CN111592727A - Antibacterial polyvinyl chloride film and preparation method thereof - Google Patents
Antibacterial polyvinyl chloride film and preparation method thereof Download PDFInfo
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- CN111592727A CN111592727A CN202010518685.4A CN202010518685A CN111592727A CN 111592727 A CN111592727 A CN 111592727A CN 202010518685 A CN202010518685 A CN 202010518685A CN 111592727 A CN111592727 A CN 111592727A
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- polyvinyl chloride
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 97
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 94
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title description 8
- 239000000463 material Substances 0.000 claims abstract description 39
- -1 silver ions Chemical class 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 30
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 10
- 239000003549 soybean oil Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000945 filler Substances 0.000 claims abstract description 3
- 229920001897 terpolymer Polymers 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 14
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 12
- 239000008116 calcium stearate Substances 0.000 claims description 12
- 235000013539 calcium stearate Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- NAEDWKNFXVUORY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;hexanedioic acid Chemical group OCC(CO)(CO)CO.OC(=O)CCCCC(O)=O NAEDWKNFXVUORY-UHFFFAOYSA-N 0.000 claims description 9
- 238000003490 calendering Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- SPIUEOWNLJQKJK-UHFFFAOYSA-J 2-sulfanylacetate tin(4+) Chemical compound [Sn+4].[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS.[O-]C(=O)CS SPIUEOWNLJQKJK-UHFFFAOYSA-J 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 26
- 241000588747 Klebsiella pneumoniae Species 0.000 abstract description 3
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 3
- 241000588724 Escherichia coli Species 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 238000004804 winding Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 108020000946 Bacterial DNA Proteins 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 230000004543 DNA replication Effects 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000191070 Escherichia coli ATCC 8739 Species 0.000 description 1
- 238000009456 active packaging Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5816—Measuring, controlling or regulating temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/07—Aldehydes; Ketones
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- Mechanical Engineering (AREA)
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides an antibacterial polyvinyl chloride film: the composition comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 0.8-1.5 parts of silver ions, 1-2 parts of epoxidized soybean oil, 1.5-3 parts of a stabilizer, 0-20 parts of a plasticizer, 0-25 parts of a filler, 0-8 parts of a methyl methacrylate-butadiene-styrene terpolymer and 0-0.2 part of a lubricant; in the antibacterial polyvinyl chloride film, polyvinyl chloride is used as a film base material, and silver ions are uniformly distributed in the film base material. The antibacterial polyvinyl chloride film provided by the invention takes silver ions as effective antibacterial components, and can effectively and durably inhibit escherichia coli, staphylococcus aureus and klebsiella pneumoniae. The content of silver ions in the raw materials of the antibacterial polyvinyl chloride film provided by the invention is lower than that of the silver-containing polyvinyl chloride (PVC) film which is generally circulated at present, but stronger and more durable antibacterial property can be achieved.
Description
Technical Field
The invention belongs to the field of antibacterial materials, and particularly relates to an antibacterial polyvinyl chloride film and a preparation method thereof.
Background
At present, a large amount of polyvinyl chloride films are used in daily life, such as polyvinyl chloride films are used as decorative surface layers on the surfaces of walls, cabinets, wardrobes, table tops, suspended ceilings, floors, household appliances and the like and the surfaces of internal and external decorations of automobiles, ships and the like. Therefore, the polyvinyl chloride film is really accessible in modern society and is inseparable from the daily life of people.
With the rise of public health consciousness, in recent years, antibacterial active packaging materials have become a research hotspot in the field of materials. Research shows that the silver ions have good antibacterial effect, and the antibacterial mechanism of the silver ions is as follows:
(1) silver ions bind to the surface of bacterial cells, thereby destroying the cell wall and preventing bacterial cell growth;
(2) silver ions are adsorbed in cell enzymes by thiol groups of bacteria to prevent the bacteria from generating energy;
(3) silver ions terminate bacterial cell DNA, impeding bacterial DNA replication and preventing new cells from forming reproduction.
