EP0274350A1 - Aqueous storage-stable auxiliary textile agent resistant to hard water - Google Patents

Aqueous storage-stable auxiliary textile agent resistant to hard water Download PDF

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Publication number
EP0274350A1
EP0274350A1 EP87810711A EP87810711A EP0274350A1 EP 0274350 A1 EP0274350 A1 EP 0274350A1 EP 87810711 A EP87810711 A EP 87810711A EP 87810711 A EP87810711 A EP 87810711A EP 0274350 A1 EP0274350 A1 EP 0274350A1
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EP
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Prior art keywords
component
carbon atoms
textile
moles
textile auxiliary
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Application number
EP87810711A
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German (de)
French (fr)
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EP0274350B1 (en
Inventor
Christian Guth
Jörg Haase
Albert Stehlin
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Novartis AG
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Ciba Geigy AG
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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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/14—De-sizing
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof

Definitions

  • the present invention relates to a new textile auxiliary and its use for wetting and deaerating fiber materials.
  • Potassium and preferably sodium hydroxide are suitable as alkali metal hydroxides.
  • Components (b) and (c) can be present as individual compounds or as mixtures.
  • Partial phosphoric acid ester as component (a) is understood to mean alkyl phosphoric acid esters which can be prepared by introducing 1 mol of phosphorus (V) oxide into 3 mol of a fatty alcohol with good cooling, 1 mol of a dialkylphosphoric acid ester and 1 mol of a monoalkylphosphoric acid ester being formed. This mixture is trivially referred to as 1 1/2 esters.
  • Suitable fatty alcohols are 6 to 10, preferably 8 to 10 and very particularly 8 carbon atoms. 2-Ethylhexanol is particularly preferred.
  • Suitable nonionic surfactants of component (b) are nonionic alkylene oxide addition products of 1 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mole of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol, an optionally substituted by alkyl or phenyl or a fatty acid with 8 to 22 carbon atoms. Monoalcohols with 8 to 22 carbon atoms are preferred.
  • the preferred addition products are preferably partially terminally blocked with alkyl groups with preferably 1 to 5 carbon atoms.
  • Such terminally blocked surfactants are prepared in a manner known per se, e.g. by reaction of the alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a fatty alcohol or short-chain alcohol.
  • the aliphatic monoalcohols are, for example, water-insoluble monoalcohols with preferably 8 to 22 carbon atoms.
  • These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. It can natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, further trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or linear primary Alcohols with average carbon atom numbers of (8-10), (I0-14), (12), (16), (18) or (20-22) are reacted with the alkylene oxide.
  • alkylene oxides that can be reacted with alkylene oxide are 3- to 6-valent alkanols. These contain 3 to 6 carbon atoms and are in particular glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol.
  • the 3- to 6-valent alcohols are preferably reacted with propylene oxide or ethylene oxide or mixtures of these alkylene oxides.
  • Suitable optionally substituted phenols are, for example, phenol, o-phenylphenol or alkylphenols, the alkyl radical of which has 1 to 16, preferably 4 to 12, carbon atoms.
  • alkylphenols are p-cresol, butylphenol, tributylphenol, octylphenol, and especially nonylphenol.
  • the fatty acids preferably have 8 to 12 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.
  • nonionic surfactants are: - Addition products of preferably 1 to 30 mol of alkylene oxides, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with Phenylphenol or alkylphenols, the alkyl radicals of which have at least 4 carbon atoms; Alkylene oxide, especially ethylene oxide and / or propylene oxide condensation products; - Reaction products from a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing these hydroxyalkyl group-containing reaction products, which have at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkyl
  • Suitable nonionic surfactants are addition products of 2 to 15 mol of ethylene oxide with 1 mol of fatty alcohol or fatty acid each with 8 to 22 carbon atoms or with 1 mol of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part or fatty acid dialkanolamides with 8 to 22 carbon atoms in the fatty acid residue.
  • Preferred nonionic surfactants have a low cloud point, i.e. one that can no longer be determined in water.
  • the anionic surfactants of component (c) are preferably derivatives of alkylene oxide adducts, such as, for example, acidic, ether groups or preferably ester groups of inorganic or organic acids containing addition products of alkylene oxides, especially ethylene oxide and / or propylene oxide or styrene oxide onto aliphatic hydrocarbon radicals having a total of at least 4 carbon atoms organic hydroxyl, carboxyl, amino and / or amido compounds or mixtures of these substances.
  • These Acidic ethers or esters can be present as free acids or as salts, for example alkali metal, alkaline earth metal, ammonium or amine salts.
  • anionic surfactants are prepared by known methods, e.g. at least 1 mole, preferably more than 1 mole, e.g. 2 to 60 mol, ethylene oxide or propylene oxide or alternately in any order, ethylene oxide or propylene oxide and then the adducts are etherified or esterified and, if appropriate, the ethers or the esters are converted into their salts.
  • Higher fatty alcohols i.e.
  • Suitable anionic surfactants are: sulfated aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, for example sulfated lauryl alcohol; - Sulphated unsaturated fatty acids or fatty acid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, for example ricinoleic acid and oils containing such fatty acids, for example castor oil; Alkane sulfonates, the alkyl chain of which contains 8 to 20 carbon atoms, for example dodecyl sulfonate; Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 6 carbon atoms, for example dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates; Sulfonates of polycarboxylic acid esters, for example dioctylsulfosuccinates or sulf
  • Highly suitable anionic surfactants of component (c) are acidic esters or their salts of a polyadduct of 2 to 30 moles of ethylene oxide with 1 mole of fatty alcohol with 8 to 22 carbon atoms or with 1 mole of a phenol which has at least one benzyl group, a phenyl group or preferably an alkyl group has at least 4 carbon atoms, such as Benzylphenol, dibenzylphenol, dibenzyl- (nonyl) phenol, o-phenylphenol, butylphenol, tributylphenol, octylphenol, nonylphenol, dodecylphenol or pentadecylphenol.
  • Particularly preferred components (c) correspond to the formula (1) R ⁇ O ⁇ (CH2CH2O- -X, wherein R is alkyl or alkenyl with 8 to 22 C atoms, alkylphenyl with 4 to 16 C atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid such as phosphoric acid or preferably sulfuric acid or the rest of an organic acid and m is 2 to 30, preferably 2 to 15.
  • the alkyl radical in the alkylphenyl is preferably in the para position.
  • the alkyl radicals in the alkylphenyl can be butyl, hexyl, n-octyl, n-nonyl, p-ter.octyl, p-iso-nonyl, decyl or dodecyl.
  • the alkyl radicals having 8 to 12 carbon atoms are preferred, in particular the octyl or nonyl radicals.
  • the fatty alcohols for the preparation of the anionic surfactants of formula (1) are e.g. those with 8 to 22, in particular 8 to 18, carbon atoms, such as octyl, decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol.
  • the acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as of maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is connected via an ester bridge to the ethylene oxide part of the molecule.
  • X is derived from inorganic polybasic acids, such as orthophosphoric acid and especially sulfuric acid.
  • the acid residue X can be in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.
  • particularly preferred components (c) correspond to the formula (2) R ⁇ O ⁇ (CH2CH2O X1 wherein R is alkyl or alkenyl having 8 to 22 carbon atoms, X1 is a carboxy-C1-C3-alkyl, such as carboxymethyl, carboxyethyl or carboxypropyl and m is 2 to 30, preferably 2 to 5.
  • the components (c) of the formula (2) are prepared in a manner known per se, for example by reacting a fatty alcohol ethoxylate with a halogenated lower carboxylic acid (C2-C4) in the presence of, for example, sodium hydroxide solution.
  • C2-C4 a halogenated lower carboxylic acid
  • They can also be used in the form of their salts, for example as the alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.
  • the sodium salts are preferred.
  • the new auxiliary mixtures can be prepared by simply stirring the components (a), (b), (c) and (d) mentioned, with or without cooling.
  • Components (a) and (c) can already be present in the form of their salts.
  • the preparation is preferably carried out by adding components (b) and (c) to the component (a) initially introduced with stirring, adding the aqueous solution of component (d) to the resulting mixture with cooling and optionally adding deionized water.
