EP1916276A1 - Emballage - Google Patents

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Publication number
EP1916276A1
EP1916276A1 EP07394025A EP07394025A EP1916276A1 EP 1916276 A1 EP1916276 A1 EP 1916276A1 EP 07394025 A EP07394025 A EP 07394025A EP 07394025 A EP07394025 A EP 07394025A EP 1916276 A1 EP1916276 A1 EP 1916276A1
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EP
European Patent Office
Prior art keywords
packaging material
metal
protection
corrosion
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07394025A
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German (de)
English (en)
Inventor
Rick Earley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Metpro Technical Services Ltd
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Metpro Technical Services Ltd
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Filing date
Publication date
Application filed by Metpro Technical Services Ltd filed Critical Metpro Technical Services Ltd
Publication of EP1916276A1 publication Critical patent/EP1916276A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
    • B65D81/267—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants the absorber being in sheet form

Definitions

  • the invention relates to packaging, and particularly to protection of packaged metal items.
  • Packaging is a very important part of the supply chain of metal parts due to the effects of humidity, for example during transportation and storage.
  • VCI Volatile Corrosion Inhibitor
  • VCI components in packaging decrease atmospheric corrosion due to the reaction of the metal with the environment, even in recessed areas where the packaging is not in direct contact with the metal surface.
  • VCIs are organic type inhibitors, being chemical compounds that have significant vapour pressure that allow vaporization of the molecules and subsequent adsorption onto metallic surfaces. Adsorbed onto the metal surface, the VCI creates a uniform thin monomolecular corrosion-protecting layer. The monomolecular layer serves as a buffer, which maintains pH level at its optimum range for corrosion resistance.
  • Fig. A presents the mechanism of VCI protection.
  • VCI protective ions Once the VCI protective ions are adsorbed onto the surface, the electrochemical process of corrosion is interrupted as the ions create a protective barrier to contaminants such as oxygen, water and other corrosion accelerators. With the protective barrier in place the corrosion cell cannot form and corrosion is halted.
  • the invention is directed towards providing an improved packaging material for metal protection.
  • the invention provides a packaging material comprising metal-protecting components including a volatile corrosion inhibitor, a desiccant, and an oxygen scavenger.
  • the metal-protecting components may further comprise a cathodic protector.
  • the packaging material may comprise polyethylene as a bulk component, and the metal-protecting components may be dispersed in said bulk component.
  • the volatile corrosion inhibitor may be in the form of a mixed inhibitor.
  • the volatile corrosion inhibitor may include phosphate esters, acids, and amines.
  • the phosphate esters may be ammoniated phosphate esters.
  • the acids may be carboxylic acids.
  • the acids may include caprylic acid and isononanoic acid.
  • the amines may be primary amines.
  • the amines may include amino-2methyl-1-proponal.
  • the desiccant may comprise a silica gel.
  • the oxygen scavenger may comprise a triazole.
  • the triazole may be benzotriazole.
  • the cathodic protector may include a sacrificial anode.
  • the sacrificial anode may comprise zinc oxide.
  • the sacrificial anode may comprise a mixture of zinc oxide, titanium dioxide and silicon oxide.
  • the packaging material may further comprise an organic salt.
  • the packaging material may further comprise sodium benzoate.
  • the packaging material may further comprise ammonia anhydrous.
  • the packaging material may further comprise calcium carbonate.
  • the packaging material may further comprise calcium stearate.
  • the packaging material may be in the form of a film.
  • the film may have a thickness of between 100 ⁇ m and 140 ⁇ m.
  • the invention provides a method of manufacturing a packaging material as described herein comprising the step of mixing metal protection components with a bulk material.
  • the bulk material may be a plastics material and the protection components and the plastics material may be mixed, heated, and extruded.
  • the plastics material may be polyethylene.
  • the invention provides an improved packaging material for metal protection, employing multiple protection components which together provide optimum corrosion protection.
  • the packaging material may provide protection against corrosion caused by oxygen and corrosion caused by moisture.
  • One of the protection components is a "mixed inhibitor" VCI, having a combination of chemical compounds in which the electron density distribution causes the molecules to be attracted to both the anodic and cathodic sites. This forms a monomolecular film which acts as a buffer, maintaining pH at optimum range for corrosion resistance and provides a universal effect on corrosion process.
  • mixed inhibitor we mean an inhibitor that functions as both an anodic and a cathodic inhibitor.
  • Anodic corrosion is characterised by the oxidation of a metal surface causing the release of metal ions and electrons which results in a reduction in the pH level at the site of corrosion.
  • Anodic corrosion inhibitors act by migrating to the anodic site to enhance chemisorption of dissolved oxygen thereby inhibiting the corrosion process.
