CN110091557A - A kind of Key works Drug packing high-resistant diaphragm and preparation method thereof - Google Patents

A kind of Key works Drug packing high-resistant diaphragm and preparation method thereof Download PDF

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Publication number
CN110091557A
CN110091557A CN201910467159.7A CN201910467159A CN110091557A CN 110091557 A CN110091557 A CN 110091557A CN 201910467159 A CN201910467159 A CN 201910467159A CN 110091557 A CN110091557 A CN 110091557A
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parts
nano
epoxy resin
drug packing
key works
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CN110091557B (en
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张辉
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Sichuan Huili Industrial Co Ltd
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Sichuan Huili Industrial 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered 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
    • B32B15/12—Layered 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 paper or cardboard
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B7/00—Layered 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS 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
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/08—Homopolymers or copolymers of vinylidene chloride
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • 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
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)

Abstract

The invention discloses a kind of Key works Drug packing high-resistant diaphragms, including aluminium layer and basal layer, aluminium layer and substrate interlayer are by adhesive adhesion, and the adhesive is made by following components: polyvinylidene chloride, epoxy resin, nano-titanium dioxide, nano aluminium oxide, carboxymethyl cellulose, graphene, plasticizer, coupling agent, curing agent, stabilizer.The barrier film is high for the barrier property of water and air, can significantly extend the shelf-life of drug, invention additionally discloses the preparation methods of above-mentioned Key works Drug packing high-resistant diaphragm.

