EP1333990B1 - Materiau d'impression pour le procede d'impression par jet d'encre - Google Patents

Materiau d'impression pour le procede d'impression par jet d'encre Download PDF

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Publication number
EP1333990B1
EP1333990B1 EP01992645A EP01992645A EP1333990B1 EP 1333990 B1 EP1333990 B1 EP 1333990B1 EP 01992645 A EP01992645 A EP 01992645A EP 01992645 A EP01992645 A EP 01992645A EP 1333990 B1 EP1333990 B1 EP 1333990B1
Authority
EP
European Patent Office
Prior art keywords
ink
pigment
receiving layer
weight
recording material
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.)
Expired - Lifetime
Application number
EP01992645A
Other languages
German (de)
English (en)
Other versions
EP1333990A1 (fr
Inventor
Gerhard Stork
Makato Kato
Karsten Lerius
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi HiTech Paper Flensburg GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi HiTech Paper Flensburg GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP1333990A1 publication Critical patent/EP1333990A1/fr
Application granted granted Critical
Publication of EP1333990B1 publication Critical patent/EP1333990B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • B41M5/506—Intermediate layers
    • 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
    • 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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants

Definitions

  • JP-A-11 277 887 is also a water resistance-increasing aid with a structural formula of the linear cationic resin which is different from the above-discussed document and which has a comparable effect, but which, according to the description text, has been expanded to reduce the so-called "ink bleeding "for print images created using inkjet printers.
  • the viscosity of the 20% strength aqueous solution each containing the proposed aid is given as 50 to 500 mPa ⁇ s (B type; 30 ° C.).
  • the object of JP-A-1 0 152 544 is to provide an ink jet recording paper which allows only slight "ink bleeding" in the case of print images produced with aqueous inks, and moreover a high color concentration and excellent water resistance of the print images allows.
  • the object is to be achieved by an addition to the coating composition in the form of a branched cationic resin which is present as a reaction product of ammonia with at least one preferably primary, secondary or tertiary amine and an epihalohydrin.
  • Polyalkylene polyamine and alkanolamine are also preferred as amine.
  • the viscosity of the 10% aqueous solution of this cationic resin is 1 to 30 m Pa ⁇ s, measured according to Brookfield (60 rpm / 25 ° C).
  • JP-A-09 240 139 proposes the application of a branched cationic resin with the aim of presenting a production process for ink jet recording papers on which the color droplets of aqueous ink run little and on which printed images with high color density and excellent water resistance are made possible , which is formed as a reaction product of a polyalkylene polyamine with an epihalohydrin and optionally also with an aliphatic amine component.
  • the viscosity of a 10% strength aqueous solution containing the proposed cationic resin is given as 30 mPas, measured according to Brookfield (60 rpm / 25 ° C.).
  • the ink receiving layer of which has a hydroxypropylmethyl cellusose of a certain viscosity. Based on 100 parts by weight, the ink jet recording layer can contain up to 20% by weight of pigment and other solid particles, the amount of inorganic pigment not exceeding 10% by weight and preferably only from 1 to 8% by weight. -% should be.
  • ink fixing agents A large number of ink fixing agents are disclosed, copolymers of polyalkylene polyamine and dicyandiamide, allylamine-diallylamine copolymers, polymers of secondary amines with epihalohydrin and (meth) acrylamide-diallylamine copolymers and mixtures thereof being preferred, without any preference for a specific addition amount of one or the other product.
  • Ink fixatives can be added to both the substrate and the ink-receiving layer, the addition amount being disclosed as 0.01 to 10 g / m 2 based on the surface of the recording material.
  • cationic polymers secondary amines, tertiary amines or quaternary ammonium salts containing cationic resins and secondary amine-epichlorohydrin addition polymers are among the large number of disclosed ink fixatives.
  • pigment-based recording inks were hardly used instead of inks based on organic dyes, in particular acidic azo dyes.
  • the problem with this type of recording ink is the low lightfastness of the organic dyes, combined with the problem of fading and discolouring printed images, which until now could only be solved unsatisfactorily by means of UV absorbers in the recording inks and by means of color stabilizers in the inkjet recording materials.
  • the pigment-based recording inks which are now used more frequently, are considerably more light-stable than the previously discussed inks based on organic dyes, but there is the problem of "ink bleeding" in the case of the recording inks based on pigments, including the running of directly adjacent, differently colored printing patterns into one another understand the printing process.
  • the recording material according to the invention has been developed for use with pigment-based recording inks and significantly reduces the problem of "ink bleeding".
  • the continuous process provides an ink jet ejected under pressure from a nozzle, which splits into very small droplets due to the surface tension at a certain distance from the nozzle.
