EP0566537A1 - Process for printing of synthetic fibrous material with transfer-printing - Google Patents
Process for printing of synthetic fibrous material with transfer-printing Download PDFInfo
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- EP0566537A1 EP0566537A1 EP93810251A EP93810251A EP0566537A1 EP 0566537 A1 EP0566537 A1 EP 0566537A1 EP 93810251 A EP93810251 A EP 93810251A EP 93810251 A EP93810251 A EP 93810251A EP 0566537 A1 EP0566537 A1 EP 0566537A1
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- printing paste
- printing
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/907—Nonionic emulsifiers for dyeing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/908—Anionic emulsifiers for dyeing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
Definitions
- the present invention relates to a method for printing synthetic fiber material in transfer printing and the printing paste used for this printing.
- the transfer printing process has basically been around for a long time, e.g. from DE-OS-2,434,753 known.
- sublimable disperse dyes are printed on carrier paper, so-called intermediate carriers, and transferred from there to the textile material by heat and pressure using transfer printing machines.
- the printing pastes applied to the intermediate carriers are subject to high demands with regard to their viscosity behavior, fastness to rubbing and adhesive strength, etc.
- printing pastes containing at least one thickener and one binder are used for transfer printing.
- Known combinations represent e.g. Sodium alginate as a thickener and polyvinyl alcohol as a binder.
- a printing paste containing these components however, has insufficient storage stability and homogeneity, which has a negative effect on the loss of pressure.
- the present invention is therefore based on the object of providing a printing paste which is free of alginate compounds and at the same time insensitive to electrolytes, homogeneous and stable in storage. Surprisingly, it has now been found that the use of certain water-soluble polymers in printing pastes meet these conditions.
- the printing pastes containing the components (a) and (b), (c) and / or (d) form a further subject of the invention.
- a further advantage of the method according to the invention is the fact that component (a) acts simultaneously as a thickener and binder. As a result, the use of a further component acting as a binder becomes obsolete, which considerably simplifies the production and handling of the stock thickening or printing paste.
- water-soluble polymers (a) there are e.g. Homo-co- or graft polymers containing 20 mol% units of a sulfo-containing monomer.
- the polymeric compounds (a) are preferably homopolymers of sulfo-containing monomers or copolymers which contain more than 50 mol%, in particular more than 75 mol%, of sulfo-containing monomer units.
- the polymers (a) can each be present as free acid or as ammonium, alkali metal (Na, K, Li) or alkaline earth metal salt (e.g. Ca); Mixtures of different cations are also possible.
- alkali metal Na, K, Li
- alkaline earth metal salt e.g. Ca
- the polymer (a) is a copolymer
- the following are used as sulfo-free comonomers, e.g. monomers containing carboxyl groups, monomers containing phosphoric acid groups or other comonomers.
- Suitable comonomers with carboxyl function are, for example, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allyl acetic acid, allyloxyacetic acid, a, ß-dimethylacrylic acid, allylmalmalonic acid, allylmalmalonic acid (meth) acrylic acid, 2-Halogeno (meth) acrylic acid, ⁇ -ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, ⁇ -carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.
- Suitable comonomers with a phosphoric acid group are e.g. Vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.
- the following monomers are also suitable as comonomers: N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl acetamide, N-vinylimidazole, N-vinyl-N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 22 alkyl vinyl ketone, C 1 -C 22 -alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1,2-dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (met h
- the polymers or copolymers used and their preparation are known per se.
- the water-soluble polymers used according to the invention are preferably prepared in aqueous solution.
- Peroxidic compounds which are capable of forming free radicals are suitable as initiators, such as hydrogen peroxide, di-tertiary butyl oxide, benzoyl peroxide, lauryl peroxide or cumene hydroperoxide.
- the polymerization can also be initiated with aliphatic azo compounds.
- the usual redox catalyst systems such as hydrogen peroxide / iron (II) sulfate, are of course very suitable for initiating the polymerization.
- the polymerization is usually carried out in the acid to new eel range.
- the temperature during the polymerization is generally 20 to 100 ° C., preferably 40 to 80 ° C.
- the polymer solutions obtained are e.g. 15 to 30% and have viscosities of e.g. 4,000 to 20,000 cP.
- the viscosity which should preferably be above 9,000 cP, is a measure of the degree of polymerization.
- deaerating agents can be used as component (b), provided that the rheological properties of the printing paste according to the invention are not adversely affected. Because of their good defoaming properties, low-silicone oil-free silicone oil-free deaerating agents are preferred, which generally contain 0 to about 10, in particular 2 to 8 percent by weight of a conventional silicone oil.
- Preferred venting agents contain e.g. as active substance high-boiling hydrocarbons, hydrogenated naphthalenes, mineral oils, fatty oils or insoluble metal soaps or mixtures thereof and optionally have the silicone oil content indicated above.
- they can also be present as aqueous solutions which, in addition to the active substances of the type mentioned, generally contain a nonionic surfactant, e.g. Include ethylene oxide adducts of an alkylphenol. Higher alcohols with boiling points above about 100 ° C., turpentine oils, mineral oils or mixtures thereof may be mentioned as preferred ingredients or active substances of the deaerating agents.
- Hydrocarbon mixtures are preferably used which generally have a flash point above about 120 ° C., preferably from about 150 to 220 ° C. and a boiling range from about 250 to 500 ° C. under normal conditions.
- deaerating agents which contain an octanol as active substance, e.g. Contain 2-ethyl-n-hexanol or its mixture with high-boiling hydrocarbon mixtures which have the above-mentioned content of silicone oils and are optionally present as an aqueous preparation, these preparations in addition to the active substances ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical as a surfactant contain.
- an octanol as active substance
- these preparations in addition to the active substances ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical as a surfactant contain.
- the anionic or nonionic dispersant corresponding to component (c) serves as a protective colloid. This has the task of suppressing the undesired orthokinetic coagulation of the dye formulations used under the influence of high shear forces. It therefore has a stabilizing effect on the dye formulations used.
- the addition of component (c) to the printing paste is advantageous, for example, if the dispersed dye formulation is present in the printing paste in amounts which are less than 12 percent by weight of the printing paste.
- Suitable anionic dispersants are lignin sulfonates, polyphosphates or formaldehyde condensation products made from aromatic sulfonic acids and formaldehyde.
- Usable nonionic dispersants are adducts of 15 to 100 moles of ethylene oxide or propylene oxide with polyhydric aliphatic C 2 -C s alcohols, such as ethylene glycol, glycerol or pentaerythritol.
- Component (c) is preferably a polyvinyl acetate hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000, preferably 15,000 to 25,000, and a degree of hydrolysis of 70 to 85 mole percent.
- the printing paste contains a C 1 -C 3 alkanol as component (d), it is methanol, ethanol, n- or iso-propanol or a mixture of different C i -C 3 alkanols; the use of ethanol or mixtures of ethanol / methanol, ethanol / n-propanol or ethanol / iso-propanol is preferred. If a mixture of two alkanols is used as component (d), the mixing ratio can vary within wide limits.
- component (a) a homo- or copolymer which has - 50 mol%, in particular - 75 mol% of 2-acrylamido-2-methylpropanesulfonic acid units, as component ( b) a deaerating agent which contains an octanol as active substance, and optionally as component (c) a polyvinyl acetate hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000 and a degree of hydrolysis of 70 to 85 mol percent.
- a preferred embodiment of the invention relates to the use of a printing paste which contains 1.5 to 6, preferably 2.5 to 5, and particularly preferably 3.2 to 4.4 percent by weight of component (a), 0.1 to 1.5 preferably 0.1 to 0.8 and particularly preferably 0.2 to 0.6 percent by weight of component (b), 0 to 1, preferably 0.3 to 0.5 percent by weight of component (c) and ad 100% by weight % Contains water.
- a further preferred embodiment of the invention relates to the use of a printing paste which contains 0.5 to 2.5, preferably 1 to 2% by weight of component (a), 0.1 to 1.5, preferably 0.4 to 1, Contains 2% by weight of component (b), 1 to 6, preferably 2 to 4% by weight of component (c) and ad 100% by weight of water.
