EP1454761A2 - Inkjet recording sheet with improved ozone and light resistance - Google Patents

Abstract

In ink-jet recording material with a substrate and recording layer(s), (a) the upper side of the recording layer is given a protective coating containing an organic sulfur compound forming complexes with metal ions and a boric acid compound and (b) the recording layer and/or protective coating contains a group VIb, VIIb, VIIIb, Ib or IIb transition metal mono- or dicarboxylate of a 4-12 carbon carboxylic acid. In ink-jet recording material with a substrate and recording layer(s), (a) the upper side of the recording layer is given a protective coating containing an organic sulfur compound (I) forming complexes with metal ions and a boric acid compound and (b) the recording layer and/or protective coating contains an organic compound (II) of formula (IIA) or (IIB). MeX (IIA) MeX2 (IIB) Me : a group VIb, VIIb, VIIIb, Ib or IIb transition metal; and X : the anion of a 4-12 C carboxylic acid.

Description

The invention relates to a recording material for the Ink-jet recording method with a carrier, one Imaging layer and a protective layer.

With the ink jet printing process (ink jet) tiny Ink droplets with the help of different, already several times techniques described on a recording material and taken up by this. To the recording material different requirements are made such as high color density of the printed dots, high ink receptivity, short drying time and related sufficient smudge resistance, one not above the necessary Cross-directional dye diffusion the printed dots (bleed) and low color coalescence and high water resistance. Further requirements, especially for photo-like prints, are more even Printing gloss and surface gloss of the recording material.

As a result of great advances in ink jet technology in terms of image quality and printing speed among printers is the market for color inkjet printers grown enormously. It is expected to change over the next Years of digital photography, in particular inkjet photo quality materials, still strongly developed. A photographic image quality to achieve with inkjet printing is that Achieve high image stability one of the most important Development tasks. This leads to new developments both in the image receiving materials as well for inks based on dyes.

Ink jet recording materials can be in two Classes are classified, namely those with in water swelling recording layers that like binders Contain gelatin or polyvinyl alcohol, and those with microporous layers.

Those with layers swelling in water have the advantage that they shine and very high color densities after the Have pressure. They offer good ozone stability because the swellable layers as a barrier to the ingress of Prevent ozone in the material. However, the material points Disadvantages with regard to image quality (bleed, Color coalescence) and the drying time.

The microporous systems, because of the cavities in the applied layer of ink during printing can absorb quickly, have excellent image quality due to the good color fixation. You own a short drying time and problems with coalescence and bleed do not occur. With the help of such microporous recording materials produced images are not light stable and are sensitive to the gases in the air, especially ozone. The Gas can easily enter the micropores of the recording layers penetrate and possibly, supports due to the catalytic effect of the contained in the layers Pigments that attack the double bonds of the dyes. The reactivity to ozone can be caused by Moisture can be increased at elevated temperatures.

The currently proposed solutions to the problem involves laminating the printed image with a polyester film or the use of inks that contain alkali metal and contain ammonium or amine salt groups. While these solutions have positive aspects, however, are not free from disadvantages. To the disadvantages includes increasing production costs, caused by the lamination step, on the other hand The metal-containing compounds tend to be significant Hue shifts cause what is called color haze to make noticable.

By adding reducing agents or ozone scavengers such as Sodium thiosulfate or sodium thiocyanate will be sufficient Ozone and gas stability achieved. The light stability, especially for the magenta color range, however significantly deteriorated.

Known additives to improve light stability such as UV absorbers, radical quenchers and antioxidants individually or as a mixture with the image recording layer given or applied as a separate layer.

However, this can in turn have a negative impact on the Image recording layer and thus on the later image to have.

UV absorbers such as benzotriazoles or benzophenones are in usually water-insoluble and tend to reduce gloss on the picture surfaces. Also adulteration of the Color rendering is observed. Because a lot of connections own color, color changes easily occur on the white surfaces. benzotriazole generally worsen ozone stability.

