CN118047989A - Antibacterial and mildew-proof plastic film and preparation method thereof - Google Patents
Antibacterial and mildew-proof plastic film and preparation method thereof Download PDFInfo
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- CN118047989A CN118047989A CN202410249978.5A CN202410249978A CN118047989A CN 118047989 A CN118047989 A CN 118047989A CN 202410249978 A CN202410249978 A CN 202410249978A CN 118047989 A CN118047989 A CN 118047989A
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- mildew
- bentonite
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000002985 plastic film Substances 0.000 title claims abstract description 41
- 229920006255 plastic film Polymers 0.000 title claims abstract description 41
- 239000000440 bentonite Substances 0.000 claims abstract description 77
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 77
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003607 modifier Substances 0.000 claims abstract description 56
- 239000003365 glass fiber Substances 0.000 claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 49
- 238000012986 modification Methods 0.000 claims abstract description 44
- 230000004048 modification Effects 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 18
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 18
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 18
- 239000004014 plasticizer Substances 0.000 claims abstract description 18
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 229920005610 lignin Polymers 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 67
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 55
- 238000011282 treatment Methods 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 37
- 238000000498 ball milling Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 32
- 230000010355 oscillation Effects 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000005543 nano-size silicon particle Substances 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 18
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 15
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 15
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 14
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 8
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 claims description 6
- 239000006013 carbendazim Substances 0.000 claims description 6
- 238000010096 film blowing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000008029 phthalate plasticizer Substances 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000009977 dual effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 230000005855 radiation Effects 0.000 description 9
- 238000007790 scraping Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- 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
- C08J2497/00—Characterised by the use of lignin-containing materials
-
- 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
- C08K3/20—Oxides; Hydroxides
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- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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- 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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2286—Oxides; Hydroxides of metals of silver
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- 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
- C08K3/32—Phosphorus-containing compounds
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
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- C08K5/3447—Five-membered rings condensed with carbocyclic rings
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention relates to the technical field of plastic films, and in particular discloses an antibacterial and mildew-proof plastic film and a preparation method thereof, wherein the antibacterial and mildew-proof plastic film comprises the following raw materials in parts by weight: 55-60 parts of low-density polyethylene, 10-15 parts of antibacterial mildew inhibitor, 8-14 parts of bentonite-based double-effect modified regulating functional agent, 5-8 parts of lignin, 4-7 parts of modifier doped with glass fiber, 2-5 parts of plasticizer and 1-2 parts of heat stabilizer. The antibacterial mildew-proof plastic film disclosed by the invention takes the low-density polyethylene resin as a matrix, the lignin, the plasticizer and the heat stabilizer are added as functional auxiliary agents, the functional effect of the film is enhanced, meanwhile, the antibacterial mildew-proof agent is added to optimize the antibacterial and mildew-proof effects of the product, and the bentonite double-effect modification-based regulating functional agent and the glass fiber doped modifier are added, so that the long-acting antibacterial mildew-proof effects of the product are obvious through the mutual coordination among raw materials.
Description
Technical Field
The invention relates to the technical field of plastic films, in particular to an antibacterial and mildew-proof plastic film and a preparation method thereof.
Background
Films made of polyvinyl chloride, polyethylene, polypropylene, polystyrene, and other resins for plastic films for packaging and for film coating; plastic packages and plastic packaging products have a larger and larger share in the market, and in particular, composite plastic flexible packages have been widely applied to the fields of food, medicine, chemical industry and the like.
In order to improve the antibacterial and mildew-proof properties of the product, the existing plastic film is added with an inorganic antibacterial agent and a mildew-proof agent, so that raw materials are easy to agglomerate, and the raw materials of the product are poor in compatibility, so that the mechanical properties of the product and the antibacterial and mildew-proof properties of the product are influenced, the mechanical properties and the antibacterial and mildew-proof properties of the product are difficult to coordinate and improve, meanwhile, the antibacterial and mildew-proof long-acting properties of the product and durability stability of the product are obviously deteriorated after washing and scraping, and the service efficiency of the product is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antibacterial and mildew-proof plastic film and a preparation method thereof, so as to solve the problems in the prior art.
The invention solves the technical problems by adopting the following technical scheme:
the invention provides an antibacterial mildew-proof plastic film which comprises the following raw materials in parts by weight:
55-60 parts of low-density polyethylene, 10-15 parts of antibacterial mildew inhibitor, 8-14 parts of bentonite-based double-effect modified regulating functional agent, 5-8 parts of lignin, 4-7 parts of modifier doped with glass fiber, 2-5 parts of plasticizer and 1-2 parts of heat stabilizer.
Preferably, the antibacterial mildew-proof plastic film comprises the following raw materials in parts by weight:
57.5 parts of low-density polyethylene, 12.5 parts of antibacterial and mildew-proof agent, 11 parts of regulating functional agent based on bentonite double-effect modification, 6.5 parts of lignin, 5.5 parts of modifier doped with glass fiber, 3.5 parts of plasticizer and 1.5 parts of heat stabilizer.
