EP1416087A1 - Method of producing a multilayer coated substrate having improved barrier properties - Google Patents

Method of producing a multilayer coated substrate having improved barrier properties Download PDF

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Publication number
EP1416087A1
EP1416087A1 EP03023090A EP03023090A EP1416087A1 EP 1416087 A1 EP1416087 A1 EP 1416087A1 EP 03023090 A EP03023090 A EP 03023090A EP 03023090 A EP03023090 A EP 03023090A EP 1416087 A1 EP1416087 A1 EP 1416087A1
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EP
European Patent Office
Prior art keywords
curtain
layer
multilayer
coated substrate
barrier
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Granted
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EP03023090A
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German (de)
French (fr)
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EP1416087B1 (en
Inventor
Robert Urscheler
Francis Dobler
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
    • D21H23/48—Curtain coaters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus 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
    • B05C9/06—Apparatus 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 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.
  • 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.
  • 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 1 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.
  • 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 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.

Abstract

The present invention refers to a method of producing a coated substrate comprising the steps of:
  • a) forming a composite, multilayer free flowing curtain, whereby the multilayer free flowing curtain comprises at least two layers imparting at least two different barrier functionalities and
  • b) contacting the curtain with a continuous web substrate.
    •

    Description

    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. However, each of these application methods has its own set of problems that can result in inferior barrier quality. Furthermore, 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. Moreover, said methods are also limited in how thin a coating layer may be applied to the substrate. Another drawback of said coating methods known in the prior art that at each coating station only a single layer can be applied to the substrate. If several barrier layers are to be applied to a substrate, then each of said coating layers needs a separate coating station or subsequent coating in a further coating machine. This sequential approach to making multilayer coatings is undesirable in that the subsequent coating steps of the prior art fail when attempting to apply an additional layer to a layer that is very hydrophobic and water repellent. Despite their drawbacks, these coating methods are still the dominant processes in the paper industry due to their economics, especially since very high line speeds can be achieved.
    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:
  • (i) The curtain coating method being used to apply a single layer of pigmented coating to a basepaper substrate to produce a single-layer-pigmented coating on paper.
  • (ii) The curtain coating method being used to apply a single priming layer of pigmented coating to a basepaper substrate prior to the application of a single layer of pigmented topcoat applied by a blade type coating process. Thus a multilayer-pigmented coating of paper was achieved by sequential applications of pigmented coating.
  • (iii) The curtain coating method being used to apply a single topcoating layer of pigmented coating to a basepaper substrate that has previously been primed with a single layer of pigmented precoat that was applied by a blade or a metering roll type coating process. Thus a multilayer-pigmented paper coating was achieved by sequential applications of pigmented coating.
  • (iv) The curtain coating method being used to apply two single layers of specialized pigmented coating to a basepaper substrate such that the single layers were applied in consecutive processes. Thus a multilayer-pigmented coating of paper was achieved by sequential applications of pigmented coating.
    • The use of a 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. However, the 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. Unfortunately, the application of consecutive single layers of pigmented coatings to paper or paperboard at successive coating stations, whether by any of the above coating methods, remains a capital-intensive process due to the number of coating stations required, the amount of ancillary hardware required, for example, drive units, dryers, etc., and the space that is required to house the machinery.
