EP1411168B1 - A method of producing a coated substrate - Google Patents

A method of producing a coated substrate Download PDF

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Publication number
EP1411168B1
EP1411168B1 EP03023328.2A EP03023328A EP1411168B1 EP 1411168 B1 EP1411168 B1 EP 1411168B1 EP 03023328 A EP03023328 A EP 03023328A EP 1411168 B1 EP1411168 B1 EP 1411168B1
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EP
European Patent Office
Prior art keywords
coating
layer
curtain
latex
component
Prior art date
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EP03023328.2A
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German (de)
English (en)
French (fr)
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EP1411168A1 (en
Inventor
Robert Urscheler
John A. Roper Iii
Pekka J. Salminen
Francis Dobler
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Trinseo Europe GmbH
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Trinseo Europe GmbH
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/30—Processes for applying liquids or other fluent materials performed by gravity only, i.e. flow coating
    • B05D1/305—Curtain coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • 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
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/007—Slide-hopper coaters, i.e. apparatus in which the liquid or other fluent material flows freely on an inclined surface before contacting the work
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/22—Paper or cardboard

Definitions

  • This invention relates to a method of producing coated substrates. In a further embodiment the present invention relates to a method of producing coated paper or paperboard.
  • coating compositions usually are applied to said substrate by, for example, blade type, bar type, or reverse roll type coating methods.
  • the line speed may exceed 1,000 m/min. Any or all of these methods are commonly employed to sequentially apply coatings to the moving substrates.
  • each of these application methods inherently has its own set of problems that can result in an inferior coated surface quality.
  • the lodgment of particles under the blade can result in streaks in the coating layer, which lowers the quality of the coated paper or paperboard.
  • the high pressure that must be applied to the blade to achieve the desired coating weight places a very high stress on the substrate and can result in breakage of the substrate web, resulting in lowered production efficiency.
  • the pigmented coatings are highly abrasive, the blade must be replaced regularly in order to maintain the evenness of the coated surface.
  • the distribution of the coating on the surface of the paper or paperboard substrate is affected by the surface irregularities of the substrate. An uneven distribution of coating across the paper or paperboard surface can result in a dappled or mottled surface appearance that can lead to an inferior printing result.
  • the bar (rod) type coating method is limited as to the solids content and viscosity of the pigmented coating color that is to be applied.
  • Pigmented coatings applied by the bar type coating method are typically lower in solids content and viscosity than pigmented coating colors applied by the blade type method. Accordingly, for the bar type coating method it is not possible to freely change the amount of coating that can be applied to the surface of the paper or paperboard substrate. Undesirable reductions in the quality of the surface of the coated paper or paperboard can result when the parameters of coating solids content, viscosity and coatweight are imbalanced. Moreover, abrasion of the bar by the pigmented coatings requires that the bar be replaced at regular intervals in order to maintain the evenness of the coated surface.
  • the roll type (film) coating method is a particularly complex process of applying pigmented coatings to paper and paperboard in that there is a narrow range of operating conditions related to substrate surface characteristics, substrate porosity, coating solids content and coating viscosity that must be observed for each operating speed and each desired coatweight to be achieved.
  • An imbalance between these variables can lead to an uneven film-split pattern on the surface of the coated paper, which can lead to an inferior printing result, or the expulsion of small droplets of coating as the sheet exits the coating nip. These droplets, if re-deposited on the sheet surface, can lead to an inferior printing result.
  • the maximum amount of coating that can be applied to a paper or paperboard surface in one pass using the roll type coating method is typically less than that which can be applied in one pass by the blade or bar type coating methods. This coating weight limitation is especially pronounced at high coating speeds.
  • 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, coating thickness, and thus ink reception properties, will vary across the surface of the coated paper resulting in irregularities in the printed image.
  • 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.
  • a feature common to all of the mentioned coating techniques is that an excess of coating liquid is applied to the substrate and then is metered off.
  • a reactive coating which is a coating comprising reagents capable of reacting with each other, the reaction occurring in the metered excess coating renders it useless.
