EP0246987B1 - Ink jet recording sheet and process for its manufacture - Google Patents

Ink jet recording sheet and process for its manufacture Download PDF

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Publication number
EP0246987B1
EP0246987B1 EP19870420131 EP87420131A EP0246987B1 EP 0246987 B1 EP0246987 B1 EP 0246987B1 EP 19870420131 EP19870420131 EP 19870420131 EP 87420131 A EP87420131 A EP 87420131A EP 0246987 B1 EP0246987 B1 EP 0246987B1
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EP
European Patent Office
Prior art keywords
sheet
base sheet
derivatives
boric acid
layer
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EP19870420131
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German (de)
French (fr)
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EP0246987A1 (en
Inventor
Claude Raymond Riou
Georges Marc Gidon
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Aussedat-Rey
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Aussedat-Rey
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Priority to FR8607355A priority patent/FR2598974B1/en
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Priority claimed from AT87420131T external-priority patent/AT71027T/en
Publication of EP0246987A1 publication Critical patent/EP0246987A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/252Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254Polymeric or resinous material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256Heavy metal or aluminum or compound thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258Alkali metal or alkaline earth metal or compound thereof
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31935Ester, halide or nitrile of addition polymer

Description

  • La présente invention concerne : The present invention provides:
    • une feuille d'enregistrement par jet d'encre, a recording sheet by ink jet,
    • les procédés utilisables pour la préparation de ladite feuille. the methods used for the preparation of said sheet.
  • La technique d'impression par jet d'encre connaît un succés certain. The printing technique of ink jet with some success. Cependant, l'étude détaillée des caractères obtenus par cette technique montre l'existence d'un certain nombre de défauts dûs à la non adaptation de la feuille sur laquelle est réalisé l'enregistrement, aux particularités de la technique de jet d'encre. However, the detailed study of the characters obtained by this technique shows the existence of a number of defects due to the non-adaptation of the sheet on which the recording is made, to the particularities of the ink jet technique.
  • On connaît déjà un certain nombre de publications et, en particulier, de brevets ou demandes de brevets, proposant des moyens d'obtenir des feuilles pour impression par jet d'encre de bonne qualité. already known a number of publications and, in particular, patents or patent applications, offering ways to get sheets for printing high-quality inkjet. Certains, en particulier, revendiquent le couchage d'un support par une composition comportant des charges absorbantes de nature ou de propriétés physiques définies, destinées à absorber l'encre, ou bien des supports papetiers ayant des caractéristiques particulières ou encore, l'association des deux. Some, especially, claim coating a support with a composition comprising absorbent fillers in the nature or physical properties defined, for absorbing the ink, or papermakers supports having specific characteristics or the association of two.
  • Ainsi, par exemple, les brevets US 4 269 891, US 4 461 174 préconisent l'emploi de charges absorbantes comprenant, en particulier, silice, diatomées, zéolite, silicates synthétiques ou naturels. Thus, for example, US Patent 4269891, US 4461174 advocate the use of absorbent fillers including, in particular, silica, diatomaceous earth, zeolite, natural or synthetic silicates.
  • Plus tard, le brevet japonais J 56 148 582 et les suivants revendiquent l'utilisation de charges de couchage du même genre et, en particulier, une micropoudre de silice amorphe avec différents liants synthétiques. Later, the Japanese patent J 56148582 and the following claim the use of coating fillers and the like, in particular, an amorphous silica micropowder with different synthetic binders.
  • Le brevet US 4 440 827 revendique le couchage de telles compositions absorbantes en au moins deux opérations de couchage identiques dans le but d'obtenir une grande résolution, sans nuire à la solidité de la couche. US Patent 4,440,827 claims the Sleeping such absorbent compositions in at least two coating operations identical in order to obtain high resolution without compromising the strength of the layer.
  • Le brevet US 4 460 637 revendique une distribution particulière de diamètres de pores dans les couches d'un papier pour impression jet d'encre, constituées de charges absorbantes. U.S. Patent 4,460,637 claims a particular distribution of pore diameters in the layers of a paper for ink jet printing, comprised of absorptive fillers.
  • Le brevet US 4 478 910 ou EP 0 121 916 revendique l'association d'un support peu collé et très absorbant pour les solutions aqueuses et d'une couche comportant un liant synthétique et une fine poudre de silice de surface spécifique BET supérieure à 200 m²/g. U.S. Patent 4,478,910 or EP 0,121,916 claims the combination of a support and very little bonded absorbent for aqueous solutions and a layer comprising a synthetic binder and a fine BET specific surface area of silica powder exceeds 200 m² / g.
  • On peut citer aussi le brevet US 4 496 629 préconisant une couche à base de charges absorbantes comme la silice, cette couche étant divisée en une multitude de lamelles séparées par des microcrevasses donnant lieu, selon l'inventeur, à une qualité supérieure. Patent may also be mentioned US 4496629 advocating a base layer absorbent fillers such as silica, this layer being divided into a plurality of slats separated by microcrevasses giving rise, according to the inventor, at a higher quality.
