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
  • 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
  • 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
• • 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
  • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
• • 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
  • B32B27/06—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
  • 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
• • 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
  • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
  • B65D35/02—Body construction
• • 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
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • 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
  • B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/40—Closed containers

Definitions

• the present invention relates to the field of aluminium barrier laminates (ABL). More specifically, the present invention relates to a laminated material suitable for forming containers able to store conventionally "hard-to-hold" chemical compositions, such as hair dye.
• ABL aluminium barrier laminates
• Aluminium barrier laminates are well known for use in forming tubes and containers suitable for holding many products, such as toothpaste, foodstuffs, creams and various skincare and cosmetic formulations.
• Some products can be corrosive.
• the aluminium necessary for the excellent barrier properties it provides, needs to be protected from the product.
• Permanent hair dye formulations are a good example and whereas they can be stored in aluminium tubes having a reinforced inner protective lacquer coating, they are not suited for the standard ABL laminate tubes.
• the corrosive formula can actually penetrate by diffusion through the inner polymer layers applied to protect the aluminium foil of the ABL and attack the interfacial joins. The attack on the joins can cause delamination of the laminate material, failure of the sealed regions and subsequent failure of the package.
• hair dye for example, is highly air-sensitive and corrosive (often having a pH of around 12). If hair dye is left exposed to air then it oxidises to a dark black and is both unsightly to consumers and, above all, ceases to work optimally.
• the present invention provides a laminated material for forming a flexible container for holding a hair dye or the like, the laminated material having a first surface which, in use, forms the internal surface of the container, and a second surface which, in use, forms the external surface of the container, the laminated material comprising an inner layer, an outer layer and an intermediate metal foil barrier layer, wherein the inner layer is on the first surface side of the metal foil barrier layer, and wherein the outer layer is on the second surface side of the metal foil barrier layer, wherein the laminated material has a total thickness of at most 240 ⁇ , and wherein the inner layer comprises polyethylene and has a mean density of 0.92 to 0.94g/cm 3 .
• container is used herein to refer to an item which may contain a product. Such products are usually liquids, gels or pastes. Preferred containers include tubes and pouches. The container may further comprise a lid and, if necessary, attachment means for the lid (such as a shoulder) before it forms a useful commercial container. Such components are well known in the art. However, the term is used herein to refer to the body of the container that contains and contacts the commercial product. Preferably the container is for holding hair dye.
• flexible as used herein describes the container which can bend or be bent easily and which does not break (unless it is bent too much).
• flexible indicates that if the container is subjected to a force, for example, by being filled with a liquid, or by applying pressure with a finger or a hand, it will change its form without breaking.
• a flexible container can also be considered to be a "squeezable" container.
• deadfold is a term in the art and is used herein to refer to the ability of the laminate to retain its shape permanently once it is folded or dented and to not spring back to an unfolded or undented state.
• aluminium foil sheeting once folded or shaped about an item, retains that shape and, thus, may be considered to have excellent dead fold characteristics.
• typical plastic food wraps tend to quickly spring back, unfold, or unwrap after being shaped about an item. This is an example of poor dead fold characteristics. Since the laminated material comprises a foil and plastic layers, the deadfold property will lie between these extremes.
• the tube of the present invention is especially suitable for holding "hard-to-hold” or "aggressive" compositions.
• These included hair colorants are chemically reactive and generally contain one or more acidic, basic, and/or oxidizing ingredients. These ingredients often fall within the chemical classes of inorganic hydroxides, inorganic halides, and peroxides.
• Inorganic hydroxides include ammonium hydroxide as well as alkali and alkaline earth metal hydroxides (e.g., potassium hydroxide and calcium hydroxide).
• Inorganic halides include fluorides, chlorides, bromides, and iodides of ammonium and metals such as transition metals, alkali metals, and alkaline earth metals.
• Peroxides include hydrogen peroxide, urea peroxide (carbamide), and alkali and alkaline earth metal peroxides (e.g., sodium peroxide).
• Representative aggressive products have pH values of less than about 4 (e.g., in the range from about 1 to about 4, or from about 1 to about 3) or otherwise pH values of greater than about 9 (e.g. , in the range from about 10 to about 13, or from about 10 to about 12), and often greater than about 11 (e.g., in the range from about 1 1 to about 14).
• the present inventors have discovered that presently-available containers for holding hard-to-hold compositions, such as hair dye, are not suitable for the purpose.
• the inventors have sought an alternative material for forming a container that minimises the amount of component materials needed to reduce cost, while still providing an effective container.
• the present inventors have discovered that it is possible to achieve this effect by using an inner layer of polyethylene having a mean density of 0.92 to 0.94g/cm 3 .
• the inner layer also has a thickness of from 30 to 90 ⁇ .
