EP3402675A1 - Stratifiés en couches avec couches adhésives absorbant l'oxygène, de blanchiment, ou absorbant l'oxygène et de blanchiment, leurs procédés de préparation et d'application - Google Patents

Stratifiés en couches avec couches adhésives absorbant l'oxygène, de blanchiment, ou absorbant l'oxygène et de blanchiment, leurs procédés de préparation et d'application

Info

Publication number
EP3402675A1
EP3402675A1 EP17738717.2A EP17738717A EP3402675A1 EP 3402675 A1 EP3402675 A1 EP 3402675A1 EP 17738717 A EP17738717 A EP 17738717A EP 3402675 A1 EP3402675 A1 EP 3402675A1
Authority
EP
European Patent Office
Prior art keywords
oxygen
laminate
layer
absorbing
layered
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Withdrawn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
EP17738717.2A
Other languages
German (de)
English (en)
Other versions
EP3402675A4 (fr
Inventor
Maciej KARLOWICZ
Krzysztof NOWACZYK
Artur Bartkowiak
Slawomir Lisiecki
Krzysztof ZYCH
Agnieszka WOLOSIAK-HNAT
Monika MEZYNSKA
Maksymilian DAJWORSKI
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.)
DrukpolFlexo Spolka Z Ograniczona Odpowiedzialnoscia Sp K
Original Assignee
DrukpolFlexo Spolka Z Ograniczona Odpowiedzialnoscia Sp K
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by DrukpolFlexo Spolka Z Ograniczona Odpowiedzialnoscia Sp K filed Critical DrukpolFlexo Spolka Z Ograniczona Odpowiedzialnoscia Sp K
Publication of EP3402675A1 publication Critical patent/EP3402675A1/fr
Publication of EP3402675A4 publication Critical patent/EP3402675A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/146—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers whereby one or more of the layers is a honeycomb structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/74—Oxygen absorber
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
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    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2553/00—Packaging equipment or accessories not otherwise provided for

Definitions

  • the present invention relates to a method of making a layered laminate with an oxygen- absorbing adhesive layer, a method of making a layered laminate with the bleached adhesive layer, oxygen-absorbing layer laminate, layered whitened laminate, layered oxygen-absorbing bleached laminate, packaging and use of these laminates.
  • oxygen absorbers are placed mostly in the form of sachets and labels.
  • examples of commercially available products are sachets of the following companies: Mitsubishi Gas Chemical Co., Toppan Pronting Co., Ltd, Nippon Soda Co., Ltd., Finetec C, labels of companies: Multisorb Technologies Inc., Standa Industries. Both sachets and labels containing oxygen absorbing substances pose a risk associated with the use of food products due to their ability to be swallowed.
  • sinks are in the form of a flexible film or a multilayer laminate involving plastics such as eg. Polyolefins, polyesters, polystyrene, ethylene and vinyl acetate).
  • plastics such as eg. Polyolefins, polyesters, polystyrene, ethylene and vinyl acetate.
  • Examples are the products Cryovac® 0S200TM, wherein the oxygen absorber is introduced into the packaging film during the extrusion process and Amosorb® - a mixture of copolyester and polybutadiene containing oxygen absorber.
  • oxygen scavengers the most commonly used substances absorbing oxygen are iron and its compounds, ascorbic acid and derivatives thereof, sulfites and derivatives thereof, boron compounds, unsaturated fatty acids and unsaturated hydrocarbons, enzymes, easily oxidizable polymers, alcohols such as ethylene glycol, propylene glycol, glycerin, sorbitol, xylitol, mannitol.
  • Publication WO 2012/091587 Al discloses compounds absorbing oxygen based on nanoiron, capable of absorbing oxygen in the presence of both water and in an anhydrous environment. These compounds - nanoiron and iron at zero oxidation of boron may be placed in a container in the form of sachets or in another form, to prevent contact with food. Furthermore, these compounds may be incorporated in the mass of certain materials, such as silicone rubber, polyamide and polyethylene.
  • Nanoiron can also be introduced into polyvinyl alcohol by mixing nanoiron with PVA dissolved in acetone and pouring a thin film with the Cast method, and then subjected to UV radiation. Iron at zero oxidation containing boron can be added to the modified cellulose acetate butyrate. Oxygen absorbers can appear in the form of nanocomposites allowing to keep them in a pack or as part of the packaging or in the form of: a film for packaging, containers, trays, bottles, pins, caps, gaskets, labels and inserts.