Preferably, the low-density polyethylene has a melt flow rate of 0.5-9.0 g/10min, a density of 0.920-0.925 g/cm3 and a molecular weight distribution of 4.0-8.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
Preferably, the preparation method of the bentonite adjustment and modification-based double-effect functional agent comprises the following steps:
s01: the bentonite is firstly heat treated for 25 to 30 minutes at 350 to 400 ℃, then cooled to 210 to 220 ℃ at the speed of 3 to 5 ℃/min, kept for 5 to 10 minutes, finally cooled to 60 to 65 ℃ at the speed of 1 to 3 ℃/min, and kept for later use;
S02: adding 4-7 parts of S01 heat-preserving bentonite and 2-4 parts of tetrabutyl titanate into 10-15 parts of ethanol solvent, then adding 0.5-0.7 part of urea, and carrying out oscillation modification treatment to obtain oscillation liquid after oscillation is finished;
s03: adding 1-3 parts of nano silica sol and 3-5 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex formulation modified liquid;
s04: ball milling treatment is carried out on bentonite complex mixing modification liquid and double-effect modifier according to the weight ratio of 3 (4-7), the ball milling rotating speed is 1000-1500 r/min, ball milling is carried out for 1-2 h, and after ball milling, water washing and drying are carried out, thus obtaining the double-effect modifier based on bentonite adjustment modification.
Preferably, the mass fraction of the sodium lignin sulfonate solution is 10-15%; the oscillation power of the oscillation modification treatment is 350-400W, and the oscillation time is 20-30 min.
Preferably, the preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1-2 mol/L to react for 40-45 min, wherein the reaction temperature is 65-70 ℃, and after the reaction, washing and drying;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4-5 parts of dried nano silicon dioxide, 1-3 parts of lanthanum oxide coating agent, 6-10 parts of chitosan aqueous solution and 0.35-0.45 part of sodium hexametaphosphate are ball-milled for 1-2 hours at the rotating speed of 1000-1500 r/min, and the double-effect regulator is obtained after the ball milling is finished, water washing and drying.
Preferably, the stirring rotation speed of the immersing and stirring treatment is 550-650 r/min, and the stirring time is 20-30 min.
Preferably, the preparation method of the modifier for the doped glass fiber comprises the following steps:
S11: stirring and mixing glass fiber in hydrochloric acid solution with the total amount of 3-5 times of the glass fiber, washing with water, drying, and then irradiating in a proton irradiation box for 15-20 min with the irradiation power of 300-350W, and obtaining a glass fiber agent after the irradiation is finished;
S12: 4 to 6 parts of glass fiber agent, 1 to 3 parts of hydroxyapatite, 1 to 2 parts of stearic acid and 5 to 10 parts of sodium dodecyl benzene sulfonate solution are subjected to ultrasonic treatment for 20 to 30 minutes under the ultrasonic power of 400 to 450W, and after the ultrasonic treatment is finished, the glass fiber-doped modifier is obtained by washing and drying.
Preferably, the mass fraction of the hydrochloric acid solution is 2-5%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 10-15%.
The invention also provides a preparation method of the antibacterial and mildew-proof plastic film, which comprises the following steps:
Sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with a single-screw length-diameter ratio of 40:1, sequentially carrying out plasticizing extrusion at 148-150 ℃ and blowing expansion treatment with a blowing ratio of 3:1, cooling and rolling to obtain the antibacterial and mildew-proof plastic film.