  • the textile auxiliary according to the invention advantageously contains, based on the entire mixture, 5 to 45% by weight of component (a), 3 to 27% by weight of component (b), 0.8 to 7% by weight of component (c), 1.2 to 19% by weight of component (d) and 2 to 90% by weight of deionized water.
  • the new textile auxiliaries are storage-stable, hard water-resistant aqueous formulations, which are particularly suitable for wetting and deaerating fiber materials.
  • the present application accordingly also relates to a method for wetting and venting fiber materials.
  • the process is characterized in that these materials are treated in an aqueous medium in the presence of the textile auxiliary according to the invention.
  • the amounts used in which the textile auxiliary according to the invention is added to the treatment liquors are between 0.1 and 20, preferably 0.5 and 10 g per liter of treatment liquor.
  • This liquor can also contain other additives, for example desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.
  • Fiber materials Cellulose, in particular untreated natural cellulose such as hemp, linen, jute, wool, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber blends, e.g. those on polyacrylonitrile / cotton or polyester / cotton.
  • untreated natural cellulose such as hemp, linen, jute, wool, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber blends, e.g. those on polyacrylonitrile / cotton or polyester / cotton.
  • the fiber material to be treated can be in various processing stages, e.g. the cellulose-containing material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers.
  • the fiber material can be treated continuously or discontinuously in an aqueous liquor.
  • the aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the padder, the liquor absorption being about 50 to 120% by weight.
  • the padding process is used in particular in the pad-steam process, the pad-thermofix process and the pad-batch process.
  • the impregnation can be carried out at 20 to 60 ° C, but preferably at room temperature.
  • the cellulose material is optionally subjected to intermediate drying, heat treatment, for example at temperatures of 95 to 210 ° C.
  • the heat treatment can be carried out after intermediate drying of the goods at 80 to 120 ° C, by heat setting at a temperature of 120 to 210 ° C, preferably 140 to 180 ° C.
  • the heat treatment is preferably carried out directly, ie without intermediate drying, by steaming at 95 to 120 ° C., preferably 100 to 106 ° C.
  • the heat treatment can take 30 seconds to 10 minutes.
  • the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.
  • the treatment of the fiber materials can also in so-called long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:25 and at 20 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger or a reel runner.
  • a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:25 and at 20 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger or a reel runner.
  • the treatment up to 150 ° C, preferably 105 to 140 ° C under pressure in so-called high-temperature equipment (HT equipment) can be carried out.
  • HT equipment high-temperature equipment
  • the fiber materials are then, if the process so requires, thoroughly rinsed with hot water at about 90 to 98 ° C. and then with warm and finally with cold water, neutralized if necessary and then preferably dewatered and dried at elevated temperatures.
  • the most important advantages of the textile auxiliaries according to the invention are, in addition to their excellent wetting action, their good hard water resistance and low foaming when used.
  • Example 2 Production of a textile auxiliary according to the invention
  • component (a) prepared according to Example 1 312.5 g of component (a) prepared according to Example 1 are placed in a vessel and, with stirring, 225 g of an addition product of 5 mol of ethylene oxide and 8 mol of propylene oxide and 1 mol of a C9-C11-alkanol partially blocked with a methyl group are stirred
  • component (b) and 50 g of the sodium salt of the addition product of 2.5 mol of ethylene oxide and 1 mol of lauryl alcohol blocked with the carboxymethyl group were added as component (c).
  • stirring is continued for a few minutes and then 187.5 g of 30% sodium hydroxide solution and then 225 g of deionized water are added with cooling and stirring.
  • the mixture obtained has a pH of 8.
  • a raw, starch-sized cotton fabric is impregnated with a desizing liquor, which is in liters 2 g of the textile aid produced according to Example 2, 4 g of a stabilized bacterial amylase and 3 g NaCl contains and has a calcium water hardness of 10 ° dH and brought to a liquor absorption of 100% by squeezing.
  • the impregnated fabric is rolled up, packed airtight with a plastic film and for 24 hours at room temperature (15-25 ° C) stored. The fabric is then first washed with hot water (90-98 ° C.) containing 4 g / l solid NaOH, then rinsed with warm and finally with cold water, neutralized and dried.
  • the degree of desizing measured according to the TEGEWA violet scale is grade 1 for the raw fabric and grade 7 for the fabric treated with the aid according to the invention, according to example 1.
  • an anionic detergent is used under otherwise identical conditions e.g. the disodium salt of 1-benzyl-2-heptadecyl-benzimidazole-disulfonic acid instead of the auxiliary according to the invention, the degree of desizing is 5 (range on the scale 1-9).
  • a peroxide stabilizer for example a mixture of sodium gluconate, magnesium chloride and a mixture of oligomeric ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, 1.0 ml / l 45 ° Bé sodium hydroxide solution and 2.0 ml / l Hydrogen peroxide 35% added and the bath heated to 90 ° C within 30 minutes. It is bleached at this temperature for 45 minutes. Allow to cool and add 3 g / l of a reducing agent to the bath to destroy residual oxygen and treat for 15 minutes. The bath is drained and the dye bath filled. The pretreatment resulted in a good basic white for the subsequent pastel coloring.
  • a peroxide stabilizer for example a mixture of sodium gluconate, magnesium chloride and a mixture of oligomeric ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, 1.0 ml / l 45 ° Bé sodium hydroxide solution and 2.0 ml
  • a fabric of polyester / cotton 65/35 of 200 g / m2 was bleached on a Steepmaster continuous bleaching machine.
  • the material with a mixed size was desized, rinsed and wet-on-wet impregnated with a bleaching bath of the following composition: 2 ml / l of the textile aid prepared according to Example 2 8 ml / l of a composition of ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, alkali metal gluconate and magnesium chloride 15 ml / l caustic soda 50 ° Bé 36 ml / l H2O2 (50%)
  • the material impregnated in this way runs through a bleaching bath heated to 60 ° C. of the following composition for 20 minutes: 2 ml / l of the textile aid prepared according to Example 2 8 ml / l of a composition of ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, alkali metal gluconate and magnesium chloride 10.5 ml / l sodium hydroxide solution 50% 18.0 ml / l H2O2 (50%).
  • the tissue is squeezed off and then steamed for 2 minutes with saturated steam. Afterwards it is rinsed thoroughly hot and cold.
  • the material treated in this way has a whiteness (Filger 46) of 85%, measured with the Elrepho device.
  • the DP value of the treated goods was 2500, the damage factor s according to Eisenhut: 0.1, ie undamaged.
  • a raw, sized cotton fabric of 208 g / m2 is impregnated with a liquor containing 100 ml of 36 ° Bé sodium hydroxide solution and squeezed to a liquor absorption of 60%. It is then steamed with saturated steam at 101 ° C for 10 minutes and then rinsed hot and cold. It is then dried and the CIBA-GEIGY whiteness is determined, which is -25, (that of the raw, untreated tissue -67). However, if 10 g / l of the textile aid prepared according to Example 2 are added to this liquor, the liquor absorption increases to 95% and the whiteness of the treated fabric has a value of +15.
  • a raw knitted cotton fabric with a basis weight of 285 g / m2 is placed on a padder at 25 ° C with a liquor in liters 50 g of the dye of the formula 5 g of the textile aid prepared according to Example 2 15 ml sodium hydroxide solution (30%) and Contains 75 ml of soda water glass solution with 26.3-27.7% silicate content, impregnated, whereupon with a diving time of 1.0 seconds at 2 passages and a roller pressure of 1.5 bar / cm2 a liquor absorption of 83% (calculated on the dry weight of the substrate) is achieved.
  • the knitted fabric is then rolled up and stored at 25 ° C. for 6 hours.
  • the knitted fabric is then rinsed and washed for 20 minutes at cooking temperature with a nonionic detergent (0.5 g / l of the addition product of 9 mol of ethylene oxide with 1 mol of nonylphenol) in a liquor ratio of 1:40.
  • a nonionic detergent 0.5 g / l of the addition product of 9 mol of ethylene oxide with 1 mol of nonylphenol
  • the substrate is then rinsed again and dried.
  • a strong, brilliant red color is obtained, which is particularly characterized by a calm product appearance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Lagerstabile, hartwasserbständige, wässerige Textilhilfsmittel enthaltend mindestens (a) einen Phosphorsäureteilester, (b) ein nicht-ionogenes Tensid, (c) ein anionisches Tensid und (d) ein Alkalimetallhydroxid. Sie können zum Netzen und Entlüften von Fasermaterialien verwendet werden.Storage-stable, hard water-resistant, aqueous textile auxiliaries containing at least (a) a partial phosphoric acid ester, (b) a non-ionic surfactant, (c) an anionic surfactant and (d) an alkali metal hydroxide. They can be used to wet and deaerate fiber materials.

