EP0246987A1 - Ink jet recording sheet and process for its manufacture - Google Patents
Ink jet recording sheet and process for its manufacture Download PDFInfo
- Publication number
- EP0246987A1 EP0246987A1 EP87420131A EP87420131A EP0246987A1 EP 0246987 A1 EP0246987 A1 EP 0246987A1 EP 87420131 A EP87420131 A EP 87420131A EP 87420131 A EP87420131 A EP 87420131A EP 0246987 A1 EP0246987 A1 EP 0246987A1
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- EP
- European Patent Office
- Prior art keywords
- coating
- support
- boric acid
- filler
- polymeric binder
- 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
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Classifications
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
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- 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
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- 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
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- 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
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- 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
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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- 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
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- 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
- Y10T428/256—Heavy metal or aluminum or compound thereof
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- 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
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
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- 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
- Y10T428/259—Silicic material
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- 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
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to: - an inkjet recording sheet, - the processes which can be used for the preparation of said sheet.
- the inkjet printing technique has been a definite success.
- the detailed study of the characters obtained by this technique shows the existence of a certain number of defects due to the non-adaptation of the sheet on which the recording is made, to the particularities of the inkjet technique.
- US Patents 4,269,891, US 4,461,174 recommend the use of absorbent fillers comprising, in particular, silica, diatoms, zeolite, synthetic or natural silicates.
- Japanese patent J 56 148 582 and the following claims the use of coating fillers of the same kind and, in particular, an amorphous silica micropowder with different synthetic binders.
- US Patent 4,460,637 claims a particular distribution of pore diameters in the layers of paper for inkjet printing, consisting of absorbent fillers.
- the support can act on the support by modifying its absorbency, its structure, the shape of its constituent elements, its smoothness, etc., which requires a precise definition of the quality of the support for each particular case.
- microcracks can be reduced by increasing the rate of binder, but we then come up against problems such as the difficulty of drying, the increase in the cost of the composition and the lowering of the color densities. It is also possible to reduce the microcracks by decreasing the temperature and the drying speed, but this leads to significant economic limitations. It is also possible to sleep in two or more passes, which is the subject of US Pat . No. 4,440,827 , but again the economic cost is considerable.
- the object of the present invention is to eliminate the defects mentioned above without bearing the harmful consequences, the difficulties and the costs which result from the application of the methods described.
- Boric acid and its derivatives have been frequently used for various industrial applications, among which it is possible to cite abrasives, antifreezes, cements and plasters, glues, enamels, fireproofing, metallurgy, products pharmaceutical and cosmetic, tanneries, glassware, stationery.
- the object of the present invention is to produce a coated printing sheet usable by the inkjet technique, which can be implemented by known papermaking techniques and which eliminate the defects noted in the results obtained by use of the inkjet technique on the printing sheets described to date.
- Figs. 1 to 6 are representations of results obtained with certain known printers using, according to two examples of implementation, an ordinary inkjet printing paper sold, a specific paper and a paper according to the invention.
- Figs. 7 to 9 show one of the advantages provided by a paper according to the invention.
- the sheet according to the invention is characterized in that it comprises, in its coating sauce, a polyhydroxylated polymeric binder whose hydroxyl groups are in the cis position, which has been gelled or coagulated with boric acid and / or its derivatives when lying down and a load having a high absorbency.
- the polyhydroxylated polymeric binder whose hydroxyl groups are in the cis position is preferably of the polyvinyl alcohol or polyvinyl alcohol copolymer type.
- the products which can be used are, for example, described in the book "Polyvinyl alcohol properties and applications" published by CA FINCH and published by J. WILEY and sons.
- a polyvinyl alcohol the characteristics of which (degree of hydrolysis and degree of polymerization) may be suitably chosen as a function, in particular, of the process for preparing the sheet used.
- the amount of gelling agent (or coagulant) used can vary depending on the mode of use of this agent.
- agent When said agent is deposited on the support of the sheet, preferably 0.05 to 2 g / m2 of boric acid and its derivatives will be used.
- the filler having a high absorbency used in the invention, is a material known for its large specific surface and can be chosen from the following products: silica, various silicates, zeolites, calcined kaolins, diatoms, barium sulphate, d hydroxides. aluminum, melamine-formaldehyde or urea-formaldehyde pigments.
- the proportions between the two main constituents of this coating layer can vary within a wide range, but are very generally between 10 and 100% by weight of binder relative to the filler.
