EP2188437A1 - Starch-based printing thickening agent for reactive printing - Google Patents

Starch-based printing thickening agent for reactive printing

Info

Publication number
EP2188437A1
EP2188437A1 EP08801247A EP08801247A EP2188437A1 EP 2188437 A1 EP2188437 A1 EP 2188437A1 EP 08801247 A EP08801247 A EP 08801247A EP 08801247 A EP08801247 A EP 08801247A EP 2188437 A1 EP2188437 A1 EP 2188437A1
Authority
EP
European Patent Office
Prior art keywords
printing
starch
pressure
thickener
reactive
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.)
Withdrawn
Application number
EP08801247A
Other languages
German (de)
French (fr)
Inventor
Sabine Ramaker-Stam
Holger Stegink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Emsland Staerke GmbH
Original Assignee
Emsland Staerke GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Emsland Staerke GmbH filed Critical Emsland Staerke GmbH
Publication of EP2188437A1 publication Critical patent/EP2188437A1/en
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • D06M15/11Starch or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04Starch derivatives, e.g. crosslinked derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04Starch derivatives, e.g. crosslinked derivatives
    • C08L3/08Ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/43Thickening agents
    • C09D7/44Combinations of two or more thickening agents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/38General 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 reactive dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/445Use of auxiliary substances before, during or after dyeing or printing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General 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
    • D06P1/44General 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
    • D06P1/46General 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 natural macromolecular substances or derivatives thereof
    • D06P1/48Derivatives of carbohydrates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/008Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated using reactive dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/001Special chemical aspects of printing textile materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04Alginic acid; Derivatives thereof

Definitions

  • the present invention relates to a printing thickener for reactive printing and its use.
  • textile printing refers to a localized, patterned dyeing of textiles, which can be carried out by various methods and in which both synthetic and natural textiles can be used.
  • Each printing technique is carried out by a special procedure involving printing, drying, steaming and washing to finally obtain the finished printed product.
  • Reactive dyes can enter into chemical bonds with a cellulose fiber due to their reactive groups in the presence of alkali (soda), whereby particularly good frictional and wet fastness properties are achieved.
  • the reactive groups react with the hydroxyl groups of the cellulose.
  • the dyes also react with the hydroxyl groups of the water and any pressure-thickening agent that is to provide a suitable viscosity for the reactive dyes used.
  • alginate has been used in the prior art as a natural raw material for pressure thickeners, since it also contains no free hydroxyl groups.
  • thickeners which are based, for example, on starch, react with the dyes. This eventually leads to a handle hardening on the goods and a deterioration of rubbing fastness.
  • a reaction of the printing thickener with the reactive dyes should be avoided, the printing thickener for all printing techniques, such as planographic printing and rotary film printing to be suitable. This is especially true for a use in stencil printing techniques that place great demands on the purity of the products used.
  • a reactive pressure printing thickener which contains at least one starch in an amount of at least 50% by weight, based on the total weight of the printing thickener, wherein the starch has a DS value of 0.2 to 0.6 and is crosslinked with 0.05 to 0.50 vol% of a crosslinking agent.
  • the DS value describes the degree of substitution DS of hydroxyl groups per glycose unit of starch, as known to those skilled in the art.
  • the starch is present in a proportion of 50 to 99% by weight, preferably 50 to 80% by weight, more preferably 65 to 75% by weight, based on the total weight of the printing thickener. It is also proposed that the starch preferably has a DS value between 0.3 and 0.4.
  • the starch is crosslinked with 0.2 to 0.4% by volume of the crosslinking agent.
  • starch corn starch is particularly preferred.
  • One embodiment is characterized in that the etherifying agent is sodium monochloroacetate and / or monochloroacetic acid and / or the crosslinking agent is epichlorohydrin.
  • the pressure thickener is mechanically modified, preferably by roll drying.
  • the pressure thickener contains at least one further natural and / or synthetic pressure thickener in addition to the at least one starch.
  • the further thickener may be selected from sodium polyacrylate, sodium alginate and mixtures thereof.
  • a starch-based pressure thickener can be provided for reactive printing wherein the starch is highly cross-linked and highly etherified which when used in a reactive printing process results in excellent printing results.
  • These print results include a high color depth, sharp contours, a level color loss and a soft touch of the substrate.
  • the basic building block of all starches is the ⁇ -amylose, with each amylose molecule within the starch chain each having three free, reactive hydroxyl groups. These hydroxyl groups are prepared by suitable modification, i. by etherification and / or crosslinking, made incapable of reaction, so that the starches in reaction with the reactive dyes in particular can no longer cause grip hardening.
  • Drack thickeners should have the highest possible viscosity, but must be easy to filter, in particular for stencil printing, since otherwise the stencils would become clogged after a short time.