Description

Die vorliegende Erfindung betrifft eine neues Textilhilfsmittel sowie seine Verwendung zum Netzen und Entlüften von Fasermateri­alien.The present invention relates to a new textile auxiliary and its use for wetting and deaerating fiber materials.

Es ist bekannt, z.B. aus US-A-3,433,574 und US-A-4,579,559 bei der Behandlung von Textilien, Hilfsmittel, besonders Netzmittel einzu­setzen um die Behandlung in alkalischen Flotten zu verbessern. Die zur Anwendung vorgeschlagenen Hilfsmittel sind aber ungenügend lagerstabil und in hartem Wasser führen sie zu Ausfällungen.It is known e.g. from US-A-3,433,574 and US-A-4,579,559 in the treatment of textiles, auxiliaries, especially wetting agents, to improve the treatment in alkaline liquors. However, the auxiliary agents proposed for use are insufficiently stable in storage and lead to precipitation in hard water.

Es wurde nun ein Textilhilfsmittel gefunden, welches diese Nachteile nicht aufweist.A textile auxiliary has now been found which does not have these disadvantages.

Das erfindungsgemässe lagerstabile, hartwasserbeständige, wässerige Textilhilfsmittel ist dadurch gekennzeichnet, dass es mindestens

  • (a) einen Phosphorsäureteilester,
  • (b) ein nicht-ionogenes Tensid,
  • (c) ein anionisches Tensid und
  • (d) ein Alkalimetallhydroxyd
enthält.The storage-stable, hard water-resistant, aqueous textile auxiliary according to the invention is characterized in that it is at least
  • (a) a partial phosphoric acid ester,
  • (b) a non-ionic surfactant,
  • (c) an anionic surfactant and
  • (d) an alkali metal hydroxide
contains.

Als Alkalimetallhydroxyde, kommen das Kalium- und vorzugsweise das Natriumhydroxyd in Betracht.Potassium and preferably sodium hydroxide are suitable as alkali metal hydroxides.

Die Komponenten (b) und (c) können als Einzelverbindungen oder als Gemische vorhanden sein.Components (b) and (c) can be present as individual compounds or as mixtures.

Unter Phosphorsäureteilester als Komponente (a) werden Alkylphos­phorsäureester verstanden, die durch Eintragen von 1 Mol Phosphor­(V)-oxid in 3 Mol eines Fettalkohols unter guter Kühlung hergestellt werden können, wobei 1 Mol eines Dialkylphosphorsäureesters und 1 Mol eines Monoalkylphosphorsäureesters entstehen. Dieses Gemisch wird trivial auch als 1 1/2 Ester bezeichnet.Partial phosphoric acid ester as component (a) is understood to mean alkyl phosphoric acid esters which can be prepared by introducing 1 mol of phosphorus (V) oxide into 3 mol of a fatty alcohol with good cooling, 1 mol of a dialkylphosphoric acid ester and 1 mol of a monoalkylphosphoric acid ester being formed. This mixture is trivially referred to as 1 1/2 esters.

