CN110049873A - Sterilizable packaging material - Google Patents

Sterilizable packaging material Download PDF

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Publication number
CN110049873A
CN110049873A CN201780076375.8A CN201780076375A CN110049873A CN 110049873 A CN110049873 A CN 110049873A CN 201780076375 A CN201780076375 A CN 201780076375A CN 110049873 A CN110049873 A CN 110049873A
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China
Prior art keywords
packaging material
additionally preferred
disinfection
alpha
weight
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CN201780076375.8A
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Chinese (zh)
Inventor
S·范米尔卢
B·范登埃舍特
P·戴维森
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SABIC Global Technologies BV
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SABIC Global Technologies BV
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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wrappers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The packaging material of disinfection, it includes the copolymer of the copolymer of-A. ethylene and at least one alpha-olefin and/or propylene and alpha-olefin and/or its two or more mixture, and-B. relative to component A by weight 50 to 200ppm alpha-tocopherol.

Description

Sterilizable packaging material
Technical field
The present invention relates to the packaging material of disinfection and it includes polyethylene and alpha-tocopherol.
Background technique
The stabilisation of polyolefin is as known in the art.
Suitable stabilizer as known in the art is, for example, to synthesize (more) phenolic compound, such as four [methylene -3- (3', 5')-di-tert-butyl-hydroxy phenyl) propionic ester] methane；3,5- di-t-butyl -4- hydroxyhydrocinnamic acid stearyl； 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane；Three (3,5- di-t-butyl-of 1,3,5- trimethyl -2,4,6- 4- hydroxybenzyl) benzene, double-[3,3- bis--(4 '-hydroxyls -3 '-tert-butyl-phenyl butyric acid]-glycol ester；Three (3,5- di-t-butyls- 4- hydroxybenzyl) chlorinated isocyanurates；1,3,5- tri- (4- tert-butyl -2,6- dimethyl -3- Hydroxy-benzvl) chlorinated isocyanurates；5- Three ester of di-t-butyl -4- hydroxyhydrocinnamic acid and 1,3,5- tri- (2- ethoxy)-s- triazine -2,4,6 (1H, 3H, 5H) triketone； Paracresol/bicyclopentadiene butylation product and bis- (2 '-bis--hydroxyl-the 3 '-tert-butyls -5 '-methylphenyl -4- of 2,6- Methyl-phenol).It is also known to the art that be the stabilizer selected from organic phosphite or phosphinate.Such as phosphorous acid three (2,4- di-tert-butyl-phenyl) ester.
Stabilized polyolefin and/or packaging material can be via such as injection molding, blow molding, extrusion molding, pressures It shortens type into or Thin-Wall Injection Molding Technology is processed.Can be by the products application of acquisition in a large amount of application, such as food In packaging applications, biomedical applications, healthcare appliances or pharmaceutical applications.
In addition, needing or it is expected disinfection in some cases.Therefore it can for example be irradiated by being heat-treated and/or passing through, Especially for example by realizing disinfection with alpha radiation and/or β-radiation and/or γ-radiation irradiation.
Thus disinfection may cause degradation, especially for example lead to the degradation of some stabilizers, this transfers to influence to produce Physical property matter, especially engineering properties.In fact, the catabolite obtained after sterilisation may have an impact to engineering properties.
In addition, synthesis (more) phenol antioxidant and/or related degradation product can be from there through used in most of Government is standardized, because they are limited by harsh.Synthetized oxidation preventive agent and/or related degradation product can especially expand It is dissipated in surrounding medium.This can transfer to cause food and/or other products by genotoxic potential or at least substance worried Or by-product and related degradation product pollution.May only because some antioxidants or catabolite or by-product one It is toxic or be to be considered only as related and lead to the problem of this to determine concentration or more.Therefore, disinfection can further increase stabilizer, pair A possibility that product and/or catabolite leak.