Radical quenchers improve the light resistance, but have a negative impact on color rendering. Antioxidants have a limited impact on ozone and light stability.

According to JP 10-264501, the ozone stability can thereby be improved that one as a binder Thermoplastic resin containing plasticizer in the Ink receiving layer begins. The ozone protecting effect is probably achieved by the pigment and the absorbed ink dyes are enveloped by the resin.

Another way to improve ozone stability is described in JP 08-164664. There will be a inorganic pigment, the surface of which with cycloamylose is modified, used in the ink receiving layer.

EP 0 524 635 A1 describes a recording material suggested that a combination of starch particles, an ethylene / vinyl acetate copolymer and a cationic dye fixative in the ink-receiving layer contains.

Furthermore, according to JP 2000-177235 in a porous, Layer containing alumina a Mg thiocyanate used to improve light and ozone stability.

EP 1 157 847 A1 describes the use of benzotriazole derivatives in the ink receiving layer for improvement described the gas resistance of the recording material.

EP 1 029 703 A1 describes to improve the Light stability the use of hydroquinone, pyrocatechol sulfonic acid salts and phenolsulfonic acid salts. This Substances can be applied in a separate layer or added directly to the receiving layer. An improvement in ozone resistance can be achieved with these Connections cannot be reached.

EP 1 138 514 A2 describes an ink jet recording material, where the bottom layer of improvement serves the light resistance and a divalent Contain metal compound such as copper, aluminum and zinc can. But an improvement in ozone resistance can can also not be achieved with this recording material.

In JP2000-103160 one of the recording layers polyvalent metal ion such as copper, nickel, cobalt and / or Given zinc. This arrangement ensures a good one Lightfastness, but has the disadvantage of being wrong Color rendering on the image parts and poor Ozone stability.

DE 101 01 309 A1 describes an ink jet recording sheet with a one sulfur compound and one cationic Ink-containing substance Layer. This layer can also be a metal compound contain. An additional protective layer for the ink absorption layer is not described.

By using organic acids with a aromatic ring or at least two carboxyl groups in the receiving layer in EP 0 614 771 A1 becomes yellowing improved in the edge area. On the printed receiving material can have good light and ozone stability, however can only be determined to a limited extent.

The invention is therefore based on the object, another Recording material for the ink jet printing process to provide improved resistance against the effects of ozone and at the same time high light stability having. In particular, a so-called Color shift / color gamut reduced become.

This object is achieved by an ink jet recording material having a support and at least one image recording layer, a protective layer being arranged on the upper side of the image recording layer, which contains an organic sulfur-containing compound which forms complexes with metal ions and a boric acid compound, and wherein the image recording layer and / or the protective layer contains an organic compound of the formula MeX or MeX ₂ , in which Me is a transition metal from the fourth subgroup of the periodic table and X is the anion of a carboxylic acid having 4 to 12 carbon atoms.

According to a further embodiment, the image recording layer have two layers, namely one upper dye-fixing and a lower ink-absorbing Layer. The dye-fixing layer is thus between the protective layer and the ink absorbent Layer arranged. In this embodiment, the sulfur-containing compound and the boric acid compound in the protective layer and the metal compound in the dye-fixing Layer included.

Surprisingly, it was found to be an impairment the color rendering that occurs when adding transition metal compounds, especially copper compounds, frequently observed, does not occur. This unwanted Phenomenon of color shift, especially the Colors magenta and red, leads to a veiled Image; the picture lacks brilliance. Through education a complex of metal compound and sulfur-containing Connection in the presence of boric acid can be done with this coating also good lightfastness and a very good ozone resistance can be achieved.

Suitable metal compounds according to the invention can be such a transition metal of group VIb, VIIb, VIIIb, Ib and IIb of the Periodic Table of the Elements. Preferably can be used as metal ion copper, cobalt, nickel or manganese. Copper is particularly preferred. Suitable metal compounds are organic metal compounds.