- a printing paste which contains 0.5 to 2.5, preferably 1 to 2% by weight of component (a), 0 to 1.5, preferably 0.4 to 1.2% by weight of Component (b), 1 to 6, preferably 2 to 4 wt .-% of component (c), 5 to 45, preferably 20 to 40 wt .-% of component (d) and ad 100 wt .-% water.
- Printing pastes according to the invention are irrimer-free from compounds containing alginate.
- the amount of dye formulations present in the printing paste depends on the desired color strength and is generally 0.1 to 40 and preferably 0.1 to 30 percent by weight of the formulation, based on the weight of the printing paste.
- a preferred embodiment of the present invention relates to the use of a printing paste consisting of 2.5 to 5% by weight of a homopolymer of alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid as component (a), 0.1 to 0.8% by weight. % of a deaerating agent which contains an octanol as active substance, as component (b), 0 to 1% by weight of a polyvinyl acetate partially hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000 and a degree of hydrolysis of 70 to 85 mol percent, as Component (c), 0.1 to 30% by weight of a formulation of a sublimable disperse dye and ad 100% by weight of water.
- the printing paste according to the invention is produced in a simple manner by mixing components (a) and (b), (c) and / or (d) with the desired dye formulation, with the amount of water required being added at the end, so that a sets a viscosity suitable for gravure printing, for example between 40 and 500, preferably between 100 to 300 and particularly preferably between 180 and 300 mPa.
- Printing pastes for rotary screen printing advantageously have a higher viscosity, for example between 2000 and 5000 mPa.s.
- the printing paste is applied over the entire surface, preferably in the form of a pattern, to the intermediate carrier, printing presses of conventional design, e.g. Rotary screen printing, flexographic and especially gravure printing machines can be used appropriately.
- the intermediate carrier used in the transfer printing process is expediently a flexible, preferably spatially stable tape, a strip or a film with a smooth surface.
- the intermediate carrier should be heat stable and inert, i.e. have no affinity for the various components of the printing paste. It can consist of different materials, e.g. made of metal, such as an aluminum or steel foil, made of plastic, paper or a textile fabric, which can optionally be coated with a film made of vinyl resin, ethyl cellulose or polyurethane resin. For cost reasons, primarily paper webs are used.
- the printed fiber material is separated from the intermediate carrier.
- no post-treatment is required, i.e. generally neither a steam treatment to fix the dye nor a washing process to improve the fastness properties.
- the materials to be printed are e.g. around coated materials, synthetic or semi-synthetic foils, e.g. Films made of polyester, or in particular around textile materials, preferably around flat structures such as nonwovens, felts, especially carpets, knitted fabrics and in particular fabrics.
- textile materials made from semi-synthetic and in particular fully synthetic fibers or their mixtures come into consideration.
- the semi-synthetic fibers are mainly regenerated cellulose fibers, e.g. Triacetate and the fully synthetic fibers mainly around polyacrylonitrile, polyamide and especially polyester fibers. Mixed fabrics of triacetate and polyamide or polyester / cotton or polyester / wool are also suitable for the process according to the invention.
- the printing pastes used according to the invention are new and form a further subject of the invention; they are characterized by good homogeneity, excellent storage stability and simple handling.
- the printed intermediate carrier is dried at 100 ° C for 8 seconds. It is storable and rub-fast. Now, in the transfer printing process, the printed side of the intermediate carrier is brought into contact with a synthetic fiber material, for example a polyester fabric with a basis weight of 100 g / m 2 , then the intermediate carrier and the fiber material are pressed together in an ironing press for 30 seconds at 210 ° C, the Dye transferred from the intermediate carrier to the fabric.
- a synthetic fiber material for example a polyester fabric with a basis weight of 100 g / m 2
- a strong, red, pattern-like print on a white background with good levelness, good fastness properties and with sharp contours is obtained on the polyester fabric.
- the printing paste has a pH of 7.8.
- the viscosity is 130 mPas, measured on the Brookfleld RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
- the printing paste has a pH of 7.9.
- the viscosity is 130 mPas, measured on the Brookfleld RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
- Example 13 If one proceeds as described in Example 13 and uses a printing paste which additionally has 5 g / kg of a deaerating agent based on 2-ethyl-n-hexanol and 295 g / kg instead of 300 g / kg of demineralized water, a printing paste is obtained, which has similarly good properties.
- the viscosity is 220 mPa.s, measured on the Brookfield RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
- Example 15 The procedure described in Example 15 is followed and a printing paste is used which contains 10 g / kg of polyvinyl acetate partially hydrolyzed to polyvinyl alcohol (molecular weight 12000-30000, degree of hydrolysis 70-85%) as a 30% aqueous solution and 290 g / kg of demineralized water instead of 5 g / kg of deaerating agent based on 2-ethyl-n-hexanol and 295 g / kg of demineralized water, a printing paste is obtained which has similarly good properties.
- Example 15 If one proceeds as described in Example 15 and uses a mixture of 200 g / kg ethanol and 200 g / kg isopropanol or n-propanol instead of 400 g / kg ethanol, printing pastes with similarly good properties are obtained.
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Bedrucken von synthetischem Fasermaterial im Transferdruck sowie die für diesen Druck verwendete Druckpaste.The present invention relates to a method for printing synthetic fiber material in transfer printing and the printing paste used for this printing.
Das Transferdruckverfahren ist grundsätzlich schon seit langer Zeit, z.B. aus der DE-OS-2,434,753, bekannt. Üblicherweise werden nach dieser Methode sublimierfähige Dispersionsfarbstoffe auf Trägerpapiere, sogenannte Zwischenträger, gedruckt und von dort durch Hitze und Druck mittels Umdruckmaschinen auf das Textilgut übertragen.The transfer printing process has basically been around for a long time, e.g. from DE-OS-2,434,753 known. Usually sublimable disperse dyes are printed on carrier paper, so-called intermediate carriers, and transferred from there to the textile material by heat and pressure using transfer printing machines.
An die auf die Zwischenträger aufgebrachten Druckpasten werden dabei hohe Anforderungen bzgl. ihres Viskositätsverhaltens, der Reibechtheit und Haftfestigkeit usw. gestellt. Damit diese Anforderungen erfüllt werden können, werden für den Transferdruck Druckpasten eingesetzt, die mindestens ein Verdickungsmittel und ein Bindemittel enthalten. Bekannte Kombinationen stellen z.B. Natrium-Alginat als Verdickungsmittel und Polyvinylalkohol als Bindemittel dar. Eine Druckpaste, die diese Komponenten enthält, weist allerdings eine ungenügende Lagerstabilität und Homogenität auf, was den Druckausfall negativ beeinflusst.The printing pastes applied to the intermediate carriers are subject to high demands with regard to their viscosity behavior, fastness to rubbing and adhesive strength, etc. To meet these requirements, printing pastes containing at least one thickener and one binder are used for transfer printing. Known combinations represent e.g. Sodium alginate as a thickener and polyvinyl alcohol as a binder. A printing paste containing these components, however, has insufficient storage stability and homogeneity, which has a negative effect on the loss of pressure.
Eine Alternative zu den natürlichen Alginaten stellen synthetische Verdickungsmittel dar. Allerdings erweisen sich diese als elektrolytempfindlich und sind daher für den Druck mit anionischen und ionisch formulierten Farbstoffen nur bedingt geeignet.Synthetic thickeners are an alternative to natural alginates. However, these have proven to be sensitive to electrolytes and are therefore only of limited suitability for printing with anionic and ionically formulated dyes.
Der vorliegenden Erfindung liegt daher die Aufgabe zu Grunde, eine Druckpaste bereitzustellen, die frei von Alginatverbindungen und gleichzeitig unempfindlich gegenüber Elektrolyten, homogen und lagerstabil ist. Überraschenderweise wurde nun gefunden, dass die Verwendung -von gewissen wasserlöslichen Polymerenin Druckpasten diese Bedingungen erfüllen.The present invention is therefore based on the object of providing a printing paste which is free of alginate compounds and at the same time insensitive to electrolytes, homogeneous and stable in storage. Surprisingly, it has now been found that the use of certain water-soluble polymers in printing pastes meet these conditions.