  • the droplets are electrically charged and then, depending on the print image to be produced, are either deflected into a collecting container by the electric field of electronically controlled deflection plates or placed on the recording material.
  • the new recording material is to guarantee an excellent fixation of the applied inks and thus reduce the so-called "ink bleeding".
  • the aim of the new recording material on pigmented inks is to make the printed images highly lightfast. Since pigmented inks are preferably used in poster printing and the posters created in this way are exposed to direct sunlight, for example as billboards, it is preferable to provide a new recording material that is characterized by great stability against any tendency to yellowing.
  • the recording material is to ensure an acceptable wet smear resistance of printed images.
  • the amine-epichlorohydrin condensation product is of medium molecular weight, provided that as a 10% aqueous solution it has a viscosity in a range of 20 m Pa • s to 50 m Pa • s.
  • the aforementioned viscosity is based on Brookfield (Spindle 1/100 rpm / 25 ° C) determined.
  • the basis of the invention is the choice of the amine-epichlorohydrin condensation product as at least one ink fixer, optionally together with other ink fixatives is incorporated into the ink receiving layer. It is essential to the invention that the amine-epichlorohydrin condensation product is branched in medium molecular weight Form is present. Other types of amine-epichlorohydrin condensation product turn out to be unsuitable for various reasons; so forbids for example the use of a low molecular weight non-branched amine-epichlorohydrin condensation product, because recording materials containing such have too strong an odor from the free amine.
  • the inventors also recognized that the ink fixing agent-pigment ratio in one Range from 1: 2 to 1: 6 - based on the weight percent of pigment and ink fixative in the ink receiving layer - must lie, with the weight percent on all ink fixing agents or pigments incorporated in the ink receiving layer Respectively.
  • the pigment from inorganic pigment consists of at least 80 wt .-% with a particle size in a range is between 6 and 12 ⁇ m, determined as a D50 value (Malvem - that is, the determination It is carried out according to the pigment manufacturers using a laser measuring device from Malvem, type Master-Sizer S). Furthermore, the pigment content of the Ink receiving layer of the recording material according to the invention in one area are between 30 and 70 wt .-%.
  • the ink fixative-pigment ratio of 1: 2 to 1: 6 according to the invention is limited on the one hand by an increasingly decreasing wet smear resistance, which is no longer acceptable with larger amounts of ink fixative beyond an ink fixative-pigment ratio of 1: 2, and on the other hand by an increasingly worsening "ink bleeding" behavior which can no longer be rejected as convincing in the case of smaller amounts of ink fixing agent beyond an ink fixing agent-pigment ratio of 1: 6.
  • the inventors recognized that the novel recording material had particularly good properties when the ink fixing agent-pigment ratio was in a range from 1: 3 to 1: 5.5 inclusive, based on the weight percent of Pigment and ink fixer in the ink-receiving layer - lies, with the weight percent again relating to all ink fixers or pigments incorporated in the ink-receiving layer.
  • the ink-receiving layer of the recording material according to the invention comprises a proportion of binder and co-binder in a range of 10 to 55 wt .-%.
  • Aqueous polymer dispersions of ethylene-vinyl acetate have proven particularly useful and in particular styrene butadiene latex, polyacrylates and solutions from partially or fully saponified polyvinyl alcohol, used alone or in combination become.
  • Aluminum hydroxide and silica (acid) in particular have proven to be inorganic pigments and precipitated silica well proven.
  • the last three pigments listed can be modified with aluminum or with aluminum oxide as well as unmodified be trained.
  • the total proportion of ink fixative in the Ink receiving layer in a range between 5 and 30 wt .-%, preferably in one Range between 5 and 20 wt .-% this total proportion when applying High basis weight ink receiving layers within the above range tends to be chosen towards the lower limit.
  • Other components such as caustic soda, optical brighteners and defoamers, but not limited to this to be added as necessary and make up up to 5% by weight the ink-receiving layer, the individual portions in the ink-receiving layer add to 100% by weight.
  • the area-related Mass of the ink receiving layer should not be chosen too small, otherwise the Wet wipe resistance decreases too much and so does "ink bleeding" in too little Mass can be reduced.
  • the mass per unit area of the ink-receiving layer is upwards limited primarily from an economic point of view.
  • the ink-receiving layer in two layers positioned one above the other, a lower layer being connected to the substrate or to a preparation layer applied to the substrate in accordance with a preferred embodiment, while an upper layer is applied to the lower layer .
  • Particularly good results can be achieved if the first layer has a mass per unit area between 4 and 12 g / m 2 , preferably between 6 and 8 g / m 2 , and the second layer prefers a mass per unit area between 2 and 10 g / m 2 has between 4 and 6 g / m 2 .
