EP0049672A1 - Coated papers and cardboards, and process for manufacturing them - Google Patents

Coated papers and cardboards, and process for manufacturing them Download PDF

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Publication number
EP0049672A1
EP0049672A1 EP81401558A EP81401558A EP0049672A1 EP 0049672 A1 EP0049672 A1 EP 0049672A1 EP 81401558 A EP81401558 A EP 81401558A EP 81401558 A EP81401558 A EP 81401558A EP 0049672 A1 EP0049672 A1 EP 0049672A1
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EP
European Patent Office
Prior art keywords
paper
microspheres
cardboard
coating layer
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP81401558A
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German (de)
French (fr)
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EP0049672B1 (en
Inventor
Sauveur Cremona
Joel Pijselman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cellulose du Pin SA
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Cellulose du Pin SA
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Application filed by Cellulose du Pin SA filed Critical Cellulose du Pin SA
Priority to AT81401558T priority Critical patent/ATE12531T1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • D21H19/66—Coatings characterised by a special visual effect, e.g. patterned, textured
    • D21H19/70—Coatings characterised by a special visual effect, e.g. patterned, textured with internal voids, e.g. bubble coatings
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape
    • D21H21/54—Additives of definite length or shape being spherical, e.g. microcapsules, beads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/508—Supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249971—Preformed hollow element-containing
    • Y10T428/249972—Resin or rubber element
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31989—Of wood

