Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/001—Printing processes to produce particular kinds of printed work, e.g. patterns using chemical colour-formers or chemical reactions, e.g. leuco dyes or acids
• • 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

Definitions

• the invention relates to a novel process for the color coding of surfaces.
• the invention describes a reactive dyeing method that can be used for ink jet (inkjet) printing, and consists of at least two non-mixed components - one on or in the material to be inscribed and one in the printer or its storage tank, for the purpose of labeling Inkjet is applied to the material to be labeled and reacts with color change, in particular color deepening.
• inkjet ink jet
• An aqueous solution contains an iron or titanium chelate, a polyhydroxy compound (tannin, pyrocatechol, pyrogallol, gallic acid or water-soluble derivatives), ascorbic acid and the sodium salt of chromotropic acid.
• a typical ink contains water, ferric ammonium oxalate, iron EDTA, titanium potassium oxalate, oxalic acid, citric acid, tannin, the sodium salt of chromotropic acid, pyrogallol, ascorbic acid, pyrocatechol, ethylene glycol and sorbitol.
• Invisible inks are known ( GB1292831, 1972-10-11 , MEREDITH CORP (US) and FR2028486 (A1 ) and DE1946393 (A1 )) with a phenolic or enolic group that reacts with an oxidizing metal ion to achieve color formation.
• Mixed are a binder and a carrier solvent).
• the reactive component is, for example, gallic acid, propyl gallate, acetoacetate, phenol, resorcinol, cresol, vanillin, guaiacol or zinc resorcinate.
• the developers used are iron salts, oxidizing metal salts, citric acid or lead ions, and congo red or yylenol orange.
• Serve as a binder Polyvinylpyrrolidone, Cellulosehydroxypropoxyether or polyamide.
• Carriers are glycols, glycol ethers, esters and ether alcohols.
• Optional additives are fluorophores, for example methylumbelliferone, citric acid, fillers, for example silica or silicates, antioxidants and UV stabilizers, for example 2,4-dihydroxybenzophenone.
• fluorophores for example methylumbelliferone
• fillers for example silica or silicates
• antioxidants and UV stabilizers for example 2,4-dihydroxybenzophenone.
• other invisible inks for example ( GB1350930, 1974-04-24 , DICK CO AB too NL7103180 (A ) FR2084649 (A5 ) DE2112380 (A1 ) from AB DICK CO) which contain eg leuco dyes in addition to gallic acid.
• Heat-sensitive inks are known (US Pat.
• inks are known ( JP58183769, 1983-10-27 , AKUTSU HIDEKAZU; FUJII TADASHI; MURAKAMI KAKUJI; ARIGA TAMOTSU; KAZAMI TAKEO by RICOH KK) from an N-alkanolamine salt of m-digallic acid to increase the water resistance of a colored material without altering the solubility of the dye.
• Inks which contain phenolic components (preferably gallic acid and pyrogallol) ( JP57207659, 1982-12-20 , OOWATARI AKIO, from EPSON CORP) to allow for rapid drying and no clogging of the printer nozzle and free dissolved oxygen at a pH of 12-14.
• a color ink JP9059547, 1997-03-04 KAWASHIMA SEIJI
• a colorless ink of eg zinc chloride, salicylic acid, tannin and the like. with a colorant as an electron donating component and the color is decolorized by the addition of water.
• Inkjettinten are known from the tannin of Kaki ( KR20040012361, 2004-02-11 , SON GYU, YOUNGDONG AGRICLTUVAL) as a substitute for common tannin, with reduced production costs and a secure supply situation.
• the ink contains various components including water, organic solvents, dyes, tannin, kaki extract containing gallic acid, ellagic acid and catechin.
• inkjet ink to prevent the clogging of the nozzles
• JP2005272762, 2005-10-06 KONO MONICHIRO; IIDA YASUHARU from TOYO INK MFG CO
• the ink contains 0.3-10 wt.% Food coloring,, 45-98.7 wt.% Ethanol, 0.5-5 wt.% Tannin,, 0-30 wt.% Propylene glycol, 0.5-5 wt.% Sodium lactate and 0-5 wt. % Water.
• a recording material for inks is known (US Pat.
• JP1241487,1989-09-26 HAYAMA KAZUHIDE; YAMASHITA AKIRA from MITSUBISHI PETROCHEMICAL CO) which contains 0.1 to 30% of a component having a phenolic OH group, and a binder of 5-95wt.% Polyvinyl alcohol and 95-5wt.% Of a cationic water-soluble resin.
• the phenolic component has at least two hydroxyl groups consisting of hydroquinone, tannin, resorcinol, di-t-butylphenol, phloroglucinol or bis (4-hydroxyphenol) methane.