  • a preferred embodiment of the invention wherein the viscosity and filterability are further improved, is characterized in that in addition to the starch (in a proportion of at least 50 wt .-%) yet another other natural and / or synthetic thickener is used.
  • Such a further thickener may, for example, be sodium polyacrylate, sodium alginate or mixtures, a particularly preferred pressure thickener consisting of 70% by weight of starch and 30% by weight of the further thickening agent.
  • corn starch is likely to be particularly well suited for use as a pressure thickener, due to its small grain size and short structure. It is also preferred that the starch used is cold water soluble.
  • Corn starch derivatives with different degrees of etherification and crosslinking were prepared and their viscosity was measured by means of a Brookfield viscometer in an 8% concentration and the filtration value.
  • Table 1 also shows the quantities of products 1-6 used in the printing paste.
  • the printing paste was composed of 5 g / kg Revatol ® NS (dyeing and printing products, Clariant), 25 g / kg sodium carbonate, 100 g / kg urea, printing thickener with a specified in Table 1 and 100 g / kg Cibacron ® Turquoise Blue P-GR 50% as a dye, the remainder being water.
  • the printing was carried out on a laboratory printing table from Zimmer with a squeegee of 10 mm, a magnetic stage of 2/3 and a speed of 1.5 m / minute.
  • the steam was fixed at a temperature of 103 ° C (saturated steam) for a period of 7 minutes.
  • a pressure wash was then performed in three consecutive baths.
  • the first wash was done cold for 3 minutes without additives, the second wash in a bath of 95 ° C for 3 minutes with an addition of 1 g / l Kieralon ® DB (washing and wetting agent, BASF).
  • a third wash was finally done cold for a minute with no additives.
  • a crosslinked corn starch ether was prepared by reacting corn starch with 10 moles of sodium monochloroacetate (DS: 0.4) and 0.375% by volume of epichlorohydrin. For this purpose, 2,000 g of corn starch were suspended in 2,400 ml of tap water and 500 ml of 1 N NaOH was added. The slurry was heated to 4O 0 C in a water bath. 7.5 ml of epichlorohydrin (0.375% by volume) were added and reacted with corn starch for 24 hours at 40-42 ° C. Then, 1,165 g (10 mol) of sodium monochloroacetate was added and the slurry gelatinized with 550 ml of NaOH (50%). The resulting mass was dried on a roll of 3 rolls at 2-3 rpm, and 7-8 bar steam pressure. The product was then screened through a 2 mm sieve.
  • the printing thickener of the present invention exhibits wet and dry rubbing fastnesses which can be compared very well with those for a 100% alginate based printing thickener.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Molecular Biology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Coloring (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention relates to a printing thickening agent for reactive printing, containing at least one starch in a quantity of at least 50 % by weight in relation to the total weight of the printing thickening agent. According to the invention, the starch has a DS value of between 0.2 and 0.6 and is cross-linked using between 0.05 and 0.50 % by volume of a cross-linking agent. The invention also relates to the use of said agent.

Description

Druckverdickungsmittel auf Stärkebasis für den Reaktivdruck Starch-based pressure thickener for the reactive pressure
Die vorliegende Erfindung betrifft ein Druckverdickungsmittel für Reaktivdruck sowie dessen Verwendung.The present invention relates to a printing thickener for reactive printing and its use.
Unter dem Begriff „Textildruck" versteht man ein örtlich begrenztes, mustermäßiges Färben von Textilien, welches nach verschiedenen Verfahren durchgeführt werden kann und bei dem sowohl synthetische als auch natürliche Textilien eingesetzt werden können.The term "textile printing" refers to a localized, patterned dyeing of textiles, which can be carried out by various methods and in which both synthetic and natural textiles can be used.
Die unterschiedlichsten Druckverfahren sind bekannt, beispielsweise Direktdruck, Ätzdruck, Reservedruck. Auch unterschiedlichsten Drucktechniken, wie Rouleauxdruck, Flachdruck, Rotationsfilmdruck, Transferdruck, Tintenstrahldruck, etc., stehen zur Verfügung.The most diverse printing methods are known, for example direct printing, etching pressure, reserve pressure. Also a wide variety of printing techniques, such as Rouleauxdruck, planographic printing, rotary film printing, transfer printing, inkjet printing, etc., are available.
Jede Drucktechnik wird mittels eines speziellen Ablaufs durchgeführt, der Drucken, Trocknen, Dämpfen und Waschen umfaßt, um schließlich das fertige Druckprodukt zu erhalten.Each printing technique is carried out by a special procedure involving printing, drying, steaming and washing to finally obtain the finished printed product.
