CN115534459A - Medicinal composite membrane and preparation method thereof - Google Patents
Medicinal composite membrane and preparation method thereof Download PDFInfo
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- CN115534459A CN115534459A CN202211249352.1A CN202211249352A CN115534459A CN 115534459 A CN115534459 A CN 115534459A CN 202211249352 A CN202211249352 A CN 202211249352A CN 115534459 A CN115534459 A CN 115534459A
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- aluminum foil
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 57
- 239000011888 foil Substances 0.000 claims abstract description 55
- 239000010410 layer Substances 0.000 claims abstract description 47
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 39
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 28
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims abstract description 13
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 13
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims description 24
- 230000001070 adhesive effect Effects 0.000 claims description 24
- 239000011265 semifinished product Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000007246 mechanism Effects 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010030 laminating Methods 0.000 claims description 8
- 229920000126 latex Polymers 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000013527 degreasing agent Substances 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 229960000359 chromic chloride Drugs 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 238000005237 degreasing agent Methods 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 12
- 230000004888 barrier function Effects 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 abstract 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003814 drug Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011521 glass Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000825 pharmaceutical preparation Substances 0.000 description 3
- 229940127557 pharmaceutical product Drugs 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011125 type II (treated soda lime glass) Substances 0.000 description 2
- 102000004506 Blood Proteins Human genes 0.000 description 1
- 108010017384 Blood Proteins Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012945 sealing adhesive Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000011123 type I (borosilicate glass) Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B15/08—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 synthetic resin
- B32B15/082—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 synthetic resin comprising vinyl resins; comprising acrylic resins
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/7244—Oxygen barrier
-
- 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
- B32B2307/7246—Water vapor barrier
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a medicinal composite membrane, which consists of a polymer layer, an aluminum foil layer and a heat sealing layer; wherein the polymer layer comprises high density polyethylene, polyethylene-vinyl alcohol copolymer and ethylene acrylic acid copolymer; the aluminum foil layer is an aluminum foil with the thickness of 45-55 mu m; the heat sealing layer is modified VC glue. The medicinal composite membrane has excellent high barrier property through the polymer layer of the medicinal composite membrane formed by using EVOH, HDPE and EAA, the barrier property of the medicinal composite membrane to water vapor, oxygen and other gases is obviously improved through the combined action of EVOH, HDPE and EAA, water vapor can be effectively prevented from passing through the aluminum foil layer through the compounding of the polymer layer and the aluminum foil, and the barrier property of the medicinal composite membrane is greatly improved.
Description
Technical Field
The invention belongs to the technical field of composite membranes, and particularly relates to a medicinal composite membrane and a preparation method thereof.
Background
The medicine is a special commodity, and the quality and safety of the medicine directly affect the health of patients. The medicine packaging material is a packaging material and a container which are in direct contact with the medicine, and is called a medicine packaging material for short, the medicine packaging material can protect the original properties of the medicine from being influenced by the external environment, and the medicine is convenient to store, transport and use. The forming property, the barrier property, the sealing stability, the heat insulation property and the like of the packaging material are the basis of the medicine packaging process and the continuous preservation.