- the coating layer may contain additives, conventionally used in such layers, such as, for example, defoamers, surfactants, brighteners, etc.
- the layer weight is approximately 0.5 to 20 g. / m2.
- the present invention also relates to methods for producing the sheets according to the invention.
- Any support will be used on which a coating sauce will be deposited.
- the support used may or may not be of a cellulosic nature and may have been obtained by paper or not. We can use paper, cardboard, synthetic film, non-woven support ... The nature and physical properties of said support are not critical and depend mainly on the type of finished product sought.
- the gelling agent will be provided with said support, either by incorporating said agent into the support itself, or by depositing said agent on the surface to receive the coating sauce.
- the coating sauce comprising the polyhydroxylated polymeric binder will simply be deposited on the support comprising said gelling agent and the charge and gelling of said binder will occur during the coating operation.
- the gelling agent will be incorporated into the coating sauce, but it will be necessary, beforehand, to deactivate (temporarily) said gelling agent and to reactivate it at the time of coating.
- the inactivated gelling agent can be boric acid which, if it causes an increase in the viscosity of the aqueous medium containing polyvinyl alcohol, does not cause total gelling of this alcohol. In this case, gelation occurs by contact between the coating preparation and the support, the pH of which should preferably be close to neutral.
- the coating of the support is carried out by conventional coating methods with a roller (size-press, engraved roller, bar, reverse roll, etc.) or with a blade (air knife, trailing blade, etc.).
- a smooth and flawless layer is thus obtained, the thickness variations of which between distant points of less than 500 microns in the direction of the plane of the sheet, are insensitive and have no measurable effect.
- the layer is smoother, has no cracks and is better individualized with respect to the support, the interpenetration area being reduced.
- the invention therefore allows, more easily and cheaply, the optimal adaptation of the quality of the recording sheet to the type of printer for which it is intended.
- these two supports were coated under identical conditions with the following coating sauce: - 70 parts by weight of synthetic silica, in fine powder, characterized by an oil intake of 250 g per gram of powder (measured according to T 30.022 or ISO R 787), - 30 parts by weight of a powdered alumina silicate, with an average particle diameter of 2.5 microns and comprising more than 95% of particles with a diameter of less than 10 microns, 30 parts by weight of a polyvinyl alcohol of average viscosity (approximately 7 to 11 cps in 4% solution) and of degree of hydrolysis 98, - sufficient amount of water to produce a preparation with 10% dry matter content.
- the solidity of the layer and its bond to the support were measured by the speed at which the layer begins to tear off by printing a Lorilleux 3802 ink on an IGT AiC 2 device.
- the tearing speeds and the layer weights are the following :
- the two papers were printed with a Diablo inkjet printer (SHARP I0.0700 technology), as well as a commercial paper c) presented as a reference for such a printer. These three papers were printed with the same black SCHARP ink.
- Figs. 7 to 9 correspond to photographs produced according to the same operating conditions as above, from papers treated in accordance with the invention and printed by a SIEMENS PT 88 printer with black SIEMENS ink. Examination of these figures shows that it is possible to widen the range of point diameters that can be obtained, while retaining the qualities of shape and uniformity highlighted above. Examination of these figures shows that it is possible to obtain points of very good quality 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 specific surface, nature and rate of binders, thickness, humidity.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Paper (AREA)
- Duplication Or Marking (AREA)
Abstract
Description
La présente invention concerne :
- une feuille d'enregistrement par jet d'encre,
- les procédés utilisables pour la préparation de ladite feuille.The present invention relates to:
- an inkjet recording sheet,
- the processes which can be used for the preparation of said sheet.
La technique d'impression par jet d'encre connaît un succés certain. 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.The inkjet printing technique has been a definite success. However, the detailed study of the characters obtained by this technique shows the existence of a certain number of defects due to the non-adaptation of the sheet on which the recording is made, to the particularities of the inkjet 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. 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.There are already known a number of publications and, in particular, patents or patent applications, proposing means of obtaining sheets for printing by ink jet of good quality. Some, in particular, claim the coating of a support with a composition comprising absorbent fillers of defined nature or physical properties, intended to absorb the ink, or else paper-making supports having particular characteristics, or even the combination of of them.
