EP1416087B1 - Procédé de fabricatioon d'un substrat revetu par couches multiples avec propriétés de barriére ameliorées - Google Patents

Procédé de fabricatioon d'un substrat revetu par couches multiples avec propriétés de barriére ameliorées Download PDF

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Publication number
EP1416087B1
EP1416087B1 EP03023090A EP03023090A EP1416087B1 EP 1416087 B1 EP1416087 B1 EP 1416087B1 EP 03023090 A EP03023090 A EP 03023090A EP 03023090 A EP03023090 A EP 03023090A EP 1416087 B1 EP1416087 B1 EP 1416087B1
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Prior art keywords
curtain
layer
multilayer
less
coated substrate
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German (de)
English (en)
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EP1416087A1 (fr
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Robert Urscheler
Francis Dobler
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/46Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
    • D21H23/48Curtain coaters
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/80Paper comprising more than one coating
    • D21H19/82Paper comprising more than one coating superposed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05CAPPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/06Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work

Definitions

  • the present invention relates to a method of producing a coated substrate having barrier properties.
  • Substrates having barrier properties are of great importance for packaging food, beverage, or other products that are sensitive to environmental influences.
  • Those substrates generally are provided with a barrier layer using well-known coating techniques such as blade coating, bar (rod) coating, reverse roll (film) coating, or air knife coating.
  • each of these application methods has its own set of problems that can result in inferior barrier quality.
  • a common feature of all these methods is that the amount of coating liquid applied to a paper web, which generally has an irregular surface with hills and valleys, is different depending on whether it is applied to a hill or a valley. Therefore, the coating thickness and thus the barrier properties will vary across the surface of the coated substrate resulting in barrier irregularities.
  • said methods are also limited in how thin a coating layer may be applied to the substrate.
  • curtain coating is a relatively new coating technique.
  • EP-A 517 223 and Japanese patent applications JP-94-89437 , JP-93-311931 , JP-93-177816 , JP-93-131718 , JP-92-298683 , JP-92-51933 , JP-91-298229 , JP-90-217327 , and JP-8-310110 disclose the use of curtain coating methods to apply one or more pigmented coating layers to a moving paper surface. More specifically, the prior art relates to:
  • curtain coating method to apply a single layer of pigmented coating to the surface of a moving web of paper, as disclosed in the prior art discussed above, is stated to offer the opportunity to produce a superior quality coated paper surface compared to that produced by conventional coating means.
  • sequential application of single layers of pigmented coating using curtain coating techniques is constrained by the dynamics of the curtain coating process. Specifically, lightweight coating applications can only be made at coating speeds below those currently employed by conventional coating processes because at high coating speeds the curtain becomes unstable and this results in an inferior coated surface. Therefore, the conventional methods of producing multi-coated papers and paperboards employ the blade, rod or roll metering processes.
  • the curtain coating method for the simultaneous coating of multiple layers is well known and is described in U.S. Patents 3,508,947 and 3,632,374 for applying photographic compositions to paper and plastic web.
  • photographic solutions or emulsions have a low viscosity and a low solids content, and are applied at low coating speeds.
  • JP-A-10-328613 discloses the simultaneous application of two coating layers onto a paper web by curtain coating to make an inkjet paper.
  • the coating compositions applied according to the teaching of that reference are aqueous solutions with an extremely low solids content of 8 percent by weight. Furthermore a thickener is added in order to obtain non-Newtonian behavior of the coating solutions.
  • the examples in JP-A-10-328613 reveal that acceptable coating quality is only achieved at line speeds below 400m/min.
  • WO 01/54828 discloses a multilayer packaging laminate produced by simultaneously applying at least two wet coating layers to a substrate web in a slide coater or curtain coater, at least one layer having oxygen barrier or scavenger properties. But there is no disclosure with respect to additional barrier properties.
  • EP-A-1 249 533 which is a prior art reference pursuant to Art. 53 EPC discloses a method for coating paper or paperboard substrates with at least two coating liquids in a free-falling curtain. But this reference is also silent with respect to multiple barrier properties.
  • WO 02/053838 relates to packaging materials whereby the appearance of grease, fat or oil staining on the packaging material is reduced or eliminated.
  • JP-B-3222221 , JP-A-4100998 and JP-A-7119083 disclose a coated paper having at least two coated layers formed on base paper by employing a curtain coater.
  • the technical problem underlying the present invention is the provision of a method of producing a coated substrate comprising barrier properties that overcomes the drawbacks of the prior art. It is a further object of the present invention to apply multiple barrier layers to a substrate, whereby each barrier layer imparts a specific barrier functionality so that by selecting said specific layers a substrate having specific barrier properties can be designed.
