CN115284707B - Preparation process of antibacterial environment-friendly medicine packaging composite film - Google Patents

Preparation process of antibacterial environment-friendly medicine packaging composite film Download PDF

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Publication number
CN115284707B
CN115284707B CN202210943663.1A CN202210943663A CN115284707B CN 115284707 B CN115284707 B CN 115284707B CN 202210943663 A CN202210943663 A CN 202210943663A CN 115284707 B CN115284707 B CN 115284707B
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stirring
composite film
montmorillonite
carvacrol
carboxymethyl cellulose
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CN115284707A (en
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张彩荣
袁晓松
周燊
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Changzhou Huajian Pharmaceutical Packaging Material Co ltd
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Changzhou Huajian Pharmaceutical Packaging Material Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • B32B15/088Layered products comprising a layer of metal comprising metal 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 comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal 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
    • B32B15/09Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/714Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145Rot proof, resistant to bacteria, mildew, mould, fungi
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/80Medical packaging
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/12Adsorbed ingredients, e.g. ingredients on carriers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Mechanical Engineering (AREA)
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a preparation process of an antibacterial environment-friendly medicine packaging composite film. The packaging composite film prepared from a large amount of green environment-friendly materials such as polylactic acid, carboxymethyl cellulose, zinc oxide, carvacrol and the like has good environment-friendliness. The carvacrol and zinc oxide are prepared into microcapsules and loaded on montmorillonite, so that the antibacterial property and mechanical property of the packaging composite film are improved. The polyamide film, the aluminum foil and the polylactic acid composite film are bonded together by using the adhesive, and the packaging composite film prepared by the method provided by the invention has good performance.

Description

Preparation process of antibacterial environment-friendly medicine packaging composite film
Technical Field
The invention relates to the technical field of packaging films, in particular to a preparation process of an antibacterial environment-friendly medicine packaging composite film.
Background
The composite packaging film is widely applied to the medical and pharmaceutical industry, and the composite packaging film consists of a base material, an adhesive and an aluminum foil. The base material is composed of plastic, so that the corrosion of air and water vapor can be effectively isolated, the medicine is prevented from being affected with damp, and the service life of the medicine is prolonged. The consumption of the medicine packaging film is increasing with the increasing sales of medicines, and the waste plastics can have adverse effects on the environment. Meanwhile, as a packaging film of a special material, the antibacterial property of plastics is poor.
In order to solve the problems, the invention provides a preparation process of an antibacterial environment-friendly medicine packaging composite film.
Disclosure of Invention
The invention aims to provide a preparation process of an antibacterial environment-friendly medicine packaging composite film, which aims to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
An antibacterial and environment-friendly medicine packaging composite film sequentially comprises a polyamide film, an aluminum foil and a polylactic acid composite film from top to bottom, wherein an adhesive is coated between the polyamide film and the aluminum foil and between the polylactic acid composite film and the aluminum foil.
More preferably, the adhesive is an epoxy adhesive.
More preferably, the method comprises the following steps:
Step one: stirring carboxymethyl cellulose and deionized water at 50-60deg.C for 50-60min, adding microcapsule-loaded montmorillonite, ultrasonic dispersing for 4-5 hr, centrifuging, washing, and drying to obtain modified montmorillonite-carboxymethyl cellulose compound;
Step two: taking the modified montmorillonite-carboxymethyl cellulose compound and deionized water, and performing ultrasonic dispersion for 50-70min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking polylactic acid and methylene dichloride, uniformly stirring at 48-55 ℃, adding modified montmorillonite-carboxymethyl cellulose compound mixed solution, performing ultrasonic dispersion for 3-5min, casting on a glass plate, drying at 25-27 ℃ for 22-24h, and stripping to obtain a polylactic acid composite film;
Step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; and coating an epoxy resin adhesive on the other side of the aluminum foil, compounding the polyamide film with one side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
More preferably, the molecular weight of the polylactic acid is 7000-10000g/mol.
