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
  • 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
  • B41M5/502—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
• • 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
  • B41M5/52—Macromolecular coatings
  • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
• • 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

Definitions

• the present invention relates to new stabilizers for recording materials for inkjet printing, nanoporous inorganic oxides or Contain oxide / hydroxide.
• an ink jet becomes pressurized from a nozzle ejected the individual at a certain distance from the nozzle Droplet disintegrates.
• the individual droplets are, depending on whether an image spot to be printed or not, deflected into a collecting container or up the recording material applied. This happens e.g. B. by the reason given digital data, droplets not required are electrically charged and then deflected into the collecting container in a static electrical field become.
• the reverse procedure is also possible, with the uncharged Droplets are deflected into the collecting container.
• Such recording materials available today do not meet all the requirements placed on them. In particular, the light resistance and the shelf life of the images produced on these materials must be improved.
• Such images are not particularly stable in contact with outside air, which normally contains sulfur dioxide and, especially in summer, photochemically generated impurities such as ozone and nitrogen oxides. In contact with the outside air, they are very strongly changed or even destroyed within a short period of time. These phenomena are described for example in the Hardcopy Supplies Journal, 6 (7), 35 (2000).
• Patent application EP 0'534'634 describes the application of salt solutions which contain an at least divalent metal cation to recording materials for inkjet printing to improve the water resistance of printed images.
• CuCl 2 , CuBr 2 , Cu (NO 3 ) 2 , Cu (ClO 3 ) 2 and Cu (C 2 H 3 O 2 ) 2 are mentioned as copper salts.
• the nanoporous contain inorganic oxides or oxide / hydroxides are in the patent application GB 2'088'777 derivatives of phenols and bisphenols proposed.
• the nanoporous inorganic oxides or oxide / hydroxides contains, the addition of dithiocarbamates, thiurams, thiocyanates or sterically hindered amines are proposed.
• the additives proposed there improve the stability of recording materials for inkjet printing, nanoporous inorganic oxides or Contain oxide / hydroxide, but not in contact with contaminated outside air sufficient extent.
• the nanoporous inorganic Containing oxides or oxide / hydroxides must be sufficiently soluble and with the other components of the mostly aqueous coating compositions be well tolerated. They must be colorless or at most lightly colored his. Likewise, the additives in the recording material have to be used for a long time maintain their quality and even after long storage of the recording material or the pictures made on it do not become ineffective or yellow. Furthermore, they must be non-toxic and harmless.
• the aim of the invention is to provide recording materials with improved Shelf life in contact with outside air, the nanoporous inorganic Contain oxides or oxide / hydroxides, in which the recorded on it Image is viewed in supervision or transparency and which one from a carrier and at least one ink receiving layer thereon.
• the recording materials according to the invention for inkjet printing contain in the applied layers in addition to the nanoporous inorganic Oxide or oxide / hydroxide and the copper salts one or more binders.
• the copper salts can be in the ink-receiving layer, which is the nanoporous inorganic Contains oxide or oxide / hydroxide, introduced, or in another Layer of the recording material.
• the salts of monovalent copper, in particular CuCl, are particularly effective.
• the invention describes a recording material for inkjet printing, the has one or more layers on a carrier which, in addition to at least a nanoporous inorganic oxide or oxide / hydroxide and binders in an ink-receiving layer containing copper salts.
• the nanoporous inorganic Oxide or oxide / hydroxide and the copper salts can be in the same or in different layers.
• suitable copper (II) salts are copper (II) chloride, copper (II) sulfate, Copper (II) nitrate and copper (II) perchlorate.
• the salts of monovalent copper such as copper (I) chloride, are particularly effective. Copper (I) bromide and copper (I) sulfite monohydrate.
• Such a recording material contains one or more of the compounds mentioned above. Their amount is 1 mg to 1,000 mg / m 2 , preferably 10 mg to 200 mg / m 2, of these compounds.
