CN115284707A - 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
CN115284707A
CN115284707A CN202210943663.1A CN202210943663A CN115284707A CN 115284707 A CN115284707 A CN 115284707A CN 202210943663 A CN202210943663 A CN 202210943663A CN 115284707 A CN115284707 A CN 115284707A
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carvacrol
stirring
composite film
montmorillonite
carboxymethyl cellulose
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CN115284707B (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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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a preparation process of an antibacterial environment-friendly medicine packaging composite film. A large amount of green environment-friendly materials such as polylactic acid, carboxymethyl cellulose, zinc oxide, carvacrol and the like are used, so that the prepared packaging composite film has good environmental protection. The carvacrol and the zinc oxide are prepared into the microcapsule and loaded on the montmorillonite, so that the antibacterial property and the 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 an adhesive, and the packaging composite film prepared by the method 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
Composite packaging films are widely used in the medical and pharmaceutical industry, and the composite packaging films comprise a base material, an adhesive and an aluminum foil. The base material is mostly made of plastics, so that the erosion 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 packaging film for the medicines is increasing with the increasing sales of the medicines, and the waste plastics have adverse effects on the environment. Meanwhile, as a packaging film made 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:
the antibacterial environment-friendly medicine packaging composite film is sequentially a polyamide film, an aluminum foil and a polylactic acid composite film from top to bottom, wherein adhesives are coated between the polyamide film and the aluminum foil and between the polylactic acid composite film and the aluminum foil.
Preferably, the adhesive is an epoxy adhesive.
Preferably, the method comprises the following steps:
the method comprises the following steps: stirring carboxymethylcellulose and deionized water at 50-60 deg.C for 50-60min, adding montmorillonite loaded with microcapsule, ultrasonic dispersing for 4-5h, centrifuging, washing, and drying to obtain modified titanium dioxide-carboxymethylcellulose compound;
step two: taking the modified titanium dioxide-carboxymethyl cellulose compound and deionized water, and performing ultrasonic dispersion for 50-70min to obtain a modified titanium dioxide-carboxymethyl cellulose compound mixed solution; uniformly stirring polylactic acid and methane at 48-55 ℃, adding the modified titanium dioxide-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 membrane;
step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polylactic acid composite film with the surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive, compounding the polyamide film with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Preferably, the molecular weight of the polylactic acid is 7000-10000g/mol.
Preferably, in the step one, 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 40-60min, adding montmorillonite, stirring for 20-24 hours at 30-35 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
Preferably, the mass ratio of the carvacrol-zinc oxide microcapsule to the dopamine to the montmorillonite is (2-4): (2-4): 1.
preferably, the preparation method of the carvacrol-zinc oxide microcapsule comprises the following steps: uniformly stirring zinc acetate dihydrate and absolute ethyl alcohol to obtain zinc acetate dihydrate solution; taking deionized water and sodium dodecyl sulfate, stirring for 40-60min at 60-65 ℃, adding paraffin, continuing to stir for 40-60min, adding carvacrol, continuing to stir for 2-4h, adding zinc acetate dihydrate, stirring for 2.5-3.5h, adding sodium hydroxide solution, continuing to stir for 50-70min, heating to 80-85 ℃, aging for 4-6h, washing, centrifuging, and drying to obtain the carvacrol-zinc oxide microcapsule.
Preferably, the mass ratio of the paraffin to the carvacrol to the 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 a good bactericidal effect, and is coated in zinc oxide which is non-toxic and good in bacteriostatic activity to prepare carvacrol-zinc oxide microcapsules, wherein the mass ratio of paraffin, carvacrol and zinc acetate dihydrate 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 that carvacrol-zinc oxide microcapsule particles are mutually agglomerated can be improved. The carvacrol-zinc oxide microcapsule and the montmorillonite are adhered together through dopamine, so that the influence of high-temperature calcination on the activity of carvacrol is avoided, the load capacity of large montmorillonite is increased, 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 is added into polylactic acid. When the modified montmorillonite-carboxymethyl cellulose composite is prepared, the water temperature is increased to 50-60 ℃, and trace carvacrol is released at the moment, so that the modified montmorillonite-carboxymethyl cellulose composite can be used as an adhesive between montmorillonite and carboxymethyl cellulose, the montmorillonite and carboxymethyl cellulose are well adhered together, and the service performance of the polylactic acid composite membrane is improved.