  • each of these coating methods have, as already mentioned, rheological constraints for obtaining good runnability so that the addition of a reactive additive may change the coating rheology profile so that it falls outside of the window of coatability.
  • reactive chemistries are used to impart functionality to the coated substrate; however, these coatings are applied through the use of a subsequent coating or converting step that adds complexity and expense.
  • 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 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.
  • Coated papers and paperboards that have received a coating that contains an additive designed to impart functional properties, such as barrier properties, printability properties, adhesive properties, release properties, and optical properties such as color, brightness, opacity, gloss, etc., are described as functional products and their coatings may be referred to as functional coatings.
  • the coating components that impart these properties may also be referred to as functional additives.
  • Functional products include paper types such as self adhesive papers, stamp papers, wallpapers, silicone release papers, food packaging, greaseproof papers, moisture resistant papers, and saturated tape backing papers.
  • 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.
  • the simultaneous application of multiple coatings by curtain coating methods is known from the art of making pressure sensitive copying paper.
  • U.S. Patent 4,230,743 discloses in one embodiment the simultaneous application of a base coating comprising microcapsules as a main component and a second layer comprising a color developer as a main component onto a travelling web.
  • the resulting paper has the same characteristics as the paper made by sequential application of the layers.
  • 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. The low operation speed of the coating process is not suitable for economic production of printing paper, especially commodity printing paper.
  • the technical problem underlying the present invention is to overcome the disadvantages of the prior art and, thus, to provide a coating method capable of applying coatings comprising one or more reactive compounds.
  • a further aspect of the present invention is to provide a coating method whereby the properties of the applied coating is not detrimentally affected by the presence of reagents in the coating capable of reacting with each other.
  • a further aim of the present invention is to provide coated substrates having improved properties and a method of producing the same.
  • the present invention is a method of producing a coated substrate comprising the steps of:
  • the problem of the invention is solved by a process for producing a coated substrate comprising the steps of:
  • the problem of the present invention is solved by a method of producing a coated substrate comprising the steps of:
  • the composition forming the at least one layer of the free flowing curtain of step a) may comprise at least one first component and at least one second component capable of reacting with each other or may contain a reaction system wherein reaction of at least one reactive component can be induced by means of catalyst, initiator or activator present in the composition or by exposure to energy such as heat or radiation.
  • reactive component means a material that is capable of reacting and/or a material that initiates, catalyzes or is otherwise involved in a reaction.
  • coating process means a process comprising coating a substrate to a point such that the coating is immoblized and/or the coated substrate is finished and ready for sale.
  • said free flowing curtain of step a) is a composite multilayer free flowing curtain.
  • curtain coating there are three main means by which the curtain coating can be used to apply reactive coatings:
  • the reaction between the first component and the second component of step a) takes place within the coating die or head, in the free flowing curtain and/or when applied to the substrate, and/or when initiated by, for example, pressure, heat, pH change, radiation and/or exposure to a gas or vapor, such as oxygen or ammonia.
  • the reaction type of which the first component and the second component of step a) react with each other is not limited, and may be, for example: an anionic-cationic interaction; a crosslinking reaction; a free radical reaction; a step growth reaction; a addition reaction; a curing reaction such as a UV induced curing reaction, an oxygen induced curing reaction, a catalyzed reaction or an electron beam induced curing reaction; an acid base reaction; a grafting reaction; a ring opening reaction; a precipitation; a phase change; a flocculation/coagulation reaction or a combination thereof.
  • reactive first and second component combinations include, for example, the following: a polyvinyl alcoholA and borax; a cationic starch and an anionic coating composition; a starch and a dialdehyde; an epoxy-functional polymer and an amine hardening agent; and a polyisocyanate and a polyol.
  • the reaction involved in the coating process proceeds readily at room temperature in the substantial absence of external energy sources.
  • a crosslinking reaction takes place between the at least first component and at least second component if said components are present in the same layer.
  • the process of the invention is conducted in the substantial absence of electron beam radiation.
  • a flocculation can be induced by adding calcium chloride solution to a coating composition.