  • the present invention relates to a control substrate obtainable by the above method.
  • coated substrate also encompasses coated basepaper or paperboard.
  • continuous web substrate encompasses a continuous web substrate of basepaper and paperboard.
  • barrier layer is to be understood as a layer imparting at least one barrier functionality as defined above.
  • the multilayer free flowing curtain of the invention has a bottom or interface layer, a top layer and optionally one or more internal layers.
  • the coating curtain of the present invention includes at least two, preferably at least three, even more preferably at least four, more preferably at least five, and most preferably at least six layers.
  • the layers of the curtain can include one or more printing layers, one or more functional layers, one or more spacing layers, one or more coating layers, and layers imparting barrier functionalities, and the like, or any combination thereof.
  • a spacing layer is a layer that separates at least two other layers.
  • Each layer of the curtain comprises a liquid, emulsion, dispersion, suspension or solution.
  • the free-flowing curtain of step a) comprises a top layer providing printability.
  • the multilayer curtain of step a) comprises at least one layer comprising at least one pigment such as clay, kaolin, calcined clay, talc, calcium carbonate, titanium dioxide, satin white, synthetic magadiite, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, silica, alumina trihydrate, mica, and diatomaceous earth.
  • Kaolin, talc, calcium carbonate, titanium dioxide, satin white and synthetic polymer pigment, including hollow polymer pigments are particularly preferred.
  • at least one layer may comprise certain platy type pigments such as, for example, talc, laminar nanoparticles, high aspect ratio clay, mica, synthetic magadiite and the like.
  • At least one layer comprises a binder.
  • Binders useful in the practice of the present invention include, for example, styrene-butadiene latex, styrene-acrylate latex, styrene-butadiene-acrylonitrile latex, styrene-acrylate-acrylonitrile latex, styrene-butadiene-acrylate-acrylonitrile latex, styrene-maleic anhydride latex, styrene-acrylate-maleic anhydride latex, polysaccharides, proteins, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, cellulose and cellulose derivatives.
  • binders examples include carboxylated styrene-butadiene latex, carboxylated styrene-acrylate latex; carboxylated styrene-butadiene-acrylonitrile latex, carboxylated styrene-maleic anhydride latex, carboxylated polysaccharides, proteins, polyvinyl alcohol, carboxylated polyvinyl acetate latex and mixtures thereof.
  • polysaccharides include agar, sodium alginate, and starch, including modified starches such as thermally modified starch, carboxymethylated starch, hydroxyelthylated starch, and oxidized starch
  • modified starches such as thermally modified starch, carboxymethylated starch, hydroxyelthylated starch, and oxidized starch
  • proteins that can be suitably employed in the process of the present invention include albumin, soy protein, and casein.
  • each layer of the curtain can be adjusted to obtain the desired coated substrate properties.
  • At least one of the layers of the multilayer curtain of step a) suitably has a dry coatweight of less than 30 g/m 2 , preferably less than 20 g/m 2 , more preferably less than 10 g/m 2 , even more preferably less than 5 g/m 2 , and most preferably less than 3 g/m 2 .
  • the coating prepared from the multilayer curtain of step a) preferably has a dry coatweight on the paper produced of from 3 to 60 g/m 2 , more preferably from 5 to 25 g/m 2 .
  • the coating prepared from the curtain desirably has a dry coatweight of less than 60 g/m 2 , alternatively less than 30 g/m 2 , alternatively less than 20 g/m 2 , alternatively less than 15 g/m 2 , alternatively less than 12 g/m 2 , alternatively less than 10 g/m 2 , and most preferably less than 5 g/m 2 .
  • each barrier layer present in the multilayer curtain of the present invention preferably has a solids content of up to 75 percent by weight and a viscosity of up to 3,000 cps (Brookfield, spindle 5, 100 rpm, 25°C) more preferably 30 to 2,000 cps.
  • the coatweight of a barrier layer is from 0.1 to 30 g/m 2 , more preferably 1 to 10 g/m 2 .
  • the viscosity of the barrier layer is at least 50 cps, is preferably at least 100 cps, is more preferably at least 200 cps, and even more preferably is from 230 cps to 2000 cps.
  • the free-flowing curtain of step a) preferably has a solids content of at least 10 weight percent, preferably at least 40 weight percent, more preferably at least 45 weight percent, and most preferably at least 50 weight percent.
  • the viscosity of the layers of the curtain is not critical so long as the layers form a free-flowing curtain.