Therefore exist to providing the constant demand of improved packaging material, the packaging material do not have dangerous influence and Also meet all requirements related with engineering properties, processing and/or short-term thermal stability
Summary of the invention
It is a feature of the present invention that the packaging material of disinfection includes:
The copolymer and/or propylene of-A. ethylene and at least one alpha-olefin and the copolymer of alpha-olefin and/or its two kinds or More kinds of mixtures, and
- B. relative to component A by weight 50 to 200ppm alpha-tocopherol.
This especially for example can allow to reduce one or more phosphate/esters and/or Di-tert-butyl-phenol and/or 7, 9- di-t-butyl -1- oxaspiro [4.5] decyl- 6,9- diene -2,8- diketone is let out from disinfection, particularly irradiated material Dew.This can for example improve organoleptic properties.
It is possible thereby to which the amount and/or relevant risk of packaging material may be migrated out by reducing one or more compounds.
In addition, sterilizable packaging material can show improved processing stability.
It effectively stabilizes sterilizable packaging material, while limiting and/or avoiding using noxious material.This can be special Be not for example allow improve processing stability, especially for example by disinfection and/or it is (multiple) squeeze out during reduction be crosslinked or Chain rupture.
Component A can be such as polyethylene, the especially such as copolymer of ethylene and at least one alpha-olefin, preferably line style Low density polyethylene (LDPE) (LLDPE), high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) and/or its two or more Mixture.Therefore the copolymer of ethylene and at least one alpha-olefin can include preferably ethylene and at least one alpha-olefin Copolymer or ethylene and a kind of only copolymer of alpha-olefin.
Packaging material according to the invention can be with 50 to 100 weight %, preferably 60 to > 99.5 weight %, it is additionally preferred to 70 to > 99.7 weight %, it is additionally preferred to 80 to > 99.8 weight %, it is additionally preferred to the amount of 90 to > 99.9 weight % includes component A, Total weight based on the material.
The production method of LDPE, HDPE and LLDPE are summarized in the Handbook of of Andrew Peacock Polyethylene(2000；Dekker；ISBN 0824795466) in, especially for example at the 43-66 pages.It is used to urge Agent may include such as ziegler natta catalyst, Phillips catalyst and single site catalysts.Latter type is different The family of the compound of type comprising metallocene catalyst.Using ziegler natta catalyst prepare polymer for example through By the phase interaction of I-III group metal organo-metallic compound or hydride and Section IV-VIII group transition metal derivative For obtaining.Thus the example of (modification) ziegler natta catalyst can be, for example, to be based on titanium tetrachloride and organometallic Close the catalyst of object triethyl aluminum.
Linear low density polyethylene (LLDPE) used herein means the ethylene-comprising ethylene and C3-C10 alpha-olefin comonomer Alpha olefin copolymer.Suitable alpha-olefin comonomer includes 1- butylene, 1- hexene, 4- methylpentene and 1- octene.Preferably Comonomer can be 1- hexene or 1- butylene.Preferably, alpha-olefin comonomer is with the pact of such as ethene-alpha-olefin copolymer 2.5 to 30 weight percent, optimal ethylene-alpha olefin copolymer 5 to about 20 weight percent, more preferable ethene-alpha-olefin The amount of about 7 to about 15 weight percent of copolymer exists.
Linear low density polyethylene (LLDPE) used herein can be thus for example comprising 3 to 200 CH3/ 1000 carbon atoms, It is preferred that 4 to 100 CH3/ 1000 carbon atoms, preferably 5 to 40 CH3/ 1000 carbon atoms, preferably 10 to 30 CH3/1000 A carbon atom, further preferred 15 to 25 CH3/ 1000 carbon atoms are such as measured by NMR.
The technology for being suitable for LLDPE manufacture includes, but are not limited to gas fluidised bed polymerisation, polymerize in solution and slurry is poly- It closes.Preferred embodiment according to the present invention is obtained by gas-phase polymerization in the presence of ziegler natta catalyst LLDPE.According to another preferred embodiment, LLDPE can be obtained by gas-phase polymerization in the presence of a metallocene catalyst.