The research on the market of polyvinyl chloride films shows that currently, the commonly used antibacterial polyvinyl chloride film is prepared by directly coating an antibacterial component on the antibacterial film on the surface of the film, and the antibacterial polyvinyl chloride film is prepared by coating an antibacterial agent solution on the surface of a base film and then bonding the antibacterial agent solution with a material in the middle layer.
Disclosure of Invention
The invention aims to provide an antibacterial polyvinyl chloride film and a preparation method thereof, so that the polyvinyl chloride film has a good antibacterial effect.
According to one aspect of the present invention, there is provided an antibacterial polyvinyl chloride film: the coating comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 0.8-1.5 parts of silver ions, 1-2 parts of epoxidized soybean oil, 1.5-3 parts of a stabilizer, 0-20 parts of a plasticizer, 0-25 parts of a filler, 0-8 parts of a methyl methacrylate-butadiene-styrene terpolymer (MBS) and 0-0.2 part of a lubricant; in the antibacterial polyvinyl chloride film, polyvinyl chloride is used as a film base material, and silver ions are uniformly distributed in the film base material.
The antibacterial polyvinyl chloride film provided by the invention takes silver ions as effective antibacterial components, and can effectively and durably inhibit Escherichia coli, staphylococcus aureus and Klebsiella pneumoniae. The content of silver ions in the raw materials of the antibacterial polyvinyl chloride film provided by the invention is lower than that of the silver-containing polyvinyl chloride (PVC) film which is generally circulated at present, but stronger and more durable antibacterial property can be achieved. In the antibacterial polyvinyl chloride film, effective antibacterial components are uniformly distributed in the film base material, so that the effective antibacterial components can be durably retained in the film base material, volatilization and falling of the effective antibacterial components are avoided, in addition, a large amount of silver ions are not required to be added in the raw materials for maintaining the antibacterial property of the film, the cost input of the raw materials is reduced, the possibility that the falling or volatile silver ions damage human bodies and the environment is greatly reduced, the antibacterial polyvinyl chloride film has higher safety, and the sustainable development requirement of green and environment protection is met.
Optionally, the component further comprises 5-10 parts of titanium dioxide by mass. Optionally, the thickness of the antibacterial polyvinyl chloride film is 0.10-0.15 mm. The titanium dioxide in the antibacterial polyvinyl chloride film can not only generate a synergistic effect with silver ions to enhance the antibacterial capability of the film, but also effectively improve the shielding force and toughness of the film, so that the film is suitable for more use occasions and has better mechanical properties.
Preferably, the stabilizer comprises at least one of tin thioglycolate, calcium stearate, zinc stearate, beta-diketone, pentaerythritol ester.
Preferably, the stabilizers include calcium stearate, zinc stearate, beta-diketones, and pentaerythritol esters.
Preferably, the pentaerythritol ester is pentaerythritol adipate.
The stabilizer compounded by calcium stearate, zinc stearate, β -diketone and pentaerythritol ester can cooperate with the epoxy soybean oil, so that the heat resistance of the PVC film is effectively improved, in the PVC heating process, the calcium stearate and the zinc stearate can quickly absorb HCl generated by PVC decomposition, and stearate radicals are used for replacing instable chlorine atoms on a PVC chain, so that the initial degradation and coloring of PVC are effectively inhibited, and β -diketone and pentaerythritol adipate can carry out reaction on ZnCl obtained by converting the zinc stearate2Plays a role in chelation and avoids the phenomenon of 'zinc burning'. And the epoxy structure of the epoxidized soybean oil can also open a ring to absorb HCl, so that the epoxy structure of the epoxidized soybean oil and the components in the thermal stabilizer are synergistic.
According to another aspect of the present invention, there is provided a method for preparing the above antibacterial polyvinyl chloride film, comprising the steps of: step one, batching; step two, plasticizing: plasticizing after extruding by a planetary extruder; step three, open milling; step four, calendering: rolling by five rollers, wherein the temperature of a first roller is 177-195 ℃, and the rotating speed is 4-10R/min; the temperature of the second roller is 180-198 ℃, and the rotating speed is 14-23R/min; the temperature of the third roller is 186-200 ℃, and the rotating speed is 12-30R/min; the temperature of the fourth roller is 186-196 ℃, and the rotating speed is 20-33R/min; the temperature of the fifth roller is 155-175 ℃, and the rotating speed is 25-36R/min; step five, cooling; and step six, rolling.
