FI104972B - Highly substituted carboxymethylsulfoethylcellulose ethers, process for their preparation and their use in textile printing pastes - Google Patents

Abstract

Carboxymethylsulphoethylcellulose with a degree of substitution of 1.4 to 2.2 is prepared in a two-stage process. After the first stage, the product is milled to a powder which has a grading limit of 100% </= 2.0 mm. This mixed cellulose ether is used as thickener in textile printing.

Description

104972

The present invention relates to carboxymethylsulfoethylcellulose ethers prepared by the two-step process and their use as thickeners in textile printing dyes.

Ink (printing paste) means a ready-made combination suitable for printing, consisting of a toner and other components necessary for printing. Of these components, mention should be made primarily of a thickener whose function is to provide a viscosity suitable for printing inks, since easy running wool dye solutions tend to spread and therefore cannot repeat the outlines sharply. In addition, the thickeners act as a protective colloid and protective film in the printing paste, regulating the moisture conditions in the printing paste, thereby continuously affecting the color yield 20 (B. Habereder, F. Beierlein, Handbuch der Textilhilfsmittel, A. Chwala, V. Anger, Verlag Chemie). , Weinheim, 1977, p. 621). The book discloses a number of weighing agents for thickeners or thickened mixtures; tims: • · · .j. 25 The thickened mixtures must be compatible with the

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; . ·, With dyestuffs and must not react with • · ·! IV dyes. For example, reaction dyes contain such reactive groups which, under dyeing conditions, react with the substrate in the presence of alkali and attach 30 dyes via a covalent bond (H. Zollinger, · ·

Angew. Chem., 73, 125 (1961)). Thickening agents having a structure similar to that of the substrate to be stained are then normally unsuitable.

, ···, In order to avoid spurious printing, which may be due to clogging of the trimmers, gauzes or rotary trimmers, the thickener must not contain any fibers or gels.

Thickening agents and thickened mixtures made from them must have good storage stability. The use of preservatives for this purpose cannot be considered acceptable.

In order to avoid poor printing, hardening of printed areas and time-consuming and expensive post-processing processes, it is necessary to be able to remove the thickener from the product by simple post-processing.

The thickened alloys must be readily available, supplied in standard quality and as cheap as possible since they do not add much value to the textile material but are rinsed away.

Of the numerous thickeners used in textile printing, alginates form the vast majority (Ciba-Rundschau, No. 1, 19-34 (1969)). The alkali salts of alginic acids, which generally have a working concentration of 3 to 4%, have the advantage that they can be very easily removed by washing. The alginates are compatible with many dyes and are quite stable over a pH range of 5 to 10. At higher pH values, transient preliminary depolymerization has been observed (A. Hang et al., Acta Chem. Sacand., 21, 2859 (1967)). ). The alkali alginates 25 are known to be incompatible with heavy metal salts, calcium. with aluminum and aluminum compounds, which require the use of complexing agents. As a biopolymer, alginate is readily degraded by microorganisms. Unprotected thickeners are generally stable for only 1 to 30 days, so preservatives such as formaldehyde solutions or phenols must be added to the thickened compositions.

When using thickened mixtures in warmer areas, thickeners require very good heat. ··. durability. The alginates may then undergo complete decarboxylation. The cumbersome and expensive methods for extracting alginate from 3 sensitive seaweed are reflected in the high cost, so one wants to obtain cheaper substitutes.

Of the thickeners used in textile printing 5, besides alginates, xanthanes, thickened emulsions and synthetic polymeric thickeners are all important, but all have a number of downsides, so that the desired effects cannot be achieved with a single thickener. Thus, for example, printing on thickened emulsions has significantly reduced for cost and ecological reasons. In addition to its high price, xanthanes are characterized by insufficient resistance to the degradation action of microorganisms. Polymer thickeners are extremely sensitive to electrolytes, making them particularly sensitive to hard water, anionic dyes and control salts.