Die vorliegende Erfindung-betrifft somit ein Verfahren zum Bedrucken von synthetischem Fasermaterial im Transferdruck, das dadurch gekennzeichnet ist, dass man eine Druckpaste verwendet, die
- (a) ein wasserlösliches sulfogruppenhaltiges Polymer und eine oder mehrere Komponenten aus der Gruppe
- (b) Entlüftungsmittel,
- (c) anionisches oder nichtionogenes Dispergiermittel und
- (d) C1-C3-Alkanol enthält.
- (a) a water-soluble polymer containing sulfo groups and one or more components from the group
- (b) deaerating agents,
- (c) anionic or nonionic dispersant and
- (d) C 1 -C 3 alkanol.
Die die Komponente (a) und (b), (c) und/oder (d) enthaltenden Druckpasten bilden einen weiteren Erfindungsgegenstand.The printing pastes containing the components (a) and (b), (c) and / or (d) form a further subject of the invention.
Die gemäss dem erfindungsgemässen Verfahren hergestellten Transferdrucke sind farbkräftig, licht-, wasch- und reibecht. Als weiterer Vorteil des erfindungsgemässen Verfahrens ist die Tatsache zu bewerten, dass die Komponente (a) gleichzeitig als Verdickungs- und Bindemittel wirkt. Dadurch wird der Einsatz einer weiteren, als Bindemittel fungierenden Komponente hinfällig, was die Herstellung und Handhabung der Stammverdickung bzw. Druckpaste wesentlich vereinfacht.The transfer prints produced according to the method according to the invention are vivid in color, lightfast, washable and rub resistant. A further advantage of the method according to the invention is the fact that component (a) acts simultaneously as a thickener and binder. As a result, the use of a further component acting as a binder becomes obsolete, which considerably simplifies the production and handling of the stock thickening or printing paste.
Als wasserlösliche Polymere (a) kommen z.B. Homo- Co- oder Pfropfpolymere, die 20 Mol-% Einheiten eines sulfogruppenhaltigen Monomeren enthalten, in Betracht.As water-soluble polymers (a) there are e.g. Homo-co- or graft polymers containing 20 mol% units of a sulfo-containing monomer.
Geeignete sulfogruppenhaltige Monomere sind z.B:
- (Meth)acrylamidomethänsulfonsäure,
- Vinylsulfonsäure,
- (Meth)allylsulfonsäure,
- 2-Acrylamido-2-methylpropansulfonsäure,
- 3-(Meth)acrylamidopropansulfonsäure,
- 3-Sulfopropyl(meth)acrylat, Bis-(3-sulfopropylitaconat),
- 4-Styrolsulfonsäure und
- 3-Allyloxy-2-hydroxypropylsulfonsäure.
- (Meth) acrylamidomethanesulfonic acid,
- Vinyl sulfonic acid,
- (Meth) allylsulfonic acid,
- 2-acrylamido-2-methylpropanesulfonic acid,
- 3- (meth) acrylamidopropanesulfonic acid,
- 3-sulfopropyl (meth) acrylate, bis (3-sulfopropyl itaconate),
- 4-styrene sulfonic acid and
- 3-allyloxy-2-hydroxypropylsulfonic acid.
Vorzugsweise handelt es sich bei den polymeren Verbindungen (a) um Homopolymere von sulfogruppenhaltigen Monomeren oder um Copolymere, die mehr als 50 Mol-%, insbesondere mehr als 75 Mol-% sulfogruppenhaltige Monomer-Einheiten enthalten.The polymeric compounds (a) are preferably homopolymers of sulfo-containing monomers or copolymers which contain more than 50 mol%, in particular more than 75 mol%, of sulfo-containing monomer units.
Besonders bevorzugt sind Homo- und Copolymerisate, die -- 50 Mol-%, insbesondere ä 75 Mol-% 2-Acrylamido-2-methylpropansulfonsäure-Einheiten enthalten.Homo- and copolymers are particularly preferred which contain - 50 mol%, in particular 75 mol%, of 2-acrylamido-2-methylpropanesulfonic acid units.
Die Polymere (a) können jeweils als freie Säure oder als Ammonium-, Alkalimetall-(Na, K, Li) oder Erdalkalimetallsalz (z.B. Ca) vorliegen; möglich sind auch Gemische verschiedener Kationen.The polymers (a) can each be present as free acid or as ammonium, alkali metal (Na, K, Li) or alkaline earth metal salt (e.g. Ca); Mixtures of different cations are also possible.
Handelt es sich bei dem Polymer (a) um ein Copolymerisat, so kommen als sulfogruppenfreie Comonomeren z.B. carboxylgruppenhaltige Monomeren, phosphorsäuregruppenhaltige Monomeren oder andere Comonomere in Betracht.If the polymer (a) is a copolymer, the following are used as sulfo-free comonomers, e.g. monomers containing carboxyl groups, monomers containing phosphoric acid groups or other comonomers.
Geeignete Comonomere mit Carboxylfunktion sind z.B. (Meth)acrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Mesaconsäure, Citraconsäure, Vinylessigsäure, Vinyloxyessigsäure, Vinylpropionsäure, Crotonsäure, Aconitsäure, Allylessigsäure, Allyloxyessigsäure, a,ß-Dimethylacrylsäure, Allylmalonsäure, Allyloxymalonsäure, Methylenmalonsäure, 2-Hydroxy(meth)acrylsäure, 2-Halogeno(meth)acrylsäure, a-Ethylacrylsäure, Acrylamidoglycolsäure, Glutaconsäure, β-Carboxyethylacrylat, Allyloxy-3-hydroxybutansäure und Allylbernsteinsäure.Suitable comonomers with carboxyl function are, for example, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allyl acetic acid, allyloxyacetic acid, a, ß-dimethylacrylic acid, allylmalmalonic acid, allylmalmalonic acid (meth) acrylic acid, 2-Halogeno (meth) acrylic acid, α-ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, β-carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.
Geeignete Comonomere mit Phosphorsäuregruppe sind z.B. Vinylphosphonsäure, (Meth)allylphosphonsäure und Acrylamidomethylpropanphosphonsäure.Suitable comonomers with a phosphoric acid group are e.g. Vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.
Des weiteren sind z.B. folgende Monomeren als Comonomeren geeignet: N-Vinylpyrrolidon, N-Vinylformamid, N-Vinyl-N-methyl-formamid, N-Vinylacetamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, N-Vinyl-N-methyl-imidazol, N-Vinylimidazolin, N-Vinyl-2-me- thylimidazolin, N-Vinylcaprolactam, Vinylacetat, Vinylpropionat, Vinylbutyrat, C1-C22-Alkylvinylketon, C1-C22-Alkylvinylether, Olefine (Ethylen, Propylen, Isobuten), 1,2-Dimethoxyethylen, Styrolderivate, Hydroxy- ethyl/propyl/butyl/-(meth)acrylat, (Met h )acrylsäurealkylester-C1-C22, (Meth)acrolein, (Meth)acrylnitril, (Meth)acrylamid, Ester/(subst.) Amide/Nitrile der Monomeren mit Carboxylfunktion, N-Mono/N-Disubstituiertes (Meth)acrylamid (C1-C22), Alkoxy-(meth)acrylate, EOx-POy-ButOz mit x,y,z = 0-250, Dimethyl/Diethyl-aminoethyl/propyl/butyl(meth)acrylate in Form der Salze oder in quaternierter Form, wobei geeignete Quaternierungsmittel z.B. Dimethyl/ethyl-sulfat, Methyl/ethyl-chlorid oder Benzylchlorid sind.The following monomers are also suitable as comonomers: N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl acetamide, N-vinylimidazole, N-vinyl-N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C 1 -C 22 alkyl vinyl ketone, C 1 -C 22 -alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1,2-dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (met h) acrylic acid alkyl ester-C1-C22, (meth) acrolein, (meth) acrylonitrile, (meth) acrylamide, esters / (subst.) amides / nitriles of the monomers with carboxyl function, N-mono / N-disubstituted (meth) acrylamide (C 1 -C 22 ), alkoxy- (meth) acrylates, EO x- POy-ButO z with x, y, z = 0-250, dimethyl / diethylaminoethyl / propyl / butyl (meth) acrylates in the form of the salts or in quaternized form, suitable quaternizing agents, for example dimethyl / ethyl sulfate, methyl / ethyl chloride or benzylch are lorid.