The copolymer of polyethylene and/or ethylene and at least one alpha-olefin can be for example with >=850kg/m3And≤ 950kg/m3, preferably >=910kg/m3And≤940kg/m3, it is additionally preferred to 913kg/m3To 923kg/m3According to ISO 1183- 1 (2012), the density of method A measurement.This can lead to the engineering properties for being adapted for use in film application.
The copolymer of polyethylene and/or ethylene and at least one alpha-olefin can be for example with 0.1dg/min to 10dg/ Min, preferably 0.5dg/min are to 6dg/min, it is additionally preferred to 0.5dg/min to 4dg/min, or even in addition preferably > 0.5dg/min To 3.5dg/min or>0.5dg/min to<2dg/min by according to ISO 1131-1 (2011) at 190 DEG C and in 2.16kg Load measure correspondence melt mass flow rate (MFR) represent MFI.This can cause suitable for the processable of film application Property.
Component B can be alpha-tocopherol.Component B for example can include 0.5 weight % to 5 weights as liquid and/or use Measure %, the preferably alpha-tocopherol of 1 to 5 weight % and/or 5 to 40 weight %, preferably the having as component C of 5 to 15 weight % The rest part for adding to 100 weight % of machine metallic stearate and masterbatch is the other polyethylene as component D, preferably The masterbatch of low density polyethylene (LDPE) is added.
According to the present invention, alpha-tocopherol can be with preferably synthetic alpha-tocopherol.This allows to carry out actual interpolation good Control.
The suitable example of alpha-tocopherol and/or synthetic alpha -tocopherol according to the present invention can be Irganox E 201 (being supplied by BASF), be all 8 kinds of alpha-tocopherol of equivalent possible stereoisomers (RRR, SSS, RRS, RSR, SSR, SRS, SRR, RSS) racemic mixture and referred to as D, L- alpha-tocopherol or totally disappeared rotation alpha-tocopherol.
It can for example allow to realize effective stabilize using the alpha-tocopherol of opposite low-load amount using alpha-tocopherol.
Sterilizable packaging material can not preferably include other tocopherols and/or not include tocotrienols and/or excellent Choosing does not include natural VE and/or not comprising other antioxidant and/or not comprising other containing at least one phenolic group sequence Compound.This can permit the effective stabilisation of packaging material, while reduce the compound that may migrate out packaging material Amount and/or associated risk.Therefore this can reduce possible health risk.
Relative to component A, the amount of component B is by weight in 25ppm to 300ppm, and preferred 50ppm is extremely by weight 200ppm, by weight in addition preferably>50ppm to<180ppm, it is additionally preferred to>75ppm to<175ppm, it is additionally preferred to>90ppm To 170 or < 170ppm.In addition to this or alternatively, according to the present invention using a kind of production of ziegler natta catalyst The ethylene of packaging material and the copolymer of at least one alpha-olefin and/or propylene and alpha-olefin copolymer and/or its two kinds Or more mixture.
This can permit effective ground stabilizing packaging material composition, while reduction may migrate out packaging material composition The amount of compound and/or associated risk.Therefore this can reduce possible health risk.
Other than component A and B, sterilizable packaging material according to the present invention can also include component C, can be At least one acid scavenger, preferably at least a kind of organic metal stearate, such as magnesium stearate, aluminum stearate, odium stearate With calcium stearate and/or at least one inorganic hydrotalcite, such as DHT4A, preferably calcium stearate.This can additionally assist in improvement Machinability.
Relative to component A, the amount of optional component C can be more excellent by weight by weight in 100ppm to 1000ppm 200ppm to 800ppm is selected, by weight in addition within the scope of preferably 400ppm to 600ppm.
Weight ratio B:C can be for example in 0.05:1 to 0.6:1, preferably 0.07:1 to 0.5:1, it is additionally preferred to which 0.1:1 is extremely Within the scope of 0.4:1.