In recent years, polysaccharides, especially sodium carboxymethylcellulose (Na-CMC), alone or in mixtures (EP-A 0 106 228, DD 158 403, SU 1 320 305-A, J 60 215 881-A, J 60 052) have been increasingly used as thickeners in textile printing. 685-A, J 60 039 491-A, DE 3 246 676-A, J 57 061 780, DD 148 342, U.S. Pat. No. 4,063,018). The degree of substitution (DS value) for commercially available sodium carboxymethylcellulose is generally 0.4 to 1.2% (≤1)! 25 (G. I. Stelzer, E. D. Klug, Handbook of Water

Soluble Gums and Resins, ed. R. L. Davidson, «· ·

McGraw-Hill, New York, 1080, pp. 4 - 1). Due to the low degree of substitution, the use as a thickening agent also results in reactions with the reaction dye. Reactive dyes deactivated in this manner are often introduced into substrate v (P. Bajaj et al., J. Macromol. Sci. Rev. Macromol. Chem., 1984, C 24 (3), 387 et seq.). The result is poor color yield and hardening of the color points. Thus, in order to achieve good wet resistance, non-covalently retained toner particles must be removed by intensive and laborious washing operations.

Therefore, to prevent a possible reaction between the thickener and the reaction dye, selected substances having a degree of substitution of about 2.0 or substantially higher are used (DE 3 208 430, US-PS 4 426 518, J 62 177 287-A, J 58 197 383-A).

The multi-step procedure yields almost completely etherified products with a marked improvement in the performance profile 10. However, the preparation of such heavily substituted products as described, e.g., in U.S. Patent No. 4,426,518, requires multiple iterations of the alkalization and etherification steps, in which the substitution yields are very poor at all stages and additionally necessitate the use of complex and expensive manufacturing methods. MU Mahmud, Acta Polym., 38 (1987) (3), 172; RR

McLaughlin, J. H. E. Herbst, Can. J. Res., 28 B (1950) 731; K. Engelskirchen in Houben-Weyl, "Mak-20 romolekulare Stoffe", Vol. E 20 / III, Georg Thieme-Verlag, Stuttgart, 1987, p.

All solutions of carboxymethylcellulose are: characterized by poor salt resistance, particularly with respect to polyvalent cations (e.g., calcium ions). When washing pressurized textile fabric with hard water, the thickener may precipitate in a detrimental manner to the fibers.

It is therefore an object of the present invention to provide an improved cellulose derivative as a thickener, dispersant or binder or rheology enhancer for the textile industry, in particular the textile head! - ··· ... * for natus. It has been claimed that the product has excellent solubility and has a marked improvement in electrolyte resistance compared to prior art (alginate, CMC). In addition, a simple and particularly economical process must be provided for the preparation of the above-mentioned cellulose derivatives, especially carboxymethylsulfoethylcellulose (CMSEC) having a total degree of substitution below 2.2. In this way, the printing drawbacks associated with the thickeners currently used in textile printing, in particular the low-substituted CMCs, can be avoided.

When printed, the product must have sufficient affinity and / or better properties than alginate. Surprisingly, it has been found that carboxymethylsulfoethylcellulose derivatives having a degree of substitution between 1.4 and 2.2, particularly between 1.5 and 2.1, eliminate the drawbacks of the prior art.

Ionic cellulose mixed ethers having a sulfo-foalkyl, especially a sulfoethyl substituent, are described in the patent literature.

U.S. Patent 2,132,181 describes a process for the preparation of polysaccharide compounds. Ionic cellulose-lozenge mixed ethers are prepared in a multi-step manner by carrying out the alkalization in the first step (mercerization alkali). Subsequent etherification with sodium vinyl sulfonate and methyl chloride, ethyl chloride, ethyl j: lene oxide or chloroacetic acid is carried out in one or two steps. Reaction of sodium vinyl sulfonate m ···. 25 preferably occurs in a mixer at about 60 ° C.

• «·«:. ·. This method employs an extremely large amount of lye • # «··, ·. on the one hand, leading to considerable side reactions and, on the other hand, making these products extremely uneconomical. In addition, experience shows that the reactions in the laboratory mixer have a low solubility, i.e., a high proportion of fiber and gel bodies. There is no mention of product quality, degree of substitution and viscosity of solutions.

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Among the water-soluble cellulose acetic ethers described in DE-OS 3 147 434, DE-A 3 306 621, DE-OS 3 316 124 and DE-OS 3 417 952 are described e.g. ionic methylcellulose mixed ethers having carboxyalkyl, sulfonoalkyl and phosphonoalkyl groups. Products whose viscosity, degree of substitution, yield and solubility are not further described are prepared either in dimethyl ether alone or in dimethoxyethane or in a mixture of alkanols, alkanediols and / or alkoxyalkanols.