Als besonders geeignet erweisen sich Homopolymerisate von Alkalimetallsalzen der 2-Acrylamido-2-methylpropansulfonsäure als Komponente (a).Homopolymers of alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid have proven to be particularly suitable as component (a).
Die verwendeten Polymerisate bzw. Copolymerisate und deren Herstellung sind an sich bekannt. Bevorzugt werden die erfindungsgemäss verwendeten wasserlöslichen Polymerisate in wässriger Lösung zubereitet. Als Initiatoren eignen sich dabei peroxidische Verbindungen, die Radikale zu bilden vermögen, wie Wasserstoffperoxid, Ditertiärbutyloxid, Benzoylperoxid, Laurylperoxid oder Cumolhydroperoxid. Auch mit aliphatischen Azoverbindungen kann die Polymerisation eingeleitet werden. Daneben sind selbstverständlich die üblichen Redoxkatalysatorsysteme, wie beispielsweise Wasserstoffperoxid/Eisen-II-sulfat zur Einleitung der Polymerisation bestens geeignet.The polymers or copolymers used and their preparation are known per se. The water-soluble polymers used according to the invention are preferably prepared in aqueous solution. Peroxidic compounds which are capable of forming free radicals are suitable as initiators, such as hydrogen peroxide, di-tertiary butyl oxide, benzoyl peroxide, lauryl peroxide or cumene hydroperoxide. The polymerization can also be initiated with aliphatic azo compounds. In addition, the usual redox catalyst systems, such as hydrogen peroxide / iron (II) sulfate, are of course very suitable for initiating the polymerization.
Die Polymerisation wird üblicherweise im sauren bis neuaalen Bereich durchgeführt. Die Temperatur bei der Polymerisation liegt in der Regel bei 20 bis 100°C, vorzugsweise bei 40 bis 80°C. Die erhaltenen Polymerisatlösungen sind z.B. 15 bis 30%ig und weisen Viskositäten von z.B. 4,000 bis 20,000 cP auf. Die Viskosität, die vorzugsweise bei über 9,000 cP liegen soll, ist dabei ein Mass für den Polymerisationsgrad.The polymerization is usually carried out in the acid to new eel range. The temperature during the polymerization is generally 20 to 100 ° C., preferably 40 to 80 ° C. The polymer solutions obtained are e.g. 15 to 30% and have viscosities of e.g. 4,000 to 20,000 cP. The viscosity, which should preferably be above 9,000 cP, is a measure of the degree of polymerization.
Als Komponente (b) sind alle handelsüblichen Entlüftungsmittel einsetzbar, sofern die rheologischen Eigenschaften dererfindungsgemässen Druckpaste nicht negativ beeinflusstwerden. Bevorzugt sind auf Grund ihrer guten Entschäumungseigenschaften silikonölarme bis silikonölfreie Entlüftungsmittel, die im allgemeinen 0 bis etwa 10, insbesondere 2 bis 8 Gewichtsprozent eines herkömmlichen Silikonöls enthalten.All commercially available deaerating agents can be used as component (b), provided that the rheological properties of the printing paste according to the invention are not adversely affected. Because of their good defoaming properties, low-silicone oil-free silicone oil-free deaerating agents are preferred, which generally contain 0 to about 10, in particular 2 to 8 percent by weight of a conventional silicone oil.
Bevorzugte Entlüftungsmittel enthalten z.B. als Aktivsubstanz hochsiedende Kohlenwasserstoffe, hydrierte Naphthalene, Mineralöle, fette Öle oder unlösliche Metallseifen oder deren Gemische und weisen gegebenenfalls den vorstehend angegebenen Gehalt an Silikonölen auf. Sie können aber auch als wässrige Lösungen vorliegen, die im allgemeinen, zusätzlich zu den Aktivsubstanzen der angegebenen Art ein nichtionisches Tensid, z.B. Ethylenoxidaddukte von einem Alkylphenol enthalten. Als bevorzugte Inhaltsstoffe bzw. Aktivsubstanzen der Entlüftungsmittel seien höhere Alkohole mit Siedepunkten über etwa 100°C, Terpentinöle, Mineralöle oder deren Gemische erwähnt. Bevorzugt werden Kohlenwasserstoffgemische eingesetzt, die im allgemeinen einen Flammpunkt über etwa 120°C, vorzugsweise von etwa 150 bis 220°C und einen Siedebereich von etwa 250 bis 500°C unter Normalbedingungen aufweisen.Preferred venting agents contain e.g. as active substance high-boiling hydrocarbons, hydrogenated naphthalenes, mineral oils, fatty oils or insoluble metal soaps or mixtures thereof and optionally have the silicone oil content indicated above. However, they can also be present as aqueous solutions which, in addition to the active substances of the type mentioned, generally contain a nonionic surfactant, e.g. Include ethylene oxide adducts of an alkylphenol. Higher alcohols with boiling points above about 100 ° C., turpentine oils, mineral oils or mixtures thereof may be mentioned as preferred ingredients or active substances of the deaerating agents. Hydrocarbon mixtures are preferably used which generally have a flash point above about 120 ° C., preferably from about 150 to 220 ° C. and a boiling range from about 250 to 500 ° C. under normal conditions.
Im Vordergrund des Interesses stehen Entlüftungsmittel, die als Aktivsubstanz ein Octanol, wie z.B. 2-Ethyl-n-hexanol oder dessen Gemisch mit hochsiedenden Kohlenwasserstoffgemischen enthalten, welche den vorstehend angegebenen Gehalt an Silikonölen aufweisen und gegebenenfalls als wässrige Zubereitung vorliegen, wobei diese Zubereitungen zusätzlich zu den Aktivsubstanzen Ethylenoxidaddukte von einem Alkylphenol mit 6 bis 12 Kohlenstoffatomen im Alkylrest als Tensid enthalten.In the foreground of interest are deaerating agents which contain an octanol as active substance, e.g. Contain 2-ethyl-n-hexanol or its mixture with high-boiling hydrocarbon mixtures which have the above-mentioned content of silicone oils and are optionally present as an aqueous preparation, these preparations in addition to the active substances ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical as a surfactant contain.
Das anionische oder nichtionogene Dispergiermittel entsprechend der Komponente (c) dient als Schutzkolloid. Dieses hat die Aufgabe, die unerwünschte orthokinetische Koagulation der mitverwendeten Farbstofformulierungen unter dem Einfluss hoher Scherkräfte zu unterdrücken. Es übt daher eine stabilisierende Wirkung auf die mitverwendeten Farbstofformulierungen aus. Der Zusatz der Komponente (c) zur Druckpaste ist z.B. von Vorteil, wenn die dispergierte Farbstofformulierung in der Druckpaste in Mengen vorhanden ist, die kleiner als 12 Gewichtsprozent der Druckpaste beträgt. Als anionische Dispergiermittel sind Ligninsulfonate, Polyphosphate oder Formaldehyd-Kondensationsprodukte aus aromatischen Sulfonsäuren und Formaldehyd geeignet. Verwendbare nichtionogene Dispergiermittel sind Anlagerungsprodukte von 15 bis 100 Mol Ethylenoxid oder Propylenoxid an mehrwertige aliphatische C2-CsAlkohole wie z.B Ethylenglykol, Glycerin oder Pentaerythrit.The anionic or nonionic dispersant corresponding to component (c) serves as a protective colloid. This has the task of suppressing the undesired orthokinetic coagulation of the dye formulations used under the influence of high shear forces. It therefore has a stabilizing effect on the dye formulations used. The addition of component (c) to the printing paste is advantageous, for example, if the dispersed dye formulation is present in the printing paste in amounts which are less than 12 percent by weight of the printing paste. Suitable anionic dispersants are lignin sulfonates, polyphosphates or formaldehyde condensation products made from aromatic sulfonic acids and formaldehyde. Usable nonionic dispersants are adducts of 15 to 100 moles of ethylene oxide or propylene oxide with polyhydric aliphatic C 2 -C s alcohols, such as ethylene glycol, glycerol or pentaerythritol.