    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. However, photographic solutions or emulsions have a low viscosity and a low solids content, and are applied at low coating speeds.
    In addition to photographic applications, the simultaneous application of multiple coatings by curtain coating methods is known from the art of making pressure sensitive copying paper. For example, U.S. Patent 4,230,743 discloses in one embodiment the simultaneous application of a base coating comprising microcapsules as main component and a second layer comprising a color developer as a main component onto a travelling web. However, it is reported that the resulting paper has the same characteristics as the paper made by sequential application of the layers. Moreover, the coating composition containing the color developer is described as having a viscosity between 10 and 20 cps at 22°C.
    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.
    In view of the deficiencies of the prior art, it would be desirable to have an economical, improved process for preparing substrates, such as paper or paperboard, having barrier properties.
    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 technical problem of the present invention is solved by a method of producing a coated substrate comprising the steps of:
  • a) forming a composite, multilayer free flowing curtain, whereby the multilayer free flowing curtain comprises at least two layers imparting at least two different barrier functionalities selected from the group consisting of oil and/or grease barrier functionality, water vapor barrier functionality, water resistance functionality, solvent barrier functionality, aroma barrier functionality, and oxygen barrier functionality and
  • b) contacting the curtain with a continuous web substrate, whereby,
    • in case an oil and/or grease barrier layer is present in the multilayer curtain the coated substrate has a Kit value of at least 5 in the flat-test,
    in case a water vapor barrier layer is present in the multilayer curtain the coated substrate has a water vapor transmission rate of less than 50 g/(m2/day) (50 percent relative humidity, 23°C),
    in case a water resistance layer is present in the multilayer curtain the coated substrate has a 10 minute Cobb value of less than 20 g/m2,
    in case an oxygen barrier layer is present in the multilayer curtain the coated substrate has an oxygen transmission rate of less than 200 cm3/(m2/24h/bar) (1 atm, 23°C, 90 percent relative humidity). For the purposes of the present invention, when an organic solvent barrier functionality is present, the coating provides a barrier to organic solvents according to commercially acceptable standards. For the purposes of the present invention, when an aroma barrier functionality is present, the coating provides a barrier to aromas according to commercially acceptable standards,
    As used herein, the term "coated substrate" also encompasses coated basepaper or paperboard. The term "continuous web substrate" encompasses a continuous web substrate of basepaper and paperboard. Furthermore, as used herein, the term "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. In a preferred embodiment, the free-flowing curtain of step a) comprises a top layer providing printability.
    Preferably, 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. For enhanced barrier properties 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.
    Furthermore, in the multilayer curtain of step a) 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. Examples of preferred binders 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. Examples of polysaccharides include agar, sodium alginate, and starch, including modified starches such as thermally modified starch, carboxymethylated starch, hydroxyelthylated starch, and oxidized starch, Examples of proteins that can be suitably employed in the process of the present invention include albumin, soy protein, and casein.
    The coatweight of 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/m2, preferably less than 20 g/m2, more preferably less than 10 g/m2, even more preferably less than 5 g/m2, and most preferably less than 3 g/m2.
    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/m2, more preferably from 5 to 25 g/m2. The coating prepared from the curtain desirably has a dry coatweight of less than 60 g/m2, alternatively less than 30 g/m2, alternatively less than 20 g/m2, alternatively less than 15 g/m2, alternatively less than 12 g/m2, alternatively less than 10 g/m2, and most preferably less than 5 g/m2.