Description

A kind of Key works Drug packing high-resistant diaphragm and preparation method thereof
Technical field
The present invention relates to drug packing fields, and in particular to a kind of Key works Drug packing high-resistant diaphragm and preparation method thereof.
Background technique
Key works Drug packing refers to former material appropriate or container, the semifinished or finished goods using packing technique to pharmaceutical preparation The operation such as point (filling), envelope, dress, labeling is carried out, provides a kind of process of quality guarantee, identification trade mark and explanation for drug General name.
For drug packing field, adhesive is essential raw material in packaging material.Drug packing material choosing Adhesive safety and sanitation performance will be got well, ought to nontoxic, free from extraneous odour, if directly contact drug also need it is non-corrosive, will not be right Packaging drug damages.And in order to extend the quality guarantee period of medicament phase, the barrier property of packaging material also there are certain requirements, usually come It says, packaging material barrier property is higher, and the quality guarantee period of medicament phase then can be longer.Current existing drug packing material, barrier property is bad, It is unfavorable for the long-term preservation of drug.
Current Key works Drug packing film is usually multilayered structure, passes through adhesive stick to each other between multilayered structure, is mentioned with reaching The effect of high barrier, wherein aluminium layer is essential part in multilayered structure, and aluminium layer can significantly improve the resistance of packaging film Separating performance.However in practical applications, composite package film is easily deformed under heated or external force, is broken even layering, Cause Key works Drug packing film barrier property in heat-sealing to change, is unfavorable for the long-term preservation of drug.
Summary of the invention
In order to solve the above-mentioned technical problem, the present invention discloses a kind of Key works Drug packing high-resistant diaphragm, the barrier film for water and The barrier property of air is high, can significantly extend the shelf-life of drug, invention additionally discloses the systems of above-mentioned Key works Drug packing high-resistant diaphragm Preparation Method.
The present invention is achieved through the following technical solutions:
A kind of Key works Drug packing high-resistant diaphragm, including aluminium layer and basal layer, aluminium layer and substrate interlayer pass through adhesive adhesion, institute Adhesive is stated to be made by following components:
Polyvinylidene chloride, epoxy resin, nano-titanium dioxide, nano aluminium oxide, carboxymethyl cellulose, graphene, increasing Mould agent, coupling agent, curing agent, stabilizer.
In the present invention, high-resistant diaphragm includes aluminium layer, basal layer and adhesive, and aluminium layer itself has certain barrier property, glue Polyvinylidene chloride its intermolecular cohesive force in stick is strong, and crystallinity is high, and the chlorine atom in molecule has hydrophobicity, not will form Hydrogen bond, oxygen molecule and hydrone are difficult to move in PVDC molecule, with excellent oxygen barrier and hinder moist, the increasing in composition Modeling agent and stabilizer are used to increase the plasticity of polyvinylidene chloride, and epoxy resin under the action of coupling agent, curing agent, hand over by solidification Connection generates reticular structure, effectively increases the mechanical strength after adhesive solidifies, and graphene is one of highest material of known strength, Also there is good toughness simultaneously, and can be bent, enhance the toughness and intensity of the adhesive after solidifying, avoid in external force Under be deformed, be broken or be layered, therefore using the adhesive and the high resistant that is bonded of aluminium layer, basal layer of said components preparation The barrier property of diaphragm and mechanically formed excellent is suitable for pharmaceutical packing, can significantly extend the quality guarantee period of medicament phase.
In the present invention, the carboxymethyl cellulose in component can be such that graphene uniform is dispersed in adhesive, avoid graphite Alkene, which is reunited, influences the mechanical performance after adhesive solidifies, containing largely homologous with coating paper body paper in carboxymethyl cellulose molecule Hydroxyl and aldehyde groups, when basal layer is coating paper body paper, carboxymethyl cellulose molecule can be fast after contacting with coating paper Speed forms hydrogen bond with coating paper surface molecular, effectively enhances the bonding force between adhesive and coating paper body paper, avoids by outer Bubble is generated after power effect between adhesive and coating paper body paper, is detached from even layering, further enhances composite membrane obtained Barrier property.
Nano-titanium dioxide, nano aluminium oxide in component can enhance the adhesion strength with aluminium layer and coating paper body paper, High-resistant diaphragm is avoided to be layered, fall off in use, after the adhesive and aluminium layer of liquid contact, nano aluminium oxide can be with The pellumina on aluminium layer surface forms stable Van der Waals force, shortens to intermolecular distance further in maximum stable shape State effectively improves the adhesion strength of adhesive and aluminium layer, avoids high-resistant diaphragm by outer force stratification or generates bubble, and reinfored glue Stick allows adhesives to come into full contact with aluminium layer surface and aluminium layer surface pinholes, bubble is avoided to produce to the wellability of aluminium layer Aluminium layer pin hole is given birth to and filled up, barrier property is further increased.
Further, the adhesive is made by the component of following mass fraction:
70-75 parts of polyvinylidene chloride, 8-12 parts of epoxy resin, 3-4 parts of nano-titanium dioxide, 6-8 parts of nano aluminium oxide, 5-7 parts of carboxymethyl cellulose, 4-5 parts of graphene, 5-8 parts of plasticizer, 2-4 parts of coupling agent, 0.5-1.2 parts of curing agent, stabilizer 5-8 parts.
Inventor obtains said components and quality proportioning by a large number of experiments, certainly using adhesive made from the quality proportioning Body is high for the barrier property of air, vapor, and good toughness, is unlikely to deform, is broken or falls off, can be with aluminium layer and basal layer It comes into full contact with and adheres to, avoid the occurrence of bubble, improve the barrier property and toughness and mechanical strength of high-resistant diaphragm.
Preferably, the adhesive is made by the component of following mass fraction:
73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 7 parts of nano aluminium oxide, carboxymethyl are fine Tie up plain 6 parts, 5 parts of graphene, 7 parts of plasticizer, 3 parts of coupling agent, 0.8 part of curing agent, 6 parts of stabilizer.
Each component of the present invention is best using the barrier property and mechanical performance of adhesive made from above-mentioned quality proportioning.
Further, the basal layer is coating paper body paper, and the aluminium layer and base layer thickness are 0.01-0.2mm.