Bevorzugt wird als Komponente (c) ein zu Polyvinylalkohol hydrolysiertes Polyvinylacetat verwendet, das ein Molekulargewicht von 12,000 bis 30,000, vorzugsweise 15,000 bis 25,000, und einen Hydrolysegrad von 70 bis 85 Molprozent aufweist.Component (c) is preferably a polyvinyl acetate hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000, preferably 15,000 to 25,000, and a degree of hydrolysis of 70 to 85 mole percent.
Enthält die Druckpaste ein C1-C3-Alkanol als Komponente (d), handelt es sich um Methanol, Ethanol, n-oder iso-Propanol oder um ein Gemisch verschiedener Ci-C3-Alkanole; bevorzugt ist die Verwendung von Ethanol oder von Gemischen von Ethanol/Methanol, Ethanol/n-Propanol oder Ethanol/iso-Propanol. Wird ein Gemisch von zwei Alkanolen als Komponente (d) eingesetzt, so kann das Mischungsverhältnis innerhalb weiter Grenzen variieren.If the printing paste contains a C 1 -C 3 alkanol as component (d), it is methanol, ethanol, n- or iso-propanol or a mixture of different C i -C 3 alkanols; the use of ethanol or mixtures of ethanol / methanol, ethanol / n-propanol or ethanol / iso-propanol is preferred. If a mixture of two alkanols is used as component (d), the mixing ratio can vary within wide limits.
Für das erfindungsgemässe Verfahren kommen vorzugsweise Druckpasten in Betracht, die als Komponente (a) ein Homo- oder Copolymerisat, das -- 50 Mol-%, insbesondere - 75 Mol-% 2-Acrylamido-2-methylpropansulfonsäure-Einheiten aufweist, als Komponente (b) ein Entlüftungsmittel, das als Aktivsubstanz ein Octanol enthält, und gegebenenfalls als Komponente (c) ein zu Polyvinylalkohol hydrolysiertes Polyvinylacetat, das ein Molekulargewicht von 12000 bis 30000 und einen Hydrolysegrad von 70 bis 85 Mol Prozent aufweist, enthalten.For the process according to the invention, preference is given to printing pastes which have as component (a) a homo- or copolymer which has - 50 mol%, in particular - 75 mol% of 2-acrylamido-2-methylpropanesulfonic acid units, as component ( b) a deaerating agent which contains an octanol as active substance, and optionally as component (c) a polyvinyl acetate hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000 and a degree of hydrolysis of 70 to 85 mol percent.
Eine bevorzugte Ausführungsform der Erfindung betrifft die Verwendung einer Druckpaste, die 1,5 bis 6, vorzugsweise 2,5 bis 5, und besonders bevorzugt 3,2 bis 4,4 Gewichtsprozent der Komponente (a), 0,1 bis 1,5, vorzugsweise 0,1 bis 0,8 und besonders bevorzugt 0,2 bis 0,6 Gewichtsprozent der Komponente (b), 0 bis 1, vorzugsweise 0,3 bis 0,5 Gewichtsprozent der Komponente (c) und ad 100% Gew.-% Wasser enthält.A preferred embodiment of the invention relates to the use of a printing paste which contains 1.5 to 6, preferably 2.5 to 5, and particularly preferably 3.2 to 4.4 percent by weight of component (a), 0.1 to 1.5 preferably 0.1 to 0.8 and particularly preferably 0.2 to 0.6 percent by weight of component (b), 0 to 1, preferably 0.3 to 0.5 percent by weight of component (c) and ad 100% by weight % Contains water.
Eine weitere bevorzugte Ausführungsform der Erfindung betrifft die Verwendung einer Druckpaste, die 0,5 bis 2,5, vorzugsweise 1 bis 2 Gew.-% der Komponente (a), 0,1 bis 1,5, vorzugsweise 0,4 bis 1,2 Gew.-% der Komponente (b), 1 bis 6, vorzugsweise 2 bis 4 Gew.-% der Komponente (c) und ad 100 Gew.-% Wasser enthält.A further preferred embodiment of the invention relates to the use of a printing paste which contains 0.5 to 2.5, preferably 1 to 2% by weight of component (a), 0.1 to 1.5, preferably 0.4 to 1, Contains 2% by weight of component (b), 1 to 6, preferably 2 to 4% by weight of component (c) and ad 100% by weight of water.
Ausserdem bevorzugt ist die Verwendung einer Druckpaste, die 0,5 bis 2,5, vorzugsweise 1 bis 2 Gew.-% der Komponente (a), 0 bis 1,5, vorzugsweise 0,4 bis 1,2 Gew.-% der Komponente (b), 1 bis 6, vorzugsweise 2 bis 4 Gew.-% der Komponente (c), 5 bis 45, vorzugsweise 20 bis 40 Gew.-% der Komponente (d) und ad 100 Gew.-% Wasser enthält.It is also preferred to use a printing paste which contains 0.5 to 2.5, preferably 1 to 2% by weight of component (a), 0 to 1.5, preferably 0.4 to 1.2% by weight of Component (b), 1 to 6, preferably 2 to 4 wt .-% of component (c), 5 to 45, preferably 20 to 40 wt .-% of component (d) and ad 100 wt .-% water.
Erfindungsgemässe Druckpasten sind irrimer frei von alginathaltigen Verbindungen.Printing pastes according to the invention are irrimer-free from compounds containing alginate.
Für das erfindungsgemässe Verfahren sind die üblichen für das Thermotransferdruckverfahren geeigneten sublimierbaren Dispersionsfarbstoffe, die bei etwa 160 bis etwa 230°C in den Dampfzustand übergehen, d.h. Farbstoffe, deren Dampfdruck bei z.B. 200°C höher als etwa 10-0 ist, verwendbar. Bei diesen Farbstoffen handelt es sich um in Wasser unlösliche bis schwerlösliche Farbstoffe verschiedener Klassen, beispielsweise um Nitrofarbstoffe, Aminoketonfarbstoffe, Ketoniminfarbstoffe, Methinfarbstoffe, Nitrodiphenylaminfarbstoffe, Chinolinfarbstoffe, Aminonaphthochinonfarbstoffe, Cumarinfarbstoffe und insbesondere um Anthrachinonfarbstoffe oder Azofarbstoffe, wie Monoazo- oder Disazofarbstoffe. Es ist auch möglich, Gemische verschiedener Dispersionsfarbstoffe einzusetzen.For the inventive process are those customary for the thermal transfer printing method suitable sublimable disperse dyes, which merge at about 160 to about 230 ° C in the vapor state, ie, dyes, whose vapor pressure at eg ° C is higher than about 10- 0 200 usable. These dyes are water-insoluble to sparingly soluble dyes of various classes, for example nitro dyes, amino ketone dyes, ketone imine dyes, methine dyes, nitrodiphenylamine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes or azo dyes or disazo dyes, such as monoazo dyes. It is also possible to use mixtures of different disperse dyes.
Es ist vorteilhaft, den Farbstoff (coupiert oder uncoupiert) nicht als solchen zu verwenden, sondern eine wässrige Formulierung, welche den in Wasser unlöslichen bis schwerlöslichen Farbstoff (oder Farbstoffmischungen) enthält.It is advantageous not to use the dye (coupled or uncoupled) as such, but rather an aqueous formulation which contains the dye (or dye mixtures) which is insoluble to poorly soluble in water.
Die erfindungsgemäss eingesetzten Farbstoffe können auf Grund der Elektrolyt beständigkeit der Komponente (a) sowohl anionisch als auch nichtionogen formuliert sein.The dyes used according to the invention can be formulated both anionically and nonionically because of the electrolyte resistance of component (a).
Die Menge der in der Druckpaste vorhandenen Farbstofformulierungen richtet sich nach der gewünschten Farbstärke und beträgt im allgemeinen 0,1 bis 40 und vorzugsweise 0,1 bis 30 Gewichtsprozent der Formulierung, bezogen auf das Gewicht der Druckpaste.The amount of dye formulations present in the printing paste depends on the desired color strength and is generally 0.1 to 40 and preferably 0.1 to 30 percent by weight of the formulation, based on the weight of the printing paste.