More optimally, in the first step, the preparation method of the montmorillonite loaded with the microcapsules comprises the following steps: taking carvacrol-zinc oxide microcapsules and deionized water, stirring for 1.5-2.5 hours, adding dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8-8.5, performing ultrasonic dispersion for 40-60 minutes, adding montmorillonite, stirring for 20-24 hours at 30-35 ℃, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules.
More optimally, the mass ratio of the carvacrol-zinc oxide microcapsule to the dopamine to the montmorillonite is (2-4): (2-4): 1.
More optimally, the preparation method of the carvacrol-zinc oxide microcapsule comprises the following steps: uniformly stirring zinc acetate dihydrate and absolute ethyl alcohol to prepare zinc acetate dihydrate solution; mixing deionized water and sodium dodecyl sulfate at 60-65deg.C for 40-60min, adding paraffin, stirring for 40-60min, adding carvacrol, stirring for 2-4 hr, adding zinc acetate dihydrate solution, stirring for 2.5-3.5 hr, adding sodium hydroxide solution, stirring for 50-70min, heating to 80-85deg.C, aging for 4-6 hr, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsule.
More preferably, the mass ratio of the paraffin, carvacrol and zinc acetate dihydrate solution is 1: (1.3-1.5): (2.2-2.5).
Compared with the prior art, the invention has the following beneficial effects:
(1) Carvacrol is a natural antibacterial agent, is safe to use and has good bactericidal effect, and is coated in zinc oxide with no toxicity and good bacteriostasis to prepare Cheng Xiangqin phenol-zinc oxide microcapsules, and the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution is controlled to be 1: (1.3-1.5): (2.2-2.5). The microcapsule has slow release effect, and the antibacterial effect of the packaging composite film is enhanced.
(2) The carvacrol-zinc oxide microcapsule is loaded on montmorillonite, so that the phenomenon of mutual agglomeration among carvacrol-zinc oxide microcapsule particles can be improved. The carvacrol-zinc oxide microcapsules and the montmorillonite are adhered together through the dopamine, so that the influence on the activity of carvacrol caused by high-temperature calcination is avoided, meanwhile, the loading capacity of large montmorillonite is added, and the mechanical and antibacterial properties of the packaging composite film are effectively improved.
(3) The montmorillonite loaded with the microcapsule is loaded on natural cellulose carboxymethyl cellulose and added into polylactic acid. When the modified montmorillonite-carboxymethyl cellulose compound is prepared, the water temperature is raised to 50-60 ℃, and trace carvacrol is released at the moment, so that the modified montmorillonite-carboxymethyl cellulose compound can be used as an adhesive between montmorillonite and carboxymethyl cellulose, the montmorillonite and carboxymethyl cellulose can be well adhered together, and the usability of the polylactic acid compound film is improved.
(4) The invention selects a large amount of green environment-friendly materials such as polylactic acid, carboxymethyl cellulose, zinc oxide, carvacrol and the like, and the prepared packaging composite film has good environment-friendly property.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: step one: preparation of carvacrol-zinc oxide microcapsules:
Taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to prepare a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring for 50min at 62 ℃, adding 5g of paraffin, continuously stirring for 50min, adding 7g of carvacrol, continuously stirring for 3h, adding zinc acetate dihydrate solution, stirring for 3h, adding 100mL of sodium hydroxide solution, continuously stirring for 60min, heating to 82 ℃, aging for 5h, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsules.
Zinc acetate dihydrate is available from Jin Jinle chemical company, inc;
Controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1.4:2.3.
Step two: preparation of microencapsulated montmorillonite:
Taking 3g of carvacrol-zinc oxide microcapsules and 500mL of deionized water, stirring for 2 hours, adding 3g of dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, performing ultrasonic dispersion for 50 minutes, adding 1g of montmorillonite, stirring at 32 ℃ for 22 hours, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules.
