EP2199094A1 - Method for chromophoric illustration of surfaces - Google Patents
Method for chromophoric illustration of surfaces Download PDFInfo
- Publication number
- EP2199094A1 EP2199094A1 EP08022228A EP08022228A EP2199094A1 EP 2199094 A1 EP2199094 A1 EP 2199094A1 EP 08022228 A EP08022228 A EP 08022228A EP 08022228 A EP08022228 A EP 08022228A EP 2199094 A1 EP2199094 A1 EP 2199094A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ink
- iron
- reactive
- paper
- printing
- 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.)
- Ceased
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Classifications
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- 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
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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
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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
Die Erfindung betrifft ein neuartiges Verfahren zur farbgebenden Beschriftung von Oberflächen. Die Erfindung beschreibt ein reaktives Färbeverfahren, das für Tintenstrahl- (Inkjet)-Bedruckung verwendet werden kann, und aus zumindest zwei nicht gemischten Komponenten besteht - eine auf oder im zu beschriftenden Material und eine im Drucker bzw. dessen Vorratstank, die zum Zwecke der Beschriftung mittels Inkjet auf das zu beschriftende Material aufgebracht wird und unter Farbänderung insbesondere Farbvertiefung reagiert.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.
Bekannt sind reaktive Tinten (
Bekannt sind unsichtbare Tinten (
Bekannt sind wärmesensitive Tinten (
Bekannt sind Aufzeichnungstinten (
Bekannt sind Tinten die phenolische Komponenten (bevorzugt Gallussäure und Pyrogallol) enthalten (
Bekannt ist weiters eine Farbtinte (
Invisible inks are known (
Heat-sensitive inks are known (US Pat.
Recording inks are known (
Inks are known which contain phenolic components (preferably gallic acid and pyrogallol) (
Also known is a color ink (
Bekannt ist eine Inkjet-Tinte die das Verstopfen der Düsen verhindern soll (
Die Tinte enthält 0.3-10 wt.% Lebensmittelfarbe, , 45-98.7 wt.% Ethanol, 0.5-5 wt.% Tannin, , 0-30 wt.% Propylenglycol, 0.5-5 wt.% Natriumlaktat und 0-5 wt.% Wasser.
Bekannt ist ein Aufzeichnungsmaterial für Tinten (
Die phenolische Komponente weist zumindest zwei Hydroxylgruppen auf besteht aus Hydrochinon, Tannin, Resorzin, Di-t-butylphenol, Phloroglucinol oder Bis(4-hydroxyphenol)methan.
Bekannt ist ein farbreaktives Schreibmaschinenpapier (
Bekannt ist ein Inkjetpapier (
Bekannt ist ein Kopiersystem (
Bekannt ist ein Kopierverfahren (
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.
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 (
An inkjet paper is known (
A copying system is known (
A copying method is known (
Bekannt ist ein thermisches Aufzeichnungsverfahren (
Bekannt ist eine drucksensitive Aufzeichnungsschicht (
Bekannt ist ein thermisches Aufzeichnungsverfahren (
Bekannt ist ein analoges thermisches Aufzeichnungsverfahren (
Bekannt ist ein verbessertes Schreibpapier und die Tinte (
Bekannt ist ein Prozess zum Schreiben und Drucken (
A pressure-sensitive recording layer is known (US Pat.
A thermal recording method is known (
An analogous thermal recording method is known (
Known is an improved writing paper and the ink (
Known is a process for writing and printing (
Bekannt ist ein Prozess zum Schreiben und Drucken (
Als Trägermaterial kommen Papier, Pappe, Wellkartons, Pigmentpartikel, Folien, spritz- oder druck-gegossene Kunststoffteile, Metall, keramische Oberflächen, Lackschichten oder Korrosionsschutzschichten in Betracht.Known is a process for writing and printing (
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.
Metallphenol-Komplexe sind in vielen Bereichen im Einsatz von Tinten, Druck- und Färbeverfahren bin hin zu Einsatz als Haarfärbemittel (z.B.
Die fertige Tinte entsteht erst auf dem Papier durch Oxidation des zweiwertigen Eisens mit Luftsauerstoff zu dreiwertigem Eisen, welches mit der Gallussäure eine tiefschwarze Komplexverbindung eingeht. Dies dauert rund einen Tag. Damit die Tinte beim Schreiben besser sichtbar ist, wird noch ein Farbstoff wie Methylenblau hinzugegeben, der später verblasst. Dies wurde bei den Vertragstinten teilweise als Stilelement ausgenützt. Die Tinten schrieben schwarzblau und wurden nach dem Trocknen mehr oder weniger schwarz.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. In order for the ink to be more visible when writing, 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.
Aber auch die Eisengallustinte selbst kann unter ungünstigen Bedingungen im Laufe der Jahre verblassen. Verblasste Eisengallus-Schriften können mit einer Lösung von Kaliumhexacyanoferrat(II) mit überschüssiger Salzsäure wieder sichtbar gemacht werden.But the 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.