• a color-reactive typewriter paper is known ( GB856188, 1960-12-14 , NEALE DAVID JOHN of CARIBONUM LTD) using a colorless "ribbon” and an impregnated paper primarily with molybdates and tungstates.
• An inkjet paper is known ( JP57087987, 1982-06-01 , MURAKAMI MUTSUAKI; SEKIGUCHI YUMIKO from MATSUSHITA ELECTRIC IND CO LTD) with improved light stability on woodfree paper by metallic oxides and the like.
• a copying system is known ( GB191016515, 1911-06-08 , CAMERON DUNCAN) using wet paper impregnated with tannin or gallic acid to pause texts written with iron gall ink.
• the additives used are sodium sulfite, borax and phenol.
• a copying method is known ( GB943401, Feb.
• a thermal recording method is known ( JP4307289, 1992-10-29 , MORITA YASUYOSHI; MURATA TATSUYA; KOYABU KYOKO of OJI PAPER CO) having a two-layered structure wherein one layer contains an iron salt of a fatty acid and a gallic acid derivative and the second layer contains an electron donating color precursor.
• a pressure-sensitive recording layer is known (US Pat.
• a thermal recording method is known ( JP60083886, 1985-05-13 , MATSUSHITA TOSHIHIKO; MORISHITA SADAO from MITSUBISHI PAPER MILLS LTD) having a layer of alkyl gallates having a melting point of 60-180 ° C and a receiving layer of iron salts (preferred as a dispersion of iron stearate).
• a color reaction writing and printing fluid for producing a colored font due to the color-forming reaction between gallic acid and heavy metal salts such as iron and Vanadinsalzen, characterized in that in the writing fluid, a mixture of about 30 - 20% Gallic acid and about 70-80% alkali gallate is disclosed.
• the mixture is mixed with alkali metal hydroxide or amine base, wherein about 30-20% of the gallic acid is converted into the alkali metal salt or amine salt.
• the invention discloses the preparation of colorless labels which are only subsequently reacted with the metal salt and describes the preparation of these colorless labels by application examples Suitable carrier material are paper, cardboard, corrugated cardboard, pigment particles, films, injection-molded or pressure-cast plastic parts, metal, ceramic surfaces, paint layers or corrosion protection layers.
• Metal phenol complexes are in many areas in the use of inks, printing and dyeing methods to use as hair dyes (eg JP61056119 ).
• Eisengallustinte or Gallustinte for short
• Chr. Documentary black ink which can be well with steel springs, but bad with fountain pens (clogging) write.
• Iron gall ink (made of iron sulphate, gallic acid, gum arabic, etc.) has the best flow properties of all inks, lasts extremely long on the feather and is very lightfast. It comes gray on the paper and takes its deep black color only after a few hours by oxidation. Iron gall ink is only suitable for steel springs, but not for many fountain pens due to its high acidity.
• the production in the Middle Ages took place from iron (II) sulfate (Eisenvitriol), Galläpfeln, water and gum arabicum.
• the dried galls are crushed and boiled to produce gallic acid (tannin).
• iron sulfate and gum arabic are added.
• the gum arabic is used for better writability and flocculation. By airtight seal, the ink can be additionally preserved and protected against flocculation.
• the finished ink is formed on the paper by oxidation of bivalent iron with atmospheric oxygen to trivalent iron, which forms a deep black complex with gallic acid. This takes about a day.
• a dye such as methylene blue is added, which later fades. This was partly exploited as a style element in contract ink. The inks wrote black blue and became more or less black after drying.
• iron gall ink itself can fade over unfavorable conditions over the years. Faded iron gallus writings can be rediscovered with a solution of potassium hexacyanoferrate (II) with excess hydrochloric acid.
• Ice inks are particularly preferred in high-value applications such as certificates.
• Important state contracts must always be written with the stable iron gall ink.
• Official regulations for certificates of origin are as follows: In one liter must be at least 27 g of tannic acid and Gallic acid and at least 4 g of metallic iron. The maximum iron content must not exceed 6 g / l with o. Amounts. After 14 days in the glass, the ink should show no formation of leaves, nor wall fitting, nor sediment. Eight-day-old lettering must remain deep-dark after washing with water and alcohol. The ink must flow easily and not be tacky even immediately after drying. Iron gall inks are considered (if the official regulations are fulfilled) to be "authentic”. For this condition to be reliably fulfilled, fresh lettering should not be "extinguished” because it deprives the paper of ink.
• Conventional coloring inscriptions of materials are usually carried out by printing, for example by means of flexographic, offset or gravure printing devices for mostly large-volume applications or via printer (known mostly inkjet printer and laser printer) or for small-volume applications on the spot or for printing goods as a thermal printer with Thermal paper, thermal labels or thermosensitive layers on packaging.
