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    • 专利摘要:
    GAS BARRIER COATINGS. The present invention relates to water-dilutable coating compositions comprising polyvinyl alcohol and / or ethylene-vinyl alcohol copolymer, dispersed clay and polycarboxylic acid polymer which can be prepared using conventional apparatus and which provide an exceptional oxygen barrier together with good laminate bond strengths in high relative unit when incorporated into adhesive formed laminates, particularly laminated PET-PE structures.
    公开号:BR112012012120B1
    申请号:R112012012120-0
    申请日:2010-11-19
    公开日:2020-10-27
    发明作者:Sarfaraz Akhtar Khan；Graham Trevor Street；Derek Ronald Illsley
    申请人:Sun Chemical B.V.；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [0001] The present invention relates to gas barrier coatings that can be used to coat and provide gas barrier properties to a variety of materials, notably packaging for food and pharmaceutical agents. Gas barrier coatings can, in particular, be useful in forming adhesive formed laminates. The gas barrier coatings of the invention advantageously have the ability to block the passage of gases and, in this way, can be particularly useful for use in packaging where prevention of gas ingress into, or gas escape from, the packaging is desirable. The coatings advantageously provide an effective gas barrier and a high bond strength in relatively high humidity environments. BACKGROUND
    [0002] Synthetic plastic materials have long been used for packaging food and other materials that need protection from handling and moisture. However, in recent years, it has been understood that many foods and other sensitive materials still benefit from being protected from atmospheric oxygen. A wide variety of multilayer laminated structures have been developed to provide barrier properties and other performance characteristics suitable for the purpose of packaging. Such laminates can be any combination of plastic, metal or cellulosic substrates and can include one or more layers of coating or adhesive. Laminates that include polymeric films having metals or inorganic compounds, such as silicon oxides, deposited on them have been found to give good general barrier properties and are widely used. For many purposes, it is desirable that the coating should have a covering as well as a substrate. Laminated materials where the gas barrier coating is to be sandwiched between two films of a laminate in this way are referred to as adhesive formed laminates. In addition to the provision of good gas barrier properties, good bond strength between the films and the coating is important in adhesive formed laminates. PVDC Based Barrier Coatings
    [0003] Most commercially applied polyvinylidene chloride (PVDC) barrier layers are applied at relatively high film weights, with film heights greater than 1.0 gsm being typical. For example, JP 62-047716B describes application of a PVDC coating to a treated polyester film, followed by adhesive lamination to a poly (ethylene) film. An oxygen barrier of 8.3 cm3 / m2 / day and a bond strength of 6.6 N / 15 mm were recorded. Here, the oxygen barrier was obtained with a dry film weight of the PVDC around 3 gsm (dry). Inorganic Films Vaporized
    [0004] The use of vapor deposition techniques to apply silicon oxide, aluminum oxide and aluminum layers to film surfaces is well known and both excellent barrier and bond strengths are possible. Compositions of the sol-gel type comprising solutions of poly (vinyl alcohol) (PVOH OR PVA) and / or copolymer of ethylene and vinyl alcohol (EVOH) and hydrolyzed alkoxysilanes can be applied to the surface of the inorganic layer before lamination. These coatings not only increase the barrier performance of the inorganic layer, but also provide a degree of protection during printing and lamination, since these organic layers are very fragile. Due to the poor flexible resistance of these inorganic layers, these additional sol-gel coatings provide an improved degree of barrier after these types of laminates have been flexed and / or folded.
    [0005] JP 2007223286 discloses coating a nylon film coated with AIOx with a sol-gel coating of the type described above. When this was adhesively laminated to a PE film an oxygen barrier of 4.2 cm3 / m2 / day and a bond strength of 10.5N / 15mm were obtained. JP2005256061 discloses the printing and adhesive lamination of PET-AlOx / SiOx films to apply a barrier of 15 cm3 / m2 / day and a bond strength of 1.8N / cm. PVQH or PVA Organic Composite Coatings
    [0006] WO 2007034943 describes a coating comprising both PVOH or PVA and an ethylene-maleic anhydride copolymer being applied to a nylon film followed by heat treatment (up to 22 ° C). When laminated to a heat sealable film, the laminate provided a barrier of 18.6 cm3 / m2 / day and a laminating bond strength of 4.0 N / cm. The high temperature treatments required to provide performance are not accessible to most printers and converters and therefore the usefulness of this type of coating is limited. Oxygen Barrier Coating based on PVOH or PVA / EVOH and Clay
    [0007] Gas barrier coatings comprising dispersed clay, especially nanoparticles, and a hydrophilic polymer, such as poly (vinyl alcohol) (PVOH or PVA) or ethylene and vinyl alcohol (EVOH) copolymer, have been used previously. However, it has been proven to be difficult to formulate and apply such coatings in an efficient manner that results in both good bond strength between the flexible plastic films and suitable gas barrier properties. Examples of such compositions are disclosed in EP 0590263 B1; US 4818782; EP 0479031 A; and JP-A-1313536. Typically, an anchor or preparation layer is required for this type of barrier coating to provide good bond strengths in adhesive formed laminates. For example, JP-A-2007136984 (Toppan) discloses the application of EVOH-Clay composite coating to a base layer having an anchor coating, prior to adhesive lamination for a second plastic film. The examples describe both wefts based on polypropylene and polyester, both requiring the use of an anchor coating before applying the EVOH-Clay composite. JP-A- 2007136984 describes a decrease in bond strength of adhesive lamination as the clay content increases.
    [0008] WO 2009098463 A1 (SunChemical) describes how PVOH or PVA / EVOH-clay composite coatings are advantageously applied as 2-pack compositions to ensure that satisfactory bond strengths have been achieved in adhesive formed laminates. Oxygen Barrier Coatings containing polycarboxylic acid polymers
    [0009] JP 11-246729 (Sumitomo) discloses a resin composition containing polyvinyl alcohol, a water soluble polyacrylic acid system compound and an inorganic laminar compound. The resin composition is obtained by processing polyvinyl alcohol, a water soluble polyacrylic acid system compound and an inorganic laminar compound with a high pressure dispersion apparatus. JP 11-246729 discloses that the inorganic laminar compound can be mixed with water before combining with a polymer solution. However, in order to fully disperse the inorganic laminar compound in the resin composition, processing of such a mixture through high pressure apparatus is required. The application of the coating to a polyester film and its subsequent lamination to an LLDPE film is described.
    [00010] US 6709735 B2 / EP 1 451 008 B1 and US 6991837 B2 (Mitsubishi) disclose the use of compositions of PVOH or PVA and copolymers of acrylic acid and maleic acid with a molecular weight of from about 3500 to about 5000 to prepare barrier coatings. Barrier Coatings with good barrier properties at high RH
    [00011] US 7521103 B2 (Mitsubishi) discloses compositions including vinyl alcohol and vinyl amine copolymers. The use of this copolymer is shown to provide a barrier higher than those in the previous patents particularly at higher RH. SUMMARY OF THE INVENTION
    [00012] The present invention provides a process for preparing a gas barrier coating composition comprising mixing (a) a polymer composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA) and / or copolymer ethylene and vinyl alcohol (EVOH) and an aqueous polycarboxylic acid polymer solution or dispersion with (b) a previously prepared clay dispersion; the gas barrier coating composition obtained through this process; and a coating prepared from this gas barrier coating composition. The invention further provides a method of preparing a gas barrier material including the step of coating a flexible polymer film with the gas barrier coating composition of the invention and also the gas barrier material obtained through this process.
    [00013] It has been found that when a gas barrier coating composition is prepared by mixing (a) a polymer composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA) and / or ethylene copolymer and vinyl alcohol (EVOH) and a polycarboxylic acid polymer solution or dispersion with (b) a preformed clay dispersion, enhanced properties can be obtained, such as improved gas barrier properties and / or laminate bond strength improved. In particular, the coatings of the invention have been found to provide excellent barrier performance in high relative humidity (RH), coupled with good lamination bond strengths in adhesive formed laminates, particularly in PET-PE structures. In addition, it has been found that excellent performance in adhesive laminates formed at high RH can be achieved using the coatings of the present invention without the need for any special additional preparation layer. BRIEF DESCRIPTION OF THE DRAWING
    [00014] Figure 1 shows a transmission electron microscope of a coating composition of the invention. DETAILED DESCRIPTION OF THE INVENTION
    [00015] In a first aspect, the present invention provides a process for preparing a gas barrier coating composition comprising mixing (i) a polymer composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA ) and / or copolymer of ethylene and vinyl alcohol (EVOH) and a polycarboxylic acid polymer solution or dispersion with (ii) a clay dispersion.
    [00016] The gas barrier coating compositions of the invention, including gas barrier coating compositions prepared according to the process of the first aspect of the invention, have been found to be particularly useful in the formation of adhesive formed laminates. In a second aspect, the invention provides a coating composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA) and / or ethylene and vinyl alcohol (EVOH) copolymer and a polycarboxylic acid polymer solution or dispersion and a dispersion of a clay obtained using the process of the first aspect of the invention. In a third aspect, the invention provides a gas barrier coating comprising poly (vinyl alcohol) (PVOH or PVA) and / or copolymer of ethylene and vinyl alcohol (EVOH) and polymer of dispersed polycarboxylic acid with clay prepared using the composition of the second aspect of the invention. Advantageously, coatings of the third aspect of the invention are prepared by applying the coating composition of the second aspect of the invention to a substrate and removal of the solvent.