Diese Vertrags- (und teilweise auch Kanzleitinten) waren bis in die 1960er Jahre auch für Füllfederhalter üblich, zumindest im Geschäftsbereich. Da die Verwendung von Eisengallustinten in Füllfederhaltern wegen der auch dort erfolgenden Oxidation des Ausgangsstoffes des Farbstoffes die Gefahr des Verstopfens bestand, waren solche Tinten mit etwas Pflege der Füllfederhalter verbunden. Neben Eisengallustinten nach antiken Rezepten, welche nicht für Füllfederhalter tauglich sind, gibt es nur mehr sehr wenige Hersteller, die eine solche Tinte für Füllhalter herstellen: Der bekannteste ist der Füllfedernproduzent Montblanc, dessen eigene blauschwarze Tinte noch Eisengallustinte enthält. Die blauschwarze Tinte von z.B. Lamy ist eine eisengallushaltige Tinte. Zudem bietet auch noch das Unternehmen Diamine eine blauschwarze "Registrars Ink" an. Diese ist ebenfalls füllfedertauglich. Tinten in Tintenpatronen sind seltener Eisengallustinten, da hier das erforderliche regelmäßige Spülen etwas schwerer ist. Die blauschwarze Tinte sowohl von Montblanc als auch Lamy ist nur aus dem Glas eisengallushaltig.These contract (and partly also Kanzleitinten) were common until the 1960s for fountain pens, at least in the business sector. Since the use of Eisengallustinten in fountain pens due to the there occurring oxidation of the starting material of the dye was a danger of clogging, such inks were associated with some care of the fountain pen. In addition to antique-style iron-bell inks, which are not suitable for fountain pens, there are very few manufacturers who produce such ink for fountain pens: The best-known is the fountain pen producer Montblanc, whose own blue-black ink still contains iron gall ink. The blue-black ink of e.g. Lamy is an iron-gallated ink. In addition, the company Diamine also offers a blue-black "Registrars Ink". This is also suitable for feathering. Inks in ink cartridges are less common than iron gall inks, as the required periodic rinse is a bit heavier. The blue-black ink of both Montblanc and Lamy is iron-gallated only from the glass.
Eisentinten werden insbesondere in hochwertigen Anwendungen wie Urkunden bevorzugt. Wichtige Staatverträge müssen stets mit der beständigen Eisengallustinte geschrieben werden. Amtliche Vorschrift für Urkundentinten sind wie folgt: In einem Liter müssen mindestens 27 g Gerbsäure und Gallussäure sowie mindestens 4 g metallisches Eisen enthalten sein. Der Maximalgehalt an Eisen darf bei o. Mengen nicht mehr als 6 g/l betragen. Die Tinte soll nach 14 Tagen im Glas weder Blätterbildung, noch Wandbeschlag, noch Bodensatz zeigen. Acht Tage alte Schriftzüge müssen nach Waschen mit Wasser und Alkohol tiefdunkel bleiben.
Die Tinte muss leicht fließen und darf selbst unmittelbar nach dem Trocknen nicht klebrig sein. Eisengallustinten gelten (wenn die amtlichen Vorschriften erfüllt werden) als "urkundenecht". Damit diese Bedingung zuverlässig erfüllt wird, sollen frische Schriftzüge nicht "abgelöscht" werden, weil damit dem Papier Tinte entzogen wird.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.
Konventionelle farbgebende Beschriftungen von Materialien erfolgen meist durch Drucken, beispielsweise mittels Flexo-, Offset- oder Tiefdruckgeräten für zumeist großvolumige Anwendungen oder via Drucker (bekannterweise zumeist Tintenstrahldrucker und Laserdrucker) oder für kleinvolumige Anwendungen an Ort und Stelle bzw. zur Bedruckung von Waren als Thermodrucker mit Thermopapier, Thermoetiketten oder thermosensitiven Schichten auf Verpackungen. Dazu wird der Drucker mit Druckfarben- bzw. Tonerpatronen bestückt, die darin enthaltenden Pigmentzusammensetzungen werden beim Druck auf dem zu bedruckenden Material abgelagert oder ein bereits auf der Oberfläche aufgebrachtes Pigment wird via Hitzeeinwirkung farblich verändert.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. For this purpose, 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.
Aufgabe der Erfindung war es, ein neues Verfahren bereitzustellen, in dem die Farbe durch Reaktion zwischen zwei Komponenten ohne Verwendung von toner-pigmenthaltigen Druckmitteln entsteht.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.
Eine weitere Aufgabe der Erfindung war es ein Verfahren zur Herstellung derartiger beschichteter Materialien bereitzustellen.Another object of the invention was to provide a process for producing such coated materials.
Eine weitere Aufgabe der Erfindung war es eine Vorrichtung bereitzustellen, mit der die erfindungsgemäßen Materialien mit den entsprechenden Informationen versehen werden können.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.
Gegenstand der Erfindung ist daher ein reaktives Tintenstrahldruckverfahren zur Durchführung auf Substraten wie Papier, Pappe, Wellkartons, Folien, spritz- oder druck-gegossenen Kunststoffteile, Metall, keramischen Oberflächen, Lackschichten oder Korrosionsschutzschichten, dadurch gekennzeichnet, dass die Substrate mit einem Polyphenol beschichtet werden, und eine reaktive Tinte bestehend aus zumindest einem gelösten Metallsalz gewählt aus der Gruppe der Verbindungen von Eisen, Molybdän, Wolfram Kupfer und Titan durch Tintenstrahldruck an oder in der Oberfläche der genannten Substrate zur Reaktion gebracht wird, wodurch ein stabiler für das menschliche Auge sofort erkennbarer Farbkomplex gebildet wird.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.
Das zu bedruckende Objekt wird durch die chemische Reaktion der Druckflüssigkeit und einer Beschichtung räumlich definiert und strukturiert farblich verändert, wobei beliebige Zeichen, Buchstaben, Zeichenketten Muster, Linien Bilder, Symbole, Designs oder graphische Information durch eine Reaktion der beide Komponenten sichtbar werden.