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 Patents 4,269,891, US 4,461,174 recommend the use of absorbent fillers comprising, in particular, silica, diatoms, zeolite, synthetic or natural 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, Japanese patent J 56 148 582 and the following claims the use of coating fillers of the same kind and, 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 coating of such absorbent compositions in at least two identical coating operations in order to obtain a high resolution, without harming the solidity 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. US Patent 4,460,637 claims a particular distribution of pore diameters in the layers of paper for inkjet printing, consisting of absorbent 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. US Patent 4,478,910 or EP 0 121,916 claims the combination of a slightly bonded and very absorbent support for aqueous solutions and a layer comprising a synthetic binder and a fine silica powder with BET specific surface greater than 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.We can also cite US Pat.
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. De plus, la qualité de ces impressions est très dépendante de celle du support utilisé pour le couchage. 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.According to the experience of the Applicant, the methods described make it possible to obtain inkjet prints, which are, unfortunately, often affected by qualitative defects the removal of which is difficult and expensive. In addition, the quality of these prints is very dependent on that of the support used for coating. In addition, although the US Pat . No. 4,460,637 evokes a relationship between the resolution, the thickness of the layer and the level of binder thereof, no publication clearly describes a means of varying the size of the dots obtained with a defined drop of ink, sent by a given inkjet 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 :
- a) Si les points sont gros, ils sont dentelés et de densité très hétérogène. Le résultat est un aspect flou de l'impression.
- 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. 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.
- a) If the points are large, they are serrated and of very heterogeneous density. The result is a blurry aspect of the print.
- b) If the dots are small, they are extremely irregular in shape, mainly due to micro cracks in the analoque layer to those advocated by US Patent 4,496,629 . In fact, these crevices laterally oppose the horizontal migration of the ink and, on the contrary, channel it in the direction of their length, giving these points very irregular and unacceptable shapes.
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 remove these defects, one can act on the support by modifying its absorbency, its structure, the shape of its constituent elements, its smoothness, etc., which requires a precise definition of the quality of the support for each particular case.
On peut aussi agir sur la composition de la couche et la méthode de couchage. 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. On peut aussi réduire les microcraquelures en diminuant la température et la vitesse de séchage, mais on arrive ainsi à d'importantes limitations économiques. 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.We can also act on the composition of the layer and the coating method. Thus, the microcracks can be reduced by increasing the rate of binder, but we then come up against problems such as the difficulty of drying, the increase in the cost of the composition and the lowering of the color densities. It is also possible to reduce the microcracks by decreasing the temperature and the drying speed, but this leads to significant economic limitations. It is also possible to sleep in two or more passes, which is the subject of US Pat . No. 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 eliminate the defects mentioned above without bearing the harmful consequences, the difficulties and the costs which 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.We have also described, for different types of paper, the use, in conjunction with the use of polyhydroxylated polymeric binders, of coagulating and gelling products.
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 various coagulating or gelling products for polyhydroxylated binders, the best known and above all the most effective are 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 on polyhydroxylated 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 frequently used for various industrial applications, among which it is possible to cite abrasives, antifreezes, cements and plasters, glues, enamels, fireproofing, metallurgy, products pharmaceutical and cosmetic, tanneries, glassware, stationery.
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 many applications, we use most time, either their gelling reaction with polyhydroxylated binders, their buffering capacity, or their antiseptic properties.
L'acide borique et ses dérivés ont été utilisés en papeterie pour l'obtention de différents résultats :
- 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. 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,
- 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. Cette application a été décrite dans les brevets japonais J 52 088 406 et J 52 126 305 (TOPPAN PRINTING K. K.) : 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. 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.Boric acid and its derivatives have been used in stationery for various results:
- In combination with polyhydroxylated binders for the production of glues and adhesives for corrugated cardboard, this application being, in particular, described in patents FR 2 469 439 and 2 331 591 . The surface bonding thus produced makes it possible to obtain a barrier to grease, solvents, varnish, an impermeability of the paper or cardboard to the air, as well as a better resistance to abrasion,
- In combination with polyvinyl alcohol to obtain a paper having a barrier effect, obtained by gelling the alcohol, allowing to fix a drop of ink as soon as it arrives on the surface of the uncoated paper. This application has been described in Japanese patents J 52 088 406 and J 52 126 305 (TOPPAN PRINTING KK) : a paper is surface treated with boric acid or a borate or a mineral or organic product capable of coagulating l polyvinyl alcohol. This paper is then intended to be printed in heliography, 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 so far this gelling or coagulation reaction of polyhydroxylated binders, by boric acid and / or its derivatives, had never been used to produce a recording sheet for inkjet absorbing ink evenly and evenly and thus leading to an inkjet recording medium 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 :
- B. A. BEARWOOD et EP. CZERWIN - TAPPI volume 43, 11, pages 944-952 (1960),
- B. A. BEARWOOD et C. J. STAPS, papier, carton et 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.The publications of the prior art, mentioning the use of this reaction on papers intended to receive a printing of conventional type, such as those of:
- BA BEARWOOD and EP. CZERWIN - TAPPI volume 43, 11, pages 944-952 (1960),
- BA BEARWOOD and CJ STAPS , paper, cardboard and cellulose, 13, 2, pages 83-90 (1964),
describe a process intended, on the contrary, to confer on the surface of the printing paper or cardboard so-called "barrier" properties, that is to say to make them impermeable to liquids such as oils, water, printing inks, liquids which therefore remain on the surface once deposited on this support.
