CN113829689A - Antibacterial modified stone paper and production and preparation method thereof - Google Patents

Antibacterial modified stone paper and production and preparation method thereof Download PDF

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Publication number
CN113829689A
CN113829689A CN202111215738.6A CN202111215738A CN113829689A CN 113829689 A CN113829689 A CN 113829689A CN 202111215738 A CN202111215738 A CN 202111215738A CN 113829689 A CN113829689 A CN 113829689A
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antibacterial
stone paper
polylactic acid
film
master batch
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梅余球
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Shenzhen Stone Paper Co Ltd
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Shenzhen Stone Paper 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/30—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being formed of particles, e.g. chips, granules, powder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • 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

Abstract

The invention discloses antibacterial modified stone paper and a production and preparation method thereof, belongs to the technical field of stone paper preparation, and comprises a co-extruded antibacterial film layer and a base layer. According to the invention, when the surface of the graphene is grafted with polyethylene, nano silver and nano zinc particles in the polyethylene can form covalent bonds to be compounded on the surface of the graphene, so that the antibacterial treatment performance is effectively improved, the paper surface appearance performance and the heat-resistant strength can be improved after the film layer is co-extruded and blown out, meanwhile, the graphene particles can be prevented from agglomerating after the bidirectional extension and stretching master batch is blown out, the flow ductility of modified particles is improved, the physical strength can be improved after polylactic acid is crosslinked with ultrafine calcium carbonate powder and polypropylene, the polylactic acid has higher tensile strength and elongation, and good wear resistance, oil resistance and antibacterial ability are realized, and the antibacterial strength of an adhesion surface is favorably realized.

Description

Antibacterial modified stone paper and production and preparation method thereof
Technical Field
The invention belongs to the technical field of stone paper preparation, and particularly relates to antibacterial modified stone paper and a production and preparation method thereof.
Background
Along with economic development, the paper industry can prepare qualified paper stock due to the fact that people need to develop the paper and wood and water resources are consumed, so that the environment is seriously damaged, and the effect on the wood and the water resources can be reduced through the existing preparation of the calcium carbonate stone paper.
Chinese patent document CN109591340A discloses a method for producing antibacterial stone paper, comprising: 1) preparing antibacterial composite modified master batches, 2) preparing modified calcium carbonate master batches, and 3) preparing antibacterial stone paper. According to the invention, the nano inorganic antibacterial agent-calcium carbonate composite modified layer is arranged on one or two surfaces of the stone paper base layer, so that the antibacterial stone paper has excellent antibacterial and bacteriostatic properties while having chemical corrosion resistance, water resistance, moisture resistance, no deformation, good tensile strength and tear strength, and can be directly applied to packaging of foods and medicines. Meanwhile, compared with the traditional antibacterial material, the antibacterial material has better environmental protection characteristic. The nano TiO2 has an antibacterial effect, can further improve the degradability of the stone paper material through photocatalysis, but has certain defects in actual use, such as lack of heat insulation treatment capability after antibacterial modification, easy particle agglomeration during extension processing, and failure in meeting the requirement of large-scale production and processing.
Disclosure of Invention
The invention aims to: the antibacterial modified stone paper and the production and preparation method are provided in order to solve the problems that the heat insulation treatment capacity after antibacterial modification is lacked and the stored particles are easy to agglomerate during extension processing.
In order to achieve the purpose, the invention adopts the following technical scheme:
the antibacterial modified stone paper comprises a co-extruded antibacterial film layer and a base layer, wherein the antibacterial film layer comprises the following components in percentage by weight: 70-80% of superfine calcium carbonate powder, 2-5% of modified antibacterial particles, 1% of coupling agent, 2-5% of extrusion auxiliary agent, 14-23% of polypropylene and 2-5% of water-absorbing particles; the base layer comprises the following components in percentage by weight: 70-80% of superfine calcium carbonate powder, 1% of coupling agent, 2-5% of extrusion auxiliary agent, 14-23% of polypropylene and 2-5% of water-absorbing particles.
As a further description of the above technical solution:
the modified particles are graphene composite polylactic acid silver-loaded zinc particles, and the loaded polylactic acid particles are a blend of silver-loaded and zinc nanoparticles.