Suitable anions are anions of carboxylic acids with 4 to 12 carbon atoms. Particularly preferred carboxylic acids are hydroxycarboxylic acids with 4 to 12 carbon atoms. Preferred hydroxycarboxylic acids include gluconic acid, Glucaric acid, succinic acid, hydroxy succinic acid (Malic acid), 2,3-dihydroxysuccinic acid (tartaric acid) and their mixtures. Other preferred hydroxy carboxylic acids are aromatic hydroxycarboxylic acids such as hydroxybenzoic acids, for example 2-hydroxybenzoic acid (Salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4,5-trihydroxybenzoic acid, 4- or 5-sulfosalicylic acid, 4- or 5-hydroxythiosalicylic acid as well their mixtures.

Finally, the suitable carboxylic acids include complexing agents like that the anions of ethylenediaminetetraacetic acid (EDTA), ethylenediaminetriacetic acid, hydroxyethylethylenediaminetetraacetic acid (HEEDTA) and nitrilotriacetic acid. These can also be mixed with each other or be used with hydroxycarboxylic acids.

The metal compound can be in the protective layer or in the image recording layer in a concentration of 1 to 20% by weight, preferably 4 to 15% by weight, based on the weight of the dried layer.

The invention used in accordance with complexing organic sulfur compound is a compound of the general formula R ₂ C = S, wherein R is the same or independently, an NH ₂ radical, an NR ¹ ₂ group, a methyl, ethyl, propyl, isopropyl, substituted or is unsubstituted aryl having 5 to 12 carbon atoms or alkoxy, in particular methoxy or ethoxy, or both radicals R form an aromatic or non-aromatic ring having 5 or 6 carbon atoms. This ring can contain nitrogen as a hetero atom. R ¹ may have the same meaning as R, independently of one another, and preferably mean hydrogen, methyl or ethyl. Thiourea is preferably used.

ist, worin Y die zur Bildung eines substituierten oder nicht substituierten aromatischen oder nicht aromatischen Rings erforderlichen Atome bedeutet.According to a further preferred embodiment, the complex-forming organic sulfur-containing compound is a compound of the general formula.

where Y is the atoms necessary to form a substituted or unsubstituted aromatic or non-aromatic ring.

According to a further preferred embodiment, the complex-forming organic sulfur-containing compound is a compound of the general formula R ₂ S, in which R is identical or independently of one another hydrogen, alkyl having 1 to 6 carbon atoms, substituted or unsubstituted aryl having 5 to 12 carbon atoms, NH ₂ - Radical, an NR ¹ ₂ radical, NH ₂ radical, NR ¹ ₂ radical, OR ¹ , in which R ^{1 may} , independently of one another, have the same meaning as R and preferably hydrogen, methyl, ethyl, methoxy or ethoxy or a Aryl radical with 5 or 6 carbon atoms.

The sulfur compound can be in the protective layer in a Concentration of 30 to 80% by weight, preferably 40 to 70 % By weight, based on the weight of the dried layer, available.

The quantity ratio of metal compound / sulfur compound can be 1: 1 to 1: 6, preferably 1: 1 to 1: 2.

The boric acid compound can be used as boric acid or as an alkali metal or alkaline earth metal salt of a boric acid. The boric acid can be an ortho-boric acid, metaboric acid or be a polyboric acid. It can be in the protective layer in a concentration of 20 to 80% by weight, preferably 30 to 70 wt.%, Based on the weight of the dried layer may be included.

In a preferred embodiment, the layer contains the metal compound additionally a hydroxyarylsulfonic acid. According to a particularly preferred embodiment this is a hydroxybenzenesulfonic acid, for example 4-hydroxybenzenesulfonic acid, or a sulfosalicylic acid hydrate, for example 5-sulfosalicylic acid dihydrate. The Hydroxyarylsulfonic acid is a water-soluble compound. The hydroxyarylsulfonic acid can in in the layer a concentration of 1 to 20% by weight, preferably 4 up to 15% by weight, based on the weight of the dried Layer.

