CN111703158A - Antibacterial biaxially oriented polyvinyl alcohol film and preparation method thereof - Google Patents

Antibacterial biaxially oriented polyvinyl alcohol film and preparation method thereof Download PDF

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Publication number
CN111703158A
CN111703158A CN202010472523.1A CN202010472523A CN111703158A CN 111703158 A CN111703158 A CN 111703158A CN 202010472523 A CN202010472523 A CN 202010472523A CN 111703158 A CN111703158 A CN 111703158A
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polyvinyl alcohol
antibacterial
layer
surface layer
biaxially oriented
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张贤宏
谢城城
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Anhui Guofeng Plastic Industry Co Ltd
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Anhui Guofeng Plastic Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08J2329/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2429/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

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  • Polymers & Plastics (AREA)
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  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention discloses an antibacterial biaxially oriented polyvinyl alcohol film and a preparation method thereof, relating to the technical field of films, wherein the film consists of an upper surface layer, a core layer and a lower surface layer; the upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of organic polymer anti-sticking master batch and 1.0-2.0% of antibacterial agent; the core layer is an antibacterial polyvinyl alcohol layer and is made of the following components in percentage by weight: 96-98% of modified polyvinyl alcohol, 1.0-2.0% of antistatic master batch and 1.0-2.0% of antibacterial agent; the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of slipping agent and 1.0-2.0% of antibacterial agent. The film prepared by the invention has excellent physical and mechanical properties and antibacterial properties, can be rapidly degraded in a specific environment, and is green and environment-friendly.

Description

Antibacterial biaxially oriented polyvinyl alcohol film and preparation method thereof
Technical Field
The invention relates to the technical field of films, in particular to an antibacterial biaxially oriented polyvinyl alcohol film and a preparation method thereof.
Background
Polyvinyl alcohol (PVA) is a few of industrially produced non-petroleum-based polymer materials that can be prepared from natural gas, and has applications in the fields of textiles, food, medicine, construction, wood processing, paper making, printing, agriculture, steel, polymer chemical industry, and the like. PVA has excellent acid and alkali resistance and organic solvent resistance, excellent barrier performance, good biocompatibility and biodegradability. However, the molecular chain of PVA has a polyhydroxy structure, and strong hydrogen bonds are generated in molecules and among molecules, so that the melting point and the decomposition temperature of the PVA are close to each other, and the PVA film is difficult to be processed by thermoplastic molding.
The biaxial stretching method has the advantages of large stretching ratio (the transverse stretching ratio can reach more than 10 times), high forming speed (the highest rolling speed can reach hundreds of meters per minute), high production efficiency, and better mechanical strength, optical property and thickness uniformity of the obtained film. At present, the PVA film is prepared by adopting a biaxial stretching method, but because the film-making process of the PVA film is complex, the PVA film is developed slowly at home, and foreign products have great impact on the industry. In addition, since a large amount of process aids such as plasticizers and lubricants are added in the preparation process of the PVA film, the PVA film is particularly easy to be damaged by microorganisms such as bacteria, fungi and mold, the mechanical property of the PVA film is influenced, and the safety and sanitation of the PVA film in the use process are also seriously influenced.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides an antibacterial biaxially oriented polyvinyl alcohol film and a preparation method thereof, and the prepared film has excellent physical and mechanical properties and antibacterial properties.
The invention provides an antibacterial biaxially oriented polyvinyl alcohol film which consists of an upper surface layer, a core layer and a lower surface layer;
the upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of organic polymer anti-sticking master batch and 1.0-2.0% of antibacterial agent;
the core layer is an antibacterial polyvinyl alcohol layer and is made of the following components in percentage by weight: 96-98% of modified polyvinyl alcohol, 1.0-2.0% of antistatic master batch and 1.0-2.0% of antibacterial agent;
the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of slipping agent and 1.0-2.0% of antibacterial agent.
Preferably, the melt index of the modified polyvinyl alcohol is 3.0-6.0 g/10min under the condition of 190 ℃/10kg, the melting point is 210-230 ℃, and the glass transition temperature is 75-85 ℃.
