EP1486345B1 - Matériau pour l'impression par jet d'encre possédant une résistance a l'ozone et a la lumière améliorée - Google Patents

Matériau pour l'impression par jet d'encre possédant une résistance a l'ozone et a la lumière améliorée Download PDF

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Publication number
EP1486345B1
EP1486345B1 EP03025169A EP03025169A EP1486345B1 EP 1486345 B1 EP1486345 B1 EP 1486345B1 EP 03025169 A EP03025169 A EP 03025169A EP 03025169 A EP03025169 A EP 03025169A EP 1486345 B1 EP1486345 B1 EP 1486345B1
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EP
European Patent Office
Prior art keywords
acid
recording material
ink
layer
hydroxyarylsulfonic
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
EP03025169A
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German (de)
English (en)
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EP1486345A1 (fr
Inventor
Richard A. Barcock
Aidan J. Lavery
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.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
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Publication of EP1486345A1 publication Critical patent/EP1486345A1/fr
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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
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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

Definitions

  • the invention relates to a recording material for the ink jet recording method comprising a support, an ink absorbing layer and a dye fixing layer.
  • tiny ink droplets are applied to and recorded on a recording material by various techniques already described several times.
  • the recording material is subject to various requirements such as high density of printed dots, high ink receptivity, short drying time and adequate wipe resistance, non-required dye diffusion in the transverse direction of the printed dots (bleed), and low color coalescence and high water resistance.
  • Other requirements, especially for photo-like prints, are uniform print gloss and surface gloss of the recording material.
  • Ink-jet recording materials can be classified into two classes, namely, water-swelling recording layers containing binders such as gelatin or polyvinyl alcohol and those having microporous layers.
  • Such water-swelling layers have the advantage that they shine and have very high color densities after printing. They provide good ozone stability because the swelling layers act as a barrier to prevent ozone from entering the material. However, the material has disadvantages in terms of image quality (bleed, color coalescence) and drying time.
  • microporous systems which because of the voids in the coated layer can rapidly absorb the ink during printing, have excellent image quality due to good ink fixation. They have a short drying time and problems with coalescence and bleed do not occur.
  • the images produced with the aid of such microporous recording materials are not stable to light and are sensitive to the gases contained in the air, in particular ozone.
  • the gas can easily penetrate into the micropores of the recording layers and, possibly supported by the catalytic action of the pigments contained in the layers, attack the double bonds of the dyes.
  • the reactivity to ozone can be enhanced by humidity at elevated temperature.
  • the cyan dye is particularly sensitive to ozone.
  • the ozone stability can be improved by using as binder a thermoplastic resin containing a plasticizer in the ink receiving layer.
  • the ozone-protecting effect is presumably achieved by enveloping the pigment and the absorbed ink dyes with the resin.
  • a Mg thiocyanate used to improve the light and ozone stability.
  • the EP 1 029 703 A1 describes the use of hydroquinone, catecholsulfonic acid salts and phenolsulfonic acid salts to improve light stability. These substances can be applied in a separate layer or added directly to the receiving layer. An improvement in ozone resistance can not be achieved with these compounds.
  • the invention is therefore based on the object to provide a further recording material for the ink-jet printing process, which has an improved resistance to ozone exposure and at the same time a high light stability.
  • an ink-jet recording material having a support, at least one ink-absorbing and at least one dye-fixing layer, in which on the upper side of the dye-fixing layer, an ⁇ -hydroxycarboxylic acid and at least one hydroxyarylsulfonic acid is applied, which in 0.01 molar aqueous solution has an acid exponent pKa of 0.5 to 2.0 and wherein the surface pH of the coated dye-fixing layer is 2.5 to 4.0.
