CN102514326B - High-barrier multilayer co-extrusion infusion film - Google Patents
High-barrier multilayer co-extrusion infusion film Download PDFInfo
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- 238000001802 infusion Methods 0.000 title claims abstract description 24
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- 239000004743 Polypropylene Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 polyethylene naphthalate Polymers 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 18
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- 238000002156 mixing Methods 0.000 claims abstract description 16
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 15
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- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
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- 230000032683 aging Effects 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- 229910052793 cadmium Inorganic materials 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Wrappers (AREA)
Abstract
The invention relates to a high-barrier multilayer co-extrusion infusion film which is a five-layer composite film with the composition from the outer layer to the inner layer: polyethylene naphthalate modified polyester/ ethylene acrylate polymer/ polypropylene, ethylene- octylene copolymer blending resin/ ethylene propylene polymer/ modified polypropylene. The advantages of various functional polymer materials are combined by the high-barrier multilayer co-extrusion infusion film, so that not only are the light transmittance, the flexibility, the high barrier performance, the low-temperature thermal sealing property, the thermal bonding strength and the like of the high-barrier multilayer co-extrusion infusion film guaranteed, but also the high-temperature-resistant (121 DEG C and 30min) sterilization performance and the low-temperature-resistant (-30 DEG C) storage performance of the high-barrier multilayer co-extrusion infusion film can be improved; therefore, the matters (including nonvolatile matter, easily-oxidized matter, heavy metal and the like) dissolved out from the infusion film are fewer, a biological or chemical reaction is not caused between the infusion film and liquid medicine after filling sterilization, and toxin is not generated or environmental pollution is not caused when the infusion film is produced, used and recovered. Compared with other similar products, the high-barrier multilayer co-extrusion infusion film has excellent competitive advantages in the aspect of all technical indexes such as production formula, production technique and performances.
Description
Technical field
The present invention relates to medical macromolecular materials technical field, specifically, relate to a kind of high-barrier infusion film.
Background technology
Plastic soft bag transfusion can realize full-closed infusion, thoroughly avoids the air pollution in infusion process.Be the main packaged form of present transfusion package, based on existing technical merit, the medicine package bag for venous transfusion generally used in practice adopts flexible PVC (PVC) composite membrane.
The vitrification point (Tg) of PVC is higher, and material hardness is large, machine-shaping difficulty.Therefore, generally in polyvinyl chloride resin, plasticizer and other auxiliary agent is all added.At present, work in-process is still using dioctyl phthalate (DOP) as primary plasticizer.But DOP is lower-molecular substance, easy migration precipitation.The PVC of DOP plasticising is used for medical catheter or container, is mixed in liquid or blood, DOP will be caused to enter human body with liquid or blood because DOP easily separates out.In the stabilizing agent of PVC processing, lead salt is poisonous to blood, causes severe anemia, and cadmium salt more very; And pink salt and epoxidized soybean oil better.And the Small molecular agents migrate that these various auxiliary agents that will add in PVC process cause and PVC self with chlorine element make it from being worked into removal process, all can discharge harmful components, be detrimental to health.
Therefore, be necessary to develop non-PVC composite membrane, but the combination property of existing various non-PVC composite membrane is all not good enough, some composite membrane is bad to the high barrier of water vapour, and some is that pliability is not good enough, and some is that high temperature-resistant disinfected performance is undesirable.Also do not have at present to ensure that transfusion long term quality is stablized, the high-barrier film for transfusion of amino acid transfusion, blood plasma substitute transfusion, therapeutic type transfusion can be applied to.
PEN (PEN) have good barrier properties for gases, chemical stability, heat resistance and. resistance to ultraviolet radiation energy, even if mechanical property excellent in HTHP situation in addition, it is very potential Medical composite membrane material.