  • Cathodic corrosion is characterised by the reduction of a metal surface which results in an increase in the pH level at the site of corrosion. Cathodic corrosion inhibitors form deposits on the site of cathodic corrosion thereby preventing the reduction of oxygen to hydroxyl ions and inhibiting the cathodic corrosion process.
  • Packaging material of the invention can be used to protect both ferrous containing and non-ferrous containing metals from corrosion.
  • Table 1 PROTECTION COMPONENT DOSE [ w/w%] 1 2 3 4 5 6 7 8 9 10 VCI Phosphate Esters Poly(oxy-1,2-ethanediol-hydro-hydroxy mono C12 0.85-1.25 X X X X X X Acids 3,5,5 Trimethylhexanoic acid 0.05-0.3 X X X X X X X Caprylic Acid 0.15-0.35 X X X X X X Amines 2, Amino-2methyl-1-proponal 0.15-0.35 X X X X X X OXYGEN SCAVENGER Triazole 0.10-0.20 X X X X X X X DESICCANT Silica Gel 1.00-1.30 X X X X X X CATHODIC PROTECTION Sacrificial anode 0.35-1.00 X
  • the films 1 through 5 are for reference only, the films 6 through 10 being of the invention.
  • the four main protection components are VCI, oxygen scavenger, desiccant, and cathodic protection.
  • the VCI component includes phosphate esters and amines as molecules attracted to the cathodic metal sites, whereas the acids provide molecules attracted to the anodic metal sites. These acids are all carboxylic acids.
  • the cathodic protection may be provided by either zinc oxide or a zinc oxide compound that includes zinc oxide, titanium dioxide, and silicon oxide.
  • the cathodic protection element may be considered as a sacrificial anode.
  • Films of the invention may further comprise additional anodic and/or cathodic inhibitors.
  • additional anodic and/or cathodic inhibitors sodium benzoate may be considered as an anodic inhibitor and calcium carbonate may be considered as a cathodic inhibitor.
  • the oxygen scavenger may be selected from the triazole class of compounds, for example the oxygen scavenger may be benzotriazole.
  • the protection component is desiccant only, consisting of the product silica gel such as that available under the Trade Name Vulkasil.
  • Vulkasil and 100g of calcium stearate were blended for 5 mins using a high speed mixer.
  • 100g of wax, 100g of calcium carbonate, 335g of MF22 and 165g of MF08 were blended with the first two ingredients for 5 mins using to the high speed mixer.
  • the resulting powder was then put through a twin screw extruder, producing a single strand, which was then pelletized.
  • the protection component is oxygen scavenger only, consisting of triazole.
  • 50g of triazole and 100g of calcium stearate were blended for 5 mins using a high speed mixer.
  • 150g of wax, 150g of calcium carbonate, 360g of MF22, and 190g of MF08 were blended with the first two ingredients for 5 mins using to the high speed mixer.
  • the resulting powder was then put through a twin screw extruder, producing a single strand, which was then pelletized.
  • the protection component is cathodic protection only, consisting of zinc oxide compound as a hybrid of sacrificial anode.
  • the protection component is cathodic protection only, consisting of zinc oxide.
  • 300g of zinc oxide, 200g of wax, 335g of MF22 AND 165g of MF08 were blended for 5 minutes using a high speed mixer.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the protection component is VCI and desiccant, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, AMP 95, and Vulkasil).
  • PAE 82g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 12g of caprylic acid and 19g of isononanoic acid were added to the ammoniated PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate was then added to the mixture.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the protection component is VCI, desiccant, and oxygen scavenger, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, AMP 95, Vulkasil, and triazole.
  • PAE 77g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 18g of caprylic acid and 10g of isononanoic acid were added to the ammoniated PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate and 9g of triazole was then added to the mixture.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the protection components are VCI, oxygen scavenger, desiccant, and cathodic protection, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, Amp 95, Vulkasil, triazole, and zinc oxide.
  • PAE 77g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 18g of caprylic acid and 10g of isononanoic acid were added to the ammoniated PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate and 9g of triazole was then added to the mixture.
  • the resulting powder was then put through a twin screw extruder, producing a single strand, which was then pelletized.
  • the protection components are VCI, oxygen scavenger, desiccant, and cathodic protection, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, AMP 95, triazole, Vulkasil, and zinc oxide.
  • PAE 77g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 18g of caprylic acid and 10g of isononanoic acid were added to the ammoniated PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate and 9g of triazole was then added to the mixture.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the protection components are VCI, oxygen scavenger, desiccant, and cathodic protection, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, AMP 95, triazole, Vulkasil, and zinc oxide compound.
  • PAE 77g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 18g of caprylic acid and 10g of isononanoic acid were added to ammoniated the PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate and 9g of triazole was then added to the mixture.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the protection components are VCI, oxygen scavenger, desiccant, and cathodic protection, consisting of ammoniated phosphate ester, caprylic acid, isononanoic acid, AMP 95, triazole, Vulkasil, and zinc oxide compound.
  • PAE 77g of PAE was placed in the mixing vessel.