Further, the polyvinylidene chloride is polyvinylidene chloride latex, and the plasticizer is dibutyl sebacate Or epoxy dioleate.
Further, the coupling agent is γ aminopropyltriethoxy silane or α-phenylaminomethyl triethoxysilicane Alkane, the epoxy resin are one of bisphenol F epoxy resin, cycloaliphatic epoxy resin, polyurethane modified epoxy resin or more Kind.
Further, the curing agent is latent curing agent, specially ethylenediamine or diethylenetriamine, the stabilizer For dibutyl tin dilaurate.
In the present invention, graphene oxide replacement is can also be used in graphene.
A kind of preparation method of Key works Drug packing high-resistant diaphragm, comprising the following steps:
(1) according to mass fraction weigh polyvinylidene chloride latex, epoxy resin, nano-titanium dioxide, nano aluminium oxide, Carboxymethyl cellulose, graphene, plasticizer, coupling agent, curing agent, stabilizer are spare；
(2) stabilizer, plasticizer are added in polyvinylidene chloride latex, stir at low speed mixing；
(3) nano aluminium oxide, nano-titanium dioxide mixing；
(3) successively epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano-titanium dioxide are mixed while stirring Object, graphene, coupling agent are added in mixed liquor obtained by step (2), vacuum high-speed stirred 50-70min at 40-60 DEG C；
(4) it is cooled to 30-35 DEG C, curing agent is added, after being stirred under vacuum 20-30min.
Stabilizer, plasticizer are added in polyvinylidene chloride latex, can effectively improve the plasticity of polyvinylidene chloride, Convenient for the mixing of remaining component, react and solidify, vacuum high-speed stirred is conducive to mix between each component and be coupled at 40-60 DEG C, It is eventually adding curing agent stirring, can be used to the bonding of aluminium layer and basal layer.
A kind of application of Key works Drug packing high-resistant diaphragm in Key works Drug packing.
Compared with prior art, the present invention having the following advantages and benefits:
1, a kind of Key works Drug packing high-resistant diaphragm of the present invention and preparation method thereof, high-resistant diaphragm includes aluminium layer, basal layer and glue Stick, aluminium layer itself have certain barrier property, and polyvinylidene chloride its intermolecular cohesive force in adhesive is strong, crystallinity Height, the chlorine atom in molecule have hydrophobicity, not will form hydrogen bond, and oxygen molecule and hydrone are difficult to move in PVDC molecule, tool There are excellent oxygen barrier and resistance moist, plasticizer and stabilizer in composition are used to increase the plasticity of polyvinylidene chloride, ring For oxygen resin under the action of coupling agent, curing agent, solidification crosslinking generates reticular structure, effectively increases the machinery after adhesive solidifies Intensity, graphene are one of highest materials of known strength, while also having good toughness, and can be bent, enhancing solidification The toughness and intensity of adhesive afterwards avoid being deformed, be broken or being layered under external force, therefore use said components system The barrier property for the high-resistant diaphragm that standby adhesive is bonded with aluminium layer, basal layer and mechanically formed excellent is suitable for drug Packaging, can significantly extend the quality guarantee period of medicament phase；
2, a kind of Key works Drug packing high-resistant diaphragm of the present invention and preparation method thereof, the carboxymethyl cellulose in component can make stone Black alkene is dispersed in adhesive, and avoiding graphene from reuniting influences the mechanical performance after adhesive solidifies, carboxymethyl cellulose Contain hydroxyl and aldehyde groups largely homologous with coating paper body paper, when basal layer is coating paper body paper, carboxymethyl in molecule Cellulosic molecule can form hydrogen bond, effective reinfored glue with coating paper body paper surface molecular rapidly after contacting with coating paper body paper Bonding force between stick and coating paper is avoided generating bubble between adhesive and coating paper body paper after by external force, is detached from It is even layered, further enhances the barrier property of composite membrane obtained；
3, a kind of Key works Drug packing high-resistant diaphragm of the present invention and preparation method thereof, nano-titanium dioxide, nano oxygen in component The adhesion strength with aluminium layer and coating paper body paper can be enhanced by changing aluminium, and high-resistant diaphragm is avoided to be layered, fall off in use, when After the adhesive of liquid is contacted with aluminium layer, nano aluminium oxide can form stable Van der Waals with the pellumina on aluminium layer surface Power makes intermolecular distance further shorten to the adhesion strength for effectively improving adhesive and aluminium layer in maximum stable state, High-resistant diaphragm is avoided by outer force stratification or generates bubble, and enhances adhesive to the wellability of aluminium layer, allow adhesives to Aluminium layer surface and aluminium layer surface pinholes come into full contact with, and avoid bubble from generating and fill up aluminium layer pin hole, further increase barrier property Energy.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below with reference to embodiment, the present invention is made Further to be described in detail, exemplary embodiment of the invention and its explanation for explaining only the invention, are not intended as to this The restriction of invention.
Embodiment 1
A kind of Key works Drug packing high-resistant diaphragm of the present invention, is made by following processing step:
1) 75 parts of polyvinylidene chloride, 8 parts of epoxy resin, 3 parts of nano-titanium dioxide, 8 parts of nano aluminium oxide, carboxylic first are weighed 7 parts of base cellulose, 5 parts of graphene, 5 parts of plasticizer, 2 parts of coupling agent, 0.5 part of curing agent, 5 parts of dibutyl tin dilaurate it is standby With；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) nano aluminium oxide, nano-titanium dioxide mixing；
4) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Graphene, coupling agent are added in mixed liquor obtained by step 2), are stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
5) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is dibutyl sebacate.
The coupling agent is γ aminopropyltriethoxy silane, and the epoxy resin is polyurethane modified epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and basal layer are respectively with a thickness of 0.05mm.
Embodiment 2
A kind of Key works Drug packing high-resistant diaphragm of the present invention, is made by following processing step:
1) 70 parts of polyvinylidene chloride, 12 parts of epoxy resin, 4 parts of nano-titanium dioxide, 6 parts of nano aluminium oxide, carboxylic are weighed 5 parts of methylcellulose, 4 parts of graphene, 8 parts of plasticizer, 4 parts of coupling agent, 1.2 parts of curing agent, 8 parts of dibutyl tin dilaurate it is standby With；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) nano aluminium oxide, nano-titanium dioxide mixing；
4) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Graphene, coupling agent are added in mixed liquor obtained by step 2), are stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