  • the same teachings apply to the two layers with regard to the selection of components essential to the invention and the relationship of these components to one another, in particular also in their preferred embodiments.
  • the two layers also have the same auxiliary components in accordance with the disclosures to be found in this document. If the tintering layer is formed as a single layer, a mass per unit area of this layer of between 4 and 15 g / m 2 is recommended, a range between 5 and 10 g / m 2 and very particularly a range between 7 and 9 g / m 2 being particularly preferred ,
  • At least one preparation layer is arranged between the substrate and the single or, in a preferred embodiment, the first layer of the ink-receiving layer, which preferably has a mass per unit area in a range from 0.1 to 2.0 g / m 2 .
  • the preparation layer can be designed as a simple application of starch.
  • the recording material according to the invention comprises, on the side opposite the side with the ink-receiving layer, a rear-side coating which can be designed as an ink-receiving layer, but also as a simple application of starch.
  • a starch application it serves to ensure good grip so that there are no transport problems in the inkjet printers.
  • improved printability can be achieved, particularly in the offset printing process.
  • the starch application designed as a back coating preferably has a mass per unit area in a range from 0.1 to 2.0 g / m 2 .
  • the substrate is a paper web.
  • the invention also encompasses a method for recording according to the discontinuous ink jet printing method with a pigment-based recording ink and with a recording material according to the invention, which can be designed in accordance with one of the further embodiments described above.
  • the new process provides for printing of the new recording material with "drop-on-demand” printers, which either use the piezoelectric effect or, as a "bubble jet” printer, use an electrically controlled heating element to eject the smallest droplets of ink.
  • a paper web is produced from bleached and ground hardwood and coniferous cellulose pulps with the addition of conventional admixtures in usual quantities with a mass per unit area of 82 g / m 2 .
  • the paper web is given a starch preparation of 0.3 g / m 2
  • a starch preparation of 1 g / m 2 is applied.
  • Non-aluminum-modified silica gel with a pore volume of 1.2 ml / g was used as pigment with the following average particle sizes and specific inner surfaces: Pigment 1 Pigment 2 Pigment 3. Particle size [ ⁇ m] 6.5 8th 10 Specific inner surface [m 2 / g] 390 290 390
  • 12 samples of different recording materials for the ink jet printing process were produced.
  • 12 different coating slips were prepared in accordance with the basic recipe above, each of the three pigments 1, 2 and 3 being introduced being combined with each of the ink fixing agents A, B, C and D.
  • the coating slips are applied to the paper web described above in their manufacture.
  • An ink-jet printer, type HP-DesignJet 2500 CP, from Hewlett Packard (print mode: normal without color adjustment, printer driver: coated paper, heavy) is again used to investigate the "ink bleeding" behavior using UV inks from the same manufacturer ,
  • a control print is applied to each of the 12 samples and the "ink bleeding" behavior of the samples is assessed visually.
  • examples 1, 5 and 9 have good or satisfactory "ink bleeding" behavior, they cannot be used due to the strong odor development.
  • the ink-fixing agent-pigment ratio was varied.
  • the samples produced in this way are to be examined with regard to their "ink bleeding" behavior and the wet smudge resistance of printed images applied.
  • the printed images, on which the "ink bleeding" behavior of the samples was previously assessed are drizzled with water. After 2 seconds of exposure, wipe a finger several times under constant pressure over the printed image. The printed image should be blurred as little as possible, ideally not at all.
  • Table 2 shows the ink-fixant-pigment ratios set and the respective visually assessed "ink-bleeding" behavior of the samples, as well as the wet smudge resistance of the printed images applied.
  • Examples according to the invention are again designated with “EB” and comparative examples with “VB”: example Ink fixer-pigment ratios Ink bleeding behavior Wet smear resistance 13 VB 1:10 Bad Very good 14 EB 1: 5 Good Good 7 EB (see also table 1) 1: 4.53 Good Good 15 EB 1: 3.3 Good Satisfying 16 VB 1: 1.5 Good Bad
  • the examples according to the invention illustrate particularly clearly that the recording material according to the invention has succeeded convincingly, an inexpensive To provide recording material for the inkjet printing process, This is particularly good when printed with pigment-based recording inks Fixation of the applied inks is guaranteed, thus reducing the so-called "ink bleeding", which is not the case with the comparative examples.
  • the invention Examples also show that the new recording material is an acceptable one Wet wiping resistance of printed images ensures, which the comparative examples are unable.
  • Prerequisite for the usability of a recording material for the inkjet printing process is i.a. a not too strong odor development, which is why part of the comparative examples is to be rejected and only those according to the invention Examples are able to convince on this point too.