  • the PAE was ammoniated at 50 PSI for 1 hour.
  • 18g of caprylic acid and 10g of isononanoic acid were added to the ammoniated PAE and heated to 100°C.
  • 27g of AMP95 was then added to the mixture and heated to 100°C. 5g of sodium benzoate and 9g of triazole was then added to the mixture.
  • a separate mixing vessel 114g of Vulkasil and 40g of calcium stearate were blended for 5 minutes using the high speed mixer.
  • the amine salt mix was added to the blend and mixed for 2 minutes using the high speed mixer until a fine powder was attained.
  • 100g of wax, 100g of calcium carbonate, 308g of MF22, 164g of MF08 and 36g of hybrid of sacrificial anode (zinc oxide compound) was added to 310g of the fine powder. This was blended for 3 minutes using the high speed mixer.
  • the resulting powder was then put through a twin screw extruder, producing a single strand which was then pelletized.
  • the thickness of all of the films was in the range of 100 - 140 ⁇ m.
  • Film No. 1 failed all of the tests. Film No. 2 failed half of the tests. Good results were achieved on D, E and F tests, which could indicate inhibiting properties of Film No. 2.
  • Film No. 3 (having only a hybrid sacrificial anode), failed all of the tests.
  • Film No. 4 (having only ZnO), failed most of the tests, even though good results were achieved on the B and D tests.
  • Film No. 5 (having VCI and desiccant), passed most of the tests, giving very good results. This indicates good corrosion protection performance when these two components are used.
  • Film No. 6 (having three aspects of corrosion control, VCi, desiccant and oxygen scavenger), passed all of the tests except F, giving excellent corrosion protection.
  • Film No. 8 (having desiccant, oxygen scavenger, VCI and zinc oxide added at the mixing stage), was able to protect the metal panels on all tests except C and F tests.
  • Film No. 9 received very good results, with the exception that it failed test F. No evidence of corrosion and very good results were observed during the test on film No. 10.
  • film No. 10 also contains all four aspects of corrosion control. The hybrid sacrificial anode of film No. 10 was added at the mixing stage.
  • Figs. 1 to 7 present the results of the tests carried out on all of the films.
  • Four films: No. 7, No. 8, No. 9 and No. 10 contain cathodic protection. It was found that, when the cathodic protection element was added at the mixing stage of formulation, (No. 8 and No. 10), these films provided better corrosion protection than films where the cathodic protection element was added at extrusion stage. Film No. 10 provided the best results among all films (see Figs. 4, 6, and 7).
  • Fig. 8 illustrates the protection mechanism.
  • Fe dissolves and releases electrons where there is a conventional PE film with a VCI protection component. Basically, the iron dissolves at the anode and releases electrons which are subsequently consumed by oxygen at the cathode, and so the metal corrodes.
  • the cathodic protection element in this case a sacrificial anode of ZnL (wherein L indicates a ligand, for example oxygen) dissolves.
  • L indicates a ligand, for example oxygen
  • protective components incorporated in the film layer, film no. 10. They can be represented as four barriers working together against unfavourable conditions which can cause the corrosion.
  • a 1 st barrier provided by the oxygen scavenger component does not allow oxygen from outside to penetrate through the film. Oxygen which is already contained in the packaging is trapped inside and neutralized by the oxygen scavenger.
  • a 2 nd barrier is provided by the desiccant of the packaging material. It provides an alternative for corrosion protection by water absorption.
  • a desiccant is a hygroscopic substance that draws and retains moisture from its environment. Different desiccant products have different properties, absorption rates, capacities and effective operating temperature ranges. They work by segregating the inside of the bag from the environment. Desiccants will absorb moisture until they are completely saturated. If new air is allowed to pass into the area to be protected, the desiccant will eventually become saturated, without some type of barrier (typically a polyethylene bag) to keep more moisture out.
  • barrier typically a polyethylene bag
  • a 3 rd barrier is provided by the VCI component, which in the presence of moisture forms an invisible protective layer.
  • the VCI molecule becomes polarized and attracted to the anode and cathode of the metal.
  • a 4 th barrier is provided by the sacrificial anode, which which may be considered as an organo-metallic compound once the zinc oxide compound has been mixed with wax which dissolves at the anode and releases electrons which are subsequently consumed by oxygen at the cathode, preventing dissolving of iron.
  • the desiccant prevents moisture from penetrating into the bag by water absorption, while the oxygen scavenger absorbs any oxygen that infiltrates through the seals or walls of packaging structures.
  • the VCI and sacrificial anode are adsorbed onto the metal to jointly form a monomolecular layer on its surface.
  • the oxygen scavenger and desiccant provide not only protection in how they operate individually, but also provide more freedom for the VCI and sacrificial anode to operate on the metal surface.
  • the latter two components can migrate from the film to the metal surface.
  • the VCI and sacrificial anode become polarized and attracted to the anode and cathode of the metal.
  • the electrochemical process of corrosion is interrupted as the ions create a protective barrier to contaminants such as oxygen, water and other corrosion accelerators. With the protective barrier in place the corrosion cell cannot form and corrosion is halted.