  • the curtain of step a) of the invention can further include one or more non-barrier-functional layers.
  • the purpose of the functional layer is to impart a desired functionality to the coated paper.
  • Functional layers can be selected to provide, for example, printability, sheet stiffness, sheet flexibility, fold crack resistance, paper sizing properties, release properties, adhesive properties, heat seal properties, abrasion resistance properties and optical properties, such as, color, brightness, opacity, gloss, etc.
  • Functional coatings that are very tacky in character would not normally be coated by conventional consecutive coating processes because of the tendency of the tacky coating material to adhere the substrate to guiding rolls or other coating equipment.
  • the simultaneous multilayer method allows such functional coatings to be placed underneath a topcoat that shields the functional coating from contact with the coating machinery.
  • the barrier properties of the coated substrate are maintained even after the substrate is folded or bent.
  • the fold crack resistance of the coated substrate can be determined according to a visual inspection of the folded substrate using a Heildelberg Quickfolder to crease the coated sample.
  • the fold crack resistance of coated substrate of the present invention is preferably at least 2.
  • a flexible functional layer and/or a flexible barrier layer is employed in order to increase the fold resistance of the coated substrate.
  • the multilayer curtain of step a) comprises at least one layer imparting barrier functionalities comprising at least one or more components such as, for example, ethylene acrylic acid copolymers, ethylene vinyl alcohol copolymers, polyurethanes, epoxy resins, polyesters, polyolefins, carboxylated styrene butadiene latexes, carboxylated styrene acrylate latexes, polyvinylidiene chlorides, polyvinyl chlorides, starches, protein styrene-acrylic copolymers, styrene maleic anhydrides, polyvinyl alcohols, polyvinyl acetates, carboxymethyl celluloses, silicones, waxes, neoprenes, polyhydroxy ethers, lacquers, polylactic acids, copolymers of polylactic acid, polymers containing fluorine atoms, copolymers of acrylonitrile such as carboxylated styrene butadiene
  • the interface layer which is the layer that comes in contact with the substrate to be coated, is not a barrier layer.
  • One important function of the interface layer is to promote wetting of the substrate.
  • the interface layer can have more than one function. For example, in addition to wetting, it may provide coverage of the substrate, and improved functional performance such as adhesion, sizing, stiffness or a combination of functions.
  • This layer is preferably a relatively thin layer if it is not providing additional functionality.
  • the coatweight of the interface layer suitably is from 0.1 to 30 g/m 2 , preferably from 1 to 3 g/m 2 .
  • the solids content of the interface layer suitably is from 0.1 to 75 percent, based on the weight of the interface layer in the curtain.
  • the interface layer is relatively low in solids, preferably having a solids content of from 0.1 to 40 percent.
  • the viscosity of the interface layer is at least 55 cps, is more preferably at least 100 cps, and is even more preferably at least 200 cps.
  • the viscosity of the interface layer is from 230 cps to 2000 cps.
  • At least one layer of the multilayer free-flowing curtain of step a) comprises additives customary to a person skilled in the art, such as, for example, at least one surfactant, at least one dispersant, at least one lubricant, at least one water-retention agent, at least one crosslinking agent, at least one optical whitening agent, at least one pigment dye or colorant, at least one thickening agent, at least one defoamer, at least one antifoaming agent, at least one biocide or at least one soluble dye or colorant, or the like.
  • additives customary to a person skilled in the art, such as, for example, at least one surfactant, at least one dispersant, at least one lubricant, at least one water-retention agent, at least one crosslinking agent, at least one optical whitening agent, at least one pigment dye or colorant, at least one thickening agent, at least one defoamer, at least one antifoaming agent, at least one biocide or at
  • the coating colors are deaerated prior to coating in order to remove air bubbles in the coating, which may cause coating defects.
  • the curtain layers can be simultaneously applied according to the present invention by using a curtain coating unit with a slide nozzle arrangement for delivering multiple liquid layers to form a continuous, multilayer curtain.
  • a curtain coating unit with a slide nozzle arrangement for delivering multiple liquid layers to form a continuous, multilayer curtain.
  • an extrusion type supplying head such as a slot die or nozzle, having several adjacent extrusion nozzles can be employed in the practice of the present invention.
  • the barrier properties of the obtained coated substrate can be determined by methods customary to a person skilled in the art.
  • the coated substrate has a Kit value of at least 5 in the flat-test and/or a Kit value of at least 3 in the creased-test when an oil and/or grease barrier layer is present in the multilayer curtain.
  • the coated substrate will pass the hot oil (oleic acid) stain resistance test, the details of which are specified herein below.