  • EP 1270206 Al discloses a multilayer oxygen-absorbing structure consisting of an outer layer consisting thermoplastic resin, an adhesive layer consisting of epoxy resin, oxygen-absorbing layer consisting of a thermoplastic resin and built-in iron, and the heat- weldable film, which made by oxygen-friendly thermoplastic resin.
  • An adhesive layer is prepared by applying a solution of epoxy resin on the external surface of the multilayer structure absorbing oxygen-containing thermoplastic resin.
  • This structure is used in materials for food packaging, pharmaceuticals, and others.
  • the disadvantage of the described solution is a very complicated preparation used for coating, as well as the complex process of preparing substances absorbing oxygen. The complicated process of obtaining individual components may not provide adequate reproducibility for the final laminate.
  • U.S. Publication 19935274024 A describes a resin composition consisting of olefin resin and a water-absorbing polymer selected from modified polyethylene oxide, acrylic acid-vinyl alcohol copolymers, sodium poly(acrylate), vinyl polymer alcohol.
  • the resin can be thermoformed and modified by oxide polyethylene or a copolymer of acrylic acid and vinyl alcohol.
  • the binder of the oxygen is made of the reduced iron and a compound which promotes the oxidation reaction, wherein the content value of copper is less than 150 ppm of sulfur and less than 500 ppm.
  • the resin composition is intended for production (extrusion process), the caps and containers used for products liquid, e.g., drinks.
  • Example on how to obtain a laminate comprising a packaging film obtained by extrusion, bleached by the addition of the inflator shown in US 25 5 449 552 describes the production of multilayer laminates comprising a layer external (which is a multilayer biaxially-oriented polypropylene film (BOPP), that is rendered white in color by the addition of inorganic fillers, ie. CaCO 3 and TiO 2 ), a two-component polyurethane adhesive gas-barrier layer, a two- component polyurethane adhesive and an inner layer consisting of a copolymer of ethylene and 30 vinyl acetate.
  • BOPP multilayer biaxially-oriented polypropylene film
  • this solution is a bleached film, which is not always is easy to use in manufacturing enviromnents with different requirements than the fixed ones.
  • the co-extrusion method for the preparation of multilayer films looking like a paper, colored white while welding is described in US 5 446 520.
  • the described multilayer films comprise isotactic polypropylene, linear low-density ethylene modified with rubber and anhydride maleic random copolymer of propylene and ethylene, and an inorganic filler.
  • the publication does not specify the use of the multilayer-drawn film thus there is no certainty as to the possibility of using this product as packaging in the food industry.
  • the described disadvantage of the invention is the use of the method for manufacturing the same extrusion. This method is not flexible to change of parameters, which makes it difficult to apply it at the production of different product range.
  • a bleached, biaxially-oriented polyester film was also obtained by co-extrusion method, as described in US 7 329 453 B2.
  • Such a film layer comprises a sealable outer layer comprising a polyester and an inorganic or organic filler and an inner layer consisting of bleached, white inorganic pigment and/or a polymer incompatible with polyester.
  • the film described in the above publication is intended for closing the trays used to hold the ready food products. It is the only described application which limits the range of products.
  • a disadvantage of the multi-layer drawn polyester film is associated with the use of co-extrusion methods for its production. As mentioned earlier, this co-extrusion method of the invention requires significant resources, which is troublesome during a time-consuming modification of technological parameters.
  • Another way to obtain a white film used for the production of packaging is bleaching typical polymeric films prior to printing the package. This makes it difficult, however, to conduct a continuous production of such a package and increases the time of manufacture for such a package.
  • both the oxygen consumption and bleaching of packaging film uses the increased temperature and extrusion or co-extrusion. With the modification of parameters the final product is difficult to determine the conditions with a minimal consumption of materials for technological tests.
  • the invention relates to a method of making a layered laminate with a coated adhesive absorbing oxygen, wherein in the first stage of introduction, the oxygen-absorbing agent is introduced to the polyurethane adhesive system to form an oxygen sorbent, which is then applied to the surface of the ribbon substrate layer and dried, and in the second step, to the adhesive layer of the oxygen absorbent the coating layer of thennoplastic material is applied by extrusion coating.
  • Preferred is a method, wherein the oxygen-absorbing adhesive system is applied to the ribbon surface layer by roll coating shaft or rotogravure method.
  • the oxygen-absorbing agent is a mixture of monohydrate iron hydroxide FeO(OH) H 2 O and ascorbic acid in a weight ratio of from 1 :2 to 2: 1, most preferably 1 : 1 or of iron oxide (III) Fe 2 O 3 and ascorbic acid in a weight ratio from 1 :2 to 2: 1, most preferably 1 : 1.
