EP0522395B1 - Use of anionic cellulose mixed ethers in textile printing - Google Patents
Use of anionic cellulose mixed ethers in textile printing Download PDFInfo
- Publication number
- EP0522395B1 EP0522395B1 EP92110957A EP92110957A EP0522395B1 EP 0522395 B1 EP0522395 B1 EP 0522395B1 EP 92110957 A EP92110957 A EP 92110957A EP 92110957 A EP92110957 A EP 92110957A EP 0522395 B1 EP0522395 B1 EP 0522395B1
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- European Patent Office
- Prior art keywords
- dyes
- cellulose
- printing
- good
- thickeners
- 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.)
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- 239000004753 textile Substances 0.000 title claims description 25
- 150000002170 ethers Chemical class 0.000 title claims description 9
- 229920006321 anionic cellulose Polymers 0.000 title claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 32
- 239000000975 dye Substances 0.000 claims description 23
- 229920002678 cellulose Polymers 0.000 claims description 15
- 235000010980 cellulose Nutrition 0.000 claims description 14
- -1 methylsulphoethyl Chemical group 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 239000000985 reactive dye Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 238000000518 rheometry Methods 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000000982 direct dye Substances 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 239000004368 Modified starch Substances 0.000 claims 1
- 229920000881 Modified starch Polymers 0.000 claims 1
- 229920002472 Starch Polymers 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 235000019426 modified starch Nutrition 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000049 pigment Substances 0.000 claims 1
- 239000004627 regenerated cellulose Substances 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 230000008719 thickening Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000006467 substitution reaction Methods 0.000 description 11
- 229920000297 Rayon Polymers 0.000 description 9
- 229920003086 cellulose ether Polymers 0.000 description 9
- YKCWQPZFAFZLBI-UHFFFAOYSA-N cibacron blue Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C(S(O)(=O)=O)C=C1NC(C=C1S(O)(=O)=O)=CC=C1NC(N=1)=NC(Cl)=NC=1NC1=CC=CC=C1S(O)(=O)=O YKCWQPZFAFZLBI-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229920000615 alginic acid Polymers 0.000 description 7
- 235000010443 alginic acid Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 101100361281 Caenorhabditis elegans rpm-1 gene Proteins 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
Classifications
-
- 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
- D06P1/46—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 natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
- D06P1/50—Derivatives of cellulose
Definitions
- the present invention relates to the use of anionic mixed cellulose ethers, preferably alkylsulfoalkylcellulose ethers, in particular methylsulfoethylcellulose ethers, as thickeners in textile printing.
- anionic mixed cellulose ethers preferably alkylsulfoalkylcellulose ethers, in particular methylsulfoethylcellulose ethers
- the composition of printing pastes in the textile sector is determined by the type of printing, the substrate, the fixing and the application method.
- all printing pastes contain thickeners.
- the thickenings have the task of giving the dye-containing, aqueous liquor a pumpable and printable consistency. On the one hand, it should be fluid and, on the other hand, it should be so immobile that it holds the dye in the place provided by the design and thus conveys a sharp contour.
- the thickener in the printing paste also takes on protective colloid and protective film functions. By regulating the moisture balance, it has a lasting influence on the color yield (P. Habereder, F. Bayerlein in: Handbuch der Textilhilhilstoff; Ed .: A.
- thickenings should have a long shelf life, with the addition of preservatives for economic and health reasons should be avoided as far as possible.
- thickenings must be compatible with the corresponding dyes and must not react with them.
- the thickenings In order to avoid faulty prints, which could be caused by clogging of the stencils, gauze or rotary stencils, the thickenings must be free of fibers and gel bodies.
- thickenings In order to avoid poor print quality, hardening of the grip on the printed areas and time-consuming and costly post-treatment processes, thickenings must be easy to wash out.
- thickenings should be available in a standardized manner and be as cheap as possible, since they do not give the textile material a higher value, but are washed out again.
- alginates The majority of the thickeners used in textile printing are the alginates, which are generally used in concentrations of 3 to 4%. They are easy to wash out, compatible with a range of dyes and largely stable in the range from pH 4 to 10. Alginates are incompatible with heavy metal salts, calcium and aluminum compounds and with basic dyes. As a biopolymer, alginate is easily broken down by microorganisms.
- Unprotected thickening usually lasts only 1 to 2 days, so that preservatives, preferably formaldehyde solutions, are added, but their use is extremely questionable due to their high risk potential.
- xanthans Of the thickeners used in textile printing, xanthans, emulsion thickeners, synthetic polymer thickeners and carboxymethylated polysaccharides are also of importance, but all of them are a number of Have disadvantages so that the desired effects cannot be achieved with a single thickener alone. For example, printing with emulsion thickening is falling sharply for reasons of price and ecology. In addition to their high costs, xanthans have insufficient stability against microbial degradation. Polymer thickeners are extremely sensitive to electrolytes, making them susceptible to hard water, anionic dyes and leveling agent salts.