  • the coated paper or paper board has a Kit value of at least 8 in the flat test, more preferably at least 11 and most preferably at least 12.
  • the coated paper or paper board has a Kit value of at least 4 in the creased Kit, more preferably at least 7.
  • the coated substrate has preferably a water vapor transmission rate of less than 40 g/(m 2 day) (50 percent relative humidity, 23°C), more preferably less than 30 g/(m 2 day) and most preferred less than 10 g/(m 2 day).
  • the coated substrate has a 10 minute Cobb value of less than 12 g/m 2 when a water resistance layer is present in the multilayer curtain, more preferably less than 6, even more preferably less than 1.5 g/m 2 , and most preferably less than 0.5 g/m 2 .
  • the coated substrate has an oxygen transmission rate of less than 150 cm 3 /(m 2 /24h/bar) (1 atm, 23°C, 90 percent relative humidity) when an oxygen barrier layer is present in the multilayer curtain, more preferably less than 100 cm 3 /(m 2 /24h/bar), and even more preferably less than 50 cm 3 /(m 2 /24h/bar).
  • the continuous web substrate of step b) is neither precoated nor precalendered. In another embodiment the continuous web substrate of step b) is not precoated, and in a further embodiment the continuous web substrate of step b) is not precalendered.
  • the continuous web substrate of step b) can have a web velocity that is suitable for preparing an acceptable coated substrate.
  • the velocity preferably is at least 200 m/min, more preferably at least 400 m/min, even more preferably at least 500 m/min, and most preferably at least 800 m/min.
  • the continuous web substrate of step b) preferably has a grammage, or basis weight, of from 30-400 g/m 2 .
  • Figure 1 is an explanatory cross-sectional view of a preferred curtain coating unit 1 with a slide nozzle arrangement 2 for delivering multiple streams 3 of curtain layer to form a continuous, multilayer curtain 4.
  • a dynamic equilibrium state is reached, the flow amount of the curtain layers flowing into the slide nozzle arrangement 2 is completely balanced with the flow amount flowing out of the slide nozzle arrangement.
  • the free falling multilayer curtain 4 comes into contact with web 5, which is running continuously, and thus the web 5 is coated with multiple layers of the respective curtain layers.
  • the running direction of the web 5 is changed immediately before the coating area by means of a roller 6 to minimize the effect of air flow accompanying the fast moving web 5.
  • the advantage of the present invention over the prior art is that a coated barrier substrate having specific barrier properties can be obtained by combining specific functional layers within the multilayer curtain. Said technique makes it possible to apply several barrier layers to a substrate in one coating step. Furthermore, the applied barrier layers can be thinner than the barrier layers of the current state of the art.
  • the method of the present invention also overcomes wetting or water repellency issues of coating color on a previously dry barrier layer, which is the case with multistep film press or blade coating.
  • the coated substrates of the present invention are useful in flexible and liquid packaging and can also be used as an economical protection for fabricated products.
  • Hot oil (oleic acid) at 60°C is placed on the sample for 1 hour at room temperature and the sample is visually inspected for staining. If there is a stain the result is a failure. Passing samples at room temperature are placed in an oven having a temperature of 60°C for 24H, after which the oil is rubbed off and the sample is visually inspected for staining. If there is no stain the result is a pass, if there is a stain present the result is a failure.
  • the water vapor barrier is measured using the Technical Association of the Pulp and Paper Industry (TAPPI) test T-448. This procedure describes the means to test moisture vapor transmission rate at a temperature of 23°C and 50 percent relative humidity. The unit is [g/m 2 /day].
  • TAPPI Technical Association of the Pulp and Paper Industry
  • the water resistance is measured as the resistance of the coating to the passage of puddled surface water.
  • the test is the Cobb Size.
  • the Cobb method measures the water absorptiveness of paper and is conducted in accordance to the test procedure defined by TAPPI T-441.
  • the 3M Kit Test is performed according to the test procedure defined by TAPPI T-559.
  • the oxygen barrier test is performed according to the test procedure defined by ASTM D 1434.
  • the fold crack resistance of the coated substrate can determined according to a visual inspection of the folded substrate using a Heildelberg Quickfolder to crease the coated sample. Prior to folding, the samples are conditioned at 25 °C at 50 percent RH for 24 hours and then a black ink film is applied to enhance the contrast. After folding the crease is visual inspected and rated on a scale of 1 to 5. A rating of 1 indicates no damage to the film in the crease. A rating of 2 indicates some damage but the film remains intact. A rating of 3 indicates the film is damaged to the point that some delaminating of the film from the substrate has occurred. A rating of 4 indicates the film has failed but there is no fiber damage. A rating of 5 indicates a failed film and fiber damage.