Other than component A, B and C, sterilizable packaging material according to the present invention can also include component D, can be with For at least one other polyethylene, preferably low density polyethylene (LDPE) or polypropylene.The amount of compound D can be 0 to 10 000ppm, preferably 2000 to 7000ppm.Preferably, polyethylene in addition can be different from component A and/or can be especially for Such as LDPE.
Thus packaging material according to the invention can for example pass through with studying in (as explained below) in NIAS The preferably shorter than 0.8mg/kg of PTV-GC-MS measurement, 2, the 6- di-t-butyl benzoquinones of preferably shorter than 0.5mg/kg and/or is lower than 7,9- di-t-butyl -1- oxaspiro [4.5] decyl- 6 of 0.4mg/kg, preferably shorter than 0.2mg/kg, 9- diene -2,8- diketone and/ Or 3- (3,5- di-tert-butyl-hydroxy phenyl) methyl propionate lower than 0.5mg/kg and/or it is lower than 10mg/kg, preferably shorter than 1mg/kg, it is additionally preferred to which the extractable amount of 2, the 4- Di-tert-butyl-phenol lower than 0.5mg/kg is (with mg compound/kg packing timber Material meter), and/or 5mg/kg, preferably shorter than 1mg/kg are lower than by LC-MS measurement in NIAS research (as explained below) Phosphate extractable amount.Therefore above-mentioned substance can be undesirable.Phosphate used herein can be therefore special Three (2,4- di-tert-butyl-phenyl) phosphates are not referred to for example.
Analysis method for NIAS research is described below (with mg compound/kg packaging material report result).
TD-GC-MS by being coupled thermal desorption (TD), gas-chromatography (GC) and mass spectrum (MS) analyzes volatile matter.
Therefore by thermal desorption unit Markes TD100 and GC Agilent 7890A and Agilent 5975C quality testing Device is used together, and in addition uses ChemStation E.02.02.1431 2 50m* of software and Agilent HP-ULTRA 0.320mm column, 0.52 μm of film.
Use following temperature program: 40 DEG C of initial temperature, keeping 2min, 3 DEG C/min of slope until 92 DEG C, 5 DEG C of slope/ For min up to 160 DEG C, 10 DEG C/min of slope keeps 10min up to 280 DEG C.Detection range is 29-450AMU.
Thermal desorption carries out 40 minutes at 110 DEG C.Sample is weighed in empty thermal desorption tube.It is counted for toluene external standard It calculates.
PTV-GC-MS by being coupled programming temperature evaporation (PTV), GC and MS analyzes half volatile matter.
Therefore by GC Agilent 6890N and 5973 mass detector of Agilent and autosampler Agilent G2614 is used together, wherein in addition using ChemStation E.02.02.1431 software and Agilent HP5MS 60M* 0.250mm column, 1.0 μm of films.Thus in 50 DEG C of 20 μ l of injection.
It uses following temperature program: 70 DEG C of initial temperature, keeping 0.5min, 10 DEG C/min of slope is kept up to 300 DEG C 45min.Detection range in MS is 30-500AMU.
The pellet of 5 grams of cryogrindings of every kind of material 200mL methylene chloride is used into boiling under reflux conditions in 8 hours It rises and extracts.Concentrated extract and solvent is evaporated to 1ml.Inject dichloromethane extract and without other place Reason.It is calculated for external standard naphthalene.
LC-MS by being coupled liquid chromatogram (LC) and MS analyzes non-volatile matter.Therefore by liquid chromatogram unit LC Waters Acquity H Class and 2 detector of Waters SQ Detector and MassLynx V4.1 software and Waters Acquity UPLC BEH Phenyl, 2.1x 100mm column, 1.7 μm of films are used together.Column temperature is 40 DEG C and infuses Penetrate 5 μ l.
Mobile phase includes 0.1% formic acid (A) in water, methanol (B) and isopropanol (C), and wherein gradient is in 6min It is interior from 20%A, 70%B and 10%C to 90%B and 10%C and to keep 1min.Flow rate set is to 0.4ml/min.
Atmospheric pressure chemical ionization (APCI) is used to carry out MS screening with positive/negative mode the range of m/z 100-2000.