    The viscosity and solids content of each barrier layer can vary widely depending on the desired function. Any combination of viscosity and solids content can be employed so long as suitable barrier properties are obtained. 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. Preferably, the coatweight of a barrier layer is from 0.1 to 30 g/m2, more preferably 1 to 10 g/m2. Desirably, 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, on the other hand, allows such functional coatings to be placed underneath a topcoat that shields the functional coating from contact with the coating machinery.
    Desirably, 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. In one embodiment of the invention, a flexible functional layer and/or a flexible barrier layer is employed in order to increase the fold resistance of the coated substrate.
    In a preferred embodiment 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 acrylonitrile copolymers, and mixtures thereof.
    Preferably, in the composite multilayer free-flowing curtain of step a) 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/m2, preferably from 1 to 3 g/m2. 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. In one embodiment, the interface layer is relatively low in solids, preferably having a solids content of from 0.1 to 40 percent. Preferably, 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. Preferably the viscosity of the interface layer is from 230 cps to 2000 cps.
    In a preferred embodiment, 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. Mixtures of additives can be employed.
    Preferably, 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. Alternatively, 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.
    Preferably, 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. Preferably, in the case where 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. In a preferred embodiment, when an oil and/or grease barrier layer is present in the multilayer curtain of step a) 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. Moreover, in case that an oil and/or grease barrier layer is present in the multilayer curtain of step a) 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/(m2 day) (50 percent relative humidity, 23°C), more preferably less than 30 g/(m2 day) and most preferred less than 10 g/(m2 day).
    Preferably, the coated substrate has a 10 minute Cobb value of less than 12 g/m2 when a water resistance layer is present in the multilayer curtain, more preferably less than 6, even more preferably less than 1.5 g/m2, and most preferably less than 0.5 g/m2.
    Preferably, the coated substrate has an oxygen transmission rate of less than 150 cm3/(m2/24h/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 cm3/(m2/24h/bar), and even more preferably less than 50 cm3/(m2/24h/bar).
    In one embodiment, 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/m2.
    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. When 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.
    The present invention is exemplified by the following examples. All parts and percentages are by weight unless otherwise indicated.
    Examples Test Methods Hot Oil Test
    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.
    Moisture Vapor Transmission Rate (MVTR)
    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/m2/day].
    Cobb Test
    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.
    Kit Test
    The 3M Kit Test is performed according to the test procedure defined by TAPPI T-559.
    Oxygen Barrier
    The oxygen barrier test is performed according to the test procedure defined by ASTM D 1434.
    Fold Cracking Resistance
    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.
    Brookfield Viscosity
    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.
    Coatweight
    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.
    Coating Density
    The density of a curtain layer is determined by weighing a 100-millilitre sample of the coating in a pyknometer.
    Paper Gloss
    Paper gloss is measured using a Zehntner ZLR-1050 instrument at an incident angle of 75°.
    Ink Gloss
    The test is carried out on a Pruefbau Test Printing unit with Lorrilleux Red Ink No. 8588.
    An amount of 0.8 g/m2 (or 1.6 g/m2 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°.
    Ink Set Off
    The test is carried out on a Pruefbau Test Printing unit. 250 mm3 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. After the strip is printed at the first station, move the strip towards second printing station, or Set off station, by moving the hand lever. At the set off station, place a blank paper strip between the printed paper and the disk. At 15, 30 60 and 120 seconds, 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