Common medicine packaging materials are mainly classified into four types, namely plastic, glass, rubber and metal packaging. The plastic package mainly comprises polyvinyl chloride and polyolefins, has the characteristics of convenient storage, transportation and clinical application, but the polyethylene has poor transparency, poor oxidation resistance and other gas resistance and is easy to degrade under illumination; the polypropylene material has large low-temperature brittleness, poor thermal bonding property and poor printing property; polyvinyl chloride has poor thermal stability, HCl gas is separated out when the temperature is higher than 50 ℃, and the gas can harm the health of human bodies, so a stabilizer is generally added; polystyrene has low impact strength and poor moisture resistance, and is easy to be soaked by various medicines. The currently adopted medicine packaging glass materials in China mainly comprise three types: type I glass, type II glass, and non-I, II glass. The glass material has good heat resistance, strong chemical stability, high mechanical strength, excellent barrier property, low price and recyclability; however, the use of glass for packaging pharmaceutical products requires special attention to the compatibility with the pharmaceutical products. For example, sodium bicarbonate injection cannot be stored in type II glass packaging, otherwise, the falling matter on the bottle wall can cause the liquid to be turbid, and the quality of the medicine is reduced. In addition, silicon oxide and boron oxide in glass readily adsorb insulin; glass may also affect the aluminum content in human blood proteins, affecting drug quality. The medicinal rubber package mainly comprises two types of natural rubber and butyl rubber. From the component point of view, the natural rubber has complex components, poor chemical stability and sealing property and easy aging. Aluminum is the most widely used metal package material and has good texture, good processability, and excellent moisture and gas barrier properties. However, in the case where the pinholes formed in the aluminum foil serving as the lid material in the blister package are arranged at positions facing the storage section, moisture passing through the pinholes may reach the object to be stored, and the pharmaceutical product or the like may absorb moisture, thereby affecting the pharmaceutical efficacy.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a medicinal composite membrane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical means:
the first aspect of the invention provides a medicinal composite film, which consists of a polymer layer, an aluminum foil layer and a heat sealing layer;
wherein the polymer layer comprises High Density Polyethylene (HDPE), polyethylene vinyl alcohol copolymer (EVOH), and ethylene acrylic acid copolymer (EAA);
the aluminum foil layer is an aluminum foil with the thickness of 45-55 mu m;
the heat sealing layer is modified VC glue.
Preferably, the polymer layer comprises 10 parts by weight HDPE, 50-80 parts by weight EVOH and 30-50 parts by weight EAA.
Preferably, the modified VC adhesive is prepared by mixing acrylic resin, polyester resin, 1,2-polybutadiene latex, polyethyl methacrylate and ethyl isobutyrate;
more preferably, the modified VC glue is prepared by mixing 80-100 parts by weight of acrylic resin, 20-50 parts by weight of polyester resin, 3-5 parts by weight of polybutadiene latex, 5-10 parts by weight of polyethyl methacrylate and 2-4 parts by weight of ethyl isobutyrate. The 1,2-polybutadiene latex is used for improving the bonding strength of the modified VC adhesive; ethyl isobutyrate is mainly used for regulating the rate of the modified VC glue from high temperature to heat sealing and solidification, and meanwhile, the ethyl isobutyrate has another function of reducing the shrinkage stress of the modified VC glue during solidification so as to improve the stability of heat sealing; the effect of the polyethyl methacrylate is to reduce the deformation amplitude of the modified VC adhesive at high temperature and increase the viscosity coefficient of the modified VC adhesive at high temperature, so that the fluidity of the modified VC adhesive is reduced, and the modified VC adhesive keeps higher heat-seal strength.
The second aspect of the invention provides a preparation method of a medicinal composite membrane, which comprises the following steps:
s1, degreasing and cleaning an aluminum foil by using a degreasing agent, and performing anti-corrosion treatment by using an anti-corrosion treatment agent to form a bright surface and a matte surface on the aluminum foil; wherein, the degreaser includes first degreaser and second degreaser, and wherein first degreaser is by ethyl acetate and castor oil polyoxyethylene ether according to mass ratio 10: 3-5; the second oil removing agent consists of 100 parts by weight of deionized water, 60-80 parts by weight of ethanol, 30-50 parts by weight of sodium carbonate and 10-15 parts by weight of sodium polyphosphate; the antiseptic treatment agent comprises chromium trichloride.
S2, adding the components in the modified VC adhesive into a screw extruder of a first laminating mechanism for mixed extrusion, extruding the mixture from a die head of the screw extruder, and laminating the mixture to the bright surface of the aluminum foil layer to form an aluminum foil layer-heat sealing layer composite semi-finished product; wherein the heating temperature of the screw extruder is 200-240 ℃, the extrusion pressure is 20Mpa, the thickness of the modified VC adhesive extruded from a die head of the screw extruder is 40-50 mu m, and the laminating composite pressure is 0.15-0.25 Mpa;
s3, placing the aluminum foil layer-heat sealing layer composite semi-finished product into a micro-concave coating mechanism, and coating the matte surface of the aluminum foil layer with glue; the coating liquid used for glue coating comprises an adhesive and a solvent, wherein the adhesive is water-soluble polyurethane, the solvent is a mixed solution of water and methanol, and the ratio of methanol: water: the mass ratio of the adhesive is 37:10:3; the temperature of the oven in the sizing coating is 150-200 ℃, the heating time is 1-2s, and the sizing thickness is 0.5 mu m and 0.8 mu m.