As a further description of the above technical solution:
the water absorption particles are one or a combination of thermoplastic starch, talcum powder, SiC micro powder and titanium dioxide.
As a further description of the above technical solution:
the coupling agent is at least one of silicone resin and polyamide resin.
As a further description of the above technical solution:
the production and preparation method of the antibacterial modified stone paper comprises the following steps:
s101, preparing modified polylactic acid, adding a polylactic acid material into a solvent, stirring at room temperature for 12 hours until the polylactic acid is completely dissolved, then adding quantitative silver nanoparticles and zinc nanoparticles into the solution, stirring for 24 hours to uniformly mix the silver nanoparticles and the zinc nanoparticles, performing ultrasonic treatment in an ultrasonic water bath for 20 minutes to uniformly disperse the silver nanoparticles and the zinc nanoparticles in the polylactic acid solvent, standing for defoaming, and keeping for later use;
s102, adding the prepared polylactic acid solvent into the graphene oxide dispersion liquid, fully heating and mixing the materials, then thermally crosslinking the polylactic acid solvent into micropores of the graphene oxide to obtain a modified graphene solution, and reserving the modified graphene solution for preparation;
s103, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing the modified graphene solution, the processing aid and the polypropylene, melting by an internal mixer, and obtaining a pellet master batch by a granulator to obtain an antibacterial film master batch;
s104, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing, synchronously adding a processing aid and polypropylene, mixing, melting by an internal mixer, and obtaining a granule master batch by a granulator to obtain a base master batch;
and S105, feeding the obtained base layer master batch and the obtained antibacterial film layer master batch into a double-screw extruder, melting and rotating the master batch by the double screws of the extruder, extruding the master batch by a machine head under pressure, stretching the master batch extruded by the machine head into a film, and cutting the film to obtain the stone paper main body.
As a further description of the above technical solution:
in the S1O1, the polylactic acid material solvent is Hexafluoroisopropanol (HFIP), and the mass fraction is 15%.
As a further description of the above technical solution:
in S105, the extrusion mode of the extruder is one of a calendered film, a cast film and a biaxial stretching blown film, the temperature of the extruder body is 175-198 ℃, and the rotating speed of the screw is controlled at 22-52 r/min.
As a further description of the above technical solution:
the bidirectional stretching and film blowing also comprises a hollow film tube extruded at the head part of the extruder, compressed inert air is introduced into the head to expand and extend the film tube outwards, and the inner cavity blowing device blows and extends and stretches towards the longitudinal two sides, and bidirectional tissues are stretched.
As a further description of the above technical solution:
and the thermal crosslinking temperature of the graphene oxide in the S102 is 55-60 ℃.
As a further description of the above technical solution:
the stirring speed in the S103 and the S104 is 1000-2000 r/min, and the temperature is controlled to be 65-70 ℃.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, when the surface of the graphene is grafted with polyethylene, nano silver and nano zinc particles in the polyethylene can form covalent bonds to be compounded on the surface of the graphene, so that the antibacterial treatment performance is effectively improved, the paper surface appearance performance and the heat-resistant strength can be improved after the film layer is co-extruded and blown out, meanwhile, the graphene particles can be prevented from agglomerating after the bidirectional extension and stretching master batch is blown out, the flow ductility of modified particles is improved, the physical strength can be improved after polylactic acid is crosslinked with ultrafine calcium carbonate powder and polypropylene, the polylactic acid has higher tensile strength and elongation, and good wear resistance, oil resistance and antibacterial ability are realized, and the antibacterial strength of an adhesion surface is favorably realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention provides a technical scheme that: the antibacterial modified stone paper comprises a co-extruded antibacterial film layer and a base layer, wherein the antibacterial film layer comprises the following components in percentage by weight: 70% of superfine calcium carbonate powder, 2% of modified antibacterial particles, 1% of coupling agent, 2% of extrusion aid, 14% of polypropylene and 2% of water-absorbing particles; the base layer comprises the following components in percentage by weight: 70% of superfine calcium carbonate powder, 1% of coupling agent, 2% of extrusion aid, 14% of polypropylene and 2% of water-absorbing particles, wherein the modified particles are graphene composite polylactic acid silver-loaded zinc particles, the loaded polylactic acid particles are a blend of silver-loaded and zinc nanoparticles, the water-absorbing particles are one or a combination of thermoplastic starch, talcum powder, SiC micropowder and titanium dioxide, and the coupling agent is at least one of organic silicon resin and polyamide resin.
