EP0121916A2 - Ink jet recording sheet - Google Patents
Ink jet recording sheet Download PDFInfo
- Publication number
- EP0121916A2 EP0121916A2 EP84103846A EP84103846A EP0121916A2 EP 0121916 A2 EP0121916 A2 EP 0121916A2 EP 84103846 A EP84103846 A EP 84103846A EP 84103846 A EP84103846 A EP 84103846A EP 0121916 A2 EP0121916 A2 EP 0121916A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording
- ink
- coating
- silicon dioxide
- soluble
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/508—Supports
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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
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. 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
- B41M5/5218—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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate 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
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
- Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
- Y10T428/277—Cellulosic substrate
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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]
- Y10T428/31971—Of carbohydrate
- Y10T428/31993—Of paper
Definitions
- the invention relates to a coated recording paper for ink jet recorders or for the ink jet recording method, which for recording is suitable at high speed.
- the ink spray recording method has the advantage that it is quiet and multi-color records can be easily made. It is used in facsimile machines and for various printers.
- the recording papers for ink-jet recording processes are divided into conventional and coated recording papers.
- the conventional recording papers with a low degree of sizing have good ink absorbency; however, the clarity of the recording suffers from the diffusion of the ink in the sheet layer, in particular the image resolution and color density are unsatisfactory in the case of multicolor recordings. Therefore, investigations were carried out with coated recording papers with superior image resolution.
- the coated recording papers provide superior image density and clarity because the dye of the ink in the coating is locally absorbed and does not bleed.
- such recording papers have the disadvantage that they are not so suitable for rapid recording because of their insufficient ink absorption capacity.
- the rapid recording by the ink jet recording method has to be improved, as in other recording methods such as screen dot recording, electrostatic recording, heat sensitive recording, etc.
- a recording device there is a faster one Multi-nozzle type printer using a foam jet system has already been developed.
- the coated recording paper which has a superior image resolution, has the disadvantage that the ink papers for ink-jet recording processes have the disadvantage that the dry state of the ink is unstable because the ink drops ejected from the nozzles after being adhered to the surface of the recording paper are absorbed inside and only seemingly are available in a dry state.
- fast recording such as the contact of papers with each other after recording, the transfer and scratching of the ink during transportation by the roller of the recording apparatus, etc., which are not found in other recording methods.
- the invention is based on the object of providing a coated recording paper for ink jet recorders or for ink spray recording processes which is better suited for rapid recording.
- This object is achieved in that a support with a degree of sizing according to Stöckigt of less than 4 seconds (based on a weight per unit area of 60 g / m 2 ) is used and this is provided with a coating which has fine silicon dioxide with a specific surface area of at least 200 m 2 / g, determined by the BET method, and with a uniformity n of the Rosin-Rammler distribution of at least 1.10 and contains a water-soluble, polymeric binder.
- Fine pigment with a specific surface area of at least 200 m 2 / g, determined by the BET method, and with a uniformity number n of the Rosin-Rammler distribution of at least 1.10 is used as the pigment according to the invention in the coating composition.
- the use of a pigment based on silicon dioxide as a coating material for the surface of the ink spray paper is described in JA-OS 51583/1980. However, the silicon dioxide described there has different properties and is of a different nature.
- the fine silica selected in accordance with the invention results in a recording paper which is superior in color density, hue, clarity and suitability for rapid recording.
- the first requirement of the silicon dioxide according to the invention is that it has a specific surface area of at least 200 m 2 / g.
- a coating that contains silicon dioxide with a large specific surface area as the main component results in superior color density and clarity.
- the silicon dioxide according to the invention must meet the second condition that it has a uniformity n of the Rosin-Rammler distribution of at least 1.10. Such a large uniformity number n means a narrow particle distribution.
- a silica with a large specific surface area and a narrow particle distribution results in a particularly superior ink absorption capacity.
- the right choice of silicon dioxide gives a coating that is particularly suitable for rapid recording. Generally the coating has the structure of a dense layer of pigment and binder. It was not believed, therefore, that the superior absorbency that conventional ink jet recording papers have can be achieved with a coated paper.
- a paper with a Stöckigt glue strength of less than 4 seconds (based on a basis weight of 60 g / m 2 ) is used according to the invention.
- a Stöckigt sizing degree of less than 4 seconds (based on a basis weight of 60 gfm 2 ) means that the ratio of Stöckigt sizing degree / basis weight [(second) / (g / m 2 )] is less than 0.07. That is, the ink component that flows through the coating easily penetrates into the carrier and is absorbed by it because the carrier has no or only a small degree of sizing.
- silica pigments that meet the above two conditions are, for example, SILCRON G100, SILCRON 600 (manufactured by Nissan Chemical Industries, Ltd.), SYLOID 404, SYLOID 79, SYLOID 74 (manufactured by Fuji-Davison Chemical Ltd. ), GASIL HP-34 (manufactured by Joseph Crossfield & Sons, Ltd.), Finesil X27, Finesil X37, Finesil 79 (manufactured by Tokuyama Soda Co., Ltd.), CARPLEX No.80 (manufactured by Shionogi & Co., Ltd.) etc.
- a water-soluble polymeric binder is suitable as the binder which is used in combination with the above-mentioned silicon dioxide pigments.