• Polyethylene compositions for forming layers are well known in the art.
• polyethylene is a thermoplastic polymer consisting of long chains of polymerised ethylene monomers.
• Polyethylene is classified into several different categories based mostly on its density and branching.
• the mechanical properties of polyethylene depend significantly on variables such as the extent and type of branching, the crystal structure and the molecular weight.
• high density PE (HDPE) is defined by a density of greater or equal to 0.941 g/cm 3 .
• HDPE has a low degree of branching and thus stronger intermolecular forces and tensile strength.
• MDPE Medium density PE
• MDPE is defined by a density range of 0.926-0.940 g/cm 3 .
• Linear low density polyethylene is defined by a density range of 0.915-0.925 g/cm 3 .
• LLDPE is a substantially linear polymer with significant numbers of short branches, com monly made by copolymerization of ethylene with short-chain alpha-olefins (for example, 1-butene, 1- hexene and 1-octene).
• Low density polyethylene is defined by a density range of 0.910-0.940 g/cm 3 .
• LDPE has a high degree of short and long chain branching, which means that the chains do not pack into the crystal structure as well. This results in a lower tensile strength and increased ductility.
• Very low density polyethylene is defined by a density range of 0.880-0.915 g/cm 3 . Synthetic methods for producing all of these compositions are well known in the art.
• the laminated material has a total thickness of at most 240 ⁇ , more preferably from 150 to 240 ⁇ , more preferably from 200 to 240 ⁇ and most preferably from 225 to 235 ⁇ .
• the inventors have discovered that if the container walls are too thin then the container feels flimsy to the end user/consumer and will not be acceptable. Accordingly, the end users prefer the container to have thicker walls.
• the preferred wall thickness reduces the amount of material required while providing sufficient structure to satisfy the consumer.
• the metal foil is an aluminium or aluminium alloy foil.
• the metal foil layer is from 5 to 30 microns, more preferably 5 to 20 microns and more preferably from 15 to 9 microns thick. This thickness provides a sufficient strength to the container product and provides a good deadfold in the present laminate of less than 240 ⁇ total thickness.
• the metal foil and, in particular, aluminium foil is expensive so a minimum suitable thickness of aluminium is employed.
• the metal foil is an aluminium foil having a thickness of from 20 to 30 microns .
• This increased thickness serves to i m prove the deadfold characteristics of the tube, albeit at an increasing material cost.
• the product-contacting side of the metal barrier foil layer is provided with a layer of polyethylene having a mean density of 0.92 to 0.94g/cm 3 and preferably a thickness of from 30 to 90 ⁇ .
• This layer is preferably in direct contact with the product.
• This layer is also preferably directly adhered to the metal foil layer with a single tie layer.
• tie layer is a layer which is placed between two layers with the object of ensuring that the two layers are joined together. Suitable materials for tie layers are well known in the art.
• a preferred tie layer material is ethylene acrylic acid (EEA).
• a preferred tie layer has a thickness of from 20 to 40 microns, more preferably about 30 microns.
• the inner layer of polyethylene is from 30 to 90 microns thick, more preferably from 30 to 70 microns thick, more preferably from 35 to 60 and most preferably from 35 to 45 microns thick.
• Scalping is a term in the art for the loss of aromas and natural ingredients from a product into the polymeric material forming a container. I n the case of hair dye, the scalping effect can take the form of indispensable formulation components present only in trace amounts being absorbed into the polyethylene.
• the inner layer of polyethylene has a mean density of 0.92 to 0.94g/cm 3 .
• This density is a selection from Medium Density Polyethylenes (MDPE).
• MDPE Medium Density Polyethylenes
• the mean density of the inner layer is from 0.930 to 0.938 g/cm 3 . More preferably the mean density of the inner layer is from 0.932 to 0.936 g/cm 3 , for instance equal to 0.932 g/cm 3 .
• the inner layer may be formed either from a single M DPE material or from two or more layers having different densities that provide the mean density range.
• the inner layer may comprise HDPE and/or LDPE.
• a preferred inner layer is formed from a mixture of high density polyethylene (HDPE) and low density polyethylene (LDPE), for example, 75% LDPE (density 0.921) and 25 % HDPE (density 0.965).
• HDPE high density polyethylene
• LDPE low density polyethylene
• the inner layer consists of polyethylene.
• Laminates in the prior art rely on LDPE or very LDPE (VLDPE) to form the inner layer.
• the inner layer has to undergo two heat sealing operations. Firstly it is required to allow heat sealing of the "side seam" of the tube during manufacture, where the multi-layer web structure is rolled into a cylinder and then seamed together to form a continuous tube (that is subsequently cut to length). Secondly, after the tube is filled, it needs to be closed by heat sealing at the tube end. In this operation the inside of the tube is heated and pinched closed in jaws that apply pressure. The use of these lower density polyethylene materials favours these two operations.