The application weight of the dried protective layer is 0.1 to 6.0 g / m ² , preferably 0.3 to 4.5 g / m ² .

The compounds of the invention can be used as a mixture or applied one after the other in separate solutions. A solution contains the metal compound and optionally the hydroxyarylsulfonic acid, the other Solution contains sulfur-containing compound and the boric acid compound.

The protective layer can also contain binders, crosslinking agents, surfactants, defoamers and light stabilizers. In particular, water-soluble and / or water-dispersible polymers with a glass transition temperature T _g of 30 to 85 ° C. (DSC) and a viscosity of at most 60 cps (measured on a 4% solution at 20 ° C.) can be used as binders. Such polymers are, for example, polyurethanes, polyacrylates, polyvinyl alcohols, gelatin, gelatin derivatives, cellulose, starches, modified starches and / or polyvinyl acetates. Polyurethanes, polyacrylates and polyvinyl alcohols are particularly preferred as binders. The coating weight of the layer can be up to 10 g / m ² , in particular up to about 8 g / m ² .

The image recording layer can be pigment-free or Receive pigments. Pigments suitable according to the invention Image recording layers are, for example, aluminum oxide, Aluminum hydroxide, aluminum oxide hydrate, silica, Barium sulfate and titanium dioxide. The is preferred Use of aluminum oxides. The concentration of the Pigments in the imaging layer can be 10 to 95 % By weight, preferably either 15 to 50% by weight or 70 to 90% by weight, based on the weight of the dried Layer.

The grain size distribution of the pigment of the image recording layer can preferably 50 to 500 nm, especially preferably 80 to 400 nm. The average particle size the pigment of this layer can preferably be 80 to 120 nm, particularly preferably around 100 nm.

The image-recording layer contains a water-soluble one and / or water-dispersible polymeric binder. suitable Binders are, for example, polyvinyl alcohol, fully or partially saponified, cationically modified Polyvinyl alcohol, silyl group-containing polyvinyl alcohol, Polyvinyl alcohol containing acetal groups, Gelatin, polyvinylpyrrolidone, starch, carboxymethyl cellulose, Polyethylene glycol, styrene / butadiene latex and styrene / acrylate latex. Partly saponified are particularly preferred Polyvinyl alcohols. The amount of binder can be 90 to 5% by weight, preferably either 85 to 50 % By weight or 30 to 10% by weight, based on the weight of the dried layer.

The image recording layer can contain conventional additives and auxiliaries such as surfactants, crosslinking agents and dye-fixing agents such as polyammonium compounds. The application weight of the image recording layer can be 5 to 60 g / m ² , preferably 10 to 50 g / m ² , particularly preferably 20 to 40 g / m ² .

In a further embodiment of the invention, the Image-recording layer made of an ink-absorbent lower layer and a dye-fixing upper layer Layer.

Ink-absorbing pigments suitable according to the invention lower layer are for example aluminum oxide, Aluminum hydroxide, aluminum oxide hydrate, silica, barium sulfate and titanium dioxide. Is in the bottom layer a pigment based on amorphous silica especially prefers. Such a pigment can be cationic be modified. The concentration of the pigment in the ink-absorbing layer is 65 to 95% by weight, preferably about 70 to 90% by weight based on weight the dried layer.

The grain size distribution of the pigment of the ink-absorbing Layer can preferably range from 100 to 1000 nm, preferably 130 to 400 nm, particularly preferred 150 to 350 nm. The average particle size of the Pigments of the ink absorbing layer can be 240 to 350 nm, preferably 270 to 330 nm.

Pigments of dye-fixing agents suitable according to the invention Layer are, for example, aluminum oxide, aluminum hydroxide, Alumina hydrate, silica, barium sulfate and titanium dioxide. The concentration of the pigment in the dye-fixing layer can be 70 to 95% by weight, preferably 80 to 90% by weight.