Compared with the prior art, the invention has the following beneficial effects:
1. The antibacterial and mildew-proof plastic film takes the low-density polyethylene resin as a matrix, lignin, a plasticizer and a heat stabilizer are added as functional auxiliary agents, so that the functional effect of the film is enhanced, meanwhile, the added antibacterial and mildew-proof agent optimizes the antibacterial and mildew-proof effects of the product, and the added bentonite double-effect modified regulating functional agent and glass fiber doped modifier cooperate with each other through mutual cooperation among raw materials, so that the antibacterial and mildew-proof performance and tensile strength performance effects of the product are enhanced, meanwhile, the performance of the antibacterial and mildew-proof performance and tensile strength performance effects can be improved in a coordinated manner, the long-acting antibacterial and mildew-proof effects of the product are obvious, and in addition, the performance stability of the product after washing and scraping of the product is still obvious;
2. The bentonite-based dual-effect functional agent is prepared by heat-treating bentonite for 25-30 min at 350-400 ℃, cooling to 210-220 ℃ at the speed of 3-5 ℃/min, preserving heat for 5-10 min, finally cooling to 60-65 ℃ at the speed of 1-3 ℃/min, heating first, cooling at a high speed, cooling in stages, expanding the lamellar spacing of the bentonite layer by layer, optimizing the interlayer spacing effect, facilitating better regulation of the product performance effect of the bentonite in a system, forming an oscillating liquid by using tetrabutyl titanate and urea to match with an ethanol solvent, forming a bentonite complex-adjusting modified liquid by matching nano silica sol and a sodium lignin sulfonate solution, adopting the bentonite complex-adjusting modified liquid as a medium modified liquid, and matching the coordination and synergistic effect of the dual-effect regulator, wherein the bentonite complex-adjusting modified liquid is interpenetrated in the system liquid by bentonite raw materials, and the mutual synergistic effect among the raw materials, thus enhancing the activity effect of the product, and optimizing the modification and coordination effect of the dual-effect regulator and the bentonite complex-adjusting modified liquid;
3. The double-effect modifier adopts nano silicon dioxide to react through potassium permanganate solution, so as to optimize the active efficiency and the active surface energy of the nano silicon dioxide, and the lanthanum oxide is soaked into and coated with sodium silicate solution through stirring, so that the lanthanum oxide coated with sodium silicate solution is ball-milled and modified with the dried nano silicon dioxide, chitosan solution and sodium hexametaphosphate, and the obtained double-effect modifier takes the nano silicon dioxide as a carrier with high surface area, and is matched with a bentonite distribution system, so that the formed double-effect modifier based on bentonite adjustment modification coordinates the interfacial property of raw materials of a product in the system, enhances the stability of the system of the product, and further coordinates and improves the antibacterial mildew-proof and tensile strength performance of the product, optimizes the antibacterial mildew-proof durability of the product, and obviously improves the stability after washing and scraping of the product;
4. The modified glass fiber-doped modifier is prepared by treating glass fibers with hydrochloric acid solution and matching with proton irradiation, and is subjected to ultrasonic improvement treatment with hydroxyapatite, stearic acid and sodium dodecyl benzene sulfonate solution, and the modified glass fiber-doped modifier is reinforced by the glass fibers and the point loading of the hydroxyapatite, so that the synergistic effect of the modified glass fiber-doped modifier and the bentonite-based modified double-effect functional agent is further enhanced, and the performance of the product is further improved.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The antibacterial mildew-proof plastic film comprises the following raw materials in parts by weight:
55-60 parts of low-density polyethylene, 10-15 parts of antibacterial mildew inhibitor, 8-14 parts of bentonite-based double-effect modified regulating functional agent, 5-8 parts of lignin, 4-7 parts of modifier doped with glass fiber, 2-5 parts of plasticizer and 1-2 parts of heat stabilizer.
The antibacterial and mildew-proof plastic film of the embodiment comprises the following raw materials in parts by weight:
57.5 parts of low-density polyethylene, 12.5 parts of antibacterial and mildew-proof agent, 11 parts of regulating functional agent based on bentonite double-effect modification, 6.5 parts of lignin, 5.5 parts of modifier doped with glass fiber, 3.5 parts of plasticizer and 1.5 parts of heat stabilizer.
The low density polyethylene of this example has a melt flow rate of 0.5-9.0 g/10min, a density of 0.920-0.925 g/cm3 and a molecular weight distribution of 4.0-8.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
The preparation method of the bentonite adjustment and modification-based double-effect functional agent comprises the following steps:
s01: the bentonite is firstly heat treated for 25 to 30 minutes at 350 to 400 ℃, then cooled to 210 to 220 ℃ at the speed of 3 to 5 ℃/min, kept for 5 to 10 minutes, finally cooled to 60 to 65 ℃ at the speed of 1 to 3 ℃/min, and kept for later use;
S02: adding 4-7 parts of S01 heat-preserving bentonite and 2-4 parts of tetrabutyl titanate into 10-15 parts of ethanol solvent, then adding 0.5-0.7 part of urea, and carrying out oscillation modification treatment to obtain oscillation liquid after oscillation is finished;
s03: adding 1-3 parts of nano silica sol and 3-5 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex formulation modified liquid;
s04: ball milling treatment is carried out on bentonite complex mixing modification liquid and double-effect modifier according to the weight ratio of 3 (4-7), the ball milling rotating speed is 1000-1500 r/min, ball milling is carried out for 1-2 h, and after ball milling, water washing and drying are carried out, thus obtaining the double-effect modifier based on bentonite adjustment modification.
The mass fraction of the sodium lignin sulfonate solution in the embodiment is 10-15%; the oscillation power of the oscillation modification treatment is 350-400W, and the oscillation time is 20-30 min.
The preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1-2 mol/L to react for 40-45 min, wherein the reaction temperature is 65-70 ℃, and after the reaction, washing and drying;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4-5 parts of dried nano silicon dioxide, 1-3 parts of lanthanum oxide coating agent, 6-10 parts of chitosan aqueous solution and 0.35-0.45 part of sodium hexametaphosphate are ball-milled for 1-2 hours at the rotating speed of 1000-1500 r/min, and the double-effect regulator is obtained after the ball milling is finished, water washing and drying.