(4) According to the invention, a large amount of green and environment-friendly materials are selected, such as polylactic acid, carboxymethyl cellulose, zinc oxide, carvacrol and the like, so that the prepared packaging composite film has good environmental protection property.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be 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 method comprises the following steps: preparing carvacrol-zinc oxide microcapsules:
taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to obtain 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 a zinc acetate dihydrate solution, stirring for 3h, adding 100mL of a sodium hydroxide solution, continuously stirring for 60min, heating to 82 ℃, aging for 5h, washing, centrifuging, and drying to obtain the carvacrol-zinc oxide microcapsule.
Zinc acetate dihydrate was obtained from gold Caragal chemical Co., ltd;
controlling the mass ratio of the paraffin, the carvacrol and the zinc acetate dihydrate solution to be 1:1.4:2.3.
step two: preparation of microcapsule-loaded montmorillonite:
taking 3g of carvacrol-zinc oxide microcapsule and 500mL of deionized water, stirring for 2h, 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 50min, adding 1g of montmorillonite, stirring for 22h at 32 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
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 complex:
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 the modified montmorillonite-carboxymethyl cellulose composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech, inc.
Step four: preparing a polylactic acid composite membrane:
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 methane, stirring uniformly at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 4min, casting on a glass plate, drying for 23h at 26 ℃, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 3001D.
Step five: coating an epoxy resin adhesive 506 on one side of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zheng state alpha chemical limited.
Example 2
The method comprises the following steps: preparing carvacrol-zinc oxide microcapsules:
taking 11g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to obtain a zinc acetate dihydrate solution; taking 100mL of deionized water and 1.6g of sodium dodecyl sulfate, stirring for 40min at 60 ℃, adding 5g of paraffin, continuing to stir for 40min, adding 6.5g of carvacrol, continuing to stir for 2h, adding a zinc acetate dihydrate solution, stirring for 2.5h, adding 100mL of a sodium hydroxide solution, continuing to stir for 50min, heating to 80 ℃, aging for 4h, washing, centrifuging, and drying to obtain the carvacrol-zinc oxide microcapsule.
Zinc acetate dihydrate was purchased from mallotus chemical ltd;
controlling the mass ratio of the paraffin, the carvacrol and the zinc acetate dihydrate solution to be 1:1.3:2.2.
step two: preparation of microcapsule-loaded montmorillonite:
taking 2g of carvacrol-zinc oxide microcapsule 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 for 20h at 30 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
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 complex:
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 the modified montmorillonite-carboxymethyl cellulose composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.
Step four: preparing a polylactic acid composite membrane:
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 methane, stirring uniformly at 48 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 3min, casting on a glass plate, drying for 22h at 25 ℃, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 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 the surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zheng state alpha chemical limited.
Example 3
The method comprises the following steps: preparing carvacrol-zinc oxide microcapsules:
taking 12.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to obtain 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, continuing to stir for 60min, adding 7.5g of carvacrol, continuing to stir for 4h, adding a zinc acetate dihydrate solution, stirring for 3.5h, adding 100mL of a sodium hydroxide solution, continuing to stir for 70min, heating to 85 ℃, aging for 6h, washing, centrifuging, and drying to obtain the carvacrol-zinc oxide microcapsule.
Zinc acetate dihydrate was obtained from gold Caragal chemical Co., ltd;
controlling the mass ratio of the paraffin, the carvacrol and the zinc acetate dihydrate solution to be 1:1.5:2.5.
step two: preparation of microcapsule-loaded montmorillonite:
taking 4g of carvacrol-zinc oxide microcapsule 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 for 24h at 35 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
Controlling the mass ratio of the carvacrol-zinc oxide microcapsule to the dopamine to the montmorillonite to be 4:4:1.
step three: preparation of modified montmorillonite-carboxymethyl cellulose complex:
taking 1g of carboxymethyl cellulose and 300mL of deionized water, stirring for 60min at 55 ℃, adding 0.5g of microcapsule-loaded montmorillonite, performing ultrasonic dispersion for 5h, centrifuging, washing, and drying to obtain the modified montmorillonite-carboxymethyl cellulose composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.
Step four: preparing a polylactic acid composite membrane:
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 methane, uniformly stirring at 55 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 5min, casting on a glass plate, drying at 27 ℃ for 24h, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 3001D.