  • carboxylic acid preferably mono- or dicarboxylic acid, most preferably acetic acid, tartaric acid, malonic acid and/or oxalic acid.
  • Preferred is a method, wherein the ratio of the carboxylic acid to the hydroxide monohydrate iron FeO(OH)H- 2 O oxide or iron (III) Fe 2 O 3 is 1 : 1.
  • Preferred is the process, wherein the layer laminate bearing the adhesive oxygen system absorbing heat is sealed under the conditions of temperature of sealing 113-132°C.
  • a ribbon surface layer the form of materials is selected from a plastic film, preferably of polyethylene (ethylene terephthalate), poly(vinyl chloride), polyethylene or polypropylene, aluminum foil, and combinations thereof.
  • thermoplastic material with the adhesion-ability of the ribbon to the backing layer is preferably selected from the group consisting of polyethylene, including LDPE, LLDPE, and HDPE, polypropylene, ethylene and vinyl acetate copolymers, ethylene and acrylic acid copolymers, ethyl methacrylate and mixtures thereof.
  • the invention also relates to a method of making a layered laminate applied with a whitening adhesive layer, wherein in the first step the white pigment is introduced into polyurethane adhesive system, to obtain a whitening of the adhesive system, which is then applied to the surface of the ribbon substrate layer and dried, and in the second stage bleaching layer of the adhesive coating is coated by extrusion with a layer of thermoplastic material.
  • Preferred is a method, wherein the white pigment is titanium dioxide, white zinc, and/or white lithopone.
  • Preferred is a method, wherein the bleaching adhesive system is applied by a coating roller shaft or a rotogravure method to the ribbon surface layer.
  • Preferred is a method, wherein the concentration of white pigment in a polyurethane adhesive system is in the range of 10-20% by weight.
  • Preferred is a method, in which a layered laminate of the coated bleaching CYM system adhesive printing the printing inks, preferably using flexographic or rotogravure printing.
  • a ribbon surface layer in the form of stripe materials is selected from a plastic film, preferably polyethylene (ethylene terephthalate), polyvinyl chloride), polyethylene or polypropylene, aluminum foil, and combinations thereof.
  • the coating layer of thermoplastic material of the adhesion-ability to the ribbon surface layer is preferably selected from the group consisting of polyethylene, including LDPE, LLDPE, and HDPE, polypropylene, ethylene and vinyl acetate copolymers, ethylene and acrylic acid copolymers, ethyl methacrylate and mixtures thereof.
  • the layer laminate and the bleaching adhesive system are sealed on conditions: sealing temperature 1 13-132°C.
  • Preferred is a method, in which the layer laminate is sealed under conditions of temperature welding 130-225°C.
  • Preferred is a method, in which on a layered laminate conducted is printing by printing inks, preferably by rotogravure or flexographic printing.
  • the invention further relates to an oxygen-absorbing layer laminate, which comprises of: - a ribbon backing layer, with a weight of 5 to 300 g/m 2 ;
  • thermoplastic material having a thickness of from 5 to 200 microns, applied by extrusion coating on the ribbon surface layer with the previously applied oxygen absorbent adhesive system layer.
  • a preferred laminate is a layer, in which an oxygen absorbing agent is a mixture of iron hydroxide monohydrate FeO(OH)-H 2 O and ascorbic acid in a weight ratio of from 1 :2 to 2: 1, most preferably 1 : 1 or of iron oxide (III) Fe 2 O 3 and ascorbic acid weight ratio of from 1 :2 to 2: 1 , preferably 1 : 1.
  • an oxygen absorbing agent is a mixture of iron hydroxide monohydrate FeO(OH)-H 2 O and ascorbic acid in a weight ratio of from 1 :2 to 2: 1, most preferably 1 : 1 or of iron oxide (III) Fe 2 O 3 and ascorbic acid weight ratio of from 1 :2 to 2: 1 , preferably 1 : 1.
  • a preferred laminate is a layer, in which oxygen absorbing agent further comprises carboxylic acid, preferably mono- or dicarboxylic acid, most preferably acetic acid, tartaric acid, malonic acid and/or oxalic acid.
  • Preferred is a layered laminate, wherein the carboxylic acid to monohydrate iron hydroxide FeO(OH)H- 2 O oxide or iron (III) Fe 2 O 3 is 1 : 1.