- Polyvinyl alcohol and its derivatives are particularly desirable in terms of color density, but one can also use oxidized starch, modified starch, rubber compounds, e.g. Guar gum and the like, sodium alginate, water-soluble cellulose derivatives, e.g. Hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose etc., water soluble proteins e.g. Soybean protein, casein and the like, water soluble polymeric compounds e.g. Polyvinyl pyrrolidone and the like.
- a fairly large amount of pigment according to the invention is preferably used in the preparation of the coating composition, i.e. a weight ratio (expressed as a solid weight) of silicon dioxide according to the invention to water-soluble polymeric binder of about 60-95: 40-5.
- the silicon dioxide according to the invention can optionally be used together with other pigments, e.g. Kaolin, talc, calcium carbonate, magnesium carbonate, barium sulfate, titanium white, organic fillers and the like can be used.
- the coating can be carried out using customary application devices, for example doctor blade spreaders, air brush spreaders, bar spreaders, roller spreaders and the like, or size presses.
- the coating amount is preferably 3 to 15 g / m 2 on one surface of the support; too much coating leads to poor ink absorbency.
- the ink spray recording was made with a Panafax 6000 (manufactured by Matsushita Graphic Communication Systems, Inc.).
- a two-nozzle ink jet recording device was used to produce two-color printing with black and red inks.
- the red ink was ejected for 10 seconds, then both red and black ink were ejected for 5 seconds, and finally a black ink was ejected for 10 seconds.
- the respective recording width of the red and black ink was 24 mm and the overlapping recording width of red and black ink in the central area was 8 mm.
- the reflection density of the recording surface was measured with a Macbeth density meter, the reflection density of the red recording surface using green filter for the magenta color and of blue filter for the yellow color and the reflection density of the black recording surface using visual filter for the black color (all filters are SPI filters).
- the reflection density (the sum) in the table was expressed as the sum of the individual reflection densities.
- the ink absorption time of a recording paper was determined by dropping 0.0018 cm 3 of cyan ink (manufactured by Matsushita-Giken) at 20 ° C and 65% RH using 1 micron micro-injectors onto the surface of a paper and determining the absorption time of the ink .
- the ink absorption speeds of the recording papers Nos. 1 to 3 are less than 30 seconds; so they are very fast, and their reflection densities are superior.
- the comparative tests (recording papers Nos. 4, 5 and 8), which have a uniformity number of less than 1.10, have a much lower ink absorption rate
- the other comparative tests (recording papers Nos. 6, 7 and 9), which have a BET specific surface area of less than 200 m 2 / g, have inferior reflection densities.
- a silica slurry (Gasil HP-34, manufactured by Joseph Crossfield & Sons, Ltd.) was added to 20 wt. (as a solid content) of a 15% aqueous solution of polyvinyl alcohol (degree of saponification: 100%, PVA 117, manufactured by Kuraray Co., Ltd.) to prepare a coating composition.
- the coating composition obtained was applied to three higher-quality papers with different degrees of sizing in an amount of 6 to 8 g / m 2 to produce three recording papers.
- the test results of the recording papers and the base paper obtained are summarized in Table 2.
- Table 2 the recording papers coated with the silicon dioxide according to the invention (No. 11, 12 and 13), regardless of the type of base paper types, have a superior reflection density.
- the ink absorption rate depends on the degree of sizing of the base paper, and with a degree of sizing of more than 4 seconds (based on a basis weight of 60 g / m 2 ) the coating of silicon dioxide works insufficiently.
Abstract
Es wird ein Aufzeichnungspapier für Tintenspritzaufzeichnungsverfahren beschrieben, das aus einem Träger mit einem spezifischen Leimungsgrad und aus einer darauf angeordneten Beschichtung besteht, die ein feines, spezielles Siliciumdioxid und ein wasserlösliches, polymeres Bindemittel enthält. Das erfindungsgemässe Papier eignet sich besser für schnelles Aufzeichnen.A recording paper for ink-jet recording processes is described which consists of a carrier with a specific degree of sizing and a coating arranged thereon, which contains a fine, special silicon dioxide and a water-soluble, polymeric binder. The paper according to the invention is better suited for fast recording.
Description
Die Erfindung betrifft ein beschichtetes Aufzeichnungspapier für Tintenstrahlschreiber bzw. für das Tintenspritzaufzeichnungsverfahren, das für die Aufzeichnung bei hoher Geschwindigkeit geeignet ist. Das Tintenspritzaufzeichnungsverfahren hat den Vorteil, daß es geräuscharm ist und mehrfarbige Aufzeichnungen leicht angefertigt werden können. Es wird bei Faksimilemaschinen und für verschiedene Drucker verwendet.The invention relates to a coated recording paper for ink jet recorders or for the ink jet recording method, which for recording is suitable at high speed. The ink spray recording method has the advantage that it is quiet and multi-color records can be easily made. It is used in facsimile machines and for various printers.