Als Fettalkohole kommen solche mit 6 bis 10, vorzugsweise 8 bis 10 und ganz besonders 8 C-Atomen in Betracht. Besonders bevorzugt ist das 2-Ethylhexanol.Suitable fatty alcohols are 6 to 10, preferably 8 to 10 and very particularly 8 carbon atoms. 2-Ethylhexanol is particularly preferred.

Geeignete nichtionogene Tenside der Komponente (b) sind nichtiono­gene Alkylenoxidanlagerungsprodukte von 1 bis 100 Mol Alkylenoxid, z.B. Ethylenoxid und/oder Propylenoxid, an 1 Mol eines aliphatischen Monoalkohols mit mindestens 4 C-Atomen, eines 3- bis 6-wertigen aliphatischen Alkohols, eines gegebenenfalls durch Alkyl oder Phenyl substituierten Phenols oder einer Fettsäure mit 8 bis 22 C-Atomen. Bevorzugt sind Monoalkohole mit 8 bis 22 C-Atomen. Die bevorzugten Anlagerungsprodukte sind vorzugsweise teilweise endständig mit Alkylgruppen mit vorzugsweise 1 bis 5 C-Atomen blockiert.Suitable nonionic surfactants of component (b) are nonionic alkylene oxide addition products of 1 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mole of an aliphatic monoalcohol with at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol, an optionally substituted by alkyl or phenyl or a fatty acid with 8 to 22 carbon atoms. Monoalcohols with 8 to 22 carbon atoms are preferred. The preferred addition products are preferably partially terminally blocked with alkyl groups with preferably 1 to 5 carbon atoms.

Die Herstellung solcher endständig blockierten Tenside geschieht in an sich bekannter Weise, so z.B. durch Umsetzung der Alkylenoxidan­lagerungsprodukte mit Thionylchlorid und nachfolgende Umsetzung der entstandenen Chlorverbindung mit einem Fettalkohol oder kurzkettigen Alkohol.Such terminally blocked surfactants are prepared in a manner known per se, e.g. by reaction of the alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a fatty alcohol or short-chain alcohol.

Bei den aliphatischen Monoalkoholen handelt es sich z.B. um wasser­unlösliche Monoalkohole mit vorzugsweise 8 bis 22 Kohlenstoffatomen. Diese Alkohole können gesättigt oder ungesättigt und verzweigt oder geradkettig sein und können allein oder im Gemisch eingesetzt werden. Es können natürliche Alkohole wie z.B. Myristylalkohol, Cetylalkohol, Stearylalkohol oder Oleylalkohol oder synthetische Alkohole wie insbesondere 2-Ethylhexanol, ferner Trimethylhexanol, Trimethylnonylalkohol, Hexadecylalkohol oder lineare primäre Alkohole mit durchschnittlichen Kohlenstoffatomzahlen von (8-10), (I0-14), (12), (16), (18) oder (20-22) mit dem Alkylenoxid umgesetzt werden.The aliphatic monoalcohols are, for example, water-insoluble monoalcohols with preferably 8 to 22 carbon atoms. These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. It can natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, further trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or linear primary Alcohols with average carbon atom numbers of (8-10), (I0-14), (12), (16), (18) or (20-22) are reacted with the alkylene oxide.

Weitere aliphatische Alkohole, die mit Alkylenoxid umgesetzt werden können, sind 3- bis 6-wertige Alkanole. Diese enthalten 3 bis 6 Kohlenstoffatome und sind insbesondere Glycerin, Trimethylol­propan, Erythrit, Mannit, Pentaerythrit und Sorbit. Die 3- bis 6-wertigen Alkohole werden vorzugsweise mit Propylenoxid oder Aethylenoxid oder Gemischen dieser Alkylenoxide umgesetzt.Other aliphatic alcohols that can be reacted with alkylene oxide are 3- to 6-valent alkanols. These contain 3 to 6 carbon atoms and are in particular glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol. The 3- to 6-valent alcohols are preferably reacted with propylene oxide or ethylene oxide or mixtures of these alkylene oxides.

Als gegebenenfalls substituierte Phenole eignen sich beispielsweise Phenol, o-Phenylphenol oder Alkylphenole, deren Alkylrest 1 bis 16, vorzugsweise 4 bis 12 Kohlenstoffatome aufweist. Beispiele dieser Alkylphenole sind p-Kresol, Butylphenol, Tributylphenol, Octyl­phenol, und besonders Nonylphenol.Suitable optionally substituted phenols are, for example, phenol, o-phenylphenol or alkylphenols, the alkyl radical of which has 1 to 16, preferably 4 to 12, carbon atoms. Examples of these alkylphenols are p-cresol, butylphenol, tributylphenol, octylphenol, and especially nonylphenol.

Die Fettsäuren weisen vorzugsweise 8 bis 12 Kohlenstoffatome auf und können gesättigt oder ungesättigt sein, wie z.B. die Caprin-, Laurin-, Myristin-, Palmitin- oder Stearinsäure bzw. die Decen-, Dodecen-, Tetradecen-, Hexadecen, Oel-, Linol-, Linolen- oder vorzugsweise Rizinolsäure.The fatty acids preferably have 8 to 12 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.

Als nichtionogene Tenside seien beispielsweise genannt:
- Anlagerungsprodukte von vorzugsweise 1 bis 30 Mol Alkylenoxiden, insbesondere Aethylenoxid, wobei einzelne Aethylenoxideinheiten durch substituierte Epoxide, wie Styroloxid und/oder Propylenoxid, ersetzt sein können, an höhere ungesättigte oder gesättigte Fettalkohole, Fettsäuren, Fettamine oder Fettamide mit 8 bis 22 Kohlenstoffatomen oder an Phenylphenol oder Alkylphenole, deren Alkylreste mindestens 4 Kohlenstoffatome aufweisen;
-Alkylenoxid-, insbesondere Aethylenoxid- und/oder Propylenoxid-­Kondensationsprodukte;
- Umsetzungsprodukte aus einer 8 bis 22 Kohlenstoffatome aufweisen­den Fettsäure und einem primären oder sekundären, mindestens eine Hydroxyniederalkyl- oder Niederalkoxyniederalkylgruppe aufweisen­den Amin oder Alkylenoxid-Anlagerungsprodukte dieser hydroxyalkyl­gruppenhaltigen Umsetzungsprodukte, wobei die Umsetzung so erfolgt, dass das molekulare Mengenverhältnis zwischen Hydroxy­alkylamin und Fettsäure 1:1 und grösser als 1, z.B. 1,1:1 bis 2:1 sein kann,
-Anlagerungsprodukte von Propylenoxid an einen drei- bis sechswer­tigen aliphatischen Alkohol von 3 bis 6 Kohlenstoffatomen, z.B. Glycerin oder Pentaerythrit, wobei die Polypropylenoxidaddukte ein durchschnittliches Molekulargewicht von 250 bis 1800, vorzugsweise 400 bis 900, aufweisen, und
- Ester von Polyalkoholen, insbesondere Mono- oder Diglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen, z.B. Monoglyceride der Laurin-, Stearin- oder Oelsäure.Examples of nonionic surfactants are:
- Addition products of preferably 1 to 30 mol of alkylene oxides, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with Phenylphenol or alkylphenols, the alkyl radicals of which have at least 4 carbon atoms;
Alkylene oxide, especially ethylene oxide and / or propylene oxide condensation products;
- Reaction products from a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide addition products containing these hydroxyalkyl group-containing reaction products, which have at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid is 1: 1 and can be greater than 1, for example 1.1: 1 to 2: 1,
Addition products of propylene oxide onto a trihydric to hexavalent aliphatic alcohol of 3 to 6 carbon atoms, for example glycerol or pentaerythritol, the polypropylene oxide adducts having an average molecular weight of 250 to 1800, preferably 400 to 900, and
- Esters of polyalcohols, especially mono- or diglycerides of fatty acids with 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid.