• the present inventors have discovered that such laminates lead to undesirable levels of scalping, leakage and oxygen ingress when used in the presence of such hard- to-hold products.
• the present inventors have found that if HDPE is used instead, then the seals formed when forming the container are more likely to fail and the advantages of the present invention are not seen.
• the present inventors have discovered that the inner layer described herein gives improved chemical resistance or reduced diffusion of product compared to conventional LDPE layers. As a consequence, there is a reduced risk of attack of the metal foil at the interface and reduced oxygen diffusion into the product. In addition, there is acceptable suck back and low cost.
• “Suck back” is a phenomenon observed in tubes made with plastic containing materials. When the tube is squeezed the plastic undergoes an elastic deformation and when the tube is released the plastic material will attempt to return to its initial shape. This will create a pressure drop inside the tube and as a result the product in the orifice area of the tube is sucked back inside the tube, followed by air if the suck back is high enough to empty the orifice area. The suck back of air into the container can cause any product therein to oxidise and perish. The presence of a partial vacuum in the container can encourage oxygen ingress through the seals that form the container. Preferably a tie layer adheres the inner layer to the metal foil barrier layer.
• the use of a single inner (MDPE type) layer is preferred.
• the use of a single relatively thin tie layer is also preferred.
• the amount of soft polymer (tie layer material) on the inner surface side is reduced.
• the inner layer disclosed herein has been found to be sufficient for this purpose.
• the laminated material further comprises an outer layer on the second surface side of the metal barrier layer, the outer layer providing a printable surface. The presence of a printable outer layer is essential to help brand and sell the product.
• a preferred printable layer comprises one or more layers of polyethylene adhered with a tie layer to the metal foil barrier layer.
• the outer layer comprises a coextruded film of LDPE and HPDE.
• the outer layer is white, or at most lightly tinted, to increase the visibility of the subsequent printing.
• the outer layer consists of polyethylene.
• the composition and form of this layer is not critical to the present invention.
• the outer layer serves to protect the foil layer from physical abuse, to provide bulk or body to the film, and to support graphics, colour, and other forms of printing.
• the outer layer is provided with a printed image and/or text.
• the present inventors have discovered that it is desirable for the outer layer to have a thickness of from 100 to 180 microns, more preferably from 120 to 130 microns.
• the outer layer is preferably adhered to the metal foil barrier layer with a tie layer.
• the tie layer is preferably from 10 to 30 microns thick and most preferably about 20 microns thick.
• the outer layer may comprise a filler.
• Preferred fillers include calcium carbonate.
• the presence of a calcium carbonate filler serves to improve the deadfold characteristic without unduly increasing the cost of manufacture.
• suitable amounts and techniques for including the fillers in polyethylene layers are well known in the art.
• the filler is added within the body of the outer layer, distanced from the outer surface of the laminated material.
• An especially preferred laminated material for forming a flexible container to hold a hair dye has a central aluminium foil barrier layer.
• the aluminium foil barrier layer has on a first side (product facing side) an inner layer adhered with a single tie layer (25 to 35 microns).
• the inner layer comprises polyethylene and has a thickness of from 35 to 45 ⁇ and a mean density of 0.93 to 0.938g/cm 3 .
• the aluminium foil barrier layer has on a second side (consumer facing side) an outer layer comprising an outermost white LDPE/HDPE coextruded film of 85 to 95 microns on an LDPE 35 to 45 micron layer, adhered to the aluminium foil barrier layer with a single tie layer of 15 to 25 microns.
• the aluminium foil barrier layer is preferably from 10 to 15 microns.
• the laminated material has a total thickness of about 230 microns. More preferably the laminated material consists of the foregoing layers and no others.
• the inner layer is 75% Dowlex 3010TM LLDPE (linear LDPE), 25% Dow 8007TM HDPE; the tie layers are Dow Primacor 3330TM EEA; the outer layer is
• the present invention provides a container for holding a hair dye, the container comprising the laminated material described herein.
• the laminated material is used to form the body of the container.
• the container is in a form resembling a toothpaste tube, albeit that the total volume of the tube is preferably less than for a standard toothpaste tube, i.e. volume sufficient for 25 to 100ml of product.
• the present invention provides a hair dye container comprising the container described herein and containing hair dye. Hair dyes are well known and the container should hold any suitable hair dye.
• the present invention provides a toothpaste tube comprising the container described herein and containing dentifrice. The design of the present tube is particularly advantageous for holding air- and/or moisture-sensitive toothpaste compositions, or toothpaste formulations containing stannous fluoride. Stannous fluoride is well known to react with the aluminium foil at any non-protected edges and/or via diffusion through the inner layer. Tooth pastes (dentifrice) are well known and the container should hold any suitable tooth paste. Preferably the foregoing containers are single use containers.