The preparation of carboxymethylsulfoethylcellulose ethers having a viscosity of 5 to 60,000 mPa1s, very good solubility and a total degree of substitution of less than 2.8 (DSBU1fioethyl 0.15 to 0.3; The etherification is preferably effected by the simultaneous addition of reagents which donate carboxy and sulfoethyl groups. In this way, the aim is to provide products with very good salt and acid resistance by a cost-saving process. The exemplified CMSEC compounds have very good solution, salt and acid resistance, but their viscosity is extremely low due to the process. The total degree of substitution of these low-substituted products is well below 1.0, which equates to 25 known in the literature that:. in the case of box-methylation in single-step etherification processes, the degree of substitution c · '.. I is generally relatively problem-free up to only about 1.0 (see, for this, «i ·• e.g. by K. Engelskirchen in Houben-Weyl," Macro- 30 Molecular Stoffe, vol. E 20 / III, p. 2074, published by A. Barth '... 1 and J. Falbe, Georg Thieme Verlag, Stuttgart / New York, 1987).

: V. JP Application Publication Sho 63-182301 describes the process of ···. method for the preparation of a CMSEC. The preparation is carried out as a single-pot process by · · · · · · · · · · ·

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7 104972 and carboxymethylated in a second reaction series and finally purified. The product is characterized by a sulfoethyl substitution degree of 0.4 to 1.0 and a carboxymethyl substitution degree of 0.2 to 1.0 and has an excellent electrolyte resistance. It is useful as an adjuvant for the introduction of petroleum deposits.

The CMSECs prepared according to DE-A-3,742,106 have a transmission value T greater than 95% in a 2% w / w solution (lambda = 550 nm, cuvette op-thickness 10 mm). The average total degree of substitution satisfies the formula ^ 1 - (N, N) carboxymethyl (N 1) -6 (D 5 -fluoroethyl = 0.1 - 1; DScarbo-ethyl-ethyl = 0.3 - 1.2).

The products can be used as thickeners or water retention agents in the petroleum and building materials industry and as thickeners or stabilizers in detergents and cosmetics. CMSECs 20 are also useful as dispersants and suspending agents, and as adjuvants and viscosity enhancers in aqueous systems, e.g., stabilizers, dispersants, and suspending agents in emulsion and suspension polymerization.

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• · · 25 SU publication 794 098 describes the use of CMSEC • · · ·:. in the printing of textile materials consisting of acetate or viscose fibers, natural or synthetic • polyamide fibers. The patent relates to the use of MSEC with DScarboethyl methyl = 0.4-0.55 and DSeulphoethyl-0.1-0.30 0.25 as a viscosity enhancer in textile printing dyes.

However, the solubility of this CMSEC described in this patent is extremely poor. The transmission of a 0.5% aqueous solution is only 89.5%, indicating a high gel and, above all, fiber content. Such products

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I f I · I f «« I «I · 8 104972 pruners, gauzes, or rotation trimmers and thus cause printing errors.

DE-A-3,742,104 describes a one-pot process for the preparation of sulphoethylcelluloses having excellent solubility. The average degree of substitution (DS) is then in the range of DS - 0.4 to 1.4. The products are useful in brushes and spray paints and cosmetics.

The 10 simple, inexpensive methods described by CMSEC according to the invention provide products which, at substantially lower levels of total substitution as compared to prior art, achieve improved printing results compared to those commonly used in textile printing (alginate, CMC).

Surprisingly, it has been found that carboxymethyl sulfoethylcellulose having a degree of substitution between 1.4 and 2.2, particularly between 1.5 and 2.1, eliminates the drawbacks of the prior art if the product is prepared as follows: 1. Carboxymethylcellulose (CMC), preparation of foethylcellulose (SEC) or carboxymethylsulfoethylcellulose (CMSEC) according to the suspension method:: to a total degree of substitution of about 0.7 to about: 0.95.

2. Grinding of the CMC, SEC, or CMSEC thus obtained. after cleaning and drying to a sieve size <2.0 mm I · I v: · [·.

• · 3. further etherification of the CMC, SEC or CMSEC in the waste etherification process (eg semi-dry, suspension method) to a CMSEC with a total degree of substitution of · ··· *, 4 to 2.2, in particular 1.5 to 2.1.

i · · 4. Dry CM of the CMSEC compound obtained according to 1-3. partial or complete removal of the reaction by-products. After this, finish in the usual and well-known manner.