Eine bevorzugte Ausführungsform der vorliegenden Erfindung bettrift die Verwendung einer Druckpaste bestehend aus 2,5 bis 5 Gew.-% eines Homopolymerisats von Alkalimetallsalzen der 2-Acrylamido-2-methylpropansulfonsäure als Komponente (a), 0,1 bis 0,8 Gew.-% eines Entlüftungsmittels, das als Aktivsubstanz ein Octanol enthält, als Komponente (b), 0 bis 1 Gew.-% eines partiell zu Polyvinylalkohol hydrolysierten Polyvinylacetats, das ein Molekulargewicht von 12000 bis 30000 und einen Hydrolysegrad von 70 bis 85 Mol Prozent aufweist, als Komponente (c), 0, 1 bis 30 Gew.-% einer Formulierung eines sublimierbaren Dispersionsfarbstoffs und ad 100 Gew.-% Wasser.A preferred embodiment of the present invention relates to the use of a printing paste consisting of 2.5 to 5% by weight of a homopolymer of alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid as component (a), 0.1 to 0.8% by weight. % of a deaerating agent which contains an octanol as active substance, as component (b), 0 to 1% by weight of a polyvinyl acetate partially hydrolyzed to polyvinyl alcohol, which has a molecular weight of 12,000 to 30,000 and a degree of hydrolysis of 70 to 85 mol percent, as Component (c), 0.1 to 30% by weight of a formulation of a sublimable disperse dye and ad 100% by weight of water.
Die Herstellung der erfindungsgemässen Druckpaste erfolgt in einfacher Weise durch Mischen der Komponenten (a) und (b), (c) und/oder (d) mit der gewünschten Farbstoffformulierung, wobei zum Schluss noch die benötigte Menge an Wasser zugesetzt wird, sodass sich eine für den Tiefdruck geeignete Viskosität einstellt, die z.B. zwischen 40 und 500, vorzugsweise zwischen 100 bis 300 und besonders bevorzugt zwischen 180 und 300 mPa liegt. Druckpasten für den Rotationssiebdruck weisen vorteilhaft eine höhere Viskosität, z.B. zwischen 2000 und 5000 mPa.s, auf.The printing paste according to the invention is produced in a simple manner by mixing components (a) and (b), (c) and / or (d) with the desired dye formulation, with the amount of water required being added at the end, so that a sets a viscosity suitable for gravure printing, for example between 40 and 500, preferably between 100 to 300 and particularly preferably between 180 and 300 mPa. Printing pastes for rotary screen printing advantageously have a higher viscosity, for example between 2000 and 5000 mPa.s.
Beim Bedrucken wird die Druckpaste ganzflächig, bevorzugt musterförmig auf den Zwischenträger aufgebracht, wobei Druckmaschinen üblicher Bauart, z.B. Rotationssiebdruck-, Flexodruck- und ganz besonders Tiefdruckmaschinen zweckmässig eingesetzt werden.When printing, the printing paste is applied over the entire surface, preferably in the form of a pattern, to the intermediate carrier, printing presses of conventional design, e.g. Rotary screen printing, flexographic and especially gravure printing machines can be used appropriately.
Der im Transferdruckverfahren eingesetzte Zwischenträger ist zweckmässig ein flexibles, vorzugsweise räumlich stabiles Band, ein Streifen oder eine Folie mit glatter Oberfläche. Der Zwischenträger soll hitzestabil und inert sein, d.h. keinerlei Affinität zu den verschiedenen Komponenten der Druckpaste aufweisen. Er kann aus verschiedenen Materialien bestehen, wie z.B. aus Metall, wie eine Aluminium- oder Stahlfolie, aus Kunststoff, Papier oder einem textilen Flächengebilde, die gegebenenfalls mit einem Film aus Vinylharz, Ethylcellulose oder Polyurethanharz beschichtet sein können. Aus Kostengründen verwendet man vor allem Papierbahnen.The intermediate carrier used in the transfer printing process is expediently a flexible, preferably spatially stable tape, a strip or a film with a smooth surface. The intermediate carrier should be heat stable and inert, i.e. have no affinity for the various components of the printing paste. It can consist of different materials, e.g. made of metal, such as an aluminum or steel foil, made of plastic, paper or a textile fabric, which can optionally be coated with a film made of vinyl resin, ethyl cellulose or polyurethane resin. For cost reasons, primarily paper webs are used.
Nach Aufbringen der Druckpaste wird der bedruckte Zwischenträger bei etwa 80 bis 140°C, insbesondere 100 bis 120°C während etwa 5 bis 20 Sekunden getrocknet. Der eigentliche Transferdruck wird auf einer Presse diskontinuierlich oder auf einer üblichen Thermodruckanlage kontinuierlich bei 120 bis 230°C, insbesondere 190 bis 220°C während einer Kontaktzeit von etwa 5 bis 90, insbesondere 20 bis 60 Sekunden unter Anwendung von Druck vorgenommen, wobei der Farbstoff vom Zwischenträger auf das Fasermaterial transferiert.After the printing paste has been applied, the printed intermediate carrier is dried at about 80 to 140 ° C., in particular 100 to 120 ° C., for about 5 to 20 seconds. The actual transfer printing is carried out discontinuously on a press or continuously on a conventional thermal printing system at 120 to 230 ° C., in particular 190 to 220 ° C., during a contact time of about 5 to 90, in particular 20 to 60 seconds, using pressure, the dye transferred from the intermediate carrier to the fiber material.
Nach abgeschlossener Wärme- und Druckbehandlung wird das bedruckte Fasermaterial vom Zwischenträger getrennt. Es bedarf in der Regel keiner Nachbehandlung, d.h. im allgemeinen weder einer Dampfbehandlung, um den Farbstoff zu fixieren, noch eines Waschvorgangs zur Verbesserung der Echtheiten.After the heat and pressure treatment has been completed, the printed fiber material is separated from the intermediate carrier. As a rule, no post-treatment is required, i.e. generally neither a steam treatment to fix the dye nor a washing process to improve the fastness properties.
Bei den zu bedruckenden Materialien handelt es sich z.B. um beschichtete Materialien, synthetische oder halbsynthetische Folien, z.B. Folien aus Polyester, oder insbesondere um Textilmaterialien, vorzugsweise um flächenförmige Gebilde wie Vliese, Filze, vor allem Teppiche, Gewirke und insbesondere Gewebe. Hierbei kommen Textilmaterialien aus halbsynthetischen und insbesondere vollsynthetischen Fasern oder deren Gemische in Betracht. Bei den halbsynthetischen Fasern handelt es sich hauptsächlich um regenerierte Cellulosefasern, z.B. Triacetat und bei den vollsynthetischen Fasern hauptsächlich um Polyacrylnitril-, Polyamid-und insbesondere Polyesterfasern. Auch Mischgewebe aus Triacetat und Polyamid oder Polyester/Baumwolle oder Polyester/Wolle sind für das erfindungsgemässe Verfahren geeignet.The materials to be printed are e.g. around coated materials, synthetic or semi-synthetic foils, e.g. Films made of polyester, or in particular around textile materials, preferably around flat structures such as nonwovens, felts, especially carpets, knitted fabrics and in particular fabrics. Here, textile materials made from semi-synthetic and in particular fully synthetic fibers or their mixtures come into consideration. The semi-synthetic fibers are mainly regenerated cellulose fibers, e.g. Triacetate and the fully synthetic fibers mainly around polyacrylonitrile, polyamide and especially polyester fibers. Mixed fabrics of triacetate and polyamide or polyester / cotton or polyester / wool are also suitable for the process according to the invention.
Man erhält nach dem vorliegenden Verfahren farbstarke, musterförmige Drucke auf weissem Grund mit guter Egalität, guten Echtheiten und mit scharfen Konturen.The present process gives strong, pattern-like prints on a white background with good levelness, good fastness properties and with sharp contours.
Die erfindungsgemäss verwendeten Druckpasten sind neu und bilden einen weiteren Gegenstand der Erfindung; sie zeichnen sich durch eine gute Homogenität, ausgezeichnete Lagerstabilität sowie einfache Handhabung aus.The printing pastes used according to the invention are new and form a further subject of the invention; they are characterized by good homogeneity, excellent storage stability and simple handling.