  • Preferred is a layered laminate, wherein the ribbon surface layers is made of materials selected from a plastic film, preferably of polyethylene (ethylene terephthalate), poly(chloride of vinyl), polyethylene or polypropylene films and mixtures thereof.
  • a plastic film preferably of polyethylene (ethylene terephthalate), poly(chloride of vinyl), polyethylene or polypropylene films and mixtures thereof.
  • the layer of coating material indicates the ability of the thermoplastic adhesion to the ribbon substrate layer, it is preferably selected from the group consisting of polyethylene, including LDPE, LLDPE, and HDPE, polypropylene, ethylene and vinyl acetate copolymers, ethylene and acrylic acid copolymers, ethyl methacrylate and mixtures thereof.
  • the invention also relates to a bleached layer laminate, which comprises of
  • a bleaching adhesive layer consisting of a white pigment introduced to a polyurethane adhesive system
  • Preferred is a bleached, layered laminate, wherein the white pigment is titanium dioxide, white zinc and/or white lithopone.
  • Preferred is a bleached, layered laminate, wherein the concentration of white pigment in the polyurethane adhesive system is in the range of 10-20% by weight.
  • Preferred is a bleached, layered laminate, wherein the laminate layer is whitened and additionally printed with inks, preferably by flexographic printing or rotogravure method.
  • Preferred is a bleached, layered laminate, wherein the ribbon surface layer is made of materials selected from a plastic film, preferably made of polyethylene (ethylene terephthalate), poly (vinyl chloride), polyethylene or polypropylene, aluminum foil, and combinations thereof.
  • a plastic film preferably made of polyethylene (ethylene terephthalate), poly (vinyl chloride), polyethylene or polypropylene, aluminum foil, and combinations thereof.
  • Preferred is a bleached, layered laminate, wherein the coating layer of a material shows the ability of the themioplastic adhesion to the ribbon surface layer, and it preferably is selected from the group consisting of polyethylene, including LDPE, LLDPE, and HDPE, polypropylene, ethylene and vinyl acetate copolymers, ethylene and acrylic acid copolymers, ethyl methacrylate and mixtures thereof.
  • polyethylene including LDPE, LLDPE, and HDPE
  • polypropylene ethylene and vinyl acetate copolymers
  • ethylene and acrylic acid copolymers ethyl methacrylate and mixtures thereof.
  • the invention further relates to a layered bleached laminate, absorbing oxygen, which comprises of:
  • a layer of a bleaching adhesive system consisting of a white pigment incorporated into a polyurethane adhesive system
  • Preferred is a bleached layered absorbing oxygen laminate, wherein the oxygen sorbent is a mixture of iron hydroxide monohydrate FeO(OH)- H20 and ascorbic acid in a weight ratio of from 1 :2 to 2: 1 , preferably 1 : 1 or of iron oxide (III) and Fe 2 O3 ascorbic acid in a weight ratio of from 1 : 2 to 2 : 1 , preferably 1 : 1.
  • a carboxylic acid preferably mono- or dicarboxylic acid preferably acetic acid, tartaric acid, malonic acid and/or oxalic acid.
  • Preferred is a bleached, layered, oxygen- absorbing laminate, wherein the ratio of carboxylic acid iron hydroxide monohydrate FeO(OH)-H 2 O or iron oxide (III) Fe 2 O 3 is 1 : 1.
  • Preferred is a bleached, layered, oxygen-absorbing laminate, wherein the ribbon-surface layer of material selected from the ribbon of plastic film, preferably poly(ethylene terephthalate), poly(vinyl chloride), polyethylene or polypropylene film aluminum and combinations thereof.
  • polyethylene including LDPE, LLDPE and HDPE
  • polypropylene ethylene and vinyl acetate copolymers
  • ethylene and acrylic acid copolymers ethyl methacrylate and mixtures thereof.
  • Preferred is a bleached, layered, oxygen-absorbing laminate, wherein the white pigment is titanium dioxide, zinc white and/or white lithopone.
  • Preferred is a bleached, layered, oxygen-absorbing laminate, wherein the concentration of white pigments in a polyurethane adhesive system is in the range of 10-20% by weight.
  • Preferred is a bleached, layered, oxygen-absorbing laminate, which is additionally printed with inks, preferably by fiexographic printing or rotogravure method.
  • Preferred is a bleached layered oxygen-absorbing laminate, wherein the ribbon surface layer of material is selected from the ribbon of plastic film, preferably poly (ethylene terephthalate), poly(vinyl chloride), polyethylene or polypropylene film aluminum, and combinations thereof.