    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.
    Dry Pick Resistance (IGT)
    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.
    Wet 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. Then, 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. Printing is done on the same test strip immediately after coming out of the wetting chamber. Off print of the printing disk is done on a second coated paper test strip fixed on a rubber-backed platen; the printing pressure is 400N. Ink densities on both test strips are measured and used in the following formulas:
    Paper Roughness
    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.
    Solvent Resistance
    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.
    Aroma Barrier
    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.
    Formulations
    The following materials were used in the coating liquids:
    • Carbonate: dispersion of calcium carbonate with particle size of 90 percent < 2 µm in water (HYDROCARB 90 ME available from Omya AG, Oftringen, Switzerland), 77 percent solids.
    • Clay: dispersion of No. 1 high brightness kaolin clay with particle size of 98 percent < 2 µm in water (HYDRAGLOSS 90 available from J.M Huber Corp., Have de Grace, Maryland, USA), 71 percent solids.
    • Latex (A): carboxylated styrene-butadiene latex (DL 966 available from The Dow Chemical Company, Midland, Michigan, USA), 50 percent solids in water.
    • Latex (B): carboxylated styrene-butadiene latex (DL 980 available from The Dow Chemical Company, Midland, Michigan, USA), 50 percent solids in water.
    • PVOH: solution of 15 percent of low molecular weight synthetic polyvinyl alcohol (MOWIOL 6/98 available from Clariant AG, Basel Switzerland)
    • Surfactant: aqueous solution of sodium di-alkylsulphosuccinate (AEROSOL OT available from Cyanamid, Wayne, New Jersey, USA), 75 percent solids.
    • PE Dispersion (A): anionic dispersion of ethylene acrylic acid copolymer in water with minimum film formation temperature of 26° C and Tg of 4° C (TECHSEAL E-799/35, available from Trueb Chemie, Ramsen, Switzerland), 35 percent solids.
    • PE Dispersion (B): ethylene vinyl alcohol copolymer in water (EXCEVAL AQ 4005, available from EVAL Europe, Zwijndrecht, Belgium, this product is delivered as a dry powder and a solution is made at coater), 15 percent solids in water
    • Whitener: fluorescent whitening agent derived from diamino-stilbenedisulfonic acid (TINOPAL ABP/Z, available from Ciba Specialty Chemicals Inc. Basel, Switzerland).
    Coating procedure
    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. In addition, 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.
    Example 1
    The above ingredients were mixed in the amounts and applied at the coatweights given in Table 1.
    Slot 1 Slot 2 Slot 3 Slot 4 Slot 5
    Carbonate 70 70 70
    Clay 30 30 30
    Latex (A) 11
    Latex (B) 50 50
    PVOH 1 1 2.5
    PE Dispersion (B) 100
    PE Dispersion (A) 100
    Surfactant 0.4 0.2 0.4 0.4 0.2
    Whitener 1
    Density (g/cc) 1.34 0.98 1.34 1.03 1.57
    Viscosity (100 rpm Brookfield)(mPa·s) 430 320 430 300 1040
    Coatweight (g/m2) 6 2 2.5 2.5 4.5
    pH 8.5 8.2 8.5 9.1 8.5
    Solids (percent) 59.9 34.7 59.9 16 65.1
    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.
    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 1
    Density (g/cc) 1.34 0.98 1.03 1.57
    Viscosity (100 rpm Brookfield)(mPa·s) 430 320 300 1040
    Coatweight (g/m2) 6 3 1.5 6
    pH 8.5 8.2 9.1 8.5
    Solids (percent) 59.9 34.7 16 65.1
    Example 3
    The method of Example 2 was repeated except that coatweight of Slot 1 was decreased to 2 g/m2 and the coatweights of the barrier layers Slot 2 and Slot 3 were increased to 5 and 2.5 g/m2 respectively.
    Table 3 contains the Cobb, MVTR, Kit and Hot Oil properties for examples.
    Cobb 10 minutes
    (g/m2)    		 Water vapor transmission rate (g/m2/24h) T=23°C, RH=50 percent/ T=38°C, RH=90 percent Kit Flat/creased Hot Oil
    Example 1 8.9 9.12/162 7/fail pass
    Example 2 10.3 n.m./119 5/n.m. pass
    Example 3 11.1 n.m./94 12/3 pass
    n.m. = not measured
    The results in 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.
    Coated Paper Properties Example 1 Example 2 Example 3
    PAPER GLOSS 75° 63 62 66
    INK GLOSS 75°; 0.8 g/m2 INK 85 77 88
    INK GLOSS 75°; 1.6 g/m2 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
    The results in Table 4 show that the multilayer curtain with barrier layers and a top printing layer gave acceptable coated paper properties compared to current commercial papers.