  • Selon l'expérience du Déposant, les méthodes décrites permettent d'obtenir des impressions par jet d'encre, qui sont, malheureusement, souvent affectées de défauts qualitatifs dont la suppression est difficile et onéreuse. In the experience of the Depositor, the methods described allow to obtain prints by inkjet, which are unfortunately often affected quality defects whose removal is difficult and expensive. De plus, la qualité de ces impressions est très dépendante de celle du support utilisé pour le couchage. Moreover, the quality of these impressions is very dependent on that of the medium used for the coating. En outre, bien que le brevet US 4 460 637 évoque une relation entre la résolution, l'épaisseur de la couche et le taux de liant de celle-ci, aucune publication ne décrit clairement un moyen de faire varier la taille des points obtenus avec une goutte d'encre définie, envoyée par un système de jet d'encre donné. Moreover, although the patent US 4,460,637 suggests a relationship between resolution, the thickness of the layer and the binder content of the latter, no publication clearly describes a way to vary the size of points obtained with an ink drop set, sent by a given ink-jet system.
  • Si par action sur certains paramètres de la couche (surface spécifique, nature et taux des liants, épaisseur de la couche, humidité) on fait varier la taille des points d'impression obtenus à partir de gouttes d'encre de dimension donnée, on constate des défauts de forme et d'uniformité de ces points : If by action on certain parameters of the layer (surface area, nature and binders rate, layer thickness, humidity) varying the size of the print points obtained from given size of ink drops, it is found defects in shape and uniformity of these points:
    • a) Si les points sont gros, ils sont dentelés et de densité très hétérogène. a) If the points are big, they are serrated and heterogeneous density. Le résultat est un aspect flou de l'impression. The result is a blurring of printing.
    • b) Si les points sont petits, ils sont de forme extrêmement irrégulière, en raison surtout de microcraquelures de la couche analoques à celles qui sont prônées par le brevet US 4 496 629 . b) If the points are small, they are extremely irregular, mainly because of the microcracks analoques layer to those advocated by US patent 4,496,629. En fait, ces crevasses s'opposent latéralement à la migration horizontale de l'encre et, au contraire, la canalisent dans le sens de leur longueur, donnant à ces points des formes très irrégulières et inacceptables. In fact, these cracks laterally opposing horizontal migration of the ink and, instead, the channel in the direction of their length, giving these points very irregular and unacceptable forms.
  • Pour supprimer ces défauts, on peut agir sur le support en modifiant son pouvoir absorbant, sa structure, la forme de ses éléments constitutifs, son lissé, etc, ce qui oblige à une définition précise de la qualité du support pour chaque cas particulier. To eliminate these defects, we can act on the support by changing its absorbency, its structure, the shape of its components, smoothness, etc., which requires a precise definition of the quality of support for each individual case.
  • On peut aussi agir sur la composition de la couche et la méthode de couchage. It can also act on the composition of the layer and the coating method. Ainsi, les microcraquelures peuvent être réduites en augmentant le taux de liant, mais on se heurte alors à des problèmes comme la difficulté de séchage, l'augmentation du coût de la composition et l'abaissement des densités de couleurs. Thus, microcracks can be reduced by increasing the binder content, but then encountered problems such as drying of difficulty, increasing the cost of the composition and the lowering of color densities. On peut aussi réduire les microcraquelures en diminuant la température et la vitesse de séchage, mais on arrive ainsi à d'importantes limitations économiques. It can also reduce the microcracks reducing the temperature and drying rate, but as happens in major economic limitations. Il est également possible de coucher en deux ou plusieurs passages, ce qui est l'objet du brevet US 4 440 827 , mais, là encore, le surcoût économique est considérable. It is also possible to sleep in two or more passes, which is the subject of US patent 4,440,827, but, again, the economic cost is considerable.
  • L'objet de la présente invention est de supprimer les défauts cités ci-dessus sans supporter les conséquences néfastes, les difficultés et les coûts qui résultent de l'application des méthodes décrites. The object of the present invention is to remove the defects mentioned above without incurring the negative consequences, difficulties and costs that result from the application of the methods described.
  • On a, par ailleurs, décrit, pour différents types de papiers, l'utilisation, en liaison avec l'emploi de liants polymériques polyhydroxylés, de produits coagulants et gélifiants. It has also described for different types of paper, use in conjunction with the use of polymeric binders polyhydroxylated of coagulants and gelling agents.
  • Parmi les différents produits coagulant ou gélifiant les liants polyhydroxylés, les plus connus et surtout les plus efficaces, sont l'acide borique et/ou ses dérivés. Among the different products or gelling coagulant polyhydroxyl binders, the best known and especially the most effective are the boric acid and / or its derivatives.