Current, the complex method of domestic and international medical high-barrier infusion film mainly contains usually: dry type compound, solvent-free compound, multi-layer co-extrudedly extrude compound etc.Dry type compound is comparatively traditional a kind of complex method that current domestic application is maximum, it is the Polyurethane adhesive adopting bi-component, to a kind of process that two-layer base film bonds, after its host and curing agent mix in proportion, then dilute with organic solvent, adjust to certain working concentration, be applied on base material by cable roll, dry through hot-air oven, then carry out pressurized adhesion by warm-up mill heating with another kind of base material, then form through Ageing Treatment.The feature of dry-lamination process is simple to operate, interlayer collocation is also versatile and flexible, but its maximum defect is that film surface tension force is larger, though adhesive solvent is through very powerful drying, but also there is the situation of dissolvent residual unavoidably, and waste energy, dry waste gas and the volatilization of organic solvent also pollute the environment.There is no the residual of solvent in the recombination process of solvent-free compound, there is no the exhaust emission environment of waste gas, but because the ratio of host and curing agent controls unstable, complex condition complexity waits many factors, is not also used widely.
The most promising multi-layer co-extruded complex method of extruding at present, it is the extruder of employing more than 3, by the resin raw material of difference in functionality as PA, PE, PP etc., melt extrude respectively, converged at a die head by respective runner, more shaping through inflation, together cooling combined.Multi-layer co-extruded multifunctional packaging film can meet the needs of various medical package very well, there is again the advantage that dry type composite membrane is incomparable, collocation by the thickness and multiple barrier material that adjust barrier layer uses, the film of different barrier property can be designed flexibly, also can change allotment hot sealing layer material flexibly, meet the demand of Different Package.
Therefore, the present invention propose a kind of utilize coextruding method to prepare by the high-barrier infusion film of PEN polyester copolymer and polyolefin compound.
Summary of the invention
The object of this invention is to provide a kind of high-barrier infusion film by PEN polyester copolymer and polyolefin compound.
High-barrier infusion film of the present invention, be five layers of composite membrane, from skin to internal layer, it consists of: PEN modified poly ester/ethylene acrylate polymer/polypropylene, ethylene-octene copolymer (EOC) blending resin/ethylene propylene polymerization thing/modified polypropene;
The thickness of described PEN modified poly ester layer is 10 μm ~ 30 μm; Preferably 17 μm ~ 21 μm;
The thickness of described ethylene acrylate polymer layer is 10 μm ~ 20 μm; Preferably 12 μm ~ 15 μm;
The thickness of described polypropylene, ethylene-octene copolymer (EOC) blending resin layer is 60 μm ~ 137 μm; Preferably 102 μm ~ 126 μm;
The thickness of described ethylene propylene polymerization nitride layer is 10 μm ~ 30 μm; Preferably 12 μm ~ 15 μm;
The thickness of described modified polypropene layer is 10 μm ~ 40 μm; Preferably 17 μm ~ 21 μm.
Wherein, functional layer is PEN modified poly ester layer, ethene improved layer and modified polypropene layer; And ethylene acrylate polymer layer and ethylene propylene polymerization nitride layer are respectively adhesive linkage.
In the present invention, in described PEN modified poly ester, PEN (PEN) content is more than 30%, preferably 45% ~ 80%, more preferably 50% ~ 60%;
PEN (PEN) is by 2,6-naphthalene diformic acid dimethyl ester (NDC) or 2,6-naphthalenedicarboxylic acid (NDA) and ethylene glycol (EG) polycondensation form, its chemical constitution is similar to polyester (PET), and difference is that in strand, PEN be instead of the phenyl ring in PET by the naphthalene nucleus that rigidity is larger.Naphthalene ring makes PEN have higher physical and mechanical properties, gas barrier property, chemical stability and heat-resisting, the performance such as UV resistant, radiation hardness than PET.The copolymer that PEN content is high and polyethylene terephthalate copolymer, thus make the blocking water of film, gas barrier properties improves greatly.
The method preparation that described PEN modified poly ester can adopt this area conventional, as adopted banbury, double screw extruder etc., PEN and polyester are carried out blended, key be carry out more than the melt temperature of PEN blended, there is ester exchange reaction, finally generate the random copolymer of PEN and polyester, i.e. PEN modified poly ester.Also commercial goods can be adopted.