Preferably, in the second step, the plasticizing temperature is 160-190 ℃. Preferably, the plasticizing time is 20-60 seconds.
Preferably, in the third step, the open milling temperature is 180-190 ℃. Preferably, the open time is 30-90 seconds.
Preferably, in the fifth step, the film led out from the fourth step passes through a plurality of groups of cooling rollers, and the temperature of the cooling rollers is 6-30 ℃.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
1. Preparation of PVC film to be tested
In this example, the polyvinyl chloride film was prepared using stabilizers of different compositions, polyvinyl chloride, and other raw materials to study the influence of the stabilizer composition on the thermal stability of the polyvinyl chloride film. In this example, 1 control group and 8 treatment groups were provided, the control group did not use a stabilizer, and the composition of the stabilizer used in each treatment group is shown in table 1.
TABLE 1 component composition (in parts by mass) of stabilizers corresponding to each treatment group
Treatment groups a to H PVC films were prepared according to the following method:
weighing 100 parts of polyvinyl chloride (with polymerization degree of 1000), 12 parts of plasticizer, 1 part of epoxidized soybean oil, 1.2 parts of silver ions, 1.6 parts of stabilizer and 0.15 part of lubricant according to parts by weight, heating to 190 ℃ to fully melt the materials, fully stirring in the heating process, pouring the obtained melt into a watch glass, and forming a film for later use after tetrahydrofuran volatilizes.
No stabilizer is added in the process of preparing the PVC membrane by the control group, and other operations are strictly consistent with those of the groups A to H.
2. Thermal stability test
The stability of the PVC film samples is tested with reference to the GB/T9349-2002 color change method, a PVC film having a thickness of about 1mm is cut at 1cm2The block of (1) was placed on an aluminum plate, heated at a constant temperature of 200 ℃ in a heat aging oven, sampled at regular intervals, and evaluated for thermal stability by observing the color of a PVC film sample.
3. Test results
The color observation results of the PVC film sample of this example are shown in table 2.
TABLE 2 color development of the PVC film sample of this example
According to the test results shown in Table 2, the PVC film samples prepared from the control group without using the stabilizer had poor heat resistance, hardly maintained colorless appearance under high temperature conditions, and rapidly deepened the color of the samples with the increase of heating time, compared to the control group, the corresponding PVC film samples had a gradual color deepening rate under high temperature conditions in the treatment groups using calcium stearate, zinc stearate, β -dione, and pentaerythritol adipate as the stabilizer alone, respectivelyThe PVC film sample prepared by the treatment group H also can generate better synergistic effect with effective components of other stabilizers, the fusant has good compatibility, probably because the melting point of the pentaerythritol adipate is lower, the materials are uniformly dispersed in a PVC melt, the heat resistance of the PVC film sample prepared by the treatment group H is optimal in all the treatment groups, the stabilizer adopted by the treatment group H simultaneously contains calcium stearate, zinc stearate, β -diketone and pentaerythritol adipate, in the process of heating the initial PVC, the calcium stearate and the initial PVC can absorb zinc stearate, and the zinc stearate can be effectively decomposed to replace zinc chloride atoms to generate zinc chloride atoms to degrade PVC, thereby effectively inhibiting zinc chloride atoms on PVC to generate zinc chloride atoms to degrade PVC2Plays a role in chelation and avoids the phenomenon of 'zinc burning'.
Example 2
The raw material components of the antibacterial polyvinyl chloride film prepared in this example are shown in table 3, and the required raw materials were weighed according to the parts by weight listed in table 3.