- sodium carboxymethyl cellulose Na-CMC
- the commercially available sodium carboxymethyl celluloses generally only have degrees of substitution (DS values) from 0.3 to 1.4 (GI Stelzer, ED Klug, in: Handbook of Water Soluble Gums and Resins, ed .: RL Davidson McGraw-Hill, New York, 1980, pages 4-1). Because of the low degree of substitution, their use as a thickener leads to reactions with the reactive dye, so that poor color yields and handle hardening result. In order to prevent a possible reaction between the thickener and the reactive dye, specialties with degrees of substitution (DS) of 2.0 or higher are therefore used (DE-A-3 208 430, JP-A-5 9192-786).
- Carboxymethyl celluloses are soluble in cold and hot water, which, in addition to being easy to wash out, offers procedural advantages. Because of the simple viscosity settings, good prints can also be achieved at higher machine speeds (HB Bush, HB Trost, Hercules Chem., 60 , 14 [1970]). However, aqueous carboxymethyl cellulose solutions are easily broken down by microorganisms. Furthermore, their poor salt stability, in particular with respect to polyvalent cations and their ability to react with the dyes (direct dyes), is a considerable disadvantage.
- the anionic cellulose mixed ethers used according to the invention have excellent qualities and are soluble in water both as purified and unpurified (technical) products without gel bodies and fibers and have average overall degrees of substitution of 0.5 to 2.5, in particular> 1.
- the anionic mixed cellulose ethers produced by one of the processes listed above are used as thickeners in printing pastes in textile printing.
- the methylsulfoethyl celluloses used according to the invention are checked for their filterability prior to their application test in textile printing.
- the flow rate per unit time of an MSEC solution of a defined concentration produced under defined conditions is suctioned off by a polyethylene filter material with a defined mesh size and at a given negative pressure.
- the polyethylene gauze was of the type PE 74 (0.074 mm) (mesh size) "Estal Mono".
- the MSEC sample to be tested is dispersed with the Kotthoff mixing siren at 2,800 rpm for 3 minutes without loss.
- the quantities of MSEC used in the air-dry state and tap water of 25 ° C are specified in Table 1 for each viscosity level. After the dispersing time is 5 minutes 1 400 rpm further stirred. The resulting solution is then stored in a temperature bath of 25 ° C ( ⁇ 0.1 ° C) for 1 hour.
- Table 1 Amount of MSEC used depending on the viscosity level Nominal viscosity [mPa ⁇ s] Use of sample [g] / tap water [g] 2,000 30th 970 5,000 20th 980 10,000 15 985 20,000 13 987 30,000 11.5 988.5 40,000 10th 990
- test solution is stirred with the Kotthoff mixing siren - 1 minute at 1400 rpm. Then 500 ml (500 g) of the test solution are transferred to the funnel of the suction apparatus. The specified amount of test solution is drawn off through the polyethylene gauze at a vacuum of 0.67 bar.
- the measured filtration time for 500 ml of MSEC solution by the filtration apparatus described at 0.67 bar negative pressure is given. If the throughput time is more than 3 minutes, the test is terminated, stating the remaining amount of test solution in the test result.
- the methylsulfoethyl celluloses (examples MSEC 1-4) produced by the process according to the invention and used in textile printing have throughput times of ⁇ 10 s due to their excellent solution quality.
- Table 2 shows the characteristic data of the thickeners MSEC 1-4.
- Table 2 Characteristic data of the thickeners MSEC 1) DS-SE 2) DS-Me 2) Viscosity 3) [mPa.s] 1 0.44 0.90 5500 2nd 0.76 0.88 900 3rd 0.50 0.80 13000 4th 0.46 1.22 20000 1) Methylsulfoethyl cellulose 2)
- DS-SE Average degree of substitution by sulfoethyl groups
- DS-Me Average degree of substitution by methyl groups see. also: K. Balser, M. Iseringhausen, in Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 9, Verlag Chemie, Weinheim, 1983, pp.
- composition of the stock thickenings produced with MSEC 1-4 and Lamitex M5 is shown in Table 3, that of the printing pastes is shown in Table 4.
- the influence of the shear rates on the viscosity (pseudoplastic behavior) of the stock thickenings or printing pastes can also be seen from the tables.
- the printing pastes used for reactive dyes consist of thickeners, urea, alkali and oxidizing agents. Mixtures of commercially available reactive dyes are used as dyes: Cibacron® yellow, Cibacron® red and Cibacron® blue (Ciba-Geigy); 90 parts of the respective stock thickenings (A, C, E, G, I) are combined with 0.577 parts of a dye mixture (for composition, see Table 4) and distilled water.
- Table 4 Printing pastes Printing paste composition pH Viscosities 1) [m Pa ⁇ s] at 2.5 rpm 20 rpm 100 rpm 1. 90 parts A + 10 parts Cibacron Blue 3 R liquid (40%) 10.8 6,000 4,000 3,040 2.
- Table 5 shows the storage stability of the stock thickenings at room temperature using viscometric measurements (Brookfield RVT, spindle 6, 20 rpm). The pH stability and the viscosity stability of the printing pastes Brookfield RVT, spindle 6, 20 rpm) are shown in Table 6.