Im allgemeinen werden die Aufzeichnungspapiere für Tintenspritzaufzeichnungsverfahren in übliche und beschichtete Aufzeichnungspapiere eingeteilt. Die üblichen Aufzeichnungspapiere mit einem niedrigen Leimungsgrad haben gute Tintenabsorptionsfähigkeit; die Klarheit der Aufzeichnung leidet aber unter der Diffusion der Tinte in der Blattschicht, insbesondere ist die Bildauflösun= und Farbdichte bei mehrfarbigen Aufzeichnungen nicht befriedigend. Daher wurden Untersuchungen mit beschichteten Aufzeichnungspapieren mit überlegener Bildauflösung durchgeführt. Die beschichteten Aufzeichnungspapiere ergeben überlegene Bilddichte und Klarheit, weil der Farbstoff der Tinte in der Beschichtung lokal absorbiert wird und nicht verläuft. Solche Aufzeichnungspapiere haben jedoch den Nachteil, daß sie wegen ungenügender Tintenabsorptionsfähigkeit für schnelle Aufzeichnung nicht so sehr geeignet sind.In general, the recording papers for ink-jet recording processes are divided into conventional and coated recording papers. The conventional recording papers with a low degree of sizing have good ink absorbency; however, the clarity of the recording suffers from the diffusion of the ink in the sheet layer, in particular the image resolution and color density are unsatisfactory in the case of multicolor recordings. Therefore, investigations were carried out with coated recording papers with superior image resolution. The coated recording papers provide superior image density and clarity because the dye of the ink in the coating is locally absorbed and does not bleed. However, such recording papers have the disadvantage that they are not so suitable for rapid recording because of their insufficient ink absorption capacity.
In dem Maße, wie sich die schnelle Verarbeitung von Informationen entwickelt, muß auch die schnelle Aufzeichnung mit Hilfe des Tintenspritzaufzeichnungsverfahrens verbessert werden, wie bei anderen Aufzeichnungsverfahren, beispielsweise der Sieb-Dot-Aufzeichnung, elektrostatischer Aufzeichnung, wärmeempfindlicher Aufzeichnung usw. Als Aufzeichnungsgerät ist ein schneller Drucker des Mehrdüsentyps, bei dem ein Schaumjetsystem verwendet wird, bereits entwickelt. Von den Aufzeichnungspapieren für Tintenspritzaufzeichnungsverfahren hat das beschichtete Aufzeichnungspapier, das eine überlegene Bildauflösung aufweist, den Nachteil, daß der trockene Zustand der Tinte unstabil ist, weil die aus den Düsen ausgeschleuderten Tintentropfen nach dem Anhaften auf der Oberfläche des Aufzeichnungspapiers in seinem Inneren absorbiert werden und dabei nur scheinbar in trockenem Zustand vorhanden sind. Bei der schnellen Aufzeichnung gibt es deshalb verschiedene Probleme, beispielsweise den Kontakt von Papieren miteinander nach der Aufzeichnung, die Übertragung und das Kratzen der Tinte beim Transport mit Hilfe der Walze des Aufzeichnungsgeräts usw., die man bei anderen Aufzeichnungsverfahren nicht hat.As the rapid processing of information evolves, the rapid recording by the ink jet recording method has to be improved, as in other recording methods such as screen dot recording, electrostatic recording, heat sensitive recording, etc. As a recording device, there is a faster one Multi-nozzle type printer using a foam jet system has already been developed. From the record The coated recording paper, which has a superior image resolution, has the disadvantage that the ink papers for ink-jet recording processes have the disadvantage that the dry state of the ink is unstable because the ink drops ejected from the nozzles after being adhered to the surface of the recording paper are absorbed inside and only seemingly are available in a dry state. There are therefore various problems in fast recording, such as the contact of papers with each other after recording, the transfer and scratching of the ink during transportation by the roller of the recording apparatus, etc., which are not found in other recording methods.
Der Erfindung liegt nun die Aufgabe zugrunde, ein beschichtetes Aufzeichnungspapier für Tintenstrahlschreiber bzw. für Tintenspritzaufzeichnungsverfahren zu schaffen, das sich besser zur schnellen Aufzeichnung eignet.The invention is based on the object of providing a coated recording paper for ink jet recorders or for ink spray recording processes which is better suited for rapid recording.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß man einen Träger mit einem Leimungsgrad nach Stöckigt von weniger als 4 Sekunden,(bezogen auf ein Flächengewicht von 60 g/m2) verwendet und diesen mit einer Beschichtung versieht, die feines Siliciumdioxid mit einer spezifischen Oberfläche von mindestens 200 m2/g, bestimmt nach dem BET-Verfahren, und mit einer Gleichmäßigkeitszahl n der Rosin-Rammler-Verteilung von mindestens 1,10 und ein wasserlösliches, polymeres Bindemittel enthält.This object is achieved in that a support with a degree of sizing according to Stöckigt of less than 4 seconds (based on a weight per unit area of 60 g / m 2 ) is used and this is provided with a coating which has fine silicon dioxide with a specific surface area of at least 200 m 2 / g, determined by the BET method, and with a uniformity n of the Rosin-Rammler distribution of at least 1.10 and contains a water-soluble, polymeric binder.