The grain size distribution of the pigment of the dye-fixing Layer may preferably range from 50 to 200 nm, preferably 80 to 120 nm. The middle Particle size of the pigment of the dye-fixing Layer may preferably be 80 to 120 nm, preferably around 100 nm.

The ink-absorbing and the dye-fixing Layer contain a water-soluble and / or water-dispersible polymeric binder. Suitable binders are, for example, polyvinyl alcohol, complete or partially saponified, cationically modified polyvinyl alcohol, Polyvinyl alcohol containing silyl groups, acetal groups containing polyvinyl alcohol, gelatin, polyvinyl pyrrolidone, Starch, carboxymethyl cellulose, polyethylene glycol, Styrene / butadiene latex and styrene / acrylate latex. The amount of binder in the dye fixative and the ink absorbing layer is each 5 to 35% by weight, preferably 10 to 30% by weight on the weight of the dried layer.

Both layers can be conventional additives and auxiliaries Contain like surfactants, crosslinking agents and dye fixatives Medium.

The application weights of the ink-absorbing and the dye-fixing layer can be 10 to 60 g / m ² , preferably 20 to 50 g / m ² .

In principle, any base paper can be used as a carrier material. Surface-sized, calendered or non-calendered or strongly sized base papers are preferred. The paper can 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 cellulose mixtures of softwood cellulose and eucalyptus cellulose are particularly suitable. In this regard, reference is made to the disclosure of EP 0 786 552 B1, which describes a base paper for an inkjet recording material. The base paper can contain other auxiliaries and additives, such as dyes, optical brighteners or defoamers, which are common in the paper industry. The use of reject pulp and refurbished waste paper is also possible. Base papers with a basis weight of 50 to 300 g / m ² can be used.

Particularly suitable as a carrier material is paper coated on one or both sides with polyolefins, in particular with polyethylene (LDPE and / or HDPE). The application amount of the polyethylene is 5 to 20 g / m ² . Plastic films, for example made of polyester or polyvinyl chloride, are also suitable as supports. The basis weight of the carrier can be 50 to 300 g / m ² .

Any, general, can be used to apply the layers known application and dosing processes used are like roller application, engraving or nipping processes as well Air brush or roller doctor metering. Particularly preferred is the application with the help of a cascade coating system or a slot caster.

For setting the curl behavior, antistatic and the back of the printer can be transported in the printer be provided with a separate functional layer. suitable Backing layers are described in EP 0 616 252 B1 and EP 0 697 620 B1, on the disclosure thereof Reference is made.

The following examples are provided for further explanation the invention.

Examples B1 to B3

A paper with a basis weight of 173 g / m ² and a neutral weight with alkyl ketene dimer and coated on both sides with polyethylene was used for the examples B1 to B3. For this purpose, the front side of the base paper was coated with a coating composition containing a low-density polyethylene (LDPE) and 10% by weight of TiO ₂ and the rear side with a clear LDPE by extrusion. The application weight of the front coating was 19 g / m ² , the back application 22 g / m ² .

The front of the support was coated with a coating composition which contained 75% by weight of a finely divided silica (300 nm) and 25% by weight of a polyvinyl alcohol (degree of saponification 88 mol%). Coating was done with a slot coater to obtain an ink absorption layer. The coating composition for the dye-fixing layer was applied to this layer, the applied weight of which was 12 g / m ² in the dried state, using a slot coater. This coating composition contained 89% by weight of a finely divided aluminum oxide (100 nm) and 11% by weight of a polyvinyl alcohol (degree of saponification 88 mol%). The application weight was 30 g / m ² in the dried state.