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9 104972

The heavily substituted CMSEC produced by the process described above is useful as a thickener or a Theology enhancer in textile printing and is an alternative to alginate and CMS thickeners.

The CMSEC produced by the process of the invention has the advantage of minimal reagent consumption (high yield and reduced total substitution degree), high concentration of active agent after purification after the first reaction step, and overall a simpler manufacturing process compared to the prior art.

The following examples further describe the process for the preparation of the CMSEC compound described in accordance with the invention and the use of such products as thickeners in textile printing.

As described below, the products are characterized by their viscosity, degree of substitution, water-soluble proportion and transmission. Viscosity is determined using a rotary viscometer (Haake) type RV 100, system M 500, sensor MV, DIN 53 019 with a shear rate D of 2.5 s-1 (t 20 ° C). The degree of carboxymethyl substitution is determined according to ASTM-D 1439-83a / Method B. The degree of substitution JJ / achieved by the sulfoethyl groups is determined by titration with Ehrenberger / Gorbach with barium perchlorate using Thorin 25 as an indicator (Ehrenberger / Gorbach: Methoden der organizchen Elementar).

MCI

; und Spurenanalysis, Verlag Chemie, Weinheim, 1973, p. 223).

For titration, dissolve according to Schöninger (Heraeus *

Druckschrift EW-F 1.6.1 (Method 1)). Transmission of solutions is measured using a Hitachi spectrophotometer Model 101, 30 Hitachi Ltd., Tokyo / Japan, in a glass cuvette with an optical thickness of 10 mm (lambda = 550 nm), 2% by weight. • · · '... · solution in distilled water.

I '.' · The carboxymethylsulfoethylcellulose prepared according to the invention is used as a base for printing ink in textile printing. In this application, nitro 10 104972 is preferably used alone, but can also be used in admixture with other basic materials for natural or semi-synthetic printing inks for textile printing, such as, for example, sodium-5-alginate, starch, modified starches, guar gum , locust bean kernel flour, acacia, chrysanthemum, tragacanth, tamarind! and / or cellulose ethers, in particular high-quality carboxymethylcellulose ethers or fully synthetic thickeners such as polymer thickeners, wherein the amount of CMSECs claimed in the invention must not be less than 10%, otherwise the benefits of the invention (salt, pH) durability, print quality, etc.).

Synthetic fibers, natural fibers, interwoven fabrics or cellulose regenerates may be used as textile materials. Dyes used are, for example, oxidation, sulfur, developmental, wool, chromium, straight, acid, dispersion, naphthol, type, metal complex 20 dyes, pigments or commercial products consisting of a mixture of the developmental dye coupling component and the diazoamine compound. , however, in particular reaction colors::: substances.

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Transmission of carboxymethylcelluloses or carboxymethylsulfoethylcelluloses mentioned in the Examples; . ·. pig values are £ 96%; the water-soluble proportion is 2 99.9%.

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EXAMPLES EXAMPLE 1 27.5 kg of finely ground pulp (95% solids content) was suspended in 605 liters of isopropanol and 12 liters of water in a thermostated reactor under nitrogen. ·· ... · pee guard. After addition of 16.3 kg of sodium hydroxide granules and 44.3 kg of a 30% sodium vinyl sulfonate solution, the mixture was alkalized for 80 minutes at 20-25 ° C. Warm-35 was heated to 75 ° C in 40 minutes and the reaction temperature.