Die Erfindung beruht dabei darauf eine dokumentenechte Drucktinte bereitzustellen die durch Reaktion eines Metallsalzes und einem Polyphenol Objekte und Materialien chemo-reaktiv beschreibbar macht. Die Generierung der farbigen Pigmentpartikel durch chemische Umwandlung erzeugt in-situ einen zumeist dunklen Farbton nach Reaktion einer farblosen oder schwach gefärbten Schicht der Precursorverbindungen. Molydän-, Wolfram- und Titanverbindungen sind zumeist farblos, Eisen(II)salze oft hellgrün, Eisen(III)salze von weiss bis tiefbraun. Beispielhaft kann hier die Umwandlung von Eisen(II)sulfat-Inkjettinte (hellgelb) auf einem Gallussäure-beschichteten Papier (farblos) zu einer schwarzen Tinte genannt werden.
Im Gegensatz zu einem Laserdruck oder Tintenstrahldruck oder ähnlicher Druckverfahren entsteht hierbei die Farbe erst in-situ und wird auf und oder innerhalb der Oberfläche des zu beschriftenden Objekts gebildet. Dies ermöglicht hohe Farbechtheit, hohe Farbstabilität und Farbbildung "im Innern" des Objekts" geschützt von Umwelteinflüssen. Die Vorteile lassen sich wie folgt zusammenfassen
- über Jahre stabile Farbe (kein Ausbleichen wie Thermopapiere)
- hoher Kontrast (im Gegensatz zu den meisten Thermopapieren)
- keine komplexen organisch-reaktiven Farbkomponenten mit hohem Allergiepotential
- nahezu reines Schwarz erzielbar (wie Russ-basierter Lasertoner)
- Sichtbare und unsichtbare Elemente kombinierbar
- gut Maschinen-lesbar durch hohen Kontrast (Scannerkassen,..)
- Extreme thermische Stabilität (keine Veränderung bei heißem Klima,..)
- Kombinierbar mit Barcode und Labeltechnik
The invention is based on providing a document-accurate printing ink which makes objects and materials chemo-reactive describable by reaction of a metal salt and a polyphenol. The generation of the colored pigment particles by chemical conversion produces in situ a mostly dark hue after reaction of a colorless or weakly colored layer of the precursor compounds. Molydane, tungsten and titanium compounds are usually colorless, iron (II) salts often pale green, iron (III) salts from white to deep brown. Exemplary here is the transformation of iron (II) sulfate ink ink (light yellow) on a gallic acid-coated paper (colorless) to a black ink.
In contrast to laser printing or inkjet printing or similar printing processes, in this case the color first arises in-situ and is formed on and / or within the surface of the object to be labeled. This allows high color fastness, high color stability and color formation "inside" of the object "protected from environmental influences." The advantages can be summarized as follows
- stable color over years (no fading like thermal papers)
- high contrast (unlike most thermal papers)
- no complex organic-reactive color components with high allergy potential
- almost pure black achievable (like soot-based laser toner)
- Visible and invisible elements can be combined
- good machine-readable by high contrast (scanner cash registers, ..)
- Extreme thermal stability (no change in hot climates, ..)
- Can be combined with barcode and label technology
Auch die Verwendung von täglich dem Licht ausgesetzten Produkten wie Druckwaren, Papier oder Folien im Außenbereich kann auf Grund der bleichechten Färbung als wichtiger Einsatzbereich des neuen Produktes gesehen werden. Hier sind alle üblichen Inkjettinten deutlich limitiert.The use of daily exposed products such as printed matter, paper or foils outdoors can be seen as an important application of the new product due to the bleach -fast color. Here are all usual Inkjettinten clearly limited.
Die schwarze bis blau-schwarze Eisengallustinte, die wie ihr Name andeutet, im Wesentlichen aus Eisensalz und Gallussäure (Gerbsäure) besteht erhält man z.B. durch Auflösen von 23,4 g Tannin (Gerbsäure), 7,7 g kristallisierter Gallussäure, 30 g grüner Eisen-II-sulfatkristalle, 10 g Gummiarabikum, 7 g roher Salzsäure und 1 g Ascorbinsäure in 1 Liter Wasser. Erfindungsgemäß werden der Metallkomplex und das Polyphenol getrennt und eine der beiden Komponenten bevorzugt das Polyphenol auf der Papieroberfläche gebunden - das Metallsalz dient gelöst als Reaktivfarbstoff.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. According to the invention, 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.
Die praktische Ausführung erfolgt durch Tränken des Materials z.B. Papiers mit einer 0.1-20%, bevorzugt 2-5% wässrigen Lösung des Polyphenols bevorzugt an dessen Oberfläche. Dabei kommen vorzugsweise Polyphenole oder carboxylierte oder sulfonierte oder phosphorylierte Phenole vorzugsweise Tannin, Gallussäure, Ellagsäure, Brenzkatechin, Resorcin, Hydrochinon, Trihydroxybenzole, Salizylsäure, Vanillinsäure, Dihydroxycarboxylbenzole, sowie deren Ether und Ester oder natürliche Gerbstoffextrakte in Frage.
Um eine schwache Gelbfärbung z.B. bei Papier zu unterdrücken, können die in der Papierindustrie üblichen Weißmacher, wie beispielsweise Weißpigment, Clay, TiO2 und dergleichen eingesetzt werden, um (durch Fluoreszenz) dem Papier ein strahlendes Weiß zu geben.
Zumeist farblose Bindemittel werden zur Erzielung einer Schichtbildung auf der Oberfläche eingesetzt - bevorzugt ohne mit dem Polyphenol (Tannin, Gallussäure, Gallaten,..) zu reagieren - bzw. dieses nur reversibel zu binden (z.B. PVP).The practical embodiment is carried out by impregnating the material eg paper with a 0.1-20%, preferably 2-5% aqueous solution of the polyphenol preferably on its surface. In this case, preferably 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.