Sofern nicht anders angegeben, beziehen sich die in den nachfolgenden Beispielen angegebenen Prozente auf das Gewicht.Unless otherwise stated, the percentages given in the examples below are based on weight.
Ein Zwischenträger aus Papier wird auf einer Tiefdruckmaschine mit einer Druckpaste folgender Zusammensetzung stellenweise bedruckt:
- 100 g/kg einer elektrolytarmen, dispergierten Handelsformulierung des Dispersionsfarbstoffes der Formel
- 150 g/kg des Homopolymerisats von 2-Acrylamido-2-methylpropansulfonsäure als 25%ige wässrige Lösung;
- 4 g/kg eines Entlüftungsmittels auf Basis von 2-Ethyl-n-Hexanol;
- 10 g/kg einer 30%igen wässrigen Lösung eines zu Polyvinylalkohol hydrolysierten Polyvinylacetats, das ein Molekulargewicht von 12000 bis 30000 und einen Hydrolysegrad von 70 bis 85 Mol Prozent aufweist;
- ad 1 kg Wasser.
- 100 g / kg of a low-electrolyte, dispersed commercial formulation of the disperse dye of the formula
- 150 g / kg of the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid as a 25% aqueous solution;
- 4 g / kg of a deaerating agent based on 2-ethyl-n-hexanol;
- 10 g / kg of a 30% aqueous solution of a polyvinyl acetate hydrolysed to polyvinyl alcohol, the has a molecular weight of 12,000 to 30,000 and a degree of hydrolysis of 70 to 85 mole percent;
- ad 1 kg of water.
Die Druckpaste weist einen pH-Wert von 7,5 auf. Die Viskosität beträgt 215 mPas, gemessen am Brookfleld Viskosimeter RVT, Spindel 2 (20 rpm) bei 25°C.The printing paste has a pH of 7.5. The viscosity is 215 mPas, measured on the Brookfleld RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
Der bedruckte Zwischenträger wird bei 100°C während 8 Sekunden getrocknet. Er ist lagerfähig und reibecht. Nun wird im Transferdruckverfahren die bedruckte Seite des Zwischenträgers mit einem synthetischen Fasermaterial, z.B. einem Polyestergewebe mit einem Flächengewicht von 100 g/m2 in Kontakt gebracht, hierauf der Zwischenträger und das Fasermaterial während 30 Sekunden bei 210°C in einer Bügelpresse zusammengepresst, wobei der Farbstoff vom Zwischenträger auf das Gewebe transferiert.The printed intermediate carrier is dried at 100 ° C for 8 seconds. It is storable and rub-fast. Now, in the transfer printing process, the printed side of the intermediate carrier is brought into contact with a synthetic fiber material, for example a polyester fabric with a basis weight of 100 g / m 2 , then the intermediate carrier and the fiber material are pressed together in an ironing press for 30 seconds at 210 ° C, the Dye transferred from the intermediate carrier to the fabric.
Man erhält auf dem Polyestergewebe einen farbstarken, roten, musterförmigen Druck auf weissem Grund mit guter Egalität, guten Echtheiten und mit scharfen Konturen.A strong, red, pattern-like print on a white background with good levelness, good fastness properties and with sharp contours is obtained on the polyester fabric.
Man verfährt wie in Beispiel 1 beschrieben mit dem Unterschied, dass man anstelle der Formulierung des Farbstoffs der Formel (I) die äquivalente Menge einer Formulierung eines in der folgenden Tabelle genannten Farbstoffs verwendet:
Man erhält jeweils auf dem Polyestergewebe, das nach der Bedruckung einen weichen Griff aufweist, einen musterförmigen Druck auf weissem Grund mit guter Egalität, guter Echtheit und mit scharfen Konturen.In each case, a pattern-like print on a white background with good levelness, good fastness and with sharp contours is obtained on the polyester fabric, which has a soft handle after printing.
Man verfährt wie im Beispiel 1 beschrieben, verwendet jedoch statt der dort eingesetzten Druckpaste eine Druckpaste folgender Zusammensetzung:
- 150 g/kg Dispersionsfarbstoff-Formulierung gemäss Beispiel 1;
- 70 g/kg des Homopolymerisats von 2-Acrylamido-2-methylpropansulfonsäure als 25%ige wässrige Lösung;
- 80 g/kg partiell zu Polyvinylalkohol hydrolisiertes Polyvinylacetat (Molgewicht 12000-30000, Hydrolysegrad 70-85 %) als 30%ige wässrige Lösung;
- 6 g/kg eines Entlüftungsmittels auf Basis von 2-Ethyl-n-hexanol;
- 694 g/kg demineralisiertes Wasser.
- 150 g / kg disperse dye formulation according to Example 1;
- 70 g / kg of the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid as a 25% aqueous solution;
- 80 g / kg polyvinyl acetate partially hydrolyzed to polyvinyl alcohol (molecular weight 12000-30000, degree of hydrolysis 70-85%) as a 30% aqueous solution;
- 6 g / kg of a deaerating agent based on 2-ethyl-n-hexanol;
- 694 g / kg demineralized water.
Die Druckpaste weist einen pH-Wert von 7,8 auf. Die Viskosität beträgt 130 mPas, gemessen am Brookfleld Viskosimeter RVT, Spindel 2 (20 rpm) bei 25°C.The printing paste has a pH of 7.8. The viscosity is 130 mPas, measured on the Brookfleld RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
Verfährt man wie im Beispiel 11 beschrieben und verwendet eine Druckpaste, die 10 g/kg anstelle von 6 g/kg Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und 690 g/kg anstelle von 694 g/kg demineralisiertes Wasser aufweist, erhält man eine Druckpaste, die ähnlich gute Eigenschaften aufweist.The procedure described in Example 11 is followed and a printing paste is used which contains 10 g / kg instead of 6 g / kg of deaerating agent based on 2-ethyl-n-hexanol and 690 g / kg instead of 694 g / kg of demineralized water a printing paste that has similarly good properties.
Man verfährt wie im Beispiel 1 beschrieben, verwendet jedoch anstelle der dort eingesetzten Druckpaste eine Druckpaste folgender Zusammensetzung:
- 150 g/kg Dispersionsfarbstoff-Formulierung gemäss Beispiel 1;
- 70 g/kg des Homopolymerisats von 2-Acrylamido-2-methylpropansulfonsäure als 25 %ige wässrige Lösung;
- 80 g/kg partiell zu Polyvinylalkohol hydrolisiertes Polyvinylacetat (Molgewicht 12000-30000, Hydrolysegrad 70-85 %) als 30%ige wässrige Lösung;
- 400 g/kg Ethanol 94%ig;
- 300 g/kg demineralisiertes Wasser.
- 150 g / kg disperse dye formulation according to Example 1;
- 70 g / kg of the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid as a 25% aqueous solution;
- 80 g / kg polyvinyl acetate partially hydrolyzed to polyvinyl alcohol (molecular weight 12000-30000, degree of hydrolysis 70-85%) as a 30% aqueous solution;
- 400 g / kg ethanol 94%;
- 300 g / kg demineralized water.
Die Druckpaste weist einen pH-Wert von 7,9 auf. Die Viskosität beträgt 130 mPas, gemessen am Brookfleld Viskosimeter RVT, Spindel 2 (20 rpm) bei 25°C.The printing paste has a pH of 7.9. The viscosity is 130 mPas, measured on the Brookfleld RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
Verfährt man wie im Beispiel 13 beschrieben und verwendet eine Druckpaste, die zusätzlich 5 g/kg eines Entlüftungsmittels auf Basis von 2-Ethyl-n-hexanol und 295 g/kg anstelle von 300 g/kg demineralisiertes Wasser aufweist, erhält man eine Druckpaste, die ähnlich gute Eigenschaften aufweist.If one proceeds as described in Example 13 and uses a printing paste which additionally has 5 g / kg of a deaerating agent based on 2-ethyl-n-hexanol and 295 g / kg instead of 300 g / kg of demineralized water, a printing paste is obtained, which has similarly good properties.