    [00017] In order to obtain good barrier properties it is important that the clay is well dispersed throughout the coating compositions of the second aspect of the invention and in the coating of the third aspect of the invention. It has been found that a good dispersion of the clay in the composition or coating is obtained if the clay is first dispersed in a liquid vehicle and the dispersion then obtained is mixed with a polymer composition. In addition, it was found that poor barrier performance properties are obtained if the clay is not well dispersed in a liquid vehicle before mixing with the polymer composition. It has also been found that gas barrier coatings of the present invention that are formed by mixing a well-dispersed clay dispersion with a polymer composition have good clarity properties and a low tendency to become cloudy and, in particular, a tendency lower in becoming cloudy than prior art coatings where the clay is less well dispersed.
    [00018] The term "dispersed clay" or "clay dispersion" as used herein refers to a clay that is substantially intercalated or exfoliated during the dispersion process. In contrast, a clay that is just slurry in a liquid is not substantially interspersed or exfoliated and substantial amounts of the clay will remain as a layered material. The person skilled in the art will be able to verify that a clay is substantially fully exfoliated and distributed in a liquid using known techniques such as high magnification analysis, X-ray diffraction or particle size analysis. A particular suitable method for confirming that the clay has been substantially fully dispersed is to melt a sample of a coating prepared using the dispersion on a copper mesh and inspect the sample using a transmission electron microscope.
    [00019] An additional particularly suitable method for confirming that a dispersed clay has been obtained is through particle size analysis of disk ultracentrifuge. Particle size analysis can be used to confirm that a clay is dispersed by measuring the peak particle diameter of a clay sample distributed in a liquid. The peak particle diameter is the maximum abundant particle size, by the relative weight of the particles. Where particles are non-spherical, the "diameter" of the particles is the maximum dimension. The peak particle diameter corresponding to a dispersed clay will vary depending on the type and source of clay used. In one embodiment, the dispersion of a clay sample for use in the process of the invention has a peak clay particle diameter of not more than 115%, preferably not more than about 110%, especially not more than about 108%, that of the peak particle diameter obtained using the following procedure:
    [00020] 25 g of clay are previously made into a slurry in 120 g of ethanol using an upper paddle stirrer. This clay slurry is then transferred to a Silverson L4R laboratory vortex mixer, equipped with a 1 mm sieve. 350 g of water is added to the slurry. Once the addition of water is complete, the power setting is increased to 50% and the clay is then dispersed for 45 minutes. The power setting is then reduced to 25% and 60 g of ethanol is added. After 5 minutes of further stirring, the dispersion is discharged.
    [00021] The peak particle size can be measured using any standard technique, for example, be measured using a CPS DC24000 disk ultracentrifugal particle size analysis instrument as described with reference to Example 32 below.
    [00022] It has also been found that the dispersion level of a clay in a coating composition is related to the cloudiness that a coating layer produced when applied to a transparent substrate, especially a clear, colorless plastic substrate, such as a film of PET. In one embodiment, the coating compositions of the invention provide a cloud value of less than about 32%, preferably less than about 24% and especially less than about 20% when applied as a dry film weight of 24 gsm to the polyester film and then dried. The cloud value can be obtained using any standard device such as the Haze-gard double device from Byk-Gardner. The polyester film is, for example, a 12 pm thick polyester film treated with corona, such as a Mylar 800 film.
    [00023] In a fourth aspect the invention provides a process for preparing a gas barrier material comprising the stage of coating a substrate, for example, a flexible polymer film, with a gas barrier coating composition of the second aspect of the invention. In one embodiment, the process of the fourth aspect of the invention includes steps (a) of preparing a gas barrier coating composition according to the process of the first aspect of the invention; and (b) coating a flexible polymer film with the gas barrier coating composition. Advantageously, step (b) is carried out within 24 hours of the end of step (a). Advantageously, the coating step (b) includes the step of drying the gas barrier composition to form a dry coating. The gas barrier materials of the invention, including gas barrier materials prepared according to a process of the fourth aspect of the invention, have been found to be particularly suitable for use in relatively high humidity.
    [00024] In a fifth aspect of the invention, a gas barrier material is provided comprising a coating of the third aspect of the invention, for example, a coating of the third aspect of the invention on a flexible polymer film. Advantageously, the gas barrier material of the fifth aspect of the invention is prepared according to a process of the fourth aspect of the invention.
    [00025] In one embodiment, the gas barrier material prepared through the process of the fourth aspect of the invention or the gas barrier material of the fifth aspect of the invention is a laminated material comprising a first film adhered to a second film. In a fourth aspect embodiment of the invention, the process comprises steps (a) of preparing a gas barrier coating composition according to the process of the first aspect of the invention; (b) coating a first flexible polymer film with the gas barrier coating composition; (c) applying an adhesive coating to one or both coated sides of said first film or to a second flexible polymer film; and (d) adhesion of the first and second films. Advantageously, the process of the fourth aspect of the invention is used to prepare an adhesive formed laminate material. In an embodiment of the fourth aspect of the invention, the gas barrier material is incorporated into an adhesive formed laminate, so that the bond strength between the two films is at least about 1.0 N / 15 mm after storage of the laminate. for 2 days at 75% relative humidity after the adhesive has fully cured. In some embodiments, each of steps (b) to (d) is performed within 24 hours of the end of step (a). The first film to which the coating is applied can be referred to as a substrate, and the second film which is adhered to the substrate can be referred to as the coating. For the avoidance of doubt, the gas barrier coating is typically interposed between the first film or substrate and the second film or cover in a finished adhesive formed laminated material prepared according to the process of the fourth aspect of the invention or in an adhesive formed laminate material of the fifth aspect of the invention. Adhesively formed laminates can optionally include areas of printed design.
    [00026] The gas barrier materials of the invention have been found to be particularly effective in blocking the passage of oxygen. The materials of the invention have also been found to be useful in blocking the passage of other gases, including inert gases, such as nitrogen, and gaseous volatile organic compounds, such as petroleum fumes. In this way the gas barrier materials of the invention can be used both in applications where the ingress of gases into the packaging is undesirable, such as protection of packaged items from the ingress of oxygen, and in applications where retention of gases with the packaging is desirable. , such as the retention of an inert gas inside a package. The gas barrier materials of the invention can also be used in applications where preventing the passage of odorous gases through the barrier is desired.
    [00027] In a sixth aspect, the invention provides a packaged article, such as a foodstuff, pharmaceutical agent or other material, for example, foodstuff, pharmaceutical agent or other oxygen sensitive material, where the packaging comprises a barrier material gas of the fifth aspect of the invention. In one embodiment, the invention provides a packaged article, such as a foodstuff, a pharmaceutical agent or other material, for example, a foodstuff, pharmaceutical agent or other oxygen sensitive material, where the package comprises a gas barrier material including a gas barrier coating comprising poly (vinyl alcohol) (PVOH or PVA) and / or copolymer of ethylene and vinyl alcohol (EVOH) and polymer of polycarboxylic acid dispersed with clay.
    [00028] In a seventh aspect, the invention provides a method of protecting an article against deterioration comprising packaging the article in a package that includes gas barrier material according to the fifth aspect of the invention. In an embodiment of the seventh aspect of the invention, the use of a gas barrier material of the fifth aspect of the invention is provided as a packaging material for an article to protect against deterioration of the article, to prolong the shelf life of the article and / or delay the deterioration of the article. In one embodiment, the article is a food product, a pharmaceutical agent or another article that is sensitive to oxygen and that, for example, deteriorates upon exposure to oxygen.
    [00029] It should be understood that features described here with respect to any of the first, second, third, fourth, fifth, sex or seventh aspect of the invention may also be present in other aspects of the invention where appropriate.
    [00030] Although previously known PVOH / EVOH-clay 2 pack composite coatings can be used to produce adhesive formed laminates with excellent oxygen barrier and laminate bond strengths at ambient conditions of 23 ° C and 50% RH, it was surprisingly found that the performance of this type of coating deteriorates at high RH, such as RH above 50%. At high RH, the performance of known coatings with compositions has been found to deteriorate significantly with respect to both oxygen barrier performance and laminate bond strength. The coating compositions of the present invention advantageously improve performance in high humidity in both aspects. In particular, gas barrier coatings prepared from coating compositions of the invention have been found to exhibit increased performance at high relative humidity (RH), such as an RH of about 50% or more, especially about 60% RH or more, more especially about 70% RH or more, for example, about 75% RH or more. The gas barrier coatings of the invention have been found to allow strong interpellicle bonding to be formed in adhesive-formed laminate, such as PET-PE laminates. In particular, it has been found that the gas barrier coatings of the invention allow strong inter-film connections to be formed at high RH, such as greater than about 50%, for example, greater than about 75%. Advantageously, the bond strength between the two films is at least about 1.0 N / 15 mm after storage of the laminate for 2 days in 75% relative humidity after the adhesive has fully cured. In addition, it has been shown that an anchor coating is not required to obtain good lamination bond strengths. Although the gas barrier coating compositions of the invention have been found to be suitable for use in forming an adhesive formed laminate material that performs well at high RH, it is understood that these gas barrier coating compositions can also be used in Lower RH, for example, less than 50%, and good performance is also typically seen at low RH values.