• Preferably 50 mg to 600 mg / m 2 of these compounds are added to the recording material.
• Colloidal silicon dioxide, colloidal aluminum oxide or colloidal aluminum oxide / hydroxide can be used as the nanoporous inorganic oxide or oxide / hydroxide.
• Colloidal aluminum oxide, colloidal aluminum oxide / hydroxide or positively charged silicon dioxide are preferred.
• Y-Al 2 O 3 is particularly preferred as the colloidal aluminum oxide and AIOOH as the colloidal AIOOH reacted with rare earth salts, as described in patent application EP 0'875'394.
• This nanoporous aluminum oxide / hydroxide contains one or more elements of atomic number 57 to 71 of the Periodic Table of the Elements, preferably in an amount between 0.4 and 2.5 mole percent based on Al 2 O 3 .
• This nanoporous pseudo-boehmite contains one or more elements of atomic number 57 to 71 of the Periodic Table of the Elements, preferably in an amount between 0.4 and 2.5 mole percent based on Al 2 O 3 .
• the recording material can also contain other inorganic oxides or oxide / hydroxides which are not nanoporous according to the above definition.
• the recording material can simultaneously contain several different nanoporous inorganic oxides or oxide / hydroxides in the same or in different layers.
• a particularly favorable combination is AIOOH reacted with rare earth salts in a lower layer and positively charged silicon dioxide in an upper layer.
• the binders are generally water-soluble polymers. Film-forming polymers are particularly preferred.
• the water-soluble polymers include e.g. B. natural or modified compounds such as albumin, gelatin, casein, starch, gum arabic, sodium or potassium alginate, hydroxyethyl cellulose, carboxymethyl cellulose, ⁇ -, ⁇ - or ⁇ -cyclodextrin, etc. If one of the water-soluble polymers is gelatin, so can all known types of gelatin are used, such as acidic pork skin gelatin or alkaline bone gelatin, acidic or basic hydrolyzed gelatins, as well as substituted gelatins, e.g.
• a preferred natural binder is gelatin.
• Synthetic binders can also be used and include, for example, polyvinyl alcohol, polyvinyl pyrrolidone, fully or partially saponified compounds of copolymers of vinyl acetate and other monomers; Homopolymers or copolymers of unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, crotonic acid, etc .; Homopolymers or copolymers of sulfonated vinyl monomers such as. B. vinyl sulfonic acid, styrene sulfonic acid, etc.
• Preferred synthetic binders are polyvinyl alcohol and polyvinyl pyrrolidone or their mixtures. These polymers can be mixed with water-insoluble natural or synthetic high-molecular compounds, in particular with acrylic latexes or styrene acrylic latexes. Although water-insoluble binders are not explicitly claimed, water-insoluble polymers should nevertheless be regarded as a system component.
• the above-mentioned polymers with crosslinkable groups can be converted into practically water-insoluble layers with the aid of a crosslinker or hardener. Such crosslinks can be covalent or ionic.
• crosslinking or hardening of the layers allows a change in the physical layer properties, such as the liquid absorption, or the resistance to layer injuries.
• the crosslinkers and hardeners are selected on the basis of the water-soluble polymers to be crosslinked.
• Organic crosslinkers and hardeners include e.g. B.
• aldehydes such as formaldehyde, glyoxal or glutaraldehyde
• N-methylol compounds such as dimethylol urea or methylol dimethyl hydantoin
• Dioxanes such as 2,3-dihydroxydioxane
• reactive vinyl compounds such as 1,3,5-trisacryloyl-hexahydro-s-triazine or bis- (vinylsulfonyl) methyl ether
• reactive halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine
• epoxides aziridines
• Inorganic crosslinkers and hardeners include, for example, chrome alum, aluminum alum or boric acid.
• the layers can also contain reactive substances which crosslink the layers under the action of UV light, electron beams, X-rays or heat.