  • Fig. 1 shows a recording material according to the invention.
  • the invention further provides a process for the preparation of the aforementioned ink-jet recording material, wherein the hydroxyarylsulfonic acid is applied in the form of a 1 to 10% aqueous solution on the upper side of the dye-fixing layer.
  • the recording material according to the invention offers a high ozone resistance and light stability. Surprisingly, a high moisture resistance was also found, whereby a mixing of colors is counteracted at the color boundaries.
  • hydroxyarylsulfonic acid is used as such and not in the form of its salts or esters.
  • the water solubility of hydroxyarylsulfonic acid at 40 ° C is preferably greater than 10 wt.%.
  • the pH at the surface of the recording material is preferably in a range of 3.0 to 3.5.
  • Aryl may be phenyl or naphthyl.
  • the hydroxyarylsulfonic acid is preferably 4-hydroxybenzenesulfonic acid and / or 5-sulfosalicylic acid dihydrate.
  • the hydroxyarylsulfonic acid is preferably applied to the dye-fixing layer in the form of an aqueous solution having a concentration of from 1 to 10% by weight, based on the weight of the solution.
  • the solution may have a pH of 1.0 to 3.0 in a temperature range of 10 to 50 ° C.
  • the hydroxyarylsulfonic acid is used as a mixture with an ⁇ -hydroxycarboxylic acid.
  • the amount ratio of hydroxyarylsulfonic acid / ⁇ -hydroxycarboxylic acid can be from 1:10 to 10: 1, preferably from 1: 5 to 5: 1.
  • the ⁇ -hydroxycarboxylic acid is a D-gluconic acid.
  • Also suitable are all ring-shaped and straight-chain or branched-chain ⁇ -hydroxycarboxylic acid having 2 to 12, preferably 5 to 8, carbon atoms.
  • the coating weight of the layer containing hydroxyarylsulfonic acid without additional binder should not exceed 2 g / m 2 , and preferably be less than about 1 g / m 2 .
  • the hydroxyarylsulfonic acid may be in the form of a layer which also contains binders, crosslinking agents, surfactants, defoamers and light stabilizers.
  • binders such as water-soluble and / or water-dispersible polymers having a glass transition temperature Tg of 30 to 85 ° C. (DSC) and a viscosity of at most 60 cps (measured on a 4% solution at 20 ° C.) may be used as binders.
  • Such polymers are, for example, polyurethanes, polyacrylates, polyvinyl alcohols, gelatin, gelatin derivatives, cellulose, starches, modified starches, and / or polyvinyl acetates.
  • the coating weight of the layer can be up to 4 g / m 2 , in particular up to about 2 g / m 2 .
  • Suitable pigments of the ink-absorbing lower layer according to the invention are aluminum oxide, aluminum hydroxide, aluminum oxide hydrate, silica, barium sulfate and titanium dioxide.
  • an amorphous silica-based pigment is particularly preferable. Such a pigment may be cationically modified.
  • the grain size distribution of the pigment of the ink absorbing layer is preferably in the range of 150 to 1,000 nm with an average particle size of 240 to 350 nm.
  • Suitable pigments of the dye-fixing layer according to the invention are, for example, aluminum oxide, aluminum hydroxide, Alumina hydrate, silica, barium sulfate and titanium dioxide.
  • the pigment used in the dye-fixing layer has an average particle size of 10 to 500 nm, in particular 50 to 100 nm.
  • the ink-absorbing and dye-fixing layers contain a water-soluble and / or water-dispersible polymeric binder.
  • Suitable binders are, for example, polyvinyl alcohol, fully or partially saponified, cationically modified polyvinyl alcohol, silyl-containing polyvinyl alcohol, acetal-containing polyvinyl alcohol, gelatin, polyvinylpyrrolidone, starch, carboxymethylcellulose, polyethylene glycol, styrene / butadiene latex and styrene / acrylate latex.
  • the amount of the binder in the dye-fixing and ink-absorbing layers is 5 to 35% by weight, preferably 10 to 30% by weight, based on the weight of the dried layer.
  • Both layers may contain conventional additives and auxiliaries such as surfactants, crosslinking agents and dye-fixing agents such as polyammonium compounds.
  • the application thicknesses of the ink-absorbing and the dye-fixing layer may be 10 to 60 ⁇ m, preferably 20 to 50 ⁇ m.
  • any base paper can be used as carrier material. Preference is given to surface-sized, calendered or non-calendered or strongly sized base papers.
  • the paper may be acid or neutral sized.
  • the base paper should have a high dimensional stability and absorb the liquid contained in the ink without undulation. Papers with high dimensional stability from pulp mixtures of softwood pulps and eucalyptus pulps are particularly suitable.