Preferably, the modified polyvinyl alcohol is prepared by blending, melting and co-extruding the following raw materials in percentage by weight: 75-89% of polyvinyl alcohol, 5-10% of glycerol, 5-10% of polyethylene glycol and 1-5% of water; preferably, the modified polyvinyl alcohol is prepared as follows: mixing polyvinyl alcohol, polyethylene glycol, glycerol and water, heating, stirring at constant temperature for reaction, and cooling after the reaction is finished to obtain the product; preferably, the heating temperature is 45-55 ℃, the stirring time is 60-90min, and preferably, the reaction is naturally cooled to 25-30 ℃ after the reaction is finished.
Preferably, the alcoholysis degree of the polyvinyl alcohol is 95-99 mol%, the polymerization degree is 1700-2400, and the average particle size is 300-400 μm; preferably, the polyethylene glycol has an average molecular weight of 200 to 400.
Preferably, the antibacterial agent is a silver-loaded zirconium phosphate antibacterial agent, the average particle size is 1-2 mu m, and the heat resistance is higher than 1300 ℃.
Preferably, the organic polymer anti-sticking master batch consists of the following raw materials in percentage by weight: 3-5% of polymethyl methacrylate microspheres and 95-97% of modified polyvinyl alcohol; preferably, the polymethyl methacrylate microsphere has an average particle size of 2.0-2.5 μm, an effective component of 2500-3000 ppm, and a thermal decomposition temperature of 250-300 ℃.
Preferably, the carrier in the antistatic master batch is polyvinyl alcohol, and the effective component is glyceryl monostearate; preferably, the content of the effective components in percentage by weight is 25-35%;
preferably, the slip agent is erucamide; preferably, the melting point of the erucamide is 72-77 ℃.
Preferably, the thicknesses of the upper surface layer and the lower surface layer respectively account for 10-15% of the total thickness of the film.
The invention also provides a preparation method of the antibacterial biaxially oriented polyvinyl alcohol film, which comprises the following steps:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 20-30 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 100-110 ℃, the stretching temperature is 95-110 ℃, and the longitudinal stretching ratio is 3.0-4.0 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 130-150 ℃, the stretching temperature is 130-150 ℃, and the transverse stretching magnification is 4.0-6.0 times.
Preferably, the extruder in the three-layer extruder die head is a single-screw extruder, the length-diameter ratio is 22-28, the screw heating area is not less than 6, the melting temperature is 160-200 ℃, and the die opening gap is less than 1 mm.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. the invention adopts a three-layer co-extrusion biaxial stretching method to directly prepare the polyvinyl alcohol film, and the prepared film has excellent physical and mechanical properties, can be quickly degraded in a specific environment, and is green and environment-friendly.
2. The invention selects the modified polyvinyl alcohol and the antibacterial agent with excellent antibacterial effect, and the prepared polyvinyl alcohol film has excellent physical and mechanical properties and antibacterial property.
3. The invention selects the novel organic polymer anti-adhesion agent, improves the film surface quality under the condition of meeting the rolling condition, and meets the requirements of downstream customers for use.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides an antibacterial biaxially oriented polyvinyl alcohol film which consists of an upper surface layer, a core layer and a lower surface layer; the thicknesses of the upper surface layer and the lower surface layer respectively account for 10 percent of the total thickness of the film.
The upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 96% of modified polyvinyl alcohol, 3.0% of organic polymer anti-sticking master batch and 1.0% of antibacterial agent; the core layer is an antibacterial polyvinyl alcohol layer, and the material of the core layer comprises the following components in percentage by weight: 98% of modified polyvinyl alcohol, 1.0% of antistatic master batch and 1.0% of antibacterial agent; the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 96% of modified polyvinyl alcohol, 3% of slipping agent and 1.0% of antibacterial agent.