In order to suppress a faint yellowing, for example in paper, the whitening agents customary in the paper industry, such as, for example, white pigment, clay, TiO 2 and the like, can be used to give the paper a bright white (by fluorescence).
In most cases 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).
Zur Vermeidung von Verfärbungen des beschichteten Papiers durch Oxidation und Umlagerung der in der Beschichtungszusammensetzung vorhandenen Polyphenole, insbesondere auch von Gallussäure, insbesondere in Gegenwart von Feuchtigkeit oder bei langer Lagerung ist es vorteilhaft, der Beschichtungszusammensetzung geeignete Stabilisatoren zuzusetzen.
Geeignete Stabilisatoren sind beispielsweise Moleküle mit mehreren OH-Gruppen (z.B. PEG, Zucker, Glykoside,..) oder Amide mit -CO-NR- oder -CO-NH- Strukturen (PVP + Copolymere, Polyamide, oligomere Amide, beliebige Amide, auch Proteine z.B. Gelatine,..) aber auch mehrwertige Ionen (z.B. Ca in Ca(OH)2,...).To avoid discoloration of the coated paper by oxidation and rearrangement of the present in the coating composition polyphenols, especially gallic acid, especially in the presence of moisture or for long-term storage, it is advantageous to add suitable stabilizers to the coating composition.
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 , ...).
Die Tinte besteht bevorzugt aus einer 1-20%igen, bevorzugt 1-10%igen Lösung eines reaktiven Metallsalzes (Eisen, Titan, Wolfram, Molybdän). Um die Viskosität, das Verdampfungs- und das Fließverhalten einzustellen werden zumeist organische Lösungsmittel (z.B. Dowanol, Glycerin, Glykol und dergleichen) und oder Polymere z.B. Gummi Arabicum zugegeben.The ink preferably consists of a 1-20%, preferably 1-10%, solution of a reactive metal salt (iron, titanium, tungsten, molybdenum). To adjust the viscosity, the evaporation and the flow behavior mostly organic solvents (eg Dowanol, glycerol, glycol and the like) and or polymers such as gum arabic added.
Gerbstoffe sind im Pflanzenreich weit verbreitet. Es handelt sich bei diesen vor allem um Polyphenole (aromatische Systeme mit mehreren Hydroxylgruppen), die sich meist von der Gallussäure ableiten lassen und oft mit anderen Phenolen und Zuckern kondensiert sind. Blauschwarze Tinten entstehen bei der Zugabe von Eisensalzen zu Extrakten der Rinde von Eiche, Fichte, Lärche, Schwarzerle, der Blätter und Früchte vieler Sumach-Arten (z.B. des Perückenbaumes), und des schwarzen Tees - synthetisch zu Tanninen, Ellagsäureverbindungen, Gallussäure und deren Derivaten sowie zu allen phenolische Verbindungen insbesondere jenen mit benachbarten Hydroxygruppen. Phenole bilden mit Eisen(III)-lonen rote (z.B. Salizylsäure), gelbe (z.B. Vanillinsäure) oder violette Komplexe. Die Komplexe mit Polyphenolen sind oft blau-schwarz und schwerlöslich. Verbindungen mit einzelnen bzw. nicht benachbarten Hydroxygruppen bilden schwache Komplexe. Eine geladene Funktion wie z.B. Carboxyl kann eine Hydroxygruppe ersetzen (z.B. Salizylsäure). Verbindungen mit benachbarten Hydroxygruppen die zusätzlich sterisch verbrückt sind bilden stark eisenbindene Pigmente - bei Eisen (III) ein Oktaeder aus z.B. 3-zweizähnigen Liganden.
Um die Verdruckbarkeit mit einem Tintenstrahldruck zu ermöglichen darf es in keinem Fall zu Ausfällungen oder Trübungen der Tinte kommen da diese den Druckkopf allenfalls sogar irreversible verstopfen. Eine Stabilisierung kann durch Komplexierung von 3-wertigem Eisen und oder durch Stabilisierung der 2-wertigen besser löslichen Form erreicht werden.
Es bieten sich Eisenammonium(III)sulfat, Eisengluconat und Eisenlaktat allenfalls gebuffert im Bereich der Nichtausfällung von Eisen(III)salzen (primär Eisenhydroxiden oder FeO(OH)) an. Zu Eisenglukonat existiert eine Vielzahl von Analoga mit ähnlichen Eigenschaften - der Vorzug ist der moderate pH-Wert der den Druckkopf wenig belastet. Alternativ dazu sind z.B. Eisenammoniumsulfate stabile aber sehr saure (pH zumeist um 1-3) Alternativen. Hier muss auf den Aufbau des Druckkopfes geachtet werden. Auch Eisenlaktat mit abgesenktem pH-Wert eignet sich als Druckertinte.
Das Reaktivpapier wird bevorzugt mit einer Schicht des Polyphenols (z.B. 5% Gallussäure) und einem geeigneten Bindemittel z.B. Stärke beschichtet. Idealerweise erfolgt die Farbbildung nahe bzw. an der Oberfläche - Polyphenole in der Tiefe des Papiers sind daher nutzlos und kostensteigernd. Eine dicke oder gelartige Präparation der Polyphenolschicht verhindert das allzu tiefe Eindringen in die Poren des Papiers. Da Polyphenole leicht oxidieren sowie polymerisieren und dies zu einer unerwünschten Verfärbung des Papiers führt ist der Zusatz von Polymerisations- und Oxidationsstabilisatoren (z.B. Sulfite, Ascorbinsäure,..) sinnvoll - auch eine Verfärbung durch Reaktion mit dem Bindemittel muss beachtet werden.