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 is to produce a coated printing sheet usable by the inkjet technique, which can be implemented by known papermaking techniques and which eliminate the defects noted in the results obtained by use of the inkjet technique on the printing 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 comparison of the results obtained illustrated by the following figures.
Les fig. 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. Figs. 1 to 6 are representations of results obtained with certain known printers using, according to two examples of implementation, an ordinary inkjet printing paper sold, a specific paper and a paper according to the invention.
Les fig. 7 à 9 montrent un des avantages procurés par un papier selon l'invention. Figs. 7 to 9 show one of the advantages provided by a paper according to the invention.
La feuille selon l'invention est caractérisée en ce qu'elle comporte, dans sa sauce de couchage, un liant polymérique polyhydroxylé dont les groupements hydroxyle sont en position cis, qui a été gélifié ou coagulé par l'acide borique et/ou ses dérivés lors du couchage et une charge présentant un grand pouvoir absorbant.The sheet according to the invention is characterized in that it comprises, in its coating sauce, a polyhydroxylated polymeric binder whose hydroxyl groups are in the cis position, which has been gelled or coagulated with boric acid and / or its derivatives when lying down and a load having a high absorbency.
Le liant polymérique polyhydroxylé dont les groupements hydroxyle sont en position cis est, préférentiellement, du type alcool polyvinylique ou copolymères d'alcool polyvinylique. Les produits utilisables sont, par exemple, décrits dans le livre "Polyvinyl alcohol properties and applications" édité par C. A. FINCH et publié par 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.The polyhydroxylated polymeric binder whose hydroxyl groups are in the cis position is preferably of the polyvinyl alcohol or polyvinyl alcohol copolymer type. The products which can be used are, for example, described in the book "Polyvinyl alcohol properties and applications" published by CA FINCH and published by J. WILEY and sons. We will preferably use a polyvinyl alcohol, the characteristics of which (degree of hydrolysis and degree of polymerization) may be suitably chosen as a function, in particular, of the process for preparing the sheet used.
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 substantial part of this polyhydroxylated polymeric binder has been gelled (or coagulated), thanks to the action of boric acid and / or its derivatives (borax, etc.), 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. 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.The amount of gelling agent (or coagulant) used can vary depending on the mode of use of this agent. When said agent is deposited on the support of the sheet, preferably 0.05 to 2 g / m² of boric acid and its derivatives will be used.
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. 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.The gelation of the polymeric binder must take place during the coating operation, hence the development of various methods which will be explained later and which form part of the invention. It will be noted here that, in the finished product (sheet), a certain proportion of the gelling agent or of derivatives of this gelling agent is generally still present, either in the coating layer, or in the support or on the surface of the support. 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 filler having a high absorbency, used in the invention, is a material known for its large specific surface and can be chosen from the following products: silica, various silicates, zeolites, calcined kaolins, diatoms, barium sulphate, d hydroxides. aluminum, melamine-formaldehyde or urea-formaldehyde pigments.
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, namely the binder and the filler, can vary within a wide range, but are very generally between 10 and 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 contain additives, conventionally used in such layers, such as, for example, defoamers, surfactants, brighteners, etc. The layer weight is approximately 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 the sheets according to the invention.
On utilisera un support quelconque sur lequel sera déposée une sauce de couchage. Le support utilisé peut être de nature cellulosique ou non et avoir été obtenu par voie papetière ou non. 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.Any support will be used on which a coating sauce will be deposited. The support used may or may not be of a cellulosic nature and may have been obtained by paper or not. We can use paper, cardboard, synthetic film, non-woven support ... The nature and physical properties of said support are not critical and depend mainly on the type of finished product sought.