Definitions

  • the present invention relates to paper or cardboard based on cellulosic fibers. It relates more particularly to a new paper or cardboard comprising at least one layer allowing or facilitating gravure printing. It also relates to a process for manufacturing these papers or cartons.
  • Paper and cardboard are generally coated (or coated) in order to improve their mechanical properties in particular and / or allow them to be printed.
  • Known coated paper or cardboard has at least one coating layer containing pigments and binders.
  • the most commonly used pigment is a clay, such as kaolin. Possibly other pigments are associated with it, such as calcium carbonate, titanium oxide, hydrargilite, talc, barium sulphate.
  • the pigments are attached to the paper using binders, for example a styrene-butadiene copolymer, an acrylic polymer, a vinyl acetate polymer, natural binders, starch, proteins, caseins, polyvinyl alcohols, or a mixture of these bodies.
  • the coating layer of known coated paper or cardboard can also comprise dispersing agents which have been used for its manufacture from aqueous compositions.
  • dispersing agents are, for example, tetrasodium pyrophosphate, sodium hexametaphosphate, low molecular weight polyacrylates, at levels of between 0.2 and 0.5% by weight relative to the pigments.
  • the coating layer may also include agents likely to improve the water retention properties such as carboxymethylcellulose, alginates.
  • coated paper or cardboard must have differ depending on the printing method for which they are intended: rotogravure, offset, letterpress printing, flexographic printing, screen printing, etc.
  • the ink In rotogravure, the ink is contained in small cells and its transfer by capillarity on the coated paper or cardboard can only be done if the periphery of each cell is in perfect contact with the latter. It was therefore important to use paper or cardboard coated with excellent smoothness. However, the smoothness obtained by calendering is higher the higher the pressure of the calender. It is however necessary to limit the calendering pressure in order to maintain a layer porosity sufficient for the printability of the coated paper or, in the case of cardboard, so as not to weaken certain physical characteristics or mechanical properties such as the thickness and / or stiffness. Or you have to use a paper or cardboard with a higher grammage of the order of 10 to 20%.
  • the invention proposes a new coated paper or cardboard having an excellent aptitude for gravure printing, at the same time as good mechanical properties, without however being of excessive grammage.
  • the paper or cardboard according to the invention comprises at least one coating layer containing hollow microspheres filled with an inert gas.
  • These hollow microspheres provide the coating layer with great flexibility or compressibility, much greater than that of conventional layers containing mineral pigments. This flexibility allows continuous contact between the coated paper or cardboard and the cells containing the ink during gravure printing, without the need for excellent smoothness.
  • the coating layer can be an outer layer.
  • the surface of the coated paper or cardboard has a high coefficient of friction which can be troublesome during the processing operations by preventing the sliding of the coated sheets.
  • the absorption of inks and varnishes is important, which can alter the freshness and gloss of the print.
  • the coating layer containing the microspheres is a sub-layer which is covered with a pel- li cu external improving the surface properties of paper or cardboard, namely e.g. slip, gloss.
  • This external film is a known layer, for example a conventional coating layer based exclusively on mineral pigments, a film of an organic polymer loaded with pigments or not, or a film of an extruded organic polymer.
  • this outer layer is very thin, so as not to alter the flexibility due to the coating layer containing the microspheres.
  • microspheres used in the composition of the compressible layer are, for example, hollow microcapsules whose flexible wall consists of a polymer capable of softening on heating, such as polyvinylidene chloride, polystyrene, a copolymer based on vinylidene chloride and of acrylonitrile, containing inside an inert gas, for example isobutane, chlorofluorinated hydrocarbons, chlorinated derivatives, carbon dioxide.
  • a polymer capable of softening on heating such as polyvinylidene chloride, polystyrene, a copolymer based on vinylidene chloride and of acrylonitrile, containing inside an inert gas, for example isobutane, chlorofluorinated hydrocarbons, chlorinated derivatives, carbon dioxide.
  • the compressible coating layer containing microspheres can have a calculated average thickness of the order of 2 to 50 t / m and more.
  • the compressible coating layer comprises pigments among which 1 to 100% and preferably 25 to 100% by weight consist of hollow microspheres filled with an inert gas
  • the other conventional pigments can be mineral pigments such as clays such as kaolin, calcium carbonate, titanium oxide, hydrargilite, talc, barium sulphate.
  • the compressible coating layer also comprises at least one binder and possibly other ingredients such as dispersing agents, agents capable of improving the water retention properties, etc.
  • the compressible coating layer has a mass of 1 to 10 g and preferably 2 to 5 g per m 2 of surface.
  • the paper can be coated on one of its faces with two or more coating layers containing microspheres.
  • the paper or cardboard comprises a coating layer or sublayer containing micro- spheres on each of its faces.
  • the invention also relates to a process for the production of coated paper or cardboard.
  • the paper or cardboard is coated on one or both sides with an aqueous composition containing synthetic polymers in the form of hollow microspheres containing an inert gas, expandable with heat, at least one binder, if necessary other pigments and other conventional ingredients as mentioned above.
  • the coated paper or cardboard is then dried at the softening temperature of the hollow microspheres, generally between 80 ° C and 120 ° C approximately. This drying lasts a few seconds, or more if necessary, and has the effect of causing the microspheres to expand.
  • an aqueous composition is used containing microspheres already expanded beforehand after having undergone a heat treatment.
  • a perfectly uniform and homogeneous layer is obtained which has a much greater flexibility than that of conventional layers based on mineral pigments.
  • the coated paper or cardboard is advantageously covered with an external film then can also undergo a finishing operation such as calendering, brushing or superglazing.
  • the air knife for the implementation of the coating process, one can use for example the air knife, the size-press, the Champion coater, the Massey coater, the trailing scraper.
  • Aqueous coating compositions are prepared with the components and in the proportions indicated in Table 1. The amounts are expressed per 100 parts by weight by weight of pigment (microspheres plus mineral pigments).
  • the microspheres consist of hollow capsules made of polyvinylidene chloride or a copolymer of vinylidene chloride and acrylonitrile containing isobutane.
  • the microspheres sold under the name SARAN by the company DOW CHEMICAL or the PVDC microspheres of the Swedish company KEMANORD are used.
  • the expandable microspheres have an average diameter of 5 ⁇ m.
  • compositions contain a binder which is a latex of styrene-butadiene. They contain a thickener such as carboxy-methyl-cellulose designated by the abbreviation CMC in the table. They also contain a lubricating agent such as a stearate. Finally, they contain a dispersant such as a polyacrylate.
  • a binder which is a latex of styrene-butadiene. They contain a thickener such as carboxy-methyl-cellulose designated by the abbreviation CMC in the table. They also contain a lubricating agent such as a stearate. Finally, they contain a dispersant such as a polyacrylate.
  • the dry extract of the aqueous compositions is generally between 10 and 30% by weight.
  • a 150 g / cm 2 paper consisting of two jets of pulp, namely 100 g of bleached pulp and 50 g of unbleached pulp, is coated on the side of the bleached pulp using the aqueous compositions according to Table 1, prepared beforehand.
  • the coated paper is then dried by a battery of driers at a temperature of 90 ° C for about 15 seconds, which has the effect of softening the microspheres and allowing their expansion to an average diameter of the order of 25 ⁇ m approximately then it undergoes a calendering by passage between two cylinders with a diameter of 25 cm exerting a force of 20 kg per linear cm.
  • the radiator grille can be equipped with a water doctor who regularly distributes, at the time of calendering, an aqueous polyethylene emulsion at a rate of 2 g / m 2 .
  • the paper is then conditioned at a temperature of 23 ° C in an atmosphere at 50% relative humidity.
  • coated papers according to Examples 1 to 14 are examined from the point of view of their aptitude for heliographic printing.
  • a suitable device is the IGT device of the "Institut Voor Graphische Technick tno Amsterdam". After having scraped off the excess ink from a hollow engraved wheel, the coated paper to be tested is dynamically printed under pressure (300 N / 3cm and 600 N / 3cm) and speed (100 cm / s) conditions data.
  • Printing in plain area allows only a qualitative judgment that is difficult to express.
  • the prints in dotted lines and in degraded range show the good printability of the papers according to the invention.
  • Printing in. dot lines determines the printability by the number of missing dots; plus the number of missing dots is low, the better the impression. On the papers according to Examples 1 to 11, zero missing points are observed. On papers 12, 13 and 14, there are respectively 6, 11 and 12 missing points.
  • Printing in degraded area determines the aptitude for printing by the distance between the start of printing, starting from the strong tone, and the first point of imitation unprinted; the greater the distance, the better the uniformity of the impressions.