    Claims (28)

    1. A method of producing a coated substrate comprising the steps of:
      a) forming a composite, multilayer free flowing curtain, whereby the multilayer free flowing curtain comprises at least two layers imparting at least two different barrier functionalities selected from the group consisting of oil and/or grease barrier functionality, water vapor barrier functionality, water resistance functionality, and oxygen barrier functionality, and
      b) contacting the curtain with a continuous web substrate, whereby,
      in case an oil and/or grease barrier layer is present in the multilayer curtain the coated substrate has a Kit value of at least 5 in the flat-test,
      in case a water vapor barrier layer is present in the multilayer curtain the coated substrate has a water vapor transmission rate of less than 50 g/(m2/day) (50 percent relative humidity, 23°C),
      in case a water resistance layer is present in the multilayer curtain the coated substrate has a 10 minute Cobb value of less than 20 g/m2,
      in case an oxygen barrier layer is present in the multilayer curtain the coated substrate has an oxygen transmission rate of less than 200 cm3/(m2/d/bar) (1 atm, 23°C, 90 percent relative humidity).
    2. A method according to claim 1, characterized in that the free flowing curtain of step a) comprises an additional top layer providing printability.
    3. A method according to any of the preceding claims, characterized in that in case an oil and/or grease barrier layer is present in step a), the coated substrate has a Kit value of at least 8 in the flat-test, preferably at least 11 in the flat-test.
    4. A method according to any of the preceding claims, characterized in that in case a water vapor barrier layer is present in step a), the coated substrate has a water vapor transmission rate of less than 40 g/(m2/day) (50 percent relative humidity, 23°C), preferably less than 30 g/(m2/day) (50 percent relative humidity, 23°C).
    5. A method according to any of the preceding claims, characterized in that in case a water resistance barrier layer is present in step a), the coated substrate has a 10 minute Cobb value of less than 12 g/m2, preferably less than 1.5 g/m2.
    6. A method according to any of the preceding claims, characterized in that in case an oxygen barrier layer is present in step a), the coated substrate has an oxygen transmission rate of less than 150 cm3/(m2/24h/bar) (1 atm, 23°C, 90 percent relative humidity), preferably less than 100 cm3/(m2/24h/bar).
    7. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) comprises an additional interface layer, which is the layer that comes in contact with the substrate.
    8. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) comprises at least an additional layer providing fold crack resistance.
    9. A method according to any of the preceding claims, characterized in that at least one of the layers of the multilayer curtain of step a) has a coat-weight when dried of less than 30 g/m2, preferably less than 20 g/m2, most preferred less than 10 g/m2.
    10. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) has a coat-weight when dried of less than 60 g/m2, preferably less than 30 g/m2.
    11. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) comprises at least 3 layers, preferably at least 4 layers, more preferred at least 5 layers and most preferred at least 6 layers.
    12. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) comprises at least one layer comprising at least one pigment.
    13. A method according to claim 12, characterized in that the pigment is selected from the group consisting of clay, kaolin, calcined clay, talc, calcium carbonate, laminar nanoparticles, high aspect ratio clays, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulfate, gypsum, synthetic magadiite, silica, alumina trihydrate, mica, and diatomaceous earth.
    14. A method according to any of the preceding claims, characterized in that at least one layer imparting barrier functionality of the multilayer curtain of step a) comprises at least one or more components selected from the group consisting of 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, proteins, 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 acrylonitrile copolymers, and mixtures thereof.
    15. A method according to any of the preceding claims, characterized in that at least one layer of the multilayer free flowing curtain of step a) comprises at least one surfactant.
    16. A method according to any of the preceding claims, characterized in that the multilayer free flowing curtain of step a) has a solids content of at least 10 weight percent, preferably of at least 40 weight percent, most preferred of at least 45 weight percent.
    17. A method according to any of the preceding claims, characterized in that the continuous web substrate of step b) is a basepaper or a paperboard.
    18. A method according to any of the preceding claims, characterized in that the continuous web substrate of step b) is neither precoated nor precalendered.
    19. A method according to any of the preceding claims, characterized in that the continuous web substrate of step b) has a web velocity of at least 200 m/min, preferably at least 400 m/min, most preferred at least 500 m/min.
    20. A method according to any of the preceding claims, characterized in that the continuous web substrate of step b) has a grammage, or basis weight, of from 30 to 400 g/m2.
    21. A coated substrate obtainable by the method of any of the preceding claims.
    22. A coated substrate according to claim 21, characterized in that the coated substrate is coated paper or paperboard.
    23. A method according to any of the preceding claims, characterized in that the multilayer curtain of step a) comprises at least an additional layer providing at least one of the following: sheet stiffness; sheet flexibility; release properties; adhesive properties; friction control; heat seal properties; and abrasion resistance properties.
    24. A method of producing a coated substrate comprising the steps of:
      a) forming a composite, multilayer free flowing curtain, whereby the multilayer free flowing curtain comprises at least two layers imparting at least two different barrier functionalities selected from the group consisting of oil and/or grease barrier functionality, water vapor barrier functionality, water resistance functionality, aroma barrier functionality, organic solvent barrier functionality, and oxygen barrier functionality, and
      b) contacting the curtain with a continuous web substrate.
    25. The method of any of the preceding claims wherein the curtain is formed with a slot die.
    26. The method of any of the preceding claims wherein the curtain is formed with a slide die.
    27. The method of any of the preceding claims wherein at least one layer of the curtain comprises polyethylene oxide.
    28. The method of any of the preceding claims wherein the curtain comprises polyethylene oxide in the interface layer.
    EP03023090A 2002-10-15 2003-10-15 Method of producing a multilayer coated substrate having improved barrier properties Expired - Lifetime EP1416087B1 (en)