Controlling the mass ratio of carvacrol-zinc oxide microcapsules to dopamine to montmorillonite to be 3:3:1.
Step three: preparation of modified montmorillonite-carboxymethyl cellulose composite:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 55min at 55 ℃, adding 0.5g of montmorillonite loaded with microcapsules, performing ultrasonic dispersion for 4.5h, centrifuging, washing and drying to obtain a modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step four: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 60min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
Step five: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Example 2: step one: preparation of carvacrol-zinc oxide microcapsules:
Taking 11g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to prepare a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring at 60 ℃ for 40min, adding 5g of paraffin, continuously stirring for 40min, adding 6.5g of carvacrol, continuously stirring for 2h, adding zinc acetate dihydrate solution, stirring for 2.5h, adding 100mL of sodium hydroxide solution, continuously stirring for 50min, heating to 80 ℃, aging for 4h, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsules.
Zinc acetate dihydrate is available from Jin Jinle chemical company, inc;
controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1.3:2.2.
Step two: preparation of microencapsulated montmorillonite:
Taking 2g of carvacrol-zinc oxide microcapsules and 500mL of deionized water, stirring for 1.5h, adding 2g of dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8, performing ultrasonic dispersion for 40min, adding 1g of montmorillonite, stirring at 30 ℃ for 20h, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules.
Controlling the mass ratio of carvacrol-zinc oxide microcapsules to dopamine to montmorillonite to be 2:2:1.
Step three: preparation of modified montmorillonite-carboxymethyl cellulose composite:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 50min at 55 ℃, adding 0.5g of montmorillonite loaded with microcapsules, performing ultrasonic dispersion for 4h, centrifuging, washing and drying to obtain a modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step four: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 50min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 48 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 3min, casting on a glass plate, drying at 25 ℃ for 22h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
Step five: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Example 3: step one: preparation of carvacrol-zinc oxide microcapsules:
Taking 12.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to prepare a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring for 60min at 65 ℃, adding 5g of paraffin, continuously stirring for 60min, adding 7.5g of carvacrol, continuously stirring for 4h, adding zinc acetate dihydrate solution, stirring for 3.5h, adding 100mL of sodium hydroxide solution, continuously stirring for 70min, heating to 85 ℃, aging for 6h, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsules.
Zinc acetate dihydrate is available from Jin Jinle chemical company, inc;
controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1.5:2.5.
Step two: preparation of microencapsulated montmorillonite:
Taking 4g of carvacrol-zinc oxide microcapsules and 500mL of deionized water, stirring for 2.5h, adding 4g of dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8.5, performing ultrasonic dispersion for 60min, adding 1g of montmorillonite, stirring at 35 ℃ for 24h, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules.
Controlling the mass ratio of carvacrol-zinc oxide microcapsules to dopamine to montmorillonite to be 4:4:1.
Step three: preparation of modified montmorillonite-carboxymethyl cellulose composite:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 60min at 55 ℃, adding 0.5g of montmorillonite loaded with microcapsules, performing ultrasonic dispersion for 5h, centrifuging, washing and drying to obtain a modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step four: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 70min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 55 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 5min, casting on a glass plate, drying at 27 ℃ for 24h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
The molecular weight of the polylactic acid is 7000-10000g/mol.
Step five: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Example 4: carvacrol was not added, the remainder being the same as in example 1.
Step one: preparation of microencapsulated montmorillonite:
Taking 3g of zinc oxide and 500mL of deionized water, stirring for 2 hours, adding 3g of dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, performing ultrasonic dispersion for 50 minutes, adding 1g of montmorillonite, stirring at 32 ℃ for 22 hours, filtering, washing and drying to obtain the zinc oxide-loaded montmorillonite.
The mass ratio of zinc oxide, dopamine and montmorillonite is controlled to be 3:3:1.