5) 30 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is dibutyl sebacate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin includes cycloaliphatic epoxy resin 6 Part, 6 parts of polyurethane modified epoxy resin.
The curing agent is diethylenetriamine, and the aluminium layer and basal layer are respectively with a thickness of 0.05mm.
Embodiment 3
A kind of Key works Drug packing high-resistant diaphragm of the present invention, is made by following processing step:
1) 73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 7 parts of nano aluminium oxide, carboxylic are weighed 6 parts of methylcellulose, 5 parts of graphene, 7 parts of plasticizer, 3 parts of coupling agent, 0.8 part of curing agent, 6 parts of dibutyl tin dilaurate it is standby With；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) nano aluminium oxide, nano-titanium dioxide mixing；
4) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Graphene, coupling agent are added in mixed liquor obtained by step 2), are stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
5) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is epoxy dioleate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin is bisphenol F epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and base layer thickness are 0.05mm.
The following are comparative examples
Embodiment 4
A kind of Key works Drug packing high-resistant diaphragm is made by following processing step:
1) 73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 5 parts of graphene, plasticizer 7 are weighed Part, 3 parts of coupling agent, 0.8 part of curing agent, 6 parts of dibutyl tin dilaurate it is spare；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) successively epoxy resin, nano-titanium dioxide, graphene, coupling agent are added to while stirring mixed obtained by step 2) It closes in liquid, 50min is stirred under vacuum with 3000r/min revolving speed at 60 DEG C；
4) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is epoxy dioleate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin is bisphenol F epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and base layer thickness are 0.05mm.
The present embodiment and the difference of embodiment 3 are: lacking component nano aluminium oxide and carboxymethyl cellulose.
Embodiment 5
A kind of Key works Drug packing high-resistant diaphragm is made by following processing step:
1) 73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 7 parts of nano aluminium oxide, carboxylic are weighed 6 parts of methylcellulose, 7 parts of plasticizer, 3 parts of coupling agent, 0.8 part of curing agent, 6 parts of dibutyl tin dilaurate it is spare；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) nano aluminium oxide, nano-titanium dioxide mixing；
4) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Coupling agent is added in mixed liquor obtained by step 2), is stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
5) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is epoxy dioleate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin is bisphenol F epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and base layer thickness are 0.05mm.
The present embodiment and the difference of embodiment 3 are: not including component graphene.
Embodiment 6
A kind of Key works Drug packing high-resistant diaphragm is made by following processing step:
1) 73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 7 parts of nano aluminium oxide, carboxylic are weighed 6 parts of methylcellulose, 5 parts of graphene, 3 parts of coupling agent, 0.8 part of curing agent it is spare；
2) nano aluminium oxide, nano-titanium dioxide mixing；
3) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Graphene, coupling agent are added in polyvinylidene chloride latex, are stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
4) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
5) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is epoxy dioleate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin is bisphenol F epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and base layer thickness are 0.05mm.
The present embodiment and the difference of embodiment 3 are: not including component dibutyl tin dilaurate and plasticizer.
Embodiment 7
A kind of Key works Drug packing high-resistant diaphragm is made by following processing step:
1) 65 parts of polyvinylidene chloride, 15 parts of epoxy resin, 5 parts of nano-titanium dioxide, 10 parts of nano aluminium oxide, carboxylic are weighed 4 parts of methylcellulose, 3 parts of graphene, 7 parts of plasticizer, 4 parts of coupling agent, 1.2 parts of curing agent, 6 parts of dibutyl tin dilaurate it is standby With；
2) dibutyl tin dilaurate, plasticizer are added in polyvinylidene chloride latex, at 50 DEG C, with 1000r/ Min revolving speed stirs 30min；
3) nano aluminium oxide, nano-titanium dioxide mixing；
4) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, Graphene, coupling agent are added in mixed liquor obtained by step 2), are stirred under vacuum 50min at 60 DEG C with 3000r/min revolving speed；
5) 35 DEG C are cooled to, curing agent is added, 30min is stirred under vacuum with 200r/min revolving speed and obtains adhesive；
6) adhesive is coated between the aluminium layer of single layer and coating paper body paper, dry 50min obtains high-resistant diaphragm, adhesive Coating thickness is 0.02-0.05mm.
In the present embodiment, the plasticizer is epoxy dioleate.
The coupling agent is α-phenylaminomethyl triethoxysilane, and the epoxy resin is bisphenol F epoxy resin.
The curing agent is ethylenediamine, and the aluminium layer and base layer thickness are 0.05mm.
The present embodiment is from the difference of embodiment 3: each component quality proportioning is different.
High-resistant diaphragm prepared by embodiment 1-7 carries out vapor, nitrogen, carbon dioxide gas, oxygen transit dose respectively And appearance is tested after heat-sealing.Wherein, steam penetrating capacity is measured referring to steam penetrating capacity measuring method-YBB00092003, Nitrogen, carbon dioxide gas, oxygen transit dose are measured referring to gas transit dose measuring method-YBB00082003, and heat-sealing experiment uses Puller system is tested, and condition is 210 DEG C, 2.0kgf/cm2, continue 15-25min.
Test result is as follows shown in table:
In upper table, number 1,2,3,4,5,6,7 respectively indicates the high-resistant diaphragm of embodiment 1-7 preparation.
As seen from the above table, the high-resistant diaphragm of 1-3 of embodiment of the present invention preparation is lower than 0.4g/ for the transit dose of vapor (m2·24h)；0.4cm3/ (m224h0.1MPa) is below for nitrogen, carbon dioxide gas, oxygen transit dose；Through heat It seals after sterilizing, internal flawless, surfacing, bubble-free in packaging film does not occur deforming or being layered, heat-sealing experiment and machinery Performance is good.
The high-resistant diaphragm of embodiment 4-7 preparation is greater than 1.1g/ (m for the transit dose of vapor2·24h)；For nitrogen, Carbon dioxide gas, oxygen transit dose are all larger than 1.0cm3/ (m224h0.1MPa)；After heat-sealing sterilizing, surface occurs Fold has bubble generation, and blind crack occurs in inside, and lamination occurs in part, and heat-sealing experiment and mechanical performance can not show a candle to The high-resistant diaphragm of embodiment 1-3 preparation.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include Within protection scope of the present invention.