Geordnet nach Farbstoffklassen unterscheidet man beim Drucken im wesentlichen zwischen Pigmentdruck, Reaktivdruck, Dispersionsdruck und Küpendruck. Etwa 30% aller bedruckten Stoffe werden weltweit mit dem Reaktivdruckverfahren hergestellt, so daß der Reaktivdruck mengenmäßig nach dem Pigmentdruck an zweiter Stelle steht.In terms of dye classes, printing generally distinguishes between pigment printing, reactive printing, dispersion pressure and cooling pressure. About 30% of all printed materials are produced worldwide using the reactive printing process, so that the reactive pressure is in second place in terms of quantity after pigment printing.
Reaktivfarbstoffe können aufgrund ihrer reaktiven Gruppen in Anwesenheit von Alkali (Soda) chemische Bindungen mit einer Cellulosefaser eingehen, wodurch besonders gute Reib- und Naßechtheiten erzielt werden. Im alkalischen Medium reagieren die Reaktivgruppen mit den Hydroxylgrupen der Cellulose. Die Farbstoffe reagieren jedoch auch mit den Hydroxylgruppen des Wassers und eines eventuell vorhandenen Druckverdickungsmittels, das eine geeignete Viskosität für die eingesetzten Reaktivfarbstoffe bereitstellen soll. Aus diesem Grunde wird neben synthetischen Produkten, die frei von OH-Gruppen sind, im Stand der Technik bislang überwiegend Alginat als ein natürlicher Rohstoff für Druckverdickungsmittel eingesetzt, da es ebenfalls keine freien Hydroxylgruppen enthält. Andere natürliche Druck- verdickungsmittel, die beispielsweise auf Basis von Stärke aufgebaut sind, reagieren hingegen mit den Farbstoffen. Dies führt schließlich zu einer Griffverhärtung auf der Ware und einer Verschlechterung der Reibechtheiten.Reactive dyes can enter into chemical bonds with a cellulose fiber due to their reactive groups in the presence of alkali (soda), whereby particularly good frictional and wet fastness properties are achieved. In the alkaline medium, the reactive groups react with the hydroxyl groups of the cellulose. However, the dyes also react with the hydroxyl groups of the water and any pressure-thickening agent that is to provide a suitable viscosity for the reactive dyes used. For this reason, in addition to synthetic products which are free of OH groups, so far mainly alginate has been used in the prior art as a natural raw material for pressure thickeners, since it also contains no free hydroxyl groups. Other natural printing However, thickeners which are based, for example, on starch, react with the dyes. This eventually leads to a handle hardening on the goods and a deterioration of rubbing fastness.
Da Alginate in immer stärkerem Maße im Nahrungsmittelbereich eingesetzt werden und die Nachfrage nach Alginaten stetig steigt, kommt es hier leicht zu Rohstoffengpässen. Ferner sind die Preise für Alginate mit etwa 3 bis 4 Euro/kg recht hoch. Derzeit gibt es noch keine Alternative zu Alginaten auf Basis eines natürlichen Rohstoffs, der für den Reaktivdruck zur Bildung eines Druckverdickungsmittels geeignet wäre.As alginates are increasingly used in the food industry and the demand for alginates is steadily rising, it is easy to find bottlenecks in raw materials. Furthermore, the prices for alginates are quite high at about 3 to 4 Euro / kg. At present there is no alternative to alginates based on a natural raw material which would be suitable for the reactive pressure to form a pressure thickener.
Es ist daher eine Aufgabe der vorliegenden Erfindung, die Nachteile aus dem Stand der Technik zu überwinden und ein Druckverdickungsmittel im wesentlichen auf Basis eines natürlichen Rohstoffs bereitzustellen, das für Reaktivdruck eingesetzt werden kann. Insbesondere soll eine Reaktion des Druckverdickungsmittels mit den Reaktivfarbstoffen vermieden werden, wobei das Druckverdickungsmittel für alle Drucktechniken, wie beispielsweise Flachdruck und Rotationsfilmdruck, geeignet sein soll. Dies gilt insbesondere für eine Einsatzmöglichkeit bei Schablonendrucktechniken, die große Anforderungen an die Reinheit der eingesetzten Produkte stellen.It is therefore an object of the present invention to overcome the disadvantages of the prior art and to provide a pressure thickening agent based essentially on a natural raw material which can be used for reactive printing. In particular, a reaction of the printing thickener with the reactive dyes should be avoided, the printing thickener for all printing techniques, such as planographic printing and rotary film printing to be suitable. This is especially true for a use in stencil printing techniques that place great demands on the purity of the products used.