  • anionic-cationic interaction refers to the reaction of an anionic compound with a cationic compound in a coating liquid, whereby the properties of said coating liquid change due to said anionic-cationic interaction.
  • the property change may be a flocculation that would make it impossible to apply said coating to substrates using blade, rod, or airbrush (air knife) coating techniques.
  • the substrate of the present invention preferably is a basepaper or paperboard so that a coated basepaper or paperboard is produced accordingly.
  • photographic papers and/or pressure sensitive copying papers are excluded from the scope of the present invention.
  • the term "excluding photographic papers should be interpreted in the sense that none of the layers of the curtain used in the practice of the present invention comprise silver compounds.
  • the term "excluding pressure sensitive copying papers” should be interpreted in the sense that the layers of the curtain do not contain a combination of a microencapsulated color former and a color developer in a single layer or in different layers.
  • 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.
  • 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 entire coating liquid that passes through the curtain coating unit is applied to the substrate.
  • a minor part of coating liquid is removed before said curtain is applied to the substrate. Coating liquids that pass through the curtain coating unit and that are not applied to the substrate may be discarded.
  • At least one curtain layer of the free falling curtain comprises at least one pigment.
  • at least two of the coating layers comprise at least one pigment.
  • a top layer ensuring printability is present. Said layer improves surface properties like gloss or smoothness and optionally is not pigmented. For the manufacture of commodity printing paper, coating with two pigmented layers is sufficient for most purposes.
  • coated substrates such as paper and paperboard
  • coating formulations comprising reactive components via the process of the invention.
  • the curtain employed in the invention has a bottom, or interface, layer, and optionally a top layer, and/or optionally one or more internal layers. Each layer comprises a liquid, emulsion, suspension, dispersion or solution.
  • the coating curtain of the present invention suitably includes at least one layer, and also includes embodiments having at least 2, at least 3, at least 4, at least 5, or at least 6 or more 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 one or more layers imparting reactive functionalities, and the like, or any combination thereof.
  • a spacing layer is a layer that separates at least two other layers. For example, a spacing layer can be employed between layers having reactive components in order to delay the initiation of a reaction between the components.
  • a coating layer of the invention preferably comprises at least one pigment and/or binder, and can be formulated to be the same or different than conventional paper coating formulations.
  • the primary function of a coating layer is to cover the surface of the substrate as is well known in the paper-coating art.
  • Conventional coating formulations referred to in the industry as coating colors, can be employed as the coating layer.
  • pigments useful in the process of the present invention include clay, kaolin, talc, calcium carbonate, titanium dioxide, satin white, synthetic polymer pigment, zinc oxide, barium sulphate, gypsum, silica, alumina trihydrate, mica, and diatomaceous earth.
  • Kaolin, talc, calcium carbonate, titanium dioxide, satin white and synthetic polymer pigments, including hollow polymer pigments, are particularly preferred.
  • Binders useful in the practice of the present invention include, for example, styrene-butadiene latex, styrene-acrylate latex, styrene-acrylate-acrylonitrile latex, styrene-butadiene-acrylate-acrylonitrile latex, styrene-butadiene-acrylonitrile latex, styrene-maleic anhydride latex, styrene-acrylate-maleic anhydride latex, polysaccharides, proteins, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, epoxy resin, cellulose derivatives, and polyurethane.
  • 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, and carboxylated polyvinyl acetate latex.
  • polysaccharides include agar, sodium alginate, and starch, including modified starches such as thermally modified starch, carboxymethylated starch, hydroxyethylated starch, and oxidized starch.
  • proteins that can be employed in the process of the present invention include albumin, soy protein, and casein. A wide variety of suitable binders are commercially available.
  • 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 desirably 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 curtain of the invention comprises an interface layer, that is the layer that comes in contact with the substrate to be coated.
  • One important function of the interface layer may be to promote wetting of the substrate paper.
  • 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.
  • the interface layer can include a reactive component or can be free of reactive compounds. This layer is preferably a relatively thin layer when employed in a multilayer curtain.
  • the coatweight of the interface layer when employed in a multilayer curtain preferably is from 0.01 to 5 g/m 2 , and more preferably is from 1 to 3 g/m 2 .