Gut geeignete nichtionogene Tenside sind Anlagerungsprodukte von 2 bis 15 Mol Aethylenoxid an 1 Mol Fettalkohol oder Fettsäure mit jeweils 8 bis 22 Kohlenstoffatomen oder an 1 Mol Alkylphenol mit insgesamt 4 bis 12 Kohlenstoffatomen im Alkylteil oder Fettsäure­dialkanolamide mit 8 bis 22 Kohlenstoffatomen im Fettsäurerest.Suitable nonionic surfactants are addition products of 2 to 15 mol of ethylene oxide with 1 mol of fatty alcohol or fatty acid each with 8 to 22 carbon atoms or with 1 mol of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part or fatty acid dialkanolamides with 8 to 22 carbon atoms in the fatty acid residue.

Bevorzugte nichtionogene Tenside weisen einen niedrigen Trübungs­punkt auf, d.h. einen solchen, der in Wasser nicht mehr bestimmbar ist.Preferred nonionic surfactants have a low cloud point, i.e. one that can no longer be determined in water.

Die anionischen Tenside der Komponente (c) sind vorzugsweise Derivate von Alkylenoxidaddukten, wie z.B. saure, Aethergruppen oder vorzugsweise Estergruppen von anorganischen oder organischen Säuren enthaltende Anlagerungsprodukte von Alkylenoxiden, besonders Aethylenoxid und/oder Propylenoxid oder auch Styroloxid an alipha­tische Kohlenwasserstoffreste mit insgesamt mindestens 4 Kohlen­stoffatomen aufweisende organische Hydroxyl-, Carboxyl-, Amino und/oder Amidoverbindungen bzw. Mischungen dieser Stoffe. Diese sauren Aether oder Ester können als freie Säuren oder als Salze, z.B. Alkalimetall-, Erdalkalimetall-, Ammonium- oder Aminsalze, vorliegen.The anionic surfactants of component (c) are preferably derivatives of alkylene oxide adducts, such as, for example, acidic, ether groups or preferably ester groups of inorganic or organic acids containing addition products of alkylene oxides, especially ethylene oxide and / or propylene oxide or styrene oxide onto aliphatic hydrocarbon radicals having a total of at least 4 carbon atoms organic hydroxyl, carboxyl, amino and / or amido compounds or mixtures of these substances. These Acidic ethers or esters can be present as free acids or as salts, for example alkali metal, alkaline earth metal, ammonium or amine salts.

Die Herstellung dieser anionischen Tenside erfolgt nach bekannten Methoden, indem man z.B. an die genannten organischen Verbindungen mindestens 1 Mol, vorzugsweise mehr als 1 Mol, z.B. 2 bis 60 Mol, Aethylenoxid oder Propylenoxid oder alternierend in beliebiger Reihenfolge Aethylenoxid oder Propylenoxid anlagert und anschlies­send die Anlagerungsprodukte veräthert bzw. verestert und gegebe­nenfalls die Aether bzw. die Ester in ihre Salze überführt. Als Grundstoffe kommen höhere Fettalkohole, d.h. Alkanole oder Alkenole je mit 8 bis 22 Kohlenstoffatomen, zwei- bis sechswertige alipha­tische Alkohole von 2 bis 9 Kohlenstoffatomen, alicyclische Alko­hole, Phenylphenole, Benzylphenole, Alkylphenole mit einem oder mehreren Alkylsubstituenten, der bzw. die zusammen mindestens 4 Kohlenstoffatome aufweisen, Fettsäuren mit 8 bis 22 Kohlenstoff­atomen, Amine, die aliphatische und/oder cycloaliphatische Kohlen­wasserstoffreste von mindestens 8 Kohlenstoffatomen aufweisen, besonders derartige Reste aufweisende Fettamine, Hydroxyalkylamine, Hydroxyalkylamide und Aminoalkylester von Fettsäuren oder Dicarbon­säuren und höher alkylierter Aryloxycarbonsäuren in Betracht.These anionic surfactants are prepared by known methods, e.g. at least 1 mole, preferably more than 1 mole, e.g. 2 to 60 mol, ethylene oxide or propylene oxide or alternately in any order, ethylene oxide or propylene oxide and then the adducts are etherified or esterified and, if appropriate, the ethers or the esters are converted into their salts. Higher fatty alcohols, i.e. Alkanols or alkenols each with 8 to 22 carbon atoms, di- to hexavalent aliphatic alcohols with 2 to 9 carbon atoms, alicyclic alcohols, phenylphenols, benzylphenols, alkylphenols with one or more alkyl substituents, which together have at least 4 carbon atoms, fatty acids with 8 to 22 carbon atoms, amines which have aliphatic and / or cycloaliphatic hydrocarbon radicals of at least 8 carbon atoms, in particular fatty amines containing such radicals, hydroxyalkylamines, hydroxyalkylamides and aminoalkyl esters of fatty acids or dicarboxylic acids and higher alkylated aryloxycarboxylic acids.