  • La réaction chimique et l'effet obtenu par l'acide borique et ses dérivés sur des liants polyhydroxylés sont bien connus et ont été déjà décrits en détail dans diverses publications. The chemical reaction and the effect obtained by boric acid and its derivatives polyhydroxy binders are well known and have already been described in detail in various publications.
  • L'acide borique et ses dérivés ont été fréquemment utilisés pour différentes applications industrielles, parmi lesquelles il est possible de citer les abrasifs, les antigels, les ciments et les plâtres, les colles, les émaux, l'ignifugation, la métallurgie, les produits pharmaceutiques et cosmétiques, les tanneries, la verrerie, la papeterie. Boric acid and its derivatives have been widely used for various industrial applications, among which we can include abrasives, antifreeze, cements and plasters, adhesives, enamels, fireproofing, metallurgy products pharmaceutical and cosmetic, tanneries, glass, paper.
  • Dans ces nombreuses applications, on exploite la plupart du temps, soit leur réaction de gélification avec les liants polyhydroxylés, soit leur pouvoir tampon, soit leurs propriétés antiseptiques. In these various applications, it operates most of the time or their gelling reaction with polyhydroxyl binders or their buffering capacity, or their antiseptic properties.
  • L'acide borique et ses dérivés ont été utilisés en papeterie pour l'obtention de différents résultats : Boric acid and its derivatives have been used in papermaking to obtain different results:
    • en combinaison avec des liants polyhydroxylés pour la réalisation de colles et adhésifs pour le carton ondulé, cette application étant, notamment, décrite dans les brevets FR 2 469 439 et 2 331 591 . in combination with polyhydroxy binders for producing glues and adhesives for corrugated cardboard, this application being in particular described in patents FR 2,469,439 and 2,331,591. Le collage de surface ainsi réalisé permet d'obtenir une barrière aux graisses, solvants, vernis, une imperméabilité du papier ou carton à l'air, ainsi qu'une meilleure résistance à l'abrasion, The thus formed bonding surface provides a barrier to fats, solvents, varnishes, impermeability of paper or paperboard to air, as well as improved abrasion resistance,
    • en combinaison avec l'alcool polyvinylique pour l'obtention d'un papier présentant un effet barrière, obtenu grâce à la gélification de l'alcool, permettant de fixer une goutte d'encre dès son arrivée sur la surface du papier non couché. in combination with the polyvinyl alcohol to obtain a paper having a barrier effect, obtained by gelation of alcohol, for fixing an ink drop from its arrival on the surface of the uncoated paper. Cette application a été décrite dans les brevets japonais J 52 088 406 et J 52 126 305 (TOPPAN PRINTING KK) : un papier est traité en surface par de l'acide borique ou un borate ou bien un produit minéral ou organique capable de coaguler l'alcool polyvinylique. This application has been described in Japanese Patent J 52,088,406 and 52,126,305 J (TOPPAN PRINTING KK): a paper is surface-treated with boric acid or a borate or a mineral or organic material capable of coagulating the polyvinyl alcohol. Ce papier est ensuite destiné à être imprimé en héliographie, flexographie ou par jet d'encre avec une encre aqueuse contenant de l'alcool polyvinylique. This paper is then intended to be printed by photogravure, flexography or by ink jet with an aqueous ink containing polyvinyl alcohol.
  • Il est à noter, toutefois, que, jusqu'à présent, cette réaction de gélification ou coagulation de liants polyhydroxylés, par l'acide borique et/ou ses dérivés, n'avait jamais été mise à profit pour réaliser une feuille d'enregistrement pour jet d'encre absorbant l'encre de façon homogène et régulière et conduisant ainsi à un support d'enregistrement jet d'encre aux propriétés remarquables. It should be noted, however, that hitherto this gelation reaction or coagulation of polyhydroxy binders, boric acid and / or its derivatives has never been exploited to realize a recording sheet inkjet ink absorbing of homogeneously and uniformly and thus leading to a jet recording medium an ink with remarkable properties.
  • Les publications de l'art antérieur, mentionnant l'emploi de cette réaction sur des papiers destinés à recevoir une impression de type classique, comme celles de : The publications of the prior art, mentioning the use of this reaction on paper for receiving printing of conventional type, such as those of:
    • BA BEARWOOD et EP. BA Bearwood and EP. CZERWIN - TAPPI volume 43, 11, pages 944-952 (1960), Gmina Czerwin - TAPPI Volume 43, 11, 944-952 pages (1960)
    • BA BEARWOOD et CJ STAPS , papier, carton et cellulose, 13, 2, pages 83-90 (1964), BA Bearwood and CJ STAPS, paper, cardboard and cellulose, 13, 2, pages 83-90 (1964),
    décrivent un procédé destiné, au contraire, à conférer à la surface du papier ou du carton d'impression des propriétés dites "barrières", c'est-à-dire à les rendre imperméables aux liquides comme les huiles, l'eau, les encres d'imprimerie, liquides qui, de ce fait, restent à la surface une fois déposés sur ce support. disclose a method for, on the contrary, to provide the surface of the paper or printing properties of said carton "barriers", that is to say to make them impermeable to fluids such as oils, water, printing inks, liquids, therefore, remain on the surface once deposited on this support.