  • the viscosity is measured using a Brookfield RVT viscometer (available from Brookfield Engineering Laboratories, Inc., Stoughton, Massachusetts, USA). For viscosity determination, 600 ml of a sample are poured into a 1000 ml beaker and the viscosity is measured at 25°C at a spindle speed of 20 and 100 rpm.
  • the coatweight achieved in each paper coating experiment is calculated from the known volumetric flow rate of the pump delivering the coating to the curtain coating head, the speed at which the continuous web of paper is moving under the curtain coating head, the density and percent solids of the curtain, and the width of the curtain.
  • the density of a curtain layer is determined by weighing a 100-millilitre sample of the coating in a pyknometer.
  • Paper gloss is measured using a Zehntner ZLR-1050 instrument at an incident angle of 75°.
  • the test is carried out on a Pruefbau Test Printing unit with Lorrilleux Red Ink No. 8588.
  • An amount of 0.8 g/m 2 (or 1.6 g/m 2 respectively) of ink is applied to coated paper test strips mounted on a long rubber-backed platen with a steel printing disk.
  • the pressure of the ink application is 1,000 N and the speed is 1 m/s.
  • the printed strips are dried for 12 hours at 20°C at 55 percent minimum room humidity.
  • the gloss is then measured on a Zehntner ZLR-1050 instrument at an incident angle of 75°.
  • the test is carried out on a Pruefbau Test Printing unit. 250 mm 3 of ink (Huber No 520068) is distributed for 1 minute on the distributor. A metal printing disk is inked by being placed on the distributor for 15 seconds. The disk is placed on the first printing station. At the second printing station an uninked metal printing disk is placed, with a pressure of 400N.
  • the coated paper strip mounted on a rubber-backed platen, is printed with a printing pressure of 1000N at a speed of 1.5m/s. Time 0 is taken when printing happens.
  • the strip is printed at the first station, move the strip towards second printing station, or Set off station, by moving the hand lever.
  • the set off station place a blank paper strip between the printed paper and the disk.
  • the blank paper is pressed against the printed sample in the set off station by moving the hand lever.
  • the amount of non-immobilized ink from the printed paper transferred to the blank paper is measured by ink densities as given by optical density measurements.
  • Brightness is measured on a Zeiss Elrepho 2000. Brightness is measured according to ISO standard 2469 on a pile of sheets. The result is given as R457.
  • This test measures the ability of the paper surface to accept the transfer of ink without picking.
  • the test is carried out on an A2 type printability tester, commercially available from IGT Reprotest BV. Coated paper strips (4 mm x 22 mm) are printed with inked aluminum disks at a printing pressure of 36 N with the pendulum drive system and the high viscosity test oil (red) from Reprotest BV. After the printing is completed, the distance where the coating begins to show picking is marked under a stereomicroscope. The marked distance is then transferred into the IGT velocity curve and the velocities in cm/s are read from the corresponding drive curve. High velocities mean high resistance to dry pick.
  • the test is carried out on a Pruefbau Test Printing unit equipped with a wetting chamber.
  • 500 mm3 of printing ink (Hueber 1, 2, 3 or 4, depending on overall wet pick resistance of the paper) is distributed for 2 min on the distributor; after each print re-inking with 60 mm3 of ink.
  • a vulcanized rubber printing disk is inked by being placed on the distributor for 15 sec.
  • 10 mm3 of distilled water is applied in the wetting chamber and distributed over a rubber roll.
  • a coated paper strip is mounted on a rubber-backed platen and is printed with a printing pressure of 600N and a printing speed of 1 m/s.
  • a central strip of coated paper is wetted with a test stripe of water as it passes through the wetting chamber.
  • the roughness of the coated paper surface is measured with a Parker PrintSurf roughness. tester.
  • a sample sheet of coated paper is clamped between a cork-melinex platen and a measuring head at a clamping pressure of 1,000 kPa.
  • Compressed air is supplied to the instrument at 400 kPa and the leakage of air between the measuring head and the coated paper surface is measured.
  • a higher number indicates a higher degree of roughness of the coated paper surface.
  • the solvent resistance of a barrier layer is its ability to withstand solvent attack with minimal change in appearance, dimensions, mechanical properties, and weight over a period of time. Test conditions include the length of exposure, concentration, temperature, and internal stress. Solvent resistance of multilayer barrier substrates can be evaluated using ASTM D543. The final classification as solvent resistant depends on the application.
  • a barrier that retards loss of aroma is a material that inhibits permeation of the aroma through the barrier layer.