The modified polyvinyl alcohol is prepared by blending, melting and co-extruding the following raw materials in percentage by weight: 89% of polyvinyl alcohol, 5% of glycerol, 5% of polyethylene glycol and 1% of water, and is prepared specifically as follows: mixing polyvinyl alcohol, polyethylene glycol, glycerol and water, heating to 45 ℃, stirring at a constant temperature for reaction for 60min, and naturally cooling to 25 ℃ after the reaction is finished to obtain the product; wherein, the alcoholysis degree of the polyvinyl alcohol is 95 mol%, the polymerization degree is 1800, and the average grain diameter is 300 mu m; the polyethylene glycol has an average molecular weight of 200.
The antibacterial agent is silver-loaded zirconium phosphate antibacterial agent with average particle size of 1 μm and heat resistance of more than 1300 deg.C.
The organic polymer anti-sticking master batch consists of the following raw materials in percentage by weight: 3% of polymethyl methacrylate microspheres and 97% of modified polyvinyl alcohol; wherein the polymethyl methacrylate microsphere has an average particle diameter of 2.0 μm, an effective component of 2500ppm, and a thermal decomposition temperature of 260 ℃.
The carrier in the antistatic master batch is polyvinyl alcohol, the effective component is glyceryl monostearate, and the weight percentage content of the effective component is 25%;
the slipping agent is erucamide, and the melting point of the slipping agent is 73 ℃.
The invention also provides a preparation method of the antibacterial biaxially oriented polyvinyl alcohol film, which comprises the following steps:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane; wherein the extruder in the three-layer extruder die head is a single-screw extruder, the length-diameter ratio is 22, the screw heating area is more than or equal to 6 areas, the melting temperature is 160-200 ℃, and the die orifice gap is less than 1 mm;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 20 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 100 ℃, the stretching temperature is 110 ℃, and the longitudinal stretching ratio is 3.0 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 140 ℃, the stretching temperature is 130 ℃, and the transverse stretching magnification is 4.5 times.
S5, air cooling the antibacterial biaxially-oriented polyvinyl alcohol film, flattening the film in a traction system, cutting edges, measuring thickness, and winding the film into a mother roll;
and S6, cutting and packaging the mother roll into a finished product after the mother roll is detected to be qualified.
Example 2
The invention provides an antibacterial biaxially oriented polyvinyl alcohol film which consists of an upper surface layer, a core layer and a lower surface layer; the thicknesses of the upper surface layer and the lower surface layer respectively account for 12 percent of the total thickness of the film.
The upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 94.5 percent of modified polyvinyl alcohol, 4.0 percent of organic polymer anti-sticking master batch and 1.5 percent of antibacterial agent; the core layer is an antibacterial polyvinyl alcohol layer, and the material of the core layer comprises the following components in percentage by weight: 97% of modified polyvinyl alcohol, 1.5% of antistatic master batch and 1.5% of antibacterial agent; the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 94.5 percent of modified polyvinyl alcohol, 4.0 percent of slipping agent and 1.5 percent of antibacterial agent.
The modified polyvinyl alcohol is prepared by blending, melting and co-extruding the following raw materials in percentage by weight: 81% of polyvinyl alcohol, 8% of glycerol, 8% of polyethylene glycol and 3% of water, and is prepared specifically as follows: mixing polyvinyl alcohol, polyethylene glycol, glycerol and water, heating to 50 ℃, stirring at constant temperature for reaction for 80min, and naturally cooling to 30 ℃ after the reaction is finished to obtain the product; wherein, the alcoholysis degree of the polyvinyl alcohol is 97mol percent, the polymerization degree is 2000, and the average grain diameter is 350 mu m; the polyethylene glycol has an average molecular weight of 300.
The antibacterial agent is silver-loaded zirconium phosphate antibacterial agent, the average grain diameter is 1.5 mu m, and the heat resistance is more than 1300 ℃.
The organic polymer anti-sticking master batch consists of the following raw materials in percentage by weight: 4% of polymethyl methacrylate microspheres and 96% of modified polyvinyl alcohol; wherein the average particle size of the polymethyl methacrylate microsphere is 2.3 μm, the effective component is 3000ppm, and the thermal decomposition temperature of the polymethyl methacrylate is 280 ℃.