The stirring speed of the immersing and stirring treatment is 550-650 r/min, and the stirring time is 20-30 min.
The preparation method of the modifier for the doped glass fiber comprises the following steps:
S11: stirring and mixing glass fiber in hydrochloric acid solution with the total amount of 3-5 times of the glass fiber, washing with water, drying, and then irradiating in a proton irradiation box for 15-20 min with the irradiation power of 300-350W, and obtaining a glass fiber agent after the irradiation is finished;
S12: 4 to 6 parts of glass fiber agent, 1 to 3 parts of hydroxyapatite, 1 to 2 parts of stearic acid and 5 to 10 parts of sodium dodecyl benzene sulfonate solution are subjected to ultrasonic treatment for 20 to 30 minutes under the ultrasonic power of 400 to 450W, and after the ultrasonic treatment is finished, the glass fiber-doped modifier is obtained by washing and drying.
The mass fraction of the hydrochloric acid solution in the embodiment is 2-5%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 10-15%.
The preparation method of the antibacterial and mildew-proof plastic film comprises the following steps:
Sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with a single-screw length-diameter ratio of 40:1, sequentially carrying out plasticizing extrusion at 148-150 ℃ and blowing expansion treatment with a blowing ratio of 3:1, cooling and rolling to obtain the antibacterial and mildew-proof plastic film.
Example 1.
The antibacterial mildew-proof plastic film comprises the following raw materials in parts by weight:
55 parts of low-density polyethylene, 10 parts of antibacterial mildew inhibitor, 8 parts of bentonite-based double-effect modified regulating function agent, 5 parts of lignin, 4 parts of glass fiber doped modifier, 2 parts of plasticizer and 1 part of heat stabilizer.
The low density polyethylene of this example had a melt flow rate of 0.5g/10min, a density of 0.920g/cm3 and a molecular weight distribution of 4.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
The preparation method of the bentonite adjustment and modification-based double-effect functional agent comprises the following steps:
s01: heat-treating bentonite at 350 ℃ for 25min, cooling to 210 ℃ at a rate of 3 ℃/min, preserving heat for 5min, and finally cooling to 60 ℃ at a rate of 1 ℃/min, preserving heat for later use;
s02: adding 4 parts of S01 heat-preserving bentonite and 2 parts of tetrabutyl titanate into 10 parts of ethanol solvent, then adding 0.5 part of urea, and carrying out oscillation modification treatment to obtain oscillation liquid;
s03: adding 1 part of nano silica sol and 3 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex-mixing modified liquid;
S04: ball milling the bentonite complex mixing modification solution and the double-effect modifier according to a weight ratio of 3:4, wherein the ball milling rotating speed is 1000r/min, ball milling is carried out for 1h, and after ball milling, water washing and drying are carried out to obtain the double-effect modifier based on bentonite adjustment modification.
The mass fraction of the sodium lignin sulfonate solution in the embodiment is 10%; the oscillation power of the oscillation modification treatment is 350W, and the oscillation time is 20min.
The preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1mol/L for reaction for 40min, wherein the reaction temperature is 65 ℃, and washing and drying after the reaction is finished;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4 parts of dried nano silicon dioxide, 1 part of lanthanum oxide coating agent, 6 parts of chitosan aqueous solution and 0.35 part of sodium hexametaphosphate are subjected to ball milling for 1h at the rotating speed of 1000r/min, and after ball milling, the double-effect regulator is obtained through water washing and drying.
The stirring speed of the immersion stirring treatment in this example was 550r/min, and the stirring time was 20min.
The preparation method of the modifier for the doped glass fiber comprises the following steps:
s11: stirring and mixing glass fibers in hydrochloric acid solution with the total amount being 3 times of that of the glass fibers, washing with water, drying, and then radiating in a proton radiation box for 15min with the radiation power of 300W, wherein the radiation is finished to obtain a glass fiber agent;
S12: 4 parts of glass fiber agent, 1 part of hydroxyapatite, 1 part of stearic acid and 5 parts of sodium dodecyl benzene sulfonate solution are subjected to ultrasonic treatment for 20 minutes under the ultrasonic power of 400W, and after ultrasonic treatment, the glass fiber-doped modifier is obtained by washing and drying.
The mass fraction of the hydrochloric acid solution in this example was 2%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 10%.
The preparation method of the antibacterial and mildew-proof plastic film comprises the following steps:
sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with the length-diameter ratio of 40:1 of a single screw, sequentially carrying out plasticizing extrusion at 148 ℃, and carrying out inflation treatment, cooling and rolling with the inflation ratio of 3:1, thereby obtaining the antibacterial and mildew-proof plastic film.
Example 2.