  • On connaît, enfin, le brevet JP-A-87 089/85 qui décrit une feuille pour enregistrement jet d'encre comprenant un pigment d'absorption d'huile, un agent coagulant pour ce pigment constitué d'un composé de magnésium, et un liant. It is known, finally, JP-A-87 089/85 describes a sheet for ink jet recording comprising an oil-absorbing pigment, a coagulating agent for this pigment consisting of a magnesium compound, and a binder.
  • La feuille ainsi obtenue possède des propriétés améliorées relatives à la vitesse de séchage. The resulting sheet has improved properties for the drying rate. La feuille ainsi obtenue n'est cependant pas susceptible de conduire à une forme élargie des points, tout en conservant une bonne qualité de forme et d'uniformité desdits points. The sheet thus obtained however is not likely to lead to an enlarged shape of the dots while maintaining a good quality of shape and uniformity of said points.
  • L'objet de la présente invention consiste à réaliser une feuille d'impression couchée utilisable par la technique du jet d'encre, que l'on puisse mettre en oeuvre par des techniques papetières connues et qui éliminent les défauts constatés dans les résultats obtenus par utilisation de la technique du jet d'encre sur les feuilles d'impression décrites à ce jour. The object of the present invention to provide a coated printing sheet usable by the technique of ink-jet, which can be implemented by known papermaking techniques that control the defects found in the results obtained by using the technique of ink jet printing on the sheets described to date.
  • L'objet de l'invention sera mieux apprécié par comparaison des résultats obtenus illustrés par les figures suivantes. The object of the invention will be better appreciated by comparing the results shown in the following figures.
  • Les fig. FIGS. 1 à 6 sont des représentations de résultats obtenus avec certaines imprimantes connues utilisant, selon deux exemples de mise en oeuvre, un papier d'impression par jet d'encre ordinaire commercialisé, un papier spécifique et un papier selon l'invention. 1 to 6 are representations of results obtained with some known printers using, as two examples of implementation, a printing paper by ink jet ordinarily marketed, one specific and a paper according to the invention.
  • Les fig. FIGS. 7 à 9 montrent un des avantages procurés par un papier selon l'invention. 7-9 show one of the benefits of a paper according to the invention.
  • La feuille selon l'invention pour impression par jet d'encre, constituée d'une feuille support dont une face est surmontée d'une couche, ladite couche étant réalisée par couchage d'une sauce sur ce support, est caractérisée en ce qu'elle comporte, dans sa couche, un liant polymérique polyhydroxylé comprenant des groupements hydroxyles en position cis, ledit liant ayant été gélifié ou coagulé par l'acide borique et/ou ses dérivés lors du couchage, et une charge présentant un pouvoir absorbant. The sheet according to the invention for ink-jet, comprising a support sheet whose one face is topped by a layer, said layer being formed by coating a sauce thereon, is characterized in that it comprises in its layer, a polyhydroxylic polymeric binder comprising hydroxyl groups in the cis position, said binder being gelled or coagulated with boric acid and / or its derivatives during the coating, and a filler having a absorbency.
  • Le liant polymérique polyhydroxylé dont les groupements hydroxyle sont en position cis est, préférentiellement, du type alcool polyvinylique ou copolymères d'alcool polyvinylique. The polymeric binder polyhydroxy whose hydroxyl groups are in the cis position is, preferably, polyvinyl alcohol or copolymers of polyvinyl alcohol type. Les produits utilisables sont, par exemple, décrits dans le livre "Polyvinyl alcohol properties and applications" édité par CA FINCH et publié par J. WILEY and sons. The products are used, for example, described in the book "properties and applications Polyvinyl alcohol" edited by CA FINCH and published by J. Wiley and Sons. On utilisera, de préférence, un alcool polyvinylique dont les caractéristiques (degré d'hydrolyse et degré de polymérisation) pourront être convenablement choisies en fonction, notamment, du procédé de préparation de la feuille employée. Will be used, preferably a polyvinyl alcohol whose characteristics (degree of hydrolysis and degree of polymerization) can be suitably selected depending, inter alia, of the employed sheet preparation process.
  • Dans la feuille selon l'invention, tout ou une partie importante de ce liant polymérique polyhydroxylé a été gélifiée (ou coagulée), grâce à l'action de l'acide borique et/ou ses dérivés (borax ...), assumant une fonction d'agent gélifiant ou coagulant. In the sheet according to the invention, all or a significant portion of the polyhydroxylic polymeric binder was gelled (or coagulated), thanks to the action of the boric acid and / or derivatives thereof (borax ...), assuming a function of gelling or coagulating agent.