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  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Steroid Compounds (AREA)
  • Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)
  • Making Paper Articles (AREA)

Abstract

Coated papers and cardboards comprising at least one compressible layer of coating containing hollow microspheres filled with a gas that is inert with respect to the microsphere-forming material. The coated papers and cardboards of this invention are used particularly for rotogravure printing. A process for manufacturing these coated papers and cardboards.

Description

La présente invention concerne les papiers ou cartons à base de fibres cellulosiques. Elle concerne plus particulièrement un nouveau papier ou carton comprenant au moins une couche permettant ou facilitant l'impression en héliogravure. Elle concerne encore un procédé de fabrication de ces papiers ou cartons.The present invention relates to paper or cardboard based on cellulosic fibers. It relates more particularly to a new paper or cardboard comprising at least one layer allowing or facilitating gravure printing. It also relates to a process for manufacturing these papers or cartons.

Les papiers et cartons subissent généralement une enduction (ou couchage) afin d'améliorer notamment leurs propriétés mécaniques et/ou d'en permettre l'impression.Paper and cardboard are generally coated (or coated) in order to improve their mechanical properties in particular and / or allow them to be printed.

Les papiers ou cartons couchés connus présentent au moins une couche d'enduction contenant des pigments et des liants. Le pigment le plus couramment utilisé est une argile, tel le kaolin. Eventuellement d'autres pigments lui sont associés, tels le carbonate de calcium, l'oxyde de titane, l'hydrargilite, le talc, le sulfate de baryum. Les pigments sont fixés au papier à l'aidé de liants, par exemple un copolymère de styrène-butadiène, un polymère acrylique, un polymère d'acétate de vinyle, des liants naturels, de l'amidon, des protéines, des caséines, des alcools polyvinyliques, ou un mélange de ces corps.Known coated paper or cardboard has at least one coating layer containing pigments and binders. The most commonly used pigment is a clay, such as kaolin. Possibly other pigments are associated with it, such as calcium carbonate, titanium oxide, hydrargilite, talc, barium sulphate. The pigments are attached to the paper using binders, for example a styrene-butadiene copolymer, an acrylic polymer, a vinyl acetate polymer, natural binders, starch, proteins, caseins, polyvinyl alcohols, or a mixture of these bodies.

La couche d'enduction des papiers ou cartons couchés connus peut encore comprendre des agents dispersants ayant servi à sa fabrication à partir de compositions aqueuses. De tels agents sont par exemple le pyrophosphate tétrasodique, l'hexamétaphosphate de sodium, les po- lyacrylates de bas poids moléculaire, à des taux compris entre 0,2 et 0,5 % en poids par rapport aux pigments.The coating layer of known coated paper or cardboard can also comprise dispersing agents which have been used for its manufacture from aqueous compositions. Such agents are, for example, tetrasodium pyrophosphate, sodium hexametaphosphate, low molecular weight polyacrylates, at levels of between 0.2 and 0.5% by weight relative to the pigments.

La couche d'enduction peut également comprendre des agents susceptibles d'améliorer les propriétés de rétention de l'eau tels, la carboxyméthylcellulose, les alginates.The coating layer may also include agents likely to improve the water retention properties such as carboxymethylcellulose, alginates.

Les propriétés que doivent posséder les papiers ou cartons enduits différent selon le mode d'impression auquel ils sont destinés : héliogravure, offset, impression typographique, impression flexogra- phique, sérigraphie, etc...The properties that coated paper or cardboard must have differ depending on the printing method for which they are intended: rotogravure, offset, letterpress printing, flexographic printing, screen printing, etc.

