EP0705357B1 - Carboxymethyliertes guargalaktomannan als schlichtemittel - Google Patents

Carboxymethyliertes guargalaktomannan als schlichtemittel Download PDF

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Publication number
EP0705357B1
EP0705357B1 EP94920454A EP94920454A EP0705357B1 EP 0705357 B1 EP0705357 B1 EP 0705357B1 EP 94920454 A EP94920454 A EP 94920454A EP 94920454 A EP94920454 A EP 94920454A EP 0705357 B1 EP0705357 B1 EP 0705357B1
Authority
EP
European Patent Office
Prior art keywords
alkali metal
metal salts
guar galactomannan
carboxymethyl guar
sizing
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.)
Expired - Lifetime
Application number
EP94920454A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0705357A1 (de
Inventor
Hans-Peter Miemietz
Kaspar SCHLÜTER
Siegrid Waltenberger-Scharffetter
Bernhard Wüstnienhaus
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.)
Cognis IP Management GmbH
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0705357A1 publication Critical patent/EP0705357A1/de
Application granted granted Critical
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Anticipated expiration legal-status Critical
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating 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
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B23/00—Component parts, details, or accessories of apparatus or machines, specially adapted for the treating of textile materials, not restricted to a particular kind of apparatus, provided for in groups D06B1/00 - D06B21/00
    • D06B23/06—Guiding means for preventing filaments, yarns or threads from sticking together
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to the use of alkali metal salts of carboxymethylguargalactomannans with degrees of substitution below 0.15 as sizing agents, and to a process for sizing natural and / or synthetic yarns using these compounds.
  • sizing agents are used in the weaving process in order to give the warp thread sufficient strength and, on the other hand, to stick protruding fibers to the yarn body or, in the case of filament yarns, to bond the individual filaments to one another. This increases the strength of the warp thread during weaving.
  • Well-known sizing agents are native or modified starches, carboxymethylcelluloses, polyvinyl alcohols and polyacrylates.
  • the sizing agents have to be removed from the fabric again after the weaving process, since they would otherwise interfere with the subsequent finishing processes.
  • One way of removing the sizing agents is to simply wash them out with water, which presupposes that the sizing agents can be washed out with water.
  • Such water-washable sizing agents are, in particular, carboxymethyl-substituted starches, carboxymethyl celluloses, polyvinyl alcohols and polyacrylates. Except for the carboxymethyl-substituted starches, the other sizing agents show only poor biodegradability.
  • the carboxymethylated starches are readily biodegradable, but leave something to be desired in their sizing effect, which is why they have to be used in large quantities, which in part has the advantage of good biodegradability is compensated again.
  • the poor biodegradability of the other sizing agents is particularly disadvantageous because sizing agents make up the main part of the wastewater pollution caused by the textile industry. It is assumed that the sizing agents cause up to 80% of the textile wastewater pollution. There has been no shortage of attempts to provide sizing agents with high efficiency and good water washability, which have improved biodegradability.
  • biodegradable sizing agents which are water-washable and which, at least in their sizing effect, are comparable or even better than the sizing agents used to date, such as carboxymethyl cellulose.
  • An object of the present invention is therefore the use of alkali salts of carboxymethylguargalactomannans with degrees of substitution below 0.15 as sizing agents for sizing natural and / or synthetic yarns.
  • carboxymethylated guar galactomannan and carboxymethyl guar galactomannan are used synonymously.
  • Guar galactomannan products are made from Guarsaat's endosperm.
  • Native guar products consist of galactomannans with small amounts of protein, fiber and fat as well as very small amounts of alkali and alkaline earth metals, iron and some trace elements.
  • the chemical structure of the galactomannans in guargalactomannan is described as a linear mannose chain, where the mannose units are fused together by (1 ⁇ 4) - ⁇ - glycosidic bonds, and every second mannose unit carries a galactose unit by substitution of the hydrogen of the primary hydroxyl group.
  • the galactose molecule is connected to the mannan main chain by a (1 ⁇ 6) - ⁇ - glycosidic bond.
  • the two sugar units have hydroxyl groups in the cis position, in contrast to glucose, the monomer of cellulose and the starch, which all hydroxyl groups have in the trans position.
  • the cis-hydroxyl groups and the elongated rigid structure of the galactomannan are the reason for many unique properties of guargalactomannan and its derivatives.
  • Guargalactomannan can be modified like other polysaccharides. One type of modification is carboxymethylation, which produces anionic guar galactomannan derivatives.