Table 3 raw material composition of antibacterial polyvinyl chloride film prepared in example 2
| Components | Parts by mass/parts | Components | Parts by mass/parts |
| PVC (degree of polymerization 1000) | 100 | Silver ion | 0.8 |
| Plasticizer | 20 | Calcium stearate | 1 |
| Calcium carbonate | 25 | Zinc stearate | 0.4 |
| Titanium dioxide | 10 | β -diones | 0.3 |
| Epoxidized soybean oil | 2 | Pentaerythritol adipate | 0.3 |
| Pigment (I) | 5 |
The antibacterial polyvinyl chloride film is prepared according to the following steps:
step one, adding all the raw materials listed in the table 3 into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the time is 360 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 180 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 186 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 186 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 179 ℃, and the rotating speed is 64 r/min; the temperature of the second roller is 180 ℃, and the rotating speed is 22.3 r/min; the temperature of the third roller is 188 ℃, and the rotating speed is 29.4 r/min; the temperature of the fourth roller is 181 ℃, and the rotating speed is 32.8 r/min; the temperature of the fifth roller is 148 ℃, and the rotating speed is 36.1 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 173 ℃, and the rotating speed is 66.7 r/min;
sixthly, leading the film out to pass through 6 groups of cooling rollers, wherein the temperature of the first group is 6 ℃, and the rotating speed is 70.3 r/min; the temperature of the second group is 6 ℃, and the rotating speed is 70.5 r/min; the third group temperature is 18 ℃, and the rotating speed is 70.5 r/min; the temperature of the fourth group is 18 ℃, the rotating speed is 70.5r/min, the temperature of the fifth group is 18 ℃, the rotating speed is 72.8r/min, and the temperature of the sixth group is 18 ℃, and the rotating speed is 72 r/min.
And step seven, drawing the cooled film to a winding machine for winding.
Comparative example 1
The raw material components of the antibacterial polyvinyl chloride film prepared in the comparative example are the same as those of example 2, and the antibacterial polyvinyl chloride film is prepared according to the following steps:
step one, adding all the raw materials listed in the table 3 except silver ions into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the stirring time is 360 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 180 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 186 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 186 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 179 ℃, and the rotating speed is 64 r/min; the temperature of the second roller is 180 ℃, and the rotating speed is 22.3 r/min; the temperature of the third roller is 188 ℃, and the rotating speed is 29.4 r/min; the temperature of the fourth roller is 181 ℃, and the rotating speed is 32.8 r/min; the temperature of the fifth roller is 148 ℃, and the rotating speed is 36.1 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 173 ℃, and the rotating speed is 66.7 r/min;
sixthly, leading the film out to pass through 6 groups of cooling rollers, wherein the temperature of the first group is 6 ℃, and the rotating speed is 70.3 r/min; the temperature of the second group is 6 ℃, and the rotating speed is 70.5 r/min; the third group temperature is 18 ℃, and the rotating speed is 70.5 r/min; the temperature of the fourth group is 18 ℃, the rotating speed is 70.5r/min, the temperature of the fifth group is 18 ℃, the rotating speed is 72.8r/min, and the temperature of the sixth group is 18 ℃, and the rotating speed is 72 r/min.
Step seven, drawing the cooled film to a winding machine for winding;
and step eight, dissolving silver ions in deionized water, uniformly coating the obtained silver ion aqueous solution on the surface of the PVC film, and performing vacuum drying at 60 ℃.
Comparative example 2
Except that the polyvinyl chloride film prepared by the comparative example does not add silver ions, the raw material components are the same as those in the example 2, and the film preparation steps and the process parameters are strictly consistent with those in the example 2.
Example 3
The raw material components of the antibacterial polyvinyl chloride film prepared in this example are shown in table 4, and the required raw materials were weighed according to the parts by mass listed in table 4.