  • the interface layer includes one or more of the following: a dispersion such as a latex, including an alkali swellable latex, a blend of starch and poly(ethylene acrylic acid) copolymer, and the like, or a water soluble polymer, such as, for example, polyvinyl alcohol, a starch, an alkali soluble latex, a polyethylene oxide, or a polyacrylamide.
  • a dispersion such as a latex, including an alkali swellable latex, a blend of starch and poly(ethylene acrylic acid) copolymer, and the like, or a water soluble polymer, such as, for example, polyvinyl alcohol, a starch, an alkali soluble latex, a polyethylene oxide, or a polyacrylamide.
  • the interface layer can optionally be pigmented, and this is preferred for certain applications.
  • the curtain of the invention can include one or more functional layers.
  • the purpose of a functional layer is to impart a desired functionality to the coated paper.
  • Functional layers can be selected to provide, for example, at least one of the following: printability; barrier properties, such as moisture barrier, aroma barrier, water and/or water vapor barrier, solvent barrier, oil barrier, grease barrier and oxygen barrier properties; sheet stiffness; fold crack resistance; paper sizing properties; release properties; adhesive properties; and optical properties, such as, color, brightness, opacity and gloss; etc.
  • the first and second reactive components can react to impart functionality to a layer in the coating.
  • the solids content of a functional layer can vary widely depending on the desired function.
  • a functional layer of the present invention preferably has a solids content of up to 75 percent by weight based on the total weight of the functional layer and a viscosity of up to 10,000 cps (Brookfield, spindle 5, 100 rpm, 25°C), more preferably 50 to 3,000 cps.
  • the coatweight of a functional layer is from 0.1 to 30 g/m 2 , more preferably 0.5 to 10 g/m 2 , and most preferably from 1 to 3 g/m 2 . In certain situations, such as, for example, when a dye layer is employed or in the case of certain reactants such as borax, the coatweight of the functional layer can be less than 0.1 g/m 2 .
  • the functional layer of the present invention can contain, for example, at least one of the following: a polymer of ethylene acrylic acid; a polyethylene; other polyolefins; a polyurethane; an epoxy resin; a polyester; an adhesive such as a styrene butadiene latex, a styrene acrylate latex, a carboxylated latex, a starch, a protein, or the like; a sizing agent such as a starch, a styrene-acrylic copolymer, a styrene-maleic anhydride, a polyvinyl alcohol, a polyvinyl acetate, a carboxymethyl cellulose or the like; and a barrier such as silicone, a wax or the like.
  • Each functional layer can include, but is not limited to include, at least one pigment and/or binder as previously described for the coating layer, and/or one or more reactive components.
  • At least one additive such as, for example, at least one dispersant, at least one lubricant, at least one water retention agent, at least one surfactant, at least one optical brightening agent, at least one pigment dye or colorant, at least one thickening agent, at least one defoamer, at least one anti-foaming agent, at least one biocide, at least one soluble dye or colorant, including any combination of these or the like may be used in at least one layer of the curtain.
  • Polyethylene oxide is an example of a preferred additive, and can be employed in any layer. In a preferred embodiment, polyethylene oxide is employed as a thickening agent, preferably at least in the interface layer.
  • the polyethylene oxide has a weight average molecular weight of at least 50,000, preferably at least 100,000, more preferably at least 500,000, and most preferably at least 800,000.
  • the amount of polyethylene oxide employed is sufficient to prevent cratering, and is preferably less than 2 weight percent, based on the weight of solids in the layer in which it is employed.
  • the layer most distant from the substrate paper is referred to as the top layer.
  • This layer typically is the layer that will be printed upon, although it is possible that the coated paper of the present invention could also be further coated using conventional means, such as rod, blade, roll, bar, or air knife (airbrush) coating techniques, and the like.
  • the top layer can be a coating layer or a functional layer, including a gloss layer, and can contain a reactive component.
  • the top layer is very thin, having a coatweight of, for example from 0.5 to 3 g/m 2 . This advantageously allows the use of less expensive materials under the top layer, while still producing a paper having good printing properties.