  • the carboxymethylation can be analogous to the American one Patents US-A-2 520 161 and US-A-2 477 544 are carried out by reacting the guar galactomannan with a cold aqueous solution of alkali hydroxides and then treating the alkali derivatives of guar galactomannan with a halogenated fatty acid or its salt. You can also carboxmethylate with other carboxylic acids or their salts such as with glycolic acid or with sodium glycolate. Depending on the amount of reactants used and reaction times and conditions, different degrees of substitution of guar galactomannan are obtained. A maximum degree of substitution of 3 is possible. For the purposes of the invention, preference is given to those alkali metal salts of carboxylmethyl guar which have degrees of substitution from 0.05 to 0.15.
  • Guar galactomannan products have molecular weights ranging from 0.5 to 11 ⁇ 10 6 . If a modification such as carboxymethylation takes place, the guar galactomannan products are generally depolymerized at the same time. Since the molecular weight determination of such polymers can cause difficulties in practice, a move has been made to indicate the viscosity associated with this instead of the molecular weight.
  • alkali metal salts of oxidatively degraded carboxymethylguargalactomannan are used which, as a 4% strength by weight aqueous solution, have a Höppler viscosity at 20 ° C. between 10 and 3000 mPas, preferably between 20 and 500 mPas.
  • the alkali metal salts of carboxymethylguargalactomannans can contain alkali metal halides as impurities.
  • the impurities in alkali halides can be reduced in a manner known per se, for example by washing out with a methanol / water mixture.
  • Another impurity that can occur according to the above production processes are the salts of the glycolic acids, which can also be removed, for example, by washing with a methanol / water mixture.
  • alkali metal salts of carboxymethylguargalactomannans the corresponding sodium salt is particularly preferred.
  • the alkali metal salts of carboxymethylated guargalactomannan can be used alone or in any mixture with conventional sizing agents, preferably with the starch derivatives, polyvinyl alcohols and polyacrylates.
  • the mixing ratios are selected depending on the desired size properties and are in the amounts customary for the person skilled in the art.
  • the alkali salts of carboxymethyl guar galactomannan can be used on all weaving machines as well as on all sizing machines such as marksmen, rapier and air jet looms.
  • the yarns can be both staple yarns and continuous yarns.
  • the yarns can be of natural origin, for example made of cotton or regenerated cellulose, and / or synthetic origin such as cellulose acetate, Polyester, polyacrylonitrile and polyamide. Particularly good results are achieved for cotton and regenerated cellulose and their blends with polyester.
  • the size coating of alkali metal salts of carboxymethylguargalactomannan with degrees of substitution below 0.15, alone or in a mixture with the usual sizes, is in the range from 1 to 25% by weight, based on the dry weight of the yarn.
  • the amount of alkali metal salts of carboxymethylated guar galactomannan is therefore in the range from about 1/3 to half of 100 parts of starch size and in the latter case in the range of the known synthetic sizes.
  • alkali metal salts of carboxymethylguargalactomannans When using the alkali metal salts of carboxymethylguargalactomannans according to the invention, there is an excellent sizing effect. Furthermore, the alkali salts of carboxymethylguargalactomannans show an excellent biodegradability, which is even better at these low degrees of substitution than with only slightly more highly substituted guargalactomannans. In addition, alkali salts of carboxymethyl guar galactomannan dissolve quickly and free of lumps in the water, show no signs of skin formation, do not foam in the liquor and can be washed out with water.
  • Another object of the present invention is a method for sizing natural and / or synthetic yarns in a known manner with alkali salts of carboxymethylguargalactomannans, which is characterized in that alkali salts of carboxymethylguargalactomannans are used with degrees of substitution below 0.15.
  • the application of the alkali salt of carboxymethylguargalactomannans takes place, as is customary for sizing agents, as an aqueous solution with product concentrations of 10 to 150 g / l in the usual sizing machines.
  • the viscosity was determined according to Höppler in accordance with DIN 53015.
  • the above sodium salts of carboxymethylguargalactomannan were tested, for example according to US-A-2 477 544 or US-A-2 520 161.
  • a scrubbing tester was developed to determine the sizing effect and was developed by the TN0, Delft / NL fiber institute.
  • the warp yarns were sized on a laboratory sizing machine from Sucker, Mönchengladbach, with 40 threads being sized from the creel.
  • Raw white cotton ring yarns with a fineness of Nm 50/1 were routinely used.
  • Table 1 summarizes the abrasion resistance found at various sizes (according to DIN 54285), expressed as the number of strokes up to the thread break (median value).
  • Table 1 Abrasion resistance table g / l product Size content Number of strokes 30 A1) 3.0 120 50 A1) 5.0 336 90 A1) 9.8 983 30 A2) 3.4 81 50 A2) 5.0 205 80 A2) 8.9 596 30 See 1) 3.4 76 50 See 1) 4.9 142 90 See 1) 9.3 385 120 See 1) 13.4 607 30 See 2) 2.9 95 50 See 2) 4.8 187 90 See 2) 9.6 481
  • Test matrix is hardened distilled water to which an amount of wet sludge corresponding to approx. 1 g / l dry matter was added. Incubation was carried out for 7 days at 19 to 25 ° C. with stirring and constant air supply. Regular DOC determinations were carried out. Table 2 summarizes the results for A1) and cf. 1). Table 2: Biodegradability Test substance Test concentration mg DOC / l % DOC decrease after days based on the 0-hour value 0.25 1 3rd 7 A1) 100 5 23 90 93 See 1) 100 4th 3rd 30th 70