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. 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 a first method, the gelling agent will be provided with said support, either by incorporating said agent into the support itself, or by depositing said agent on the surface to receive the coating sauce. In this case, the coating sauce comprising the polyhydroxylated polymeric binder will simply be deposited on the support comprising said gelling agent and the charge and gelling 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. 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. 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 a second process, the gelling agent will be incorporated into the coating sauce, but it will be necessary, beforehand, to deactivate (temporarily) said gelling agent and to reactivate it at the time of coating. For example, the inactivated gelling agent can be boric acid which, if it causes an increase in the viscosity of the aqueous medium containing polyvinyl alcohol, does not cause total gelling of this alcohol. In this case, gelation occurs by contact between the coating preparation and the support, the pH of which should preferably be close to neutral.
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 ...).The coating of the support is carried out by conventional coating methods with a roller (size-press, engraved roller, bar, reverse roll, etc.) or with a blade (air knife, trailing blade, etc.).
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. 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.In all cases, a smooth and flawless layer is thus obtained, the thickness variations of which between distant points of less than 500 microns in the direction of the plane of the sheet, are insensitive and have no measurable effect. The layer is smoother, has no cracks and is better individualized with respect to the support, the interpenetration area being reduced.
Les avantages de l'invention peuvent être résumés comme suit.
- 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.
- 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).
- 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. Il en résulte plus de facilité, plus de sécurité et un coût réduit de fabrication.
- 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.
- 5°) - L'invention permet un accroissement de la solidité de la couche.
- 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.
- 1) - With a sheet according to the invention, the quality of the dots obtained by inkjet printing is higher than that which would be obtained by the methods already described, both from the point of view of their circularity and of their uniformity internal, regardless of their diameter.
- 2 °) - As a result, it is possible to widen the range of point diameters that can be obtained by retaining this quality of shape and uniformity, from the minimum diameter to the maximum diameter which are in a ratio of 1 to 3 (this for the same volume of ink drop).
- 3 °) - The result obtained no longer depends as much as before on the quality of the support used, which can be practically any, both from the point of view of composition, morphology of its constituents (fibers, fillers, etc.), absorbency ( porosity, bonding ...), internal structure, surface smoothness, etc. This results in more ease, more security and a reduced manufacturing cost.
- 4 °) - This result can be obtained in a single coating operation, whatever the desired stitch size, without having to resort to difficult and expensive coating operations in two or more of two successive operations.
- 5 °) - The invention allows an increase in the strength of the layer.
- 6 °) - It allows an increase in the density of the prints, both by a modification of the formulation of the coating allowed by the increase in its solidity and by the possibility of increasing the diameter of the points under good 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 allows, more easily and cheaply, the optimal adaptation of the quality of the recording sheet to the type of printer for which it is intended.
Les exemples non limitatifs ci-après illustrent l'invention par rapport à l'art antérieur.The following nonlimiting examples illustrate the invention with respect to the prior art.
On a employé deux supports différents.
- a) Un papier absorbant, relativement poreux et peu lissé, caractérisé par les tests suivants :
- porosité à l'air AFNOR ............... 2,1
- collage COBB (1 min) ................. 300
- lissé BEKK ........................... 40 - b) Le même papier support a été enduit d'une solution de borax à 5 % de concentration, résultant en un dépôt de borax de 0,4 g/m² en matières sèches.
- a) An absorbent paper, relatively porous and not very smooth, characterized by the following tests:
- AFNOR air porosity ............... 2.1
- COBB collage (1 min) ................. 300
- smoothed BEKK ........................... 40 - b) The same support paper was coated with a borax solution at 5% concentration, resulting in a borax deposit of 0.4 g / m² in dry matter.