  • polyethylene including LDPE, LLDPE and HDPE
  • polypropylene ethylene and vinyl acetate copolymers
  • ethylene and acrylic acid copolymers ethyl methacrylate, and mixtures thereof.
  • the invention also relates to a package particularly for the food industry, which consists of an oxygen-absorbing layer laminate as defined above, a layered bleached laminate as defined above, or a layered bleached laminate absorbing oxygen as defined above.
  • the invention also relates to the use of an oxygen-absorbing layer laminate as defined above, a bleached layered laminate as defined above, or a layered bleached oxygen-absorbing laminate as defined above for the preparation of packaging in the food industry.
  • An important advantage of the present invention is the use of ingredients approved for food contact according to Commission Regulation (EC) No 10/201 1 on materials and articles of plastic materials intended for contact with food, and easy availability, low price and uncomplicated chemical structure of the substances used.
  • EC Commission Regulation
  • the present invention has also a simple method for preparing modified adhesive systems, since all the mixture components are pre-mixed, whereby the process for producing a packaging film boils down only to the operation of coating, laminating and printing, by using white pigment it obtains a white background; it is excellent for further printing including various dyes, yielding a packaging film accurately reproducing the colors of the print in demand (e.g. company logo, trademark, etc.).
  • the present invention is the only one suitable to specific applications, i.e. printing on packaging films by a gravure method.
  • Fig. 1 shows a schematic cross-section of the packaging material and laminate built from the packaging film of PET/PE with a layer of polyurethane adhesive system containing oxygen consuming substances.
  • Figure 2 shows a schematic cross-section of the packaging material and laminate built from the packaging film BOPP/PE layer of a polyurethane adhesive system of any addition of white pigment.
  • Figure 3 shows a schematic cross-section of the packaging material and laminate built from the packaging film of PET/BOPP/PE layer of a polyurethane adhesive system with the addition of oxygen-absorbing layer and the polyurethane adhesive system with the addition of white pigment.
  • oxygen absorbents are mixtures of hydroxide monohydrate iron FeO(OH) ⁇ H 2 O and ascorbic acid in a weight ratio of from 1 :2 to 2: 1 , most preferably 1 : 1 or of iron oxide (III) Fe 2 O3 and ascorbic acid in a weight ratio of 1 :2 to 2: 1 , preferably 1 : 1.
  • the oxygen absorbents described herein are intended for containers of flexible plastic, e.g., polyethylene terephthalate (PET) and polyethylene (PE) for the packaging of products containing water, for example meat, dairy.
  • PET polyethylene terephthalate
  • PE polyethylene
  • PE polyethylene
  • carboxylic acids with oxygen absorbers In the case of products with low water content it is possible to generate a small quantities of water by the introduction of carboxylic acids with oxygen absorbers into a polyurethane adhesive system.
  • Carboxylic and boxylic acids used in the described embodiment are the mono- and dicarboxylic acids, for example, acetic acid, tartaric acid, malonic acid, oxalic acid. These acids are introduced in a weight ratio 1 : 1 to use oxygen absorbents.
  • a polyurethane adhesive system is obtained by combining isocyanate resin and hardener which is a mixture of polyester and polyether in a suitable weight ratio of 12.5:0,7-37,5:2.10, preferably CYM 25: 1.39.
  • An adhesive composition as well as oxygen absorbents contain components released for direct contact with food - to meet the requirements of Commission Regulation (EC) No 10/201 1 on materials and plastic products intended for contact with food.
  • the invention further relates to a process for the preparation of layered laminate applied an adhesive layer containing a white pigment which is a modification of the polyurethane adhesive system with white pigments and applying it to the packaging film by coating with a shaft roller or by rotogravure method.
  • the method for obtaining a layered laminate with an adhesive layer applied, containing a white pigment of the present invention is much simpler compared to existing methods of whitening a film packaging.
  • the finished product i.e. the package with a certain degree of whitening may be used for packaging all kinds of food products, and printing any prints.
  • Preferred is a three-fold laminate.
  • the white pigments in the present invention are titanium dioxide, zinc oxide and white lithopone. These pigments are added in amounts of 5-30% by weight to the polyurethane adhesive system with an organic solvent, e.g. ethyl acetate.
  • the polyurethane adhesive system is obtained, as already described above, by the combination of the isocyanate resin and a hardener being a mixture of polyester and polyether in a suitable weight ratio of 12.5:0,7-37,5:2.10 preferred ratio of 25: 1.39.