The molecular weight of the polylactic acid is 7000-10000g/mol.
Step five: coating an epoxy resin adhesive 506 on one side of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zheng state alpha chemical limited.
Example 4: the procedure of example 1 was repeated except that carvacrol was not added.
The method comprises the following steps: preparation of microcapsule-loaded montmorillonite:
taking 3g of zinc oxide and 500mL of deionized water, stirring for 2h, adding 3g of dopamine, stirring uniformly, adding a Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8.3, performing ultrasonic dispersion for 50min, adding 1g of montmorillonite, stirring for 22h at 32 ℃, filtering, washing and drying to obtain the montmorillonite loaded with zinc oxide.
Controlling the mass ratio of zinc oxide to dopamine to montmorillonite to be 3:3:1.
step two: preparation of modified montmorillonite-carboxymethyl cellulose complex:
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 the modified montmorillonite-carboxymethyl cellulose composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.
Step three: preparing a polylactic acid composite membrane:
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 methane, stirring uniformly at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 4min, casting on a glass plate, drying for 23h at 26 ℃, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 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 the surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zhengzhou alpha chemical company, ltd.
Example 5: the carvacrol-zinc oxide microcapsules were not loaded on montmorillonite, but the rest was the same as in example 1.
The method comprises the following steps: preparing carvacrol-zinc oxide microcapsules:
taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to obtain 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, 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 the carvacrol-zinc oxide microcapsule.
Zinc acetate dihydrate was purchased from mallotus chemical ltd;
controlling the mass ratio of the paraffin, the carvacrol and the 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 composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech Co., ltd.
Step three: preparing a polylactic acid composite membrane:
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 methane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 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 the surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zheng state alpha chemical limited.
Example 6: controlling the mass ratio of the paraffin, the carvacrol and the zinc acetate dihydrate solution to be 1:1:2, the rest was the same as in example 1.
The method comprises the following steps: preparing carvacrol-zinc oxide microcapsules:
taking 11.5g of zinc acetate dihydrate and 100mL of absolute ethyl alcohol, and uniformly stirring to obtain 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, 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 the carvacrol-zinc oxide microcapsule.
Zinc acetate dihydrate was purchased from mallotus chemical ltd;
controlling the mass ratio of the paraffin, the carvacrol and the zinc acetate dihydrate solution to be 1:1.4:2.3.
step two: preparation of microcapsule-loaded montmorillonite:
taking 3g of carvacrol-zinc oxide microcapsule and 500mL of deionized water, stirring for 2h, 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 50min, adding 1g of montmorillonite, stirring for 22h at 32 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
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 complex:
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 the modified montmorillonite-carboxymethyl cellulose composite.
Carboxymethyl cellulose was purchased from Sichuan Huayuan Shengtai Biotech, inc.
Step four: preparing a polylactic acid composite membrane:
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 methane, uniformly stirring at 50 ℃, adding the modified montmorillonite-carboxymethyl cellulose composite mixed solution, carrying out ultrasonic dispersion for 4min, casting on a glass plate, drying at 26 ℃ for 23h, and stripping to obtain the polylactic acid composite membrane.
Polylactic acid is available from Nature Works, USA under model 3001D.
Step five: coating an epoxy resin adhesive 506 on one side of an aluminum foil with the thickness of 50 mu m, compounding a polylactic acid composite film with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive 506, compounding the polyamide film with the thickness of 25 mu m with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
Epoxy adhesive 506 was purchased from zhengzhou alpha chemical company, ltd.
Experiment of the invention
The polylactic acid composite films prepared in examples 1 to 6 were subjected to a performance test, the packaging films were prepared into 10mm × 100mm samples, and the mechanical properties of the pharmaceutical packaging films were tested using an electronic universal mechanical tester at 25 ℃, a loading speed of 5mm/min, and an initial gauge length of 25 mm. The polylactic acid composite membranes prepared in examples 1 to 6 were prepared into samples with a diameter of 11mm, and the samples were UV-sterilized for 1 hour to give a concentration of 10 to 0.1mL 5 And (3) coating the surface of the culture medium with CFU/mL staphylococcus aureus, covering the sterilized polylactic acid composite membrane, culturing at 37 ℃ for 24 hours, and testing the antibacterial performance.