  • the top layer is free of mineral pigment.
  • the top layer comprises a glossing formulation.
  • glossing formulation and simultaneous multilayer curtain coating combines the advantages of curtain coating with good gloss.
  • the glossing formulations useful in the present invention comprise gloss additives, such as synthetic polymer pigments, including hollow or solid polymer pigments, produced by polymerization of, for example, styrene, acrylonitrile and/or acrylic monomers.
  • the synthetic polymer pigments preferably have a glass transition temperature of 40 - 200°C, more preferably 50 - 130°C, and a particle size of 0.02 -10 ⁇ m, more preferably 0.05 - 2 ⁇ m.
  • the glossing formulations contain 5 - 100 weight percent, based on solids, of gloss additive, more preferably 60-100 weight percent.
  • glossing formulation comprises gloss varnishes, such as those based on epoxyacrylates, polyesters, polyesteracrylates, polyurethanes, polyetheracrylates, oleoresins, nitrocelluloses, polyamides, vinyl copolymers and various forms of polyacrylates.
  • the viscosity of the top layer is greater than 20 cps (at 25°C).
  • a preferred viscosity range is from 90 cps to 2,000 cps, more preferably from 200 cps to 1,000 cps.
  • the internal layer preferably is a functional layer or a coating layer.
  • the internal layers can comprise a combination of identical or different functional layers, a combination of identical or different coating layers, or a combination of coating and functional layers.
  • An internal layer may contain a reactive component.
  • the process of the invention expands the limits of paper coating technology, gives the coated paper producer unprecedented flexibility, and the ability to prepare novel coated papers.
  • the free flowing curtain desirably 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 free flowing curtain has a solids content of from 10 to 80 weight percent.
  • At least one layer of a multilayer free flowing curtain of the invention preferably has a solids content of at least 40 weight percent, preferably at least 50 weight percent, and most preferably at least 65 weight percent.
  • a particular advantage of one embodiment of the present invention is that, by the simultaneous application of at least two coating layers by curtain coating, very thin layers or in other words very low coatweights of the respective layers can be obtained even at very high application speeds.
  • the coatweight of each layer in the composite curtain can be from 0.01 to 10 g/m 2 , more preferably 0.1 to 3 g/m 2 .
  • the coatweight of each layer can be the same as the others, or can vary widely from the other layers; thus, many combinations are possible.
  • the process of the invention can produce substrates having a wide range of coatweights.
  • the coatweight of the coating on the paper produced is 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 .
  • the coatweight of the top layer is lower than the coatweight of the layer contacting the basepaper or baseboard.
  • the coatweight of the top layer is less than 75 percent, more preferably less than 50 percent, of the coatweight of the layer contacting the basepaper or baseboard.
  • the coatweight of the top layer is higher than the coatweight of the layer(s) below it.
  • the simultaneous multilayer coating method of the present invention allows the use of much larger quantities of relatively inexpensive raw materials such as, for example, under an extremely thin top layer of more expensive raw materials or in combination with an expensive reactant, such as a curing agent, without compromising the quality of the finished coated product.
  • the method of the invention allows the preparation of papers that have never been produced before. For example, a tacky functional internal layer can be included in the curtain.
  • a pronounced advantage of the present invention irrespective of which embodiment is used is that the process of the present invention can be run at very high coating speeds that hitherto in the production of printing paper could only be achieved using blade, bar or roll application methods.
  • Usual line speeds in the process of the invention are at least 300 m/min, preferably at least 400 m/min, more preferably at least 500 m/min, such as in a range of 600 - 3200 m/min, and more preferably at least 800 m/min, such as in a range of 800 to 2500 m/min.
  • the line speed, or speed of the moving substrate is at least 1000 m/min, preferably at least 1500 m/min.
  • the continuous web substrate of step b) is neither precoated nor precalendered.
  • 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) preferably has a grammage, or basis weight, of from 20-400 g/m 2 .
  • Figure 1 is an explanatory cross-sectional view of a 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 curtain.
  • 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.