The carrier in the antistatic master batch is polyvinyl alcohol, the effective component is glyceryl monostearate, and the weight percentage content of the effective component is 30%;
the slipping agent is erucamide, and the melting point of the slipping agent is 75 ℃.
The invention also provides a preparation method of the antibacterial biaxially oriented polyvinyl alcohol film, which comprises the following steps:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane; wherein the extruder in the three-layer extruder die head is a single-screw extruder, the length-diameter ratio is 26, the screw heating area is more than or equal to 6 areas, the melting temperature is 160-200 ℃, and the die orifice gap is less than 1 mm;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 23 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 105 ℃, the stretching temperature is 100 ℃, and the longitudinal stretching ratio is 3.5 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 130 ℃, the stretching temperature is 140 ℃, and the transverse stretching magnification is 5.0 times.
S5, air cooling the antibacterial biaxially-oriented polyvinyl alcohol film, flattening the film in a traction system, cutting edges, measuring thickness, and winding the film into a mother roll;
and S6, cutting and packaging the mother roll into a finished product after the mother roll is detected to be qualified.
Example 3
The invention provides an antibacterial biaxially oriented polyvinyl alcohol film which consists of an upper surface layer, a core layer and a lower surface layer; the thicknesses of the upper surface layer and the lower surface layer respectively account for 15 percent of the total thickness of the film.
The upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 93 percent of modified polyvinyl alcohol, 5.0 percent of organic polymer anti-sticking master batch and 2.0 percent of antibacterial agent; the core layer is an antibacterial polyvinyl alcohol layer, and the material of the core layer comprises the following components in percentage by weight: 96% of modified polyvinyl alcohol, 2.0% of antistatic master batch and 2.0% of antibacterial agent; the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 93 percent of modified polyvinyl alcohol, 5.0 percent of slipping agent and 2.0 percent of antibacterial agent.
The modified polyvinyl alcohol is prepared by blending, melting and co-extruding the following raw materials in percentage by weight: 75% of polyvinyl alcohol, 10% of glycerol, 10% of polyethylene glycol and 5% of water, and is prepared specifically as follows: mixing polyvinyl alcohol, polyethylene glycol, glycerol and water, heating to 55 ℃, stirring at a constant temperature for reaction for 90min, and naturally cooling to 30 ℃ after the reaction is finished to obtain the product; wherein, the alcoholysis degree of the polyvinyl alcohol is 99 mol%, the polymerization degree is 2400, and the average grain diameter is 400 μm; the polyethylene glycol has an average molecular weight of 400.
The antibacterial agent is silver-loaded zirconium phosphate antibacterial agent, the average particle size is 2 mu m, and the heat resistance is more than 1300 ℃.
The organic polymer anti-sticking master batch consists of the following raw materials in percentage by weight: 5% of polymethyl methacrylate microspheres and 95% of modified polyvinyl alcohol; wherein the average particle diameter of the polymethyl methacrylate microsphere is 2.5 μm, the effective component is 3000ppm, and the thermal decomposition temperature of the polymethyl methacrylate is 300 ℃.
The carrier in the antistatic master batch is polyvinyl alcohol, the effective component is glyceryl monostearate, and the weight percentage content of the effective component is 35%;
the slipping agent is erucamide, and the melting point of the slipping agent is 77 ℃.
The invention also provides a preparation method of the antibacterial biaxially oriented polyvinyl alcohol film, which comprises the following steps:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane; wherein the extruder in the three-layer extruder die head is a single-screw extruder, the length-diameter ratio is 22-28, the screw heating area is more than or equal to 6 areas, the melting temperature is 160-200 ℃, and the die opening gap is less than 1 mm;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 30 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 110 ℃, the stretching temperature is 95 ℃, and the longitudinal stretching ratio is 4.0 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 150 ℃, the stretching temperature is 140 ℃, and the transverse stretching magnification is 6.0 times.
S5, air cooling the antibacterial biaxially-oriented polyvinyl alcohol film, flattening the film in a traction system, cutting edges, measuring thickness, and winding the film into a mother roll;
and S6, cutting and packaging the mother roll into a finished product after the mother roll is detected to be qualified.