The pellet of 5 grams of cryogrindings is mentioned with 200mL methylene chloride using boiling under reflux conditions in 8 hours It takes.By solvent being evaporated to dryness and is dissolved in the 2- propanol/water of 1ml 80/20 come concentrated extract.Methylene chloride is mentioned It takes object to evaporate and is dissolved in isopropanol/water (80/20).Target components are quantified using the external standard of every kind of component.
Method for migration research is described below (with mg compound/kg food report result).
Migration calculates completely:
6dm2* the thickness * additive concentration of density polyethylene * film=to the migration in 1kg food
Using fair in the plastics instruction (Plastics Directive, 2002/72/EC, through revising) based on latest edition Perhaps the migration of Migratest EXP2013 software (Fabes) the verifying additive of generally acknowledged migration models.Thus 60 DEG C with Fatty foodstuff contacts the migration calculated from packaging in 10 days (diffusion only in packaging just determines migration, limits without subregion).
Therefore packaging material according to the invention can have < 1mg/kg (in terms of mg compound/kg food) based on answering With modeling software Migratest EXP2013 (Fabes) and/or completely the migration migration research (as described above) calculated The amount of the compound of migration.
The packaging material of disinfection according to the present invention can be preferably for example comprising following and/or be made up of:
The copolymer and/or propylene of-A. ethylene and at least one alpha-olefin and the copolymer of alpha-olefin and/or its two kinds or More kinds of mixtures, and
- B. relative to component A by weight 50 to 200ppm alpha-tocopherol, and
Acid scavenger of-the C. relative to component A 100ppm to 1000ppm by weight, such as organic metal stearate, It is preferred that calcium stearate,
- D. optional other polyethylene.
Therefore the sterilizable packaging material being grouped as by listed above group can preferably mean that other antioxygens are not present Agent and/or there is no other acid scavengers and/or there is no other acid scavengers and/or that there is no other organic metal is stearic Hydrochlorate or hydrotalcite and/or be not present other compound/components.
Sterilizable packaging material according to the present invention can be used to produce specific packing articles.Preferred product Example is film and/or bag, especially for application such as food and/or beverage packaging application, for healthcare appliances and/or medicine Application and/or medicine or biomedical applications are learned, wherein packaging material according to the invention is sterilized.
The invention further relates to the purposes of sterilizable packaging material according to the present invention, and it is specific can be used for production Product.The example of preferred product is film and/or bag, especially for application such as food and/or beverage packaging application, for defending Raw healthcare applications and/or pharmaceutical applications and/or medicine or biomedical applications, wherein packaging material according to the invention is disappeared Poison.
Sterilizable packaging material according to the present invention can be, for example, multilayered structure, especially for example comprising at least one Aluminium layer, preferably at least an aluminum middle layer and/or at least one pet layer, preferably at least a PET outer layer, and/or at least one A part of the multilayered structure of the internal layer of a packaging material according to the invention.
Packaging material according to the invention can be especially used to so-called blow-fill-sealing applications and technique.It blows-fills out Fill-therefore sealing applications and technique can be such application and technique, such as in pharmacy industry, wherein make container at Shape, filling, is preferably for example filled with liquid, and seal in a technique, and the process preferably needs as few as possible artificial It interacts and/or is carried out in machine and/or in the enclosed environment of disinfection.This can improve antibacterial processing.
Packaging material according to the invention can be, for example, multilayered structure, excellent especially for example comprising at least one pet layer Select a part of the multilayered structure of at least one PET outer layer and/or the internal layer of at least one packaging material according to the invention. Such multilayered structure for example can be used for pallet as epiphragma, especially for example for food service tray.
" sterilizable " therefore can especially refer to can be for example subjected in the sense of the present invention for example, by 20 kilograys, preferably 25 kilograys, it is additionally preferred to γ-radiation disinfection of 35 kilograys (kGy).
However, " sterilizable " is also used as the synonym of " (actually) disinfection " herein and exchanges with it It uses, described " (actually) disinfection " is especially for example for example, by 20 kilograys, preferably 25 kilograys, it is additionally preferred to 35,000 The γ of gray(Gy) (kGy)-radiation carries out.