Table 4 raw material composition of antibacterial polyvinyl chloride film prepared in example 3
| Components | Parts by mass/parts | Components | Parts by mass/parts |
| PVC (degree of polymerization 1000) | 100 | Calcium stearate | 0.8 |
| Silver ion | 1.2 | Zinc stearate | 0.3 |
| Plasticizer | 12 | β -diones | 0.2 |
| Epoxidized soybean oil | 1 | Pentaerythritol adipate | 0.3 |
| Lubricant agent | 0.15 |
The antibacterial polyvinyl chloride film is prepared according to the following steps:
step one, adding all the raw materials listed in the table 4 except silver ions into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the stirring time is 310 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 180 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 182 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 185 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 191 ℃, and the rotating speed is 9.6 r/min; the temperature of the second roller is 191 ℃, and the rotating speed is 14.4 r/min; the temperature of the third roller is 196 ℃, and the rotating speed is 18.1 r/min; the temperature of the fourth roller is 190 ℃, and the rotating speed is 20.9 r/min; the temperature of the fifth roller is 175 ℃, and the rotating speed is 25 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 170 ℃, and the rotating speed is 82 r/min;
step six, leading out the film and then passing through 6 groups of cooling rollers, wherein the first group of cooling rollers has the temperature of 18 ℃ and the rotating speed of 111 r/min; the temperature of the second group is 18 ℃, and the rotating speed is 111 r/min; the third group temperature is 20 ℃, and the rotating speed is 112 r/min; the temperature of the fourth group is 18 ℃, the rotating speed is 112r/min, the temperature of the fifth group is 20 ℃, the rotating speed is 112r/min, the temperature of the sixth group is 20 ℃, and the rotating speed is 112 r/min.
And step seven, drawing the cooled film to a winding machine for winding.
Comparative example 3
The raw material components of the antibacterial polyvinyl chloride film prepared in the comparative example were the same as those of example 3, and the antibacterial polyvinyl chloride film was prepared according to the following steps:
step one, adding all the raw materials listed in the table 4 into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the time is 310 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 180 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 182 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 185 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 191 ℃, and the rotating speed is 9.6 r/min; the temperature of the second roller is 191 ℃, and the rotating speed is 14.4 r/min; the temperature of the third roller is 196 ℃, and the rotating speed is 18.1 r/min; the temperature of the fourth roller is 190 ℃, and the rotating speed is 20.9 r/min; the temperature of the fifth roller is 175 ℃, and the rotating speed is 25 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 170 ℃, and the rotating speed is 82 r/min;
step six, leading out the film and then passing through 6 groups of cooling rollers, wherein the first group of cooling rollers has the temperature of 18 ℃ and the rotating speed of 111 r/min; the temperature of the second group is 18 ℃, and the rotating speed is 111 r/min; the third group temperature is 20 ℃, and the rotating speed is 112 r/min; the temperature of the fourth group is 18 ℃, the rotating speed is 112r/min, the temperature of the fifth group is 20 ℃, the rotating speed is 112r/min, the temperature of the sixth group is 20 ℃, and the rotating speed is 112 r/min.
Step seven, drawing the cooled film to a winding machine for winding;
and step eight, dissolving silver ions in deionized water, uniformly coating the obtained silver ion aqueous solution on the surface of the PVC film, and performing vacuum drying at 60 ℃.
Comparative example 4
Except that the polyvinyl chloride film prepared by the comparative example does not contain silver ions, the raw material components are the same as those in example 3, and the film preparation steps and the process parameters are strictly consistent with those in example 3
Example 4
The raw material components of the antibacterial polyvinyl chloride film prepared in this example are shown in table 5, and the required raw materials were weighed according to the parts by weight listed in table 5.