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u 104972 75 ° C was maintained for 180 minutes. It was then cooled to 65 ° C and 24.1 kg of 80% monochloroacetic acid were added over 20 minutes. Warmed to 75 ° C for 20 minutes and then etherified at this temperature for 120 minutes. The batch was cooled and isolated by centrifugation. The product was slurried in 600 liters of 85% methanol, desalted by centrifugation in 500 liters of methanol, dried at 70 ° C and finally ground in a knife cutter. The degree of substitution of the carboxymethylsulphoethylcellulose carboxymethyl groups was 0.75 and that of the sulfoethyl groups 0.35. The purified product had a viscosity of 5,740 mPa1s (2% w / w solution, rotary viscometer type RV 100, M 500 system, MV according to DIN 53 019, D = 2.5 s 11, 15h to 20 ° C). For the next reaction, 14 kg of the CMSEC described above (solids content 93.6%) and 19.6 kg of isopropanol were added to an aura bath mixer under a nitrogen shield. By spraying and stirring, 10.1 kg of a 50% solution of brine was added. Subsequently, the alkali was alkalized for 80 minutes at about 25 ° C. 7.1 kg of 80% monochloroacetic acid were added by spraying. Warmed to 75 ° C for 60 minutes and maintained for 120 minutes. The batch was dried at 70 ° C. Carboxymethyl Sulphide: produced by carboxymethyl groups of foamethylcellulose

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The? 25 substitution ratio was 1.40. The corresponding value for the sulfoethyl groups lllt:, ·, was 0.32. The purified product had a viscosity of 1 · · · · 100 V mPa · s. Characteristic values for CMSEC are expressed in • f *,.! Table 1.

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Example 2 290.5 parts of a commercially available CMC powder (Walocel® CRT 30,000 P (92.95% solids solids)) were dispersed in a suitable ··· thermostable reactor under nitrogen shielding to 2,193 parts of isopropanol, to 75 parts Water, and 192.8 parts of a 30.5% aqueous solution of sodium vinyl sulphonate and stirred for 15 minutes. This i i v t • 1 f • · · • f I 4

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After 1049723 63.3 parts of sodium hydroxide granules were added and alkalized for 30 minutes at 25-30 ° C. The mixture was heated to 75 ° C for 30 minutes and the reaction temperature maintained at 75 ° C for 150 minutes. After allowing to cool to about 25 -5 ° C, another 63.3 parts of sodium hydroxide was added and alkalized for a further 30 minutes at 25-30 ° C. 189 parts of 80% aqueous monochloroacetic acid solution were added dropwise and with stirring. Thereafter, the mixture was warmed to 75 ° C for 30 minutes and the etherification was continued for 10 150 minutes at 75 ° C. The product was isolated from the suspension and dried at room temperature and ground. The degree of substitution by the sulfoethyl groups of CMSEC was 0.25 and that of the carboxymethyl groups was 1.58. The viscosity of the product was 4,300 mPa * s.

15 Example 3

137 parts of the finely ground, bleached, refined liner pulp (solids content 94.8%) were dispersed in a suitable stirrer thermosetting reactor under nitrogen shielding to 2,193 parts of isopropyl panol, 136.5 parts of 30.5% sodium vinyl sulphate and water and stirred for 15 minutes. Then 89.6 parts of sodium hydroxide granules were added and alkalized for 80 minutes at 25-30 ° C. The heating was heated to 75 ° C for 30 minutes and the reaction temperature 75 ° C to 25 ° C maintained for 150 minutes. 133 parts of 80% aqueous monochloroacetic acid were added dropwise to the hot mixture. After a further 150 minutes at 75 ° C, cooled to 25-30 ° C, the product was isolated and washed desalted with 70% methanol.

The product was dried at room temperature and then milled. the degree of substitution obtained by the carboxymethyl groups of the product obtained was 0.83. The viscosity • · * of the purified product was 5,900 mPa * s.

To continue etherification from the first step: the CMSEC obtained was dispersed in a suitable stirrer in a suitable thermostable reactor under nitrogen shield in 2,193 parts of isopropanol and 210 ml of water with a suitable stirrer and stirred for 15 minutes. After the addition of 73.5 parts of sodium hydroxide granules, the mixture was alkalized for 30 minutes at 25-30 ° C. After addition of 109.1 parts of 80% monochloroacetic acid, the mixture was heated to 75 ° C for 30 minutes and the reaction temperature maintained at 75 ° C for 150 minutes. The product was isolated after cooling to room temperature. The CMSEC was dried at room temperature and ground. The degree of substitution of the product with sulfoethyl-10 groups was 0.25 and the degree of substitution of carboxymethyl was 1.42. The viscosity of the purified product was 1,900 mPa * s. Characteristic values for the CMSEC are shown in Table 1.