Als erfindungsgemäßes Pigment in der Beschichtungsmasse wird feines Siliciumdioxid mit einer spezifischen Oberfläche von mindestens 200 m2/g, bestimmt nach dem BET-Verfahren, und mit einer Gleichmäßigkeitszahl n der Rosin-Rammler-Verteilung von mindestens 1,10 verwendet. Die Verwendung eines Pigments auf Basis von Siliciumdioxid als Beschichtungsmaterial für die Oberfläche des Tintenaufspritzpapiers ist in der JA-OS 51583/1980 beschrieben. Das dort beschriebene Siliciumdioxid hat aber andere Eigenschaften und ist von anderer Beschaffenheit. Das erfindungsgemäß gewählte, feine Siliciumdioxid ergibt ein Aufzeichnungspapier, das in Farbdichte, Farbton, Klarheit und Eignung für die schnelle Aufzeichnung überlegen ist.Fine pigment with a specific surface area of at least 200 m 2 / g, determined by the BET method, and with a uniformity number n of the Rosin-Rammler distribution of at least 1.10 is used as the pigment according to the invention in the coating composition. The use of a pigment based on silicon dioxide as a coating material for the surface of the ink spray paper is described in JA-OS 51583/1980. However, the silicon dioxide described there has different properties and is of a different nature. The fine silica selected in accordance with the invention results in a recording paper which is superior in color density, hue, clarity and suitability for rapid recording.
Das erfindungsgemäße Siliciumdioxid muß als erste Bedingung erfüllen, daß es eine spezifische Oberfläche von mindestens 200 m2/g hat. Eine Beschichtung, die als Hauptbestandteil ein Siliciumdioxid mit großer spezifischer Oberfläche enthält, ergibt überlegene Farbdichte und Klarheit.The first requirement of the silicon dioxide according to the invention is that it has a specific surface area of at least 200 m 2 / g. A coating that contains silicon dioxide with a large specific surface area as the main component results in superior color density and clarity.
Das erfindungsgemäße Siliciumdioxid muß als zweite Bedingung erfüllen, daß es eine Gleichmäßigkeitszahl n der Rosin-Rammler-Verteilung von mindestens 1,10 hat. Eine solch große Gleichmäßigkeitszahl n bedeutet eine schmale Teilchenverteilung. Ein Siliciumdioxid mit einer großen spezifischen Oberfläche und einer schmalen Teilchenverteilung ergibt eine besonders überlegene Tintenabsorptionsfähigkeit. Überraschenderweise erhält man also eine Beschichtung, die sich besonders gut für die schnelle Aufzeichnung eignet, durch die richtige Wahl des Siliciumdioxids. Im allgemeinen hat die Beschichtung die Struktur einer dichten Schicht aus Pigment und Bindemittel. Man glaubte daher nicht, daß die überlegene Absorptionsfähigkeit, die herkömmliche Tintenspritzaufzeichnungspapiere haben, mit einem beschichteten Papier erzielbar sei.The silicon dioxide according to the invention must meet the second condition that it has a uniformity n of the Rosin-Rammler distribution of at least 1.10. Such a large uniformity number n means a narrow particle distribution. A silica with a large specific surface area and a narrow particle distribution results in a particularly superior ink absorption capacity. Surprisingly, the right choice of silicon dioxide gives a coating that is particularly suitable for rapid recording. Generally the coating has the structure of a dense layer of pigment and binder. It was not believed, therefore, that the superior absorbency that conventional ink jet recording papers have can be achieved with a coated paper.
Der Mechanismus der verbesserten Tintenabsorptionsfähigkeit der Beschichtung durch die Wahl des Siliciumdioxids ist unklar. Man vermutet aber, daß die größere Zahl gleichmäßiger Lücken einer bestimmten Größe, die für überlegene Tintenabsorptionsfähigkeit geeignet ist, den vorteilhaften Effekt bewirkt, was bei einem Siliciumdioxid mit einer großen spezifischen Oberfläche besonders ausgeprägt ist.The mechanism of the coating's improved ink absorbency through the choice of silica is unclear. However, it is believed that the larger number of uniform gaps of a certain size suitable for superior ink absorbency produce the beneficial effect, which is particularly pronounced with a silica having a large specific surface area.
Im Zusammenhang mit der oben angegebenen Tintenabsorptionsfähigkeit der Beschichtung wird erfindungsgemäß ein Papier mit einer Leimfestigkeit nach Stöckigt von weniger als 4 Sekunden (bezogen auf ein Flächengewicht von 60 g/m2) verwendet. Ein Stöckigt-Leimungsgrad von weniger als 4 Sekunden (bezogen auf ein Flächengewicht von 60 gfm2) bedeutet, daß das Verhältnis von Stöckigt-Leimungsgrad/Flächengewicht [(Sekunde)/(g/m2)] weniger als 0,07 beträgt. Das heißt, der Tintenbestandteil, der die Beschichtung durchfließt, dringt leicht in den Träger ein und wird von ihm absorbiert, weil der Träger keinen oder nur einen geringen Leimungsgrad hat. Außerdem werden durch schnelle Imprägnierungmit dem wasserlöslichen Bindemittel bei dem Beschichtungsprozeß die Lücken der Beschichtung selbst vergrößert, was eine Zunahme der Tintenabsorptionsfähigkeit der Beschichtung verursacht. Daher kann man das im Handel erhältliche Oberklassepapier erfindungsgemäß nicht verwenden, weil es einen hohen Leimungsgrad aufweist.In connection with the ink absorption capacity of the coating indicated above, a paper with a Stöckigt glue strength of less than 4 seconds (based on a basis weight of 60 g / m 2 ) is used according to the invention. A Stöckigt sizing degree of less than 4 seconds (based on a basis weight of 60 gfm 2 ) means that the ratio of Stöckigt sizing degree / basis weight [(second) / (g / m 2 )] is less than 0.07. That is, the ink component that flows through the coating easily penetrates into the carrier and is absorbed by it because the carrier has no or only a small degree of sizing. In addition, rapid impregnation with the water-soluble binder in the coating process increases the gaps in the coating itself, causing an increase in the ink absorbency of the coating. Therefore, the commercially available premium paper cannot be used according to the invention because it has a high degree of sizing.