Dans un deuxiéme stade, ces deux supports ont été couchés dans des conditions identiques par la sauce de couchage suivante :
- 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),
- 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 % de particules de diamètre inférieur à 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,
- quantité d'eau suffisante pour aboutir à une préparation à 10 % de teneur en matières sèches.In a second stage, these two supports were coated under identical conditions with the following coating sauce:
- 70 parts by weight of synthetic silica, in fine powder, characterized by an oil intake of 250 g per gram of powder (measured according to T 30.022 or ISO R 787),
- 30 parts by weight of a powdered alumina silicate, with an average particle diameter of 2.5 microns and comprising more than 95% of particles with a diameter of less than 10 microns,
30 parts by weight of a polyvinyl alcohol of average viscosity (approximately 7 to 11 cps in 4% solution) and of degree of hydrolysis 98,
- sufficient amount of water to produce a preparation with 10% dry matter 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 AiC 2. Les vitesses d'arrachage et les poids de couche sont les suivants :
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. Ces trois papiers ont été imprimés avec la même encre SIEMENS noire.These two coated papers were printed by ink jet on a
L'examen des impressions, réalisées sur ces divers papiers et illustrées par les fig. 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. Les représentations des fig. 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.Examination of the prints made on these various papers and illustrated by figs. 1 to 3, shows that the points obtained on paper coated on a support with the use of borax (b) are much more regular than those obtained on other papers. The representations of fig. 1 to 3 correspond to photographs taken with the same POLAROID SX70 camera with the same magnification, under the same lighting conditions and within the same deadlines after printing.
De la même façon, deux supports ont été fabriqués à partir de la même base.
- a) Un papier assez imperméable à l'eau et à l'air et relativement lisse, caractérisé par les tests ci-dessous :
- porosité à l'air AFNOR ............... 0,6
- collage COBB (1 min) ................. 15
- lissé BEKK ........................... 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.
- a) A paper that is fairly impermeable to water and air and relatively smooth, characterized by the tests below:
- AFNOR air porosity ............... 0.6
- COBB collage (1 min) ................. 15
- smoothed BEKK ........................... 200 - b) The same paper was coated with a 10% concentration borax solution, which gave a dry borax deposit of 0.7 g / m².
Ces deux supports ont été couchés et séchés dans des conditions identiques par la sauce de couchage suivante :
- 100 parts en poids de silice synthétique, de qualité identique à celle de l'exemple 1,
- 20 parts en poids d'un alcool polyvinylique complètement hydrolysé et de viscosité à 4 % comprise entre 26 et 32 cps,
- quantité d'eau suffisante pour obtenir une préparation à 18 % de teneur en matières sèches.These two supports were coated and dried under identical conditions with the following coating sauce:
100 parts by weight of synthetic silica, of quality identical to that of Example 1,
- 20 parts by weight of a completely hydrolyzed polyvinyl alcohol with a viscosity at 4% of between 26 and 32 cps,
- sufficient amount of water to obtain a preparation with 18% dry matter content.
Les dépôts de couche et les résistances à l'arrachage figurent sur le tableau ci-dessous .
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. Ces trois papiers ont été imprimés avec la même encre SCHARP noire.The two papers were printed with a Diablo inkjet printer (SHARP I0.0700 technology), as well as a commercial paper c) presented as a reference for such a printer. These three papers were printed with the same black SCHARP ink.
Là encore, l'examen des taches d'encre obtenues montre clairement, par comparaison des fig. 4 à 6, que sur le papier selon l'invention lesdites taches sont plus précises et ont un contour plus net.Here again, the examination of the ink spots obtained clearly shows, by comparison of FIGS. 4 to 6, that on the paper according to the invention said spots are more precise and have a sharper outline.
Des conditions opératoires identiques à celles ci-dessus ont été retenues pour réaliser les photographies de base des représentations selon les fig. 4 à 6.Operating conditions identical to those above were used to make the basic photographs of the representations according to FIGS. 4 to 6.