The antibacterial mildew-proof plastic film comprises the following raw materials in parts by weight:
60 parts of low-density polyethylene, 15 parts of antibacterial mildew inhibitor, 14 parts of bentonite double-effect modified regulating functional agent, 8 parts of lignin, 7 parts of glass fiber doped modifier, 5 parts of plasticizer and 2 parts of heat stabilizer.
The low density polyethylene of this example had a melt flow rate of 9.0g/10min, a density of 0.925g/cm3 and a molecular weight distribution of 8.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
The preparation method of the bentonite adjustment and modification-based double-effect functional agent comprises the following steps:
s01: heat-treating bentonite at 400 ℃ for 30min, cooling to 220 ℃ at a rate of 5 ℃/min, preserving heat for 10min, and finally cooling to 65 ℃ at a rate of 3 ℃/min, preserving heat for later use;
S02: 7 parts of S01 heat-preserving bentonite and 4 parts of tetrabutyl titanate are added into 15 parts of ethanol solvent, then 0.7 part of urea is added, and the oscillating modification treatment is carried out firstly, and the oscillating liquid is obtained after the oscillating is finished;
S03: adding 3 parts of nano silica sol and 5 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex-mixing modified liquid;
S04: ball milling the bentonite complex-mixing modifying liquid and the double-effect modifier according to a weight ratio of 3:7, wherein the ball milling rotating speed is 1500r/min, ball milling is carried out for 2 hours, and after ball milling, water washing and drying are carried out to obtain the double-effect modifier based on bentonite modification.
The mass fraction of the sodium lignin sulfonate solution in the embodiment is 15%; the oscillation power of the oscillation modification treatment was 400W and the oscillation time was 30min.
The preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 2mol/L for reaction for 45min, wherein the reaction temperature is 70 ℃, and washing and drying after the reaction is finished;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
5 parts of dried nano silicon dioxide, 3 parts of lanthanum oxide coating agent, 10 parts of chitosan aqueous solution and 0.45 part of sodium hexametaphosphate are subjected to ball milling for 2 hours at the rotating speed of 1500r/min, and after ball milling, the double-effect regulator is obtained through water washing and drying.
The stirring speed of the immersion stirring treatment in this example was 650r/min and the stirring time was 30min.
The preparation method of the modifier for the doped glass fiber comprises the following steps:
S11: stirring and mixing glass fibers in hydrochloric acid solution with the total amount being 5 times of that of the glass fibers, washing with water, drying, and then radiating for 20min in a proton radiation box with the radiation power of 350W, and obtaining a glass fiber agent after the radiation is finished;
S12: and (3) carrying out ultrasonic treatment on 6 parts of glass fiber agent, 3 parts of hydroxyapatite, 2 parts of stearic acid and 10 parts of sodium dodecyl benzene sulfonate solution for 30min under the ultrasonic power of 450W, and then washing and drying to obtain the glass fiber doped modifier.
The mass fraction of the hydrochloric acid solution in this example is 5%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 15%.
The preparation method of the antibacterial and mildew-proof plastic film comprises the following steps:
sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with the length-diameter ratio of 40:1 of a single screw, sequentially carrying out plasticizing extrusion at 150 ℃, and carrying out inflation treatment, cooling and rolling with the inflation ratio of 3:1, thereby obtaining the antibacterial and mildew-proof plastic film.
Example 3.
The antibacterial mildew-proof plastic film comprises the following raw materials in parts by weight:
57.5 parts of low-density polyethylene, 12.5 parts of antibacterial and mildew-proof agent, 11 parts of regulating functional agent based on bentonite double-effect modification, 6.5 parts of lignin, 5.5 parts of modifier doped with glass fiber, 3.5 parts of plasticizer and 1.5 parts of heat stabilizer.
The low density polyethylene of this example had a melt flow rate of 4.5g/10min, a density of 0.922g/cm3 and a molecular weight distribution of 6.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
The preparation method of the bentonite adjustment and modification-based double-effect functional agent comprises the following steps:
S01: the bentonite is firstly heat-treated for 27min at 375 ℃, then cooled to 215 ℃ at the speed of 4 ℃/min, kept for 7.5min, finally cooled to 62 ℃ at the speed of 2 ℃/min, and kept for later use;
s02: 5.5 parts of bentonite with S01 heat preservation and 3 parts of tetrabutyl titanate are added into 12.5 parts of ethanol solvent, then 0.6 part of urea is added, the oscillation modification treatment is carried out, and the oscillation is finished, so as to obtain oscillation liquid;
S03: adding 2 parts of nano silica sol and 4 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex-mixing modified liquid;
S04: ball milling treatment is carried out on the bentonite complex-mixing modification solution and the double-effect modifier according to the weight ratio of 3:5.5, the ball milling rotating speed is 1250r/min, the ball milling is carried out for 1.5 hours, and the double-effect modifier based on bentonite adjustment modification is obtained after the ball milling is finished, water washing and drying.
The mass fraction of the sodium lignin sulfonate solution of the embodiment is 12.5%; the oscillation power of the oscillation modification treatment is 375W, and the oscillation time is 25min.
The preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1.5mol/L for reaction for 42min, wherein the reaction temperature is 67 ℃, and after the reaction is finished, washing and drying;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4.5 parts of dried nano silicon dioxide, 2 parts of lanthanum oxide coating agent, 8 parts of chitosan aqueous solution and 0.40 part of sodium hexametaphosphate are subjected to ball milling for 1.5 hours at the rotating speed of 1250r/min, and after ball milling, the double-effect regulator is obtained through water washing and drying.
The stirring speed of the immersion stirring treatment in this example was 600r/min, and the stirring time was 25min.
The preparation method of the modifier for the doped glass fiber comprises the following steps:
S11: stirring and mixing glass fibers in hydrochloric acid solution with the total amount of 4 times of the glass fibers, washing with water, drying, and radiating in a proton radiation box for 17min with the radiation power of 325W, wherein the radiation is finished to obtain a glass fiber agent;
s12: 5 parts of glass fiber agent, 2 parts of hydroxyapatite, 1.5 parts of stearic acid and 7.5 parts of sodium dodecyl benzene sulfonate solution are subjected to ultrasonic treatment under the ultrasonic power of 425W for 25min, and after ultrasonic treatment, the glass fiber-doped modifier is obtained by washing and drying.
The mass fraction of the hydrochloric acid solution of this example was 3.5%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 12.5%.
The preparation method of the antibacterial and mildew-proof plastic film comprises the following steps:
Sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with a single-screw length-diameter ratio of 40:1, sequentially carrying out plasticizing extrusion at 149 ℃, and carrying out inflation treatment, cooling and rolling with an inflation ratio of 3:1, thereby obtaining the antibacterial and mildew-proof plastic film.
Comparative example 1.
The difference from example 3 is that no dual effect functional agent based on bentonite conditioning modification was added.
Comparative example 2.
Unlike example 3, the dual effect functional agent preparation based on bentonite conditioning modification did not employ the S01 step treatment.
Comparative example 3.
The difference from example 3 is that the cooling to 215℃at a rate of 4℃per minute was not employed in the S01 step treatment, and the heat was preserved for 7.5 min.
Comparative example 4.
The difference from example 3 is that nano silica sol and sodium lignin sulfonate solution are not added in the preparation of the bentonite-based modified double-effect functional agent.
Comparative example 5.
The difference from example 3 is that 5.5 parts of S01 heat-preserving bentonite, 12.5 parts of ethanol solvent, 2 parts of nano silica sol and 4 parts of sodium lignin sulfonate solution are directly stirred fully in the preparation of the bentonite-based regulating and modifying double-effect functional agent, so as to obtain bentonite complex regulating and modifying liquid.
Comparative example 6.
The difference from example 3 is that the dual effect modifier treatment is not used in the dual effect modifier preparation based on bentonite modification.
Comparative example 7.
The difference from example 3 is that no modifier for the doped glass fibers is added.
Comparative example 8.
The difference from example 3 is the preparation of the modifier for doped glass fibers: the step S11 process is not adopted.
Comparative example 9.
The difference from example 3 is the preparation of the modifier for doped glass fibers: the step S12 process is not adopted.
Comparative example 10.
Unlike example 3, no hydroxyapatite or stearic acid was added in the treatment of step S12.
Comparative example 11.
Unlike example 3, which is a step S12 method, 2 parts of hydroxyapatite, 1.5 parts of stearic acid and 7.5 parts of sodium dodecyl benzene sulfonate solution were sonicated for 25 minutes under a ultrasonic power of 425W, and the sonication was ended, followed by washing with water and drying to obtain a hydroxyapatite modifier, and a glass fiber agent was not added.