S4, adding all components in the polymer layer into a screw extruder of a second spraying mechanism, mixing and extruding the components, extruding the components from a die head of the screw extruder, spraying a film to a matte surface of the aluminum foil layer, cooling for the first time to form a polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product, continuously heating, melting and pressing the polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product for the second time, and cooling for the second time to obtain a polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product; and coating the polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product to obtain the medicinal composite film.
Preferably, in step S4, the heating temperature of the screw extruder of the second spraying and repeating mechanism is 300 ℃ to 320 ℃, the extrusion pressure is 100Mpa to 120Mpa, the thickness of the polymer layer extruded from the die head of the screw extruder is 25 μm to 100 μm, the cooling temperature of the first cooling and the second cooling is 12 ℃ to 35 ℃, and the cooling time is 0.6S. The temperature of the secondary heating and melting is 140-180 ℃.
The invention has the advantages of
Compared with the prior art, the invention has the following beneficial effects:
the medicinal composite membrane has excellent high barrier property through the polymer layer of the medicinal composite membrane formed by using EVOH, HDPE and EAA, the barrier property of the medicinal composite membrane to water vapor, oxygen and other gases is obviously improved through the combined action of EVOH, HDPE and EAA, water vapor can be effectively prevented from passing through the aluminum foil layer through the compounding of the polymer layer and the aluminum foil, and the barrier property of the medicinal composite membrane is greatly improved.
The preparation method of the medicinal composite membrane provided by the invention does not need to additionally use an adhesive, but the medicinal composite membrane is attached to the surface of the aluminum foil after the material is melted, so that the obtained product has stable performance and good chemical resistance, the curing time of the traditional dry compounding is saved, the processing time is relatively short, and the processing working hour is greatly shortened.
Detailed Description
Unless otherwise indicated, implicit from the context, or customary in the art, all parts and percentages herein are based on weight and the testing and characterization methods used are in step with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101, 102, etc., and all subranges, e.g., 100 to 166, 155 to 170, 198 to 200, etc., are explicitly recited. For ranges containing values less than 1 or fractions greater than 1 (e.g., 1.1,1.5, etc.), then 1 unit is considered to be 0.0001,0.001,0.01 or 0.1, as appropriate. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms as well.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any such term as are hereinafter recited, out of those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments.
Examples
The following examples are used herein to demonstrate preferred embodiments of the invention. It will be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function in the invention, and thus can be considered to constitute preferred modes for its practice. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit or scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the disclosures and materials cited therein are hereby incorporated by reference.
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.
Example 1
The embodiment provides a medicinal composite film, which consists of a polymer layer, an aluminum foil layer and a heat sealing layer; wherein the polymer layer comprises 10 parts by weight HDPE, 50 parts by weight EVOH and 30 parts by weight EAA; the aluminum foil layer is an aluminum foil with the thickness of 50 mu m;
the heat sealing layer is modified VC glue and is prepared by mixing 80 parts by weight of acrylic resin, 20 parts by weight of polyester resin, 3 parts by weight of 1,2-polybutadiene latex, 5 parts by weight of polyethyl methacrylate and 3 parts by weight of ethyl isobutyrate.
The embodiment also provides a preparation method of the medicinal composite membrane, which comprises the following steps:
s1, carrying out first oil removal cleaning on an aluminum foil by using a first oil removal agent, then carrying out second oil removal cleaning on the aluminum foil by using a second oil removal agent, and carrying out anti-corrosion treatment by using a chromium trichloride solution to form a bright surface and a matte surface on the aluminum foil; wherein the first oil removing agent is prepared from ethyl acetate and castor oil polyoxyethylene ether according to the mass ratio of 10:3, preparing a composition; the second oil removal agent consists of 100 parts by weight of deionized water, 70 parts by weight of ethanol, 40 parts by weight of sodium carbonate and 13 parts by weight of sodium polyphosphate.