En héliogravure, l'encre est contenue dans de petites alvéoles et son transfert par capillarité sur le papier ou le carton enduit ne peut se faire que si le pourtour de chaque alvéole est en contact parfait avec ce dernier. Il importait donc d'utiliser un papier ou un carton couché d'excellent lissé. Or le lissé obtenu par calandrage est d'autant plus élevé que la pression de la calandre est plus forte. Il est cependant nécessaire de limiter la pression du calandrage afin de maintenir une porosité de couche suffisante pour l'imprimabilité du papier couché ou encore, dans le cas des cartons, pour ne pas affaiblir certaines caractéristiques physiques ou propriétés mécaniques comme l'épaisseur et/ou la rigidité. Ou alors il faut utiliser un papier ou carton d'un grammage supérieur de l'ordre de 10 à 20 %.In rotogravure, the ink is contained in small cells and its transfer by capillarity on the coated paper or cardboard can only be done if the periphery of each cell is in perfect contact with the latter. It was therefore important to use paper or cardboard coated with excellent smoothness. However, the smoothness obtained by calendering is higher the higher the pressure of the calender. It is however necessary to limit the calendering pressure in order to maintain a layer porosity sufficient for the printability of the coated paper or, in the case of cardboard, so as not to weaken certain physical characteristics or mechanical properties such as the thickness and / or stiffness. Or you have to use a paper or cardboard with a higher grammage of the order of 10 to 20%.

C'est pourquoi les papiers ou cartons couchés connus, c'est-à-dire enduits de compositions contenant des pigments minéraux, présentent généralement une aptitude médiocre à l'impression en héliogravure.This is why the known coated papers or cardboards, that is to say coated with compositions containing mineral pigments, generally have a poor aptitude for printing in gravure printing.

L'invention propose un nouveau papier ou carton couché ayant une excellente aptitude à l'impression en héliogravure, en même temps que de bonnes propriétés mécaniques, sans pour autant être d'un grammage excessif. Le papier ou carton selon l'invention comprend au moins une couche d'enduction contenant des microsphères creuses remplies d'un gaz inerte.The invention proposes a new coated paper or cardboard having an excellent aptitude for gravure printing, at the same time as good mechanical properties, without however being of excessive grammage. The paper or cardboard according to the invention comprises at least one coating layer containing hollow microspheres filled with an inert gas.

Ces microsphères creuses procurent à la couche d'enduction une grande souplesse ou compressibilité, très supérieure à celle des couches classiques contenant des pigments minéraux. Cette souplesse permet un contact continu entre le papier ou le carton couché et les alvéoles contenant l'encre lors de l'impression en héliogravure, sans qu'il soit nécessaire d'avoir un lissé excellent.These hollow microspheres provide the coating layer with great flexibility or compressibility, much greater than that of conventional layers containing mineral pigments. This flexibility allows continuous contact between the coated paper or cardboard and the cells containing the ink during gravure printing, without the need for excellent smoothness.

La couche d'enduction peut être une couche externe. Dans ce cas cependant, la surface du papier ou carton couché présente un coefficient de frottement élevé qui peut être gênant lors des opérations de transformation en empêchant le glissement des feuilles enduites. En outre, l'absorption des encres et vernis est importante, ce qui peut altérer la fraîcheur et le brillant de l'impression.The coating layer can be an outer layer. In this case, however, the surface of the coated paper or cardboard has a high coefficient of friction which can be troublesome during the processing operations by preventing the sliding of the coated sheets. In addition, the absorption of inks and varnishes is important, which can alter the freshness and gloss of the print.

C'est pourquoi, avantageusement, la couche d'enduction contenant les microsphères est une sous-couche qui est recouverte d'une pel- licule externe améliorant les propriétés superficielles du papier ou carton à savoir par exemple le glissement, le brillant. Cette pellicule externe est une couche connue, par exemple une couche d'enduction classique à base exclusive de pigments minéraux, un film d'un polymère organique chargé de pigments ou non, ou encore un film d'un polymère organique extrudé.Therefore, advantageously, the coating layer containing the microspheres is a sub-layer which is covered with a pel- li cu external improving the surface properties of paper or cardboard, namely e.g. slip, gloss. This external film is a known layer, for example a conventional coating layer based exclusively on mineral pigments, a film of an organic polymer loaded with pigments or not, or a film of an extruded organic polymer.

De préférence, cette couche externe est très mince, pour ne pas altérer la souplesse due à la couche d'enduction contenant les microsphères.Preferably, this outer layer is very thin, so as not to alter the flexibility due to the coating layer containing the microspheres.