Die Gleichmäßigkeitszahl n der Rosin-Rammler-Verteilung wird wie folgt bestimmt: Siliciumdioxid-Pigment wird in Wasser dispergiert; man bestimmt ein integriertes Maß R (Dp) von Teilchen mit einer Teilchengröße Dp mit Hilfe eines üblichen Geräts (z.B. einem Gerät, das die Trübung oder die Lichtstreuung mißt) zur Bestimmung der Teilchengrößenverteilung in einem Teilchengrößenbereich von 0,4 bis 10/um. Wenn- man die erhaltenen Werte im Rosin-Rammler-Diagramm (nachstehend R-R-Diagramm genannt), basierend auf der Rosin-Rammler-Gleichung R (Dp) = 100 x exp. (-bDpn) (wobei b und n jeweils eine Konstante sind und n eine Gleichmäßigkeitszahl oder eine Verteilungskonstante genannt wird), aufträgt, kann man eine gerade Linie erhalten. Anschließend zieht man durch einen Punkt P in dem R-R-Diagramm eine parallele Linie zu dieser Linie und liest den Exponenten n auf der exponierten Linie ab. Auf diese Weise kann man n leicht erhalten. Der erfindungsgemäße Effekt ist auch erzielbar, wenn der Meßwert der Teilchengrößenverteilung, der nach dem obigen Verfahren ermittelt wird, annähernd als gerade Linie betrachtet wird.The uniformity number n of the Rosin-Rammler distribution is determined as follows: silicon dioxide pigment is dispersed in water; an integrated measure R (Dp) of particles with a particle size Dp is determined with the aid of a conventional device (for example a device which measures the turbidity or light scattering) in order to determine the particle size distribution in a particle size range from 0.4 to 10 / μm. If the values obtained in the Rosin-Rammler diagram (hereinafter referred to as RR diagram) are based on the Rosin-Rammler equation R (Dp) = 100 x exp. (-bDp n ) (where b and n are each a constant and n is called a uniformity number or a distribution constant), a straight line can be obtained. Then you draw a line parallel to this line through a point P in the RR diagram and read the exponent n on the exposed line. This way you can easily get n. The effect according to the invention can also be achieved if the measured value of the particle size distribution, which is determined by the above method, is approximately regarded as a straight line.
Die im Handel erhältlichen Siliciumdioxid-Pigmente, die die beiden obigen Bedingungen erfüllen, sind beispielsweise SILCRON G100, SILCRON 600 (hergestellt von Nissan Chemical Industries, Ltd.), SYLOID 404, SYLOID 79, SYLOID 74 (hergestellt von Fuji-Davison Chemical Ltd.), GASIL HP-34 (hergestellt von Joseph Crossfield & Sons, Ltd.), Finesil X27, Finesil X37, Finesil 79 (hergestellt von Tokuyama Soda Co., Ltd.), CARPLEX Nr.80 (hergestellt von Shionogi & Co., Ltd.) usw.The commercially available silica pigments that meet the above two conditions are, for example, SILCRON G100, SILCRON 600 (manufactured by Nissan Chemical Industries, Ltd.), SYLOID 404, SYLOID 79, SYLOID 74 (manufactured by Fuji-Davison Chemical Ltd. ), GASIL HP-34 (manufactured by Joseph Crossfield & Sons, Ltd.), Finesil X27, Finesil X37, Finesil 79 (manufactured by Tokuyama Soda Co., Ltd.), CARPLEX No.80 (manufactured by Shionogi & Co., Ltd.) etc.
Als Bindemittel, das in Kombination mit den oben angegebenen Siliciumdioxid-Pigmenten verwendet wird, ist ein wasserlösliches, polymeres Bindemittel geeignet. Polyvinylalkohol und seine Derivate sind besonders bezüglich der Farbdichte wünschenswert, aber man kann auch oxidierte Stärke, modifizierte Stärke, Gummiverbindungen, z.B. Guargummi und dergl., Natriumalginat, wasserlösliche Cellulosederivate, z.B. Hydroxyethylcellulose, Methylcellulose, Carboxymethylcellulose usw., wasserlösliche Proteine, z.B. Sojabohnenprotein, Casein und dergl., wasserlösliche, polymere Verbindungen, z.B. Polyvinylpyrrolidon und dergl., verwenden.A water-soluble polymeric binder is suitable as the binder which is used in combination with the above-mentioned silicon dioxide pigments. Polyvinyl alcohol and its derivatives are particularly desirable in terms of color density, but one can also use oxidized starch, modified starch, rubber compounds, e.g. Guar gum and the like, sodium alginate, water-soluble cellulose derivatives, e.g. Hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose etc., water soluble proteins e.g. Soybean protein, casein and the like, water soluble polymeric compounds e.g. Polyvinyl pyrrolidone and the like.