Die Aufgabe wird gelöst durch ein Druckverdickungsmittel für Reaktivdruck, das zumindest eine Stärke in einem Anteil von mindestens 50 Gew.-%, bezogen auf das Gesamtgewicht des Druckverdickungsmittels enthält, wobei die Stärke einen DS-Wert von 0,2 bis 0,6 aufweist und mit 0,05 bis 0,50 Vol-% eines Vernetzungsmittels vernetzt ist. Der DS-Wert beschreibt den Grad des Ersatzes (Degree of Substitution DS) der Hydroxylgruppen pro Glycoseeinheit der Stärke, wie es Fachleuten auf dem Gebiet bekannt ist.The object is achieved by a reactive pressure printing thickener which contains at least one starch in an amount of at least 50% by weight, based on the total weight of the printing thickener, wherein the starch has a DS value of 0.2 to 0.6 and is crosslinked with 0.05 to 0.50 vol% of a crosslinking agent. The DS value describes the degree of substitution DS of hydroxyl groups per glycose unit of starch, as known to those skilled in the art.
Dabei ist bevorzugt, daß die Stärke in einem Anteil von 50 bis 99 Gew.-%, bevorzugt 50 bis 80 Gew.-%, bevorzugter 65 bis 75 Gew.-%, bezogen auf das Gesamtgewicht des Druckverdickungsmittels, vorliegt. Auch wird vorgeschlagen, daß die Stärke bevorzugt einen DS-Wert zwischen 0,3 und 0,4 aufweist.It is preferred that the starch is present in a proportion of 50 to 99% by weight, preferably 50 to 80% by weight, more preferably 65 to 75% by weight, based on the total weight of the printing thickener. It is also proposed that the starch preferably has a DS value between 0.3 and 0.4.
Ebenfalls bevorzugt ist die Stärke mit 0,2 bis 0,4 Vol-% des Vernetzungsmittels vernetzt.Also preferably, the starch is crosslinked with 0.2 to 0.4% by volume of the crosslinking agent.
Besonders bevorzugt ist die Stärke Maisstärke.Particularly preferred is the starch corn starch.
Eine Ausführungsform zeichnet sich dadurch aus, daß das Veretherungsmittel Natriummono- chloracetat und/oder Monochloressigsäure ist und/oder das Vernetzungsmittel Epichlorhydrin ist.One embodiment is characterized in that the etherifying agent is sodium monochloroacetate and / or monochloroacetic acid and / or the crosslinking agent is epichlorohydrin.
Auch wird vorgeschlagen, daß das Druckverdickungsmittel mechanisch modifiziert ist, bevorzugt durch Walztrocknung.It is also proposed that the pressure thickener is mechanically modified, preferably by roll drying.
Besonders bevorzugt ist, daß das Druckverdickungsmittel neben der zumindest einen Stärke zumindest ein weiteres natürliches und/oder synthetisches Druckverdickungsmittel enthält.It is particularly preferred that the pressure thickener contains at least one further natural and / or synthetic pressure thickener in addition to the at least one starch.
Das weitere Verdickungsmittel kann ausgewählt sein aus Natriumpolyacrylat, Natriumalginat und Mischungen derselben.The further thickener may be selected from sodium polyacrylate, sodium alginate and mixtures thereof.
Erfindungsgemäß ist ebenfalls die Verwendung des Druckverdickungsmittels in Kombination mit Reaktivfarbstoffen.The use of the pressure thickener in combination with reactive dyes is also according to the invention.
Dabei ist die Verwendung auf natürlichen Fasern, wie Baumwolle und Viskose, bevorzugt.The use on natural fibers, such as cotton and viscose, is preferred.
Überraschenderweise wurde festgestellt, daß ein Druckverdickungsmittel auf Stärkebasis für Reaktivdruck bereitgestellt werden kann, wobei die Stärke hoch vernetzt und hoch verethert ist, das bei Einsatz in einem Reaktivdruckverfahren zu ausgezeichneten Druckresultaten führt. Diese Druckresultate beeinhalten eine hohe Farbtiefe, scharfe Konturen, einen egalen Farbausfall und einen weichen Griff des Bedruckstoffes.Surprisingly, it has been found that a starch-based pressure thickener can be provided for reactive printing wherein the starch is highly cross-linked and highly etherified which when used in a reactive printing process results in excellent printing results. These print results include a high color depth, sharp contours, a level color loss and a soft touch of the substrate.
Der Grundbaustein aller Stärken ist die α-Amylose, wobei jedes Amylosemolekül innerhalb der Stärkekette jeweils drei freie, reaktionsfähige Hydroxylgruppen aufweist. Diese Hydroxylgruppen werden durch geeignete Modifikation, d.h. durch Veretherung und/oder Vernetzung, reaktionsunfähig gemacht, so daß die Stärken bei Reaktion mit den Reaktivfarbstoffen insbesondere keine Griffverhärtungen mehr verursachen können.The basic building block of all starches is the α-amylose, with each amylose molecule within the starch chain each having three free, reactive hydroxyl groups. These hydroxyl groups are prepared by suitable modification, i. by etherification and / or crosslinking, made incapable of reaction, so that the starches in reaction with the reactive dyes in particular can no longer cause grip hardening.