Es kann aber auch das Metallsalz auf die Papiermatrix aufgebracht werden und sodann das Polyphenol im Tintenstrahldrucker verdruckt werden.
Als Drucksysteme werden erfindungsgemäß Tintenstrahldrucker (Matrixdrucker) eingesetzt die durch den gezielten Abschuss oder das Ablenken kleiner reaktiver Tröpfchen ein Druckbild durch chemische Reaktion mit der Oberflächenbeschichtung erzeugen. Man unterscheidet Continuous Ink Jet, also Geräte mit kontinuierlichem Tintenstrahl und Drop On Demand, d. h., Geräte die einzelne Tropfen verschießen.
Continuous-Ink-Jet-Drucker werden nur in der Industrie eingesetzt, dort aber in verschiedenen Bereichen (z. B. Rubbellose, Haltbarkeitsdatum, EAN-Code, Adressierung, Personalisierung usw.). Hier tritt der Tintenstrahl über eine Düse aus dem Druckkopf aus. Dieser Strahl wird über einen piezoelektrischen Wandler, der sich hinter der Düse befindet, moduliert, so dass ein gleichmäßiger Zerfall in einzelne Tropfen erreicht wird und elektrostatisch aufgeladen. Die Tropfen durchfliegen anschließend eine größere Ablenkelektrode, wo sie - abhängig von ihrer spezifischen elektrischen Ladung - seitlich abgelenkt werden.
Drop on Demand - Tintendrucker findet man sowohl in der Industrie, als auch im Büro- und Heimbereich. Die Geräte werden zusätzlich danach unterschieden, mit welcher Technik die Tintentropfen ausgestoßen werden.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.
In order to allow the printability with an ink jet printing, it must never come to precipitation or clouding of the ink because they clog the print head possibly even irreversible. Stabilization can be achieved by complexing of trivalent iron and or by stabilization of the 2-valent more soluble form.
At best, 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. Alternatively, eg ferric ammonium sulphates are stable but very acidic (pH mostly around 1-3) Alternatives. Here, attention must be paid to the structure of the print head. Also 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. Ideally, 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.
However, it is also possible to apply the metal salt to the paper matrix and then to print the polyphenol in the inkjet printer.
Ink jet printers (dot matrix 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. There is a distinction between 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.). Here, 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. The drops then pass through a larger deflection electrode, where they are deflected laterally, depending on their specific electrical charge.
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.
Aber auch elektrische Schaltungen kann man damit aufbauen und 3D-Modelle erzeugen. Anstatt Tinte werden auch Wachs, langkettige Polymere oder heiße, flüssige Lote verwendet. Bubble-Jet-Drucker erzeugen winzige Tintentropfen mit Hilfe eines Heizelements. Hierbei kommen zwei Systeme zum Einsatz: Lexmark und HP bei der Deskjet-Reihe setzt auf flache Düsenelemente. Das Verfahren ist sehr einfach herzustellen und preiswert, hat aber den Nachteil einer begrenzten Lebensdauer der Druckköpfe. Canon arbeitet bei seinen Druckern mit Düsen im rechten Winkel zu den Heizelementen befinden (Edgeshooter). Das einzelne Heizelement arbeitet mit einer Frequenz bis 10.000 Hz. Piezo-Drucker nutzen Piezokristalle um Drucktinte durch eine feine Düse zu pressen. Es erfolgt eine Tropfenbildung der Tinte, deren Tropfenvolumen sich über den angelegten elektrischen Impuls steuern lässt z.B. Epson und Siemens ab 1977. Bei Druck-Ventil-Druckern sind einzelne Ventile an den Düsen angebracht.
Allen "On-Demand"-Druckern gemeinsam ist die Eigenschaft, dass die Tinte mit der Zeit eintrocknet bzw. die Düsen verstopft. Um dies zu verhindern, sind die Tinten nicht sehr schnelltrocknend - entsprechende Zusätze von zumeist höher-siedenden Lösungsmitteln bis etwa 30% sind zumeist notwendig. Die meisten Drucker fahren einen Reinigungszyklus. Eine weitere Möglichkeit besteht darin, den Druckkopf so zu parken, so dass wenig Luft an die Düsen gelangt. Je nach Druckermodell und Größe der Tintenpatrone kann die Patrone nach 40 bis 100 Reinigungen leer sein.
Die in Tinten(strahl)druckern verwendete Tinte wird zumeist auf Wasserbasis hergestellt und mit Additiven versetzt. Diese verhindern das zu schnelle Eintrocknen und insbesondere das Durchtrocknen in der Düse.But you can also build electrical circuits and generate 3D models. Instead of ink, wax, long-chain polymers or hot, liquid solders are used. 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. There is a drop formation of the ink whose drop volume can be controlled by the applied electrical impulse eg Epson and Siemens from 1977. In pressure valve printers, individual valves are attached to the nozzles.
Common to all "on-demand" printers is the tendency for the ink to dry over time or clog the nozzles. To prevent this, the inks are not very fast drying - corresponding additions of mostly higher-boiling solvents to about 30% are usually necessary. Most printers drive a cleaning cycle. Another possibility is to park the printhead so that little air reaches the nozzles. Depending on the printer model and the size of the ink cartridge, the cartridge may be empty after 40 to 100 cleanings.
The ink used in ink (jet) printers is usually prepared on a water basis and added with additives. These prevent over-drying and especially drying in the nozzle.