- Table 5 Storage stability of the stock thickening at room temperature Trunk thickening Viscosities 1) [mPa ⁇ s] right away after 3 days after 1 week after 2 weeks after 4 weeks A 7,000 4,300 2,700 1,900 1,100 C. 5,300 4,100 3,800 3,200 2,000 E 5,000 4,000 4,000 3,800 3,100 G 4,700 3,600 3,300 2,900 2,000 I. 5,300 4,300 4,300 3,700 2,200 1) Brookfield RVT, spindle 6, 20 rpm
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Description
Die vorliegende Erfindung betrifft den Einsatz von anionischen Cellulosemischethern, bevorzugt Alkylsulfoalkylcelluloseether, insbesondere Methyl-Sulfoethylcelluloseether als Verdickungsmittel im Textildruck.The present invention relates to the use of anionic mixed cellulose ethers, preferably alkylsulfoalkylcellulose ethers, in particular methylsulfoethylcellulose ethers, as thickeners in textile printing.
Die Zusammensetzung von Druckpasten im Textilbereich wird, unabhängig vom verwendeten Farbstoff, durch die Druckart, das Substrat, die Fixier- und die Applikationsmethode bestimmt. Neben Farbstoffen bzw. Chemikalien enthalten alle Druckpasten Verdickungsmittel. Die Verdickungen haben die Aufgabe, der farbstoffhaltigen, wäßrigen Flotte eine pump- und druckbare Konsistenz zu geben. Dabei soll sie einerseits fließfähig und andererseits so unbeweglich sein, daß sie den Farbstoff an der vom Dessin vorgesehenen Stelle festhält und somit einen scharfen Konturenstand vermittelt. Ferner übernimmt das Verdickungsmittel in der Druckpaste Schutzkolloid- und Schutzfilmfunktionen. Über die Regulierung des Feuchtigkeitshaushaltes beeinflußt es nachhaltig die Farbausbeute (P. Habereder, F. Bayerlein in: Handbuch der Textilhilfsmittel; Hgb.: A. Chwala, V. Anger, Verlag Chemie, Weinheim, 1977, Seite 621). Hieraus ergeben sich eine Reihe von Anforderungen, die an Verdickungsmittel und Verdickungen gestellt werden:
Verdickungsmittel und die daraus hergestellten Verdickungen sollen gut lagerfähig sein, wobei auf einen Zusatz von Konservierungsmitteln aus ökonomischen und gesundheitlichen Gründen möglichst verzichtet werden soll. Darüber hinaus müssen Verdickungen mit den entsprechenden Farbstoffen verträglich sein und dürfen nicht mit ihnen reagieren. Um fehlerhafte Drucke, die durch Verstopfungen der Schablonen, Gaze oder Rotationsschablonen entstehen könnten zu vermeiden, müssen die Verdickungen faser- und gelkörperfrei sein. Zur Vermeidung schlechter Druckqualitäten, Griffverhärtungen der bedruckten Stellen sowie zeit- und kostenintensiver Nachbehandlungsprozesse müssen Verdickungen gut auswaschbar sein. Schließlich sollten Verdickungen standardisiert lieferbar und so billig wie möglich sein, da sie dem Textilmaterial keinen höheren Wert verleihen, sondern wieder ausgewaschen werden.The composition of printing pastes in the textile sector, regardless of the dye used, is determined by the type of printing, the substrate, the fixing and the application method. In addition to dyes and chemicals, all printing pastes contain thickeners. The thickenings have the task of giving the dye-containing, aqueous liquor a pumpable and printable consistency. On the one hand, it should be fluid and, on the other hand, it should be so immobile that it holds the dye in the place provided by the design and thus conveys a sharp contour. The thickener in the printing paste also takes on protective colloid and protective film functions. By regulating the moisture balance, it has a lasting influence on the color yield (P. Habereder, F. Bayerlein in: Handbuch der Textilhilhilmittel; Ed .: A. Chwala, V. Anger, Verlag Chemie, Weinheim, 1977, page 621). This results in a number of requirements for thickeners and thickeners:
Thickeners and the thickeners produced from them should have a long shelf life, with the addition of preservatives for economic and health reasons should be avoided as far as possible. In addition, thickenings must be compatible with the corresponding dyes and must not react with them. In order to avoid faulty prints, which could be caused by clogging of the stencils, gauze or rotary stencils, the thickenings must be free of fibers and gel bodies. In order to avoid poor print quality, hardening of the grip on the printed areas and time-consuming and costly post-treatment processes, thickenings must be easy to wash out. Finally, thickenings should be available in a standardized manner and be as cheap as possible, since they do not give the textile material a higher value, but are washed out again.
Die Hauptmenge der im Textildruck eingesetzten Verdickungsmittel stellen die Alginate dar, die im allgemeinen in Konzentrationen von 3 bis 4 % eingesetzt werden. Sie sind leicht auswaschbar, mit einer Reihe von Farbstoffen verträglich und im Bereich von pH 4 bis 10 weitgehend stabil. Alginate sind unverträglich mit Schwermetallsalzen, Calcium- und Aluminiumverbindungen sowie gegenüber basischen Farbstoffen. Als Biopolymer wird Alginat leicht durch Mikroorganismen abgebaut.The majority of the thickeners used in textile printing are the alginates, which are generally used in concentrations of 3 to 4%. They are easy to wash out, compatible with a range of dyes and largely stable in the range from pH 4 to 10. Alginates are incompatible with heavy metal salts, calcium and aluminum compounds and with basic dyes. As a biopolymer, alginate is easily broken down by microorganisms.