  • La quantité d'agent gélifiant (ou coagulant) utilisée peut varier selon le mode d'utilisation de cet agent. The amount of gelling agent (or coagulating) used may vary depending on the use of this agent mode. Lorsque ledit agent est déposé sur le support de la feuille on en utilisera, de préférence, de 0,05 à 2 g/m² d'acide borique et de ses dérivés. When said agent is deposited on the support of the sheet is in use, preferably, 0.05 to 2 g / m² of boric acid and its derivatives.
  • La gélification du liant polymérique doit avoir lieu au cours de l'opération de couchage, d'où la mise au point de divers procédés qui seront explicités ultérieurement et qui font partie de l'invention. The gelling of the polymeric binder to take place during the coating operation, resulting in the development of various methods which will be explained later and are part of the invention. On notera ici que, dans le produit fini (feuille), une certaine proportion de l'agent gélifiant ou de dérivés de cet agent gélifiant est généralement encore présente, soit dans la couche de couchage, soit dans le support ou à la surface du support de la feuille. It should be noted here that, in the finished product (sheet), a proportion of the gelling agent or derivatives of this gelling agent is generally still present, either in the coating layer, either in the support or the support surface of the sheet.
  • La charge présentant un grand pouvoir absorbant, utilisée dans l'invention, est un matériau connu pour sa grande surface spécifique et peut être choisie parmi les produits suivants : silice, silicates divers, zéolites, kaolins calcinés, diatomées, sulfate de baryum, hydroxydes d'aluminium, pigments de mélamine-formol ou d'urée-formol. The load of great absorbency, used herein, is a material known for its large surface area and can be chosen from the following products: silica, various silicates, zeolites, calcined kaolin, diatomaceous earth, barium sulfate, hydroxides aluminum, melamine-formaldehyde pigments or urea-formaldehyde.
  • Les proportions entre les deux principaux constituants de cette couche de couchage, à savoir le liant et la charge, peuvent varier dans un large domaine, mais sont comprises, très généralement, entre 10 et 100 % en poids de liant par rapport à la charge. The proportions between the two main constituents of this coating layer, i.e. the binder and filler, can be varied within a wide range, but are understood, very generally, from 10 to 100% by weight of binder relative to the filler.
  • Il est clair que la couche de couchage peut comporter des additifs, classiquement utilisés dans de telles couches, comme, par exemple, des antimousses, des tensioactifs, des azurants ... Le poids de couche est d'environ 0,5 à 20 g/m². It is clear that the coating layer may comprise additives conventionally used in such layers, such as, for example, defoamers, surfactants, brighteners ... The coating weight is about 0.5 to 20 g / m².
  • La présente invention concerne, également, des procédés pour la réalisation des feuilles selon l'invention. The present invention also relates to methods for producing sheets according to the invention.
  • On utilisera un support quelconque sur lequel sera déposée une sauce de couchage. We will use any medium on which is deposited a coating color. Le support utilisé peut être de nature cellulosique ou non et avoir été obtenu par voie papetière ou non. The media may be cellulosic or non nature and have been obtained by paper path or not. On pourra utiliser un papier, un carton, un film synthétique, un support non tissé ... La nature et les propriétés physiques dudit support ne sont pas critiques et dépendent, principalement, du type de produit fini recherché. may be used a paper, a cardboard, a synthetic film, a nonwoven support ... The nature and physical properties of said substrate are not critical and depend mainly on the type of desired finished product.
  • Dans un premier procédé, l'agent gélifiant sera apporté avec ledit support, soit par incorporation dudit agent dans le support lui-même, soit par dépôt dudit agent sur la surface devant recevoir la sauce de couchage. In a first method, the gelling agent will be provided with said support, or by incorporating said agent in the carrier itself, or by delivery of said agent on the surface to receive the coating color. Dans ce cas là, on déposera simplement sur le support comportant ledit agent gélifiant la sauce de couchage comportant le liant polymérique polyhydroxylé et la charge et la gélification dudit liant se produira durant l'opération de couchage. In this case, it is simply deposited on the substrate having said coating slip gelling agent comprising the polymeric binder and the polyhydroxy load and gelation of said binder will occur during the coating operation.
  • Dans un deuxième procédé, l'agent gélifiant sera incorporé dans la sauce de couchage, mais il conviendra, au préalable, de désactiver (temporairement) ledit agent gélifiant et de le réactiver au moment du couchage. In a second method, the gelling agent will be incorporated into the coating, but it should, in advance, disable (temporarily) said gelling agent and to reactivate the at the time of coating. Par exemple, l'agent gélifiant inactivé peut être l'acide borique qui, s'il provoque une agumentation de la viscosité du milieu aqueux contenant l'alcool polyvinylique, ne provoque pas une gélification totale de cet alcool. For example, the inactivated gelling agent may be boric acid, which if agumentation causes the viscosity of the aqueous medium containing the polyvinyl alcohol does not cause complete gelation of this alcohol. Dans ce cas, la gélification se produit par contact entre la préparation de couchage et le support dont le pH doit être, de préférence, voisin de la neutralité. In this case, gelation occurs by contact between the preparation and the coating medium, the pH should be preferably close to neutrality.