  • the disclosure of the EP 0 786 552 B1 which describes a base paper for an ink-jet recording material.
  • the base paper may contain other auxiliaries and additives customary in the paper industry, such as dyes, optical brighteners or defoamers.
  • the use of scrap pulp and recycled waste paper is also possible. It can be used with a basis weight of 50 to 300 g / m 2 raw papers.
  • carrier material is a paper coated on one or both sides with polyolefins, in particular with polyethylene (LDPE and / or HDPE).
  • polyethylene LDPE and / or HDPE
  • the application amount of the polyethylene is 5 to 20 g / m 2 .
  • plastic films for example of polyester or polyvinyl chloride, are suitable as a carrier.
  • the basis weight of the carrier may be 50 to 300 g / m 2 .
  • any, well-known application and metering process can be used, such as roller application, engraving or nipping method as well as air brush or roller doctor metering.
  • Particularly preferred is the application by means of a cascade coating machine or a Schlitzg fabricers.
  • the back can be provided with a separate functional layer.
  • Suitable backsheets are in the EP 0 616 252 B1 and EP 0 697 620 B1 described, the disclosure of which reference is made.
  • FIG. 1 An exemplary embodiment of the recording material according to the invention is shown in FIG.
  • the carrier used is a base paper 1 coated on both sides with polyethylene 2, 2 '.
  • an ink absorbing layer 3 is disposed on one of the polyethylene layers 2, 2 '.
  • This layer 3 contains a finely divided pigment and a binder.
  • a dye-fixing layer 4 is arranged, which also contains a finely divided pigment and a binder.
  • the inventive, containing hydroxyarylsulfonic layer 5 is located on the dye-fixing layer 4th
  • Examples B3 and B6 are examples according to the invention, the remaining examples are for comparison purposes.
  • a paper neutral-sized with alkyl ketene dimer and coated on both sides with polyethylene was used with a basis weight of 173 g / m 2 as support.
  • the front of the base paper was coated with a low density polyethylene (LDPE) and 10 wt% TiO 2 containing coating mass and the backside coated with a clear LDPE by extrusion.
  • the coating weight of the front coating was 19 g / m 2 , the backsize 22 g / m 2 .
  • the front surface of the support was coated with a coating composition containing 75% by weight of a finely divided silica (300 nm) and 25% by weight of a polyvinyl alcohol (degree of saponification 88 mol%).
  • the coating was carried out with a slot caster to obtain an ink absorbing layer.
  • the coating weight of which, when dried, was 12 g / m 2
  • the coating composition for the dye-fixing layer was applied with a slot caster.
  • This coating composition contained 89% by weight of a finely divided alumina (100 nm) and 11% by weight of a polyvinyl alcohol (saponification degree 88 mol%).
  • the application weight was 30 g / m 2 in the dried state.
  • the support, the ink absorbing layer and the dye fixing layer are the same as in Examples B1 to B3.
  • a recording sheet was used as in Examples B1 to B6 but without the hydroxyarylsulfonic acid coating and ⁇ -hydroxycarboxylic acid coating according to the invention.
  • the experiment was carried out as in Examples 1 to 3 with the difference that in the aqueous coating solution for the upper layer, a salicylic acid sodium salt (B8), a 4-hydroxybenzenesulfonic acid sodium salt dihydrate (B9) and a benzenesulfonic acid (B10) were used ,
  • the concentration of the compounds was 3% by weight in each case.
  • the application rates of the substances used in the dried state were 0.8 g / m 2 .
  • the pH of the surface was 5.4 (B7), 4.1 (B8) and 4.2 (B9).
  • the obtained recording materials were tested for light resistance, ozone resistance, color density and moisture resistance.
  • the samples were stored for 24 hours in an ozone chamber at an ozone concentration of 3.5 ppm, a temperature of 20 to 22 ° C and a relative humidity of 40 to 50%. Subsequently, the L * a * b * values were measured again and the degree of bleaching ⁇ E was determined.
  • the L * a * b * values were measured with an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA).
  • % ⁇ E ( ⁇ E / ⁇ E standard) x 100%.
  • the L * a * b * values were measured with an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA).
  • the samples are conditioned for 12 hours at 23 ° C / 50% RH , followed by a five-day storage at 35 ° C / 80% RH.
  • the migration of the colors at the edges of the color areas is assessed visually with grades 2 (no migration) to 5 (strong migration).