Ungeschützte Verdickungen halten sich in der Regel nur 1 bis 2 Tage, so daß man Konservierungsmittel, vorzugsweise Formaldehydlösungen, hinzusetzt, deren Einsatz jedoch aufgrund ihres hohen Gefahrenpotentials in höchstem Maße bedenklich ist.Unprotected thickening usually lasts only 1 to 2 days, so that preservatives, preferably formaldehyde solutions, are added, but their use is extremely questionable due to their high risk potential.
Für einen Einsatz von Verdickungen im Textildruck in wärmeren Regionen, ist eine sehr gute Temperaturstabilität der Verdickungsmittel erforderlich. Bei der Verwendung von Alginaten kann es hierbei zu quantitativen Decarboxylierungen kommen. Das in den letzten Jahren immer arbeits- und kostenintensivere Verfahren zur Herstellung der aus anfallendem Seetang gewonnen Alginate, spiegelt sich zudem in hohen, deutlich gestiegenen Preisen wider, so daß nach preisgünstigen Ersatzmöglichkeiten gesucht wird.When using thickeners in textile printing in warmer regions, very good temperature stability of the thickeners is required. When using alginates, quantitative decarboxylation can occur. The increasingly labor-intensive and cost-intensive process for producing the alginates obtained from seaweed is also reflected in high, significantly increased prices, so that inexpensive alternatives are sought.
Von den im Textildruck verwendeten Verdickungsmitteln sind ferner Xanthane, Emulsionsverdickungen, synthetische Polymerisat-Verdickungsmittel und carboxymethylierte Polysaccharide von Bedeutung, die jedoch alle eine Reihe von Nachteilen aufweisen, so daß die gewünschten Effekte nicht mit einem einzigen Verdickungsmittel allein erreicht werden können. So ist zum Beispiel der Druck mit Emulsionsverdickungen aus Preis- und Ökologiegründen stark rückläufig. Xanthane weisen neben ihren hohen Kosten ungenügende Stabilitäten gegenüber mikrobiellem Abbau auf. Polymerisatverdicker sind extrem elektrolytempfindlich, wodurch sie anfällig gegenüber hartem Wasser, anionischen Farbstoffen und Stellmittelsalzen sind.Of the thickeners used in textile printing, xanthans, emulsion thickeners, synthetic polymer thickeners and carboxymethylated polysaccharides are also of importance, but all of them are a number of Have disadvantages so that the desired effects cannot be achieved with a single thickener alone. For example, printing with emulsion thickening is falling sharply for reasons of price and ecology. In addition to their high costs, xanthans have insufficient stability against microbial degradation. Polymer thickeners are extremely sensitive to electrolytes, making them susceptible to hard water, anionic dyes and leveling agent salts.
In den letzten Jahren hat es nicht an Versuchen gefehlt, Polysaccharide, insbesondere Natriumcarboxymethylcellulose (Na-CMC), als Verdickungsmittel im Textildruck einzusetzen. Die kommerziell erhältlichen Natriumcarboxymethylcellulosen weisen in der Regel lediglich Substitutionsgrade (DS-Werte) von 0,3 bis 1,4 auf (G.I. Stelzer, E.D. Klug, in: Handbook of Water Soluble Gums and Resins, Hgb.: R.L. Davidson McGraw-Hill, New York, 1980, Seite 4-1). Aufgrund des niedrigen Substitutionsgrades führt ihr Einsatz als Verdickungsmittel zu Reaktionen mit dem Reaktivfarbstoff, so daß schlechte Farbausbeuten und Griffhärtungen resultieren. Um eine mögliche Reaktion zwischen dem Verdickungsmittel und dem Reaktivfarbstoff zu unterbinden, werden daher Spezialitäten mit Substitutionsgraden (DS) von 2,0 oder höher eingesetzt (DE-A-3 208 430, JP-A-5 9192-786).In recent years there has been no lack of attempts to use polysaccharides, in particular sodium carboxymethyl cellulose (Na-CMC), as thickeners in textile printing. The commercially available sodium carboxymethyl celluloses generally only have degrees of substitution (DS values) from 0.3 to 1.4 (GI Stelzer, ED Klug, in: Handbook of Water Soluble Gums and Resins, ed .: RL Davidson McGraw-Hill, New York, 1980, pages 4-1). Because of the low degree of substitution, their use as a thickener leads to reactions with the reactive dye, so that poor color yields and handle hardening result. In order to prevent a possible reaction between the thickener and the reactive dye, specialties with degrees of substitution (DS) of 2.0 or higher are therefore used (DE-A-3 208 430, JP-A-5 9192-786).