Ihre Leistungsfähigkeit entfalten Tintenstrahldrucker erst auf Spezialpapier. Bei Normalpapier dringt die Tinte in das Papier ein und breitet sich dort zu einem teils inhomogenen Fleck aus, der wesentlich größer als der eigentliche Tintentropfen ist. Das Ergebnis sind unscharfe Abgrenzungen - durch die erfindungsgemäß reaktiven Tinten kann dies verhindert bzw. deutlich reduziert werden.Inkjet printers first show their performance on special paper. For plain 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.
Die Nachteile bestehender Tintendruckverfahren gegenüber anderen Verfahren sind die Empfindlichkeit gegenüber dem zu bedruckenden Medium, viele Tinten sind nicht archivfest und bleichen erheblich stärker aus als bei anderen Verfahren. Das erfindungsgemäße Verfahren ermöglicht den Druck dokumentenechter Farbkomplexe.
Manche Patronentypen, wie z. B. die Schwarzpatronen von HP, stehen unter Unterdruck und laufen aus, wenn man sie nach dem Befüllen nicht luftdicht verschließt. Andere, wie die Farbpatronen von HP, haben innen Atmosphärendruck und dürfen nicht luftdicht abgeschlossen werden. Da Eisen(II)-komplexe teils Luft-reaktiv sind ist hier der Einsatz von luftdichten Patronen vorzuziehen.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. For example, 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.
Die folgenden Beispiele beschreiben die technische Realisierung ohne diese zu beschränken:The following examples describe the technical realization without limiting it:
Gallussäure wird in Wasser gelöst und in variablem Mengenverhältnis (typisch bis zu 5% w/v) mit einem in der Papierindustrie üblichen Blankophor (Weißmacher) vermischt. Es wird ein Filmbildner wie Stärke, Polyvinylpyrrolidon, Hydroxyethylcellulose, Carboxymethylzellulose, Polyvinylalkohol, PVP-co-Polyvinylacetat, lösliche Polyamide, Polyethylenimin oder vergleichbare Polymere zugegeben und bis zur Auflösung gerührt. Allenfalls werden Stabilisatoren wie z.B. Natriumsulfit oder Ascorbinsäure zugesetzt. Die Mischung wird in einer Coatingmaschine (z.B. Papiermaschine mit Streichwerk) in dünner Schicht auf das Trägermaterial z.B. Papier aufgebracht. Es entsteht eine glänzend weiße Papieroberfläche.
Nach Kontakt mit einer durch Inkjet aufgebrachten Eisenlösung entsteht eine schwarze Schrift.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. At best, 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.
Aufbau laut Beispiel 1. Die Gallussäure wird durch Tannin, Ellagsäure, Gallussäureester (insbesondere jene die eine Zulassung in der Lebensmittelindustrie besitzen und durch E-Nummern gekennzeichnet sind), Gerbstoffextrakte unterschiedlicher Pflanzen oder beliebige andere Polyphenole oder Carboxyphenole(z.B. Salizylsäure) ersetzt.
Nach Kontakt mit Eiseninkjettinte entsteht eine Schrift in unterschiedlichen Farbtönen (z.B. rot bis violett mit Salizylsäure, gelb mit Vanillinsäure,...)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).
After contact with Eiseninkjettinte, a font is produced in different shades (eg red to violet with salicylic acid, yellow with vanillic acid, ...)
Durch Zusatz von Farbpigmenten oder Weißmacher (Calciumcarbonat, organische Weißpigmente, Titanoxid, Clay kann das Material abgetönt werden.By adding color pigments or whitening agents (calcium carbonate, organic white pigments, titanium oxide, clay the material can be tinted.
Pigmente können nach Exposition durch Licht oder durch Hitzebelastung gelbliche oder graue Verfärbungen zeigen. Die Reaktivschicht kann daher auch mit UV-Filtern und anderen Stabilisatoren versetzt werden - diese verhindern ein vorzeitiges Vergilben der Papiere. Als Filter können alle aus der Fotographie oder aus dem Sonnenschutz bekannte Filterpolymere und Pigmente verwendet werden.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.
Eine typische Inkjettinte kann durch Lösen von 3-5% Eisenglukonat in Wasser hergestellt werden. Meist wird ein nicht verdampfbares organisches Lösungsmittel zugesetzt in dem das Eisensalz löslich sein sollte (zum Schutz des Druckkopfes gegen Austrocknen wie schwerflüchtige organische Lösungsmittel z.B. Glyzerin, Alkoholester oder Ether) und ein Stabilisator gegen Trübung (zumeist ein Polymer wie Gummi Arabicum), insbesondere beim Einsatz von unter Oxidation trübenden Eisen(II)-Salzen.
Nach vollständiger Lösung wird die Tinte filtriert und in die Druckköpfe verfüllt.A typical inkjet ink can be prepared by dissolving 3-5% iron gluconate in water. Usually, 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.
When complete, the ink is filtered and filled into the printheads.
Analog zu Beispiel 5 können andere Metallsalze von Eisen, Molybdän, Wolfram oder Titan verwendet werden. Wichtig ist die absolute Stabilität der Lösung da jede Trübung zu einer Zerstörung des Druckkopfes führen würde.
Titan wird zumeist als Triethanolamin-Komplex oder Laktat eingesetzt, Molybdän und Wolfram als Molybdate oder Wolframate z.B. Natriummolybdat, Natriumphosphomolybdat, Natriumwolframat.Analogously to Example 5, other metal salts of iron, molybdenum, tungsten or titanium may be used. Important is the absolute stability of the solution because any turbidity would lead to the destruction of the printhead.
Titanium is mostly used as triethanolamine complex or lactate, molybdenum and tungsten as molybdate or tungstates eg sodium molybdate, sodium phosphomolybdate, sodium tungstate.