Claims (9)

1. a kind of Key works Drug packing high-resistant diaphragm, which is characterized in that including aluminium layer and basal layer, aluminium layer and substrate interlayer pass through gluing Agent adhesion, the adhesive are made by following components:
Polyvinylidene chloride, epoxy resin, nano-titanium dioxide, nano aluminium oxide, carboxymethyl cellulose, graphene, plasticizer, Coupling agent, curing agent, stabilizer.
2. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the adhesive passes through following matter The component for measuring number is made:
70-75 parts of polyvinylidene chloride, 8-12 parts of epoxy resin, 3-4 parts of nano-titanium dioxide, 6-8 parts of nano aluminium oxide, carboxylic first 5-7 parts of base cellulose, 4-5 parts of graphene, 5-8 parts of plasticizer, 2-4 parts of coupling agent, 0.5-1.2 parts of curing agent, stabilizer 5-8 Part.
3. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the adhesive passes through following matter The component for measuring number is made:
73 parts of polyvinylidene chloride, 10 parts of epoxy resin, 3 parts of nano-titanium dioxide, 7 parts of nano aluminium oxide, carboxymethyl cellulose 6 Part, 5 parts of graphene, 7 parts of plasticizer, 3 parts of coupling agent, 0.8 part of curing agent, 6 parts of stabilizer.
4. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the basal layer is that coating paper is former Paper, the aluminium layer and base layer thickness are 0.01-0.2mm.
5. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the polyvinylidene chloride is inclined Polyvinyl dichloride latex, the plasticizer are dibutyl sebacate or epoxy dioleate.
6. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the coupling agent is gamma-amino Propyl-triethoxysilicane or α-phenylaminomethyl triethoxysilane, the epoxy resin are bisphenol F epoxy resin, alicyclic One of epoxy resin, polyurethane modified epoxy resin are a variety of.
7. a kind of Key works Drug packing high-resistant diaphragm according to claim 1, which is characterized in that the curing agent is solid for latency Agent, specially ethylenediamine or diethylenetriamine, the stabilizer are dibutyl tin dilaurate.
8. such as a kind of described in any item preparation methods of Key works Drug packing high-resistant diaphragm of claim 1-7, which is characterized in that including Following steps:
(1) polyvinylidene chloride latex, epoxy resin, nano-titanium dioxide, nano aluminium oxide, carboxylic first are weighed according to mass fraction Base cellulose, graphene, plasticizer, coupling agent, curing agent, stabilizer are spare；
(2) stabilizer, plasticizer are added in polyvinylidene chloride latex, stir at low speed mixing；
(3) nano aluminium oxide, nano-titanium dioxide mixing；
(3) while stirring successively by epoxy resin, carboxymethyl cellulose, nano aluminium oxide and nano titanium dioxide mixture, stone Black alkene, coupling agent are added in mixed liquor obtained by step (2), vacuum high-speed stirred 50-70min at 40-60 DEG C；
(4) it is cooled to 30-35 DEG C, curing agent is added, after being stirred under vacuum 20-30min.
9. if a kind of described in any item Key works Drug packing high-resistant diaphragms of claim 1-7 are in the application of Key works Drug packing.
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Publication number Priority date Publication date Assignee Title
CN112060728A (en) * 2020-08-27 2020-12-11 上海春宜药品包装材料有限公司 High-barrier film for medicine packaging and preparation method thereof
CN112537101A (en) * 2019-09-20 2021-03-23 韩国铝业株式会社 Graphene-containing sheet for packaging pharmaceutical agents
CN113512344A (en) * 2020-04-09 2021-10-19 宣城亨旺新材料有限公司 Water-blocking and air-blocking coating and water-blocking and air-blocking structure using same
WO2022002735A1 (en) * 2020-06-29 2022-01-06 Unilever Ip Holdings B.V. A container
CN115534470A (en) * 2022-10-09 2022-12-30 常州市华健药用包装材料有限公司 High-barrier medicinal packaging film and preparation method thereof
CN116176058A (en) * 2022-07-21 2023-05-30 南通惠得成包装材料有限公司 High-barrier medicine composite packaging film and preparation method thereof