  • An advantage of the process of the present invention over the prior art is that a coated substrate having specific properties can be obtained by applying a curtain comprising at least two reactive compounds to a substrate. Said method allows one to prepare a coated substrate having specific layers imparting, due to the reaction of said reactive compounds, specific properties. As the methods known in the prior art apply an excess of coating color, they cannot effectively apply coatings comprising reactive compounds to substrates. Preferably, the coated substrates can be printed using any printing method known to a person skilled in the art.
  • the above ingredients were mixed in the amounts given in tables herein below, where all parts are based on dry weights unless otherwise indicated.
  • the pH of the pigmented coating formulations was adjusted by adding NaOH solution (10 percent) as indicated in Table 1. Water was added as needed to adjust the solids content of the formulations.
  • the formulations were coated onto paper according to one of the following procedures.
  • Coating Procedure 1 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. Volumetric pumps were employed to provide precise volumes to the die in order to achieve the desired coatweights.
  • 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. After coating on the web the paper was dried with a hot air drier.
  • Coating Procedure 2 This procedure is identical to Coating Procedure 1 except for the following differences.
  • the formulations were coated onto paper using a multilayer slide die type curtain coater, manufactured by Leuthold AG. When volatile components were present in the formulation, the formulations were poured into the feed containers at least 12 hours before application, without stirring, so natural deaeration could take place. When two coating formulations needed to be reacted just before entering the slide die they were pumped through a small closed vessel and agitated by a paddle at up to 600 rpm.
  • 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 100 rpm.
  • 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 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 is measured on a Zeiss Ekepho 2000. Brightness is measured according to ISO standard 2469 on a pile of sheets. The result is given as R457.
  • Opacity is measured on a Zeiss Ekepho 2000. Opacity is measured on a single sheet backed by black standard (R 0 ) and on a pile of sheets (R ⁇ ). The result is given as R 0 /R ⁇ x 100 (percentage).
  • the test is used to illustrate coating distributions and uniformity on unprinted or printed papers (exc. full-tone specimens).
  • 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 roughness of the coated paper surface is measured with a Parker PzintSurf 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.
  • Paper stiffness is measured using the Kodak Stiffness method, TAPPI 535-PM-79, or the Gurely Stiffness method, TAPPI 543.
  • the coatweight achieved in each 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 resistance of the coated paper to coating breakdown after it absorbs water is tested with the Adams Wet rub test.
  • a strip of paper (24x2.5cm) is fixed onto a bronze wheel, rolling under constant speed and load over a rubber roll, which dips into a pan containing distilled water for either 45 or 60 sec. The rolling makes the water in the pan turbid if the coating breaks down. After the rolling is completed, the light transmission of the water form the pan is measured with a turbidity meter. A low transmission reading indicates significant coating breakdown.
  • the coatings were applied at 1000 m/min onto a wood-containing basepaper with a roughness of 4.3 microns using Coating Procedure 1.
  • Two coating conditions were used for Examples 1, 2 and 3: Coating Condition 1 - where the bottom layer coatweight was 1 g/m 2 and top layer coatweight was 7 g/m 2 and Coating Condition 2 - where the bottom layer coatweight was 2 g/m 2 and top layer coatweight was 6 g/m 2 .
  • These two coating conditions tested the effect of increasing the amount of the reactive bottom layer.
  • the comparative experiment used the same two coating conditions but the reactive ingredient (borax) was left out.
  • Example 4 used a three-layer coating having a thin middle layer containing the borax.
  • Example 4 the bottom layer coatweight was fixed at 1 g/m 2 and the top layer coatweight was 7 g/m 2 while the coatweight of the middle layer was varied from 0.018 g/m 2 (Condition 1) to 0.036 g/m 2 (Condition 2).
  • the coated paper properties for these examples are shown in Tables 2 and 3.
  • the coatings were applied at 1000 m/min to a wood-containing basepaper with a roughness of 6.2 microns using Coating Procedure 1.
  • the bottom layer coatweight was 0.5 g/m 2 and top layer coatweight was 6.5 g/m 2 .
  • the coated paper properties are in Table 5.