In described polypropylene, ethylene-octene copolymer (EOC) blending resin, the addition of ethylene-octene copolymer is 0.2 ~ 15wt% of blending resin, preferably 5 ~ 15wt%; Described polypropylene is metallocene polypropylene, and its melting speed is 3.5 ~ 27.5g/10min, and density is 0.81 ~ 0.93g/cm
3; Described ethylene-octene copolymer can select commercial goods, as the POE that DOW chemical company produces.The effect of ethylene-octene (EOC) blending resin improves film temperature tolerance.Particularly cryogenic property.
Described modified polypropene is metallocene polypropylene and styrene-ethylene-butylene-styrene copolymer (SEBS) blending resin, and the addition of SEBS is 0.2 ~ 30wt% of blending resin, preferably 15 ~ 25wt%; The melting speed of described metallocene polypropylene is 3.5 ~ 27.5g/10min, and density is 0.81 ~ 0.93g/cm
3; Described styrene-ethylene-butylene-styrene copolymer (SEBS) blending resin selects commercial goods.
Hot sealing layer uses chain length homogeneous, narrow molecular weight distribution, and interchain comonomer distribution replaces polypropylene uniformly, thus expands the heat-sealing temperature scope of film.
Ethylene acrylate polymer (EEA) is the polymer with thermoplasticity and high cementability, usual structure is the random copolymer of ethene and ethyl acrylate, ethyl acrylate part provides flexibility and polarity for it, mainly be used as the binder couse of plural layers in the present invention, therefore adopt ethyl acrylate to account for the EEA of 5 ~ 30wt% content of polymer, preferred ethyl acrylate accounts for the EEA of 15 ~ 30wt% content of polymer;
Ethylene propylene polymerization thing is with ethene, propylene for raw material, and through being polymerized a kind of amorphous copolymer obtained, be a kind of thermoplastic adhesive, in the present invention, select melting speed to be 3.5 ~ 27.5g/10min, density is 0.81 ~ 0.93g/cm
3ethylene propylene polymerization thing, its ethylene contents can be 5 ~ 95wt%; Preferably 5 ~ 15wt%, 20 ~ 35wt% or 75 ~ 85wt%; Preferred molten speed is 5.5 ~ 17.5g/10min, and density is 0.84 ~ 0.90g/cm
3ethylene propylene polymerization thing.
High-barrier infusion film of the present invention adopts coextruding method to produce, and selects lower blowing water cold process coextrusion film blowing method to realize especially, carries out as adopted following method:
Even in stirrer for mixing respectively by each layer film component, then on seven-layer co-extrusion cast film machine production line, each layer raw material is carried out mixed melting plasticizing respectively, by dosage coextrusion curtain coating, obtain high-barrier coextruded film.
The time of described hybrid reaction can be 12 ~ 20h; Described melting, Twin-screw extruder melt extrudes granulation, and 9 district's heating-up temperatures of described double screw extruder can be respectively 170 ~ 180 DEG C, 180 ~ 200 DEG C, 200 ~ 220 DEG C, 210 ~ 220 DEG C, 210 ~ 220 DEG C, 200 ~ 210 DEG C, 190 ~ 210 DEG C, 190 ~ 200 DEG C, 180 ~ 190 DEG C.