The production and preparation method of the antibacterial modified stone paper specifically comprises the following steps:
s101, preparing modified polylactic acid, namely adding a polylactic acid material into a solvent, stirring at room temperature for 12 hours until the polylactic acid is completely dissolved, then adding quantitative silver nanoparticles and zinc nanoparticles into the solution, stirring for 24 hours to uniformly mix the silver nanoparticles and the zinc nanoparticles, performing ultrasonic treatment in an ultrasonic water bath for 20 minutes to uniformly disperse the silver nanoparticles and the zinc nanoparticles in the polylactic acid solvent, standing for defoaming, and reserving the solution for preparation, wherein in S1O1, the polylactic acid material solvent is Hexafluoroisopropanol (HFIP), and the mass fraction of the polylactic acid material solvent is 15%;
s102, adding the prepared polylactic acid solvent into the graphene oxide dispersion liquid, fully heating and mixing the materials, and then thermally crosslinking the polylactic acid solvent into micropores of the graphene oxide to obtain a modified graphene solution and reserving the modified graphene solution for preparation, wherein the thermal crosslinking temperature of the graphene oxide in the S102 is 55-60 ℃;
s103, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing the modified graphene solution, the processing aid and the polypropylene, melting by an internal mixer, and obtaining a pellet master batch by a granulator to obtain an antibacterial film master batch;
s104, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing, synchronously adding a processing aid and polypropylene, mixing, melting by an internal mixer, and obtaining a granule master batch by a granulator to obtain a base master batch;
the stirring speed in the S103 and the S104 is 1000-2000 r/min, and the temperature is controlled to be 65-70 ℃;
and S105, feeding the obtained base layer master batch and the obtained antibacterial film layer master batch into a double-screw extruder, melting and rotating the master batch by double screws of the extruder, extruding the master batch by the extruder through a machine head under pressure, stretching and film-forming the master batch by the machine head, and cutting to obtain the stone paper main body, wherein in the S105, the extrusion mode of the extruder is one of a calendered film, a cast film and a bidirectional stretching and blowing film, the temperature of the machine body of the extruder is 175-198 ℃, the rotating speed of the screw rod is controlled at 22-52r/min, the bidirectional stretching and blowing film further comprises extruding a hollow film pipe at the head part of the extruder, introducing compressed inert air into the machine head part to expand and extend the film pipe outwards, blowing and extending the film pipe to the longitudinal two sides by an inner cavity blowing device, and stretching the bidirectional tissue.
The implementation mode is specifically as follows: the water absorption particles are thermoplastic starch, talcum powder, SiC micro powder and titanium dioxide, water molecules in the production of the stone paper can be removed by utilizing the self water absorption after the stone paper is prepared, the moisture-proof and corrosion-resistant strength is effectively improved, meanwhile, air bubbles extruded from the interior of the stone paper after the stone paper is prepared can be reduced through the water absorption, and the attractive strength of the stone paper after the stone paper is produced is effectively improved.
Example 2
The invention provides a technical scheme that: the antibacterial modified stone paper comprises a co-extruded antibacterial film layer and a base layer, wherein the antibacterial film layer comprises the following components in percentage by weight: 80% of superfine calcium carbonate powder, 5% of modified antibacterial particles, 1% of coupling agent, 5% of extrusion aid, 23% of polypropylene and 5% of water-absorbing particles; the base layer comprises the following components in percentage by weight: the composite material comprises 80% of superfine calcium carbonate powder, 1% of coupling agent, 5% of extrusion aid, 23% of polypropylene and 5% of water-absorbing particles, wherein the modified particles are graphene composite polylactic acid silver-zinc-loaded particles, the loaded polylactic acid particles are a blend of silver-loaded and zinc nanoparticles, the water-absorbing particles are one or a combination of thermoplastic starch, talcum powder, SiC micropowder and titanium dioxide, and the coupling agent is at least one of organic silicon resin and polyamide resin.