Figure BDA0003786804510000091
Figure BDA0003786804510000101
And (4) conclusion: as can be seen from the data in the table, the antibacterial property is deteriorated when no carvacrol is added in the example 4, and the mechanical property of the packaging composite film is influenced by the addition of carvacrol, so that the tensile strength of the composite film is better. Example 5 carvacrol-zinc oxide microcapsules are not loaded on montmorillonite, and the carvacrol-zinc oxide microcapsules are easy to agglomerate in a system, so that the performance of a packaging composite film is influenced. Example 6 the mass ratio of paraffin, carvacrol and zinc acetate dihydrate solution is controlled to be 1:1:2, the overall performance of the packaging film is inferior to that of examples 1 to 3.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. The utility model provides an antibiotic environmental protection medicine packaging complex film which 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.
2. The composite film for packaging antibacterial and environment-friendly medicines according to claim 1, characterized in that: the adhesive is an epoxy adhesive.
3. A preparation process of an antibacterial environment-friendly medicine packaging composite film is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: stirring carboxymethyl cellulose and deionized water at 50-60 deg.C for 50-60min, adding montmorillonite loaded with microcapsule, ultrasonic dispersing for 4-5 hr, centrifuging, washing, and drying to obtain modified titanium dioxide-carboxymethyl cellulose compound;
step two: taking the modified titanium dioxide-carboxymethyl cellulose compound and deionized water, and performing ultrasonic dispersion for 50-70min to obtain a modified titanium dioxide-carboxymethyl cellulose compound mixed solution; uniformly stirring polylactic acid and methane at 48-55 ℃, adding the modified titanium dioxide-carboxymethyl cellulose compound mixed solution, ultrasonically dispersing for 3-5min, casting on a glass plate, drying at 25-27 ℃ for 22-24h, and stripping to obtain a polylactic acid composite membrane;
step three: coating an epoxy resin adhesive on one surface of an aluminum foil, compounding a polylactic acid composite film with the surface of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain a film A; coating the other side of the aluminum foil with the epoxy resin adhesive, compounding the polyamide film with the side of the aluminum foil coated with the epoxy resin adhesive, and rolling to obtain the high-barrier medicinal packaging film.
4. The preparation process of the antibacterial environment-friendly medicine packaging composite film according to claim 3, characterized by comprising the following steps: the molecular weight of the polylactic acid is 7000-10000g/mol.
5. The preparation process of the antibacterial environment-friendly medicine packaging composite film according to claim 3, characterized by comprising the following steps: in the first step, the preparation method of the microcapsule-loaded montmorillonite comprises the following steps: taking carvacrol-zinc oxide microcapsules and deionized water, stirring for 1.5-2.5h, adding dopamine, stirring uniformly, adding Tris-HCl buffer solution, adding hydrochloric acid, adjusting the pH value to 8-8.5, performing ultrasonic dispersion for 40-60min, adding montmorillonite, stirring for 20-24h at 30-35 ℃, filtering, washing and drying to obtain the microcapsule-loaded montmorillonite.
6. The preparation process of the antibacterial environment-friendly medicine packaging composite film according to claim 5, characterized by comprising the following steps: the mass ratio of the carvacrol-zinc oxide microcapsule to the dopamine to the montmorillonite is (2-4): (2-4): 1.
7. the preparation process of the antibacterial environment-friendly medicine packaging composite film according to claim 5, characterized by comprising the following steps: the preparation method of the carvacrol-zinc oxide microcapsule comprises the following steps: uniformly stirring zinc acetate dihydrate and absolute ethyl alcohol to obtain zinc acetate dihydrate solution; taking deionized water and sodium dodecyl sulfate, stirring for 40-60min at 60-65 ℃, adding paraffin, continuing to stir for 40-60min, adding carvacrol, continuing to stir for 2-4h, adding zinc acetate dihydrate, stirring for 2.5-3.5h, adding sodium hydroxide solution, continuing to stir for 50-70min, heating to 80-85 ℃, aging for 4-6h, washing, centrifuging, and drying to obtain the carvacrol-zinc oxide microcapsule.
8. The preparation process of the antibacterial environment-friendly medicine packaging composite film according to claim 7, characterized by comprising the following steps: the mass ratio of the paraffin to the carvacrol to the zinc acetate dihydrate solution is 1: (1.3-1.5): (2.2-2.5).
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