Les microsphères entrant dans la composition de la couche compressible sont par exemple des_microcapsules creuses dont la paroi souple est constituée d'un polymère susceptible de se ramollir par chauffage, tel le chlorure de polyvinylidène, le polystyrène, un copolymère à base de chlorure de vinylidène et d'acrylonitrile, contenant à l'intérieur un gaz inerte, par exemple l'isobutane, des hydrocarbures chlorofluorés, des dérivés chlorés, du gaz carbonique.The microspheres used in the composition of the compressible layer are, for example, hollow microcapsules whose flexible wall consists of a polymer capable of softening on heating, such as polyvinylidene chloride, polystyrene, a copolymer based on vinylidene chloride and of acrylonitrile, containing inside an inert gas, for example isobutane, chlorofluorinated hydrocarbons, chlorinated derivatives, carbon dioxide.

Suivant une caractéristique de l'invention, la couche d'enduction compressible contenant des microsphères peut avoir un épaisseur moyenne calculée de l'ordre de 2 à 50 t/m et plus.According to a characteristic of the invention, the compressible coating layer containing microspheres can have a calculated average thickness of the order of 2 to 50 t / m and more.

Sous un des aspects de l'invention, la couche d'enduction compressible comprend des pigments parmi lesquels 1 à 100 % et de préférence 25 à 100 % en poids sont constitués de microsphères creuses remplies d'un gaz inerte, les autres pigments classiques pouvant être des pigments minéraux tels les argiles comme le kaolin, du carbonate de calcium, de l'oxyde de titane, de l'hydrargilite, du talc, du sulfate de baryum.In one aspect of the invention, the compressible coating layer comprises pigments among which 1 to 100% and preferably 25 to 100% by weight consist of hollow microspheres filled with an inert gas, the other conventional pigments can be mineral pigments such as clays such as kaolin, calcium carbonate, titanium oxide, hydrargilite, talc, barium sulphate.

La couche d'enduction compressible comprend également au moins un liant et éventuellement d'autres ingrédients comme les agents dispersants, les agents susceptibles d'améliorer les propriétés de rétention de l'eau, etc...The compressible coating layer also comprises at least one binder and possibly other ingredients such as dispersing agents, agents capable of improving the water retention properties, etc.

Généralement, la couche d'enduction compressible a une masse de 1 à 10 g et de préférence de 2 à 5 g par m2 de surface.Generally, the compressible coating layer has a mass of 1 to 10 g and preferably 2 to 5 g per m 2 of surface.

Pour augmenter la souplesse du papier, on peut l'enduire sur une de ses faces de deux couches d'enduction et plus contenant des microsphères.To increase the flexibility of the paper, it can be coated on one of its faces with two or more coating layers containing microspheres.

Suivant une caractéristique de l'invention, le papier ou carton comprend une couche ou sous-couche d'enduction contenant des micro- sphères sur chacune de ses faces.According to a characteristic of the invention, the paper or cardboard comprises a coating layer or sublayer containing micro- spheres on each of its faces.

L'invention concerne également un procédé pour la fabrication de papiers ou de cartons enduits.The invention also relates to a process for the production of coated paper or cardboard.

Selon le procédé, on enduit le papier ou carton sur une de ses faces ou sur les deux par une composition aqueuse contenant des polymères synthétiques sous forme de microsphères creuses renfermant un gaz inerte, expansibles à la chaleur, au moins un liant, le cas échéant d'autres pigments et d'autres ingrédients classiques comme cités précédemment. On sèche ensuite le papier ou carton enduit à la température de ramollissement des microsphères creuses, comprise généralement entre 80°C et 120°C environ. Ce séchage dure quelques secondes, ou plus le cas échéant, et il a pour effet de provoquer l'expansion des microsphères.According to the method, the paper or cardboard is coated on one or both sides with an aqueous composition containing synthetic polymers in the form of hollow microspheres containing an inert gas, expandable with heat, at least one binder, if necessary other pigments and other conventional ingredients as mentioned above. The coated paper or cardboard is then dried at the softening temperature of the hollow microspheres, generally between 80 ° C and 120 ° C approximately. This drying lasts a few seconds, or more if necessary, and has the effect of causing the microspheres to expand.

Dans une variante, on utilise une composition aqueuse contenant des microsphères déjà expansées au préalable après avoir subi un traitement thermique.In a variant, an aqueous composition is used containing microspheres already expanded beforehand after having undergone a heat treatment.

On obtient une couche parfaitement unie et homogène qui présente un souplesse très supérieure à celle des couches classiques à base de pigments minéraux.A perfectly uniform and homogeneous layer is obtained which has a much greater flexibility than that of conventional layers based on mineral pigments.

Après séchage, le papier ou carton couché est avantageusement recouvert d'une pellicule externe puis peut encore subir une opération de finissage telle que le calandrage, le brossage ou le surglaçage.After drying, the coated paper or cardboard is advantageously covered with an external film then can also undergo a finishing operation such as calendering, brushing or superglazing.