Les fig. 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. 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. 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.Figs. 7 to 9 correspond to photographs produced according to the same operating conditions as above, from papers treated in accordance with the invention and printed by a
Claims (5)
Priority Applications (1)
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AT87420131T ATE71027T1 (en) | 1986-05-20 | 1987-05-19 | INK-JET RECORDING SHEET AND METHOD OF PRODUCTION. |
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FR8607355 | 1986-05-20 | ||
FR8607355A FR2598974B1 (en) | 1986-05-20 | 1986-05-20 | SHEET FOR INK JET RECORDING AND PROCESS FOR ITS PREPARATION. |
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EP0246987A1 true EP0246987A1 (en) | 1987-11-25 |
EP0246987B1 EP0246987B1 (en) | 1992-01-02 |
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EP19870420131 Expired - Lifetime EP0246987B1 (en) | 1986-05-20 | 1987-05-19 | Ink jet recording sheet and process for its manufacture |
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US (1) | US4877686A (en) |
EP (1) | EP0246987B1 (en) |
AT (1) | ATE71027T1 (en) |
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ES (1) | ES2033337T3 (en) |
FR (1) | FR2598974B1 (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0493100A1 (en) * | 1990-12-26 | 1992-07-01 | Sanyo Kokusaku Pulp Co. Ltd. | Ink jet recording paper and labels made therefrom |
EP0824077A2 (en) * | 1996-08-12 | 1998-02-18 | TOYO BOSEKI KABUSHIKI KAISHA Trading under the name of Toyobo Co., Ltd. | Ink-receptive recording material |
EP0888904A1 (en) * | 1997-07-01 | 1999-01-07 | Konica Corporation | Ink-jet recording method |
Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5141797A (en) * | 1991-06-06 | 1992-08-25 | E. I. Du Pont De Nemours And Company | Ink jet paper having crosslinked binder |
US5684068A (en) * | 1995-07-31 | 1997-11-04 | International Cellulose Corp. | Spray-on insulation |
US6713550B2 (en) | 1996-06-28 | 2004-03-30 | Stora Enso North America Corporation | Method for making a high solids interactive coating composition and ink jet recording medium |
US6051306A (en) * | 1996-11-15 | 2000-04-18 | Fargo Electronics, Inc. | Ink jet printable surface |
US6270858B1 (en) | 1996-11-15 | 2001-08-07 | Fargo Electronics, Inc. | Method of coating using an ink jet printable mixture |
DE19709735A1 (en) * | 1997-03-10 | 1998-09-17 | Sihl Gmbh | Inkjet recording material |
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US6682788B2 (en) * | 1998-04-30 | 2004-01-27 | Konica Corporation | Aqueous coating composition, coating method thereof, and ink-jet recording sheet |
GB2356374A (en) * | 1999-11-18 | 2001-05-23 | Ilford Imaging Uk Ltd | Printing process |
US6419987B1 (en) * | 1999-12-17 | 2002-07-16 | Eastman Kodak Company | Method for providing a high viscosity coating on a moving web and articles made thereby |
US6477948B1 (en) * | 2000-08-14 | 2002-11-12 | The Proctor & Gamble Company | Means for enhancing print color density |
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WO2002085635A1 (en) | 2001-04-19 | 2002-10-31 | Stora Enso North America Corporation | Ink jet recording media |
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US20030044578A1 (en) * | 2001-08-14 | 2003-03-06 | Nissing Nicholas James | Printed substrate with variable local attributes |
US6623819B2 (en) | 2001-12-04 | 2003-09-23 | Eastman Kodak Company | Ink jet recording element |
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EP1318026A3 (en) | 2001-12-04 | 2004-10-20 | Eastman Kodak Company | Ink jet recording element and printing method |
US20050174414A1 (en) * | 2002-03-28 | 2005-08-11 | Yoshio Yoshida | Ink jet recording medium |
AU2003241942A1 (en) * | 2002-06-04 | 2003-12-19 | Canon Kabushiki Kaisha | Recording medium having ink receptive layer and process for producing the same |
EP1378369B1 (en) | 2002-07-01 | 2004-12-01 | ILFORD Imaging Switzerland GmbH | Method for coating a moving web |
US6908191B2 (en) | 2002-07-31 | 2005-06-21 | Eastman Kodak Company | Ink jet printing method |
EP1419893A1 (en) | 2002-11-18 | 2004-05-19 | Agfa-Gevaert | Improved ink jet recording material |
US7427129B2 (en) * | 2004-02-04 | 2008-09-23 | Hewlett-Packard Development Company, L.P. | Boronic acid containing dyes to improve permanence of images |