  • Permeability is determined by measurement of aroma transmission through specimens under controlled conditions of temperature and driving force. Numerous analytical techniques, depending on the nature of the aroma compound, can be used to detect permeation. Permeation results are reported in units of mass over path length, time and pressure difference.
  • the formulations were coated onto paper moving at 500m/min according to the following procedure.
  • a multilayer slide die type curtain coater manufactured by Troller Schweizer Engineering (TSE, Murgenthal, Switzerland) was used.
  • the curtain coating apparatus was equipped with edge guides lubricated with a trickle of water and with a vacuum suction device to remove this edge lubrication water at the bottom of the edge guide just above the coated paper edge.
  • the curtain coater was equipped with a vacuum suction device to remove interface surface air from the paper substrate upstream from the curtain impingement zone. The height of the curtain was 300 mm. Coating formulations were deaerated prior to use to remove air bubbles.
  • the pH of the pigmented coatings formulations was adjusted by adding NaOH solution (10 percent) to a value as indicated in table 1. Water was added as needed to adjust the solids content of the formulations.
  • a pigmented layer (slot 1) was placed next to the paper.
  • This formulation contained a high amount of a low Tg latex to ensure good fold cracking resistance for the barrier paper and a water soluble polymer to form the interface layer.
  • the next layer (slot 2) contained an ethylene acrylic acid dispersion to form a water and water vapor barrier layer.
  • the next layer (slot 3) contained a pigmented layer with a high amount of a low Tg latex to ensure good fold cracking resistance for the barrier paper.
  • the next layer (slot 4) contained a water soluble ethylene vinyl alcohol copolymer to provide good grease and oil resistance.
  • the top layer (slot 5) was a pigment layer with an optical brightening agent in the formulation to form a good printing surface.
  • Example 2 The method of Example 1 was repeated except that the intermediate coating layer (Slot 3 of Table 1) was removed and the coatweights of the barrier coating layers as well as the top printing layer were adjusted as shown in Table 2.
  • Table 2 Slot 1 Slot 2 Slot 3 Slot 4 Carbonate 70 70 Clay 30 30 Latex (A) 11 Latex (B) 50 PVOH 1 2.5 PE Dispersion (B) 100 PE Dispersion (A) 100 Surfactant 0.4 0.2 0.4 0.2 Whitener 1 Density (g/cc) 1.34 0.98 1.03 1.57 Viscosity (100 rpm Brookfield)(mPa ⁇ s) 430 320 300 1040 Coatweight (g/m 2 ) 6 3 1.5 6 pH 8.5 8.2 9.1 8.5 Solids (percent) 59.9 34.7 16 65.1
  • Example 2 The method of Example 2 was repeated except that coatweight of Slot 1 was decreased to 2 g/m 2 and the coatweights of the barrier layers Slot 2 and Slot 3 were increased to 5 and 2.5 g/m 2 respectively.
  • Table 3 contains the Cobb, MVTR, Kit and Hot Oil properties for examples.
  • Example 1 8.9 9.12/162 7/fail pass
  • Example 2 10.3 n.m./119 5/n.m. pass
  • Table 3 shows that it is possible to have a combination of improved water and oil/grease barrier properties from the multilayer curtain.
  • Table 4 summarizes the coated paper properties for the examples.