  • Le couchage du support est réalisé par des méthodes de couchage classique à rouleau (size-press, rouleau gravé, barre, reverse roll ...) ou bien à lame (lame d'air, lame traînante ...). Coating of the support is realized by conventional roller coating methods (size-press, gravure roll, rod, reverse roll ...) or blade (air knife, trailing blade ...).
  • Dans tous les cas, on obtient ainsi une couche lisse et sans défaut, dont les variations d'épaisseur entre points distants de moins de 500 microns dans le sens du plan de la feuille, sont insensibles et n'ont pas d'effet mesurable. In all cases, we obtain a smooth coat and without blemish, the variations in thickness between remote points of less than 500 microns in the direction of the plane of the sheet, are insensitive and do not have a measurable effect. La couche est plus lisse, ne comporte pas de craquelures et se trouve mieux individualisée par rapport au support, la zone d'interpénétration étant réduite. The layer is smoother, has no cracks and is better individualized with respect to the support, the interpenetration zone being reduced.
  • Les avantages de l'invention peuvent être résumés comme suit. The advantages of the invention can be summarized as follows.
    • 1°) - Avec une feuille selon l'invention, la qualité des points obtenus par impression jet d'encre est supérieure à celle que l'on obtiendrait par les procédés déjà décrits, tant du point de vue de leur circularité que de leur uniformité interne, et ceci quel que soit leur diamètre. 1) - with a sheet according to the invention, the quality of points obtained by ink jet printing is greater than that which would be obtained by the methods already described, both from the point of view of their circularity as their uniformity internal, and this regardless of their diameter.
    • 2°) - De ce fait, il est possible d'élargir la gamme des diamètres de points que l'on peut obtenir en leur conservant cette qualité de forme et d'uniformité, du diamètre mini au diamètre maxi qui sont dans un rapport de 1 à 3 (ceci pour un même volume de goutte d'encre). 2 °) - Therefore, it is possible to expand the range of diameters of points that we can get this quality retaining their shape and consistency, the minimum diameter to maximum diameter which are in a ratio of 1 to 3 (this for the same volume of ink droplet).
    • 3°) - Le résultat obtenu ne dépend plus autant qu'avant de la qualité du support utilisé, qui peut être pratiquement quelconque, tant du point de vue composition, morphologie de ses constituants (fibres, charges ...), pouvoir absorbant (porosité, collage ...), structure interne, lissé de surface, etc. 3) - The result obtained no longer as dependent before the quality of the medium used, which can be virtually any, both the composition point of view, morphology of its components (fibers, fillers ...), absorbency ( porosity, gluing ...), internal structure, surface smoothness, etc. Il en résulte plus de facilité, plus de sécurité et un coût réduit de fabrication. The result is easier, more security and a reduced manufacturing cost.
    • 4°) - Ce résultat peut être obtenu en une seule opération de couchage, quelle que soit la taille des points désirée, sans avoir à recourir à de difficiles et onéreuses opérations de couchage en deux ou plus de deux opérations successives. 4 °) - This can be achieved in a single coating operation, regardless of the size of the desired points, without resorting to difficult and costly coating operations in two or more than two successive operations.
    • 5°) - L'invention permet un accroissement de la solidité de la couche. 5) - The invention allows an increase in the strength of the layer.
    • 6°) - Elle permet une augmentation de la densité des impressions, à la fois par une modification de la formulation du couchage permise par l'accroissement de sa solidité et par la possibilité d'augmenter le diamètre des points dans de bonnes conditions. 6.) - It allows an increase in the density of impressions, both by changing the wording of sleeping permitted by its increasing strength and the possibility to increase the diameter of the points in the right conditions.
  • L'invention permet donc, plus facilement et à moindres frais, l'adaptation optimale de la qualité de la feuille d'enregistrement au type d'imprimante à laquelle on la destine. The invention therefore, more easily and at lower cost, optimum adaptation of the quality of the recording sheet to the printer type to which it was intended.
  • Les exemples non limitatifs ci-après illustrent l'invention par rapport à l'art antérieur. Non-limiting examples below illustrate the invention compared to the prior art.
  • EXEMPLE 1 : EXAMPLE 1
  • On a employé deux supports différents. We used two different media.
    • a) Un papier absorbant, relativement poreux et peu lissé, caractérisé par les tests suivants : a) An absorbent paper, porous and relatively little smoothed, characterized by the following tests:
      • porosité à l'air AFNOR 2,1 air porosity AFNOR 2.1
      • collage COBB (1 min) 300 bonding COBB (1 min) 300
      • lissé BEKK 40 Bekk smoothness 40
    • b) Le même papier support a été enduit d'une solution de borax à 5 i de concentration, résultant en un dépôt de borax de 0,4 g/m² en matières sèches. b) The same paper was coated with a solution of borax to 5 i concentration, resulting in a borax deposit of 0.4 g / m² on a dry basis.