Landscapes

  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Ink Jet (AREA)
  • Paper (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Claims (10)

  1. Matériau pour l'impression par jet d'encre avec un support, au moins une couche absorbant l'encre et au moins une couche fixant les colorants, caractérisé en ce que sur la face supérieure de la couche fixant les colorants, est disposé un acide α-hydroxycarboxylique et au moins un acide hydroxyarylsulfonique soluble dans l'eau, qui présente en solution aqueuse 0,01 molaire, une constante d'acidité allant de 0,5 à 2,0, et où le pH en surface de la couche fixant les couleurs revêtues se situe dans l'intervalle allant de 2,5 à 4,0.
  2. Matériau pour l'impression selon la revendication 1, caractérisé en ce que l'acide hydroxyarylsulfonique présente une solubilité dans l'eau de plus de 10% en poids à 40°C.
  3. Matériau pour l'impression selon la revendication 1 ou 2, caractérisé en ce que l'acide hydroxyarylsulfonique est l'acide 4-hydroxybenzènesulfonique et/ou l'acide 5-sulfosalicylique dihydraté.
  4. Matériau pour l'impression selon l'une des revendications 1 à 3, caractérisé en ce que l'acide α-hydroxycarboxylique est l'acide D-gluconique.
  5. Matériau pour l'impression selon l'une des revendications 1 à 4, caractérisé en ce que le rapport quantitatif acide hydroxyarylsulfonique/acide hydroxycarboxylique se situe dans l'intervalle allant de 1:10 à 10:1.
  6. Matériau pour l'impression selon la revendication 5, caractérisé en ce que le rapport quantitatif acide hydroxyarylsulfonique/acide hydroxycarboxylique se situe dans l'intervalle allant de 1:5 à 5:1.
  7. Matériau pour l'impression selon l'une des revendications 1 à 6, caractérisé en ce que le poids appliqué d'acide hydroxyarylsulfonique se situe à maximum 2 g/m2.
  8. Matériau pour l'impression selon la revendication 7, caractérisé en ce que le poids appliqué d'acide hydroxyarylsulfonique se situe à moins de 1 g/m2.
  9. Procédé de préparation d'un matériau pour l'impression selon la revendication 1, caractérisé en ce que l'on applique l'acide hydroxyarylsulfonique sous forme d'une solution aqueuse à 1 à 10% sur la face supérieure de la couche fixant les colorants.
  10. Procédé selon la revendication 9, caractérisé en ce que le pH de la solution d'acide hydroxyarylsulfonique se situe dans l'intervalle allant de 1 à 3 dans un intervalle de température allant de 10 à 50°C.
EP03025169A 2002-11-05 2003-11-04 Matériau pour l'impression par jet d'encre possédant une résistance a l'ozone et a la lumière améliorée Expired - Lifetime EP1486345B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10251340A DE10251340B4 (de) 2002-11-05 2002-11-05 Ink-Jet Aufzeichnungsblatt mit verbesserter Ozon- und Lichtstabilität
DE10251340 2002-11-05

Publications (2)

Publication Number Publication Date
EP1486345A1 EP1486345A1 (fr) 2004-12-15
EP1486345B1 true EP1486345B1 (fr) 2008-01-09

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ID=32115202

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Application Number Title Priority Date Filing Date
EP03025169A Expired - Lifetime EP1486345B1 (fr) 2002-11-05 2003-11-04 Matériau pour l'impression par jet d'encre possédant une résistance a l'ozone et a la lumière améliorée

Country Status (6)

Country Link
EP (1) EP1486345B1 (fr)
AT (1) ATE383244T1 (fr)
DE (2) DE10251340B4 (fr)
DK (1) DK1486345T3 (fr)
ES (1) ES2298461T3 (fr)
PT (1) PT1486345E (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5509957A (en) * 1992-11-09 1996-04-23 Ciba-Geigy Corporation Ink compositions
EP1029703B1 (fr) * 1999-02-16 2004-05-12 Oji Paper Co., Ltd. Matériau pour l'enregistrement par jet d'encre avec meilleure résistance à la lumière
US6773771B1 (en) * 1999-04-27 2004-08-10 Mitsubishi Paper Mills Limited Ink-jet recording sheet
DE10101309B4 (de) * 2000-01-14 2004-11-18 Mitsubishi Paper Mills Limited Tintenstrahl-Aufzeichnungsmaterial
ATE277774T1 (de) * 2000-10-11 2004-10-15 Ilford Imaging Ch Gmbh Aufzeichnungsmaterial für den tintenstrahldruck
EP1231071B1 (fr) * 2001-02-12 2003-05-14 ILFORD Imaging Switzerland GmbH Feuille d'enregistrement pour l'impression par jet d'encre contenant des sels de cuivre
JP2003039824A (ja) * 2001-05-22 2003-02-13 Fuji Photo Film Co Ltd インクジェット記録用シート

Also Published As

Publication number Publication date
PT1486345E (pt) 2008-04-03
DE50308968D1 (de) 2008-02-21
DE10251340A1 (de) 2004-05-19
DE10251340B4 (de) 2004-12-02
EP1486345A1 (fr) 2004-12-15
ATE383244T1 (de) 2008-01-15
ES2298461T3 (es) 2008-05-16
DK1486345T3 (da) 2008-05-19

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