• the container is a multi-use container.
• Such containers are useful for professional salon use or, for example, for use with toothpaste (dentifrice). The minimisation of suck back allows the product to be kept oxygen free and in optimal condition.
• the present invention provides a method of forming a container, the method comprising folding the laminated material described herein into a desired configuration and heat sealing the overlapping edges to form the container.
• Tech ni ques for form i ng such contai ners are wel l known i n the art, for exam ple EP0321 172 discloses a technique for forming containers including toothpaste tubes.
• the present invention provides the use of the laminated material as described herein to form a hair dye container or a toothpaste tube.
• Figure 1 shows a conventional squeezable tube suitable for storing a hair dye composition or toothpaste.
• the body of the tube is formed from an aluminium barrier laminate.
• One end is provided with a shoulder and a lid, the end has been crimped closed.
• the tube depicted has suffered from de-lamination at the fold (longitudinal seal) and staining is evident (bottom right of the picture).
• Figure 2 shows the end of a conventional squeezable tube suitable for storing a hair dye composition or toothpaste.
• the tube depicted has suffered from de-lamination at the end crimp and staining is evident (bottom left of the picture).
• Figure 3 shows a schematic diagram of the layers that form the laminate of the present invention.
• Figure 4 shows a sketch of the overlapping join formed when a tube (10) is made from a laminate web.
• the aluminium ends (15) of the aluminium foil are overlapped to form an overlapping region (20) .
• Some excess material is squeezed out of the overlapping region 20 to form the polymer "flow out” region (25).
• this region protects the innermost aluminium end from corrosion by contact with the tube contents.
• the aluminium foil (1) is provided with an MDPE layer (2) on a first side to form the inner side when forming a tube.
• the MDPE layer (2) is attached with a tie layer (3).
• a co- extruded LDPE/HDPE film (5) is adhered to the aluminium foil (1) with an LDPE layer (4) and a tie layer (3).
• the total layer thickness is 229 microns, comprising: 13 microns of aluminium foil (1), 41 microns of MDPE layer (2) adhered with a 28 micron tie layer (3); 89 microns of co-extruded LDPE/HDPE film (5) adhered with 38 microns of LDPE layer (4) and 20 microns of tie layer (3).
• the MDPE layer (2) is 75% Dowlex 3010TM LLDPE (linear LDPE), 25% Dow 8007TM HDPE; the tie layers (3) are Dow Primacor 3330TM EEA; the LDPE layer (4) is Equistar NA204-000TM LDPE.
• Tubes of the present disclosure and comparative conventional laminated material tubes were made and tested by direct contact with the aggressive hair dye products (commercial products purchased from the shop shelves or various brands and compositions). This involved making tubes with the various webs (laminated materials) under test, filling the tubes with the hair dye product, sealing them and storing for up to 3 months at 45 °C. At various time periods the tubes were extracted, cut open and emptied. The inside of the tube webs were evaluated for corrosion by visual observation; i.e. adherence of the side seam, copper sulphate analysis to reveal bare aluminium, end seam integrity.
• Tubes were also produced with the web (laminated material) of the present invention except that the inner layer was LDPE instead of MPDE. These were tested in the same manner and showed failure due to oxidation of the hair dye formula in the two weak zones, i.e. the end seal and the side seam areas. This is observed by discolouration of the hair dye formula and migration of the hair dye product through these regions towards the outside, leading to visible discolouration of the tube. In general this discolouration seen on the outside of the tube is predominantly a phenomenon seen in the side seam rather than the end seam.
• the laminate of the present invention is chemically compatible with hair dye (aggressive, product pH approx 12, oxidizing), eliminates oxygen ingress into the container that can result in oxidation of the formulation and a significant colour change, has a minimal thickness to reduce cost for what is a very cost sensitive market. Furthermore, the present inventors have discovered that the laminate greatly reduces "suck back" into the tube that could otherwise cause degradation of the hair dye formula by oxidation.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Tubes (AREA)
• Laminated Bodies (AREA)
• Wrappers (AREA)

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• 2012
  • 2012-02-16 CN CN201811358675.8A patent/CN109591421A/zh active Pending
  • 2012-02-16 WO PCT/EP2012/052727 patent/WO2012110622A1/en active Application Filing
  • 2012-02-16 CN CN2012800086849A patent/CN103459142A/zh active Pending
  • 2012-02-16 RU RU2013140483/05A patent/RU2600365C2/ru active
  • 2012-02-16 BR BR112013020505-9A patent/BR112013020505B1/pt active IP Right Grant
  • 2012-02-16 MX MX2013009494A patent/MX2013009494A/es unknown

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