Drackverdickungsmittel sollen eine möglichst hohe Viskosität aufweisen, müssen jedoch, insbesondere für einen Schablonendruck, gut filtrierbar sein, da ansonsten die Schablonen nach kurzer Zeit verstopfen würden. Durch Einsatz der hoch vernetzten und hoch veretherten Stärken ist es nun erfindungsgemäß möglich, eine optimale Viskosität und Filtrierbarkeit für das Druckverdickungsmittel bereitzustellen. Eine bevorzugte Ausführungsform der Erfindung, bei der Viskosität und Filtrierbarkeit noch weiter verbessert sind, zeichnet sich dadurch aus, daß neben der Stärke (in einem Anteil von wenigstens 50 Gew.-%) noch ein weiteres anderes natürliches und/oder synthetisches Verdickungsmittel eingesetzt wird. Ein solches weiteres Verdickungsmittel kann beispielsweise Natriumpolyacrylat, Natriumalginat oder Mischungen sein, wobei ein besonders bevorzugtes Druckverdickungsmittel aus 70 Gew.-% Stärke und 30 Gew.-% des weiteren Verdickungsmittels besteht.Drack thickeners should have the highest possible viscosity, but must be easy to filter, in particular for stencil printing, since otherwise the stencils would become clogged after a short time. By using the highly crosslinked and highly etherified starches, it is now possible according to the invention to provide optimum viscosity and filterability for the pressure thickener. A preferred embodiment of the invention, wherein the viscosity and filterability are further improved, is characterized in that in addition to the starch (in a proportion of at least 50 wt .-%) yet another other natural and / or synthetic thickener is used. Such a further thickener may, for example, be sodium polyacrylate, sodium alginate or mixtures, a particularly preferred pressure thickener consisting of 70% by weight of starch and 30% by weight of the further thickening agent.
Ferner hat sich gezeigt, daß Maisstärke wahrscheinlich aufgrund ihrer geringen Korngröße und kurzen Struktur für den Einsatz als Druckverdickungsmittel besonders gut geeignet ist. Ebenfalls ist bevorzugt, daß die eingesetzte Stärke kaltwasserlöslich ist.It has also been found that corn starch is likely to be particularly well suited for use as a pressure thickener, due to its small grain size and short structure. It is also preferred that the starch used is cold water soluble.
Entsprechende Produkte auf Stärkebasis konnten bisher nur zu einem sehr kleinen Prozentsatz für den Reaktivdruck eingesetzt werden. Weitere Merkmale und Vorteile der Erfindung ergeben sich aus der folgenden detaillierten Beschreibung von Ausführungsbeispielen, auf die die Erfindung keineswegs beschränkt sein soll.Corresponding starch-based products have so far only been used for a very small percentage of the reactive pressure. Further features and advantages of the invention will become apparent from the following detailed description of exemplary embodiments, to which the invention should by no means be restricted.
Maisstärkederivate mit unterschiedlichem Veretherungs- und Vernetzungsgrad wurden hergestellt und deren Viskosität über ein Brookfield-Viskosimeter in einer 8%igen Konzentration sowie der Filtrationswert gemessen.Corn starch derivatives with different degrees of etherification and crosslinking were prepared and their viscosity was measured by means of a Brookfield viscometer in an 8% concentration and the filtration value.
Zur Bestimmung der Viskosität werden 460 g Leitungswasser in eine 1 1 Mensur eingewogen und dann unter Rühren mit einem Doppelbalkenrührer und einem Heidolph-Rührwerk 40 g Produkt zugegeben. Die Lösung wird 15 Minuten bei 800 Upm gelöst. Gemessen wird mit einem Brookfield-Viskosimeter Typ RVT bei 20 Upm und 2O0C.To determine the viscosity, 460 g of tap water are weighed into a 1 1 scale and then added with stirring with a double-bladed stirrer and a Heidolph stirrer 40 g of product. The solution is dissolved for 15 minutes at 800 rpm. Is measured with a Brookfield viscometer type RVT at 20 rpm and 2O 0 C.
Zur Bestimmung der Filtrierbarkeit bzw. des Filtrationswertes werden 100 g Produkt in 1.900 g Leitungswasser für 1 Stunde bei 700 Upm (Doppelbalkenrührer und Heidolph-Rührwerk) gelöst. Anschließend ruht die Lösung für 1 Stunde. Danach wird die Lösung unter Vakuum über ein 45 μm Sieb abfiltriert. Zeit und Unterdruck werden gemessen.To determine the filterability or the filtration value, 100 g of product are dissolved in 1,900 g of tap water for 1 hour at 700 rpm (double-bar stirrer and Heidolph stirrer). Subsequently, the solution rests for 1 hour. Thereafter, the solution is filtered off under vacuum through a 45 μm sieve. Time and negative pressure are measured.