S2, adding the components in the modified VC adhesive into a screw extruder of a first laminating mechanism according to a ratio, mixing and extruding the mixture, extruding the mixture from a die head of the screw extruder, and laminating the mixture to the bright surface of the aluminum foil layer to form an aluminum foil layer-heat sealing layer composite semi-finished product; wherein the heating temperature of the screw extruder is 220 ℃, the extrusion pressure is 20Mpa, the thickness of the VC adhesive extruded from a die head of the screw extruder is 45 mu m, and the laminating composite pressure is 0.20Mpa;
s3, placing the aluminum foil layer-heat sealing layer composite semi-finished product into a micro-concave coating mechanism, and coating the matte surface of the aluminum foil layer with glue; the coating liquid used for glue coating comprises an adhesive and a solvent, wherein the adhesive is water-soluble polyurethane, the solvent is a mixed solution of water and methanol, and the ratio of methanol: water: the mass ratio of the adhesive is 37:10:3; the temperature of the oven in the sizing coating is 175 ℃, the heating time is 1.5s, and the sizing thickness is 0.6 mu m.
S4, adding the components in the polymer layer into a screw extruder of a second spraying and repeating mechanism according to the proportion, mixing and extruding at the heating temperature of 310 ℃, extruding from a die head of the screw extruder at the extrusion pressure of 110Mpa, then spraying a film to a matte surface of the aluminum foil layer, cooling at the temperature of 20 ℃ for 0.6S after primary cooling to form a polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product, continuously performing secondary heating, melting and pressing on the polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product at the temperature of 160 ℃, cooling again at the cooling temperature of 25 ℃ for 0.6S to obtain a polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product; and coating the polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product to obtain the medicinal composite film.
Example 2
The embodiment provides a medicinal composite film, which consists of a polymer layer, an aluminum foil layer and a heat sealing layer; wherein the polymer layer comprises 10 parts by weight HDPE, 65 parts by weight EVOH and 40 parts by weight EAA; the aluminum foil layer is an aluminum foil with the thickness of 50 mu m;
the heat sealing layer is modified VC glue and is prepared by mixing 90 parts by weight of acrylic resin, 35 parts by weight of polyester resin, 4 parts by weight of 1,2-polybutadiene latex, 7 parts by weight of polyethyl methacrylate and 3 parts by weight of ethyl isobutyrate.
This example also provides a method for preparing a pharmaceutical composite membrane, which is the same as in example 1.
Comparative example 1
Comparative example 1 compares to example 1 with the difference that the polymer layer of comparative example 1 comprises 10 parts by weight HDPE, 150 parts by weight EVOH and 40 parts by weight EAA.
Comparative example 2
Comparative example 2 is compared to example 1 with the difference that the polymer layer of comparative example 2 has nylon instead of EVOH.
Comparative example 3
Comparative example 3 compares to example 1 with the difference that the polymer layer of comparative example 3 has PVC instead of EVOH.
Comparative example 4
Comparative example 4 is compared to example 1 with the difference that the EVOH is replaced by polystyrene in the polymer layer of comparative example 4.
Comparative example 5
Comparative example 5 compares with example 1 with the difference that the polymer layer of comparative example 5 has ethylene-vinyl acetate copolymer instead of EAA.
Comparative example 6
Comparative example 6 compares to example 1 with the difference that the VC gum of comparative example 6 is the commercially available "riding eagle" brand VC-1600.
The pharmaceutical composite films of examples 1-2 and comparative examples 1-6 were subjected to performance tests, the test structures of which are shown in table 1.
Water vapor transmission amount: measuring the amount of transmitted water vapor by a first cup method under the selected experimental conditions B, placing the hot-seal adhesive surface at a position with low humidity in the experimental process, setting the humidity to be (90 +/-5)%, the temperature to be (38 +/-2) ° C, and the concentration to be not higher than 0.5g/m 2 The standing time is one day.
Oxygen transmission amount: measuring the amount of irradiated gas transmission by pressure difference method, placing a hot-sealing adhesive surface at oxygen low pressure, setting the temperature at (23 + -2) deg.C and the concentration at 0.5cm or below 3 /(m 2 ·24h·0.1MPa)。
TABLE 1 Performance test Table
As can be seen from table 1, examples 1 and 2 of the present invention have excellent barrier properties and heat-sealing properties.