A protective layer as an aqueous solution was applied to the dye-fixing layer in two steps. In the first step, the copper compound (Examples 2 and 3) was applied with the hydroxybenzenesulfonic acid (Example 1). Boric acid and thiourea were applied in the second stage. The weight data relate to the dried layer. The total application weight of the protective layer in Examples B1 to B3 was 3.2 g / m ² . connection B1 (% by weight) B2 (% by weight) B3 (% by weight) boric acid 50 50 40 thiourea 37.5 40 40 Copper (II) gluconate 6.26 10 - Copper (II) EDTA - 20 4-Hydroxybenzoesulfonsäure 6.25 - -

Examples B4 to B6

For examples B4 to B6, the carrier of the examples 1 to 3 used.

The front of the support was coated with a coating composition which contained 89% by weight of a finely divided aluminum oxide (average particle size 100 nm; BET specific surface area 150-200 m ² / g; zeta potential +30 to 40 mV) and 11% by weight of a Polyvinyl alcohol (degree of saponification 88 mol%) contained. The application weight of this image recording layer was 38 g / m ² in the dried state.

A protective layer was applied to the image recording layer as an aqueous solution in two steps. In the first step, the copper compound (Examples 5, 6) was applied with the hydroxybenzenesulfonic acid (Example 4). Boric acid and thiourea were applied in the second step. The weight data relate to the dried layer. The total application weight in Examples B4 to B6 was 3.2 g / m ² . connection B4 (wt%) B5 (% by weight) B6 (wt%) boric acid 50 50 40 thiourea 37.5 40 40 Copper (II) gluconate 6.26 10 - Copper (II) EDTA - 20 4-Hydroxybenzoesulfonsäure 6.25 - -

Examples B7 to B9

For examples B7 to B9, the carrier of the examples 1 to 3 used.

A coating composition which contained 89% by weight of a finely divided aluminum oxide (100 nm) and 11% by weight of a polyvinyl alcohol (degree of saponification 88 mol%) was mixed with the copper compound and 4-hydroxybenzenesulfonic acid mentioned in the table and applied to the front of the support , The application weight of this image recording layer was 38 g / m ² in the dried state.

Boric acid and thiourea were applied in a separate protective layer in the concentrations shown in Table 3. The application weight of the protective layer was 2.7 g / m ² . The weight data relate to the dried layer. connection B7 [g] B8 [g] B9 [g] boric acid 1.5 1.5 1.35 thiourea 1.2 1.2 1.35 Copper (II) gluconate 0.1 0.25 - Copper (II) EDTA - 0.4 4-Hydroxybenzoesulfonsäure 0.1 - -

Comparative Examples Comparative Examples V1 to V3

A recording sheet was used as in Examples B1 to B3 and coated with the compounds from aqueous solution mentioned in Table 4 in one step. The weight data relate to the dried layer. The application weight for V1 to V3 was 1.8 g / m ^{2 in} each case. connection V1% by weight V2% by weight V3% by weight boric acid 80 100 60 thiourea - - 40 Copper (II) gluconate 20 - -

Comparative Example 4

The carrier material served as comparative example 4 Examples B1 to B3 without the compounds according to the invention.

Comparative Example 5

A commercial paper was used as comparative example 5 "Epson Premium Glossy Photo Paper".

Comparative Example 6

A commercial paper was used as comparative example 6 "Canon PR 101".

exam

The recording materials obtained were tested for light resistance, Resistance to ozone and color shift (Color gamut) checked.

The tests were based on four different color prints Printer types Epson Stylus 890 Photo Printer, Canon S800 Photo Printer and Hewlett-Pacckard 990 Printer. Circular dots with a diameter were printed of 10 mm for the colors cyan, magenta, yellow, Black and red (color shift). The printing took place at 23 ° C under a relative humidity of 50%. With these conditions, the prints could last for 8 hours dry. The test results are in Tables 3 to 7 summarized.

Ozone resistance - The printed paper samples were dried and stored for 24 hours with the exclusion of light, gas and moisture. The colorimetric L * a * b * values of the colored areas were then determined.