Step two: preparation of modified montmorillonite-carboxymethyl cellulose composite:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 55min at 55 ℃, adding 0.5g of montmorillonite loaded with zinc oxide, performing ultrasonic dispersion for 4.5h, centrifuging, washing and drying to obtain a modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step three: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 60min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
Step four: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Example 5: carvacrol-zinc oxide microcapsules were not supported on montmorillonite, the remainder being the same as in example 1.
Step one: preparation of carvacrol-zinc oxide microcapsules:
Taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to prepare a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring for 50min at 62 ℃, adding 5g of paraffin, continuously stirring for 50min, adding 7g of carvacrol, continuously stirring for 3h, adding zinc acetate dihydrate solution, stirring for 3h, adding 100mL of sodium hydroxide solution, continuously stirring for 60min, heating to 82 ℃, aging for 5h, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsules.
Zinc acetate dihydrate is available from Jin Jinle chemical company, inc;
Controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1.4:2.3.
Step two: preparation of modified microcapsule-carboxymethyl cellulose complex:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 55min at 55 ℃, adding 0.5g of carvacrol-zinc oxide microcapsule, performing ultrasonic dispersion for 4.5h, centrifuging, washing and drying to obtain the modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step three: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 60min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
Step four: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Example 6: controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1:2, the remainder being the same as in example 1.
Step one: preparation of carvacrol-zinc oxide microcapsules:
Taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to prepare a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring for 50min at 62 ℃, adding 5g of paraffin, continuously stirring for 50min, adding 7g of carvacrol, continuously stirring for 3h, adding zinc acetate dihydrate solution, stirring for 3h, adding 100mL of sodium hydroxide solution, continuously stirring for 60min, heating to 82 ℃, aging for 5h, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsules.
Zinc acetate dihydrate is available from Jin Jinle chemical company, inc;
Controlling the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution to be 1:1.4:2.3.
Step two: preparation of microencapsulated montmorillonite:
Taking 3g of carvacrol-zinc oxide microcapsules and 500mL of deionized water, stirring for 2 hours, adding 3g of dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, performing ultrasonic dispersion for 50 minutes, adding 1g of montmorillonite, stirring at 32 ℃ for 22 hours, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules.
Controlling the mass ratio of carvacrol-zinc oxide microcapsules to dopamine to montmorillonite to be 3:3:1.
Step three: preparation of modified montmorillonite-carboxymethyl cellulose composite:
Taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 55min at 55 ℃, adding 0.5g of montmorillonite loaded with microcapsules, performing ultrasonic dispersion for 4.5h, centrifuging, washing and drying to obtain a modified montmorillonite-carboxymethyl cellulose compound.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co.
Step four: preparation of polylactic acid composite film:
Taking 20g of modified montmorillonite-carboxymethyl cellulose compound and 200mL of deionized water, and performing ultrasonic dispersion for 60min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking 120g of polylactic acid and 2L of dichloromethane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, performing ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite film.
Polylactic acid is available from Nature Works, inc., USA under the model number 3001D.
Step five: coating an epoxy resin adhesive 506 on one surface of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; epoxy resin adhesive 506 is coated on the other side of the aluminum foil, and a polyamide film with the thickness of 25 mu m is compounded with one side of the aluminum foil coated with the epoxy resin adhesive and is rolled up, so that the high-barrier medicinal packaging film is obtained.
Epoxy adhesive 506 is available from zheng alpha chemical company.
Experiment
The polylactic acid composite films prepared in examples 1 to 6 were subjected to performance test, packaging films were prepared into 10mm×100mm samples, and the mechanical performance test was performed on the medicinal packaging films using an electronic universal mechanical tester at 25 ℃ and a loading speed of 5mm/min and an initial gauge length of 25 mm. Taking the polylactic acid composite membranes prepared in examples 1 to 6, preparing a sample with the diameter of 11mm, sterilizing for 1h by ultraviolet, coating 0.1mL of staphylococcus aureus with the bacterial concentration of 10 5 CFU/mL on the surface of a culture medium, covering the sterilized polylactic acid composite membrane, culturing for 24h at 37 ℃, and testing the antibacterial performance.