  • the invention further provides a method of making a layered laminate bearing polyurethane adhesive system containing an oxygen absorbing agent, and a polyurethane adhesive system modified with a white pigment.
  • Absorbing oxygen agents, white pigments and polyurethane adhesive system are those used for the preparation of three-layer laminates absorbing oxygen and three-layer laminates with high degree of whiteness described in this invention.
  • the laminate may in a preferred embodiment consist of the following layers:
  • Preferred is a layered laminate of five layers.
  • FIG. 3 The diagram of a preferred five-layer laminate is shown in FIG. 3.
  • a process for preparing a layered laminate of the present invention combines the advantages of the above three-fold laminate according to the invention. As a result of this method is obtained a laminate which has excellent oxygen absorption and at the same time gives way to printing any prints. Such a finished product can be used for different kinds of packaging of food products.
  • Layered laminates favorably weld in the following conditions: 0,4-4,0 kN clamping force, time pressure 0.5-4 s.
  • Example 1 method of preparing a three layer laminate with the adhesion layer absorbing oxygen
  • a slurry of ferrous hydroxide monohydrate FeO(OH)- H 2 O (Rob. Europe) and ascorbic acid (Chempur) is made in a weight ratio of 1: 1 ethyl acetate (JarbuR).
  • the suspension is vigorously stirred by a magnetic stirrer for 30 mins, after which the resin is incorporated into Liofol UR 3720 (Henkel) and hardener Liofol UR 6055 (Henkel) and stirring is continued for 15 mins.
  • the concentration of both oxygen absorbents on the total the adhesive is 10% by weight.
  • the system is coated on the shaft roller with a PET film of a thickness of 12 ⁇ , which is dried for 1 h at 75°C.
  • the thickness of the layer is 4-10 microns.
  • the formed laminate of a polyethylene film (PE) with a thickness microns using the Cast method is conditioned in a climatic chamber at preset weight under conditions of temperature 23°C and 50% RH for 2 to 4 days.
  • Laminates are used in the manufacture of packaging with dimensions: 9 x 13 cm of food by heat-sealing conditions: temperature of sealing 1 13°C, 0.41 kN clamping force, holding time of 0.5 s.
  • Fig. 1 shows a cross-section of packaging marked with various layers.
  • Example 2 a method of preparing a three-layer laminate with an adhesive, oxygenabsorbing layer applied
  • a slurry of iron oxide (III) Fe 2 O 3 (ROHA Europe) and ascorbic acid (Chempur) is made in a weight ratio of 1 : 1 and malonic acid (Alfa Cesar) at 1 : 1 ratio of iron oxide (III) in ethyl acetate (JarbuR).
  • the solution is intense by stirring with a magnetic stirrer for 30 min, then the resin is incorporated into Liofol UR 3720 (Henkel) and a hardening agent Liofol UR 6055 (Henkel) and stirring is continued for 15 mins.
  • the concentration of oxygen absorbent of the entire adhesive system is 5 wt.%, and malonic acid is 2.5% by weight.
  • the system is coated on the roller shaft with a thick PET film of 12 microns, which is dried for 1 h at 75°C.
  • the thickness of the layer is 4-10 microns.
  • the laminate is formed of a polyethylene film (PE) with a thickness of 20 ⁇ m by the Cast method and conditioned in a climatic chamber at preset conditions at 23 °C and 50% RH for one day.
  • Laminates are used to produce containers of dimensions: 18 x 26 cm of food by heat-sealing in modified atmosphere conditions: sealing temperature 1 13°C, 0.41 kN clamping force, holding time of 0.5 s.
  • Fig. 1 shows cross-section of the package with the selected individual layers.
  • Table 2 The results of measurements of the composition of the atmosphere inside the packaging made with laminates PET/PE bearing adhesive system containing an oxygen absorbing agent: iron oxide (III), ascorbic acid and malonic acid.
  • the packaging agar is provided as a model product.
  • Example 3 a process for preparing a three-layer laminate with an adhesive oxygen- absorbing layer applied
  • a slurry of ferrous hydroxide monohydrate FeO(OH)- H 2 O (Roh Europe) and ascorbic acid (Chempur) in a weight ratio of 1 : 1 is formed and malonic acid in an amount of 1 : 1 in relation to the iron oxide hydroxide monohydrate in ethyl acetate (JarbuR).
  • the slurry is subjected to intensive mixing by magnetic stirring for 30 min, the resin is incorporated into Liofol UR 3720 (Henkel) and hardener Liofol UR 6055 (Henkel) and stirring is continued for 15 min.