  • Table 4 Coated Paper Properties Example 1
  • Example 2 Example 3 PAPER GLOSS 75° 63 62 66 INK GLOSS 75°; 0.8 g/m 2 INK 85 77 88 INK GLOSS 75°; 1.6 g/m 2 INK 91 88 93 SMOOTHNESS PPS H 1000 1.3 1.3 1.0 ISO BRIGHTNESS R 457 92.5 93.7 93.7 IGT DRY PICK >110 >110 >110 WET PICK: INK TRANSFER 2 24 23 WET PICK: INK REFUSAL 98 70 75 WET PICK: WET PICK 0 6 2 INK SET OFF AFTER 15 SEC. 1.22 1.09 1.13 INK SET OFF AFTER 30 SEC. 1.14 0.92 1.10 INK SET OFF AFTER 60 SEC. 1.10 0.72 0.93 INK SET OFF AFTER 120 SEC. 1.07 0.64 0.89

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Claims (26)

  1. Procédé de production de substrats revêtus, lequel procédé comprend les étapes suivantes :
    a) former un rideau composite multicouche en écoulement libre, lequel rideau multicouche en écoulement libre comporte au moins deux couches qui apportent au moins deux fonctions différentes de barrière, choisies parmi les suivantes : fonction de barrière aux huiles et/ou aux graisses, fonction de barrière à la vapeur d'eau, fonction de résistance à l'eau, fonction de barrière aux arômes, fonction de barrière aux solvants organiques, et fonction de barrière à l'oxygène ;
    b) et mettre ce rideau en contact avec un substrat en bande continue ; étant entendu que :
    - dans le cas où il y a dans le rideau multicouche une couche formant barrière aux huiles et/ou aux graisses, le substrat revêtu obtient une note d'au moins 5 dans le test Kit sur échantillon plat ;
    - dans le cas où il y a dans le rideau multicouche une couche formant barrière à la vapeur d'eau, le substrat revêtu laisse passer de la vapeur d'eau à une vitesse inférieure à 50 g/(m2.jour), à 23 °C et sous 50 % d'humidité relative ;
    - dans le cas où il y a dans le rideau multicouche une couche de résistance à l'eau, le substrat revêtu obtient un indice Cobb à 10 minutes inférieur à 20 g/m2 ;
    - et dans le cas où il y a dans le rideau multicouche une couche formant barrière à l'oxygène, le substrat revêtu laisse passer de l'oxygène à une vitesse inférieure à 200 cm3/(m2.bar.jour), à 23 °C sous 1 atm et sous 90 % d'humidité relative.
  2. Procédé conforme à la revendication précédente, caractérisé en ce que le rideau en écoulement libre de l'étape (a) comprend une couche supplémentaire de dessus, qui permet au rideau d'être imprimé.
  3. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le cas où il y a dans le rideau de l'étape (a) une couche formant barrière aux huiles et/ou aux graisses, le substrat revêtu obtient une note d'au moins 8, et de préférence d'au moins 11, dans le test Kit sur échantillon plat.
  4. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le cas où il y a dans le rideau de l'étape (a) une couche formant barrière à la vapeur d'eau, le substrat revêtu laisse passer de la vapeur d'eau à une vitesse inférieure à 40 g/(m2.jour), à 23 °C et sous 50 % d'humidité relative, et de préférence inférieure à 30 g/(m2.jour), à 23 °C et sous 50 % d'humidité relative.
  5. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le cas où il y a dans le rideau de l'étape (a) une couche de résistance à l'eau, le substrat revêtu obtient un indice Cobb à 10 minutes inférieur à 12 g/m2, et de préférence inférieur à 1,5 g/m2.
  6. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le cas où il y a dans le rideau de l'étape (a) une couche formant barrière à l'oxygène, le substrat revêtu laisse passer de l'oxygène à une vitesse inférieure à 150 cm3/(m2.bar.(24 h)), à 23 °C sous 1 atm et sous 90 % d'humidité relative, et de préférence inférieure à 100 cm3/(m2.bar.(24 h)), à 23 °C sous 1 atm et sous 90 % d'humidité relative.
  7. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le rideau multicouche de l'étape (a) comporte une couche d'interface supplémentaire qui est la couche qui entre en contact avec le substrat.
  8. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le rideau multicouche de l'étape (a) comporte au moins une couche supplémentaire qui apporte de la résistance à la fissuration au pliage.
  9. Procédé conforme à l'une des revendications précédentes, caractérisé en ce qu'au moins l'une des couches du rideau multicouche de l'étape (a) présente à sec un poids de couche inférieur à 30 g/m2, de préférence inférieur à 20 g/m2, et mieux encore inférieur à 10 g/m2.
  10. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le rideau multicouche de l'étape (a) présente à sec un poids de couche inférieur à 60 g/m2, et de préférence inférieur à 30 g/m2.
  11. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le rideau multicouche de l'étape (a), il y a au moins 3 couches, de préférence au moins 4 couches, mieux encore au moins 5 couches et surtout au moins 6 couches.
  12. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le rideau multicouche de l'étape (a), il y a au moins une couche qui contient au moins un pigment.
  13. Procédé conforme à la revendication 12, caractérisé en ce que le pigment est choisi dans l'ensemble formé par les suivants : argile, kaolin, argile calcinée, talc, carbonate de calcium, nanoparticules laminaires, argiles à haut rapport de forme, dioxyde de titane, blanc satin, pigments polymères synthétiques, oxyde de zinc, sulfate de baryum, gypse, magadiite synthétique, silice, trihydrate d'alumine, mica, et terre de diatomées.