Landscapes

  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Claims (6)

  1. Matériau d'enregistrement pour le procédé d'impression par jet d'encre, comportant un support et une couche de réception de l'encre qui est appliquée sur au moins une face du support, la couche de réception de l'encre contenant un produit de condensation amine-épichlorhydrine ainsi qu'un pigment, caractérisé en ce que
    La couche de réception de l'encre comporte au moins un fixateur d'encre qui consiste en un produit de condensation amine-épichlorhydrine ramifié de masse moléculaire moyenne,
    Le produit de condensation amine-épichlorhydrine ramifié de masse moléculaire moyenne représentant au moins 70 % en poids de la quantité totale de fixateur d'encre dans la couche de réception de l'encre,
    Le pigment consiste en un pigment minéral qui est présent à raison d'au moins 80 % en poids avec une taille de particules dans une plage comprise entre 6 et 12 µm,
    La teneur en pigment de la couche de réception d'encre est comprise entre 30 et 70 % en poids et
    Le rapport fixateur d'encre/pigment se situe dans une plage allant de 1:2 à 1:6.
  2. Matériau d'enregistrement selon la revendication 1, caractérisé en ce que le rapport fixateur d'encre/pigment se situe dans une plage allant de 1:3 inclus à 1:5,5 inclus.
  3. Matériau d'enregistrement selon la revendication 1 ou 2, caractérisé en ce que la masse par rapport à la surface de la couche de réception de l'encre est comprise entre 4 et 15 g/m2.
  4. Matériau d'enregistrement selon la revendication 1 ou 2, caractérisé en ce que la masse par rapport à la surface de la couche de réception de l'encre est comprise entre 7 et 9 g/m2.
  5. Matériau d'enregistrement selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'au moins une couche intermédiaire est disposée entre support et couche de réception de l'encre.
  6. Procédé pour l'enregistrement selon le procédé d'impression discontinue par jet d'encre, avec une encre d'enregistrement à base de pigment et avec un matériau d'enregistrement qui comprend un support et une couche de réception de l'encre qui est appliquée sur au moins une face du support, la couche de réception de l'encre contenant un produit de condensation amine-épichlorhydrine ainsi qu'un pigment, caractérisé en ce que
    La couche de réception de l'encre comporte au moins un fixateur d'encre qui consiste en un produit de condensation amine-épichlorhydrine ramifié de masse moléculaire moyenne,
    Le produit de condensation amine-épichlorhydrine ramifié de masse moléculaire moyenne représentant au moins 70 % en poids de la quantité totale de fixateur d'encre dans la couche de réception de l'encre,
    Le pigment consiste en un pigment minéral qui est présent à raison d'au moins 80 % en poids avec une taille de particules dans une plage comprise entre 6 et 12 µm,
    La teneur en pigment de la couche de réception d'encre est comprise entre 30 et 70 % en poids et
    Le rapport fixateur d'encre/pigment se situe dans une plage allant de 1:2 à 1:6.
EP01992645A 2000-11-01 2001-10-19 Materiau d'impression pour le procede d'impression par jet d'encre Expired - Lifetime EP1333990B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10054219 2000-11-01
DE10054219A DE10054219C2 (de) 2000-11-01 2000-11-01 Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren
PCT/EP2001/012116 WO2002036354A1 (fr) 2000-11-01 2001-10-19 Materiau d'impression pour le procede d'impression par jet d'encre