In the next step, the samples were in for 24 hours an ozone chamber with an ozone concentration of 3.5 ppm, a temperature of 20 to 22 ° C and a relative Humidity of 40 to 50% stored. Subsequently the L * a * b * values were measured again and the degree of the bleaching ΔE determined.

L * a * b * values were measured using an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA). The color difference ΔE is calculated according to the equation: ΔE = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2 . The fading of each color area compared to the standard material is calculated as% ΔE according to the following equation (DIN 6174) and summarized in Tables 3 to 5:% ΔE = (ΔE / ΔE standard) x 100%. The smaller the% ΔE value, the better the material's ozone resistance.

Lightfastness - The paper samples were printed with the color magenta in a color coverage of 40%, 60% and 80% and for 48 hours at 30 ° C and a relative humidity of 60% in an Atlas 3000i Weatherometer (1.2 W / m ² ) brought in. The fading of the color was assessed using the CIE L * a * b * system.

L * a * b * values were measured using an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA). The color difference ΔE is calculated according to the equation: ΔE = [(ΔL *) ² + (Δa *) ² + (Δb *) ² ] ^1/2 .

Color shift (color gamut) - The color shift was determined by determining the values of a * and b * on the colors red and magenta using an X-Rite Color Digital Swatchbook (X-Rite Inc., Grandville, Michigan, USA). The color red consisted of 50 parts of Epson yellow and Epson magenta.

Comparative example V4 is used as the standard in this test, since this material does not contain any compounds which can cause a color shift. The closer the measured values of the examples and comparative examples are to V4, the less the color shift. Lightfastness (Epson 890 Printer) ΔE (40%) ΔE (60%) ΔE (80%) Total% ΔE B1 11.21 10.22 14.22 35,65 B2 11.29 10.78 14.55 36.62 B3 9.70 7.36 14,88 31.94 B4 11.42 10.35 14.55 36.32 B5 11.49 10.87 14.68 37.04 B6 9.90 7.69 15,01 32,60 B7 11.47 10.41 14,50 36.38 B8 11.58 11.02 14.66 37.26 B9 10.04 7.65 14.96 32.65 V1 10.83 12.83 13.11 36.77 V2 16,66 23.35 17.63 57.65 V3 20.62 32.22 30.34 83.18 V4 14.68 15.77 11.93 42.39 V5 13.29 19.41 19,02 51.72 V6 15.70 21.58 19.71 56,99 Ozone resistance Total ΔE Epson 890 Canon S800 HP 990cxi B1 16 41 19 B2 18 45 21 B3 18 46 22 B4 16 42 19 B5 19 45 22 B6 19 48 22 B7 17 44 20 B8 19 46 23 B9 19 48 23 V1 64 128 152 V2 70 137 182 V3 19 53 23 V4 93 142 198 V5 39 - - V6 - 149 -

As can be seen from Tables 5 and 6, the compounds used according to the invention can significantly improve the ozone resistance and good light resistance. Thiourea alone (V3) shows good ozone resistance but has an adverse effect on the light resistance of the magenta dye (Epson 40-80%) in microporous ink jet recording materials. Boric acid alone (V2) has little influence on the ozone resistance of microporous recording materials; however, it improves the surface strength (scratch resistance) of the recording material since it crosslinks with the PVA and aluminum oxide of the layer. Copper (II) gluconate alone shows only a slight improvement in ozone resistance, but a significant improvement in the light resistance of the magenta dye. However, the color shift is not acceptable; the colors show a cloudy cloudiness. The samples according to the invention show a significant improvement in ozone resistance and light resistance. The results regarding the color shift in the area of red and magenta are very good, an image with a natural and lively coloring is obtained. -Color shift Epson Stylus 890 Photo Printer red red magenta magenta a * b * a * b * B1 71.11 42.19 80.49 4.08 B2 71.07 42,10 80.45 4.08 B3 71.21 42.22 80.59 4.11 B4 71.58 41,99 80.87 4.18 B5 71.55 41.91 80.85 4.15 B6 71,60 41.91 80,99 4.18 B7 71.49 42.05 80.61 4.14 B8 71.45 42,11 80.57 4.12 B9 71.57 42.01 80.69 4.16 V1 65,50 36.39 77.22 -1.47 V2 72.46 44.63 81.67 4.69 V3 71.46 41,85 80.93 4.33 V4 72.22 41,65 81.42 4.32 V5 67.94 38.48 79.64 4.49 V6 - - - -