• the printer is equipped with ink cartridges or toner cartridges, the pigment compositions contained therein are deposited during printing on the material to be printed or a pigment already applied to the surface is changed color by heat.
• the object of the invention was to provide a novel process in which the color is formed by reaction between two components without the use of toner-pigment-containing printing agents.
• Another object of the invention was to provide a process for producing such coated materials.
• a further object of the invention was to provide a device with which the materials according to the invention can be provided with the corresponding information.
• the invention therefore provides a reactive ink jet printing method for carrying out on substrates such as paper, cardboard, corrugated cardboard, films, injection-molded or pressure-cast plastic parts, metal, ceramic surfaces, lacquer layers or anticorrosion layers, characterized in that the substrates are coated with a polyphenol, and reacting a reactive ink consisting of at least one dissolved metal salt selected from the group of the compounds of iron, molybdenum, tungsten copper and titanium by ink jet printing on or in the surface of said substrates, thereby providing a stable color complex readily recognizable to the human eye is formed.
• the black to blue-black iron gall ink which, as its name implies, consists essentially of iron salt and gallic acid (tannic acid) is obtained, for example, by dissolving 23.4 g of tannin (tannic acid), 7.7 g of crystallized gallic acid, 30 g of green iron -II sulfate crystals, 10 g gum arabic, 7 g crude hydrochloric acid and 1 g ascorbic acid in 1 liter of water.
• the metal complex and the polyphenol are separated and one of the two components preferably bound the polyphenol on the paper surface - the metal salt is dissolved as a reactive dye.
• polyphenols or carboxylated or sulfonated or phosphorylated phenols are preferably tannin, gallic acid, ellagic acid, pyrocatechol, resorcinol, hydroquinone, trihydroxybenzenes, salicylic acid, vanillic acid, Dihydroxycarboxylbenzole, and their ethers and esters or natural tannin extracts in question.
• the whitening agents customary in the paper industry can be used to give the paper a bright white (by fluorescence).
• colorless binders are used to achieve a layer formation on the surface - preferably without reacting with the polyphenol (tannin, gallic acid, gallates, ..) - or to bind this only reversibly (eg PVP).
• Suitable stabilizers are, for example, molecules with several OH groups (eg PEG, sugars, glycosides, ..) or amides with -CO-NR- or -CO-NH- structures (PVP + copolymers, polyamides, oligomeric amides, any amides, also Proteins eg gelatin, ..) but also multivalent ions (eg Ca in Ca (OH) 2 , ).
• the ink preferably consists of a 1-20%, preferably 1-10%, solution of a reactive metal salt (iron, titanium, tungsten, molybdenum).
• a reactive metal salt iron, titanium, tungsten, molybdenum.
• organic solvents eg Dowanol, glycerol, glycol and the like
• polymers such as gum arabic added.
• Tannins are widely used in the plant kingdom. These are mainly polyphenols (aromatic systems with multiple hydroxyl groups), which are usually derived from gallic acid and are often condensed with other phenols and sugars. Blue-black inks result from the addition of iron salts to extracts of the bark of oak, spruce, larch, black alder, the leaves and fruits of many sumac species (eg the wig-tree), and black tea - synthetic to tannins, ellagic acid compounds, gallic acid and their derivatives and to all phenolic compounds, especially those with adjacent hydroxy groups. Phenols form red (eg salicylic acid), yellow (eg vanillic acid) or violet complexes with iron (III) ions.
• the complexes with polyphenols are often blue-black and poorly soluble.
• Compounds with single or non-adjacent hydroxy groups form weak complexes.
• a charged function such as carboxyl can replace a hydroxy group (eg salicylic acid).
• Compounds with adjacent hydroxy groups which are additionally sterically bridged form strongly iron-binding pigments - in iron (III) an octahedron of, for example, 3-bidentate ligands.
• Stabilization can be achieved by complexing of trivalent iron and or by stabilization of the 2-valent more soluble form.
• iron ammonium (III) sulfate, iron gluconate and iron lactate are buffered in the area of non-precipitation of iron (III) salts (primarily iron hydroxides or FeO (OH)).
• Iron gluconate has a variety of analogues with similar properties - the preference being for the moderate pH of the printhead.
• ferric ammonium sulphates are stable but very acidic (pH mostly around 1-3) Alternatives.
• iron lactate with lowered pH value is suitable as a printer ink.
• the reactive paper is preferably coated with a layer of polyphenol (eg 5% gallic acid) and a suitable binder, eg starch.
• the color formation occurs near or at the surface - polyphenols in the depth of the paper are therefore useless and cost-increasing.
• a thick or gelatinous preparation of the polyphenol layer prevents too deep penetration into the pores of the paper. Since polyphenols easily oxidize and polymerize and this leads to an undesired discoloration of the paper is the addition of polymerization and oxidation stabilizers (eg sulfites, ascorbic acid, ..) makes sense - a discoloration by reaction with the binder must be considered.