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CN103171203A (en) * 2011-12-20 2013-06-26 顾锁忠 Medicinal composite film
CN103240934A (en) * 2013-05-22 2013-08-14 四川汇利实业有限公司 Composite film with high barrier property for steam and light
CN104512068A (en) * 2013-09-29 2015-04-15 谢超 Composite membrane with high barrier property
CN109161363A (en) * 2018-09-07 2019-01-08 刘建林 High-barrier aqueous adhesive

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CN103171203A (en) * 2011-12-20 2013-06-26 顾锁忠 Medicinal composite film
CN103240934A (en) * 2013-05-22 2013-08-14 四川汇利实业有限公司 Composite film with high barrier property for steam and light
CN104512068A (en) * 2013-09-29 2015-04-15 谢超 Composite membrane with high barrier property
CN109161363A (en) * 2018-09-07 2019-01-08 刘建林 High-barrier aqueous adhesive

Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN112537101A (en) * 2019-09-20 2021-03-23 韩国铝业株式会社 Graphene-containing sheet for packaging pharmaceutical agents
CN113512344A (en) * 2020-04-09 2021-10-19 宣城亨旺新材料有限公司 Water-blocking and air-blocking coating and water-blocking and air-blocking structure using same
WO2022002735A1 (en) * 2020-06-29 2022-01-06 Unilever Ip Holdings B.V. A container
CN112060728A (en) * 2020-08-27 2020-12-11 上海春宜药品包装材料有限公司 High-barrier film for medicine packaging and preparation method thereof
CN116176058A (en) * 2022-07-21 2023-05-30 南通惠得成包装材料有限公司 High-barrier medicine composite packaging film and preparation method thereof
CN116176058B (en) * 2022-07-21 2023-12-22 南通惠得成包装材料有限公司 High-barrier medicine composite packaging film and preparation method thereof
CN115534470A (en) * 2022-10-09 2022-12-30 常州市华健药用包装材料有限公司 High-barrier medicinal packaging film and preparation method thereof
CN115534470B (en) * 2022-10-09 2024-04-12 常州市华健药用包装材料有限公司 High-barrier medicinal packaging film and preparation method thereof

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