    [00031] Advantageously, the present invention provides a method of preparing a gas barrier coating composition with good oxygen barrier performance and good adhesion properties at high RH using conventional equipment. The gas barrier coating composition of the invention is generally prepared by mixing (i) solutions or dispersions of the poly (vinyl alcohol) polymers (PVOH or PVA) / ethylene and vinyl alcohol copolymer (EVOH) and polycarboxylic acid with (ii) a clay dispersion. The process typically allows well-controlled proportions of each of the three components to be obtained. In addition, the process results in the clay being well dispersed in the polymer components of the coating composition. A preferred technique in the preparation of the coating composition is to use a high shear dispersion apparatus to prepare the clay dispersion through a separate process before mixing the dispersion with a polymer composition comprising a poly (vinyl alcohol) solution or dispersion ( PVOH or PVA) / ethylene and vinyl alcohol copolymer (EVOH) and a polymeric acid solution or dispersion, for example, a poly (vinyl alcohol) solution (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer and polymeric acid. In one embodiment, the first aspect of the invention provides a process for preparing a gas barrier coating composition comprising the clay dispersion steps using a high-shear dispersion apparatus; and then mixing (i) a polymer composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA) and / or ethylene and vinyl alcohol copolymer (EVOH) and a polycarboxylic acid polymer solution or dispersion with (ii) the clay dispersion. The dispersion apparatus may, for example, be a vortex, cavitation or high shear dispersion apparatus of the bead grinder type. Preferably, the dispersion apparatus is a vortex-type dispersion apparatus. Vortex dispersion devices have been found to be particularly suitable for dispersing clays. The clay is dispersed in a liquid vehicle to form a clay dispersion. Suitable liquid vehicles where the clay is dispersed include aqueous solvents and water-miscible solvents such as alcohols, especially C1-C3 alkyl alcohols and ketones, especially acetone. Advantageously, the solvent includes water and a miscible co-solvent. Preferred co-solvents include ethanol, n-propanol and isopropanol. For the avoidance of doubt, the term "aqueous solvent" as used herein comprises pure water and mixtures comprising water and one or more water miscible co-solvents. Typically, water forms the major part, for example, at least 50% w / w of the aqueous solvent. Typically a water-miscible co-solvent makes up less than 50% w / w of the solvent. Advantageously, the clay is dispersed in the presence of water and a water-soluble alcohol. High shear dispersion devices, such as vortex and cavitation types, are common for the coating industry and, in contrast to the devices used in the process described in JP11-246729, do not generate high pressures. It was found that when a coating is prepared by dispersing the clay in situ with the solutions or dispersions of poly (vinyl alcohol) polymer (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) and / or polycarboxylic acid copolymer, the resulting compositions have oxygen barrier properties low in RH of around 75% and the clay dispersion is unstable, with the clay settling over time. In this way, conventional dispersion devices will not produce suitable coatings through a 1-container process. Without wishing to be limited by any theory, it is believed that in order to provide the required oxygen barrier performance at high RH, the inclusion of well-dispersed clay is required. Furthermore, it was shown that without the presence of dispersed clay, the oxygen barrier performance of coatings containing poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol copolymer (EVOH) is compromised by the inclusion of poly (acrylic acid) ) at high RH.
    [00032] The clay content of the coating compositions of the invention can, for example, be in the range of about 5% by weight to about 70% by weight based on the total solid content of the coating. Advantageously, the coating compositions of the invention include about 30% by weight (% by weight) or more of clay, based on the total solid content of the coating. In some embodiments, coatings comprising 35% by weight or more of clay, especially 37% or more, for example, 40% by weight or more of clay, such as 45% by weight or more of clay based on the solid content total coating. Particularly good gas barrier properties were observed when clay contents of at least 37% by weight were used. In contrast to JP 11-246729 coatings, which are described as exhibiting a decrease in bond strength as the concentration of inorganic laminar compound increases, it has been found that with the carboxylic acid polymer coatings of the present invention good bond strengths can maintained as the clay concentration increases. In particular, good bond strengths have been observed with the coatings of the present invention having clay contents from from about 35% by weight to at least about 50% by weight based on the total solid content of the coating. For example, in PET-PE laminates, good strengths were obtained with coating compositions comprising up to at least 47.5% by weight of clay based on the total solid content of the coating. Advantageously, the coating of the invention includes no more than 60% by weight of clay, as well as no more than about 55% by weight of clay, for example, no more than about 50% by weight of clay based in the total solid content of the coating. In one embodiment, the coating of the invention has a clay content of from about 30% by weight to about 55% by weight, for example, from about 35% by weight to about 50% by weight. weight based on the total solid content of the coating.
    [00033] Advantageously, the coating of the invention includes about 2% by weight or more of polycarboxylic acid polymer, for example, about 3% or more, especially about 5% by weight or more, of polycarboxylic acid polymer with based on the total solid content of the coating. Advantageously, the coating of the invention does not include more than about 30% by weight of polycarboxylic acid polymer, for example, not more than about 25% by weight, especially not more than about 20% by weight, of polycarboxylic acid polymer based on the total solid content of the coating. In one embodiment, the coating of the invention has a polycarboxylic acid polymer content of from about 3% by weight to about 25% by weight, for example, from about 5% by weight to about 20% by weight based on the total solid content of the coating.
    [00034] Advantageously, the coating of the invention includes about 20% or more of poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer, for example, about 25% by weight or more, especially about 30% by weight or more of poly (vinyl alcohol) (PVOH or PVA) / ethylene copolymer and vinyl alcohol (EVOH) based on the total solid content of the coating. Advantageously, the coating of the invention does not include more than about 70% by weight of poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer, for example, no more than about 75% by weight, especially not more than about 60% by weight, of poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer based on the total solid content of the coating. In one embodiment, the coating of the invention has a content of poly (vinyl alcohol) (PVOH or PVA) / copolymer of ethylene and vinyl alcohol (EVOH) of from about 25% by weight to about 65% by weight, for example, from about 30% by weight to about 60% by weight based on the total solid content of the coating.
    [00035] In one embodiment, the coating of the invention has a clay content from about 30% by weight to about 55% by weight, a polymer content of polycarboxylic acid from about 3% by weight. weight to about 25% by weight and a content of poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer from from about 25% by weight to about 65% by weight with based on the total solid content of the coating. In a further embodiment, the coating of the invention has a clay content of from about 35% by weight to about 50% by weight, a polymer content of polycarboxylic acid from about 5% by weight to about 20% by weight and a content of poly (vinyl alcohol) (PVOH or PVA) / copolymer of ethylene and vinyl alcohol (EVOH) from from about 30% by weight to about 60% by weight based on total solid content of the coating.
    [00036] The coatings of the invention typically have solid contents of at least about 0.5% by weight, preferably at least about 1% by weight, more preferably at least about 2% by weight. The coatings of the invention typically have solid contents of not more than about 15% by weight, preferably not more than about 10% by weight, more preferably not more than about 8% by weight. In one embodiment, the coatings have a solid content of from about 1% by weight to about 15% by weight, for example, from about 3% by weight to about 9% by weight.
    [00037] The adhesive formed laminated materials of the invention have been found to have superior adhesion and / or also good gas barrier properties at high RH. It has now been found that a laminated material that provides an advantageous balance of properties can be obtained if the coating is applied in a way that the criterion below is satisfied: X = A / B.C / D> about 15 where; A = Oxygen Transmission Rate (OTR) to the laminate (23 ° C / RH 75%) without the coating (where OTR is the rate of diffusion of pure oxygen through a substrate as measured with a Mocon Oxtran 2/21 (cm3 / m2 / day)); B = Oxygen Transmission Rate to the Laminate (23 ° C / RH 75%) with the coating; C = Bond strength at 75% relative humidity (N / 15 mm) (The bond strength and the force required to separate the two plastic films from the laminate in a T stripping test, using a Lloyds Instruments LRX Plus device with a separation speed of 200 mm / min); and D = Dry Coating Weight (gsm) (The dry coating weight is determined from the amount of coating deposited on the film, as well as the solid content of the coating).
    [00038] Advantageously, A / B> about 8, C> about 1.0 and / or D <about 1.0.
    [00039] Advantageously, the gas barrier material of the invention, that is, the gas barrier material prepared according to the process of the fourth aspect of the invention or the gas barrier material of the fifth aspect of the invention, is a laminate adhesive formed where the above criteria are satisfied. The interrelationship between coating weight, barrier properties and bond strength was assessed and it was found that when a process for preparing a gas barrier laminate material is made especially to satisfy this criterion, an optimal balance of properties must be obtained.