Pour la mise en oeuvre du procédé d'enduction, on peut utiliser par exemple la lame d'air, la size-press, la coucheuse Champion, la coucheuse Massey, la râcle traînante.For the implementation of the coating process, one can use for example the air knife, the size-press, the Champion coater, the Massey coater, the trailing scraper.

D'autres caractéristiques et avantages apparaîtront dans la description suivante d'exemples selon l'invention.Other characteristics and advantages will appear in the following description of examples according to the invention.

EXEMPLES 1 A 11EXAMPLES 1 TO 11

On prépare des compositions aqueuses d'enduction avec les composants et dans les proportions indiqués dans le tableau 1. Les quantités sont exprimées pour 100 parties pondérales en poids de pigment (microsphères plus pigments minéraux). Les microsphères sont constituées de capsules creuses en chlorure de polyvinylidène ou en un copolymère de chlorure de vinylidène et d'acrylonitrile contenant de l'isobutane. On utilise par exemple les microsphères commercialisées sous l'appellation SARAN par la Société DOW CHEMICAL ou encore les microsphères PVDC de la Société suédoise KEMANORD. Les microsphères expansibles ont un diamètre moyen de 5 um.Aqueous coating compositions are prepared with the components and in the proportions indicated in Table 1. The amounts are expressed per 100 parts by weight by weight of pigment (microspheres plus mineral pigments). The microspheres consist of hollow capsules made of polyvinylidene chloride or a copolymer of vinylidene chloride and acrylonitrile containing isobutane. For example, the microspheres sold under the name SARAN by the company DOW CHEMICAL or the PVDC microspheres of the Swedish company KEMANORD are used. The expandable microspheres have an average diameter of 5 µm.

Les compositions contiennent un liant qui est un latex de styrêne-butadiêne. Elles contiennent un épaississant tel la carboxy- méthyl-cellulose désignée par l'abréviation CMC dans le tableau. Elles contiennent également un agent lubrifiant tel un stéarate. Elles contiennent enfin un dispersant tel un polyacrylate.The compositions contain a binder which is a latex of styrene-butadiene. They contain a thickener such as carboxy-methyl-cellulose designated by the abbreviation CMC in the table. They also contain a lubricating agent such as a stearate. Finally, they contain a dispersant such as a polyacrylate.

L'extrait sec des compositions aqueuses est généralement compris entre 10 et 30 % en poids.

Figure imgb0001
The dry extract of the aqueous compositions is generally between 10 and 30% by weight.
Figure imgb0001

Un papier de 150 g/cm2, constitué de deux jets de pâte, à savoir 100 g de pâte blanchie et 50 g de pâte écrue est enduit sur le côté de la pâte blanchie à l'aide des compositions aqueuses selon le tableau 1, préparées au préalable.A 150 g / cm 2 paper, consisting of two jets of pulp, namely 100 g of bleached pulp and 50 g of unbleached pulp, is coated on the side of the bleached pulp using the aqueous compositions according to Table 1, prepared beforehand.

Le papier enduit est ensuite séché par une batterie de sécheurs à une température de 90°C pendant 15 secondes environ, ce qui a pour effet de ramollir les microsphères et de permettre leur dilatation jusqu'à un diamètre moyen de l'ordre de 25 µm environ puis il subit un calandrage par passage entre deux cylindres d'un diamètre de 25 cm exerçant une force de 20 kg par cm linéaire.The coated paper is then dried by a battery of driers at a temperature of 90 ° C for about 15 seconds, which has the effect of softening the microspheres and allowing their expansion to an average diameter of the order of 25 µm approximately then it undergoes a calendering by passage between two cylinders with a diameter of 25 cm exerting a force of 20 kg per linear cm.

Lorsqu'avantageusement la couche contenant des microsphères est revêtue d'une pellicule externe, on peut équiper la calandre d'un docteur d'eau qui distribue régulièrement, au moment du calandrage par exemple, une émulsion aqueuse de polyéthylène à raison de 2 g/m2.When the layer containing microspheres is advantageously coated with an external film, the radiator grille can be equipped with a water doctor who regularly distributes, at the time of calendering, an aqueous polyethylene emulsion at a rate of 2 g / m 2 .

On peut encore extruder un film d'un polymère organique par exemple du polyéthylène puis l'appliquer sur la couche contenant les microsphères.It is also possible to extrude a film of an organic polymer by example of polyethylene then apply it on the layer containing the microspheres.

Le papier est ensuite conditionné à la température de 23°C dans une atmosphère à 50 % d'humidité relative.The paper is then conditioned at a temperature of 23 ° C in an atmosphere at 50% relative humidity.