The production and preparation method of the antibacterial modified stone paper specifically comprises the following steps:
s101, preparing modified polylactic acid, namely adding a polylactic acid material into a solvent, stirring at room temperature for 12 hours until the polylactic acid is completely dissolved, then adding quantitative silver nanoparticles and zinc nanoparticles into the solution, stirring for 24 hours to uniformly mix the silver nanoparticles and the zinc nanoparticles, performing ultrasonic treatment in an ultrasonic water bath for 20 minutes to uniformly disperse the silver nanoparticles and the zinc nanoparticles in the polylactic acid solvent, standing for defoaming, and reserving the solution for preparation, wherein in S1O1, the polylactic acid material solvent is Hexafluoroisopropanol (HFIP), and the mass fraction of the polylactic acid material solvent is 15%;
s102, adding the prepared polylactic acid solvent into the graphene oxide dispersion liquid, fully heating and mixing the materials, and then thermally crosslinking the polylactic acid solvent into micropores of the graphene oxide to obtain a modified graphene solution and reserving the modified graphene solution for preparation, wherein the thermal crosslinking temperature of the graphene oxide in the S102 is 55-60 ℃;
s103, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing the modified graphene solution, the processing aid and the polypropylene, melting by an internal mixer, and obtaining a pellet master batch by a granulator to obtain an antibacterial film master batch;
s104, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing, synchronously adding a processing aid and polypropylene, mixing, melting by an internal mixer, and obtaining a granule master batch by a granulator to obtain a base master batch;
the stirring speed in the S103 and the S104 is 1000-2000 r/min, and the temperature is controlled to be 65-70 ℃;
and S105, feeding the obtained base layer master batch and the obtained antibacterial film layer master batch into a double-screw extruder, melting and rotating the master batch by double screws of the extruder, extruding the master batch by the extruder through a machine head under pressure, stretching and film-forming the master batch by the machine head, and cutting to obtain the stone paper main body, wherein in the S105, the extrusion mode of the extruder is one of a calendered film, a cast film and a bidirectional stretching and blowing film, the temperature of the machine body of the extruder is 175-198 ℃, the rotating speed of the screw rod is controlled at 22-52r/min, the bidirectional stretching and blowing film further comprises extruding a hollow film pipe at the head part of the extruder, introducing compressed inert air into the machine head part to expand and extend the film pipe outwards, blowing and extending the film pipe to the longitudinal two sides by an inner cavity blowing device, and stretching the bidirectional tissue.
Example 3
The invention provides a technical scheme that: the antibacterial modified stone paper comprises a co-extruded antibacterial film layer and a base layer, wherein the antibacterial film layer comprises the following components in percentage by weight: 75% of superfine calcium carbonate powder, 3.5% of modified antibacterial particles, 1% of coupling agent, 3.5% of extrusion aid, 18% of polypropylene and 3.5% of water-absorbing particles; the base layer comprises the following components in percentage by weight: 75% of superfine calcium carbonate powder, 1% of coupling agent, 3.5% of extrusion aid, 18% of polypropylene and 3.5% of water-absorbing particles, wherein the modified particles are graphene composite polylactic acid silver-zinc-loaded particles, the loaded polylactic acid particles are a blend of silver-loaded and zinc nanoparticles, the water-absorbing particles are one or a combination of thermoplastic starch, talcum powder, SiC micropowder and titanium dioxide, and the coupling agent is at least one of organic silicon resin and polyamide resin.