    [00040] Component A / B is essentially a 'barrier-raising' factor; the ratio of oxygen transmission rates achieved without, and with the barrier coating, at a relative humidity of 75%. In a preferred embodiment, this factor would be greater than about 8. For a typical PET-PE laminate with no barrier layer, the oxygen transmission rate would typically be about 100 cm3 / m2 / day. This means that the preferred maximum oxygen transmission rate, in RH of about 75%, with a barrier coating of the present invention would be about 12.5 cm3 / m2 / day. The oxygen transmission rate in cm3 / m2 / day is measured at 23 ° C and relative humidity (RH) of 75% using any standard method known to the person skilled in the art. For example, standard ASTM test methods include: • Standard Test Method D3985 for Transmission Rate of Oxygen Gas Through Plastic Film and Lamination Using a Coulometric Sensor; • Standard Test Method F1927 for Determining Oxygen Gas Transmission Rate, Permeability and Permeability in Controlled Relative Humidity Through Barrier Materials Using a Coulometric Detector; and • Standard Test Method F2622 for Oxygen Gas Transmission Rate Through Plastic Film and Lamination Using Various Sensors.
    [00041] The ASTM tests above measure oxygen transmission in cm3 / m2 / day at 23 ° C and 50% relative humidity (RH) and then, for the purposes of the present invention, they are adapted in such a way that the test is performed in 75% RH.
    [00042] C is a figure for bond strength, given in N / 15 mm; the force required to separate the coating film from the coated substrate. Preferably, the bond strength is at least 1.0 N / 15 mm. A bond strength of 1.0N / 15 mm or more has been found to provide a degree of laminate strength resulting in adequate integrity of a finished package, but lower rates are possible. Bond strength can be measured by registering the force (in N / 15 mm units, where a 15 mm wide laminate tape is tested) required to separate the 2 pleats of a laminate in a T stripping test. The separation speed used in the examples was 200 mm / min and the instrument used was a JJ Lloyd LRX tensiometer, equipped with a 50 N load cell. The peeling test T is a well recognized test in the packaging industry. The minimum value of C is 1.0N / 15 mm which is considered the minimum required to provide a degree of laminate strength resulting in adequate integrity of a finished package.
    [00043] D is a figure for dry film weight. The gas barrier coatings of the invention will generally have a solid content of less than about 10% by weight when applied by processes or by engraving or flexography. In this way it is unlikely that especially thick dry film thicknesses will be realistically applicable. For example, a coating having about 6% by weight of solids, when applied to a film thickness of about 10 microns, would apply about 0.60 g / m2 of poly (vinyl alcohol) (PVOH or PVA) / copolymer of ethylene and vinyl alcohol (EVOH) and clay (some differences would occur due to differences in density of the polymer and clay of the solvent medium). As a wet film thickness of about 10 microns is likely to be in the upper practicable range of this type of technology applied through an engraving process, then a preferred upper limit of about 1.0 g / cm3 for the dry film weight is reasonable for this type of coating. Typically the dry coating thickness is less than about 10,000 nm, for example, less than about 5000 nm, especially less than about 2000 nm, such as less than about 1500 nm. Advantageously, the thickness of the dry coating is from about 50 to about 1000 nm.
    [00044] In one aspect, the invention relates to the surprising embodiment that a gas barrier coating that satisfies the above test can be obtained using conventional dispersion apparatus, such as high shear mixing apparatus, if the clay is dispersed in a liquid vehicle before combining with a polymer composition.
    [00045] Advantageously, the polymer composition used in the process of preparing the coating composition of the invention comprises copolymers of PVOH and / or EVOH in solution. Advantageously, the composition comprises polymers of polycarboxylic acid in solution. The solutions or dispersions of poly (vinyl alcohol) polymers (PVOH or PVA) / ethylene and vinyl alcohol (EVOH) copolymer and polycarboxylic acid used in the process of the invention are advantageously aqueous solutions. Suitable solvents where polymers are dispersed or dissolved include aqueous solvents and water-miscible solvents such as alcohols, especially C1-C3 alkyl alcohols and ketones, especially acetone. Advantageously, the solvent includes water and a miscible co-solvent. Preferred co-solvents include ethanol, n-propanol and iso-propanol. For the avoidance of doubt, the term "aqueous solvent" as used herein comprises pure water and mixtures comprising water and one or more water miscible co-solvents. Typically, water constitutes the major part, for example, at least 50% w / o of the aqueous solvent. Typically, a water-miscible co-solvent makes up less than 50% w / w of the solvent. In one embodiment, the invention provides a process for preparing a gas barrier coating composition comprising mixing (a) an aqueous solution of PVOH and / or EVOH copolymer and polycarboxylic acid polymer with (ii) a clay dispersion .
    [00046] The clay compound is advantageously one that readily disperses in aqueous media, a high degree of exfoliation of the mineral lamellae being required to provide maximum barrier performance. There is no restriction on the type of clay used in the present invention, as long as it is sufficiently dispersible in an aqueous medium, it is capable of being intercalated or exfoliated during dispersion and / or is suitable for use in an oxygen barrier coating. Advantageously, the clay is dispersed in an aqueous solvent or a water-miscible solvent, preferably an aqueous solvent.
    [00047] The clay used is preferably in nanoparticle. A nanoparticle clay is a clay with particles having at least one dimension in the nanometer range, that is, less than 100 nm. Typically, nanoparticle clay particles have a maximum thickness dimension of less than 100 nm, for example, a maximum dimension of less than 50 nm, such as a maximum dimension of less than 20 nm. In an exfoliated form, the aspect ratio of the clay (that is, the ratio of the length to the thickness of a single clay "sheet") will have an impact on the oxygen barrier level obtained. The higher the aspect ratio, the more the rate of oxygen diffusion through the dry and laminated coating will be reduced. Advantageously, the clay has an aspect ratio greater than about 20 in its exfoliated form. Clay minerals with aspect ratios between 20 and 10,000 are typically used. Particularly preferred are those minerals having an aspect ratio greater than about 50, for example, greater than about 100.
    [00048] Examples of suitable clays include kaolinite, montmorillonite, atapulgite, illite, bentonite, haloisite, kaolin, mica, vermiculite, diatomaceous earth and fuller earth, calcined aluminum silicate, hydrated aluminum silicate, aluminum magnesium silicate sodium and magnesium silicate. Of these, montmorillonite clays, including bentonites, are preferred, nanoparticle clays being more preferred. Commercial examples of suitable materials are Cloisite Na + (available from Southern Clay), Bentona ND (available from Elementis).
    [00049] Advantageously, the carboxylic acid polymer (s) present in the compositions of the invention are homo- and copolymers of acids, typically unsaturated acids, for example, ethylenically unsaturated acids, such as acrylic, methacrylic and maleic. In one embodiment, the polycarboxylic acid polymer is selected from poly (acrylic) acid, poly (methacrylic acid) or copolymers thereof or a maleic acid copolymer or with acrylic or methacrylic acid or mixtures thereof. In an additional embodiment, the polycarboxylic acid polymer is poly (acrylic) acid. There is no restriction on the molecular weight of the polycarboxylic acid polymer, as long as it is not so high that the viscosity of the coating is very high in solid contents useful to prevent application through processes or flexographic or engraving. The coatings of the present invention have been found to perform well with a range of polymeric acids and are not limited to low molecular weight copolymers of maleic anhydride and acrylic acid. For example, a coating prepared using the process of the present invention that includes a polymeric acid which is a copolymer of acrylic and methacrylic acids with a molecular weight of about 20,000 has been found to perform well. Advantageously, the polycarboxylic acid polymer has a molecular weight of less than about 300,000, for example, less than about 200,000, especially less than about 150,000. In a preferred embodiment, the carboxylic acid polymer is used in its predominantly non-neutralized form. Advantageously, the carboxylic acid polymer used is predominantly in the form of the free acid, for example, at least 50 mol% of the carboxylic acid groups in the polymer are in the form of free acid, especially at least 70 mol% and more especially at minus 90 mol% of the carboxylic acid groups in the polymer are in the form of free acid. It has been shown that partially or fully neutralized analogs where substantial proportions of the acidic moieties have been converted to salts can induce a deterioration in performance of both the oxygen barrier and laminate bond strength at high humidity. Advantageously, the pH of the solution or dispersion of polycarboxylic acid or dispersion used in forming the gas barrier coating compositions has a pH of about 4 or less, for example, about 3.5 or less, especially about 3 or any less. Typically, the carboxylic acid solution or dispersion has a solids content of from about 10 to about 50% by weight. In one embodiment, the gas barrier coating composition is substantially free of partially or integrally neutralized polycarboxylic acid polymers. Preferably the gas barrier coating composition is prepared substantially without any basic components that are capable of forming salts with the polycarboxylic acid polymers.
    [00050] In one embodiment, the gas barrier coating composition comprises a solution or dispersion, preferably a solution, of EVOH copolymer. In an additional embodiment, the EVOH copolymer is dispersed in the coating of the invention. Advantageously, the EVOH copolymer is a vinyl-ethylene alcohol copolymer where the ethylene content is less than 20 mol%. Conventional EVOH copolymer, as used in the barrier coating of JP 2007136984A, US 4818782 and EP 0479031 mentioned above, has a molar ethylene concentration greater than 20%. It has been found that when the main polymer component of the coatings described here is a vinyl-ethylene alcohol copolymer where the ethylene content is less than 20 mol% (such as in the range of EVOH polymers available from Kuraray under the brand name) registered 'Exceval'), a more stable solution is provided than when a conventional EVO copolymer is used. Although conventional EVOH copolymer solutions are generally applied under elevated temperature to ensure clarity of the coating as it dries, it has been found that coatings of the invention that include an EVOH copolymer where the ethylene content is less than 20 mol% can be successfully applied under ambient conditions.