EXEMPLES 12 A 14EXAMPLES 12 TO 14

Ces exemples concernent des papiers couchés à l'aide de compositions aqueuses classiques ne contenant que des pigments minéraux et autres ingrédients comme indiqués dans le tableau 2.

Figure imgb0002
These examples relate to papers coated with conventional aqueous compositions containing only mineral pigments and other ingredients as indicated in Table 2.
Figure imgb0002

Les papiers enduits selon les exemples 1 à 14 sont examinés au point de vue de leur aptitude à l'impression héliographique.The coated papers according to Examples 1 to 14 are examined from the point of view of their aptitude for heliographic printing.

Pour effectuer ces tests, on utilise un appareil mettant en oeuvre le principe du procédé d'impression héliographique. Un appareil convenable est l'appareil IGT de "l'Institut Voor Graphische Technick tno Amsterdam". Après avoir raclé l'excès d'encre d'une molette gravée en creux, on imprime dynamiquement le papier couché à tester dans des conditions de pression (300 N/3cm et 600 N/3cm) et de vitesse (100 cm/s) données.To carry out these tests, an apparatus using the principle of the heliographic printing process is used. A suitable device is the IGT device of the "Institut Voor Graphische Technick tno Amsterdam". After having scraped off the excess ink from a hollow engraved wheel, the coated paper to be tested is dynamically printed under pressure (300 N / 3cm and 600 N / 3cm) and speed (100 cm / s) conditions data.

Trois types de gravure sont réunies sur la même molette : une plage unie à trame conventionnelle, une plage dégradée à trame, des lignes de points.Three types of engraving are combined on the same wheel: a solid area with conventional weft, a degraded area with weft, lines of dots.

On examine les papiers sur lesquels a été effectuée l'impression.We examine the papers on which the printing was carried out.

L'impression en plage unie ne permet qu'un jugement qualitatif difficile à exprimer. Par contre les impressions en lignes de points et en plage dégradée montrent la bonne aptitude à l'impression des papiers selon l'invention.Printing in plain area allows only a qualitative judgment that is difficult to express. On the other hand, the prints in dotted lines and in degraded range show the good printability of the papers according to the invention.

L'impression en. lignes de points détermine l'aptitude à l'impression par le nombre de points manquants ; plus le nombre de points manquants est faible, meilleure est l'impression. Sur les papiers selon les exemples 1 à 11, on observe zéro point manquant. Sur les papiers 12, 13 et 14, on observe respectivement 6, 11 et 12 points manquants.Printing in. dot lines determines the printability by the number of missing dots; plus the number of missing dots is low, the better the impression. On the papers according to Examples 1 to 11, zero missing points are observed. On papers 12, 13 and 14, there are respectively 6, 11 and 12 missing points.

L'impression en plage dégradée détermine l'aptitude à l'impression par la distance entre le début de l'impression, en partant du ton fort, et le premier point de simili non imprimé ; plus la distance est grande, meilleure est l'uni des impressions. Sur les papiers selon les exemples 1 à 11, il n'y a jamais de point de simili non imprimé. Pour les papiers réalisés selon les exemples 12 à 14, on note respectivement 24, 45 et 35 mm.Printing in degraded area determines the aptitude for printing by the distance between the start of printing, starting from the strong tone, and the first point of imitation unprinted; the greater the distance, the better the uniformity of the impressions. On the papers according to examples 1 to 11, there is never an unprinted imitation dot. For the papers produced according to Examples 12 to 14, 24, 45 and 35 mm are noted respectively.

Claims (15)