Geeignete Eisenverbindungen sind z.B. Eisen(II)sulfat, Ammoniumeisensulfat, Eisenlaktat, Eisenglukonat. Starke Komplexbildner (Phosphat, Zitrat, EDTA,..) stören die Reaktion mit den Polyphenolen und verringern bzw. verhindern die Ausbildung des farbigen Komplexes.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.
Claims (18)
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EP08022228A EP2199094A1 (en) | 2008-12-22 | 2008-12-22 | Method for chromophoric illustration of surfaces |
US13/141,434 US20120038701A1 (en) | 2008-12-22 | 2009-12-21 | Method for the colour-imparting inscribing of surfaces |
PCT/EP2009/009175 WO2010072388A2 (en) | 2008-12-22 | 2009-12-21 | Method for the colour-imparting inscribing of surfaces |
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EP08022228A EP2199094A1 (en) | 2008-12-22 | 2008-12-22 | Method for chromophoric illustration of surfaces |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011082716A1 (en) * | 2011-09-14 | 2013-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Indicators element used in cell culture vessel for determining pH value of substance comprises polymeric material and indicator dye |
CN113528837A (en) * | 2021-07-26 | 2021-10-22 | 中南大学 | Method for removing impurity metals by pretreating and sorting waste circuit board copper powder |
Citations (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE595169A (en) | 1959-02-11 | |||
GB189724560A (en) | 1897-10-23 | 1897-12-11 | Fred Cox | An Improved Writing Paper, and Ink therefor. |
GB191016515A (en) | 1910-07-11 | 1911-06-08 | Duncan Cameron | A Preparation to be used in Making Copies of Ink-written Documents. |
GB280088A (en) | 1927-03-09 | 1927-11-10 | Ubaldo Alejandro D Inzeo | A new process for obtaining indelible writings and prints |
GB666450A (en) * | 1948-11-16 | 1952-02-13 | Ncr Co | Marking fluid and methods for the physical application thereof |
GB856188A (en) | 1957-08-02 | 1960-12-14 | Caribonum Ltd | Improvements in or relating to typewriter and like ribbons |
GB1116159A (en) * | 1965-03-08 | 1968-06-06 | Dymo Industries Inc | Methods and compositions for duplicating |
FR2028486A1 (en) | 1969-01-17 | 1970-10-09 | Meredith Corp | |
NL7103180A (en) | 1970-03-16 | 1971-09-20 | ||
DE2505077A1 (en) | 1975-02-07 | 1976-08-19 | Pelikan Werke Wagner Guenther | Colour reaction writing system - contg. mixt. of gallic acid and alkali gallate reacting with heavy metal salts |
GB1469437A (en) | 1975-06-12 | 1977-04-06 | Ozalid Co Ltd | Ink |
US4111702A (en) * | 1969-05-06 | 1978-09-05 | Minnesota Mining And Manufacturing Company | Hidden entry or latent image methods and systems |
JPS5787987A (en) | 1980-11-21 | 1982-06-01 | Matsushita Electric Ind Co Ltd | Ink jet recording sheet |
JPS57207659A (en) | 1981-06-17 | 1982-12-20 | Seiko Epson Corp | Ink for ink-jet recording |
JPS58183769A (en) | 1982-04-21 | 1983-10-27 | Ricoh Co Ltd | Ink for ink jet recording |
JPS6063192A (en) | 1983-09-17 | 1985-04-11 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPS6083886A (en) | 1983-10-17 | 1985-05-13 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPS6083885A (en) | 1983-10-17 | 1985-05-13 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPS6156119B2 (en) | 1982-01-09 | 1986-12-01 | Nichei Kako Kk | |
JPH01241487A (en) | 1988-03-24 | 1989-09-26 | Mitsubishi Petrochem Co Ltd | Recording material for water-based ink recording |
JPH01271284A (en) | 1988-04-22 | 1989-10-30 | Kanzaki Paper Mfg Co Ltd | Pressure-sensitive recoding sheet |
JPH02266978A (en) | 1989-04-10 | 1990-10-31 | Nippon Columbia Co Ltd | Optical information recording medium |
US5123999A (en) * | 1989-08-07 | 1992-06-23 | Aussedat-Rey | Forgery-proof security paper and aqueous or organic composition especially useful for rendering paper forgery-proof |
JPH04307289A (en) | 1991-04-04 | 1992-10-29 | Oji Paper Co Ltd | Thermal recording material |
JPH0959547A (en) | 1995-08-29 | 1997-03-04 | Seiji Kawashima | Colored ink and writing system using the same |
JPH09228292A (en) * | 1996-02-28 | 1997-09-02 | Asahi Denka Kogyo Kk | Recording medium for water-soluble ink |
EP0985538A2 (en) * | 1998-09-11 | 2000-03-15 | Xerox Corporation | Ink jet printing process |
EP1029703A1 (en) * | 1999-02-16 | 2000-08-23 | Oji Paper Co., Ltd. | Ink-jet recording material with improved light-resistance |
US20030134093A1 (en) * | 1999-02-16 | 2003-07-17 | Ryu Kitamura | Ink jet recording material |
KR20040012361A (en) | 2002-08-02 | 2004-02-11 | 영동특산영농조합법인 | Ink-Jet Ink Composition Include Extracted Tannin from Persimmon |
JP2005272762A (en) | 2004-03-26 | 2005-10-06 | Toyo Ink Mfg Co Ltd | Inkjet ink |
-
2008
- 2008-12-22 EP EP08022228A patent/EP2199094A1/en not_active Ceased