    [00051] If desired, in addition to the PVA and / or EVOH copolymer, and the carboxylic acid, other polymers or resins can be included in the coating composition, as long as these co-resins are compatible in the final composition. Examples of such polymers and resins include acrylic emulsions, acrylic emulsions, polyesters, alkyls, sulfopolyesters, polyurethanes, vinyl acetate emulsions, poly (vinyl butyral), poly (vinyl pyrrolidone), polyamides, polysaccharides, proteins, epoxies, etc. It is also possible to include sol-gel precursors in these compositions, for example, a tetraethyl orthosilicate hydrolyzate. Advantageously, the coating composition does not include substantial levels of basic polymers or resins, such as polyethyleneimine, which form salts with the polycarboxylic acid polymers.
    [00052] There is no particular restriction on the nature of the substrate, although it is preferable that a flexible substrate, such as a plastic film, and any material suitable for the intended use can be employed. However, where the material being packaged with the coating film of the present invention is a foodstuff or pharmaceutical agent, it will normally be preferred that the plastic film or substrate is food grade. Examples of suitable materials include: polyolefins, such as polyethylene or polypropylene; polyesters, such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthenate; polyamides, including nylon such as nylon-6 or nylon-66; and other polymers, such as polyvinyl chloride, polyimides, acrylic polymers, polystyrenes, celluloses or polyvinylidene chloride. The coating of the invention has been found to be particularly suitable for use with polyesters. It is also possible to use copolymers of any two or more of the compatible monomers used to produce these polymers. In addition, the compositions of the present invention can be included in adhesive formed laminates comprising paper substrates (such as polyester or polyolefin coated cartons generally found in foodstuff packaging).
    [00053] The gas barrier coatings of the invention have been found to be particularly suitable for use with flexible plastic film substrates that have inherently relatively poor oxygen barrier properties. In one embodiment, the OTR of the laminated material without the coating is at least 50 cm3 / m2 / day at 23 ° C at 75% RH, especially at least 80 cm3 / m2 / day at 23 ° C at 75% RH. In one embodiment, the OTR of the uncoated laminated material is at least 1000 cm3 / m2 / day at 23 ° C at 75% RH.
    [00054] The substrate is preferably treated by corona discharge just before being coated with the composition of the present invention. This process is well known in the art and is described, for example, in "Plastics Finishing and Decoration", edited by Donatas Satas, published by Van Nostrand Reinhold Company in 1986, on pages 80-86. In the following Examples, for the treatment of corona discharge the applicant obtained a surface energy greater than 50 Dynes / cm. In one embodiment, the coating is applied to the plastic film treated with corona discharge, such as PET (polyester), and laminated to a second plastic film, such as poly (ethylene), using a suitable laminating adhesive.
    [00055] There is no particular restriction on the nature of the coating film. The types of plastic film described above for use as a substrate are generally also suitable for use as the coating film. The cover film can be the same as the substrate film or they can be different from each other.
    [00056] There is no particular restriction as to the nature of the adhesive used, and any adhesive generally used for the adhesion of two or more plastic films can be employed in the present invention. Examples of suitable adhesives include solvent-based (polyurethane) types such as those from Henkel (Liofol UR3969 / UR 6055, Liofol UR3640 / UR6800, Liofol UR3894 / UR6055), Rohm & Haas (Adcote 811 / 9L10) and Coim (CA2525 / 2526) . Solvent-free polyurethane adhesives, such as Liofol 7780 / UR6082, UR7750 / UR6071 from Henkel and Mor-Free ELM-415A / Mor-Free CR140 from Rohm & Haas, can also be used. Like polyurethane adhesives, epoxy-based types, such as Lamal 408-40A / C5083, can be used. Water based adhesives, such as Aqualam 300A / 300D, an epoxy type from Rohm & Haas, can also be used.
    [00057] The adhesive can be applied directly to one of the films and then adhered to the gas barrier coating on the other film or it can be applied to the gas barrier coating on one film and then adhered to the other film. In any case, the order of the layers will be: a plastic film; the gas barrier coating; an adhesive; and another plastic film. If desired, the layers of other materials can be interposed between any of these two layers or on either side of the flexible plastic film substrates 2 having the barrier coating between them.
    [00058] In an embodiment of the fourth aspect of the invention, the gas barrier material is incorporated into an adhesive formed laminate, so that the bond strength between the two films is at least about 1.0 N / 15 mm after storage of the laminate for 2 days at 75% relative humidity after the adhesive has fully cured.
    [00059] The coating compositions can be applied to any wet film weight; but ultimately the maximum wet film weight will be determined by the need to apply these coatings at realistic press speeds on conventional presses. In this way, a preferred maximum applied film weight would be about 10 gsm (wet). Since the solid content of these coatings will be in the range of about 4-9%, then the maximum probable dry film weight applied would likely be about 1.0 gsm (dry). Due to the different densities of poly (vinyl alcohol) (PVOH or PVA) / ethylene and vinyl alcohol copolymer (EVOH) (for PVOH about 1.3) and clay (for montmorillonite about 2.5), the weight of Film is a more relevant feature for the gas barrier materials of the invention than film thickness.
    [00060] In one embodiment, the invention provides a process for preparing a gas barrier material comprising mixing a solution or dispersion of a PVOH and / or EVOH and an aqueous solution or dispersion of polycarboxylic acid polymer with a previously dispersion prepared from a clay, and then carrying out the steps: a. coating a first flexible polymer film with the resulting mixture; B. applying an adhesive coating to one or both coated sides of the first film or to a second flexible polymer film; and c. adhesion of the first and second films together, the bond strength between the two films being at least about 1.0N / 15 mm (after storage of the laminate for 2 days in 75% relative humidity) and more preferably more than about 1.5N / 15 mm after the adhesive has been fully cured.
    [00061] Advantageously, steps a, b and c are performed within about 24 hours of completion of mixing the three components. Advantageously, the clay is present in the amount of about 35-50% by weight, the polycarboxylic acid polymer is present in the amount of about 5-20% by weight and the poly (vinyl alcohol) (PVOH or PVA) / copolymer ethylene and vinyl alcohol (EVOH) is present in the amount of about 30-60% by weight of the total solid content of the coating. Advantageously, the polycarboxylic acid polymer is predominantly in its non-neutralized form. Advantageously, the polycarboxylic acid polymer is a homo- or copolymer of acrylic acid and / or methacrylic acid or a copolymer of maleic acid and acrylic acid. Advantageously, the carboxylic acid polymer has a molecular weight of less than about 200,000. Advantageously, the thickness of the dry coating is from about 50 to 1000 nm. Advantageously, the clay (in its exfoliated form) has an aspect ratio greater than about 20. Advantageously, the clay dispersion is made using conventional high-shear dispersion apparatus. Advantageously, the dispersion apparatus is a vortex, cavitation or bubble grinder type, preferably a vortex dispersion apparatus. Advantageously, the clay is dispersed in the presence of water and a water-soluble alcohol.
    [00062] Advantageously, the process of the invention provides a gas barrier material where: (A / B). (C / D)> about 15, where A = Oxygen Transmission Rate (23 ° C / RH 75% ) for the laminate without the coating; B = Oxygen Transmission Rate (23 ° C / RH 75%) for the laminate with the coating; C = Bond strength in relative humidity at 75% (N / 15 mm); D = Coating Weight [gsm (dry)]; as long as: A / B about 8, C> about 1.0 and D <about 1.0.
    [00063] The invention further provides a foodstuff, pharmaceutical agent or other packaged oxygen sensitive material, where the packaging comprises a gas barrier material of the invention, for example, a gas barrier material prepared according to the process of invention.
    [00064] The invention further provides water-dilutable coating compositions comprising poly (vinyl) and / or ethylene-polyvinyl alcohol copolymers, a dispersed clay and a polycarboxylic acid polymer. Preferred polycarboxylic acid polymers include homo- and copolymers of acrylic acid, methacrylic acid and maleic acid. The coatings provide an exceptional oxygen barrier when incorporated into adhesive formed laminates, together with good laminate bonding strengths, particularly for PET-PE laminated structures. EXAMPLES
    [00065] The following examples illustrate the specific aspects of the present invention and are not intended to limit its scope in any case and should not be considered to do so.
    [00066] The oxygen transmission rates (OTR) of the coated samples were determined on a Mocon Oxtran 2/21 gas permeability tester at 23 ° C and 75% relative humidity. The substrate used in all cases was a newly treated 12 micron Mylar 800 with corona discharge. The coatings were applied with a K No. 2 bar (about 12 microns) and dried in a stream of warm air (lab impressions were dried with a hair dryer). The dry coating weight was approximately 0.84 gsm. The coatings were applied to Mylar 800 shortly after mixing the clay dispersion and the polymer composition, typically within two hours. The laminates were prepared by applying the coating to the treated side of the polyester film, an adhesive was applied on top of the dry coating, then laminated to the treated side of a 30 pm gauge poly (ethylene). The adhesive used was supplied by Morchem, PS220 / CA40, and was prepared according to the manufacturer's instructions and applied in order to obtain a final dry film weight of about 2.5 gsm. The laminates were then stored for 10 days at 25 ° C to ensure complete curing of the isocyanate-based adhesive.