Die Ergebnisse für die einzelnen Maisstärkederivate sind unten in Tabelle 1 angegeben. In Tabelle 1 sind ebenfalls die Einsatzmengen der Produkte 1-6 in der Druckpaste angegeben. The results for the individual corn starch derivatives are given below in Table 1. Table 1 also shows the quantities of products 1-6 used in the printing paste.
Tabelle 1Table 1
Für alle Maisstärkederivate wurden Reaktivdruckversuche auf reiner Baumwolle durchgeführt, wobei ein Labordrucktisch der Firma Zimmer und ein Fixierer der Firma Mathis verwendet wurde. Die Qualität des Druckes war 100% CO mit einem Dessin von 002/1-60 Mesh.Reactive pressure tests on pure cotton were carried out for all corn starch derivatives, using a laboratory printing table from Zimmer and a fixer from Mathis. The quality of the print was 100% CO with a pattern of 002 / 1-60 mesh.
Die Druckpaste setzte sich zusammen aus 5 g/kg Revatol® NS (Färbe- und Druckhilfsmittel, Clariant), 25 g/kg Soda, 100 g/kg Harnstoff, Druckverdickungsmittel mit einer in Tabelle 1 angegebenen Menge und 100 g/kg Cibacron® Türkisblau P-GR 50% als Farbstoff, wobei der Rest Wasser ist. Der Druck wurde auf einem Labordrucktisch der Firma Zimmer mit einem Rakel von 10 mm, einer Magnetstufe von 2/3 und einer Geschwindigkeit von 1,5 m/Minute durchgeführt. Die Dampffixierung erfolgte bei einer Temperatur von 103°C (Sattdampf) für eine Dauer von 7 Minuten. Eine Druckwäsche wurde anschließend durchgeführt in drei aufeinanderfolgenden Bädern. Die erste Wäsche erfolgte kalt für 3 Minuten ohne Zusätze, die zweite Wäsche in einem Bad von 95°C für 3 Minuten mit einer Zugabe von 1 g/l Kieralon® DB (Wasch- und Netzmittel, BASF). Eine dritte Wäsche wurde schließlich kalt für eine Minute ohne Zusätze durchgeführt.The printing paste was composed of 5 g / kg Revatol ® NS (dyeing and printing products, Clariant), 25 g / kg sodium carbonate, 100 g / kg urea, printing thickener with a specified in Table 1 and 100 g / kg Cibacron ® Turquoise Blue P-GR 50% as a dye, the remainder being water. The printing was carried out on a laboratory printing table from Zimmer with a squeegee of 10 mm, a magnetic stage of 2/3 and a speed of 1.5 m / minute. The steam was fixed at a temperature of 103 ° C (saturated steam) for a period of 7 minutes. A pressure wash was then performed in three consecutive baths. The first wash was done cold for 3 minutes without additives, the second wash in a bath of 95 ° C for 3 minutes with an addition of 1 g / l Kieralon ® DB (washing and wetting agent, BASF). A third wash was finally done cold for a minute with no additives.
Für alle Produkte wurden gute Druckergebnisse erhalten. Dabei zeigte sich, daß das Produkt mit der Nummer 2 die besten Druckresultate auf reiner Baumwolle lieferte. Insbesondere wurden eine hohe Farbtiefe, scharfe Konturen, ein egaler Farbausfall sowie ein weicher Griff der Baumwolle erhalten. Jedoch waren die Viskosität und die Filtrierbarkeit noch verbesserungsfähig.Good print results were obtained for all products. It showed that the product with the number 2 delivered the best print results on pure cotton. In particular, a high color depth, sharp contours, a level color loss and a soft handle of cotton. However, the viscosity and the filterability were still improved.
Diese Nachteile konnten durch Zugabe anderer natürlicher und/oder synthetischer Verdickungsmittel beseitigt werden.These disadvantages could be eliminated by adding other natural and / or synthetic thickeners.