• polymerization and oxidation stabilizers eg sulfites, ascorbic acid, ..
• Ink jet printers are used according to the invention as printing systems which produce a printed image by chemical reaction with the surface coating by targeted firing or by deflecting small reactive droplets.
• Continuous Ink Jet ie devices with continuous ink jet and Drop On Demand, ie devices that shoot single drops.
• Continuous ink-jet printers are used only in the industry, but there are various areas (eg scratch-off, expiration date, EAN code, addressing, personalization, etc.).
• the ink jet exits through a nozzle from the print head. This beam is modulated through a piezoelectric transducer located behind the nozzle so that uniform disintegration into individual drops is achieved and electrostatically charged.
• Drop on Demand - Ink printers can be found in the industry, as well as in the office and home. The devices are additionally distinguished according to which technique the ink drops are ejected.
• Bubble Jet printers produce tiny drops of ink with the help of a heating element.
• Two systems are used: Lexmark and HP in the Deskjet series rely on flat nozzle elements. The process is very easy to manufacture and inexpensive, but has the disadvantage of a limited life of the printheads.
• Canon works with its printers with nozzles located at right angles to the heating elements (Edgeshooter). The single heating element operates at a frequency of up to 10,000 Hz.
• Piezo printers use piezo crystals to force printing ink through a fine nozzle.
• Inkjet printers first show their performance on special paper.
• the ink penetrates the paper and spreads to a partly inhomogeneous spot, much larger than the actual ink drop.
• the result is blurred boundaries - this can be prevented or significantly reduced by the inventively reactive inks.
• the disadvantages of existing inkjet printing processes over other processes are the sensitivity to the medium to be printed, many inks are not archival-proof and bleach significantly more than other processes.
• the method according to the invention enables printing of color complexes of the same color.
• Some types of cartridges such as.
• the black cartridges from HP are under negative pressure and run out if you do not close airtight after filling.
• Others, such as HP ink cartridges have atmospheric pressure inside and must not be hermetically sealed. Since iron (II) complexes are partly air-reactive, the use of airtight cartridges is preferable here.
• Gallic acid is dissolved in water and mixed in a variable proportion (typically up to 5% w / v) with a standard in the paper industry Blankophor (whitener).
• a film former such as starch, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, PVP-co-polyvinyl acetate, soluble polyamides, polyethylenimine or comparable polymers is added and stirred until dissolved.
• stabilizers such as sodium sulfite or ascorbic acid are added.
• the mixture is applied in a coating machine (eg paper machine with brush) in a thin layer on the carrier material such as paper. The result is a shiny white paper surface. After contact with an applied by inkjet iron solution creates a black font.
• composition according to Example 1 The gallic acid is replaced by tannin, ellagic acid, gallic acid esters (especially those which are approved in the food industry and are marked by E numbers), tannin extracts of different plants or any other polyphenols or carboxyphenols (eg salicylic acid).
• tannin extracts of different plants or any other polyphenols or carboxyphenols eg salicylic acid.
• Eiseninkjettinte a font is produced in different shades (eg red to violet with salicylic acid, yellow with vanillic acid, ...)
• color pigments or whitening agents calcium carbonate, organic white pigments, titanium oxide, clay the material can be tinted.
• Pigments may show yellowish or gray discoloration after exposure to light or heat.
• the reactive layer can therefore also be treated with UV filters and other stabilizers - these prevent premature yellowing of the papers.
• As a filter all known from the photography or from the sunscreen filter polymers and pigments can be used.
• Example 5 Inkjet inks
• a typical inkjet ink can be prepared by dissolving 3-5% iron gluconate in water.
• a non-volatile organic solvent is added in which the iron salt should be soluble (to protect the print head against drying such as low-volatility organic solvents such as glycerol, alcohol esters or ethers) and a stabilizer against turbidity (usually a polymer such as gum arabic), especially in use of oxidation-clouding iron (II) salts.
• the ink is filtered and filled into the printheads.
• Example 6 Inkjet Inks - Variations
• titanium is mostly used as triethanolamine complex or lactate, molybdenum and tungsten as molybdate or tungstates eg sodium molybdate, sodium phosphomolybdate, sodium tungstate.
• Suitable iron compounds are e.g. Iron (II) sulphate, ammonium iron sulphate, iron lactate, iron gluconate. Strong complexing agents (phosphate, citrate, EDTA, ..) interfere with the reaction with the polyphenols and reduce or prevent the formation of the colored complex.

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Citations (31)

• 2008
  • 2008-12-22 EP EP08022228A patent/EP2199094A1/fr not_active Ceased

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