Present invention incorporates various functional high molecule material advantage, wherein, as functional layer, PEN has good physical and mechanical properties, gas barrier property, chemical stability and heat-resisting, the performance such as UV resistant, radiation hardness, the copolymer that PEN content is high and polyethylene terephthalate copolymer, thus make the blocking water of film, gas barrier properties improves, greatly even if also have excellent mechanical property in HTHP situation, the physical stability of polypropylene (PP), mechanical strength, air-tightness is better, transparency and glossiness higher, but black brittleness, low-temperature impact-resistant intensity is low, poor rigidity, molding shrinkage is large, easily aging, after adding EOC, its shock resistance, toughness strengthens greatly, as the intermediate layer of co-extrusion film, its advantage can be made full use of, as the two adhesive layer, ethylene acrylate polymer (EEA) is the polymer with thermoplasticity and high cementability, its transparency, good toughness, rigidity, moist steam transmissivity, creep resistance, chemical resistance is good, fusing point and softening point lower, very be suitable as adhesive linkage, greatly can improve combined strength bination and the combination property of co-extrusion film, in ethylene propylene polymerization thing, adding of ethylene unit, the length of polyacrylic crystallizable ordered sequence will be reduced, a kind of thermoplastic adhesive, hot sealing layer uses chain length homogeneous, narrow molecular weight distribution, interchain comonomer distribution replaces polypropylene uniformly, thus expands the heat-sealing temperature scope of film.Above-mentioned each layer organic composite material synergy, not only ensure that the light transmittance of film, pliability, high barrier, low temperature heat seal and heat sealing strength etc., also improve its high temperature resistant (121 DEG C, 30min) sterilizing and low temperature resistant (-30 DEG C) shelf characteric, make the leachable (nonvolatile matter, readily oxidizable substance, heavy metal etc.) of infusion film few, after filling sterilizing, do not play biology, chemical reaction with liquid, produce, use and reclaim time do not produce toxin or cause environmental pollution.Compared with other like products, on all technicals such as factory formula, production technology, performance, there is very large competitive advantage.
Accompanying drawing explanation
Fig. 1 is high-resistant diaphragm cross sectional representation of the present invention, wherein: 1-PEN modified poly ester layer; 2-ethylene acrylate polymer layer; 3-polypropylene, ethylene-octene copolymer (EOC) blending resin layer; 4-ethylene propylene polymerization nitride layer; 5-modified polypropene layer.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.As without specializing, the present invention's raw material used is commercial, and all manufacture processes are carried out ten thousand grades of clean area (adopting macromolecular material to combine).
Adopt lower blowing water cold type coextrusion process to prepare multireel high temperature resistant sterilized medical equipment film for blister package, the thickness of film is 160 μm, 180 μm, 160 μm.Its concrete performance is as shown in table 1.
Table 1
Sealed by the medical clear paper that each volume thin-film material of above-mentioned preparation is produced with Zhejiang Heng Da Paper Co., Ltd after sided corona treatment, test its performance, concrete condition is as table 2:
Table 2
The packaging GBT19633-2005 of reference final sterilization medicine equipment, composite membrane for packaging medicine, bag general rule YBB00132002, national drug packing container (material) standard YBB00102005 detect.Wherein, hot strength and percentage elongation adopt DLS series electronic tensile testing machine to carry out; Oxygen transit dose adopts DKY-30 type headspace analysis instrument to carry out; Peel strength adopts DLS-1 electron detachment machine to carry out.
In addition, detect content of beary metal according to Chinese Pharmacopoeia 2000 editions two annex VIII H first methods, nonvolatile matter, readily oxidizable substance, metal ion (barium, copper, cadmium, lead, tin, chromium ion must not cross 1,000,000/; Aluminium ion) content; Bacterial endotoxin experiment is carried out, priming experiments with reference to YBB00052003; Inspection technique (YBB00062003) is stimulated to measure intracutaneous IR, acute systemic toxicity, hemolytic test according to intracutaneous; By " Chinese Pharmacopoeia 2005 version drug compatibility test direction carries out compatibility test.Result is as follows:
[heavy metal] be less than 1,000,000/.
[nonvolatile matter] is less than 2.5mg.
[readily oxidizable substance] is less than 1.5ml.
[metal ion] barium, copper, cadmium, lead, tin, chromium ion be less than 1,000,000/;
Aluminium ion is less than 1,000,000/zero point zero five.
[bacterial endotoxin] is less than 0.25EU/ml.
[sensitization test (STT)] is less than I degree.
[picosecond laser pulse] vacuum response.
[acute systemic toxicity] reacts without Acute systemic toxicity.
[hemolytic test] hemolysis rate is less than 5%.
Obviously, packaging film of the present invention can meet following performance requirement: 1, hot strength is all not less than 20Mpa; 2, percentage elongation is all not less than 350%; 3, oxygen transit dose is all less than 50cm
3/ (m
224h0.1Mpa); 4, peel strength is all greater than 3.0N, can realize object of the present invention.