  • Table 5 Coated Paper Properties Comparative B Example 5 PAPER GLOSS 75° (percent) 35 37 INK GLOSS 75°; 0.8 g/m 2 INK (percent) 47 52 INK GLOSS 75°; 1.6 g/m 2 INK (percent) 58 68 IGT DRY PICK (cm/s) 52 57 INK SET OFF AFTER 15 SEC.
  • This example demonstrated an interfacial reaction of a starch-containing formulation with a dialdehyde solution (Glyoxal) capable of reacting with the starch.
  • the starch was formulated into the bottom layer and the Glyoxal solution was the middle layer.
  • the total Glyoxal used in the formulation was 15 percent of the starch amount.
  • the top layer of the coating was a conventional pigmented printing layer.
  • a starch- containing two-layer reference without glyoxal was coated as a control. The details of the coating formulations are given in Table 6.
  • the use of the reactive starch/glyoxal system improved the coating strength as measured by IGT dry pick.
  • the samples with Glyoxal showed increased stiffness and excellent water resistance.
  • This example demonstrated the use of a quick-setting latex to improve the properties of a coated paper.
  • the trigger for the quick setting reaction was believed to be the conversion of a nitrogen containing polymer from a neutral to a cationic charged state as the pH changes upon the evaporation of ammonia from the formulation during coating and/or drying of the paper.
  • the details of the formulations are shown in Table 9.
  • the coatings were applied with a 3-layer configuration at 1000 m/min with the coatweights shown in Table 9 onto a wood free basepaper with a basis weight of 120 g/m 2 .
  • Coating Procedure 2 was used.
  • the top layer contained the reactive system.
  • the contact angle of the papers containing the quick set system was 74°, and 64° for the comparative paper.
  • the quick set polymer apparently served to form a combination of hydrophobic linkages that render the paper more water resistant.
  • This example demonstrated coating using an amino-ethoxysilane (Ameo) and a glycidyl functionalized ethoxysilane (Glyeo). Multiple reactions can occur. In addition to the reaction between the amino group and the glycidyl group, a hydrolysis/condensation reaction took place via the glycidyl-functionalized silane reacting with itself to form a siloxane linkage when the pH was sufficiently high to hydrolyze the ethoxysilane. Three approaches for coating the paper were demonstrated. First the self-reaction of the Glyeo was demonstrated, then in addition to the self-reaction, a simultaneous interfacial reaction was demonstrated with the reaction between Ameo and Glyeo occurring in a layered structure.
  • Ameo amino-ethoxysilane
  • Glyeo glycidyl functionalized ethoxysilane
  • the coatings were applied to wood-containing base paper using Coating Procedure 2. Coatweight and coater speed were as shown in Table 10. Uncalendered and calendered paper gloss were as shown in Table 11, which also includes a comparison of the ink gloss results. Paper gloss was reduced with these reactive systems. The ink gloss was significantly improved. The improvement was greatest for the calendered papers. The reacted samples showed an improvement in the delta between the ink gloss and sheet gloss for two ink loads.
  • This example demonstrated the reaction between an amino-based epoxy curing agent and an epoxide.
  • This example used an in-line approach, where a blend of curing agent and the epoxide was fed to a single layer slot of the die.
  • the reference sample does not contain the hardener or the epoxide.
  • the details of the formulations are shown in Table 13.
  • the water resistance and stiffness of the coated paper increased with the epoxy/hardener reaction.
  • the paper containing the polyurethane showed good dry pick resistance and good water resistance.
  • the polyurethane also enhanced the uncalendered gloss.
EP03023328.2A 2002-10-15 2003-10-15 A method of producing a coated substrate Expired - Lifetime EP1411168B1 (en)

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PCT/US2002/033113 WO2004035930A1 (en) 2002-10-15 2002-10-15 A method of producing a coated substrate
WOPCT/US02/33113 2002-10-15

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EP1411168A1 (en) 2004-04-21
JP2004154773A (ja) 2004-06-03
AU2002337877A1 (en) 2004-05-04
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BR0305488A (pt) 2004-06-15
JP4943627B2 (ja) 2012-05-30
CN100400748C (zh) 2008-07-09

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