The products of examples 1 to 3 and comparative examples 1 to 11 were subjected to performance tests, using E.coli and A.flavus as examples, to test the antibacterial property, the mold-proof durability, and the tensile strength properties of the products, and the test results were as follows
Soaking the product in water for 12 hours, scraping for 100 times, and testing the water resistance and scraping stability of the product, wherein the test results are as follows;
immersing the product in water for 12 hours, then scraping 100 times, and performing conventional tests, and it can be seen from comparative examples 1 to 11 and examples 1 to 3;
The product of the embodiment 3 has excellent escherichia coli and mould antibacterial rate and tensile strength performance, can realize coordinated improvement, has obvious antibacterial persistence effect, and has obvious water resistance and scratch stability effects;
As shown in comparative examples 1, 7 and 3, the invention has no addition of bentonite-based modifying double-effect functional agent or modifier doped with glass fiber, the performance of the product has obvious deterioration tendency, and the two components are cooperated to cooperate together, so that the performance effect of the product is most remarkable;
From comparative examples 1 to 6 and example 3, the preparation of the dual-effect functional agent based on bentonite adjustment and modification does not adopt S01 step treatment, the treatment of S01 step does not adopt the cooling to 215 ℃ at the speed of 4 ℃/min, the treatment of heat preservation is carried out for 7.5min, the preparation of the dual-effect functional agent based on bentonite adjustment and modification does not add nano silica sol and sodium lignin sulfonate solution, the preparation of the dual-effect functional agent based on bentonite adjustment and modification directly carries out the stirring of 5.5 parts of bentonite subjected to S01 heat preservation, 12.5 parts of ethanol solvent, 2 parts of nano silica sol and 4 parts of sodium lignin sulfonate solution fully to obtain bentonite complex-adjustment modified liquid, the performance of the product has a deterioration trend, the specific S01 step treatment is adopted to match with the specific bentonite complex-adjustment modified liquid, and the performance effect of the product is most obvious;
The double-effect modifier is not adopted in the preparation of the double-effect modifier based on bentonite regulation and modification, the performance of the product has a larger influence trend in the preparation of the double-effect modifier based on bentonite regulation and modification, the double-effect modifier based on bentonite regulation and modification prepared by the method has the most obvious performance effect, and other methods are adopted to replace the double-effect modifier with less obvious effect;
As can be seen from comparative examples 7 to 11 and example 3, the preparation method of the modifier for doped glass fiber is different: the method does not adopt the step S11 treatment, does not adopt the step S12 treatment, is different in the step S12 treatment without adding hydroxyapatite, stearic acid and the step S12 treatment, and comprises the steps of carrying out ultrasonic treatment on 2 parts of hydroxyapatite, 1.5 parts of stearic acid and 7.5 parts of sodium dodecyl benzene sulfonate solution under the ultrasonic power of 425W for 25min, finishing ultrasonic treatment, washing with water and drying to obtain a hydroxyapatite modifier, and does not add a glass fiber agent, wherein the performance of the product is in a poor trend, and the special step S12 method is matched with the step S11 treatment of the invention, so that the performance effect of the product is most remarkable.
The preparation method of the double-effect regulator comprises the following steps:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1.5mol/L for reaction for 42min, wherein the reaction temperature is 67 ℃, and after the reaction is finished, washing and drying;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4.5 parts of dried nano silicon dioxide, 2 parts of lanthanum oxide coating agent, 8 parts of chitosan aqueous solution and 0.40 part of sodium hexametaphosphate are subjected to ball milling for 1.5 hours at the rotating speed of 1250r/min, and after ball milling, the double-effect regulator is obtained through water washing and drying.
The stirring speed of the immersion stirring treatment in this example was 600r/min, and the stirring time was 25min.
The invention further explores the product performance through the preparation of the double-effect regulator;
Experimental example 1.
The only difference from example 3 is that no dry nanosilica was added in the dual use regulator preparation.
Experimental example 2.
The only difference from example 3 is that no nanosilica was used in the preparation of the dual effect regulator and was subjected to a reaction treatment in a sufficient amount of 1.5mol/L potassium permanganate solution.
Experimental example 3.
The only difference from example 3 is that no lanthanum oxide coating agent was added in the preparation of the dual effect regulator.
Experimental example 4.
The only difference from example 3 is that the lanthanum oxide coating agent is replaced by lanthanum oxide.
Experimental example 5.
The only difference from example 3 is that the chitosan aqueous solution was replaced with deionized water.
The product is soaked in water for 12 hours, then scraped for 100 times, and the water resistance and the scraping stability of the product are tested as the basic performance test, wherein the performance test is as follows;
As can be seen from experimental examples 1-5, the preparation of the double-effect regulator is not added with dried nano silicon dioxide and lanthanum oxide coating agent, the performance of the product has a larger deterioration trend, meanwhile, the nano silicon dioxide is not adopted to be placed in enough potassium permanganate solution with the concentration of 1.5mol/L for reaction treatment, the lanthanum oxide coating agent is replaced by lanthanum oxide and the chitosan aqueous solution is replaced by deionized water, the performance of the product has a deterioration trend, the double-effect regulator obtained by different methods is not better than the double-effect regulator prepared by the specific method, the performance effect of the product is the most remarkable, and the effect of the product is not better than that of the product prepared by other methods.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. An antibacterial and mildew-proof plastic film is characterized by comprising the following raw materials in parts by weight:
55-60 parts of low-density polyethylene, 10-15 parts of antibacterial mildew inhibitor, 8-14 parts of bentonite-based double-effect modified regulating functional agent, 5-8 parts of lignin, 4-7 parts of modifier doped with glass fiber, 2-5 parts of plasticizer and 1-2 parts of heat stabilizer.
2. The antibacterial and mildew-proof plastic film according to claim 1, wherein the antibacterial and mildew-proof plastic film comprises the following raw materials in parts by weight:
57.5 parts of low-density polyethylene, 12.5 parts of antibacterial and mildew-proof agent, 11 parts of regulating functional agent based on bentonite double-effect modification, 6.5 parts of lignin, 5.5 parts of modifier doped with glass fiber, 3.5 parts of plasticizer and 1.5 parts of heat stabilizer.