Carboxymethylcellulosen sind in kaltem und heißem Wasser löslich, was neben der leichten Auswaschbarkeit verfahrenstechnische Vorteile bietet. Aufgrund der einfachen Viskositätseinstellungen lassen sich gute Drucke auch bei höheren Maschinengeschwindigkeiten erzielen (H.B. Bush, H.B. Trost, Hercules Chem., 60, 14 [1970]). Wäßrige Carboxymethylcelluloselösungen werden jedoch leicht durch Mikroorganismen abgebaut. Ferner ist ihre schlechte Salzstabilität, insbesondere gegenüber mehrwertigen Kationen und ihr Vermögen mit den Farbstoffen (Direktfarbstoffe) Reaktionen einzugehen, von erheblichem Nachteil. Es wurde daher versucht, durch Zusatz von Boraten während der Alkalisierung (EP-A-0 055 820), Mischveretherungen bzw. Erhöhungen des Substitutionsgrades (DE-A-3 303 153, US-A-4 426 518), ihre Stabilität gegenüber Elektrolyten und Bakterien sowie die Verträglichkeit gegenüber Farbstoffen zu verbessern.Carboxymethyl celluloses are soluble in cold and hot water, which, in addition to being easy to wash out, offers procedural advantages. Because of the simple viscosity settings, good prints can also be achieved at higher machine speeds (HB Bush, HB Trost, Hercules Chem., 60 , 14 [1970]). However, aqueous carboxymethyl cellulose solutions are easily broken down by microorganisms. Furthermore, their poor salt stability, in particular with respect to polyvalent cations and their ability to react with the dyes (direct dyes), is a considerable disadvantage. Attempts have therefore been made to add stability to electrolytes by adding borates during the alkalization (EP-A-0 055 820), mixed etherification or increasing the degree of substitution (DE-A-3 303 153, US Pat. No. 4,426,518) and bacteria and to improve the compatibility with dyes.
Die so hergestellten, durch mehrstufige Fahrweise nahezu vollständig veretherten Produkte führen zu einem deutlich verbesserten Eigenschaftsprofil der Carboxymethylcellulose (CMC). Solche hochsubstituierten Produkte erfordern jedoch eine mehrfache Wiederholung des Alkalisierungs- und Veretherungsschrittes, wobei, über alle Stufen betrachtet, sehr schlechte Substitutionsausbeuten resultieren, was komplexe und kostenintensive Herstellungsverfahren notwendig macht. (K. Engelskirchen, in Houben-Weyls "Makromolekulare Stoffe", Bd. E20/III, Georg Thieme Verlag, Stuttgart, 1987, S. 2072-2076).The products produced in this way, which are almost completely etherified by a multi-stage procedure, lead to a significantly improved property profile of carboxymethyl cellulose (CMC). However, such highly substituted products require a repeated repetition of the alkalization and etherification step, which, viewed over all stages, results in very poor substitution yields, which makes complex and costly production processes necessary. (K. Engelskirchen, in Houben-Weyl's "Macromolecular Substances", Vol. E20 / III, Georg Thieme Verlag, Stuttgart, 1987, pp. 2072-2076).
Aufgabe der vorliegenden Erfindung war es deshalb, Cellulosemischether als Verdickungs-, Dispergier- oder Bindemittel für die Textilindustrie bereitzustellen, die ausgezeichnete Qualitäten, d.h. sehr gute Löslichkeitseigenschaften besitzen und nicht die Nachteile der zur Zeit im Textildruck eingesetzten Verdickungsmittel aufweisen
Die nach der vorliegenden Erfindung im Textildruck einsetzbaren anionischen Cellulosemischether, bevorzugt Alkyl-Sulfoethylcellulosemischether, insbesondere Methyl-Sulfoethylcellulosemischether, weisen Substitutionsgrade bezüglich Sulfoethyl von DS = 0,01 bis 0,9 auf, besitzen einen mittleren Gesamtsubstitutionsgrad von DS >1 und können z.B. nach DE-A-3 742 104, DE-A-4 113 892 oder DE-A-3 742 106 hergestellt werden.It was therefore an object of the present invention to provide mixed cellulose ethers as thickeners, dispersants or binders for the textile industry which have excellent qualities, ie very good solubility properties and do not have the disadvantages of the thickeners currently used in textile printing
The anionic cellulose mixed ethers which can be used in textile printing according to the present invention, preferably alkyl sulfoethyl cellulose mixed ethers, in particular methyl sulfoethyl cellulose mixed ethers, have degrees of substitution with respect to sulfoethyl of DS = 0.01 to 0.9, have an average total degree of substitution of DS> 1 and can, for example, according to DE -A-3 742 104, DE-A-4 113 892 or DE-A-3 742 106.
Die so hergestellten, nach dem weiter unten beschriebenen Meßverfahren charakterisierten, gel- und faserfreien Cellulosederivate zeichnen sich durch ausgezeichnete Lösungsqualität aus und können als Verdickungs-, Dispergier- oder Bindemittel in der Textilindustrie eingesetzt werden und zeigen gegenüber den zur Zeit in der Textilindustrie verwendeten Verdickungsmitteln folgende Vorteile:
- 1. Ausgezeichnete Elektrolytstabilität, insbesondere gegenüber mehrwertigen Kationen, insbesondere Calciumionen.
- 2. Sehr gute Säure-, Alkali- und Temperaturstabilität.
