passive and active barrier systems - ctnc iv symposium... · oxygen scavengers in sachets the...
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Passive and Active Barrier Systems for the best packaging Performance
Applications, developments and Legal Frame
IV Symposium Internacional Sobre tecnologia alimentariafood technology international symposium
26-27 October 09Murcia Spain
CTC Centro Tecnológico Nacional de la Conserva y AlimentaciónDidier Houssier
OutlookCompany IntroductionDefinitionsPassive Barriers
Analytical Methods, Barrier Properties and ProductsActive Barriers
Analytical Methods, Properties and ProductsDevelopmentsLegal FrameSummary
Company Introduction
Kuraray Co. Ltd.Established June 24, 1926Net Sales ¥385 Billion (€2.48 Billion) FY2007Total Assets ¥509 Billion (€3.28 Billion) FY2007Employees 6,812 (March 31, 2007)Head Office TokyoKuraray in Europe
Kuraray Europe GmbH (www.kuraray.eu)Kuraray Specialities GmbH (www.kuraray-kse.com )EVAL Europe (www.eval.eu )
Tokyo Antwerp Houston
Kuraray / EVAL Europe History1926 Kurashiki Kenshoku Co. founded1949 name changed to Kurashiki Rayon (Kuraray)1958 Poval sales begin1965 European representative office in Hamburg (Düsseldorf from 1968)1970 name changed to Kuraray Co. Ltd.1972 EVAL sales begin1983 EVAL America established, production starts in 19861995 Kuraray EVAL Europe GmbH sales company established1997 EVAL Europe nv established for plant construction1999 EVAL Europe nv and KEE unified in Antwerp1999 EVAL Europe nv production begins, total capacity 12,000T2004 EVAL Europe doubles capacity to 24,000T
Antwerp, Belgium• EVAL™ EVOH resins• EVAL™ Film• KURARISTER™
Frankfurt, Germany• POVAL™ MOVIOL™ PVOH resins• other Chemicals and Resins• High Performance Materials• Medical materials• Fibres and Textiles
Europe
Okayama Antwerp Houston10,000T 24,000T 35,000T
Europe’s Largest EVOH production site
24,000T annual production capacity
ISO9000:2000 since 2001
TS16949 since 2003
European Technical Centre Processing/Development Hall in 2005
European Technical Centre Analytical work/Development since 1999
Definitions
Active materials and articlesCOMMISSION REGULATION (EC) No 450/2009 of 29 May 2009 defines ‘active materials and articles’ asmaterials and articles that are intended to extend the shelf-life or to maintain or improve the condition of packaged food; they are designed to deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food;
Barrier MaterialsA Barrier is a material which limits the transfer of a permeating substance.A barrier Polymer can be defined as a macromolecule having the ability to limit the passage of gases, vapors, and liquids (…)Unlike glass and metals, no polymer offers an infinite gas barrier. Combinations of different polymers in multilayer structures enable to provide barrier to various productsNo limited time efficiency and no specificity to a substance
Barrier DefinitionThe Barrier is defined by the Permeability Value:
Product of the Diffusion and the SolubilityP = D . S
To be consider as a Barrier, the Permeability Value must be low. Not Real Scientific Value but usually < 250cc per µm thicknessThe Units will depend on the Permeant
Active BarriersCan be defined as materials that can absorb substances when it is brought into contact with itIt actively react with a specific substance by chemical reactionIt has limited time efficiency (contact with the substance will consume the material)Trigger to initiate the reactionIt is usually specific to a substance: Oxygen, Ethylene, Water or OdoursRequires the use of a Passive Barrier type EVOH EVAL™
Passive Barriers Polymers
Analytical Methods and EquipmentsBarrier Properties and Polymers
Barrier to Oxygen
Standard Gas for testing is OxygenO2GTR
Determination of steady-state rate of Transmission of Oxygen gas through Ethylene/vinyl alcohol Copolymers in the form of film using Coulometric Sensor is standardised by the ISO 14663-2: 1999 (Annex C)Determination of steady-state rate of Transmission of Oxygen gas through films using Coulometric sensor is standardised by the ASTM D3985
The UnitsThe unit in Europe :
Officially (ISO) :Femtometre per Pascal SecondFm/Pa.s
1 fm/Pa.s = 8.752 cm³/m².24h.atm1 cc/m².day.atm = 0.1143 fm/Pa.s
Practically : cc/m².day.atmFor comparative data :
cc.µm/m².day.atm or cc.20µm/m².day.atm(cc of Oxygen at 0°C under standard atmospheric pressure)
The Unit in the US : cm³.mil/100 in².day.bar1 cm³.µm/m².day.atm = 394 cm³.mil/100 in².day.bar
Oxygen Barrier AnalysesAnalyses on film Analyses on packages
The Permeability Equipment at EVAL Europe
Ox-Tran 2/20 and 2/21 MH and SH Modules
Permatran C4/41MC moduleTo determine the Carbon Dioxide Transmision Ratetrough film, bottle, tray, ... samples at well definedconditions of temperature (10 40°C) and 0% RH.