The production and preparation method of the antibacterial modified stone paper specifically comprises the following steps:
s101, preparing modified polylactic acid, namely adding a polylactic acid material into a solvent, stirring at room temperature for 12 hours until the polylactic acid is completely dissolved, then adding quantitative silver nanoparticles and zinc nanoparticles into the solution, stirring for 24 hours to uniformly mix the silver nanoparticles and the zinc nanoparticles, performing ultrasonic treatment in an ultrasonic water bath for 20 minutes to uniformly disperse the silver nanoparticles and the zinc nanoparticles in the polylactic acid solvent, standing for defoaming, and reserving the solution for preparation, wherein in S1O1, the polylactic acid material solvent is Hexafluoroisopropanol (HFIP), and the mass fraction of the polylactic acid material solvent is 15%;
s102, adding the prepared polylactic acid solvent into the graphene oxide dispersion liquid, fully heating and mixing the materials, and then thermally crosslinking the polylactic acid solvent into micropores of the graphene oxide to obtain a modified graphene solution and reserving the modified graphene solution for preparation, wherein the thermal crosslinking temperature of the graphene oxide in the S102 is 55-60 ℃;
s103, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing the modified graphene solution, the processing aid and the polypropylene, melting by an internal mixer, and obtaining a pellet master batch by a granulator to obtain an antibacterial film master batch;
s104, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing, synchronously adding a processing aid and polypropylene, mixing, melting by an internal mixer, and obtaining a granule master batch by a granulator to obtain a base master batch;
the stirring speed in the S103 and the S104 is 1000-2000 r/min, and the temperature is controlled to be 65-70 ℃;
and S105, feeding the obtained base layer master batch and the obtained antibacterial film layer master batch into a double-screw extruder, melting and rotating the master batch by double screws of the extruder, extruding the master batch by the extruder through a machine head under pressure, stretching and film-forming the master batch by the machine head, and cutting to obtain the stone paper main body, wherein in the S105, the extrusion mode of the extruder is one of a calendered film, a cast film and a bidirectional stretching and blowing film, the temperature of the machine body of the extruder is 175-198 ℃, the rotating speed of the screw rod is controlled at 22-52r/min, the bidirectional stretching and blowing film further comprises extruding a hollow film pipe at the head part of the extruder, introducing compressed inert air into the machine head part to expand and extend the film pipe outwards, blowing and extending the film pipe to the longitudinal two sides by an inner cavity blowing device, and stretching the bidirectional tissue.
Test examples
The stone paper prepared in examples 1-3 and commercially available stone paper are used as comparative examples, colony culture tests are carried out, colonies are preferably staphylococcus aureus which is common in families, 20x20mm sample pieces are placed in a culture medium, strains are inoculated to the surface of the sample stone paper and are placed in a constant-temperature incubator for culture under the condition of 35 ℃ for 24 hours, the bacterial state is washed by a proper amount of 0.03mol/L phosphate buffer solution, microscopic counting is carried out, the appearance condition is observed at the same time, and the result is obtained by baking and curling at 100 ℃ as shown in the following table:
number of colonies Apparent condition Crimp time
Example 1 283 Is smooth and smooth 45.4s
Example 2 295 Is smooth and smooth 59.2s
Example 3 289 Is smoother 55.2s
Comparative example 350 Is smoother 40.1s
From the above table, with the addition of the amount of the modified particles, the agglomeration phenomenon gradually increases, which results in the reduction of the contact surface between the silver and zinc ions and the bacterial colony, and the change of the antibacterial capability and the fire resistance capability is affected, and the stone paper prepared in example 2 has higher antibacterial capability, smooth appearance and longer fire-resistant curling time, so that example 2 is a preferred embodiment of the present invention.
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. The antibacterial modified stone paper is characterized by comprising a co-extruded antibacterial film layer and a base layer, wherein the antibacterial film layer comprises the following components in percentage by weight: 70-80% of superfine calcium carbonate powder, 2-5% of modified antibacterial particles, 1% of coupling agent, 2-5% of extrusion auxiliary agent, 14-23% of polypropylene and 2-5% of water-absorbing particles; the base layer comprises the following components in percentage by weight: 70-80% of superfine calcium carbonate powder, 1% of coupling agent, 2-5% of extrusion auxiliary agent, 14-23% of polypropylene and 2-5% of water-absorbing particles.
2. The antibacterial modified stone paper as claimed in claim 1, wherein the modified particles are graphene composite polylactic acid silver-zinc-loaded particles, and the loaded polylactic acid particles are a blend of silver-loaded and zinc nanoparticles.
3. The antibacterial modified stone paper as claimed in claim 1, wherein the water-absorbing particles are one or a combination of thermoplastic starch, talcum powder, SiC micropowder and titanium dioxide.
4. The antibacterial modified stone paper as claimed in claim 1, wherein the coupling agent is at least one of silicone resin and polyamide resin.