Comparative example 1
A common biaxially oriented polyvinyl alcohol film comprises an upper surface layer, a core layer and a lower surface layer; the thicknesses of the upper surface layer and the lower surface layer respectively account for 10 percent of the total thickness of the film.
The upper surface layer is an inorganic silica anti-sticking layer and consists of the following components in percentage by weight: 97% of polyvinyl alcohol and 3% of anti-sticking master batch; the core layer is a polyvinyl alcohol layer and consists of the following components in percentage by weight: 99% of polyvinyl alcohol and 1.0% of antistatic agent; the lower surface layer is a polyvinyl alcohol layer and consists of the following components in percentage by weight: 100 percent of polyvinyl alcohol.
Wherein the melt index of the polyvinyl alcohol is 3g/10min under the condition of 190 ℃/10 kg.
The anti-sticking master batch is composed of polyvinyl alcohol and silica particles, wherein the particle size of the silica is 2 mu m, and the effective component of the silica is 2000 ppm.
The preparation method comprises the following steps:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane; wherein the extruder in the three-layer extruder die head is a single-screw extruder, the length-diameter ratio is 22, the screw heating area is more than or equal to 6 areas, the melting temperature is 160-200 ℃, and the die orifice gap is less than 1 mm;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 20 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 100 ℃, the stretching temperature is 110 ℃, and the longitudinal stretching ratio is 3.0 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 140 ℃, the stretching temperature is 130 ℃, and the transverse stretching magnification is 4.5 times.
S5, air cooling the antibacterial biaxially-oriented polyvinyl alcohol film, flattening the film in a traction system, cutting edges, measuring thickness, and winding the film into a mother roll;
and S6, cutting and packaging the mother roll into a finished product after the mother roll is detected to be qualified.
To verify the effect of the present invention, the samples prepared in examples 1 to 3 and comparative example 1 were subjected to a comparative test, and the results are shown in table 1:
table 1: main physical property indexes of biaxially oriented polyvinyl alcohol films in examples 1 to 3 and comparative example 1
Figure BDA0002514801620000101
As can be seen from Table 1, the modified polyvinyl alcohol is selected for the antibacterial biaxially oriented polyvinyl alcohol film prepared by the invention, so that the strength of the film is improved; the organic polymer anti-adhesion master batch is adopted, and the friction coefficient is smaller than that of a common polyvinyl alcohol film; the antibacterial performance of the film is greatly improved by adding the high-efficiency antibacterial agent.
In the present invention, in the process for preparing the biaxially oriented polyvinyl alcohol film, additives such as a plasticizer and a lubricant may be added to each layer.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. An antibacterial biaxially oriented polyvinyl alcohol film is characterized by comprising an upper surface layer, a core layer and a lower surface layer;
the upper surface layer is an anti-sticking layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of organic polymer anti-sticking master batch and 1.0-2.0% of antibacterial agent;
the core layer is an antibacterial polyvinyl alcohol layer and is made of the following components in percentage by weight: 96-98% of modified polyvinyl alcohol, 1.0-2.0% of antistatic master batch and 1.0-2.0% of antibacterial agent;
the lower surface layer is an antibacterial smooth layer and is made of the following components in percentage by weight: 93-96% of modified polyvinyl alcohol, 3.0-5.0% of slipping agent and 1.0-2.0% of antibacterial agent.
2. The antibacterial biaxially oriented polyvinyl alcohol film according to claim 1, wherein the modified polyvinyl alcohol has a melt index of 3.0 to 6.0g/10min at 190 ℃/10kg, a melting point of 210 to 230 ℃ and a glass transition temperature of 75 to 85 ℃.