Man verfährt wie im Beispiel 1 beschrieben, verwendet jedoch anstelle der dort eingesetzten Druckpaste eine Druckpaste folgender Zusammensetzung:
- 150 g/kg Dispersionsfarbstoff-Formulierung gemäss Beispiel 1;
- 150 g/kg des Homopolymerisats von 2-Acrylamido-2-methylpropansulfonsäure als 25%ige wässrige Lösung;
- 5 g/kg eines Entlüftungsmittels auf Basis von 2-Ethyl-n-hexanol;
- 400 g/kg Ethanol 94%ig
- 295 g/kg demineralisiertes Wasser.
- 150 g / kg disperse dye formulation according to Example 1;
- 150 g / kg of the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid as a 25% aqueous solution;
- 5 g / kg of a deaerating agent based on 2-ethyl-n-hexanol;
- 400 g / kg ethanol 94%
- 295 g / kg demineralized water.
Die Viskosität beträgt 220 mPa.s, gemessen am Brookfield Viskosimeter RVT, Spindel 2 (20 rpm) bei 25°C.The viscosity is 220 mPa.s, measured on the Brookfield RVT viscometer, spindle 2 (20 rpm) at 25 ° C.
Verfährt man wie im Beispiel 15 beschrieben und verwendet eine Druckpaste, die 10 g/kg partiell zu Polyvinylalkohol hydrolisiertes Polyvinylacetat (Molgewicht 12000-30000, Hydrolysegrad 70-85 %) als 30%ige wässrige Lösung und 290 g/kg demineralisiertes Wasser anstelle von 5 g/kg Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und 295 g/kg demineralisiertem Wasser aufweist, erhält man eine Druckpaste, die ähnlich gute Eigenschaften aufweist.The procedure described in Example 15 is followed and a printing paste is used which contains 10 g / kg of polyvinyl acetate partially hydrolyzed to polyvinyl alcohol (molecular weight 12000-30000, degree of hydrolysis 70-85%) as a 30% aqueous solution and 290 g / kg of demineralized water instead of 5 g / kg of deaerating agent based on 2-ethyl-n-hexanol and 295 g / kg of demineralized water, a printing paste is obtained which has similarly good properties.
Verfährt man wie im Beispiel 15 beschrieben und verwendet anstelle von 400 g/kg Ethanol ein Gemisch aus 200 g/kg Ethanol und 200 g/kg Isopropanol oder n-Propanol, erhält man Druckpasten mit ähnlich guten Eigenschaften.If one proceeds as described in Example 15 and uses a mixture of 200 g / kg ethanol and 200 g / kg isopropanol or n-propanol instead of 400 g / kg ethanol, printing pastes with similarly good properties are obtained.
Man verfährt wie im Beispiel 1 beschrieben und verwendet anstelle der dort verwendeten Druckpaste eine Druckpaste folgender Zusammensetzung:
- 150 g/kg Dispersionsfarbstoff-Formulierung gemäss Beispiel 1;
- 150 g/kg des Homopolymerisats von 2-Acrylamido-2-methylpropansulfonsäure als 25%ige wässrige Lösung;
- 5 g/kg eines Entlüftungsmittels auf Basis von 2-Ethyl-n-hexanol;
- 695 g/kg demineralisiertes Wasser.
- 150 g / kg disperse dye formulation according to Example 1;
- 150 g / kg of the homopolymer of 2-acrylamido-2-methylpropanesulfonic acid as a 25% aqueous solution;
- 5 g / kg of a deaerating agent based on 2-ethyl-n-hexanol;
- 695 g / kg demineralized water.
Man erhält eine Druckpaste mit ähnlich guten Eigenschaften.A printing paste with similarly good properties is obtained.
Claims (19)
enthält.10. The method according to any one of claims 1 to 9, characterized in that the printing paste
contains.
enthält.11. The method according to any one of claims 1 to 9, characterized in that the printing paste
contains.
enthält.12. The method according to any one of claims 1 to 8, characterized in that the printing paste
contains.
enthält.19. Printing paste according to claim 17 or 18, characterized in that it
contains.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1246/92 | 1992-04-15 | ||
CH124692 | 1992-04-15 |
Publications (2)
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EP0566537A1 true EP0566537A1 (en) | 1993-10-20 |
EP0566537B1 EP0566537B1 (en) | 1996-09-18 |
Family
ID=4205902
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Application Number | Title | Priority Date | Filing Date |
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EP93810251A Expired - Lifetime EP0566537B1 (en) | 1992-04-15 | 1993-04-05 | Process for printing of synthetic fibrous material with transfer-printing |
Country Status (7)
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US (1) | US5376148A (en) |
EP (1) | EP0566537B1 (en) |
CZ (1) | CZ63193A3 (en) |
DE (1) | DE59303808D1 (en) |
DK (1) | DK0566537T3 (en) |
SK (1) | SK33893A3 (en) |
ZA (1) | ZA932612B (en) |
Families Citing this family (2)
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ATE340809T1 (en) * | 2002-10-30 | 2006-10-15 | Lubrizol Corp | SYSTEMS CONTAINING FIBER DISPERSANTS |
JP5558357B2 (en) | 2008-09-12 | 2014-07-23 | 株式会社日本触媒 | Method for producing sulfonic acid group-containing ether compound |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0100808A2 (en) * | 1982-08-06 | 1984-02-22 | Ciba-Geigy Ag | Thickeners and their use in printing pastes for the printing of transfer sheets used in transfer printing |
EP0161038A1 (en) * | 1984-02-01 | 1985-11-13 | Ciba Specialty Chemicals Water Treatments Limited | Use of polymeric thickeners in printing |
EP0190002A2 (en) * | 1985-01-30 | 1986-08-06 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric compositions, their preparation and their uses in printing pastes |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1595680A1 (en) * | 1966-09-16 | 1970-04-23 | Bayer Ag | Polymers containing sulfonic acid groups |
DE2434753A1 (en) * | 1974-07-19 | 1976-02-05 | Henkel & Cie Gmbh | PROCESS FOR PRINTING TEXTILES MADE FROM SYNTHETIC FIBER MATERIALS |
-
1993
- 1993-04-05 DE DE59303808T patent/DE59303808D1/en not_active Expired - Fee Related
- 1993-04-05 DK DK93810251.4T patent/DK0566537T3/en active
- 1993-04-05 EP EP93810251A patent/EP0566537B1/en not_active Expired - Lifetime
- 1993-04-08 US US08/045,454 patent/US5376148A/en not_active Expired - Fee Related
- 1993-04-13 SK SK338-93A patent/SK33893A3/en unknown
- 1993-04-13 CZ CZ93631A patent/CZ63193A3/en unknown
- 1993-04-14 ZA ZA932612A patent/ZA932612B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0100808A2 (en) * | 1982-08-06 | 1984-02-22 | Ciba-Geigy Ag | Thickeners and their use in printing pastes for the printing of transfer sheets used in transfer printing |
EP0161038A1 (en) * | 1984-02-01 | 1985-11-13 | Ciba Specialty Chemicals Water Treatments Limited | Use of polymeric thickeners in printing |
EP0190002A2 (en) * | 1985-01-30 | 1986-08-06 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric compositions, their preparation and their uses in printing pastes |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 113 Columbus, Ohio, US; abstract no. 233284, JOZWIK, BOGUSLAW ET AL. 'Binding agent for finishing, printing, and dyeing of woven fabrics' * |
CHEMICAL ABSTRACTS, vol. 93 Columbus, Ohio, US; abstract no. 73688, FUKUI, KIYOSHI 'Coloring assistants for dyeing or printing of textiles' * |
DATABASE WPI Week 7535, Derwent Publications Ltd., London, GB; AN 75-57771W & JP-A-50 014 887 (SUMIMOTO CHEM IND KK) 17. Februar 1975 * |
Also Published As
Publication number | Publication date |
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DK0566537T3 (en) | 1996-10-07 |
EP0566537B1 (en) | 1996-09-18 |
ZA932612B (en) | 1993-10-26 |
CZ63193A3 (en) | 1993-12-15 |
SK33893A3 (en) | 1993-11-10 |
DE59303808D1 (en) | 1996-10-24 |
US5376148A (en) | 1994-12-27 |
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