- 3. Sehr gute Stabilität gegenüber mikrobiellem Abbau aufgrund homogener Veretherung der Cellulose.
- 4. Optimale Farbstoff-Fixierung durch sehr gute Auswaschbarkeit (Griff) des Verdickungsmittels und praktisch vollständige Abgabe des Farbstoffes an das Substrat.
- 5. Verbesserte drucktechnische Eigenschaften, wie Egalität und Standschärfe durch gel- und faserfreie Losungsqualität.
- 6. Sehr gute Verträglichkeit mit Farbstoffen und Chemikalien durch hohen Gesamtsubstitutionsgrad.
- 7. Problemlose Produktion der Celluloseether in großem Maßstab.
- 8. Einfache Technologie der Herstellung von Cellulosederivaten in Pulver- oder Granulatform.
- 9. Gute Umweltverträglichkeit der Celluloseether.
- 1. Excellent electrolyte stability, especially with respect to polyvalent cations, especially calcium ions.
- 2. Very good acid, alkali and temperature stability.
- 3. Very good stability against microbial degradation due to homogeneous etherification of the cellulose.
- 4. Optimal dye fixation through very good washability (handle) of the thickener and practically complete release of the dye to the substrate.
- 5. Improved printing properties such as levelness and sharpness due to gel and fiber-free solution quality.
- 6. Very good compatibility with dyes and chemicals due to the high degree of total substitution.
- 7. Trouble-free production of cellulose ethers on a large scale.
- 8. Simple technology of manufacturing cellulose derivatives in powder or granule form.
- 9. Good environmental compatibility of cellulose ethers.
Die erfindungsgemäß eingesetzten anionischen Cellulosemischether weisen ausgezeichnete Qualitäten auf und sind sowohl als gereinigte, wie auch ungereinigte (technische) Produkte gelkörper- und faserfrei in Wasser löslich und besitzen durchschnittliche mittlere Gesamtsubstitutionsgrade von 0,5 bis 2,5, insbesondere >1.The anionic cellulose mixed ethers used according to the invention have excellent qualities and are soluble in water both as purified and unpurified (technical) products without gel bodies and fibers and have average overall degrees of substitution of 0.5 to 2.5, in particular> 1.
Die verwendeten Cellulosemischether besitzen Viskositäten von 5 bis 80 000 mPa·s, insbesondere von 100 bis 30 000 mPa·s (gemessen in 2 gew.-%iger wäßriger Lösung bei einem Schergefälle von D = 2,5 s⁻¹ bei 20°C) und besitzen Transmissionswerte von mehr als 95 %, insbesondere mehr als 96 % (gemessen an einer 2 gew.-%igen wäßrigen Lösung in einer Küvette mit einer optischen Weglänge von 10 mm mit Licht der Wellenlänge λ = 550 nm).The mixed cellulose ethers used have viscosities of 5 to 80,000 mPa · s, in particular 100 to 30,000 mPa · s (measured in 2% by weight aqueous solution at a shear rate of D = 2.5 s⁻¹ at 20 ° C ) and have transmission values of more than 95%, in particular more than 96% (measured on a 2% by weight aqueous solution in a cuvette with an optical path length of 10 mm with light of the wavelength λ = 550 nm).
Die nach einem der oben aufgeführten Verfahren hergestellten anionischen Cellulosemischether werden erfindungsgemäß als Verdickungsmittel in Druckpasten im Textildruck eingesetzt.According to the invention, the anionic mixed cellulose ethers produced by one of the processes listed above are used as thickeners in printing pastes in textile printing.
In den nachfolgend aufgeführten Beispielen ist die Wirkung verschiedener erfindungsgemäß eingesetzter Methylsulfoethylcellulosen als Verdickungsmittel im Textildruck, einem handelsüblichen Natriumalginat (Lamitex M 5, Firma Protan/Norwegen) gegenübergestellt. Verglichen wurde Natriumalginat als 6 %ige und MSEC als 1,8-, 2,1-, 2,6- und 4,5 %ige Lösung, wobei in der Druckpaste Natriumalginat mit 3,3 und MSEC mit 1,0, 1,3, 1,6 und 2,9 % Anwendung fand. Gedruckt wurde per Labordrucker auf verschiedenen Baumwoll- und Zellwollqualitäten mit unterschiedlichen Druckbildern (Vollflächendruck, Konturendruck, Naß-in-Naßdruck-Verfahren, Nuancendruck) verschiedenen Farben und Variationen der Fixierbedingungen. Die Lösungen (Verdicker, Stamm, Druckpaste) wurden über einen längeren Zeitraum (teils bis zu 8 Wochen) hinsichtlich ihrer Stabilität, ihrer Rheologie und ihrer Farbechtheit überprüft.In the examples listed below, the effect of various methylsulfoethyl celluloses used according to the invention as a thickening agent in textile printing is compared with a commercially available sodium alginate (Lamitex M 5, from Protan / Norway). Sodium alginate was compared as a 6% solution and MSEC as a 1.8, 2.1, 2.6 and 4.5% solution, whereby in the printing paste sodium alginate with 3.3 and MSEC with 1.0, 1, 3, 1.6 and 2.9% were used. The laboratory printer printed on different qualities of cotton and rayon wool with different print images (full-surface printing, contour printing, wet-on-wet printing process, nuance printing), different colors and variations of the fixing conditions. The solutions (thickener, strain, printing paste) were checked over a longer period (sometimes up to 8 weeks) with regard to their stability, their rheology and their color fastness.