• the layers can be further modified by adding fillers. Possible fillers are e.g. B. kaolin, Ca or Ba carbonates, silicon dioxide, titanium dioxide, bentonites, zeolites, aluminum silicate, calcium silicate or colloidal silicon dioxide.
• Inert organic particles such as plastic beads can also be used. These beads can consist of polyacrylates, polyacrylamides, polystyrene or various copolymers of acrylates and styrene.
• the fillers are selected based on the intended use of the images produced.
• the recording materials can contain further soluble metal salts, for example alkaline earth metal salts or salts of the rare earths.
• at least one ink-receiving layer and any auxiliary layers are applied to a support.
• a wide variety of carriers is known and is also used. Thus, all supports that are used in the production of photographic materials can be used.
• transparent supports made of cellulose esters such as cellulose triacetate, cellulose acetate, cellulose propionate, or cellulose acetate / butyrate, polyesters such as polyethylene terephthalate or polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinyl acetals, polyethers, polyvinyl chloride and polyvinyl sulfones are used. Polyesters, in particular polyethylene terephthalate or polyethylene naphthalate, are preferred because of their excellent dimensional stability.
• opaque supports used in the photographic industry for example, baryta paper, papers coated with polyolefins, white opaque polyesters such as, for. B.
• Melinex® from DuPont can be used.
• Polyolefin-coated papers or white-opaque polyester are particularly preferred. It is advantageous to provide these substrates, in particular polyester, with a substrate layer prior to casting in order to improve the adhesion of the ink-receiving layers to the substrate.
• substrate layers are well known in the photographic industry and contain e.g. B. terpolymers of vinylidene chloride, acrylonitrile and acrylic acid or of vinylidene chloride, methyl acrylate and itaconic acid.
• Uncoated papers of different types can also be used as carriers, which can have great differences in their composition and properties. Pigmented papers and glossy papers can also be used, as can metal foils made of aluminum, for example.
• the layers can also be applied to textile fiber materials made of, for example, polyamides, polyester, cotton, viscose and wool.
• the additive according to the invention can be introduced into each layer of the recording material.
• the ink-receiving layers according to the invention are generally cast from aqueous solutions or dispersions which contain all the necessary components. In many cases, wetting agents are added as sprue aids to improve the casting behavior and the layer uniformity. In addition to their effect during the casting process, these compounds can also have an impact on the image quality and can therefore be selected accordingly. Although such surface-active compounds are not claimed in the invention, they nevertheless form an essential part of the invention. It is also possible to apply the copper salts to the recording material which contains nanoporous inorganic oxides in a separate process.
• the recording materials according to the invention can contain additional compounds in order to further improve its properties, for example optical brighteners to improve the degree of whiteness, such as stilbenes, coumarins, triazines, oxazoles or other compounds known to the person skilled in the art.
• UV absorbers such as 2-hydroxybenzotriazoles, 2-hydroxybenzophenones, triazine derivatives or cinnamic acid derivatives can be used to improve the light fastness.
• the amount of the UV absorber is 200-2000 mg / m 2 , preferably 400-1000 mg / m 2 .
• the UV absorber can be introduced into each layer of the recording material according to the invention, but it is particularly advantageous if it is introduced into the top layer.
• radical scavengers examples include sterically hindered phenols, sterically hindered amines, chromanols, ascorbic acid, phosphinic acids and their derivatives, sulfur-containing compounds such as sulfides, mercaptans, thiocyanates, thioamides or thioureas.
• the compounds mentioned can be added to the casting solutions as aqueous solutions. If the compounds are not sufficiently water-soluble, they can be introduced into the casting solutions by other known methods.
• the compounds can be dissolved in a water-miscible organic solvent such as lower alcohols, glycols, ketones, esters or amides. It is also possible to introduce the compounds into the casting solution as fine-grain dispersions, as oil emulsions, as cyclodextran inclusion compounds or as a latex which contains the compound.