  • the concentration of both oxygen absorbents on the total adhesive system is 5 wt.% malonic acid and 2.5% by weight.
  • the system is coated with a shaft roller on a PET film having a thickness of 12 microns, which is dried for 1 h at 75°C.
  • the thickness of the applied layer is 4- 10 microns.
  • the laminate is formed with a polyethylene film (PE) with a thickness of 20 microns using the Cast method and conditioned in a climatic chamber with the preset conditions of temperature 23°C and 50% RH for one day.
  • Laminates are used for manufacturing the package size: 18 x 26 cm for the food sealing in modified atmosphere conditions: sealing temperature 1 13°C, downforce of 0.41 kN, the pressing time of 0.5 s.
  • Fig. 1 shows a cross- sectional view the package with the selected individual layers.
  • Table 3 The results of measurements of the composition of the atmosphere inside packages made of thePET V PE laminates, bearing adhesive system containing an oxygen- absorbing agent: iron oxide hydroxide monohydrate, ascorbic acid and nialonic acid. Agar was placed as a product model in the packaging
  • Example 4 - a method for producing a three-layer laminate with a whitening adhesive layer
  • a 19.6% by weight suspension of titanium dioxide (Chemical Plant POLICE SA) in ethyl acetate (JarbuR) is made, which is obtained by mixing a magnetic stirrer NYM at room temperature for 0.5 h period with a high degree of agitation.
  • the concentration of titanium dioxide (Chemical Plant POLICE) of the resulting adhesive system is 10.0% by weight.
  • the system is coated with a shaft on a biaxially oriented polypropylene film (BOPP) having a thickness 10 40 Pm, which is then subjected to drying for 1 h at 75°C.
  • the thickness of the layer is 4-10 microns.
  • Laminates are subjected to conditioning in a temperature of 23 °C with 50% humidity for a period 1-5 days.
  • This laminate can be used to form a package with dimensions of 9 x 13 cm or 18 x 26 cm for food by welding PE film under the following conditions: welding temperature 1 13°C, downforce of 0.41 kN time pressure of 0.5 s.
  • Fig, 2 shows a cross-section of the package with the selected individual layers.
  • Example 5 a process for preparing a three layer laminate applied to a bleaching adhesive layer
  • Example 6 a method of producing three-layer laminate with a whitening adhesive layer applied
  • Example 7 - a method for producing three-layer laminate with an adhesive whitening layer applied
  • Example 8 process for preparing a three layer laminate applied to the bleaching adhesive layer The process is carried out analogously to Example 4, wherein the pigment there is a white zinc (Chempur) and its concentration in the adhesive system is 20% by weight.
  • the pigment there is a white zinc (Chempur) and its concentration in the adhesive system is 20% by weight.
  • Example 9 - a process for preparing a three layer laminate applied to the bleaching adhesive layer
  • Example 4 The process is carried out analogously to Example 4, wherein the pigment is a white lithopone (P. P. H. STANLAB Sp. J.) ⁇ and its concentration in the system the adhesive is 20% by weight.
  • the results of the degree of whiteness laminates described in Examples 4 - 9 shows Table 4.
  • Example 10 process for preparing a five-layer oxygen-absorbing bleached laminate
  • a slurry of ferrous hydroxide monohydrate FeO(OHH)' 2 O (Roh Europe) and ascorbic acid (Chempur) is made in a weight ratio of 1 : 1 ethyl acetate (JarbuR).
  • the suspension is vigorously stirred by a magnetic stirrer for 30 min. after which the resin is incorporated into Liofol UR 3720 (Henkel) and hardener Liofol UR 6055 (Henkel) and stirring continued for 15 mins.
  • the concentration of both oxygen scavengers on the total the adhesive is 10% by weight.
  • the system is coated on a biaxial roller shaft with a polypropylene film (BOPP) oriented on it, having a thickness of 40 microns, which is dried by 1 h at 75°C.
  • the thickness of the applied layer is 4-10 microns.
  • BOPP polypropylene film
  • POLICE SA in ethyl acetate.
  • the system is stirred with a magnetic stirrer at room temperature for a time of 0.5 h, with a high degree of intensity.
  • Into the solution resin of 10 Liofol UR 3720 (Henkel) and hardener Liofol UR 6055 (Henkel) are introduced. The mixture is stirred for about 15 min.
  • the concentration of titanium dioxide in the obtained adhesive system is 10.0%.