  • Dans un deuxième stade, ces deux supports ont été couchés dans des conditions identiques par la sauce de couchage suivante : In a second stage, these two supports were coated under identical conditions by the following coating color:
    • 70 parts en poids de silice synthétique, en poudre fine, caractérisée par une prise d'huile de 250 g par gramme de poudre <mesuré suivant T 30.022 ou ISO R 787), 70 parts by weight of synthetic silica, fine powder, characterized by an oil absorption of 250 g per gram of powder <measured according to T 30 022 or ISO R 787)
    • 30 parts en poids d'un silicate d'alumine en poudre, d'un diamètre moyen de particules de 2,5 microns et comportant plus de 95 96 de particules de diamètre inférieur à 10 microns, 30 parts by weight of a powder of alumina silicate, having an average particle diameter of 2.5 microns and comprising more than 95 96 particles of diameter less than 10 microns,
    • 30 parts en poids d'un alcool polyvinylique de viscosité moyenne <environ 7 à 11 cps en solution à 4 et de degré d'hydrolyse 98, 30 parts by weight of a polyvinyl alcohol of medium viscosity <11 cps to about in 7 solution at 4 and hydrolysis degree 98,
    • quantité d'eau suffisante pour aboutir à une préparation à 10 % de teneur en matières sèches. amount of water sufficient to result in a preparation of 10% solids content.
  • La solidité de la couche et sa liaison au support ont été mesurées par la vitesse à laquelle la couche commence à s'arracher par impression d'une encre Lorilleux 3802 sur un appareil IGT Ait 2. Les vitesses d'arrachage et les poids de couche sont les suivants : The strength of the layer and its connection to the support were measured by the speed at which the layer starts to tear by printing an ink on an IGT Lorilleux 3802 Ait apparatus 2. The tear speeds and coating weight are the following :
    Figure imgb0001
  • Ces deux papiers couchés ont été imprimés par jet d'encre sur une imprimante SIEMENS PT 88, ainsi qu'un papier du commerce c) vendu sous le nom de Neujet 1/7 comme étant adapté à cette imprimante entre autres. Both of these coated papers were printed by ink jet on a Siemens PT 88 printer and a paper trade c) sold under the name Neujet 1/7 as suitable for this printer among others. Ces trois papiers ont été imprimés avec la même encre SIEMENS noire. These three papers were printed with the same black ink SIEMENS.
  • L'examen des impressions, réalisées sur ces divers papiers et illustrées par les fig. Examination of impressions made on these various papers and illustrated in FIGS. 1 à 3 , montre que les points obtenus sur le papier couché sur support avec utilisation de borax (b) sont beaucoup plus réguliers que ceux obtenus sur les autres papiers. 1 to 3 shows that the points obtained on coated paper support with use of borax (b) are much more regular than those obtained in other papers. Les représentations des fig. The representations of FIGS. 1 à 3 correspondent à des photographies réalisées avec un même appareil POLAROID SX70 avec le même grossissement, dans les mêmes conditions d'éclairage et dans les mêmes délais après impression. 1-3 correspond to photographs made with a POLAROID SX70 same device with the same magnification under the same lighting conditions and within the same time after printing.
  • EXEMPLE 2 : EXAMPLE 2
  • De la même façon, deux supports ont été fabriqués à partir de la même base. Similarly, two materials have been made from the same base.
    • a) Un papier assez imperméable à l'eau et à l'air et relativement lisse, caractérisé par les tests ci-dessous : a) A paper relatively impermeable to water and air and relatively smooth, characterized by the following tests:
      • porosité à l'air AFNOR ............ 0,6 air porosity AFNOR ............ 0.6
      • collage COBB (1 min) .............. 15 bonding COBB (1 min) .............. 15
      • lissé BEKK ...................... 200 Bekk smoothness ...................... 200
    • b) Le même papier a été enduit d'une solution de borax à 10 % de concentration, ce qui a donné un dépôt de borax sec de 0,7 g/m². b) The same paper was coated with a solution of borax at 10% concentration, to give a deposit of dry borax 0.7 g / m².
  • Ces deux supports ont été couchés et séchés dans des conditions identiques par la sauce de couchage suivante : These two materials were coated and dried under the same conditions by the following coating color:
    • 100 parts en poids de silice synthétique, de qualité identique à celle de l' exemple 1 , 100 parts by weight of synthetic silica, of identical quality to that of Example 1,
    • 20 parts en poids d'un alcool polyvinylique complètement hydrolysé et de viscosité à 4 % comprise entre 26 et 32 cps, 20 parts by weight of a polyvinyl alcohol completely hydrolyzed and viscosity at 4% between 26 and 32 cps,
    • quantité d'eau suffisante pour obtenir une préparation à 18 % de teneur en matières sèches. amount of water sufficient to obtain a formulation with 18% solids content.