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    WOPCT/US02/32938 2002-10-15
    PCT/US2002/032938 WO2004035929A1 (en) 2002-10-15 2002-10-15 Method of producing a multilayer coated substrate having improved barrier properties

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    EP1416087A1 true EP1416087A1 (en) 2004-05-06
    EP1416087B1 EP1416087B1 (en) 2010-09-29

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    JP (1) JP4903359B2 (en)
    CN (1) CN1323766C (en)
    AT (1) ATE483065T1 (en)
    AU (1) AU2002335033A1 (en)
    BR (1) BR0305415B1 (en)
    DE (1) DE60334356D1 (en)
    WO (1) WO2004035929A1 (en)

    Cited By (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2005028750A1 (en) * 2003-09-16 2005-03-31 Voith Paper Patent Gmbh Method and device for producing decorative paper and the use thereof
    EP1664219A2 (en) 2003-08-22 2006-06-07 Celanese International Corporation Improved pvoh barrier performance on substrates
    WO2008148934A1 (en) * 2007-06-05 2008-12-11 Upm-Kymmene Corporation A method for manufacturing paper
    US7473333B2 (en) * 2002-04-12 2009-01-06 Dow Global Technologies Inc. Process for making coated paper or paperboard
    WO2010042162A1 (en) * 2008-10-10 2010-04-15 Dow Global Technologies, Inc. Multilayer coating for paper based substrate
    CN105665222A (en) * 2016-02-01 2016-06-15 苏州哈恩新材料有限公司 Multicoating device capable of achieving one-time molding
    EP3286378B1 (en) 2015-04-20 2019-04-10 Kotkamills Group Oyj Method and system for manufacturing a coated paperboard and a coated paperboard
    WO2022049286A1 (en) * 2020-09-04 2022-03-10 Koehler Innovation & Technology Gmbh Coated paper
    EP3733406B1 (en) * 2017-10-04 2022-04-06 Nippon Paper Industries Co., Ltd Barrier material