3. The antibacterial and mildew-proof plastic film according to claim 1, wherein the low-density polyethylene has a melt flow rate of 0.5-9.0 g/10min, a density of 0.920-0.925 g/cm3 and a molecular weight distribution of 4.0-8.0; the plasticizer is phthalate plasticizer; the heat stabilizer is calcium stearate; the antibacterial mildew inhibitor is prepared from nano silver oxide and carbendazim according to a weight ratio of 5:3.
4. The antibacterial and mildew-proof plastic film according to claim 1, wherein the preparation method of the bentonite-based modified double-effect functional agent is as follows:
s01: the bentonite is firstly heat treated for 25 to 30 minutes at 350 to 400 ℃, then cooled to 210 to 220 ℃ at the speed of 3 to 5 ℃/min, kept for 5 to 10 minutes, finally cooled to 60 to 65 ℃ at the speed of 1 to 3 ℃/min, and kept for later use;
S02: adding 4-7 parts of S01 heat-preserving bentonite and 2-4 parts of tetrabutyl titanate into 10-15 parts of ethanol solvent, then adding 0.5-0.7 part of urea, and carrying out oscillation modification treatment to obtain oscillation liquid after oscillation is finished;
s03: adding 1-3 parts of nano silica sol and 3-5 parts of sodium lignin sulfonate solution into the S02 oscillating liquid, and continuously stirring the mixture sufficiently to obtain bentonite complex formulation modified liquid;
s04: ball milling treatment is carried out on bentonite complex mixing modification liquid and double-effect modifier according to the weight ratio of 3 (4-7), the ball milling rotating speed is 1000-1500 r/min, ball milling is carried out for 1-2 h, and after ball milling, water washing and drying are carried out, thus obtaining the double-effect modifier based on bentonite adjustment modification.
5. The antibacterial and mildew-proof plastic film according to claim 4, wherein the mass fraction of the sodium lignin sulfonate solution is 10-15%; the oscillation power of the oscillation modification treatment is 350-400W, and the oscillation time is 20-30 min.
6. The antibacterial and mildew-proof plastic film according to claim 4, wherein the preparation method of the double-effect regulator is as follows:
Putting nano silicon dioxide into a sufficient amount of potassium permanganate solution with the concentration of 1-2 mol/L to react for 40-45 min, wherein the reaction temperature is 65-70 ℃, and after the reaction, washing and drying;
Immersing lanthanum oxide into a sodium silicate solution with the mass fraction of 10% according to the weight ratio of 1:5, and immersing and stirring to obtain a lanthanum oxide coating agent after stirring;
4-5 parts of dried nano silicon dioxide, 1-3 parts of lanthanum oxide coating agent, 6-10 parts of chitosan aqueous solution and 0.35-0.45 part of sodium hexametaphosphate are ball-milled for 1-2 hours at the rotating speed of 1000-1500 r/min, and the double-effect regulator is obtained after the ball milling is finished, water washing and drying.
7. The antibacterial and mildew-proof plastic film according to claim 6, wherein the stirring speed of the immersing and stirring treatment is 550-650 r/min, and the stirring time is 20-30 min.
8. The antibacterial and mildew-proof plastic film according to claim 1, wherein the preparation method of the modifier doped with glass fibers is as follows:
S11: stirring and mixing glass fiber in hydrochloric acid solution with the total amount of 3-5 times of the glass fiber, washing with water, drying, and then irradiating in a proton irradiation box for 15-20 min with the irradiation power of 300-350W, and obtaining a glass fiber agent after the irradiation is finished;
S12: 4 to 6 parts of glass fiber agent, 1 to 3 parts of hydroxyapatite, 1 to 2 parts of stearic acid and 5 to 10 parts of sodium dodecyl benzene sulfonate solution are subjected to ultrasonic treatment for 20 to 30 minutes under the ultrasonic power of 400 to 450W, and after the ultrasonic treatment is finished, the glass fiber-doped modifier is obtained by washing and drying.
9. The antibacterial and mildew-proof plastic film according to claim 8, wherein the mass fraction of the hydrochloric acid solution is 2-5%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 10-15%.
10. A method for producing an antibacterial and mildewproof plastic film as claimed in any one of claims 1 to 9, comprising the steps of:
Sequentially adding the raw materials into a stirrer, stirring and fully mixing, and then feeding the raw materials into a stirrer with the length-diameter ratio of 44:1, granulating at 165 ℃ in a double-screw extrusion granulator, adding the granulating material into a film blowing machine with a single-screw length-diameter ratio of 40:1, sequentially carrying out plasticizing extrusion at 148-150 ℃ and blowing expansion treatment with a blowing ratio of 3:1, cooling and rolling to obtain the antibacterial and mildew-proof plastic film.
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