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  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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EP07394025A 2006-10-24 2007-10-24 Emballage Withdrawn EP1916276A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IE20060775 2006-10-24
IE20060832 2006-11-16

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EP1916276A1 true EP1916276A1 (fr) 2008-04-30

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017023201A1 (fr) * 2015-07-31 2017-02-09 Cheng Kit Yew Nelson Composition chimique pour papier minéral anti-corrosion
EP3192850A1 (fr) 2016-01-14 2017-07-19 Omya International AG Traitement caco3 de balayage o2
EP3192838A1 (fr) 2016-01-14 2017-07-19 Omya International AG Traitement de carbonate de calcium traité par réaction en surface
CN108359175A (zh) * 2018-02-11 2018-08-03 江阴通利光电科技有限公司 一种缓释型气相防锈拉伸聚丙烯薄膜的制备方法
EP3425696A4 (fr) * 2017-01-13 2019-05-29 LG Chem, Ltd. Plateau d'éléments de batteries incluant un inhibiteur de corrosion volatil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4973448A (en) * 1986-11-18 1990-11-27 Cortec Corporation Vapor phase corrosion inhibitor product and method containing a desiccant
EP0662527A1 (fr) * 1994-01-11 1995-07-12 Cortec Corporation Matériau inhibiteur de la corrosion en phase vapeur et dessiccatif
US6540959B1 (en) * 1998-07-29 2003-04-01 Excor Korrosionsforschung Gmbh Vapor-phase corrosion inhibitors and methods for their production
WO2005058481A1 (fr) * 2003-12-17 2005-06-30 Stopak (Pty) Ltd Composition deshydratante

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4973448A (en) * 1986-11-18 1990-11-27 Cortec Corporation Vapor phase corrosion inhibitor product and method containing a desiccant
EP0662527A1 (fr) * 1994-01-11 1995-07-12 Cortec Corporation Matériau inhibiteur de la corrosion en phase vapeur et dessiccatif
US6540959B1 (en) * 1998-07-29 2003-04-01 Excor Korrosionsforschung Gmbh Vapor-phase corrosion inhibitors and methods for their production
WO2005058481A1 (fr) * 2003-12-17 2005-06-30 Stopak (Pty) Ltd Composition deshydratante

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017023201A1 (fr) * 2015-07-31 2017-02-09 Cheng Kit Yew Nelson Composition chimique pour papier minéral anti-corrosion
EP3192850A1 (fr) 2016-01-14 2017-07-19 Omya International AG Traitement caco3 de balayage o2
EP3192838A1 (fr) 2016-01-14 2017-07-19 Omya International AG Traitement de carbonate de calcium traité par réaction en surface
WO2017121774A1 (fr) 2016-01-14 2017-07-20 Omya International Ag Traitement de piégeage de l'o2 par le caco3
WO2017121675A1 (fr) 2016-01-14 2017-07-20 Omya International Ag Traitement de carbonate de calcium ayant réagi en surface
US11161088B2 (en) 2016-01-14 2021-11-02 Omya International Ag O2 scavenging CaCO3 treatment
US11753548B2 (en) 2016-01-14 2023-09-12 Omya International Ag Treatment of surface-reacted calcium carbonate
EP3425696A4 (fr) * 2017-01-13 2019-05-29 LG Chem, Ltd. Plateau d'éléments de batteries incluant un inhibiteur de corrosion volatil
US10938008B2 (en) 2017-01-13 2021-03-02 Lg Chem, Ltd. Battery cell tray including volatile corrosion inhibitor
CN108359175A (zh) * 2018-02-11 2018-08-03 江阴通利光电科技有限公司 一种缓释型气相防锈拉伸聚丙烯薄膜的制备方法

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