Table 5 raw material composition of antibacterial polyvinyl chloride film prepared in example 4
| Components | Parts by mass/parts | Components | Parts by mass/parts |
| PVC (degree of polymerization 800) | 100 | Silver ion | 1.5 |
| Plasticizer | 2 | Calcium stearate | 1 |
| Calcium carbonate | 2 | Zinc stearate | 0.4 |
| Titanium dioxide | 5 | β -diones | 0.3 |
| Epoxidized soybean oil | 2 | Pentaerythritol adipate | 0.3 |
| MBS | 8 |
The antibacterial polyvinyl chloride film is prepared according to the following steps:
step one, adding all the raw materials listed in the table 5 into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the time is 280 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 190 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 188 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 185 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 194 ℃, and the rotating speed is 9.4 r/min; the temperature of the second roller is 196 ℃, and the rotating speed is 12.5 r/min; the temperature of the third roller is 200 ℃, and the rotating speed is 15.5 r/min; the temperature of the fourth roller is 195 ℃ and the rotating speed is 19.2 r/min; the temperature of the fifth roller is 153 ℃, and the rotating speed is 22 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 173 ℃, and the rotating speed is 41 r/min;
sixthly, leading the film out to pass through 6 groups of cooling rollers, wherein the temperature of the first group is 30 ℃, and the rotating speed is 33.4 r/min; the temperature of the second group is 30 ℃, and the rotating speed is 35 r/min; the third group temperature is 20 ℃, and the rotating speed is 35.1 r/min; the temperature of the fourth group is 20 ℃, the rotating speed is 35.3r/min, the temperature of the fifth group is 20 ℃, the rotating speed is 35.3r/min, the temperature of the sixth group is 20 ℃, and the rotating speed is 35.3 r/min.
And step seven, drawing the cooled film to a winding machine for winding.
Comparative example 5
The raw material components of the antibacterial polyvinyl chloride film prepared in the comparative example were the same as those of example 4, and the antibacterial polyvinyl chloride film was prepared according to the following steps:
step one, adding all the raw materials listed in the table 5 except silver ions into a high-speed mixer for stirring and mixing, wherein the stirring speed is 1480r/min, and the stirring time is 280 s;
conveying the mixed materials to a planetary extruder for plasticizing, wherein the plasticizing temperature is 190 ℃ and the plasticizing time is 30 s;
conveying the material extruded by the planetary extruder to an open mill through a conveying belt, wherein the temperature is 188 ℃, and the open mill time is 60 s;
and step four, conveying the plasticized material to a five-roller calender, wherein the material temperature is 185 ℃, and the mechanical equipment parameters are as follows: the temperature of the first roller is 194 ℃, and the rotating speed is 9.4 r/min; the temperature of the second roller is 196 ℃, and the rotating speed is 12.5 r/min; the temperature of the third roller is 200 ℃, and the rotating speed is 15.5 r/min; the temperature of the fourth roller is 195 ℃ and the rotating speed is 19.2 r/min; the temperature of the fifth roller is 153 ℃, and the rotating speed is 22 r/min;
step five, leading out the film blank subjected to calendaring molding through a traction roller, wherein the temperature is 173 ℃, and the rotating speed is 41 r/min;
sixthly, leading the film out to pass through 6 groups of cooling rollers, wherein the temperature of the first group is 30 ℃, and the rotating speed is 33.4 r/min; the temperature of the second group is 30 ℃, and the rotating speed is 35 r/min; the third group temperature is 20 ℃, and the rotating speed is 35.1 r/min; the temperature of the fourth group is 20 ℃, the rotating speed is 35.3r/min, the temperature of the fifth group is 20 ℃, the rotating speed is 35.3r/min, the temperature of the sixth group is 20 ℃, and the rotating speed is 35.3 r/min.
Step seven, drawing the cooled film to a winding machine for winding;
and step eight, dissolving silver ions in deionized water, uniformly coating the obtained silver ion aqueous solution on the surface of the PVC film, and performing vacuum drying at 60 ℃.
Comparative example 6
Except that the polyvinyl chloride film prepared by the comparative example does not contain silver ions, the raw material components are the same as those in example 4, and the film preparation steps and the process parameters are strictly consistent with those in example 4
Test example
1. The sample to be tested and the grouping mode are as follows: in the test example, the antibacterial polyvinyl chloride films prepared in the same day in the examples 2 to 4 and the comparative examples 1 to 6 are used as samples to be tested, and antibacterial experiments are carried out in groups, wherein the grouping mode is as follows: grouping one, example 2, comparative example 1 and comparative example 2; group two, example 3, comparative example 3 and comparative example 4; grouping three, example 3, comparative example 5 and comparative example 6.