  • This system is coated on the shaft with a PET film having a thickness of 12 microns, which is then treated is dried for 1 h at 75 °C.
  • the thickness of the applied layer is 4-10 microns.
  • the laminate After drying, the laminate is formed into a PET film of the adhesive system with the addition of di titanium oxide is laminated BOPP film coated with the adhesive system of the oxygen absorbers, which is then laminated with a PE film having a thickness of 20 ⁇ by the Cast method and conditioned in programmed climatic chamber conditions at 23 °C and 50% RH for 1 day.
  • This laminate can be used to form a package with the dimensions 9 x 13 cm for food by welding PE film under the following conditions: temperature welding 131°C, 0.41 kN clamping force, holding time of 0.5 s.
  • a laminate according to Example 10, as schematically shown in FIG. 3 comprises of the following layers:
  • the laminates of the present invention show good oxygen absoiption, allowing them to be used in the food industry. Additionally, through the use of white pigment, a white background is obtained, ideally suitable for further printing of other dyes.
  • the method of the invention is simple, fast and can easily be adapted to other requirements of relevant parameters of the derived end products.

Abstract

L'invention concerne un procédé de réalisation d'un stratifié en couches avec une couche adhésive absorbant l'oxygène, lequel procédé consiste en ce que, dans la première étape, le sorbant d'oxygène est introduit dans le système de polyuréthane adhésif, pour former un système adhésif absorbant l'oxygène, qui est ensuite appliqué sur la surface de couche de lit en ruban et séché ultérieurement, et en ce que, dans la seconde étape, une couche de revêtement de matière thermoplastique est appliquée sur une couche du système adhésif absorbant l'oxygène par un procédé de revêtement par extrusion. L'invention concerne également un procédé de fabrication d'un stratifié en couches avec une couche adhésive de blanchiment appliquée sur ce dernier, et concerne également un stratifié en couches absorbant l'oxygène, un stratifié en couches blanchi, un stratifié blanchi en couches absorbant l'oxygène, ainsi que l'utilisation de ces stratifiés pour la fabrication d'emballages dans l'industrie alimentaire.
EP17738717.2A 2016-01-11 2017-01-10 Stratifiés en couches avec couches adhésives absorbant l'oxygène, de blanchiment, ou absorbant l'oxygène et de blanchiment, leurs procédés de préparation et d'application Withdrawn EP3402675A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL415760A PL415760A1 (pl) 2016-01-11 2016-01-11 Sposób wytwarzania warstwowego laminatu z naniesioną warstwą adhezyjną pochłaniającą tlen, sposób wytwarzania warstwowego laminatu z naniesioną wybielającą warstwą adhezyjną, warstwowy laminat pochłaniający tlen, warstwowy wybielony laminat, warstwowy wybielony laminat pochłaniający tlen, opakowanie oraz zastosowanie tych laminatów
PCT/PL2017/050001 WO2017123108A1 (fr) 2016-01-11 2017-01-10 Stratifiés en couches avec couches adhésives absorbant l'oxygène, de blanchiment, ou absorbant l'oxygène et de blanchiment, leurs procédés de préparation et d'application

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EP3402675A1 true EP3402675A1 (fr) 2018-11-21
EP3402675A4 EP3402675A4 (fr) 2019-11-06

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EP3891215B1 (fr) * 2018-12-07 2023-11-08 SABIC Global Technologies B.V. Compositions de polyoléfines ayant une capacité améliorée de piégeage de l'oxygène
JP7296496B1 (ja) 2022-02-24 2023-06-22 東京インキ株式会社 酸素吸収性グラビアインキ組成物、酸素吸収性印刷物、積層体、酸素吸収性印刷物の製造方法、積層体の製造方法および包装袋、包装容器

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US6391407B1 (en) * 1997-06-12 2002-05-21 Mitsubishi Gas Chemical Company, Inc. Oxygen absorbing multi-layer film and oxygen absorbing packaging container
JP2006224399A (ja) * 2005-02-16 2006-08-31 Dainippon Printing Co Ltd 酸素吸収性多層積層フィルムおよびそれを使用した積層体、包装用袋、包装製品
JP2008308625A (ja) * 2007-06-15 2008-12-25 Mitsui Mining & Smelting Co Ltd 酸素吸収性接着剤組成物及び積層体並びに酸素吸収性接着剤組成物の製造方法
BRPI0921653A2 (pt) * 2008-11-25 2016-02-10 Valspar Sourcing Inc artigo, método, filme, e, método para afixar o filme

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