The peel strength of examples 1-2 and comparative examples 1-6 were tested according to YBB00242002-2015 and the results are shown in tables 2 and 3.
TABLE 2 results of longitudinal Peel Strength test
TABLE 3 transverse Peel Strength test results
As can be seen from tables 2 and 3, when the VC adhesive is a modified VC adhesive, the transverse and longitudinal peel strength is stronger than that of the commercially available VC adhesive.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims of the present application.
Claims (8)
1. A medicinal composite film comprises a polymer layer, an aluminum foil layer and a heat sealing layer, and is characterized in that the polymer layer comprises high-density polyethylene, ethylene-vinyl alcohol copolymer and ethylene acrylic acid copolymer; the aluminum foil layer is an aluminum foil with the thickness of 45-55 mu m; the heat sealing layer is modified VC glue.
2. A pharmaceutical composite film according to claim 1 wherein the polymer layer comprises 10 parts by weight of high density polyethylene, 50 to 80 parts by weight of ethylene vinyl alcohol copolymer and 30 to 50 parts by weight of ethylene acrylic acid copolymer.
3. The pharmaceutical composite film according to claim 1, wherein the modified VC adhesive is prepared by mixing acrylic resin, polyester resin, 1,2-polybutadiene latex, polyethyl methacrylate and ethyl isobutyrate.
4. The pharmaceutical composite film according to claim 1, wherein the modified VC adhesive is prepared by mixing 80-100 parts by weight of acrylic resin, 20-50 parts by weight of polyester resin, 3-5 parts by weight of polybutadiene latex, 5-10 parts by weight of polyethyl methacrylate and 2-4 parts by weight of ethyl isobutyrate.
5. A method of preparing the pharmaceutical composite membrane of claim 1, comprising the steps of:
s1, degreasing and cleaning an aluminum foil by using a degreasing agent, and performing anti-corrosion treatment by using an anti-corrosion treatment agent to form a bright surface and a matte surface on the aluminum foil;
s2, adding the modified VC adhesive into a screw extruder of a first spraying and repeating mechanism for mixed extrusion, extruding the mixture from a die head of the screw extruder, and then spraying a film to the bright surface of the aluminum foil layer to form an aluminum foil layer-heat sealing layer composite semi-finished product;
s3, placing the aluminum foil layer-heat sealing layer composite semi-finished product into a micro-concave coating mechanism, and gluing and coating the matte surface of the aluminum foil layer;
s4, adding all components in the polymer layer into a screw extruder of a second spraying and repeating mechanism for mixed extrusion, extruding the mixture from a die head of the screw extruder, then spraying a film to a matte surface of the aluminum foil layer, performing primary cooling to form a polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product, continuously performing secondary heating, melting and pressing on the polymer layer-aluminum foil layer-heat sealing layer primary composite semi-finished product, and performing secondary cooling to obtain a polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product; and coating the polymer layer-aluminum foil layer-heat sealing layer composite semi-finished product to obtain the medicinal composite film.
6. The preparation method according to claim 5, wherein in step S1, the oil removing agent comprises a first oil removing agent and a second oil removing agent, wherein the first oil removing agent is prepared from ethyl acetate and castor oil polyoxyethylene ether according to a mass ratio of 10: 3-5; the second oil removing agent consists of 100 parts by weight of deionized water, 60-80 parts by weight of ethanol, 30-50 parts by weight of sodium carbonate and 10-15 parts by weight of sodium polyphosphate; the antiseptic treatment agent comprises chromium trichloride.
7. The preparation method according to claim 5, wherein in the step S2, the heating temperature of the first laminating mechanism screw extruder is 200 ℃ and 240 ℃, the extrusion pressure is 20MPa, the thickness of the modified VC glue extruded from the die head of the screw extruder is 40-50 μm, and the laminating composite pressure is 0.15-0.25 MPa.
8. The preparation method according to claim 5, wherein in step S4, the heating temperature of the screw extruder of the second spraying mechanism is 300-320 ℃, the extrusion pressure is 100-120 MPa, the thickness of the polymer layer extruded from the die head of the screw extruder is 25-100 μm, the cooling temperature of the first cooling and the second cooling is 12-35 ℃, the cooling time is 0.6S, and the temperature of the second heating and melting is 140-180 ℃.
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