Bei der Zubereitung der Beschichtungsmasse wird vorzugsweise eine ziemlich große Menge an erfindungsgemäßem Pigment verwendet, d.h. ein Gewichtsverhältnis (als Feststoffgewicht ausgedrückt) von erfindungsgemäßem Siliciumdioxid zu wasserlöslichem, polymerem Bindemittel von etwa 60-95:40-5. Dabei kann das erfindungsgemäße Siliciumdioxid gegebenenfalls zusammen mit anderen Pigmenten, z.B. Kaolin, Talk, Calciumcarbonat, Magnesiumcarbonat, Bariumsulfat, Titanweiß, organischen Füllstoffen und dergl., verwendet werden.A fairly large amount of pigment according to the invention is preferably used in the preparation of the coating composition, i.e. a weight ratio (expressed as a solid weight) of silicon dioxide according to the invention to water-soluble polymeric binder of about 60-95: 40-5. The silicon dioxide according to the invention can optionally be used together with other pigments, e.g. Kaolin, talc, calcium carbonate, magnesium carbonate, barium sulfate, titanium white, organic fillers and the like can be used.
Bei der Beschichtung kann man übliche Auftragsvorrichtungen, z.B. Rakelstreicher, Luftbürststreicher, Bar-Streicher, Walzen-Streicher und dergl., oder Leimpressen verwenden. Die Beschichtungsmenge beträgt vorzugsweise 3 bis 15 g/m2 auf einer Oberfläche des Trägers; eine zu große Beschichtungsmenge führt zu einer schlechteren Tintenabsorptionsfähigkeit.The coating can be carried out using customary application devices, for example doctor blade spreaders, air brush spreaders, bar spreaders, roller spreaders and the like, or size presses. The coating amount is preferably 3 to 15 g / m 2 on one surface of the support; too much coating leads to poor ink absorbency.
Anhand der nachfolgenden Beispiele wird die Erfindung näher erläutert. Als Abkürzung für "Gewichtsteil" wird hier "Gewt" verwendet.The invention is explained in more detail using the following examples. As an abbreviation for "part by weight" "Gewt" is used here.
Zur Prüfung der Qualität der erfindungsgemäßen Aufzeichnungspapiere wurde die Tintenspritzaufzeichnung mit einem Panafaxgerät 6000 (hergestellt von Matsushita Graphic Communication Systems, Inc.) angefertigt. Man verwendete eine Vorrichtung mit zwei Düsen für die Tintenspritzaufzeichnung, um einen Zweifarbendruck mit Schwarz- und Rottinten herzustellen. Dabei wurde die Rottinte 10 Sekunden ausgestoßen, dann wurden sowohl Rot- als auch Schwarztinte 5 Sekunden ausgestoßen, schließlich wurde eine Schwarztinte 10 Sekunden ausgestoßen. Die jeweilige Aufzeichnungsbreite der Rot- und Schwarztinte betrug 24 mm und die überlappende Aufzeichnungsbreite von Rot- und Schwarztinte im Zentralbereich betrug 8 mm. Die Reflexionsdichte der Aufzeichnungsfläche wurde mit einem Macbeth-Dichtemesser gemessen, wobei die Reflexionsdichte der roten Aufzeichnungsfläche unter Verwendung von Grün-Filter für die Magentafarbe und von Blau-Filter für die Gelbfarbe und die Reflexionsdichte der schwarzen Aufzeichnungsfläche unter Verwendung von Visuell-Filter für die Schwarzfarbe (alle Filter sind SPI-Filter) bestimmt wurde. Die Reflexionsdichte (die Summe) in der Tabelle wurde als Summe der einzelnen Reflexionsdichten ausgedrückt. Die Tintenabsorptionszeit eines Aufzeichnungspapiers wurde ermittelt, indem man 0,0018 cm3 Zyantinte (hergestellt von Matsushita-Giken) bei 20°C und 65% RH unter Verwendung von Mikroeinspritzer aus 1 cm Höhe auf die Oberfläche eines Papiers tropfte und die Absorptionszeit der Tinte bestimmte.To test the quality of the recording papers of the present invention, the ink spray recording was made with a Panafax 6000 (manufactured by Matsushita Graphic Communication Systems, Inc.). A two-nozzle ink jet recording device was used to produce two-color printing with black and red inks. The red ink was ejected for 10 seconds, then both red and black ink were ejected for 5 seconds, and finally a black ink was ejected for 10 seconds. The respective recording width of the red and black ink was 24 mm and the overlapping recording width of red and black ink in the central area was 8 mm. The reflection density of the recording surface was measured with a Macbeth density meter, the reflection density of the red recording surface using green filter for the magenta color and of blue filter for the yellow color and the reflection density of the black recording surface using visual filter for the black color (all filters are SPI filters). The reflection density (the sum) in the table was expressed as the sum of the individual reflection densities. The ink absorption time of a recording paper was determined by dropping 0.0018 cm 3 of cyan ink (manufactured by Matsushita-Giken) at 20 ° C and 65% RH using 1 micron micro-injectors onto the surface of a paper and determining the absorption time of the ink .