Um fehlerhafte Drucke zu vermeiden, werden die erfindungsgemäß eingesetzten Methylsulfoethylcellulosen vor ihrer anwendungstechnischen Ausprüfung im Textildruck auf ihre Filtrierbarkeit überprüft Hierbei wird die Durchflußmenge pro Zeiteinheit einer unter definierten Bedingungen hergestellten MSEC-Lösung einer definierten Konzentration bestimmt Abgesaugt wird durch ein Polyethylen-Filtermaterial mit definierter Maschenweite und bei vorgegebenem Unterdruck. Als Gerät wurde eine Kotthoff-Mischsirene "Modell M 52" mit 15 Speichen und Mischkopfeinsatz, ein Temperierbad (T = 25°C, Firma Haake D 8), eine Vakuumpumpe, eine Saugapparatur aus Metall und eine Oberschalenwaage (Genauigkeit: ± 1 g) aus Metall eingesetzt Die Polyethylengaze waren vom Typ PE 74 (0,074 mm) Maschenweite) "Estal Mono".In order to avoid faulty prints, the methylsulfoethyl celluloses used according to the invention are checked for their filterability prior to their application test in textile printing. The flow rate per unit time of an MSEC solution of a defined concentration produced under defined conditions is suctioned off by a polyethylene filter material with a defined mesh size and at a given negative pressure. A Kotthoff mixing siren "Model M 52" with 15 spokes and mixing head insert, a temperature bath (T = 25 ° C, Haake D 8), a vacuum pump, a suction device made of metal and an upper pan scale (accuracy: ± 1 g) were used as the device. made of metal The polyethylene gauze was of the type PE 74 (0.074 mm) (mesh size) "Estal Mono".
Die zu prüfende MSEC-Probe wird mit der Kotthoff-Mischsirene bei 2.800 UpM 3 Minuten verlustfrei dispergiert Die Einsatzmengen an MSEC im lufttrockenen Zustand und an Leitungswasser von 25°C sind in der Tabelle 1 für jede Viskositätsstufe festgelegt. Nach Ablauf der Dispergierzeit wird 5 Minuten bei 1 400 UpM weitergerührt. Anschließend wird die entstandene Lösung 1 Stunde in einem Temperierbad von 25°C (± 0,1°C) gelagert.
Nach Ablauf der Temperierzeit erfolgt ein Aufrühren der Prüflösung mit der Kotthoff-Mischsirene - 1 Minute bei 1 400 UpM. Anschließend werden 500 ml (500 g) der Prüflösung in den Trichter der Saugapparatur überführt. Die angegebene Menge Prüflösung wird bei 0,67 bar Unterdruck über die Polyethylengaze abgesaugt.After the tempering time has elapsed, the test solution is stirred with the Kotthoff mixing siren - 1 minute at 1400 rpm. Then 500 ml (500 g) of the test solution are transferred to the funnel of the suction apparatus. The specified amount of test solution is drawn off through the polyethylene gauze at a vacuum of 0.67 bar.
Als Prüfergebnis wird die gemessene Filtrationszeit für 500 ml MSEC-Lösung durch die beschriebene Filtrationsapparatur bei 0,67 bar Unterdruck angegeben. Beträgt die Durchlaufzeit mehr als 3 Minuten, wird die Prüfung unter Angabe der Restmenge an Prüflösung im Prüfergebnis abgebrochen. Die nach dem erfindungsgemäßen Verfahren hergestellten und im Textildruck eingesetzten Methylsulfoethylcellulosen (Beispiele MSEC 1-4) besitzen aufgrund ihrer exzellenten Lösungsqualität Durchlaufzeiten von <10 s.As a test result, the measured filtration time for 500 ml of MSEC solution by the filtration apparatus described at 0.67 bar negative pressure is given. If the throughput time is more than 3 minutes, the test is terminated, stating the remaining amount of test solution in the test result. The methylsulfoethyl celluloses (examples MSEC 1-4) produced by the process according to the invention and used in textile printing have throughput times of <10 s due to their excellent solution quality.
Tabelle 2 zeigt die charakteristischen Daten der Verdickungsmittel MSEC 1-4.
Die Zusammensetzung der mit MSEC 1-4 und Lamitex M5 hergestellten Stammverdickungen ist in Tabelle 3, diejenige der Druckpasten ist in Tabelle 4 aufgeführt. Aus den Tabellen läßt sich ebenfalls der Einfluß der Schergeschwindigkeiten auf die Viskosität (strukturviskoses Verhalten) der Stammverdickungen bzw. Druckpasten entnehmen.