1. Papier ou carton à base de fibres cellulosique revêtu d'au moins une couche d'enduction contenant des pigments, caractérisé en ce que la couche d'enduction contient des microsphères creuses remplies d'un gaz inerte.1. Paper or cardboard based on cellulosic fibers coated with at least one coating layer containing pigments, characterized in that the coating layer contains hollow microspheres filled with an inert gas. 2. Papier ou carton selon la revendication 1, caractérisé en ce que la couche d'enduction comprenant des microsphères creuses rem- plies d'un gaz inerte est une sous-couche revêtue d'une pellicule externe améliorant les propriétés superficielles du papier ou carton.2. Paper or cardboard according to claim 1, characterized in that the coating layer comprising hollow microspheres rem - plies of an inert gas is an under-layer coated with an outer film improving the surface properties of paper or paperboard . 3. Papier ou carton selon la revendication 2, caractérisé en ce que la pellicule externe est choisie parmi une couche d'enduction classique à base exclusive de pigments minéraux, un film d'un polymère organique chargé de pigments ou non, un film extrudé.3. Paper or cardboard according to claim 2, characterized in that the external film is chosen from a conventional coating layer based exclusively on mineral pigments, a film of an organic polymer loaded with pigments or not, an extruded film. 4. Papier ou carton selon une des revendications 1 à 3, caractérisé en ce que les microsphères sont expansées.4. Paper or cardboard according to one of claims 1 to 3, characterized in that the microspheres are expanded. 5. Papier ou carton selon une des revendications 1 à 4, caractérisé en ce que les microsphères forment de 1 à 100 % en poids des pigments et de préférence de 25 % à 100 %.5. Paper or cardboard according to one of claims 1 to 4, characterized in that the microspheres form from 1 to 100% by weight of the pigments and preferably from 25% to 100%. 6. Papier ou carton selon une des revendications 1 à 5, caractérisé en ce que les microsphères ont des parois formées par des polymères expansés et qu'elles contiennent un gaz inerte.6. Paper or cardboard according to one of claims 1 to 5, characterized in that the microspheres have walls formed by expanded polymers and that they contain an inert gas. 7. Papier ou carton selon la revendication 6, caractérisé en ce que le polymère formant les parois des microsphères est choisi parmi le chlorure de polyvinylidène, le polystyrène, un copolymère à base de chlorure de vinylidène et d'acrylonitrile, et que le gaz inerte est choisi parmi l'isobutane, des hydrocarbures chlorofluorés, des dérivés chlorés, du gaz carbonique.7. Paper or cardboard according to claim 6, characterized in that the polymer forming the walls of the microspheres is chosen from polyvinylidene chloride, polystyrene, a copolymer based on vinylidene chloride and acrylonitrile, and that the inert gas is chosen from isobutane, chlorofluorinated hydrocarbons, chlorinated derivatives, carbon dioxide. 8. Papier ou carton selon la revendication 7, caractérisé en ce que les microsphères sont en chlorure de polyvinylidène et qu'elles contiennent de l'isobutane.8. Paper or cardboard according to claim 7, characterized in that the microspheres are made of polyvinylidene chloride and that they contain isobutane. 9. Papier ou carton selon le revendication 7, caractérisé en ce que les microsphères sont en un copolymère à base de chlorure de vinylidène et d'acrylonitrile et qu'elles contiennent de l'isobutane.9. Paper or cardboard according to claim 7, characterized in that the microspheres are made of a copolymer based on vinylidene chloride and acrylonitrile and that they contain isobutane. 10. Papier ou carton selon une des revendications 1 à 9, caractérisé en ce que la couche d'enduction contenant des microsphères contient d'autres ingrédients tels les liants, les adjuvants, les pigments minéraux.10. Paper or cardboard according to one of claims 1 to 9, characterized in that the coating layer containing microspheres contains other ingredients such as binders, adjuvants, mineral pigments. 11. Papier ou carton selon une des revendications 1 à 10, caractérisé en ce que la couche d'enduction contenant les microsphères a une masse de 1 à 10 g par m2 et de préférence 2 à 5 g.11. Paper or cardboard according to one of claims 1 to 10, characterized in that the coating layer containing the microspheres has a mass of 1 to 10 g per m 2 and preferably 2 to 5 g. 12. Papier ou carton présentant une couche d'enduction très souple et compressible selon une des revendications 1 à 11, caractérisé en ce qu'il est utilisé pour l'impression en héliogravure.12. Paper or cardboard having a very flexible and compressible coating layer according to one of claims 1 to 11, characterized in that it is used for gravure printing. 13. Procédé de fabrication du papier ou carton revêtu d'au moins une couche d'enduction, caractérisé en ce qu'on enduit le papier ou carton à l'aide d'une composition aqueuse contenant des microsphères expansibles, puis qu'on chauffe la couche enduite afin de dilater les microsphères.13. A method of manufacturing paper or cardboard coated with at least one coating layer, characterized in that the paper or cardboard is coated with an aqueous composition containing expandable microspheres, then heated the coated layer to expand the microspheres. 14. Procédé selon la revendication 13, caractérisé en ce qu'on revêt la couche d'enduction à l'aide d'une pellicule externe.14. The method of claim 13, characterized in that the coating layer is coated with an external film. 15. Procédé selon la revendication 13, caractérisé en ce qu'après séchage, on fait subir au papier ou carton enduit une opération de finissage telle que le calandrage, le brossage, ou le surglaçage.15. The method of claim 13, characterized in that after drying, the coated paper or cardboard is subjected to a finishing operation such as calendering, brushing, or superglaze.
EP81401558A 1980-10-08 1981-10-08 Coated papers and cardboards, and process for manufacturing them Expired EP0049672B1 (en)

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ES506092A0 (en) 1982-09-01
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ATE12531T1 (en) 1985-04-15
ES8304245A1 (en) 1982-09-01

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