Therefore packing timber that packaging material according to the invention and/or sterilizable packaging material can be sterilized preferably Material.
When being subjected to the blown film with 25 and/or 125 microns of film thicknesses by 20 kilogray of dosage, preferably 25,000 dagger-axes It is auspicious, it is additionally preferred to when γ-radiosterilization of 35 kilograys (kGy), compared with not being subjected to such sample sterilized, according to this hair Bright sterilizable packaging material according to ASTM D882 measurement 1% secant of stretch modulus MD (in terms of MPa) and/or according to ISO7765-2 measurement impact resistance F max (N) and/or according to ASTM D1003 measurement mist degree (%) each and/or All variation is no more than 50%, preferably more than 25%, it is additionally preferred to be no more than 20%, it is additionally preferred to be no more than 10%, in addition Preferably more than 5%.
The packaging material of disinfection according to the present invention can be so that the Mw/Mn of linear low density polyethylene (LLDPE) is 4 to 12, it is excellent Select 4.5 to 11, it is additionally preferred to 4.7 to 10, it is additionally preferred to 5 to 8, it is additionally preferred to>5 to<7, it is additionally preferred to>5.5 to<6.5 and/or The Mz/Mw of linear low density polyethylene (LLDPE) is 4 to 12, preferably 4.5 to 11, it is additionally preferred to 4.7 to 10, it is additionally preferred to 5 to 8, in addition It is preferred that>5 to<7, it is additionally preferred to>5.8 to<6.8.
The packaging material of disinfection according to the present invention can be so that linear low density polyethylene (LLDPE) has >=850kg/m3And And≤950kg/m3, preferably >=910kg/m3And≤940kg/m3, it is additionally preferred to 913kg/m3To 923kg/m3, it is additionally preferred to > 915kg/m3To < 921kg/m3Density and/or 0.1dg/min to 12dg/min, preferably 1dg/min to 11dg/min, it is in addition excellent 3dg/min to 10dg/min is selected, or even in addition preferably 4dg/min to 9dg/min, or even in addition preferably>4dg/min to<9dg/ The melt mass flow rate (MFR) of the load measure according to ISO 1131-1 (2011) at 190 DEG C and in 2.16kg of min.
The packaging material of disinfection according to the present invention can be so that packaging material does not include other tocopherols and/or do not wrap Containing tocotrienols and/or does not include natural VE and/or do not include other antioxidants and/or do not include containing at least The other compounds and/or its packaging material of one phenolic group sequence only include alpha-tocopherol as antioxidant.
The invention further relates to the packaging of the disinfection comprising multilayered structure, the multilayered structure includes at least one aluminum middle layer And/or at least PET outer layer and/or the internal layer of at least one packaging material according to the invention.
The invention additionally relates to the packagings of disinfection, and wherein multilayered structure is especially to use for food and/or beverage packaging In the lid or bag of food service tray, and/or as lid or bag for drug, implantation material, patch or medicine or biomedical applications The packaging of other articles.
Embodiment
Using sterilizable packaging material according to the present invention with 35kg/h (die head size 120mm, die gap 25 and 125 μm and BUR=2 of blown film is produced on Kuhne blown film line 2.7mm).
Make the blown film experience γ radiation with 25 and 125 microns of film thicknesses.The dosage for being set as that there is 35kGy of selection γ radiation.Dosemeter is added into sample to ensure to apply required dosage.It, will for the γ radiation with high-penetration depth Polymer packaging is in transparent bag without especially handling.
Irradiation can need a few houres.Gamma-rays can by radioactive isotope cobalt -60 (60Co decay) generates.They have There is high penetration depth and complete pellet or agglomerate (lots) can be penetrated.
Conveyer system is around the source frame transmission for accommodating radiation source.Control, which ensures, abides by the total γ fixed to every kind of product Dose of radiation.