2. The detection method comprises the following steps: GB/T31402-2015/ISO 22196:2007(IDT)
3. Test strains: escherichia coli ATCC 8739, Staphylococcus aureus ATCC 6538P, Klebsiella pneumoniae ATCC 4352.
4. Test results
The test results for the grouping one to three are shown in tables 6 to 8.
Calculation of antimicrobial Performance values: the log mean of the number of bacteria 24 hours after inoculation of the non-antibacterial treated sample was subtracted from the log mean of the number of bacteria 24 hours after inoculation of the antibacterial treated sample, and the result was exposed to 1 digit after decimal point.
The results of the antibacterial experiments show that the antibacterial polyvinyl chloride films prepared in the examples 2, 3 and 4 have obviously stronger antibacterial effect. The embodiment 2, the embodiment 3 and the embodiment 4 respectively adopt a calendering mode to prepare the antibacterial polyvinyl chloride film, and the effective antibacterial ingredients are uniformly distributed in the film base material, so that the effective antibacterial ingredients can be durably retained in the film base material, volatilization and falling of the effective antibacterial ingredients are avoided, and the prepared antibacterial polyvinyl chloride film has better weather resistance and antibacterial property.
TABLE 6 antibacterial test results grouped in one
TABLE 7 antibacterial test results of group two
TABLE 8 antibacterial test results grouped in three
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes, modifications, and equivalents may be made therein without departing from the spirit and scope of the invention.
Claims (9)
1. An antibacterial polyvinyl chloride film, which is characterized in that:
the composition comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 0.8-1.5 parts of silver ions, 1-2 parts of epoxidized soybean oil, 1.5-3 parts of a stabilizer, 0-20 parts of a plasticizer, 0-25 parts of a filler, 0-8 parts of a methyl methacrylate-butadiene-styrene terpolymer and 0-0.2 part of a lubricant;
in the antibacterial polyvinyl chloride film, the polyvinyl chloride is used as a film base material, and the silver ions are uniformly distributed in the film base material.
2. The antimicrobial polyvinyl chloride film of claim 1, wherein: the titanium dioxide-containing paint also comprises 5-10 parts of titanium dioxide according to parts by mass.
3. The antimicrobial polyvinyl chloride film of claim 1, wherein: the stabilizer comprises at least one of tin thioglycolate, calcium stearate, zinc stearate, beta-diketone and pentaerythritol ester.
4. The antibacterial polyvinyl chloride film according to claim 3, wherein: the stabilizers include calcium stearate, zinc stearate, beta-diketones, and pentaerythritol esters.
5. The antibacterial polyvinyl chloride film according to claim 4, wherein: the pentaerythritol ester is pentaerythritol adipate.
6. The method for preparing an antibacterial polyvinyl chloride film according to any one of claims 1 to 5, comprising the steps of:
step one, batching;
step two, plasticizing: plasticizing after extruding by a planetary extruder;
step three, open milling;
step four, calendering: rolling by five rollers, wherein the temperature of a first roller is 177-195 ℃, and the rotating speed is 4-10R/min; the temperature of the second roller is 180-198 ℃, and the rotating speed is 14-23R/min; the temperature of the third roller is 186-200 ℃, and the rotating speed is 12-30R/min; the temperature of the fourth roller is 186-196 ℃, and the rotating speed is 20-33R/min; the temperature of the fifth roller is 155-175 ℃, and the rotating speed is 25-36R/min;
step five, cooling;
and step six, rolling.
7. The method for preparing an antibacterial polyvinyl chloride film according to claim 6, wherein: in the second step, the plasticizing temperature is 160-190 ℃.
8. The method for preparing an antibacterial polyvinyl chloride film according to claim 6, wherein: in the third step, the open milling temperature is 180-190 ℃.
9. The method for preparing an antibacterial polyvinyl chloride film according to claim 6, wherein: in the fifth step, the film led out in the fourth step passes through a plurality of groups of cooling rollers, and the temperature of the cooling rollers is 6-30 ℃.
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