3. The antibacterial biaxially oriented polyvinyl alcohol film according to claim 1 or 2, wherein the modified polyvinyl alcohol is prepared by blending, melting and co-extruding the following raw materials in percentage by weight: 75-89% of polyvinyl alcohol, 5-10% of glycerol, 5-10% of polyethylene glycol and 1-5% of water; preferably, the modified polyvinyl alcohol is prepared as follows: mixing polyvinyl alcohol, polyethylene glycol, glycerol and water, heating, stirring at constant temperature for reaction, and cooling after the reaction is finished to obtain the product; preferably, the heating temperature is 45-55 ℃, the stirring time is 60-90min, and preferably, the reaction is naturally cooled to 25-30 ℃ after the reaction is finished.
4. The antibacterial biaxially oriented polyvinyl alcohol film according to claim 3, wherein the polyvinyl alcohol has an alcoholysis degree of 95 to 99 mol%, a polymerization degree of 1700 to 2400, and an average particle size of 300 to 400 μm; preferably, the polyethylene glycol has an average molecular weight of 200 to 400.
5. The antibacterial biaxially oriented polyvinyl alcohol film according to any one of claims 1 to 4, wherein the antibacterial agent is a silver-loaded zirconium phosphate antibacterial agent, the average particle diameter is 1 to 2 μm, and the heat resistance is > 1300 ℃.
6. The antibacterial biaxially oriented polyvinyl alcohol film according to any one of claims 1 to 5, wherein the organic polymer anti-adhesion master batch consists of the following raw materials in percentage by weight: 3-5% of polymethyl methacrylate microspheres and 95-97% of modified polyvinyl alcohol; preferably, the polymethyl methacrylate microsphere has an average particle size of 2.0-2.5 μm, an effective component of 2500-3000 ppm, and a thermal decomposition temperature of 250-300 ℃.
7. The antibacterial biaxially oriented polyvinyl alcohol film according to any one of claims 1 to 6, wherein the carrier in the antistatic master batch is polyvinyl alcohol, and the effective component is glyceryl monostearate; preferably, the content of the effective components in percentage by weight is 25-35%;
preferably, the slip agent is erucamide; preferably, the melting point of the erucamide is 72-77 ℃.
8. The antibacterial biaxially oriented polyvinyl alcohol film according to any one of claims 1 to 7, wherein the thicknesses of the upper surface layer and the lower surface layer respectively account for 10 to 15% of the total thickness of the film.
9. A method for preparing an antibacterial biaxially oriented polyvinyl alcohol film according to any one of claims 1 to 9, comprising the steps of:
s1, mixing the raw materials of each component of the core layer, adding the mixture into a main extruder for melt extrusion, and filtering the mixture by a filter to obtain a core layer melt; respectively adding the raw materials of the upper surface layer and the lower surface layer into two auxiliary extruders, melting, vacuumizing, and filtering by a filter to remove oligomers, water and impurities in the raw materials to obtain an upper surface layer melt and a lower surface layer melt; converging and extruding the upper-layer melt, the core-layer melt and the lower-layer melt in a three-layer extruder die head to obtain a membrane;
s2, attaching the membrane to a chill roll by electrostatic adsorption and quenching to form a cast sheet; wherein the cooling and shaping temperature of the cast sheet is 20-30 ℃;
s3, longitudinally stretching the cast sheet to obtain a thick sheet; wherein the preheating temperature of longitudinal stretching is 100-110 ℃, the stretching temperature is 95-110 ℃, and the longitudinal stretching ratio is 3.0-4.0 times;
s4, transversely stretching the thick sheet to obtain the antibacterial biaxially oriented polyvinyl alcohol film; wherein the preheating temperature of transverse stretching is 130-150 ℃, the stretching temperature is 130-150 ℃, and the transverse stretching magnification is 4.0-6.0 times.
10. The preparation method of the antibacterial biaxially oriented polyvinyl alcohol film according to claim 9, wherein an extruder in a die head of the three-layer extruder is a single-screw extruder, the length-diameter ratio is 22-28, a screw heating area is not less than 6, the melting temperature is 160-200 ℃, and the gap of the die opening is less than 1 mm.
CN202010472523.1A 2020-05-29 2020-05-29 Antibacterial biaxially oriented polyvinyl alcohol film and preparation method thereof Pending CN111703158A (en)

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Application publication date: 20200925