Beispiel 1example 1
Ein vernetzter Maisstärkeether wurde hergestellt durch Umsetzung von Maisstärke mit 10 Mol Natriummonochloracetat (DS: 0,4) und 0,375 Vol-% Epichlorhydrin. Dazu wurden 2.000 g Maisstärke in 2.400 ml Leitungswasser suspendiert und 500 ml 1 N NaOH zugegeben. Die erhaltene Slurry wurde auf 4O0C im Wasserbad erhitzt. 7,5 ml Epichlorhydrin (0,375 Vol-%) wurden zugegeben und 24 Stunden bei 40-42°C mit der Maisstärke umgesetzt. Dann wurden 1.165 g (10 Mol) Natriummonochloracetat zugegeben und die Slurry mit 550 ml NaOH (50%ig) verkleistert. Die erhaltene Masse wurde auf einer Walze mit 3 Rollen bei 2-3 Up, und 7-8 bar Dampfdruck getrocknet. Das Produkt wurde anschließend über ein Sieb von 2 mm abgesiebt.A crosslinked corn starch ether was prepared by reacting corn starch with 10 moles of sodium monochloroacetate (DS: 0.4) and 0.375% by volume of epichlorohydrin. For this purpose, 2,000 g of corn starch were suspended in 2,400 ml of tap water and 500 ml of 1 N NaOH was added. The slurry was heated to 4O 0 C in a water bath. 7.5 ml of epichlorohydrin (0.375% by volume) were added and reacted with corn starch for 24 hours at 40-42 ° C. Then, 1,165 g (10 mol) of sodium monochloroacetate was added and the slurry gelatinized with 550 ml of NaOH (50%). The resulting mass was dried on a roll of 3 rolls at 2-3 rpm, and 7-8 bar steam pressure. The product was then screened through a 2 mm sieve.
70 Gew.-% des so erhaltenen vernetzten und walzengetrockneten Maisstärkeethers wurden mit 30 Gew.-% Natriumpolyacrylat vermischt und zusammen auf einer Walze getrocknet. Die Brookfield- Viskosität wurde wie oben angegeben gemessen und betrug 20.000 mPa.s, während die Filtrierbarkeit Werte von < 60 Sekunden bei 0,2 bar ergab. Die Einsetzmenge des so hergestellten Maisstärkeethers in der Druckpaste betrug 50 g/kg.70% by weight of the crosslinked and roller-dried corn starch ether thus obtained was mixed with 30% by weight of sodium polyacrylate and dried together on a roller. The Brookfield viscosity was measured as indicated above and was 20,000 mPa.s, while the filterability gave values of <60 seconds at 0.2 bar. The incorporation amount of the corn starch ether thus prepared in the printing paste was 50 g / kg.
Für das so erhaltene Druckverdickungsmittel wurden Druckversuche wie oben beschrieben durchgeführt und die Druckergebnisse mit einem Druckverdickungsmittel auf Basis von 100% Alginat verglichen. Dabei wurde festgestellt, daß Farbtiefe, Egalität und Konturenstand des erfindungsgemäßen Druckverdickungsmittels besser waren als bei einem Druckverdi- ckungsmittels auf Basis von 100% Alginat. Der Griff war bei beiden Druckverdickungsmit- teln identisch. Ferner wurden Naß- und Trockenreibechtheiten, die mit einem Crockmeter (Crockmeter Modell 255 von James H. Heal, Halifax, England, Methode ISO 105-A03) gemessen wurden, für das erfindungsgemäße Druckverdickungsmittel und das Druckverdi- ckungsmittel auf Basis von Alginat verglichen. Zur Messung wurden zu prüfende bedruckte Stellen eines Baumwollstoffs unter kontrollierten Bedingungen gegen einen weißen Baumwollstoff gerieben. Die Farbe des Abriebs wurde mit der Grau-Skala verglichen und benotet. Je kleiner der Wert ist, desto schlechter ist dabei die Echtheit. Die Skale reicht von 1 bis 5. Die Ergebnisse des Tests der Naß- und Trockenreibechtheiten sind in Tabelle 2 gezeigt.For the printing thickener thus obtained, printing tests were carried out as described above, and the printing results were compared with a printing thickener based on 100% alginate. It was found that the depth of color, levelness and contours of the printing thickener according to the invention were better than with a pressure-reducing agent based on 100% alginate. The handle was identical for both pressure thickeners. Furthermore, wet and dry rub fastnesses were measured with a Crockmeter (Crockmeter Model 255 from James H. Heal, Halifax, England, method ISO 105-A03) were compared for the pressure thickener according to the invention and the alginate-based pressure diluent. For measurement, printed areas of a cotton fabric to be tested were rubbed under controlled conditions against a white cotton fabric. The color of the abrasion was compared with the gray scale and graded. The smaller the value, the worse the authenticity. The scale ranges from 1 to 5. The results of the wet and dry rub fastness tests are shown in Table 2.
Tabelle 2Table 2
Wie sich aus Tabelle 2 ergibt, zeigt das erfindungsgemäße Druckverdickungsmittel Naß- und Trockenreibechtheiten, die sehr gut mit denjenigen für ein Druckverdickungsmittel auf Basis von 100% Alginat verglichen werden können.As shown in Table 2, the printing thickener of the present invention exhibits wet and dry rubbing fastnesses which can be compared very well with those for a 100% alginate based printing thickener.
In der vorstehenden Beschreibung und in den Ansprüchen offenbarten Merkmale der Erfindung können sowohl einzeln als auch in jeder beliebigen Kombination für die Verwirklichung der Erfindung in ihren verschiedenen Ausführungsformen wesentlich sein. Features of the invention disclosed in the foregoing description and in the claims may be essential to the practice of the invention in its various embodiments both individually and in any combination thereof.