Beispielsweise kommen als anionische Tenside in Frage:
- sulfatierte aliphatische Alkohole, deren Alkylkette 8 bis 18 Koh­lenstoffatome aufweist, z.B. sulfatierter Laurylalkohol;
- sulfatierte ungesättigte Fettsäuren oder Fettsäureniederalkyl­ester, die im Fettrest 8 bis 20 Kohlenstoffatome aufweisen, z.B. Rizinolsäure und solche Fettsäuren enthaltende Oele, z.B. Rizi­nusöl;
- Alkansulfonate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält, z.B. Dodecylsulfonat;
- Alkylarylsulfonate mit geradkettiger oder verzweigter Alkylkette mit mindestens 6 Kohlenstoffatomen, z.B. Dodecylbenzolsulfonate oder 3,7-Diisobutyl-naphthalinsulfonate;
- Sulfonate von Polycarbonsäureestern, z.B. Dioctylsulfosuccinate oder Sulfosuccinamide;
- die als Seifen bezeichneten Alkalimetall- Ammonium- oder Aminsalze von Fettsäuren mit 10 bis 20 Kohlenstoffatomen, z.B. Kolophonium­salze;
- die mit einer organischen Dicarbonsäure wie z.B. Maleinsäure, oder Sulfobernsteinsäure, vorzugsweise jedoch mit einer anorganischen mehrbasischen Säure wie o-Phosphorsäure oder Schwefelsäure in einen sauren Ester übergeführten Anlagerungsprodukte von 1 bis 60 Aethylenoxid und/oder Propylenoxid an Fettamine, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen, an Alkylphenole mit 4 bis 16 Kohlenstoffatomen in der Alkylkette oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen.Examples of suitable anionic surfactants are:
sulfated aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, for example sulfated lauryl alcohol;
- Sulphated unsaturated fatty acids or fatty acid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, for example ricinoleic acid and oils containing such fatty acids, for example castor oil;
Alkane sulfonates, the alkyl chain of which contains 8 to 20 carbon atoms, for example dodecyl sulfonate;
Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 6 carbon atoms, for example dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
Sulfonates of polycarboxylic acid esters, for example dioctylsulfosuccinates or sulfosuccinamides;
- The so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, for example rosin salts;
- The adducts of 1 to 60 ethylene oxide and / or propylene oxide with fatty amines, fatty acids or fatty alcohols each converted to 8 with an organic dicarboxylic acid such as maleic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid such as o-phosphoric acid or sulfuric acid up to 22 carbon atoms, on alkylphenols with 4 to 16 carbon atoms in the alkyl chain or on tri- to hexavalent alkanols with 3 to 6 carbon atoms.

Gut geeignete anionische Tenside der Komponente (c) sind saure Ester oder deren Salze eines Polyadduktes von 2 bis 30 Mol Aethylenoxid an 1 Mol Fettalkohol mit 8 bis 22 Kohlenstoffatomen oder an 1 Mol eines Phenols, das mindestens eine Benzylgruppe, eine Phenylgruppe oder vorzugsweise eine Alkylgruppe mit mindestens 4 Kohlenstoffatomen aufweist, wie z.B. Benzylphenol, Dibenzylphenol, Dibenzyl-(nonyl)­phenol, o-Phenylphenol, Butylphenol, Tributylphenol, Octylphenol, Nonylphenol, Dodecylphenol oder Pentadecylphenol.Highly suitable anionic surfactants of component (c) are acidic esters or their salts of a polyadduct of 2 to 30 moles of ethylene oxide with 1 mole of fatty alcohol with 8 to 22 carbon atoms or with 1 mole of a phenol which has at least one benzyl group, a phenyl group or preferably an alkyl group has at least 4 carbon atoms, such as Benzylphenol, dibenzylphenol, dibenzyl- (nonyl) phenol, o-phenylphenol, butylphenol, tributylphenol, octylphenol, nonylphenol, dodecylphenol or pentadecylphenol.

Besonders bevorzugte Komponenten (c) entsprechen der Formel
(1)      R―O―(CH₂CH₂O-

Figure imgb0001
-X,
worin R Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, Alkylphenyl mit 4 bis 16 C-Atomen im Alkylteil oder o-Phenylphenyl, X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure wie z.B. Phos­phorsäure oder vorzugsweise Schwefelsäure oder auch den Rest einer organischen Säure und m 2 bis 30, vorzugsweise 2 bis 15 bedeuten. Der Alkylrest im Alkylphenyl befindet sich vorzugsweise in para-­Stellung. Die Alkylreste im Alkylphenyl können Butyl, Hexyl, n-Octyl, n-Nonyl, p-ter.Octyl, p-iso-Nonyl, Decyl oder Dodecyl sein. Bevorzugt sind die Alkylreste mit 8 bis 12 Kohlenstoffatomen, insbesondere die Octyl- oder Nonylreste.Particularly preferred components (c) correspond to the formula
(1) R ― O― (CH₂CH₂O-
Figure imgb0001
-X,
wherein R is alkyl or alkenyl with 8 to 22 C atoms, alkylphenyl with 4 to 16 C atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid such as phosphoric acid or preferably sulfuric acid or the rest of an organic acid and m is 2 to 30, preferably 2 to 15. The alkyl radical in the alkylphenyl is preferably in the para position. The alkyl radicals in the alkylphenyl can be butyl, hexyl, n-octyl, n-nonyl, p-ter.octyl, p-iso-nonyl, decyl or dodecyl. The alkyl radicals having 8 to 12 carbon atoms are preferred, in particular the octyl or nonyl radicals.

Die Fettalkohole zur Herstellung der anionischen Tenside der Formel (1) sind z.B. solche mit 8 bis 22, insbesondere 8 bis 18 Kohlenstoffatomen, wie Octyl-, Decyl-, Lauryl-, Tridecyl-, Myristyl-, Cetyl-, Stearyl-, Oleyl-, Arachidyl- oder Behenylalkohol.The fatty alcohols for the preparation of the anionic surfactants of formula (1) are e.g. those with 8 to 22, in particular 8 to 18, carbon atoms, such as octyl, decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol.

Der Säurerest X leitet sich beispielsweise von niedermolekularen Dicarbonsäuren ab, wie z.B. von Maleinsäure, Malonsäure, Bern­steinsäure oder Sulfobernsteinsäure, und ist über eine Esterbrücke mit dem Aethylenoxiteil des Moleküls verbunden. Insbesondere leitet sich X jedoch von anorganischen mehrbasischen Säuren, wie Ortho­phosphorsäure und insbesondere Schwefelsäure ab. Der Säurerest X kann in Salzform, d.h. z.B. als Alkalimetall-, Ammonium- oder Aminsalz, vorliegen. Beispiele für solche Salze sind Lithium-, Natrium-, Kalium-, Ammonium-, Trimethylamin-, Aethanolamin-, Diäthanolamin- oder Triäthanolaminsalze.The acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as of maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is connected via an ester bridge to the ethylene oxide part of the molecule. In particular, however, X is derived from inorganic polybasic acids, such as orthophosphoric acid and especially sulfuric acid. The acid residue X can be in salt form, i.e. e.g. as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.