The Polymers Permeability to Oxygen
OXYGEN TRANSMISSION RATE OF VARIOUS POLYMERS VERSUS RELATIVE HUMIDITY at 20°C
0.1
1
10
100
1000
10000
0 20 40 60 80 100
Relative Humidity, %
O2G
TR, c
c.20
µm/m
².day
.atm
EVAL Film (EF-XL)EVAL-F
EVAL-E
PVDC (Saranex)
PAN (Barex 210)OPA-6
OPET
UPVC
BOPP
LDPE
MXD-6
A bit of Marketing… EVAL is the best…
0.1
1.0
10.0
100.0
0 20 40 60 80 100
EVAL Resins
O2GTR, cc.20µm/m².day.atm
Relative humidity,%
G Grade
E Grade
H Grade J Grade
T GradeF Grade L Grade
EVAL - O2GTR vs RH
The permeating Gases
MAP : vacuum, CO2/N2 70/30, CO2/N2 30/70! Air : 21% Oxygen
Active Barriers
Analytical Methods and EquipmentsEfficiency and Products
Analytical methodOxygen scavenger, Ethylene Adsorber, Dessicant or Odour AbsorberVarious Technologies depending on the substance of interest: gas detectors, reactants, chromatographIn food packaging applications: Oxygen scavengers and Ethylene Adsorber are usedNo ISO norm
And Equipments Examples
Head Space Analyser for Dansensorwww.pbi-dansensor.comOxygen Analyser from
Oxtranwww.mocon.com
Non-Invasive Oxygen Sensors from presenshttp://www.presens.de/
• Evolution of the Oxygen in the head space in Oxygen Scavenger containing PP/EVOH/PP multilayer barrier containers
• Study conducted in cooperation with Ciba and RPC (www.rpc-group.com )
Oxygen in the headspace
O2 content measurement after 6 months
0.000.501.001.502.002.503.003.504.004.505.005.506.006.50
0 200
400600
800
1000
12001400
1600
1800
20002200
2400
2600
28003000
3200
3400
36003800
4000
4200
4400
hours
% O
2
0%1.9%3%4.5%3% Alu
1st month 2nd month 3rd month 5th month4th month 6th month
O2 content measurement after 6 months
0.000.501.001.502.002.503.003.504.004.505.005.506.006.50
0 200
400600
800
1000
12001400
1600
1800
20002200
2400
2600
28003000
3200
3400
36003800
4000
4200
4400
hours
% O
2
0%1.9%3%4.5%3% Alu
1st month 2nd month 3rd month 5th month4th month 6th month
Scavenging TechnologiesVarious Technologies to act on the head space composition during shelf lifeChoice will depend on the application and the requirements for the packaging: transparency, shelf life, temperature, Humidity, convenience,…costRequires a good know-how about the various constraints of the packaging and the packaged product (water activity for example)Oxygen scavenging systems are the most commonly used scavenging system today for food packaging applications
In practice Oxygen scavenging system
Segments Applications Requirements Commercial Systems in place
Bottles Beer, sauces, drinks Transparency, O2 and CO2 barrier
Inorganic in Caps or Closures; Organic in Bottle wall
Semi-rigid Packaging
Premium Chilled Meats (Sliced Ham, salami,…), Ham, sausage, chicken nuggets
High temperature and Humidity; low temperature storage 4°C
Inorganic as sachet or sticker in the head space
Semi-rigid Packaging
Pizza, pasta Packaging Room temperature storage
Inorganic as sachet or sticker in the head space
Rigid Packaging Wet Pet Food and Ready Meal
Retort resistant system Inorganic in Container Wall
Not presumed to be an exhaustive list but rather examples
Developments
DevelopmentsDevelopment of the Packaging system to improve food preservation has been conducted among the supply chain and still continuesProgress in
Food preservativesModified Atmosphere Packaging orPackaging technologies
Have been completed byOptimisation of passive barrier andDevelopment of Active barrier systems
More developments are to be expected in the future…
Legal Frame
Legal Frame (I)Thanks to the Regulation (EC) No 1935/2004 of the European Parliament and of the Council of 27 October 2004 on materials and articles intended to come into contact with foodrepealing Directives 80/590/EEC and 89/109/EEC (the mother directive)States thatPending the adoption of additional rules in a specific measure on active and intelligent materials and articles, substances deliberately incorporated into active materials and articles to be released into the food or the environment surrounding the food shall be authorised …