5. The antibacterial modified stone paper as claimed in any one of claims 1 to 4, further comprising a production method of the antibacterial modified stone paper, which specifically comprises the following steps:
s101, preparing modified polylactic acid, adding a polylactic acid material into a solvent, stirring at room temperature for 12 hours until the polylactic acid is completely dissolved, then adding quantitative silver nanoparticles and zinc nanoparticles into the solution, stirring for 24 hours to uniformly mix the silver nanoparticles and the zinc nanoparticles, performing ultrasonic treatment in an ultrasonic water bath for 20 minutes to uniformly disperse the silver nanoparticles and the zinc nanoparticles in the polylactic acid solvent, standing for defoaming, and keeping for later use;
s102, adding the prepared polylactic acid solvent into the graphene oxide dispersion liquid, fully heating and mixing the materials, then thermally crosslinking the polylactic acid solvent into micropores of the graphene oxide to obtain a modified graphene solution, and reserving the modified graphene solution for preparation;
s103, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing the modified graphene solution, the processing aid and the polypropylene, melting by an internal mixer, and obtaining a pellet master batch by a granulator to obtain an antibacterial film master batch;
s104, stirring the superfine calcium carbonate powder at a high temperature, adding water-absorbing particles, mixing, adding a coupling agent, mixing, synchronously adding a processing aid and polypropylene, mixing, melting by an internal mixer, and obtaining a granule master batch by a granulator to obtain a base master batch;
and S105, feeding the obtained base layer master batch and the obtained antibacterial film layer master batch into a double-screw extruder, melting and rotating the master batch by the double screws of the extruder, extruding the master batch by a machine head under pressure, stretching the master batch extruded by the machine head into a film, and cutting the film to obtain the stone paper main body.
6. The method for producing antibacterial modified stone paper as claimed in claim 5, wherein in S1O1, the polylactic acid material solvent is Hexafluoroisopropanol (HFIP) and the mass fraction is 15%.
7. The method for producing the antibacterial modified stone paper as claimed in claim 5, wherein in S105, the extruder extrusion mode is one of a calendered film, a cast film and a biaxial stretching blown film, the temperature of the extruder body is 175-198 ℃, and the screw rotation speed is controlled at 22-52 r/min.
8. The method for producing the antibacterial modified stone paper as claimed in claim 7, wherein the bidirectional stretching and film blowing further comprises extruding a hollow film tube at the head part of the extruder, introducing compressed inert air into the head to expand and extend the film tube, blowing and extending the film tube to the longitudinal two sides by an inner cavity blowing device, and stretching the bidirectional tissue.
9. The antibacterial modified stone paper as claimed in claim 5, wherein the thermal crosslinking temperature of graphene oxide in S102 is 55-60 ℃.
10. The antibacterial modified stone paper and the production and preparation method thereof as claimed in claim 1, wherein the stirring rate in S103 and S104 is 1000-2000 r/min, and the temperature is controlled to be 65-70 ℃.
CN202111215738.6A 2021-10-19 2021-10-19 Antibacterial modified stone paper and production and preparation method thereof Pending CN113829689A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104059344A (en) * 2014-07-01 2014-09-24 南京理工大学 Polylactic acid/modified graphene oxide antibacterial plastic and preparation method
CN107415211A (en) * 2017-07-14 2017-12-01 成都新柯力化工科技有限公司 A kind of method for efficiently dispersing graphene in polymer
CN108329577A (en) * 2017-01-19 2018-07-27 合肥杰事杰新材料股份有限公司 A kind of feed back water suction master batch and preparation method thereof
CN109591340A (en) * 2018-12-13 2019-04-09 云南昆钢石头纸环保材料有限公司 A kind of production method of antibacterial stone paper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104059344A (en) * 2014-07-01 2014-09-24 南京理工大学 Polylactic acid/modified graphene oxide antibacterial plastic and preparation method
CN108329577A (en) * 2017-01-19 2018-07-27 合肥杰事杰新材料股份有限公司 A kind of feed back water suction master batch and preparation method thereof
CN107415211A (en) * 2017-07-14 2017-12-01 成都新柯力化工科技有限公司 A kind of method for efficiently dispersing graphene in polymer
CN109591340A (en) * 2018-12-13 2019-04-09 云南昆钢石头纸环保材料有限公司 A kind of production method of antibacterial stone paper

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