• the recording material according to the invention normally has a dry layer thickness of 0.5 to 100 ⁇ m, but in particular of 5 to 50 ⁇ m.
• the casting solutions can be applied to the carrier in various ways.
• the casting processes include, for example, extrusion casting, air knife casting, slot casting, cascade casting and curtain casting.
• the casting solutions can also be applied using a spray process.
• the ink-receiving layers can consist of several individual layers, which can be applied individually one after the other or together.
• a support can also be coated on both sides with ink-receiving layers.
• the chosen casting process does not limit the invention in any way. It is also possible to introduce the copper salts into the recording material by dipping a recording material in a solution of the copper salt or to spray it on, for example with the aid of an inkjet printer.
• Inks for ink jet printing essentially consist of a liquid carrier substance and a dye or pigment dissolved or dispersed therein.
• the liquid carrier substance for ink jet printing inks is generally water or a mixture of water and a water-miscible solvent such as ethylene glycol, glycols with a higher molecular weight, glycerin, dipropylene glycol, polyethylene glycol, amides, polyvinylpyrrolidone, N-methyrrolidone, cyclohexylpyrrolidone, ether carbons and their esters , Alcohols, organic sulfoxides, sulfolane, dimethylformamide, dimethyl sulfoxide, cellosolve, polyurethane, acrylates etc.
• the non-aqueous ink components generally serve as humectants, auxiliary solvents, viscosity regulators, penetration aids or drying accelerators.
• the organic compounds mostly have a boiling point that is above that of water.
• Inks for continuous ink jet printing can also contain inorganic or organic salts to increase the conductivity. Examples of such salts are nitrates, chlorides, phosphates, and the water-soluble salts of water-soluble organic acids such as acetates, oxalates and citrates.
• the dyes or pigments which can be used to produce the inks which can be used together with the recording materials according to the invention contain practically all known classes of these colored compounds.
• Typical examples of dyes or pigments used are listed in patent application EP 0'559'324.
• the recording materials according to the invention can be used with almost all inks corresponding to the prior art.
• the inks can additionally contain other additives such as surface-active substances, optical brighteners, UV absorbers, light stabilizers, preservatives, precipitants such as multiply charged metal compounds and polymeric compounds.
• the aforementioned copper salts can also be incorporated into the inks.
• the description of the inks is for illustration purposes only and is in no way limitative of the invention. The present invention is described in more detail by the following examples, without being restricted in any way thereby.
• Disperal® aluminum oxide / hydroxide, available from CONDEA GmbH, Hamburg, Germany
• Lactic acid solution 0.7%) was dispersed and then 76.95 g of a solution of polyvinyl alcohol (10%, degree of hydrolysis 98-99%, molecular weight 85,000 up to 146,000, available from ALDRICH Chemie, Buchs, Switzerland).
• the final weight of the casting solution was adjusted to 449.7 g with deionized water and sonicated the solution for 3 minutes.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , and 2.56 g of polyvinyl alcohol.
• the casting solution from Comparative Example C-1 was at a temperature of 40 ° C 0.3 g CuCI (available from Fluka Chemie AG, Buchs, Switzerland) as a solid substance added.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , 2.56 g of polyvinyl alcohol and 100 mg of CuCl.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , and 2.56 g of polyvinyl alcohol.
• the casting solution from Comparative Example C-2 was at a temperature of 40 ° C 0.3 g CuCI added as a solid.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , 2.56 g of polyvinyl alcohol and 100 mg of CuCl.
• the casting solution from comparative example C-2 was adjusted to a final weight of 447 g and then 3 g of a solution (10%) of CuSO 4 (available from Fluka Chemie AG, Buchs, Switzerland) were added at a temperature of 40 ° C.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , 2.56 g of polyvinyl alcohol and 100 mg of CuSO 4 .
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, each 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , 2.56 g of polyvinyl alcohol and 100 mg of the corresponding metal salt.