The packaging material of disinfection according to the present invention can be (after sterilisation) thus it is shown that in NIAS research (as herein Middle explanation) in by PTV-GC-MS measurement preferably shorter than 0.8mg/kg, 2, the 6- di-tert-butyl of preferably shorter than 0.5mg/kg Quinone and/or be lower than 0.4mg/kg, 7,9- di-t-butyl -1- oxaspiro [4.5] decyl- 6 of preferably shorter than 0.2mg/kg, 9- diene - 2,8- diketone and/or 3- (3,5- di-tert-butyl-hydroxy phenyl) methyl propionate lower than 0.5mg/kg and/or it is lower than 10mg/ Kg, preferably shorter than 1mg/kg, it is additionally preferred to which the extractable amount of 2, the 4- Di-tert-butyl-phenol lower than 0.5mg/kg is (with mg chemical combination Object/kg packaging material meter), and/or by the 5mg/kg that is lower than of LC-MS measurement in NIAS research (as explained herein), it is excellent The extractable amount of phosphate of the choosing lower than 1mg/kg.

Claims (15)

1. the packaging material of disinfection, it includes
The copolymer and/or propylene of-A. ethylene and at least one alpha-olefin and the copolymer of alpha-olefin and/or its two or more The mixture of kind, and
- B. relative to component A by weight 50 to 200ppm alpha-tocopherol.
2. the packaging material of disinfection according to claim 1, wherein composition is additionally comprised:
- C. acid scavenger, preferably organic metal stearate.
3. the packaging material of -2 described in any item disinfections according to claim 1, wherein the amount of component B is relative to component A with weight Meter is in>50ppm to<180ppm, it is additionally preferred to>75ppm to<175ppm, it is additionally preferred to>90ppm to 170 or<170ppm model In enclosing and/or the copolymer of the copolymer and/or propylene of ethylene and at least one alpha-olefin and alpha-olefin and/or its two kinds or More kinds of mixtures are produced using a kind of ziegler natta catalyst.
4. according to the packaging material of the described in any item disinfections of claim 2-3, wherein the amount of component C is relative to component A with weight Meter is within the scope of 100ppm to 1000ppm.
5. the packaging material of disinfection according to claim 1-4, wherein the amount of component A is 50 to < 100 weights Measure %, preferably 60 to > 99.5 weight %, it is additionally preferred to 70 to > 99.7 weight %, it is additionally preferred to 80 to > 99.8 weight %, in addition It is preferred that 90 to > 99.9 weight %, the total weight based on material.
6. the packaging material of disinfection according to claim 1-5, wherein the Mw/Mn of linear low density polyethylene (LLDPE) is 4 to 12, preferably 4.5 to 11, it is additionally preferred to 4.7 to 10, it is additionally preferred to 5 to 8, it is additionally preferred to>5 to<7, it is additionally preferred to>5.5 to< 6.5 and/or linear low density polyethylene (LLDPE) Mz/Mw be 4 to 12, preferably 4.5 to 11, it is additionally preferred to 4.7 to 10, it is additionally preferred to 5 To 8, it is additionally preferred to>5 to<7, it is additionally preferred to>5.8 to<6.8.
7. the packaging material of disinfection according to claim 1-6, wherein linear low density polyethylene (LLDPE) have >= 850kg/m3And≤950kg/m3, preferably >=910kg/m3And≤940kg/m3, it is additionally preferred to 913kg/m3To 923kg/m3, In addition preferably > 915kg/m3To < 921kg/m3Density and/or 0.1dg/min to 12dg/min, preferably 1dg/min to 11dg/ Min, it is additionally preferred to 3dg/min to 10dg/min, or even in addition preferably 4dg/min to 9dg/min, or even in addition preferably > 4dg/ Min to < 9dg/min according to ISO 1131-1 (2011) in 190 DEG C and the melt mass flow rate of the load measure in 2.16kg (MFR)。
8. the packaging material of disinfection according to claim 1-7, wherein the packaging material does not include other lifes Educate phenol and/or not comprising tocotrienols and/or not comprising natural VE and/or not comprising other antioxidants and/or not Comprising other compounds for containing at least one phenolic group sequence and/or wherein the packaging material only includes alpha-tocopherol as antioxygen Agent.