Weitere, besonders bevorzugte Komponenten (c) entsprechen der Formel
(2)      R―O―(CH₂CH₂O

Figure imgb0002
X₁
worin R Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, X₁ einen Carboxy-­C₁-C₃-Alkyl, wie Carboxymethyl, Carboxyethyl oder Carboxypropyl und m 2 bis 30, vorzugsweise 2 bis 5 bedeuten.Further, particularly preferred components (c) correspond to the formula
(2) R ― O― (CH₂CH₂O
Figure imgb0002
X₁
wherein R is alkyl or alkenyl having 8 to 22 carbon atoms, X₁ is a carboxy-C₁-C₃-alkyl, such as carboxymethyl, carboxyethyl or carboxypropyl and m is 2 to 30, preferably 2 to 5.

Die Komponenten (c) der Formel (2) werden in an sich bekannter Weise hergestellt, so z.B. durch Umsetzung eines Fettalkoholethoxylates mit einer halogenierten niederen Carbonsäure (C₂-C₄) in Gegenwart von z.B. Natronlauge. Sie können auch in Form ihrer Salze, z.B. als Alkalimetall-, Ammonium- oder Aminsalz zur Anwendung gelangen. Beispiele für solche Salze sind Lithium-, Natrium-, Kalium-, Ammonium-, Trimethylamin-, Ethanolamin-, Diethanolamin- oder Triethanolaminsalze. Die Natriumsalze sind bevorzugt.The components (c) of the formula (2) are prepared in a manner known per se, for example by reacting a fatty alcohol ethoxylate with a halogenated lower carboxylic acid (C₂-C₄) in the presence of, for example, sodium hydroxide solution. They can also be used in the form of their salts, for example as the alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts. The sodium salts are preferred.

Die neuen Hilfsmittelgemische können durch einfaches Verrühren der genannten Komponenten (a), (b), (c) und (d), gegebenenfalls unter Kühlung hergestellt werden. Die Komponenten (a) und (c) können dabei bereits in Form ihrer Salze vorliegen. Die Herstellung erfolgt vorzugsweise dadurch, dass man der vorgelegten Komponente (a) die Komponenten (b) und (c) unter Rühren zugibt, die entstandene Mischung unter Kühlung mit der wässrigen Lösung der Komponente (d) versetzt und gegebenenfalls noch deionisiertes Wasser zugibt.The new auxiliary mixtures can be prepared by simply stirring the components (a), (b), (c) and (d) mentioned, with or without cooling. Components (a) and (c) can already be present in the form of their salts. The preparation is preferably carried out by adding components (b) and (c) to the component (a) initially introduced with stirring, adding the aqueous solution of component (d) to the resulting mixture with cooling and optionally adding deionized water.

Das erfindungsgemässe Textilhilfsmittel enthält mit Vorteil, bezogen auf das gesamte Gemisch,
5 bis 45 Gew.% der Komponente (a),
3 bis 27 Gew.% der Komponente (b),
0,8 bis 7 Gew.% der Komponente (c),
1,2 bis 19 Gew.% der Komponente (d) und
2 bis 90 Gew.% deionisiertes Wasser.The textile auxiliary according to the invention advantageously contains, based on the entire mixture,
5 to 45% by weight of component (a),
3 to 27% by weight of component (b),
0.8 to 7% by weight of component (c),
1.2 to 19% by weight of component (d) and
2 to 90% by weight of deionized water.

Die neuen Textilhilfsmittel stellen lagerstabile, hartwasserbestän­dige wässerige Formulierungen dar, welche sich insbesondere zum Netzen und Entlüften von Fasermaterialien eignen.The new textile auxiliaries are storage-stable, hard water-resistant aqueous formulations, which are particularly suitable for wetting and deaerating fiber materials.

Gegenstand der vorliegenden Anmeldung ist demnach auch ein Verfahren zum Netzen und Entlüften von Fasermaterialien. Das Verfahren ist dadurch gekennzeichnet, dass man diese Materialien in Gegenwart des erfindungsgemässen Textilhilfsmittels in wässrigem Medium behandelt.The present application accordingly also relates to a method for wetting and venting fiber materials. The process is characterized in that these materials are treated in an aqueous medium in the presence of the textile auxiliary according to the invention.

Die Einsatzmengen, in denen das erfindungsgemässe Textilhilfsmittel den Behandlungsflotten zugesetzt wird, betragen zwischen 0,1 und 20, vorzugsweise 0,5 und 10 g pro Liter Behandlungsflotte. Diese Flotte kann noch weitere Zusätze enthalten, z.B. Entschlichtungsmittel, Farbstoffe, optische Aufheller, Kunstharze und Alkalien wie Natrium­hydroxid.The amounts used in which the textile auxiliary according to the invention is added to the treatment liquors are between 0.1 and 20, preferably 0.5 and 10 g per liter of treatment liquor. This liquor can also contain other additives, for example desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.

Als Fasermaterialien kommen in Betracht:
Cellulose insbesondere unvorbehandelte natürliche Cellulose wie z.B. Hanf, Leinen, Jute, Zwellwolle, Viskose, Azetatreyon, native Cellu­losefaser und besonders Rohbaumwolle, Wolle, Polyamid-, Polyacryl­nitril- oder Polyesterfasermaterialien sowie Fasermischungen, z.B. solche auf Polyacrylnitril/Baumwolle oder Polyester/Baumwolle.The following are considered as fiber materials:
Cellulose, in particular untreated natural cellulose such as hemp, linen, jute, wool, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber blends, e.g. those on polyacrylonitrile / cotton or polyester / cotton.

Das zu behandelnde Fasermaterial kann in den verschiedensten Verarbeitungsstufen vorliegen, so z.B. das cellulosehaltige Material als loses Material, Garn, Gewebe oder Gewirke. Hierbei handelt es sich also in der Regel stets um textile Fasermaterialien, die aus reinen textilen Cellulosefasern oder aus Gemischen aus textilen Cellulosefasern mit textilen Synthesefasern hergestellt werden. Das Fasermaterial kann kontinuierlich oder diskontinuierlich in wässe­riger Flotte behandelt werden.The fiber material to be treated can be in various processing stages, e.g. the cellulose-containing material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers. The fiber material can be treated continuously or discontinuously in an aqueous liquor.