• the casting solution from Comparative Example C-2 was at a temperature of 40 ° C 0.3 g CuCI (available from Fluka Chemie AG, Buchs, Switzerland) and 600 mg Cyclohexanedione (available from Acros Organics, Geel, Belgium), both as solid substances, added.
• CuCI available from Fluka Chemie AG, Buchs, Switzerland
• Cyclohexanedione available from Acros Organics, Geel, Belgium
• 1 m 2 of the cast support contains, in addition to the other casting additives, 22.2 g of nanoporous inorganic oxide, calculated as Al 2 O 3 , 2.56 g of polyvinyl alcohol, 100 mg of CuCl and 200 mg of cyclohexanedione.
• Aerosil 200 available from DEGUSSA AG, Frankfurt / Main, Germany
• Aerosil 200 available from DEGUSSA AG, Frankfurt / Main, Germany
• aqueous acetic acid 8.7%
• 9.86 g of an aqueous aluminum chlorohydrate solution 47.7%, made from aluminum chlorohydrate of the formula Al 2 (OH) 5 Cl • 2.5 H 2 O, which is available as Locron from Clariant AG, Muttenz, Switzerland
• the final weight was then set to 300 g.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 12 g of positively charged silicon dioxide and 2.28 g of polyvinyl alcohol.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 12 g of positively charged silicon dioxide, 2.28 g of polyvinyl alcohol and 50 mg of CuCI.
• 1 m 2 of the cast carrier contains, in addition to the other casting additives, 18.13 g of Al 2 O 3 and 2.28 g of polyvinyl alcohol.
• 1 m 2 of the cast support contains, in addition to the other casting additives, 18.13 g of Al 2 O 3 , 2.28 g of polyvinyl alcohol and 100 mg of CuCl.
• the bottom layer is identical to the cast layer of Example 2.
• 1 m 2 of the cast carrier contains a total of 25.08 g of nanoporous inorganic oxides, 100 mg of CuCI and 277 mg of cyclohexanedione.
• the recording materials according to the invention were printed on using an inkjet printer EPSON STYLUS TM COLOR 750 in PQ glossy film mode (720 dpi) with original inks Gray fields with an approximate density of 1.60 with the Printed in three colors black.
• the printed samples were left open on a table with moderate circulation of outside air for 2 weeks with average daylight of 1000 - 2000 lux.
• the loss of density due to the effect of light alone is very small with this amount of light.
• the density loss of the cyan dye was measured with an X-Rite® densitometer behind a red filter. It is given as a percentage loss of density of the teal starting from the original density.
• the recording materials according to the invention were printed on using an inkjet printer EPSON STYLUS TM COLOR 750 in PQ glossy film mode (720 dpi) with original inks. Color fields of approximate density 1.60 in colors Dark purple, dark teal and blue, and color swatches of the approximate ones Density 0.50 printed in light purple and light teal.
• the printed samples were irradiated in an Atlas Ci35A Weather-O-Meter® with a 6500 W xenon lamp until 40 kJoules / cm 2 were reached.
• the densities of the color fields were measured before and after the irradiation with an X-Rite® densitometer is measured and the density loss is expressed as a percentage Loss of density given based on the original density.
• the recording material for inkjet printing contains copper (I) chloride and additionally cyclohexanedione, practically no loss of density Cyan dye shows more. Even after 8 weeks of storage, the density loss of the cyan dye is only 4% with this recording material.
• the corresponding recording material which probably contains the same amount of CuCl but no cyclohexanedione, shows a loss in density of the cyan dye of 41%.
• the corresponding recording material which contains no CuCl but the same amount of cyclohexanedione, shows a loss in density of the cyan dye of 55%.
• the corresponding recording material without CuCl and without cyclohexanedione shows a loss in density of the cyan dye of 60%.

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• 2001
  • 2001-02-12 AT AT01810139T patent/ATE240214T1/de not_active IP Right Cessation
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