    Families Citing this family (32)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    EP1249533A1 (en) 2001-04-14 2002-10-16 The Dow Chemical Company Process for making multilayer coated paper or paperboard
    WO2007120299A2 (en) 2005-11-29 2007-10-25 The Regents Of The University Of California Signal-on architecture for electronic, oligonucleotide-based detectors
    CN103459721A (en) * 2011-03-29 2013-12-18 日本制纸株式会社 Coated white paperboard and method for manufacturing same
    WO2012133092A1 (en) * 2011-03-30 2012-10-04 日本製紙株式会社 Coated white board and manufacturing method thereof
    WO2013039986A1 (en) 2011-09-15 2013-03-21 Imerys Pigments, Inc. Compositions comprising kaolin treated with a styrene-based polymer and related methods
    WO2013069788A1 (en) * 2011-11-10 2013-05-16 日本製紙株式会社 Barrier paper packaging material
    MX366743B (en) * 2012-04-13 2019-07-04 Sigma Alimentos Sa De Cv Hydrophobic paper or cardboard with self-assembled nanoparticles and method for the production thereof.
    WO2013189550A1 (en) * 2012-06-22 2013-12-27 Styron Europe Gmbh A coated substrate and system and method for making the same
    CN102815454B (en) * 2012-08-31 2014-04-09 河南李烨包装科技有限公司 Blister packaging base material and production method and application thereof
    CN104562844B (en) * 2015-01-08 2017-04-19 江南大学 Antibacterial bee wax emulsion as well as preparation method and application thereof
    CN104562843B (en) * 2015-01-08 2017-04-12 江南大学 Multifunctional modified palm wax emulsion as well as preparation method and application thereof
    US9920485B2 (en) 2015-02-11 2018-03-20 Westrock Mwv, Llc Printable compostable paperboard
    US9771688B2 (en) * 2015-02-11 2017-09-26 Westrock Mwv, Llc Oil, grease, and moisture resistant paperboard
    US20170022658A1 (en) * 2015-07-20 2017-01-26 Goodrich Corporation Gas barrier fabric
    JP6234654B1 (en) 2016-03-28 2017-11-22 日本製紙株式会社 Paper barrier material
    CN106515153A (en) * 2016-10-14 2017-03-22 无锡三帝特种高分子材料有限公司 Aluminum laminated film
    CN110073056B (en) * 2016-10-31 2022-05-17 太阳化学公司 Grease-resistant, oil-resistant and water-resistant coating composition
    SE541012C2 (en) 2016-12-22 2019-02-26 Stora Enso Oyj Method for manufacturing a heat-sealable packaging material and a heat-sealable packaging material made by the method
    FI20175144L (en) * 2017-02-17 2018-08-18 Valmet Technologies Oy Treatment section of a production line for producing a barrier coated fiber web and treatment method for producing a barrier coated fiber web
    CN110312833B (en) * 2017-02-27 2022-06-14 维实洛克Mwv有限责任公司 Heat sealable barrier paperboard
    BR112019017836B1 (en) * 2017-04-27 2023-12-05 Westrock Mwv, Llc CARDBOARD RESISTANT TO OIL, GREASE, AND MOISTURE WITH A NATURAL APPEARANCE
    CN110770397A (en) * 2017-06-15 2020-02-07 凯米拉公司 Barrier coating compositions, sheet products and uses thereof
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    TW202106949A (en) 2019-05-28 2021-02-16 日商大金工業股份有限公司 Oil-resistant agent composition for paper
    EP3943661A1 (en) 2020-07-20 2022-01-26 Schoeller Technocell GmbH & Co. KG Packaging material with a barrier layer
    US11549216B2 (en) 2020-11-11 2023-01-10 Sappi North America, Inc. Oil/grease resistant paper products
    CN114656670A (en) * 2022-02-16 2022-06-24 江阴宝柏包装有限公司 Transparent high-barrier recyclable composite film and preparation method thereof
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    Citations (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3508947A (en) 1968-06-03 1970-04-28 Eastman Kodak Co Method for simultaneously applying a plurality of coated layers by forming a stable multilayer free-falling vertical curtain
    US3632374A (en) 1968-06-03 1972-01-04 Eastman Kodak Co Method of making photographic elements
    US4230743A (en) 1976-06-28 1980-10-28 Fuji Photo Film Co., Ltd. Process for producing pressure-sensitive copying paper
    JPH04100998A (en) 1990-08-17 1992-04-02 Mitsubishi Paper Mills Ltd Coated paper for rotary offset printing
    JPH07119083A (en) 1993-07-19 1995-05-09 Mitsubishi Paper Mills Ltd Pigment-coated paper and its production
    JPH10328613A (en) 1997-06-02 1998-12-15 Mitsubishi Paper Mills Ltd Coating method
    WO2001054828A1 (en) 2000-01-26 2001-08-02 Tetra Laval Holdings & Finance S A Method of manufacturing a multi-layer packaging laminate and packaging laminate obtained by the method
    JP3222221B2 (en) 1992-11-09 2001-10-22 三菱製紙株式会社 Pigment coated paper for printing and method for producing the same
    WO2002053838A1 (en) 2000-12-28 2002-07-11 Rock-Tenn Company Grease masking packaging materials and methods thereof
    EP1249533A1 (en) 2001-04-14 2002-10-16 The Dow Chemical Company Process for making multilayer coated paper or paperboard

    Family Cites Families (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    JPH10249978A (en) * 1997-03-18 1998-09-22 Oji Paper Co Ltd Barrier laminate
    DE19716466A1 (en) * 1997-04-21 1998-10-22 Bachofen & Meier Ag Method and device for applying dispersions to a material web
    CN1117660C (en) * 1998-03-10 2003-08-13 利乐拉瓦尔集团及财务有限公司 Laminated packaging materials and packaging containers produced therefrom