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Biological Depolymerization Polymers (AREA)
EP94920454A 1993-06-24 1994-06-15 Carboxymethyliertes guargalaktomannan als schlichtemittel Expired - Lifetime EP0705357B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4321016A DE4321016A1 (de) 1993-06-24 1993-06-24 Carboxymethyliertes Guargalaktomannan als Schlichtemittel
DE4321016 1993-06-24
PCT/EP1994/001948 WO1995000696A1 (de) 1993-06-24 1994-06-15 Carboxymethyliertes guargalaktomannan als schlichtemittel

Publications (2)

Publication Number Publication Date
EP0705357A1 EP0705357A1 (de) 1996-04-10
EP0705357B1 true EP0705357B1 (de) 1997-05-14

Family

ID=6491134

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94920454A Expired - Lifetime EP0705357B1 (de) 1993-06-24 1994-06-15 Carboxymethyliertes guargalaktomannan als schlichtemittel

Country Status (6)

Country Link
US (1) US5612475A (ja)
EP (1) EP0705357B1 (ja)
JP (1) JP3300358B2 (ja)
DE (2) DE4321016A1 (ja)
ES (1) ES2101547T3 (ja)
WO (1) WO1995000696A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6548296B1 (en) 1997-07-23 2003-04-15 Roche Diagnostics Gmbh Methods for identifying human cell lines useful for endogenous gene activation, isolated human lines identified thereby, and uses thereof
FR2815355B1 (fr) * 2000-10-18 2003-03-14 Rhodia Chimie Sa Composition a base de polysaccharide anionique pour le soin du linge

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2477544A (en) * 1945-08-25 1949-07-26 Gen Mills Inc Carboxyalkyl ethers of carbohydrate gums
US2520161A (en) * 1946-04-25 1950-08-29 Gen Mills Inc Carboxyalkyl ethers of carbohydrate gums
US4011393A (en) * 1975-04-28 1977-03-08 Celanese Corporation Polygalactomannan gum formate esters
US4031306A (en) * 1975-12-15 1977-06-21 Celanese Corporation Polygalactomannan allyl ether compositions
DE3016561C2 (de) * 1980-04-29 1982-04-01 Diamalt AG, 8000 München Schlichtemittel und Verfahren zu seiner Herstellung
DE3709698C1 (de) * 1987-03-25 1988-10-27 Diamalt Ag Schlichtemittel

Also Published As

Publication number Publication date
EP0705357A1 (de) 1996-04-10
US5612475A (en) 1997-03-18
DE4321016A1 (de) 1995-01-05
JP3300358B2 (ja) 2002-07-08
WO1995000696A1 (de) 1995-01-05
JPH08511832A (ja) 1996-12-10
DE59402765D1 (de) 1997-06-19
ES2101547T3 (es) 1997-07-01

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