Es wurden die folgenden neun Beschichtungsmassen hergestellt:
- 85 Gewt (als Feststoffgehalt) jeweils des Siliciumdioxids I (Silcron G100, hergestellt von Nissan Chemical Industries, Ltd.), des Siliciumdioxids II (Finesil X27, hergestellt von Tokuyama Soda Co., Ltd.) und des Siliciumdioxids III (Syloid Nr.74, hergestellt von Fuji-Davison Chemical Ltd.) als erfindungsgemäße Beispiele und des Siliciumdioxids IV (Carplex FPS-1, hergestellt von Shionogi & Co., Ltd.), des Siliciumdioxids V (Carplex FPS-3, hergestellt von Shionogi & Co., Ltd.), des Siliciumdioxids VI (Carplex Nr.1120, hergestellt von Shionogi & Co., Ltd.), des Siliciumdioxids VII (Nipsil E 200 A, hergestellt von Nippon Silica Industrial Corporation), des Siliciumdioxids VIII (Nipsil E 220 A, hergestellt von Nippon Silica Industrial Corp.) und des Siliciumdioxids IX (Mizukasil P526, hergestellt von Mizusawa Industrial Chemicals, Ltd.) als Vergleichsversuche,wurden zu 15 Gewt. (Feststoffgehalt) einer 15%igen wäßrigen Lösung von Polyvinylalkohol (Verseifungsgrad: 100%, PVA 117, hergestellt von Kuraray Co., Ltd.) gegeben. Die erhaltenen Beschichtungsmassen wurden in einer Beschichtungsmenge von 9 bis 12 g/m2 auf ein höherwertiges Papier mit einem Stöckigt-Leimungsgrad von 3,6 Sekunden und einem Flächengewicht von 63 g/m2 aufgetragen, wodurch die Aufzeichnungspapiere Nr. 1 bis 9 erhalten wurden. Die Tintenabsorptionsfähigkeit und die Prüfungsergebnisse dieser Aufzeichnungspapiere sind in Tabelle 1 zusammengefaßt.
- 85% by weight (as a solid content) of each of the silica I (Silcron G100, manufactured by Nissan Chemical Industries, Ltd.), the silica II (Finesil X27, manufactured by Tokuyama Soda Co., Ltd.) and the silica III (Syloid No. 74 , manufactured by Fuji-Davison Chemical Ltd.) as examples of the present invention, and the silica IV (Carplex FPS-1 manufactured by Shionogi & Co., Ltd.), the silica V (Carplex FPS-3 manufactured by Shionogi & Co., Ltd.), the silica VI (Carplex No. 1120, manufactured by Shionogi & Co., Ltd.), the silica VII (Nipsil E 200 A, manufactured by Nippon Silica Industrial Corporation), the silica VIII (Nipsil E 220 A, manufactured by Nippon Silica Industrial Corp.) and silica IX (Mizukasil P526, manufactured by Mizusawa Industrial Chemicals, Ltd.) as comparative experiments, were made up to 15 wt. (Solids content) of a 15% aqueous solution of polyvinyl alcohol (degree of saponification: 100%, PVA 117, manufactured by Kuraray Co., Ltd.). The coating compositions obtained were applied in a coating amount of 9 to 12 g / m 2 onto a higher-quality paper with a Stöckigt sizing degree of 3.6 seconds and a basis weight of 63 g / m 2 , whereby the recording papers Nos. 1 to 9 were obtained . The ink absorbency and test results of these recording papers are summarized in Table 1.
Wie aus Tabelle 1 ersichtlich ist, betragen die Tintenabsorptionsgeschwindigkeiten der Aufzeichnungspapiere Nr. 1 bis 3 weniger als 30 Sekunden; sie sind also sehr schnell, wobei ihre Reflexionsdichten überlegen sind. Dagegen haben die Vergleichsversuche (Aufzeichnungspapiere Nr. 4, 5 und 8), die eine Gleichmäßigkeitszahl von weniger als 1,10 haben, eine wesentlich geringere Tintenabsorptionsgeschwindigkeit, und die anderen Vergleichsversuche (Aufzeichnungspapiere Nr. 6, 7 und 9), die eine BET-spezifische Oberfläche von weniger als 200 m2/g haben, weisen unterlegene Reflexionsdichten auf.As can be seen from Table 1, the ink absorption speeds of the recording papers Nos. 1 to 3 are less than 30 seconds; so they are very fast, and their reflection densities are superior. On the other hand, the comparative tests (recording papers Nos. 4, 5 and 8), which have a uniformity number of less than 1.10, have a much lower ink absorption rate, and the other comparative tests (recording papers Nos. 6, 7 and 9), which have a BET specific surface area of less than 200 m 2 / g, have inferior reflection densities.