Publications (2)

Publication Number Publication Date
EP1333990A1 EP1333990A1 (fr) 2003-08-13
EP1333990B1 true EP1333990B1 (fr) 2004-09-29

Family

ID=7661835

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01992645A Expired - Lifetime EP1333990B1 (fr) 2000-11-01 2001-10-19 Materiau d'impression pour le procede d'impression par jet d'encre

Country Status (8)

Country Link
US (1) US6880927B2 (fr)
EP (1) EP1333990B1 (fr)
JP (1) JP2004512983A (fr)
CN (1) CN1243645C (fr)
AT (1) ATE277775T1 (fr)
DE (2) DE10054219C2 (fr)
ES (1) ES2225638T3 (fr)
WO (1) WO2002036354A1 (fr)

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DE10140677C2 (de) * 2001-08-24 2003-10-30 Mitsubishi Hitec Paper Flensbu Aufzeichnungsmaterial für das Tintenstrahl-Druckverfahren
US6962735B2 (en) 2001-08-31 2005-11-08 Milliken & Company Textile printing substrate
US7037346B2 (en) 2001-10-22 2006-05-02 Milliken & Company Textile substrate having coating containing multiphase fluorochemical and cationic material thereon for image printing
DE10155863B4 (de) * 2001-11-06 2008-08-28 J. S. Staedtler Gmbh & Co. Kg Markierungstinte auf wässriger Basis und deren Verwendung
AU2011373248B2 (en) * 2011-07-21 2014-10-09 Hewlett-Packard Development Company, L.P. Print medium
MY175902A (en) * 2012-12-28 2020-07-15 Surface Tech Gmbh & Co Kg Method for producing a printing material and a directly printed decorative panel
ES2606479T3 (es) 2014-02-21 2017-03-24 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible con una combinación novedosa de aceptores cromogénicos
ES2623811T3 (es) * 2014-07-29 2017-07-12 Mitsubishi Hitec Paper Europe Gmbh Material de registro termosensible con un derivado del ácido salicílico como revelador (del color) capaz de reaccionar con un precursor de colorante
US10287438B2 (en) 2015-05-08 2019-05-14 Evonik Degussa Gmbh Color-bleed resistant silica and silicate pigments and methods of making same
EP3458276B1 (fr) * 2016-10-26 2021-02-17 Hewlett-Packard Development Company, L.P. Support d'enregistrement imprimable

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US5075153A (en) * 1989-07-24 1991-12-24 Xerox Corporation Coated paper containing a plastic supporting substrate
JPH0692012A (ja) * 1992-09-09 1994-04-05 Showa Highpolymer Co Ltd インクジェット記録用紙
JPH06234268A (ja) * 1992-12-16 1994-08-23 Mitsubishi Paper Mills Ltd インクジェット記録シート
JP3943159B2 (ja) * 1995-05-31 2007-07-11 三菱製紙株式会社 インクジェット記録シート
JP3861313B2 (ja) * 1996-03-11 2006-12-20 星光Ｐｍｃ株式会社 インクジェット記録用紙の製造方法
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JPH10152544A (ja) * 1996-11-22 1998-06-09 Nippon P M C Kk 塗工用カチオン性樹脂、インクジェット記録用紙及びインクジェット記録用紙の製造方法
JP3367397B2 (ja) 1997-11-05 2003-01-14 王子製紙株式会社 インクジェット記録媒体
EP0947350B1 (fr) 1998-03-31 2003-06-04 Oji Paper Co., Ltd. Matériau pour l'impression par jet d'encre
JPH11277888A (ja) * 1998-03-31 1999-10-12 Nicca Chem Co Ltd インクジェット記録用紙用耐水性向上剤及びインクジェット記録用紙
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Also Published As

Publication number Publication date
ATE277775T1 (de) 2004-10-15
CN1243645C (zh) 2006-03-01
JP2004512983A (ja) 2004-04-30
ES2225638T3 (es) 2005-03-16
DE50103913D1 (de) 2004-11-04
WO2002036354A1 (fr) 2002-05-10
CN1471476A (zh) 2004-01-28
DE10054219A1 (de) 2002-05-08
US6880927B2 (en) 2005-04-19
US20040027433A1 (en) 2004-02-12
EP1333990A1 (fr) 2003-08-13
DE10054219C2 (de) 2003-04-24

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