Legal Frame (II)COMMISSION REGULATION (EC) No 450/2009 on active and intelligent materials and articles intended to come into contact with food was adopted on 29 May 2009 It is a specific Directive as per 1935/2004/EC regulation.This Regulation establishes specific requirementsfor the marketing of active and intelligent materials and articles intended to come into contact with food.Only substances which are included in the ‘Community list’ of authorised substances may be used in components of active and intelligent materials and articles.
In Practice, what does it means forOxygen Scavenging systems
EVAL Europe Understanding
The Field of 450/2009/ECMany different types of active and intelligent materials and articles exist.
The substances responsible for the active and/or intelligent function can be contained in a separate container, for example, inclusion in a small paper sachet or, the substances can be directly incorporated into the packaging material, for example, incorporation in the plastic of a plastic bottle.
Those substances, responsible for creating the active and/or intelligent function of those materials and articles (the components) should be evaluated in accordance with this specific Regulation. The passive parts if all plastic is covered by 2002/72/EC Directive
O2 content measurement after 6 months
0.000.501.001.502.002.503.003.504.004.505.005.506.006.50
0 200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
3800
4000
4200
4400
hours
% O
2
0%1.9%3%4.5%3% Alu
1st month 2nd month 3rd month 5th month4th month 6th month
O2 content measurement after 6 months
0.000.501.001.502.002.503.003.504.004.505.005.506.006.50
0 200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
3600
3800
4000
4200
4400
hours
% O
2
0%1.9%3%4.5%3% Alu
1st month 2nd month 3rd month 5th month4th month 6th month
Shelfplus 02
0.0000
0.0050
0.0100
0.0150
0.0200
0.0250
0.0300
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0Time (days)
O2G
TR (c
c/tr
ay.d
ay)
4.5% SPO2 3% SPO2
1.9% SPO2 0% SPO2
Evolution of the Oxygen in the head space Oxygen Permeation after retort
Designed to Deliberately incorporate components that would absorb Oxygen from
the environment surrounding the food?
Oxygen Scavengers in Sachets
The free-oxygen absorbing agent, AGELESS™, absorbs oxygen in a sealed container and creates a deoxidized environment, where theconcentration of oxygen is 0.1% or lower.2002/72/EC listing: PM Ref. 81760: Powders, flakes and fibres of brass, bronze, copper, stainless steel, tin and alloys of copper, tin and iron SML = 48 mg/kg (expressed as iron)Designed to Deliberately incorporate components that would absorb Oxygen from the environment surrounding the food
Multilayer bottleO2 Scavenging layer
Tie layersPolyolefin layers
No
O2
envi
ronm
ent
O2
O2
O2
0 200 400
600
800 1000200
Oxygen Scavenger Polymeric Systems
NotNot Designed toDesigned to DeliberatelyDeliberatelyincorporate components that would incorporate components that would
absorb Oxygen absorb Oxygen from thefrom theenvironment surrounding environment surrounding the food.the food.
SUMMARY
SUMMARYKuraray / EVAL Europe is a major actor in the barrier packaging systemsOur presentation reviewed Active and Passive barrier systems from
The definition stands-pointThe Analytical MethodsThe Properties in terms of barrier or scavenging performanceThe Products applications and developments
A snap shot on the legal frame was madebefore getting to the end of our presentation
Thanks… visit us at www.eval.be