    [00067] The laminates were then tested for bond strength (N / 15 mm) after being stored for 2 days at 75% RH.
    [00068] The coating examples that follow were prepared according to a design-mixing experiment with restriction by mixing a PVOH solution having 12% by weight of solids with a clay dispersion having a solid content of 4.5% by weight and with an aqueous solution of a carboxylic acid polymer. The PVOH solution comprised 12% Exceval AQ4104 and 30% n-propanol. The rest of the solution was deionized water. The clay dispersion contained 4.5% by weight of Cloisite Na + and 30% isopropanol; the rest being deionized water. The clay was dispersed using a high shear mixer. This was achieved initially by forming a slurry of the clay in the alcohol to which the deionized water was then added. Unless otherwise stated, a Dispermant CV cavitation mixer with a 1 L cylindrical container and a 4 cm blade at 2500 rpm for 45 minutes was used to prepare the dispersion. The total mass of the dispersion was 500 g. The coatings were made at a total solid content of about 7.0% by weight by mixing the PVOH solution, clay dispersion and poly (acid) solutions in the correct amounts. The rest of the coating was complete with deionized water. Examples 1-13: Performance of Poly (Acrylic) Acid Based Barrier Coatings
    [00069] Table 1 provides details of coatings prepared with Acriflow 041S, a poly (acrylic) acid solution obtained from Witton Chemicals, along with its oxygen barrier performance, bond strengths and calculated A / B and X values. Table 1

    Note: The OTR of My ar 800 without any coating was about 102 cm3 / m2 / day * Results outside the preferred limits specified above.
    [00070] In each of Examples 1 to 13, good bond strengths between the films were observed. Larger barrier-raising factors were achieved in the examples where the clay content was about 38% by weight or more. Only the coating of Example 5 provided an X value below 15.
    [00071] Examples 14-26: Examples 1-13 were repeated except that these coatings were made using Sokalan CP12S, a copolymer of acrylic and maleic acids, obtained from BASF [aka poly (maleic-co-acrylic acid) Table 2
    * Results outside the preferred limits specified above. Example 27: A repeat of Example 25, but replacing Sokalan CP12S with Sokalan CP13S [Poly (acrylic-cometacrylic acid) Table 3

    [00072] In order to confirm that the clay had been substantially fully dispersed, a sample of the material of Example 27 was diluted with deionized water and then melted in a copper mesh and allowed to dry. The sample was then inspected under a transmission electron microscope to confirm that a substantial portion of the mineral had been fully dispersed. The results are shown in figure 1.
    [00073] X-ray diffraction analysis was also used to confirm that the clay dispersion used in the preparation of Example 27 was fully dispersed. As powder X-ray diffraction analysis is performed on a dry and ground coating, it provides indirect information on the degree of dispersion of the wet dispersion. In addition, higher concentrations of clay can agglomerate again during the drying process, and in this way, information on the dispersion level of the clay is more reliably obtained when testing coating composition compared using low concentrations of clay.
    [00074] A coating similar to that of Example 27, but with 10% by weight of Cloisite Na +, the diffraction peak at 12.1 Ansgstrons corresponding to dooi (the distance between the clay plates observed in a sample of non-Cloisite Na + dispersed) had disappeared indicating that the clay had been exfoliated. As the clay concentration had been increased to 25% and the 40-45% of Example 27, a diffraction pattern reappeared, at 35 and 26 Angstrons, respectively. This clearly indicates the reordering of the clay in order to provide a diffraction pattern; as the clay concentration increases, the distance between the coverslips decreases, as would be expected. These data show that in order to confirm that the dispersion used to prepare Example 27 was fully exfoliated, instead of, for example, an interleaved composite, it is necessary to analyze a coating comprising 10% by weight of the clay.
    [00075] This analysis confirmed that the preparation of a clay dispersion using a Dispermat CV cavitation mixer using the techniques described above is sufficient to cause a high level of clay exfoliation.
    [00076] Comparative Examples 1 & 2: Example 27 was repeated, but without the Sokalan CP13S (Comparative Example 1). Also, a coating having a clay concentration below the preferred level of at least 30% by weight was prepared (Comparative Example 2). The following results have been obtained. Table 4
    Example Relative concentration of
    [00077] It is evident from Comparative Example 1 that the inclusion of (polymeric) acid facilitates the advantageous application of the combination of oxygen barrier and laminate bond strength at high RH. Comparative Example 2 demonstrates the effect of lowering the clay level on the oxygen barrier performance of the coating and indicates that clay levels below 30% by weight do not result in coatings with particularly good barrier performance.
    [00078] Comparative Examples 3-5: To demonstrate the role of (polymeric) acid in combination with PVHO and clay, the compositions were prepared without any clay. These compositions are provided in Table 5 below, together with the OTR results in RH 75%. Table 5

    [00079] Comparative Examples 3 to 5, together with Comparative Examples 1 and 2, demonstrate that the combination of the 3 components is key to obtaining improved oxygen barrier and laminate bond strength performance in high relative humidity. In addition, they demonstrate that the inclusion of the 3 components in the preferred levels specified here is advantageous in providing an optimal balance of properties. Comparative Examples 6-8: In situ preparation of the clay dispersion
    [00080] JP 11-246729 indicates that compositions of this type can be made using high pressure dispersion apparatus to disperse a clay in the presence of a solution of poly (vinyl) alcohol and an aqueous solution of poly (acrylic) acid . However, the applicant found that using conventional (high shear) dispersion equipment typical of those used in the coatings industry (such as Dispermat (cavitation) and Silverson (vortex) types) this "all-in" approach does not produce satisfactory effects.
    [00081] With the composition represented by Example 27, clay dispersions were made with the following compositions: Comparative example 6: Cloisite Na + 4%, Sokalan CP13S 4.3% (supplied as a 25% solution), EtOH 3%, deionized water 61.7%, Comparative example 7: Cloisite Na + 4%, 31.2% of a 12.65% solution of Exceval AQ-4104, 20.3% EtOH, 44.5% deionized water. Comparative example 8: Cloisite Na + 3.1%, 24.2% of a 12.65% solution of Exceval AQ-4104, 3.3% of Sokalan CP13S, 20.8% ethanol, 48.6% deionized water . This example is the manufacturing equivalent of the coating by the 'all-in' process.
    [00082] In Comparative Examples 6 to 8, ethanol was added first to the dispersion vessel, followed by clay. Deionized water was added, followed by other components. The clay was then dispersed according to the procedure described above.
    [00083] In the cases of Comparative Examples 5 and 6, these were subsequently made in coatings equivalent to the composition of Example 27 by adding the other components and diluted with water to obtain the total solid content of about 7.0%.
    [00084] OTRs following 23 ° C / 75% RH have been combined: Comparative example 6: 35.3 cm3 / m2 / day Comparative example 7: 52.9 cm3 / m2 / day Comparative example 8: 82.0 cm3 / m2 / day
    [00085] These oxygen barrier results are significantly poorer than for Example 27 where the clay dispersion was prepared in a separate process and subsequently mixed with the polymer solutions. In addition, it was observed for the clay dispersions prepared in Comparative Examples 7 and 8 that the clay quickly settle, indicating that appropriate dispersion had not been obtained.
    [00086] In this way, an additional aspect of the present invention is preferably to prepare the coatings by mixing a dispersion of aqueous clay with solutions of poly (vinyl) alcohol and / or copolymers of ethylene and vinyl alcohol together with solutions of (polymeric) acids. . Examples 28-33: Dependence on clay dispersion performance
    [00087] The cloudiness of a coating when applied to a polyester film (12 pm Mylar 800 treated with corona discharge) was measured in order to assess the quality of the clay dispersion and its impact on the oxygen barrier of a resulting coating It was determined. The level of cloudiness in a coating has been found to be indicative of the quality of the clay dispersion used to prepare the coating, with poorly dispersed coating compositions resulting in coatings that have a high level of cloudiness.
    [00088] Example 27 was repeated, but in each case Cloisite Na + was dispersed in varying ways, using either Dipermat CV, as mentioned above, or using a Silverson L4R. Both mixers are laboratory scale devices, Dispermat being of the cavitation type and Silverson of the vortex type. In each case approximately 500 g of clay dispersion was prepared.
    [00089] As an example, the dispersion of Example 33 was prepared as follows: 25 g of Cloisite Na + were initially pre-slurried in 120 g of ethanol using an upper paddle stirrer. This clay slurry was then transferred to a Silverston L4R laboratory vortex mixer equipped with a 0.5 mm sieve. 350 g of deionized water was added to the slurry. Once the water addition was complete, the power setting was increased to 50%, and the clay was then dispersed for 90 minutes. The solid content of the dispersion produced was 4.8% (w / w). Note: the reason for a solid content lower than the theoretical value is that Cloisite Na + contains a residue of water that it absorbs during storage. The other dispersions were prepared by varying the procedure according to the details provided in Table 6 below.