Die für Reaktivfarbstoffe eingesetzten Druckpasten bestehen aus Verdickungsmittel, Harnstoff, Alkali und Oxidationsmittel. Als Farbstoffe werden Mischungen handelsüblicher Reaktivfarbstoffe eingesetzt: Cibacron® Gelb, Cibacron® Rot und Cibacron® Blau (Ciba-Geigy); jeweils 90 Teile der jeweiligen Stammverdickungen (A, C, E, G, I) werden mit jeweils 0,577 Teilen einer Farbstoffmischung (Zusammensetzung siehe Tabelle 4) und destilliertem Wasser zusammengegeben.
Tabelle 5 zeigt die Lagerstabilität der Stammverdickungen bei Raumtemperatur anhand von vikosimetrischen Messungen (Brookfield RVT, Spindel 6, 20 UpM). Die pH-Stabilität und die Viskositätsstabilitäten der Druckpasten Brookfield RVT, Spindel 6, 20 UpM) gehen aus Tabelle 6 hervor.
Mit Fertigdruckpasten aus Tabelle 4 werden unterschiedliche Substrate bedruckt. Da die Bindung Farbstoff-Cellulose und die Erzielung tiefer, brillanter und klarer Drucke durch gut vorbereitetes Material begünstigt wird, werden die verschiedenen Substrate unterschiedlich vorbehandelt Für den Druckvorgang wird eine 64-T-Schablone (Rechtecke) und eine Rakel mit dem Durchmesser 8 mm eingesetzt (Magnetstufe 6, Geschwindigkeitsstufe 3). Als Substrate werden Cotton, Schussatin (mercerisiert, gebleicht), Cotton-Renfore (gebleicht), Cotton-Viskose-Cretonne (gesenkt, abgekocht, gebleicht, laugiert), Cotton-Viskose-Cretonne (gesenkt, abgekocht, gebleicht) verwendet. Das Textilgut wird bei ca. 90°C getrocknet Bei der Sattdampffixierung (100 bis 102°C) beträgt die Dämpfzeit 8 Minuten (Mathis-Trockner). Das Substrat Cotton-Schussatin wird darüber hinaus durch Trockenhitze (Heißluft) fixiert (1 Minute bei 200°C, Mathis-Trockner). Der Auswaschprozeß erfolgt in drei Stufen:
- ◇ gründliches, kaltes Spülen,
- ◇ Behandlung in der Nähe der Kochtemperatur (10 Minuten),
- ◇ kaltes Spülen.
- ◇ thorough, cold rinsing,
- ◇ treatment near the cooking temperature (10 minutes),
- ◇ cold rinse.
Die Ergebnisse der unterschiedlichen Druckvorgänge sind in den Tabellen 7 bis 10 aufgeführt.
Aus den nachfolgend aufgeführten Wertetabellen ist die Überlegenheit der im Textildruck eingesetzten, erfindungsgemäß beanspruchten MSEC klar erkennbar.The superiority of the MSEC used in textile printing and claimed according to the invention can be clearly seen from the value tables listed below.
Die in den Tabellen verwendeten Fachausdrücke sind dem Cellulose- bzw. Textildruckfachmann bekannt und bedürfen keiner weiteren Erklärung. Verwiesen sei in diesem Zusammenhang auf die Kapitel "Textildruck" und "Textilfärberei" in Ullmanns Encyclopädie der technischen Chemie, Bd. 22, Seite 565 ff und Seite 635 ff (Verlag Chemie, Weinheim, 1982).
Claims (5)
- Use of anionic cellulose mixed ethers as thickeners or rheology improvers in textile printing.
- Use according to claim 1, characterised in that the anionic cellulose mixed ethers are alkylsulphoethyl celluloses, in particular methylsulphoethyl cellulose (MSEC).
- Use according to one of claims 1 or 2, characterised in that the thickener additionally contains starch, modified starch, sodium alginate, a gum of natural origin and/or carboxymethyl cellulose or mixtures thereof.
- Use according to one of claims 1 to 3, characterised in that union fabric, natural fibres or regenerated cellulose are used as the textile materials.
- Use according to one of claims 1 to 4, characterised in that oxidation dyes, sulphur dyes, anionic dyes, developed dyes, wool chrome dyes, substantive dyes, copper dyes, metallic complex dyes, dispersion dyes, pigments, but in particular reactive dyes are used as the dyes.
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DE4122869 | 1991-07-11 | ||
DE4122869A DE4122869A1 (en) | 1991-07-11 | 1991-07-11 | USE OF ANIONIC CELLULOSE MIXERS IN TEXTILE PRINTING |
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EP0522395A1 EP0522395A1 (en) | 1993-01-13 |
EP0522395B1 true EP0522395B1 (en) | 1994-12-14 |
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DE3742104A1 (en) * | 1987-12-11 | 1989-06-22 | Wolff Walsrode Ag | SULFOETHYL CELLULOSE WITH EXCELLENT SOLUTION QUALITY AND METHOD FOR THE PRODUCTION THEREOF |
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1991
- 1991-07-11 DE DE4122869A patent/DE4122869A1/en not_active Withdrawn
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Title |
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M. PETER & H. K. ROUETTE:'Grundlagen der Textilveredlung', Dezember 1989, DEUTSCHER FACHVERLAG, FRANKFURT AM MAIN, S. 297,298,558-564,620-629 * |
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