9. the packaging material of disinfection according to claim 1-8, wherein the packaging material is with the packing timber The amount of 50 to < 100 weight % of material includes LLDPE as component A, and wherein LLDPE includes 3 to 200 CH3/ 1000 carbon originals Son, preferably 4 to 100 CH3/ 1000 carbon atoms, preferably 5 to 40 CH3/ 1000 carbon atoms, preferably 10 to 30 CH3/ 1000 carbon atoms, further preferred 15 to 25 CH3/ 1000 carbon atoms, are measured by NMR.
10. the packaging material of -9 described in any item disinfections according to claim 1, wherein when making that there are 25 and/or 125 micron membranes The blown film of thickness is subjected to through dosage being 20 kilograys, preferably 25 kilograys, it is additionally preferred to γ-spoke of 35 kilograys (kGy) When penetrating disinfection, compared with not being subjected to such sample sterilized, sterilizable packaging material according to the present invention according to ASTM 1% secant of stretch modulus MD (in terms of MPa) of D882 measurement and/or the impact resistance F max measured according to ISO 7765-2 (N) and/or according to ASTM D1003 measurement mist degree (%) each and/or all variation be no more than 50%, preferably do not surpass Cross 25%, it is additionally preferred to be no more than 20%, it is additionally preferred to be no more than 10%, it is additionally preferred to be no more than 5%.
11. the film or bag of disinfection, it includes according to claim 1-10 described in any item packaging materials.
12. the purposes of the packaging material of -10 described in any item disinfections according to claim 1, is used for food and/or beverage packets Fill the film and/or bag of application, wherein packaging material according to the invention and article for a person to use, such as beverage or food item or Other articles of alimentary uses directly contact.
13. the purposes of the packaging material of -10 described in any item disinfections according to claim 1, be used for healthcare appliances and/ Or the film and/or bag of pharmaceutical applications and/or medicine or biomedical applications, wherein packaging material according to the invention makes with for people Article, as other articles of drug, implantation material, patch or medicine or biomedical applications directly contact.
14. the packaging of disinfection, it includes contain at least one aluminum middle layer and/or at least PET outer layer and/or at least one basis The multilayered structure of the internal layer of the described in any item packaging materials of claim 1-10.
15. the packaging of disinfection according to claim 14, wherein the multilayered structure is for food and/or beverage packets Dress is especially used for the lid or bag of food service tray, and/or is used for drug, implantation material, patch or medicine or biology as lid or bag The packaging of other articles of medical usage.
CN201780076375.8A 2016-10-14 2017-10-15 Sterilizable packaging material Pending CN110049873A (en)

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EP16193912.9 2016-10-14
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Citations (2)

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EP0878502A2 (en) * 1997-05-05 1998-11-18 Ciba SC Holding AG Formulations of Vitamin E for stabilisation of polymeric organic materials
WO2015078886A1 (en) * 2013-11-29 2015-06-04 Saudi Basic Industries Corporation Stabilised polyolefin composition

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Publication number Priority date Publication date Assignee Title
CA2146034A1 (en) * 1994-05-12 1995-11-13 Kenneth W. Willcox Polymer stabilization
EP2164892A1 (en) * 2007-07-10 2010-03-24 Basf Se Stabilizer compositions
IN2015DN04086A (en) * 2012-10-16 2015-10-09 Saudi Basic Ind Corp
WO2017114782A1 (en) * 2015-12-29 2017-07-06 Sabic Global Technologies B.V. Stabilised polyolefin composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0878502A2 (en) * 1997-05-05 1998-11-18 Ciba SC Holding AG Formulations of Vitamin E for stabilisation of polymeric organic materials
WO2015078886A1 (en) * 2013-11-29 2015-06-04 Saudi Basic Industries Corporation Stabilised polyolefin composition

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