  14. Procédé conforme à l'une des revendications précédentes, caractérisé en ce qu'au moins l'une des couches conférant une fonction de barrière du rideau multicouche de l'étape (a) comprend au moins un ou plusieurs composants choisi(s) dans l'ensemble constitué par les suivants : copolymères d'éthylène et d'acide acrylique, copolymères d'éthylène et d'alcool vinylique, polyuréthanes, résines époxy, polyesters, polyoléfines, latex de butadiène et de styrène carboxylés, latex d'acrylate et de styrène carboxylés, poly(chlorure de vinylidène), poly(chlorure de vinyle), amidons, protéines, copolymères de styrène et de monomère acrylique, copolymère de styrène et d'anhydride maléique, poly(alcool vinylique), poly(acétate de vinyle), carboxyméthyl-celluloses, silicones, cires, caoutchoucs néoprènes, polyéthers hydroxylés, laques, poly(acide lactique), copolymères à base d'acide lactique, polymères fluorés, copolymères à base d'acrylonitrile, tels les copolymères de styrène, de butadiène et d'acrylonitrile carboxylés, ainsi que leurs mélanges.
  15. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le rideau multicouche en écoulement libre de l'étape (a), il y a au moins une couche qui comprend au moins un tensioactif.
  16. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le rideau multicouche en écoulement libre de l'étape (a) contient au moins 10 % en poids de solides, de préférence au moins 40 % en poids de solides, et surtout au moins 45 % en poids de solides.
  17. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le substrat en bande continue de l'étape (b) est un papier support ou un carton.
  18. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le substrat en bande continue de l'étape (b) n'a subi ni couchage préalable, ni passage préalable en calandre.
  19. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le substrat en bande continue de l'étape (b) se déplace avec une vitesse de bande d'au moins 200 m/min, de préférence d'au moins 400 m/min, et surtout d'au moins 500 m/min.
  20. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le substrat en bande continue de l'étape (b) présente un grammage ou un poids surfacique de 30 à 400 g/m 2
  21. Procédé conforme à l'une des revendications précédentes, carac-térisé en ce que le rideau multicouche de l'étape (a) comporte au moins une couche supplémentaire qui apporte au moins l'une des propriétés suivantes : rigidité de feuille, flexibilité de feuille, caractéristiques anti-adhésives, caractéristiques adhésives, maîtrise du frottement, aptitude au thermoscellage, et résistance à l'abrasion.
  22. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que le rideau est formé au moyen d'une filière en fente.
  23. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le rideau, il y a au moins une couche qui comprend un poly(oxyéthylène).
  24. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que, dans le rideau, la couche d'interface comprend un poly(oxyéthylène).
  25. Substrat revêtu, accessible par un procédé conforme à l'une des revendications précédentes.
  26. Substrat revêtu, conforme à la revendication 25, caractérisé en ce que le substrat revêtu est un papier couché ou un carton couché.
EP03023090A 2002-10-15 2003-10-15 Procédé de fabricatioon d'un substrat revetu par couches multiples avec propriétés de barriére ameliorées Expired - Lifetime EP1416087B1 (fr)

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PCT/US2002/032938 WO2004035929A1 (fr) 2002-10-15 2002-10-15 Procede de production de substrat a revetement multicouche aux proprietes barriere ameliorees
WOPCT/US02/32938 2002-10-15

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EP1416087B1 true EP1416087B1 (fr) 2010-09-29

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JP (1) JP4903359B2 (fr)
CN (1) CN1323766C (fr)
AT (1) ATE483065T1 (fr)
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BR (1) BR0305415B1 (fr)
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US7909962B2 (en) 2001-04-14 2011-03-22 Dow Global Technologies Llc Process for making multilayer coated paper or paperboard
US9903072B2 (en) 2011-09-15 2018-02-27 Imerys Usa, Inc. Compositions comprising kaolin treated with a styrene-based polymer and related methods
US11504952B2 (en) 2017-10-04 2022-11-22 Nippon Paper Industries Co., Ltd. Barrier material
EP3943661A1 (fr) 2020-07-20 2022-01-26 Schoeller Technocell GmbH & Co. KG Matière d'emballage doté d'une couche barrière à base d'eau
US11549216B2 (en) 2020-11-11 2023-01-10 Sappi North America, Inc. Oil/grease resistant paper products

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EP1416087A1 (fr) 2004-05-06
JP4903359B2 (ja) 2012-03-28
CN1500563A (zh) 2004-06-02
ATE483065T1 (de) 2010-10-15
CN1323766C (zh) 2007-07-04
BR0305415B1 (pt) 2013-12-10
AU2002335033A1 (en) 2004-05-04
DE60334356D1 (de) 2010-11-11
BR0305415A (pt) 2004-06-15
JP2004148307A (ja) 2004-05-27

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