80 Gewt. (als Feststoffgehalt) eines Siliciumdioxidschlamms (Gasil HP-34, hergestellt von Joseph Crossfield & Sons, Ltd.) wurden zu 20 Gewt. (als Feststoffgehalt) einer 15%igen wäßrigen Lösung von Polyvinylalkohol (Verseifungsgrad: 100%, PVA 117, hergestellt von Kuraray Co., Ltd.) gegeben, um eine Beschichtungsmasse herzustellen. Die erhaltene Beschichtungsmasse wurde auf drei höherwertige Papiere mit verschiedenen Leimungsgraden in einer Menge von 6 bis 8 g/m2 aufgetragen, um drei Aufzeichnungspapiere herzustellen.80 wt. (as a solid content) of a silica slurry (Gasil HP-34, manufactured by Joseph Crossfield & Sons, Ltd.) was added to 20 wt. (as a solid content) of a 15% aqueous solution of polyvinyl alcohol (degree of saponification: 100%, PVA 117, manufactured by Kuraray Co., Ltd.) to prepare a coating composition. The coating composition obtained was applied to three higher-quality papers with different degrees of sizing in an amount of 6 to 8 g / m 2 to produce three recording papers.
Die Prüfungsergebnisse der erhaltenen Aufzeichnungspapiere und des Rohpapiers sind in Tabelle 2 zusammengefaßt.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP58059968A JPS59185690A (en) | 1983-04-07 | 1983-04-07 | Ink jet recording paper |
JP59968/83 | 1983-04-07 |
Publications (3)
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EP0121916A2 true EP0121916A2 (en) | 1984-10-17 |
EP0121916A3 EP0121916A3 (en) | 1984-12-05 |
EP0121916B1 EP0121916B1 (en) | 1987-01-07 |
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Application Number | Title | Priority Date | Filing Date |
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EP84103846A Expired EP0121916B1 (en) | 1983-04-07 | 1984-04-06 | Ink jet recording sheet |
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US (1) | US4478910A (en) |
EP (1) | EP0121916B1 (en) |
JP (1) | JPS59185690A (en) |
DE (1) | DE3461942D1 (en) |
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GB2162442A (en) * | 1984-06-29 | 1986-02-05 | Canon Kk | Ink jet recording medium |
EP0174859A2 (en) * | 1984-09-13 | 1986-03-19 | Canon Kabushiki Kaisha | Ink-jet recording medium and method |
EP0174859A3 (en) * | 1984-09-13 | 1987-08-19 | Canon Kabushiki Kaisha | Ink-jet recording medium and method |
GB2167973A (en) * | 1984-10-23 | 1986-06-11 | Canon Kk | Ink-jet recording medium |
US4902568A (en) * | 1986-02-07 | 1990-02-20 | Canon Kabushiki Kaisha | Recording medium and recording method by use thereof |
GB2187137A (en) * | 1986-02-07 | 1987-09-03 | Canon Kk | Recording medium containing spherical silica for ink jet recording |
GB2187137B (en) * | 1986-02-07 | 1990-10-17 | Canon Kk | Recording medium and recording method which makes use thereof |
DE3832112A1 (en) * | 1987-09-21 | 1989-03-30 | Jujo Paper Co Ltd | RECORDING PAPER FOR INK RADIUS PRINTER |
US4900620A (en) * | 1987-10-08 | 1990-02-13 | Oji Paper Co., Ltd. | Ink jet recording sheet |
GB2210812A (en) * | 1987-10-08 | 1989-06-21 | Oji Paper Co | Ink jet recording sheet |
GB2210812B (en) * | 1987-10-08 | 1991-09-25 | Oji Paper Co | Ink jet recording sheet |
EP0379964A1 (en) * | 1989-01-18 | 1990-08-01 | Nippon Paper Industries Co., Ltd. | Ink jet printer recording sheet |
FR2661432A1 (en) * | 1990-04-25 | 1991-10-31 | Arjomari Prioux | PAPER FOR SPRAYER SPRAYING INKS UNDER THE COMPRESSED AIR PRESSURE AND LAYER DEPOSITED ON SUCH PAPER. |
WO1991016494A1 (en) * | 1990-04-25 | 1991-10-31 | Arjomari Europe | Paper for ink spray using compressed air pressure and layer so obtained |
US5656369A (en) * | 1991-04-12 | 1997-08-12 | Moore Business Forms, Inc. | Business form having integral label associated therewith coated with composition capable of receiving toner images thereon, and method for producing same |
DE4307241A1 (en) * | 1993-03-08 | 1994-09-15 | Steinbeis Temming Papier Gmbh | Wood-containing recording paper for ink-jet recording |
WO1996039305A1 (en) * | 1995-06-06 | 1996-12-12 | Moore Business Forms, Inc. | Business form having integral label associated therewith coated with composition capable of receiving toner images thereon, and method for producing the business form |
CN1071633C (en) * | 1995-06-06 | 2001-09-26 | 穆尔商用表格有限公司 | Business form having integral lable associated therewith cloated with composition capable of receiving toner images thereon, and method for producing the business form |
DE19532303A1 (en) * | 1995-09-01 | 1997-03-20 | Renker Gmbh | Ink=jet printing substrate giving strong, brilliant, sharp print |
WO2000005452A1 (en) * | 1998-07-22 | 2000-02-03 | Security Transfer B.V. | Paint and paper coated with said paint |
Also Published As
Publication number | Publication date |
---|---|
EP0121916A3 (en) | 1984-12-05 |
DE3461942D1 (en) | 1987-02-12 |
JPH0326665B2 (en) | 1991-04-11 |
EP0121916B1 (en) | 1987-01-07 |
JPS59185690A (en) | 1984-10-22 |
US4478910A (en) | 1984-10-23 |
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