Example 4 127 parts of the finely milled, bleached, refined liner pulp were dispersed in 2,193 parts of isopropanol in a suitable stirrer thermostated reactor. After addition of 88 parts of sodium hydroxide granules in 210 parts of water, the mixture was alkalized for 80 minutes at 20 to 30 ° C. 130 parts of 80% aqueous monochloroacetic acid solution were added. Warmed to 70 ° C for 30 minutes and maintained for 120 minutes.

. A further 88 parts of sodium '··' hydroxide granules were then added to the hot mixture followed by continuous 130 parts of 80% aqueous monochloroacetic acid solution for 120 minutes. The etherification was continued for another 120 minutes at 70 ° C. The product was isolated and the reaction by-products were removed-

was washed by washing with 70% methanol. CMC

dried at room temperature and ground. The degree of substitution provided by the carboxyl 30 methyl groups was 1.73.

-. ···. The viscosity of the purified product was 19,000 mPa * s.

• ·. ···. In order to improve the solubility of the thickener

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In textile printing, it is advisable to mill the products before use and screening so that 100% £ 0.5, especially £ 0.4, especially S 0.35 mm.

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The milling after the first and possibly the second stage is carried out by dry or wet milling. Rollers, ball, impact and centrifugal, shower or vibratory mills and the like can be used as mill types.

Gel and fiber-free cellulose derivatives prepared by the process of the invention characterized by the measuring method described below are characterized by excellent solubility and can be used as dispersants, binders or thickeners, or as rheology improvers in the textile industry, especially in the textile industry. Cellulose lozenge ethers are excellent in quality and soluble in water without gelling or fiber formation, both as purified, partially purified and unpurified (technical) products, with viscosities in the range of 10 to 50,000 mPa * s (measured by rotating viscosity 2 wt.% shear rate D - 2.5 s "at 20 ° C) and transmission values greater than 95%, particularly greater than 96% (measured from 2% w / w aqueous solution in a cuvette having an optical thickness of 10 mm and a wavelength of 550 nm Water soluble content was over 99.9%.

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The following examples compare the effect of various carboxymethylsulfoethyl cellulose ethers and commercial sodium alginate (Lamitex M5, Protan / Norway) used as thickeners in textile printing according to the invention. Sodium alginate as a 6% solution was compared with crude, i.e., technical CMSECs or purified carboxymethyl cellulose (CMC 4 (control sample)). The viscosity of the products was adjusted in the same aqueous solution, i.e., the viscosity was about 30,000 mPa1s (Brookfield RVS, spindle 4, 20 rpm).

The composition of the thickened masterbatches made with carboxymethylsulfoethylcellulose ethers or carboxymethylcelluloses is shown in Table 2. The Pai-15 sponges are obtained by mixing a predetermined amount of each thickened masterbatch (90 parts) and a portion of the dye (10 parts) and distilled water. A commercial reaction dye (Cibacron Turkis PG 3R (40%)) was used as the dye.

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Table 2

Composition of thickened masterbatches

Ingredients of Thickened Base Thickened Base Mixtures11 A B C D E F

5 Lamitex M52) 6% - 550 - - 275 CMSEC 3 8.5 -% - 500 - CMS EC 2 8 -% - - 500 - - - CMSEC 1 9 -% - 500 CMC 4 2.5% - 700 350 10 Lyoprint APR 3) 3 3 3 3 3 3

Lyoprint RGR 4) 10 10 10 10 10 10

Urea 180 180 180 180 180 180

NaHC03 25 25 25 25 25 25

Permutite Water 232 282 282 282 82 157 15 Total 1000 g ^ Declared in parts by weight 2) Lamitex M5 contains 5 g / kg sodium hexametaphosphate (Calgon T) and 5 g / kg formalin (37%) 3} Antifoam, BASF / Ludwigshafen 20 4) Hapetin, BASF / Ludwigshafen

Ready printing pastes were subjected to printing tests using cotton fabric satin (mercerized, bleached) as the substrate. The textile material was dried for about 10 minutes at 102-105 ° C (fixation with saturated steam (Mathis dryer)) and fixed in a dry

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Mathis-dryer). The washing was carried out in three stages: * ·; ·, (a) thorough rinsing in cold 30 (b) close to boiling (10 min) ... (c) rinsing in cold.