Conclusion: from the data in the table, the example 4 does not add carvacrol, the antibacterial property is poor, and the addition of carvacrol also affects the mechanical properties of the packaging composite film, so that the tensile strength of the composite film is better. Example 5 without loading carvacrol-zinc oxide microcapsules on montmorillonite, carvacrol-zinc oxide microcapsules are easily agglomerated in the system, affecting the packaging composite film performance. Example 6 control of paraffin, carvacrol, zinc acetate dihydrate solution mass ratio 1:1:2, the overall properties of the packaging film were inferior to those of examples 1 to 3.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. A preparation process of an antibacterial and environment-friendly medicine packaging composite film is characterized by comprising the following steps of: the method comprises the following steps:
Step one: stirring carboxymethyl cellulose and deionized water at 50-60deg.C for 50-60min, adding microcapsule-loaded montmorillonite, ultrasonic dispersing for 4-5 hr, centrifuging, washing, and drying to obtain modified montmorillonite-carboxymethyl cellulose compound;
Step two: taking the modified montmorillonite-carboxymethyl cellulose compound and deionized water, and performing ultrasonic dispersion for 50-70min to obtain a modified montmorillonite-carboxymethyl cellulose compound mixed solution; taking polylactic acid and methylene dichloride, uniformly stirring at 48-55 ℃, adding modified montmorillonite-carboxymethyl cellulose compound mixed solution, performing ultrasonic dispersion for 3-5min, casting on a glass plate, drying at 25-27 ℃ for 22-24h, and stripping to obtain a polylactic acid composite film;
Step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polylactic acid composite film with one surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating an epoxy resin adhesive on the other side of the aluminum foil, compounding a polyamide film with one side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a high-barrier medicinal packaging film;
In the first step, the preparation method of the montmorillonite loaded with the microcapsule comprises the following steps: taking carvacrol-zinc oxide microcapsules and deionized water, stirring for 1.5-2.5 hours, adding dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8-8.5, performing ultrasonic dispersion for 40-60 minutes, adding montmorillonite, stirring for 20-24 hours at 30-35 ℃, filtering, washing and drying to obtain the montmorillonite loaded with the microcapsules;
The preparation method of the carvacrol-zinc oxide microcapsule comprises the following steps: uniformly stirring zinc acetate dihydrate and absolute ethyl alcohol to prepare zinc acetate dihydrate solution; mixing deionized water and sodium dodecyl sulfate at 60-65deg.C for 40-60min, adding paraffin, stirring for 40-60min, adding carvacrol, stirring for 2-4 hr, adding zinc acetate dihydrate solution, stirring for 2.5-3.5 hr, adding sodium hydroxide solution, stirring for 50-70min, heating to 80-85deg.C, aging for 4-6 hr, washing, centrifuging, and drying to obtain carvacrol-zinc oxide microcapsule.
2. The process for preparing the antibacterial environment-friendly medicine packaging composite film according to claim 1, which is characterized in that: the molecular weight of the polylactic acid is 7000-10000g/mol.
3. The process for preparing the antibacterial environment-friendly medicine packaging composite film according to claim 1, which is characterized in that: the mass ratio of carvacrol-zinc oxide microcapsule to dopamine to montmorillonite is (2-4): (2-4): 1.
4. The process for preparing the antibacterial environment-friendly medicine packaging composite film according to claim 1, which is characterized in that: the mass ratio of the paraffin, carvacrol and zinc acetate dihydrate solution is 1: (1.3-1.5): (2.2-2.5).
5. A composite film prepared by the preparation process of the antibacterial environment-friendly medicine packaging composite film according to any one of claims 1 to 4, which is characterized in that: the adhesive is coated between the polyamide film and the aluminum foil and between the polylactic acid composite film and the aluminum foil;
The adhesive is an epoxy adhesive.
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