  • Les dépôts de couche et les résistances à l'arrachage figurent sur le tableau ci-dessous . layer deposition and resistance to picking shown in the table below.
    Figure imgb0002
  • Les deux papiers ont été imprimés avec une imprimante à jet d'encre Diablo (technologie SHARP I0.0700), ainsi qu'un papier c) du commerce présenté comme référence pour une telle imprimante. Both papers were printed with an ink jet printer Diablo (SHARP I0.0700 technology) and a paper c) trade presented as a reference to such a printer. Ces trois papiers ont été imprimés avec la même encre SCHARP noire. These three papers were printed with the same black ink SCHARP.
  • Là encore, l'examen des taches d'encre obtenues montre clairement, par comparaison des fig. Again, examination of the ink spots obtained clearly demonstrates, by comparison of Fig. 4 à 6 , que sur le papier selon l'invention lesdites taches sont plus précises et ont un contour plus net. 4 to 6, on paper according to the invention said spots are more accurate and have a sharp outline.
  • Des conditions opératoires identiques à celles ci-dessus ont été retenues pour réaliser les photographies de base des représentations selon les fig. Operating conditions identical to those above were selected to perform basic photographic representations of FIGS. 4 à 6 . 4 to 6.
  • Les fig. FIGS. 7 à 9 correspondent à des photographies réalisées selon les mêmes conditions opératoires que ci-dessus, à partir de papiers traités conformément à l'invention et imprimés par une imprimante SIEMENS PT 88 avec une encre SIEMENS noire. 7-9 correspond to photographs taken under the same operating conditions as above, from papers treated according to the invention and printed by a printer SIEMENS PT 88 with a black ink SIEMENS. L'examen de ces figures permet de constater qu'il est possible d'élargir la gamme de diamètres de points que l'on peut obtenir, tout en leur conservant les qualités de forme et d'uniformité mises en évidence précédemment. The examination of these figures reveals that it is possible to expand the range of points of diameters that can be achieved, while maintaining those qualities of form and consistency demonstrated previously. L'examen de ces figures permet de constater qu'il est possible d'obtenir des points de très bonne qualité dont les diamètres sont dans un rapport de 1 à 3 pour un même volume d'encre, en agissant sur certains paramètres de la couche de traitement du papier, tels que surface spécifique, nature et taux des liants, épaisseur, humidité. The examination of these Figures reveals that it is possible to obtain very good points whose diameters are in a ratio of 1 to 3 for the same volume of ink, by acting on certain parameters of the layer paper processing, such as surface area, nature and binders rate, thickness, moisture.

Claims (5)

  1. Sheet for ink-jet printing constituted by a base sheet of which at least one face is topped by a layer produced by coating of a slip, said layer including a gel or a coagulate,
       characterized in that the layer comprises :
    - a gel or a coagulate constituted by reacting boric acid salt and/or its derivatives with a polyhydroxylic polymeric binder comprising hydroxyl groups in the cis position,
    - a filler with an absorption capacity.
  2. Sheet according to claim 1, characterized in that the polyhydroxylic polymeric binder is polyvinyl alcohol or a polyvinyl alcohol copolymer.
  3. Sheet according to claim 1 or 2, characterized in that the filler is selected from the group comprising silica, silicated, zeolites, calcined kaolins, diatomaceous earths, barium sulfate, aluminium hydroxides and melamine/formaldehyde or urea/formaldehyde pigments.
  4. Process for the preparation of a sheet for ink-jet printing from a base sheet, for obtaining a sheet according to one of claims 1 to 3, in which a gellying or coagulating reaction is caused in the layer topping at least one face of the base sheet,
       characterized in that :
    - boric acid and/or its derivatives are applied to the base sheet by incorporation or surface deposition,
    - a coating slip containing a filler with an absorption capacity and a polyhydroxylic polymeric binder with the hydroxyl groups in the cis position is coated then onto said base sheet, said binder being gelled or coagulated with boric acid and/or its derivatives.
  5. Process for the preparation of a sheet for jet-ink printing from a base sheet, for obtaining a sheet according to one of claims 1 to 3, in which a gellying or coagulating reaction is caused in the layer topping at least one face of the base sheet,
       characterized in that :
    - a coating slip is produced which contains :
    . a polyhydroxylic polymeric binder with the hydroxyl groups in the cis position,
    . a filler with an absorption capacity and boric acid and/or its derivatives,
    - said slip is applied onto the base sheet whose pH is close to neutrality in order to cause gellyfication or coagulation of the polyhydroxylic polymeric binder by boric acid and/or its derivatives.
EP19870420131 1986-05-20 1987-05-19 Ink jet recording sheet and process for its manufacture Expired - Lifetime EP0246987B1 (en)

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FR8607355A FR2598974B1 (en) 1986-05-20 1986-05-20 An ink jet recording sheet and process for its preparation.

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AT87420131T AT71027T (en) 1986-05-20 1987-05-19 Sheet for inkjet recording and process for its production.

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