'\\\ Color intensity, penetration, hue, sense · * ·; ·', and smoothness were evaluated using a 64-T trimmer (rectangle) and a Rake, 8 mm diameter (magnet degree • · 35 3, velocity 3) ( room flat film weight). Positioning * .. · A 68-T trimmer and a crude, 8 mm diameter (magnet grade 3, velocity grade 3) were used to estimate positioning accuracy.

'···' The printing results are shown in Table 3.

18 104972

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The terms used in the tables are familiar to one of ordinary skill in the art of cellulose and textile printing and are not further explained by Kalpa. Reference is made in this connection to the figures "Textildruck" and "Textilfärberei" in 5 Ullmanns Enzyklopädie der Technischen Chemie, Vol. 22, p. 565 et seq. (Verlag Chemle, Weinheim, 1982).

The superiority of the CMSECs used in textile printing, described in accordance with the invention, is clearly shown in the following table. In addition to the known electrolyte and pH resistance in the literature (see, e.g., US-PS 2,811,519, J 63182-301A and EP 0 319 865.A2), these products include e.g. The following benefits.

15 Table 4

Exemplary Comparison Between Conventional Thickening Agents Used in Textile Printing and Cellulose Ethers Described in accordance with the Invention 20 Parameter Alginate CMSEC 4 CMC 4 (Reference _ (Protan) _ (Invention) Example) _ 1. Preservation (Formalde strictly does not claim essential hyd) essential «· ·« «·. 2. Shear resistance good good good 25 ·; · 3. Smoothness- good good ····: · · · · ·; 4 · Positioning accuracy good good good · · · · · ίρίΣ 5. printed pad good very bad 30 feel (washability) good:: 6. penetration vessel good good «» ·. 7. Color tone good good good · · f * 8. repeatability bad good good 35: ·, 9. electrolyte and bad very bad · · «pH resistance good« «• · • t ·

Claims (7)

104972 Carboxymethylsulfoethylcellulose (CMSEC), characterized in that the CMSEC is prepared by a two-step process comprising the following steps: 10 degrees of female substitution to about 0.7 to about 0.95; 2. the CMC, SEC, or CMSEC thus obtained is ground, after purification and drying, to a mesh size of 2.0 mm; Carboxymethyl according to claim 1; sulfoethyl cellulose, characterized in that it is ·. 2% by weight of an aqueous solution of viscous material. 25 t is from 10 to 50,000 mPa.s (rotating viscometer; shear, seasonal speed D = 2.5 s -1, T = 20 C). • · · V. '.' Carboxymethylsulfoethylcellulose according to claim 1 or 2, characterized in that the transmission values of the carboxymethylsulfoethylcellulose are greater than 95%, in particular greater than 96% (measured by a · · 2% by weight aqueous solution in a cuvette, having an optical thickness of 10 mm at a wavelength of light of λ 550 = 550 nm) and a water-soluble proportion of 98%, in particular 99.9%. <» Use of the carboxymethylsulfoethylcellulose according to any one of claims 1 to 3 as a thickener 104972 or as a rheology enhancer in textile printing, in particular in reaction textile printing. Use according to claim 4, characterized in that CMSEC is used as a mixture of sodium-5 alginate, starch, modified starches, guar gum, locust bean gum, acacia, crystalline gum, tragacanth, tamarind and / or cellulose ethers, in particular -methyl cellulose ethers. Use according to claim 4, characterized in that synthetic fibers, natural fibers, interwoven or cellulose regenerates are used as textile materials. Use according to Claim 4, characterized in that the dyes used are oxidation, sulfur, developmental, wool, chromium, straight, acid, dispersion, naphthol, type, metal complex dyes, pigments or commercial products consisting of a blend of a developmental dye component and a di-azoamine compound, in particular reaction dyes. «· ·« · Ml • •• f * • •••••••••••••••••••••••••••••••••••••••••••• · I · »• M '· · • · ··· ♦ • M • · • • • • •• I * II ·« I · III « 3. The CMC, SEC or CMSEC is further etherified by a further etherification process (e.g., semi-dry, suspension method) to a CMSEC compound having a total degree of substitution of 1.4 to 2.2, in particular 1.5 to 2.1; The CMSEC compound obtained according to paragraphs 1-3 is dried, preceded or not by partial or complete removal of the reaction by-products, and after 20 drying is finished in the usual and known manner. 4. I f i 4 I {«I I« 104972