Patent Citations (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB189724560A (en) | 1897-10-23 | 1897-12-11 | Fred Cox | An Improved Writing Paper, and Ink therefor. |
GB191016515A (en) | 1910-07-11 | 1911-06-08 | Duncan Cameron | A Preparation to be used in Making Copies of Ink-written Documents. |
GB280088A (en) | 1927-03-09 | 1927-11-10 | Ubaldo Alejandro D Inzeo | A new process for obtaining indelible writings and prints |
GB666450A (en) * | 1948-11-16 | 1952-02-13 | Ncr Co | Marking fluid and methods for the physical application thereof |
GB856188A (en) | 1957-08-02 | 1960-12-14 | Caribonum Ltd | Improvements in or relating to typewriter and like ribbons |
DE1269630B (en) | 1959-02-11 | 1968-06-06 | Imagic Process Ltd | Method and device for producing a right-sided copy |
NL248292A (en) | 1959-02-11 | |||
NL267030A (en) | 1959-02-11 | |||
GB943401A (en) | 1959-02-11 | |||
GB991599A (en) | 1959-02-11 | 1965-05-12 | Imagic Process Ltd | Improvements relating to reproduction processes |
BE595169A (en) | 1959-02-11 | |||
GB1116159A (en) * | 1965-03-08 | 1968-06-06 | Dymo Industries Inc | Methods and compositions for duplicating |
FR2028486A1 (en) | 1969-01-17 | 1970-10-09 | Meredith Corp | |
DE1946393A1 (en) | 1969-01-17 | 1970-10-15 | Meredith Corp | Invisible printing ink |
GB1292831A (en) | 1969-01-17 | 1972-10-11 | Meredith Corp | Method for high speed printing of invisible printing ink |
US4111702A (en) * | 1969-05-06 | 1978-09-05 | Minnesota Mining And Manufacturing Company | Hidden entry or latent image methods and systems |
NL7103180A (en) | 1970-03-16 | 1971-09-20 | ||
DE2112380A1 (en) | 1970-03-16 | 1971-10-07 | Dick Co Ab | Reproduction material for making copies containing an invisible image and means for developing the invisible image |
FR2084649A5 (en) | 1970-03-16 | 1971-12-17 | Dick Co Ab | |
GB1350930A (en) | 1970-03-16 | 1974-04-24 | Dick Co Ab | Concealed printing |
DE2505077A1 (en) | 1975-02-07 | 1976-08-19 | Pelikan Werke Wagner Guenther | Colour reaction writing system - contg. mixt. of gallic acid and alkali gallate reacting with heavy metal salts |
GB1469437A (en) | 1975-06-12 | 1977-04-06 | Ozalid Co Ltd | Ink |
JPS5787987A (en) | 1980-11-21 | 1982-06-01 | Matsushita Electric Ind Co Ltd | Ink jet recording sheet |
JPS57207659A (en) | 1981-06-17 | 1982-12-20 | Seiko Epson Corp | Ink for ink-jet recording |
JPS6156119B2 (en) | 1982-01-09 | 1986-12-01 | Nichei Kako Kk | |
JPS58183769A (en) | 1982-04-21 | 1983-10-27 | Ricoh Co Ltd | Ink for ink jet recording |
JPS6063192A (en) | 1983-09-17 | 1985-04-11 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPS6083886A (en) | 1983-10-17 | 1985-05-13 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPS6083885A (en) | 1983-10-17 | 1985-05-13 | Mitsubishi Paper Mills Ltd | Thermal transfer recording material |
JPH01241487A (en) | 1988-03-24 | 1989-09-26 | Mitsubishi Petrochem Co Ltd | Recording material for water-based ink recording |
JPH01271284A (en) | 1988-04-22 | 1989-10-30 | Kanzaki Paper Mfg Co Ltd | Pressure-sensitive recoding sheet |
JPH02266978A (en) | 1989-04-10 | 1990-10-31 | Nippon Columbia Co Ltd | Optical information recording medium |
US5123999A (en) * | 1989-08-07 | 1992-06-23 | Aussedat-Rey | Forgery-proof security paper and aqueous or organic composition especially useful for rendering paper forgery-proof |
JPH04307289A (en) | 1991-04-04 | 1992-10-29 | Oji Paper Co Ltd | Thermal recording material |
JPH0959547A (en) | 1995-08-29 | 1997-03-04 | Seiji Kawashima | Colored ink and writing system using the same |
JPH09228292A (en) * | 1996-02-28 | 1997-09-02 | Asahi Denka Kogyo Kk | Recording medium for water-soluble ink |
EP0985538A2 (en) * | 1998-09-11 | 2000-03-15 | Xerox Corporation | Ink jet printing process |
EP1029703A1 (en) * | 1999-02-16 | 2000-08-23 | Oji Paper Co., Ltd. | Ink-jet recording material with improved light-resistance |
US20030134093A1 (en) * | 1999-02-16 | 2003-07-17 | Ryu Kitamura | Ink jet recording material |
KR20040012361A (en) | 2002-08-02 | 2004-02-11 | 영동특산영농조합법인 | Ink-Jet Ink Composition Include Extracted Tannin from Persimmon |
JP2005272762A (en) | 2004-03-26 | 2005-10-06 | Toyo Ink Mfg Co Ltd | Inkjet ink |
Non-Patent Citations (1)
Title |
---|
MARTIN HEINRICH KLAPROTH, FRIEDRICH WOLFF: "Chemische Wörterbuch zweiter Band", 1807, BERLIN, XP002532349 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011082716A1 (en) * | 2011-09-14 | 2013-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Indicators element used in cell culture vessel for determining pH value of substance comprises polymeric material and indicator dye |
CN113528837A (en) * | 2021-07-26 | 2021-10-22 | 中南大学 | Method for removing impurity metals by pretreating and sorting waste circuit board copper powder |
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