Claims (12)

Ink jet recording material with a support and at least one image recording layer, characterized in that a protective layer is applied on the upper side of the image recording layer, which contains an organic sulfur-containing compound forming metal ion complexes and a boric acid compound, and wherein the image recording layer and / or the protective layer is an organic Compound of the formula MeX or MeX ₂ contains, in which Me is a transition metal from group VIb, VIIb, VIIIb, Ib and IIb of the periodic table and X is the anion of a carboxylic acid having 4 to 12 carbon atoms. Recording material according to claim 1, characterized in that the image recording layer contains at least one dye-fixing layer and at least one ink-absorbing layer. Recording material according to claim 1 or 2, characterized in that the transition metal is copper, cobalt, nickel or manganese. Recording material according to one of claims 1 to 3, characterized in that the anion is an anion of a hydroxycarboxylic acid. Recording material according to claim 4, characterized in that the hydroxycarboxylic acid is selected from gluconic acid, glucaric acid, succinic acid, hydroxysuccinic acid (malic acid), 2,3-dihydroxysuccinic acid (tartaric acid) and mixtures thereof. Recording material according to one of claim 4, characterized in that the hydroxycarboxylic acid is selected from the group of compounds containing an aromatic ring, in particular hydroxybenzoic acids such as 2-hydroxybenzoic acid (salicylic acid), 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4,5-trihydroxybenzoic acid , 4- or 5-sulfosalicylic acid, 4- or 5-hydroxythiosalicylic acid. Recording material according to one of claims 1 to 3, characterized in that the anion is selected from ethylenediaminetetraacetic acid (EDTA), ethylenediaminetriacetic acid, hydroxyethylethylenediaminetetraacetic acid (HEEDTA), nitrilotriacetic acid or salts thereof. Recording material according to one of claims 1 to 7, characterized in that the layer containing a metal compound contains, as a further constituent, a hydroxybenzenesulfonic acid. Recording material according to one of Claims 1 to 8, characterized in that the complex-forming organic sulfur-containing compound is a compound of the general formula R ₂ C = S, in which R is, independently of one another, hydrogen, an NH ₂ radical, an NHR ¹ radical, an NR ¹ ₂ group, a methyl, ethyl, propyl, isopropyl, substituted or unsubstituted aryl group having 5 to 12 carbon atoms or alkoxy having 1 to 3 carbon atoms or both radicals R is an aromatic or non-aromatic ring having 5 or 6 Form carbon atoms, which may contain nitrogen and / or sulfur as the hetero atom, where R ¹ has the same meaning as R or independently of one another. Recording material according to one of claims 1 to 8, characterized in that the complex-forming organic sulfur-containing compound is a compound of the general formula.

where Y is the atoms necessary to form a substituted or unsubstituted aromatic or non-aromatic ring. Recording material according to one of Claims 1 to 8, characterized in that the complex-forming organic sulfur-containing compound is a compound of the general formula R ₂ S, in which R is, independently of one another, hydrogen, alkyl having 1 to 6 carbon atoms, substituted or unsubstituted aryl having 5 to 12 carbon atoms, alkoxy having 1 to 3 carbon atoms, NH ₂ radical, an NHR ¹ radical, an NR ¹ ₂ radical, OR ¹ , in which R ^{1 has the} same meaning as R. Recording material according to one of claims 1 to 11, characterized in that the weight ratio of metal compound / sulfur-containing compound is 1: 1 to 1: 6, in particular 1: 1 to 1: 2.