Claims (5)
1. a high-barrier multilayer co-extrusion infusion film, it is characterized in that, be five layers of composite membrane, from skin to internal layer, it consists of: PEN modified poly ester/ethylene acrylate polymer/polypropylene, ethylene-octene copolymer blending resin/ethylene propylene polymerization thing/modified polypropene;
In described PEN modified poly ester, PEN content is more than 30%;
In described polypropylene, ethylene-octene copolymer blending resin, the addition of ethylene-octene copolymer is 0.2 ~ 15wt% of blending resin; Described polypropylene is metallocene polypropylene, and its melting speed is 3.5 ~ 27.5g/10min, and density is 0.81 ~ 0.93g/cm
3;
Described modified polypropene is metallocene polypropylene and the copolymer blended resin of styrene-ethylene-butylene-styrene, and the addition of styrene-ethylene-butylene-styrene copolymer is 0.2 ~ 30wt% of blending resin; The melting speed of described metallocene polypropylene is 3.5 ~ 27.5g/10min, and density is 0.81 ~ 0.93g/cm
3;
Described ethylene acrylate polymer is the EEA that ethyl acrylate accounts for 5 ~ 30wt% content of polymer;
Described ethylene propylene polymerization thing is melting speed is 3.5 ~ 27.5g/10min, and density is 0.81 ~ 0.93g/cm
3ethylene propylene polymerization thing, its ethylene contents is 5 ~ 95wt%;
The thickness of described PEN modified poly ester layer is 10 μm ~ 30 μm;
The thickness of described ethylene acrylate polymer layer is 10 μm ~ 20 μm;
The thickness of described polypropylene, ethylene-octene copolymer blending resin layer is 60 μm ~ 137 μm;
The thickness of described ethylene propylene polymerization nitride layer is 10 μm ~ 30 μm;
The thickness of described modified polypropene layer is 10 μm ~ 40 μm.
2. high-barrier multilayer co-extrusion infusion film according to claim 1, is characterized in that, in described PEN modified poly ester, PEN content is 45% ~ 80%.
3. high-barrier multilayer co-extrusion infusion film according to claim 1, is characterized in that, described ethylene acrylate polymer is the EEA that ethyl acrylate accounts for 15 ~ 30wt% content of polymer.
4. high-barrier multilayer co-extrusion infusion film according to claim 1, it is characterized in that, the ethylene propylene polymerization thing of described ethylene propylene polymerization thing to be ethylene contents be 5 ~ 15wt%, 20 ~ 35wt% or 75 ~ 85wt%, melting speed is 5.5 ~ 17.5g/10min, and density is 0.84 ~ 0.90g/cm
3ethylene propylene polymerization thing.
5., according to the arbitrary described high-barrier multilayer co-extrusion infusion film of claim 1-4, it is characterized in that, produce by lower blowing water cold process coextrusion film blowing method.
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| CN201110391646.3A CN102514326B (en) | 2011-12-01 | 2011-12-01 | High-barrier multilayer co-extrusion infusion film |
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| CN102514326B true CN102514326B (en) | 2015-05-27 |
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| CN105252866B (en) * | 2015-10-12 | 2017-12-26 | 宁波华丰包装有限公司 | A kind of multilayer complex films and its preparation method and application |
| CN108340647B (en) * | 2018-01-23 | 2020-08-18 | 湖北华强科技有限责任公司 | Five-layer co-extrusion infusion film for liquid-liquid multi-chamber bag and preparation method thereof |
| CN114030763B (en) * | 2021-11-24 | 2022-12-16 | 成都众恒印务有限责任公司 | Anti-aging packaging bag and preparation method thereof |
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| CN101879800B (en) * | 2010-06-08 | 2013-03-13 | 湖北恒泰橡塑有限公司 | High-barrier medical film |
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Denomination of invention: High-barrier multilayer co-extrusion infusion film Effective date of registration: 20180410 Granted publication date: 20150527 Pledgee: The Bank of Hangzhou Limited by Share Ltd Ningbo Yuyao branch Pledgor: Ningbo Huafang Package Co., Ltd. Registration number: 2018330000079 |
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