    Patent Citations (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3508947A (en) 1968-06-03 1970-04-28 Eastman Kodak Co Method for simultaneously applying a plurality of coated layers by forming a stable multilayer free-falling vertical curtain
    US3632374A (en) 1968-06-03 1972-01-04 Eastman Kodak Co Method of making photographic elements
    US4230743A (en) 1976-06-28 1980-10-28 Fuji Photo Film Co., Ltd. Process for producing pressure-sensitive copying paper
    JPH04100998A (en) 1990-08-17 1992-04-02 Mitsubishi Paper Mills Ltd Coated paper for rotary offset printing
    JP3222221B2 (en) 1992-11-09 2001-10-22 三菱製紙株式会社 Pigment coated paper for printing and method for producing the same
    JPH07119083A (en) 1993-07-19 1995-05-09 Mitsubishi Paper Mills Ltd Pigment-coated paper and its production
    JPH10328613A (en) 1997-06-02 1998-12-15 Mitsubishi Paper Mills Ltd Coating method
    WO2001054828A1 (en) 2000-01-26 2001-08-02 Tetra Laval Holdings & Finance S A Method of manufacturing a multi-layer packaging laminate and packaging laminate obtained by the method
    WO2002053838A1 (en) 2000-12-28 2002-07-11 Rock-Tenn Company Grease masking packaging materials and methods thereof
    EP1249533A1 (en) 2001-04-14 2002-10-16 The Dow Chemical Company Process for making multilayer coated paper or paperboard

    Non-Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Title
    DATABASE WPI Section Ch Week 199221, Derwent World Patents Index; Class A82, AN 1992-170429, XP002235256 *
    DATABASE WPI Section Ch Week 199527, Derwent World Patents Index; Class A82, AN 1995-204515, XP002235257 *
    DATABASE WPI Section Ch Week 200169, Derwent World Patents Index; Class F09, AN 1994-222740, XP002236766 *

    Cited By (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US7473333B2 (en) * 2002-04-12 2009-01-06 Dow Global Technologies Inc. Process for making coated paper or paperboard
    EP1664219A2 (en) 2003-08-22 2006-06-07 Celanese International Corporation Improved pvoh barrier performance on substrates
    WO2005028750A1 (en) * 2003-09-16 2005-03-31 Voith Paper Patent Gmbh Method and device for producing decorative paper and the use thereof
    WO2008148934A1 (en) * 2007-06-05 2008-12-11 Upm-Kymmene Corporation A method for manufacturing paper
    WO2010042162A1 (en) * 2008-10-10 2010-04-15 Dow Global Technologies, Inc. Multilayer coating for paper based substrate
    US9200409B2 (en) 2008-10-10 2015-12-01 Dow Global Technologies Llc Multilayer coating for paper based substrate
    EP3286378B1 (en) 2015-04-20 2019-04-10 Kotkamills Group Oyj Method and system for manufacturing a coated paperboard and a coated paperboard
    US11220788B2 (en) 2015-04-20 2022-01-11 Kotkamills Group Oyj Method and system for manufacturing a coated paperboard and a coated paperboard
    CN105665222A (en) * 2016-02-01 2016-06-15 苏州哈恩新材料有限公司 Multicoating device capable of achieving one-time molding
    EP3733406B1 (en) * 2017-10-04 2022-04-06 Nippon Paper Industries Co., Ltd Barrier material
    WO2022049286A1 (en) * 2020-09-04 2022-03-10 Koehler Innovation & Technology Gmbh Coated paper

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    CN1323766C (en) 2007-07-04
    BR0305415B1 (en) 2013-12-10
    DE60334356D1 (en) 2010-11-11
    CN1500563A (en) 2004-06-02
    AU2002335033A1 (en) 2004-05-04
    JP2004148307A (en) 2004-05-27
    BR0305415A (en) 2004-06-15
    WO2004035929A1 (en) 2004-04-29
    EP1416087B1 (en) 2010-09-29
    ATE483065T1 (en) 2010-10-15

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