein the composite modifier a consists of coconut oil fatty acid diethylamide, diethanolamide stearic acid monoglyceride and ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium, the addition amount of the composite modifier a is 2.9-3.6% of the mass of the calcium carbonate powder, the mass ratio of the coconut oil fatty acid diethylamide, the diethanolamide stearic acid monoglyceride and the ethylene-bis (N-ethanesulfonic acid-dodecanoamide) sodium is 1:2.4-4.3:1.4-3.2, and the mixture a is prepared by stirring at the microwave power of 300-400W, the temperature of 66-70 ℃ and the rotation speed of 200-400r/min for 0.7-1.1 h;
(3) adding the mixture a prepared in the step (2) and a composite modifier b into a mixer, wherein the composite modifier b consists of N-sulfonic acid furfuryl chitosan and 2-methyl-5-vinyl pyridine, the addition amount of the composite modifier b is 1.2-2% of the mass of the calcium carbonate powder, the mass ratio of the N-sulfonic acid furfuryl chitosan to the 2-methyl-5-vinyl pyridine is 1:4.1-5, and the mixture b is prepared by stirring for 2.5-3.5h under the conditions that the microwave power is 200-300W, the temperature is 85-92 ℃, and the rotating speed is 300-500 r/min;
(4) and (4) drying the mixture b prepared in the step (3) at the temperature of 65-72 ℃ until the water content is less than or equal to 1%, grinding the dried mixture into powder, and sieving the powder to obtain the modified calcium carbonate with the granularity of more than 600 meshes.
2. A modified calcium carbonate prepared according to the method of claim 1.
3. The use of the modified calcium carbonate according to claim 2 for the production of an antibacterial powder coating, wherein the antibacterial powder coating comprises the following raw materials in percentage by mass: 42.1 to 46.5 percent of modified calcium carbonate, 38.9 to 48.7 percent of epoxy resin, 2.8 to 4.2 percent of curing agent, 0.3 to 0.9 percent of benzoin, 0.7 to 1.1 percent of flatting agent, 0.3 to 0.6 percent of surfactant, 0.2 to 0.5 percent of defoaming agent, 0.1 to 0.4 percent of dispersing agent, 0.5 to 0.8 percent of brightener and 0.2 to 0.4 percent of pigment;
the production method of the antibacterial powder coating comprises the following steps:
A. mixing raw materials: weighing the raw materials according to the proportion, respectively adding into a mixer, pre-crushing for 1-2min, and then mixing for 3-5min to obtain uniformly mixed raw materials;
B. melt extrusion: b, putting the uniformly mixed raw materials prepared in the step A into an extruder, performing melt extrusion, tabletting and cooling, and then crushing into sheet materials, wherein the melt extrusion temperature is 104-112 ℃, the temperature in the area I is 104-107 ℃, and the temperature in the area II is 109-112 ℃;
C. grinding and crushing: and C, placing the sheet materials crushed in the step B into an ACM (acid-activated mechanical grinding) mill for milling, and performing cyclone separation and screening to produce the antibacterial powder coating.
4. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, wherein the curing agent is TGIC curing agent.
5. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, wherein the levelling agent is the levelling agent GLP 588.
6. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, characterized in that the surfactant is polyvinylpyrrolidone.
7. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, wherein the defoamer is a TP-39 defoamer.
8. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, characterized in that the dispersant is dispersant NC.
9. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, wherein the brightener is brightener LD-608.
10. Use of the modified calcium carbonate according to claim 3 for the production of an antibacterial powder coating, characterized in that the pigment is lead chrome yellow PY-34.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135342A (en) * | 2018-09-28 | 2019-01-04 | 贺州钟山县双文碳酸钙新材料有限公司 | Paint-emulsion paint modified calcium carbonate |
| CN109337242A (en) * | 2018-09-28 | 2019-02-15 | 贺州钟山县双文碳酸钙新材料有限公司 | The preparation method and applications of PVC calcium-plastic board material modified calcium carbonate |
| CN111440515A (en) * | 2020-05-07 | 2020-07-24 | 广西福宝信科技有限公司 | Antibacterial powder coating and preparation method thereof |
| CN112940591A (en) * | 2021-03-31 | 2021-06-11 | 广西福宝信科技有限公司 | High-performance antibacterial powder coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135342A (en) * | 2018-09-28 | 2019-01-04 | 贺州钟山县双文碳酸钙新材料有限公司 | Paint-emulsion paint modified calcium carbonate |
| CN109337242A (en) * | 2018-09-28 | 2019-02-15 | 贺州钟山县双文碳酸钙新材料有限公司 | The preparation method and applications of PVC calcium-plastic board material modified calcium carbonate |
| CN111440515A (en) * | 2020-05-07 | 2020-07-24 | 广西福宝信科技有限公司 | Antibacterial powder coating and preparation method thereof |
| CN112940591A (en) * | 2021-03-31 | 2021-06-11 | 广西福宝信科技有限公司 | High-performance antibacterial powder coating and preparation method thereof |
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