Claims

Ansprfiche Ansprfiche
1. Druckverdickungsmittel für Reaktivdruck, das zumindest eine Stärke in einem Anteil von mindestens 50 Gew.-%, bezogen auf das Gesamtgewicht des Druckverdickungs- mittels, enthält, wobei die Stärke einen DS-Wert von 0,2 bis 0,6 aufweist und mit 0,05 bis 0,50 Vol-% eines Vernetzungsmittels vernetzt ist.1. pressure-sensitive reactive pressure printing agent which contains at least one starch in a proportion of at least 50 wt .-%, based on the total weight of the Druckverdickungs- means, wherein the starch has a DS value of 0.2 to 0.6 and with 0.05 to 0.50% by volume of a crosslinking agent is crosslinked.
2. Druckverdickungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß die Stärke in einem Anteil von 50 bis 99 Gew.-%, bevorzugt 50 bis 80 Gew.-%, bevorzugter 65 bis 75 Gew.-%, bezogen auf das Gesamtgewicht des Druckverdickungsmittels, vorliegt.2. Printing thickener according to claim 1, characterized in that the starch in an amount of 50 to 99 wt .-%, preferably 50 to 80 wt .-%, more preferably 65 to 75 wt .-%, based on the total weight of the pressure thickener, is present.
3. Druckverdickungsmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Stärke einen DS-Wert zwischen 0,3 und 0,4 aufweist.3. Pressure thickener according to claim 1 or 2, characterized in that the starch has a DS value between 0.3 and 0.4.
4. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Stärke mit 0,2 bis 0,4 Vol-% des Vernetzungsmittels vernetzt ist.4. Pressure thickener according to one of the preceding claims, characterized in that the starch is crosslinked with 0.2 to 0.4% by volume of the crosslinking agent.
5. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Stärke Maisstärke ist.5. Pressure thickener according to one of the preceding claims, characterized in that the starch is corn starch.
6. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das Veretherungsmittel Natriummonochloracetat und/oder Monochlor- essigsäure ist.6. Pressure thickener according to one of the preceding claims, characterized in that the etherifying agent is sodium monochloroacetate and / or monochloroacetic acid.
7. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das Vernetzungsmittel Epichlorhydrin ist.7. Pressure thickener according to one of the preceding claims, characterized in that the crosslinking agent is epichlorohydrin.
8. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß es mechanisch modifiziert ist, bevorzugt durch Walztrocknung. 8. Pressure thickener according to one of the preceding claims, characterized in that it is mechanically modified, preferably by roller drying.
9. Druckverdickungsmittel nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß es neben der zumindest einen Stärke zumindest ein weiteres natürliches und/oder synthetisches Verdickungsmittel enthält.9. pressure thickener according to one of the preceding claims, characterized in that it contains at least one additional natural and / or synthetic thickening agent in addition to the at least one starch.
10. Druckverdickungsmittel nach Anspruch 9, dadurch gekennzeichnet, daß das weitere Verdickungsmittel ausgewählt ist aus Natriumpolyacrylat, Natriumalginat und Mischungen derselben.10. Pressure thickener according to claim 9, characterized in that the further thickener is selected from sodium polyacrylate, sodium alginate and mixtures thereof.
11. Verwendung des Druckverdickungsmittels nach einem der Ansprüche 1 bis 10 als ein Druckverdickungsmittel in Kombination mit Reaktivfarbstoffen.11. Use of the printing thickener according to one of claims 1 to 10 as a printing thickener in combination with reactive dyes.
12. Verwendung nach Anspruch 10 auf natürlichen Fasern, wie Baumwolle und Viskose. 12. Use according to claim 10 on natural fibers, such as cotton and viscose.
EP08801247A 2007-09-10 2008-08-28 Starch-based printing thickening agent for reactive printing Withdrawn EP2188437A1 (en)

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DE102007043109A DE102007043109A1 (en) 2007-09-10 2007-09-10 Starch-based pressure thickener for the reactive pressure
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CN108708192A (en) * 2018-06-08 2018-10-26 山东港源海洋生物工程有限公司 A kind of reactive printing gum and preparation method thereof

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GB1240404A (en) * 1969-02-12 1971-07-21 Scholten Honig Res N V Textile printing pastes
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Publication number Priority date Publication date Assignee Title
WO2013071881A1 (en) * 2011-11-17 2013-05-23 长胜纺织科技发展(上海)有限公司 Cold transferring printing thickener and preparation method of color paste thereof
CN108708192A (en) * 2018-06-08 2018-10-26 山东港源海洋生物工程有限公司 A kind of reactive printing gum and preparation method thereof

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