    [00090] In the case of Dispermat, a 4 cm blade was used, and the speed was varied as described in Table 6. In the case of dispersions prepared using Silverson, the rotor was adjusted to 50% of the maximum energy (75% of the maximum energy for Example 33) and the sieve was changed according to the details in Table 6.
    [00091] The oxygen barrier of these coatings was evaluated in the same way as described in the previous examples. The coatings were also applied to the PET film, but at a wet coating thickness of 24 pm, using a K-Bar No. 3 (example, RK Print). The coatings were dried and then the cloudiness of these coated films was determined using the double Haze-gard apparatus from Byk-Gardner Table 6
    1 The oxygen transmission rate was measured at 23 ° C / 75% RH, with a 12 gsm (wet) coating on PET. 2 Cloudiness was an average of 8 readings with a 24 gsm (wet) coating on PET. * Results outside the preferred limits specified above.
    [00092] The clay used in the preparation of the coating composition of Comparative Example 9 was not fully dispersed and as a result provided a coating with a high cloud cover and an oxygen barrier increase factor (A / B) of 5.3. The results presented in Table 6 above demonstrate the presence of a correlation between the cloudiness of a coating, which is a measure of the degree of clay dispersion, and the oxygen barrier performance of the resulting coating.
    [00093] The above results demonstrate that adequate levels of dispersion can be obtained using a cavitation type high shear dispersion apparatus when used at a sufficiently high rpm. However, a higher degree of dispersion has been found to be obtainable using a vortex-type dispersion apparatus.
    [00094] A dispersion of Cloisite Na + made according to Example 32 was analyzed for peak particle size using a CPS DC24000 instrument; disk speed 10,000 rpm; Standard diameter calc. 0.377 pm; Standard calc density. 1.385 g / ml; particle size density 2.5 g / ml; particle size absorption 0.01, particle non-sphericity 1.0, fluid density 1.064 g / mL, number of data points 1775; analysis time 5.5 minutes; total weight 44.44 pg; no offset, no noise filtering; peak detection factors: height = 0.5, width = 10; peaks detected 0.2156 pm. The test indicated a polydispersed sample with a maximum peak equivalent of 216 nm which is what would be expected from a fully exfoliated mineral of this type.
    [00095] In contrast, when a dispersion of Cloisite Na + made according to the procedure of Comparative Example 9 was analyzed using an identical procedure, a peak maximum of 252 nm was observed, the significantly larger peak particle size indicates that the clay was not fully exfoliated, as confirmed by the poor gas barrier performance of the final coating of Comparative Example 9.
    [00096] The present invention has been described in detail, including its preferred embodiments. However, it will be understood that those skilled in the art, when considering the present invention, can make modifications and / or improvements to the present invention that fit the scope and spirit of the invention.
    权利要求:
    Claims (29)
    [0001]
    1. Process for preparing a gas barrier coating composition characterized by the fact that it comprises at least one step of mixing (i) a polymer composition comprising a poly (vinyl alcohol) solution or dispersion (PVOH or PVA ) and / or ethylene vinyl alcohol (EVOH) and a carboxylic acid polymer solution or dispersion with (ii) a clay dispersion in an amount of at least 40% by weight, wherein the composition comprises a solution or dispersion of EVOH copolymer, which is a vinyl-ethylene alcohol copolymer having an ethylene content of less than 20 mol%.
    [0002]
    2. Process for preparing a gas barrier coating composition according to claim 1, characterized by the fact that the clay is present in an amount between 35-50% by weight of the total solid content of the coating composition.
    [0003]
    3. Process for preparing a gas barrier coating composition according to claim 2, characterized in that the PVOH / EVOH copolymer is present in an amount between 30-60% by weight of the content of total solid of the coating composition.
    [0004]
    4. Process for preparing a gas barrier coating composition according to claim 3, characterized by the fact that the carboxylic acid polymer is present in the amount of 5-20% by weight of the content of total solid of the coating composition.
    [0005]
    5. Process for preparing a gas barrier coating composition according to claim 4, characterized in that the polycarboxylic acid polymer is predominantly in its non-neutralized form.
    [0006]
    6. Process for preparing a gas barrier coating composition according to claim 5, characterized in that the polycarboxylic acid polymer is a homo- or copolymer of acrylic acid and / or methacrylic acid or a copolymer of maleic acid and acrylic acid or methacrylic acid.
    [0007]
    7. Process for preparing a gas barrier coating composition according to claim 6, characterized by the fact that the polycarboxylic acid polymer has a molecular weight less than 200,000.
    [0008]
    8. Process for preparing a gas barrier coating composition according to claim 7, characterized in that the solution or dispersion of the polycarboxylic acid has a pH less than or equal to 4.
    [0009]
    Process for preparing a gas barrier coating composition according to claim 8, characterized in that the polymeric composition comprises the EVOH copolymer.
    [0010]
    10. Process for preparing a gas barrier coating composition according to claim 9, characterized in that the clay is dispersed in water and / or in a water-soluble alcohol.
    [0011]
    11. Process for preparing a gas barrier coating composition according to claim 10, characterized by the fact that the clay is dispersed using a high shear dispersion apparatus.
    [0012]
    12. Process for preparing a gas barrier coating composition according to claim 11, characterized by the fact that the high shear dispersion apparatus is configured like a high shear dispersion apparatus of the vortex type.
    [0013]
    13. Process for preparing a gas barrier coating composition, according to claim 12, characterized by the fact that the clay has an aspect ratio greater than 20 in its exfoliated form.
    [0014]
    14. Gas barrier coating composition characterized by the fact that it is obtained through the process as defined in any one of claims 1 to 10 and 12 to 14.
    [0015]
    15. Gas barrier coating composition characterized by the fact that it comprises PVOH and / or EVOH copolymer, polymer of polycarboxylic acid and clay, in which the clay is present in the amount of 40-50% by weight, the polymer of polycarboxylic acid is present in the amount of 5-20% by weight and the PVOH / EVOH copolymer is present in the amount of 30-60% by weight of the total solid content of the coating composition.
    [0016]
    16. Process for the preparation of a gas barrier material characterized by the fact that it comprises the step of coating a substrate with the gas barrier coating composition as defined in claims 14 or 15.
    [0017]
    17. Process for preparing a gas barrier material according to claim 16, characterized in that it comprises the following steps (a) preparing a gas barrier coating composition according to the process of any of the claims 1 to 13; and (b) coating a substrate with the gas barrier coating composition.
    [0018]
    18. Process for preparing a gas barrier material according to claim 17, characterized in that it comprises step (b) of coating a substrate with the gas barrier coating composition is carried out within 24 hours after the completion of step (a) of preparing a gas barrier coating composition.
    [0019]
    19. Process for preparing a gas barrier material according to claim 18, characterized in that the substrate is a flexible polymer film.
    [0020]
    20. Process for preparing a gas barrier material according to claim 19, characterized in that the flexible polymer film is a first flexible polymer film, wherein the process for preparing a gas barrier material The gas further comprises the following steps: (c) applying an adhesive coating to at least one coated side of said first film or to a second flexible polymer film; and (d) coupling the first and second films together.
    [0021]
    21. Process for preparing a gas barrier material according to claim 20, characterized in that the gas barrier material is incorporated into an adhesive laminate formed so that the bonding strength between the two films is at least 1.0 N / 15 mm after storage of the laminate for 2 days at 75% relative humidity after the adhesive has fully cured.
    [0022]
    22. Process for preparing a gas barrier material according to claim 21, characterized in that the barrier coating composition is applied in such a way that a dry coating thickness between 50 to 1000 nm is formed.
    [0023]
    23. Process for preparing a gas barrier material according to claim 22, characterized by the fact that: (A / B). (C / D)> 15 where A = Oxygen Transmission Rate (23 ° C / RH 75%) for the laminate without the coating; B = Oxygen Transmission Rate (23 ° C / RH 75%) for the laminate with the coating; C = Bond strength at 75% relative humidity (N / 15 mm) D = Coating Weight [g / m2 (dry)]; where: A / B> 8; C> 1.0; and D <1.0, where the rate of oxygen transmission rate is configured as the rate of diffusion of pure oxygen through a substrate in cm3 / m2 / day as measured with a Mocon Oxtran 2 / 21, bond strength is measured after storage for 2 days at 75% RH, bond strength being configured as a force required to separate the 2 pleats of a 15mm wide laminate tape in a T peeling test using a Lloyd Instruments LRX Plus device configured with a separation speed of 200 mm / min.
    [0024]
    24. Gas barrier material characterized by the fact that it is obtained by means of the process as defined in any one of claims 17 to 23.
    [0025]
    25. Adhesively formed laminated material, characterized by the fact that (A / B). (C / D)> 15 where A = Oxygen Transmission Rate (23 ° C / RH 75%) for the laminate without the coating; B = Oxygen Transmission Rate (23 ° C / RH 75%) for the laminate with the coating; C = Bond strength at 75% relative humidity (N / 15 mm) D = Coating Weight [g / m2 (dry)]; where: A / B> 8; C> 1.0; and D <1.0 where the rate of oxygen transmission rate is configured as the rate of diffusion of pure oxygen through a substrate in cm3 / m2 / day as measured with a Mocon Oxtran 2/21 , bond strength is measured after storage for 2 days at RH 75%, bond strength being configured as a force required to separate the 2 pleats of a 15mm wide laminate tape in a T peeling test using an apparatus Lloyd Instruments LRX Plus configured with a separation speed of 200 mm / min.