US20060065161A1 (en) * | 2004-06-24 | 2006-03-30 | Miller Gerald D | Substrate coating compositions and their use |
GB0415212D0 (en) | 2004-07-07 | 2004-08-11 | Eastman Kodak Co | Ink-jet receiver having improved gloss |
US8956490B1 (en) | 2007-06-25 | 2015-02-17 | Assa Abloy Ab | Identification card substrate surface protection using a laminated coating |
US8247044B2 (en) * | 2007-11-08 | 2012-08-21 | Eastman Kodak Company | Inkjet recording element |
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US8470415B2 (en) | 2010-07-12 | 2013-06-25 | Carestream Health, Inc. | Transparent ink-jet recording film |
US8974878B2 (en) * | 2010-09-10 | 2015-03-10 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
DK2847570T3 (en) | 2012-05-08 | 2020-03-23 | Bentley Instr S A R L | REAGENT TO CLEAR EMULSIONS AND PROCEDURE TO CLEAR |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1476288A (en) * | 1965-04-22 | 1967-04-07 | Cumberland Chemical Corp | Finishing process, in particular paper, using polyvinyl alcohol |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3438808A (en) * | 1965-04-22 | 1969-04-15 | Air Reduction | Polyvinyl alcohol-boric acid-containing composition,treatment of paper web therewith and the treated paper web |
DE2614869C3 (en) * | 1976-04-06 | 1980-08-21 | Centralnyj Nautschno-Issledovatelskij Institut Bumagi, Moskovskaya Oblast (Sowjetunion) | Crosslinking agent and process for its preparation |
JPS54116407A (en) * | 1978-03-02 | 1979-09-10 | Kuraray Co | Pigment coating composition for paper and surface treating method of paper |
JPS59211699A (en) * | 1983-05-17 | 1984-11-30 | 本州製紙株式会社 | Coated paper |
JPS6067190A (en) * | 1983-09-22 | 1985-04-17 | Ricoh Co Ltd | Ink jet recording medium |
JPS6087089A (en) * | 1983-10-20 | 1985-05-16 | Honshu Paper Co Ltd | Recording sheet |
US4592951A (en) * | 1984-07-18 | 1986-06-03 | Polaroid Corporation | Ink jet recording sheet |
-
1986
- 1986-05-20 FR FR8607355A patent/FR2598974B1/en not_active Expired - Fee Related
-
1987
- 1987-05-19 EP EP19870420131 patent/EP0246987B1/en not_active Expired - Lifetime
- 1987-05-19 AT AT87420131T patent/ATE71027T1/en not_active IP Right Cessation
- 1987-05-19 DE DE8787420131T patent/DE3775619D1/en not_active Expired - Fee Related
- 1987-05-19 ES ES87420131T patent/ES2033337T3/en not_active Expired - Lifetime
-
1988
- 1988-10-04 US US07/253,413 patent/US4877686A/en not_active Expired - Fee Related
-
1992
- 1992-01-03 GR GR91401912T patent/GR3003492T3/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1476288A (en) * | 1965-04-22 | 1967-04-07 | Cumberland Chemical Corp | Finishing process, in particular paper, using polyvinyl alcohol |
Non-Patent Citations (3)
Title |
---|
ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 51, no. 3, septembre 1980, page 360, résumé no 3249, Appleton, Wisconsin, US; & JP-A-54 116 407 (KURARAY CO. LTD) 10-09-1979 * |
ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 56, no. 11, mai 1986, page 1416, résumé no. 12935, Appleton, Wisconsin, US; & JP-A-60 087 089 (HONSHU PAPER MFG, CO.) 16-05-1985 * |
ABSTRACT BULLETIN OF THE INSTITUTE OF PAPER CHEMISTRY, vol. 56, no. 3, septembre 1985, page 409, résumé no. 3615, Appleton, Wisconsin, US; & JP-A-59 211 699(HONSHU PAPER CO. LTD) 30-11-1984 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0493100A1 (en) * | 1990-12-26 | 1992-07-01 | Sanyo Kokusaku Pulp Co. Ltd. | Ink jet recording paper and labels made therefrom |
EP0824077A2 (en) * | 1996-08-12 | 1998-02-18 | TOYO BOSEKI KABUSHIKI KAISHA Trading under the name of Toyobo Co., Ltd. | Ink-receptive recording material |
EP0824077A3 (en) * | 1996-08-12 | 1999-06-02 | TOYO BOSEKI KABUSHIKI KAISHA Trading under the name of Toyobo Co., Ltd. | Ink-receptive recording material |
EP0888904A1 (en) * | 1997-07-01 | 1999-01-07 | Konica Corporation | Ink-jet recording method |
US6217166B1 (en) | 1997-07-01 | 2001-04-17 | Konica Corporation | Ink jet recording method |
Also Published As
Publication number | Publication date |
---|---|
US4877686A (en) | 1989-10-31 |
FR2598974B1 (en) | 1990-04-27 |
GR3003492T3 (en) | 1993-02-17 |
FR2598974A1 (en) | 1987-11-27 |
EP0246987B1 (en) | 1992-01-02 |
DE3775619D1 (en) | 1992-02-13 |
ES2033337T3 (en) | 1993-03-16 |
ATE71027T1 (en) | 1992-01-15 |
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