    [0026]
    26. Packaged foodstuff, pharmaceutical agent or other material characterized by the fact that a package comprises a gas barrier material as defined in claim 24.
    [0027]
    27. Method of protecting a foodstuff, pharmaceutical agent or other article that is sensitive to oxygen characterized by the fact that it comprises packaging the article in a package that includes gas barrier material as defined in claim 24.
    [0028]
    28. Process for preparing a gas barrier coating composition, according to claim 1, characterized by the fact that at least one of the following conditions is met: - An amount of poly (vinyl alcohol) ( PVOH or PVA) and / or ethylene vinyl alcohol (EVOH) is 20 to 70% by weight of the total solid content of the coating composition; - An amount of carboxylic acid is 2 to 30% by weight of the total solid content of the coating composition.
    [0029]
    29. Process for preparing a gas barrier coating composition, according to claim 1, characterized by the fact that both of the following conditions are met: - An amount of poly (vinyl alcohol) (PVOH or PVA) and / or ethylene vinyl alcohol (EVOH) is 20 to 70% by weight of the total solid content of the coating composition; - An amount of carboxylic acid is 2 to 30% by weight of the total solid content of the coating composition.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPS6247716B2|1983-06-15|1987-10-09|Toyo Boseki|
    US4818782A|1987-07-30|1989-04-04|E. I. Du Pont De Nemours And Company|Ethylene vinyl alcohol copolymers containing platelet-type mica fillers, processes for preparing same and multi-layer containers with layers thereof|
    JPH01313536A|1988-06-10|1989-12-19|Toray Ind Inc|Barrier film|
    EP0479031B1|1990-09-21|1996-12-11|Kuraray Co., Ltd.|Resin composition, process for its production and multilayered structure|
    AU662429B2|1992-07-29|1995-08-31|Sumitomo Chemical Company, Limited|Gas barrier resin composition and its film and process for producing the same|
    US5766751A|1994-01-24|1998-06-16|Sumitomo Chemical Company, Ltd.|Laminate, laminate film and shaped article comprising inorganic laminar compound|
    JPH07251871A|1994-01-26|1995-10-03|Sumitomo Chem Co Ltd|Laminated film|
    JP3367628B2|1995-11-30|2003-01-14|東レ株式会社|Gas barrier film and method for producing the same|
    JP3674228B2|1996-04-05|2005-07-20|東レ株式会社|Gas barrier film|
    JP3900555B2|1996-08-30|2007-04-04|住友化学株式会社|Method for producing the composition|
    JPH11246729A|1998-03-04|1999-09-14|Sumitomo Chem Co Ltd|Resin composition|
    JP4743885B2|2001-03-23|2011-08-10|キヤノン株式会社|Ink composition containing stimuli-responsive polymer, and image forming method using the ink composition|
    US6709735B2|2001-11-14|2004-03-23|Mitsubishi Polyester Film, Llc|Oxygen barrier coating and coated film|
    JP2004035833A|2002-07-05|2004-02-05|Toyo Ink Mfg Co Ltd|Gas barrier film and its manufacturing process|
    JP4321197B2|2002-10-03|2009-08-26|三菱瓦斯化学株式会社|Method for producing polyamide composite material|
    DE10302036A1|2003-01-21|2004-07-29|Mitsubishi Polyester Film Gmbh|Biaxially-oriented polyester film for use in food and other packaging has a base layer containing poly and a barrier layer containing a maleic acid/acrylic acid copolymer|
    US8063119B2|2003-08-29|2011-11-22|Inmat Inc.|Barrier coating of a non-elastomeric polymer and a dispersed layered filler in a liquid carrier and coated articles|
    JP2005256061A|2004-03-10|2005-09-22|Dainippon Printing Co Ltd|Laminate|
    DE602006009663D1|2005-06-22|2009-11-19|Mitsubishi Polyester Film Inc|COATED POLYMER FILM WITH OXYGEN BARRIER PROPERTIES|
    JP5081417B2|2005-09-26|2012-11-28|ユニチカ株式会社|Gas barrier laminate and laminate|
    JP5081415B2|2005-09-26|2012-11-28|ユニチカ株式会社|Gas barrier laminate|
    CN101272904B|2005-09-26|2012-12-19|尤尼吉可株式会社|Gas barrier multilayer body and article|
    JP2007136984A|2005-11-22|2007-06-07|Toppan Printing Co Ltd|Gas barrier laminated film|
    JP5092371B2|2005-11-30|2012-12-05|住友化学株式会社|Manufacturing method of resin film and laminate|
    US20070122557A1|2005-11-30|2007-05-31|Sumitomo Chemical Company, Limited|Method for producing resin film and layered article|
    JP2007223286A|2006-02-27|2007-09-06|Toppan Printing Co Ltd|High-adhesion transparent gas-barrier film and high-adhesion transparent gas-barrier laminate using it|
    JP4930917B2|2006-08-28|2012-05-16|株式会社巴川製紙所|Clay thin film, method for producing the same, and clay thin film laminate|
    WO2008038839A1|2006-09-29|2008-04-03|Sumitomo Chemical Company, Limited|Process for producing multilayer molding|
    US8158192B2|2006-12-21|2012-04-17|Novartis Ag|Process for the coating of biomedical articles|
    JP2008200976A|2007-02-20|2008-09-04|Sumitomo Chemical Co Ltd|Multilayered structure and method for manufacturing multilayered structure|
    GB2452086A|2007-08-24|2009-02-25|Sun Chemical Ltd|Gas barrier materials containing PVA and/or EVOH with clay|
    JP5076800B2|2007-10-17|2012-11-21|住友化学株式会社|Method for producing multilayer structure|
    GB2457294A|2008-02-08|2009-08-12|Sun Chemical Ltd|Oxygen barrier coating composition|MX354706B|2011-03-08|2018-03-16|Valspar Sourcing Inc|Water-based coating compositions and systems with improved sag resistance, and related methods.|
    US20140141262A1|2011-06-29|2014-05-22|Sun Chemical Corporation|Vinyl alcohol polymers with silane side chains and compositions comprising the same|
    GB201113385D0|2011-08-03|2011-09-21|Imerys Minerals Ltd|Coating composition|
    ITVI20120080A1|2012-04-04|2013-10-05|Gen Membrane S P A|NON-STICK PROTECTIVE PAINT FOR WATERPROOFING MEMBRANES AND ITS APPLICATION METHOD|
    CN102673078B|2012-05-11|2015-03-25|上海冠生园食品有限公司|Candy wrapping capable of reducing oxygen permeability and preparation method thereof|
    JP6006561B2|2012-07-18|2016-10-12|救急薬品工業株式会社|Inspection method for film pharmaceuticals|
    CN103881480A|2014-02-14|2014-06-25|程实|Permeability-resistant LEDheat dissipation paint and preparation method thereof|
    WO2015178856A1|2014-05-21|2015-11-26|Agency For Science, Technology And Research|One-step process for making a polymer composite coating with high barrier|
    KR102334395B1|2014-12-05|2021-12-01|삼성전자주식회사|Barrier coating compositions, composites prepared therefrom, and quantum dot polymer composite articles including the same|
    JP6841604B2|2015-06-03|2021-03-10|日本ペイント・サーフケミカルズ株式会社|Aqueous resin dispersion, manufacturing method of aqueous resin dispersion, hydrophilization treatment agent, hydrophilization treatment method, metal material and heat exchanger|
    CN105153825A|2015-08-14|2015-12-16|常德市金润新材料科技有限公司无锡新材料研究院|Moisture-retention waterborne coating as well as preparation method and application thereof|
    CN105064129B|2015-08-14|2017-12-22|常德市金润新材料科技有限公司无锡新材料研究院|The production technology and its production system of high-barrier cigarette humectation paper|
    KR102086354B1|2018-05-29|2020-03-09|중앙대학교 산학협력단|Method of forming a gas barrier film, and organic-inorganic hybrid gas barrier film|
    EP3660114A1|2018-11-27|2020-06-03|BillerudKorsnäs AB|Enhanced pvoh-based barrier layer composition, barrier layer and methods for its manufacture|
    US20220009684A1|2018-11-27|2022-01-13|Billerudkorsnas Ab|Enhanced pvoh-based barrier layer composition, barrier layer and methods for its manufacture|
    EP3660113A1|2018-11-27|2020-06-03|BillerudKorsnäs AB|Method for forming a pvoh based barrier layer on a substrate|
    CN111703165A|2020-06-12|2020-09-25|江南大学|Coating type multilayer composite high-barrier film, preparation method and application thereof|
    JP2022011056A|2020-06-29|2022-01-17|サカタインクス株式会社|Barrier coating composition and barrier composite film|
    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-02-12| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-09-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-02-27| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-08-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-10-27| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US26297909P| true| 2009-11-20|2009-11-20|
    US61/262,979|2009-11-20|
    PCT/GB2010/002148|WO2011061510A1|2009-11-20|2010-11-19|Gas barrier coatings|
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