Die wässerigen Behandlungsflotten können in bekannter Weise auf die Fasermaterialien aufgebracht werden, vorteilhaft durch Imprägnieren am Foulard, wobei die Flottenaufnahme etwa 50 bis 120 Gew.% beträgt. Das Foulardierverfahren kommt insbesondere beim Pad-Steam-Ver­fahren, dem Pad-Thermofixverfahren sowie Pad-Batch-Verfahren zur Anwendung.The aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the padder, the liquor absorption being about 50 to 120% by weight. The padding process is used in particular in the pad-steam process, the pad-thermofix process and the pad-batch process.

Die Imprägnierung kann bei 20 bis 60°C, vorzugsweise jedoch bei Raumtemperatur, vorgenommen werden. Nach der Imprägnierung und Abquetschung wird das Cellulosematerial gegebenenfalls nach einer Zwischentrocknung, einer Hitzebehandlung, z.B. bei Temperaturen von 95 bis 210°C unterworfen. Beispielsweise kann die Hitzebehandlung nach einer Zwischentrocknung der Ware bei 80 bis 120°C, durch Thermofixieren bei einer Temperatur von 120 bis 210°C, vorzugsweise 140 bis 180°C, durchgeführt werden. Vorzugsweise erfolgt die Hitzebehandlung direkt, d.h. ohne Zwischentrocknung, durch Dämpfen bei 95 bis 120°C, vorzugsweise 100 bis 106°C. Je nach Art der Hitzeentwicklung und des Temperaturbereiches kann die Hitzebe­handlung 30 Sekunden bis 10 Minuten dauern. Bei dem Pad-Batch-­ Verfahren wird die imprägnierte Ware ohne Trocknung aufgerollt und anschliessend gegebenenfalls mit einer Plastikfolie verpackt, und bei Raumtemperatur 1 bis 24 Stunden gelagert.The impregnation can be carried out at 20 to 60 ° C, but preferably at room temperature. After impregnation and squeezing, the cellulose material is optionally subjected to intermediate drying, heat treatment, for example at temperatures of 95 to 210 ° C. For example, the heat treatment can be carried out after intermediate drying of the goods at 80 to 120 ° C, by heat setting at a temperature of 120 to 210 ° C, preferably 140 to 180 ° C. The heat treatment is preferably carried out directly, ie without intermediate drying, by steaming at 95 to 120 ° C., preferably 100 to 106 ° C. Depending on the type of heat development and the temperature range, the heat treatment can take 30 seconds to 10 minutes. With the pad batch In the process, the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.

Die Behandlung der Fasermaterialien kann aber auch in sogenannten langen Flotten bei einem Flottenverhältnis von z.B. 1:3 bis 1:100, vorzugsweise 1:8 bis 1:25 und bei 20 bis 100, vorzugsweise 80 bis 98°C während etwa 1/4 bis 3 Stunden unter Normalbedingungen, d.h. unter atmosphärischem Druck in üblichen Apparaturen, z.B. einem Jigger oder einer Haspelkufe erfolgen. Gegebenenfalls kann aber auch die Behandlung bis 150°C, vorzugsweise 105 bis 140°C unter Druck in sogenannten Hochtemperatur-Apparaturen (HT-Apparaturen) durchgeführt werden.The treatment of the fiber materials can also in so-called long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:25 and at 20 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger or a reel runner. Optionally, however, the treatment up to 150 ° C, preferably 105 to 140 ° C under pressure in so-called high-temperature equipment (HT equipment) can be carried out.

Anschliessend werden die Fasermaterialien, wenn es das Verfahren verlangt, mit heissem Wasser von etwa 90 bis 98°C und dann mit warmem und zuletzt mit kaltem Wasser gründlich gespült, gegebenen­falls neutralisiert und hierauf vorzugsweise bei erhöhten Tempera­turen entwässert und getrocknet.The fiber materials are then, if the process so requires, thoroughly rinsed with hot water at about 90 to 98 ° C. and then with warm and finally with cold water, neutralized if necessary and then preferably dewatered and dried at elevated temperatures.

Als wesentlichste Vorteile der erfindungsgemässen Textilhilfsmittel sind neben deren ausgezeichneten Netzwirkung, ihre gute Hartwasser­beständigkeit und Schaumarmut bei der Anwendung zu verzeichnen.The most important advantages of the textile auxiliaries according to the invention are, in addition to their excellent wetting action, their good hard water resistance and low foaming when used.

In den nachfolgenden Beispielen beziehen sich Prozente stets auf das Gewicht.In the examples below, percentages always refer to weight.

Beispiel 1: Herstellung einer Komponente (a)Example 1: Preparation of a component (a)

In einem Reaktionskolben werden 781,0 g 2-Ethylhexanol vorgelegt und unter Rühren 264,0 g P₂O₅ innerhalb von 120 Minuten bei einer Temperatur von 25-30°C eingerührt. Die erhaltene schwach trübe Reaktionsmasse wird noch während 3 Stunden weitergerührt. Man erhält ein Produkt das aus

Figure imgb0003
besteht.781.0 g of 2-ethylhexanol are placed in a reaction flask and, while stirring, 264.0 g of P₂O₅ are stirred in at a temperature of 25-30 ° C. within 120 minutes. The slightly cloudy reaction mass obtained is stirred for a further 3 hours. You get a product that out
Figure imgb0003
 consists.

Beispiel 2: Herstellung eines erfindungsgemässen TextilhilfsmittelsExample 2: Production of a textile auxiliary according to the invention

In einem Gefäss werden 312,5 g der gemäss Beispiel 1 hergestellten Komponente (a) vorgelegt und nacheinander unter Rühren 225 g eines teilweise endständig mit einer Methylgruppe blockierten Anlagerungs­produktes von 5 Mol Ethylenoxid und 8 Mol Propylenoxid an 1 Mol eines C₉-C₁₁-Alkanols als Komponente (b) und 50 g des Natriumsalzes des endständig mit der Carboxymethylgruppe blockierten Anlagerungs­produktes von 2,5 Mol Ethylenoxid an 1 Mol Laurylalkohol als Komponente (c) zugegeben. Nach abgeschlossener Zugabe wird noch einige Minuten lang weitergerührt und dann werden unter Kühlung und Rühren 187,5 g 30%-ige Natronlauge und anschliessend 225 g deionisiertes Wasser zugegeben. Die erhaltene Mischung weist einen pH von 8 auf.312.5 g of component (a) prepared according to Example 1 are placed in a vessel and, with stirring, 225 g of an addition product of 5 mol of ethylene oxide and 8 mol of propylene oxide and 1 mol of a C₉-C₁₁-alkanol partially blocked with a methyl group are stirred Component (b) and 50 g of the sodium salt of the addition product of 2.5 mol of ethylene oxide and 1 mol of lauryl alcohol blocked with the carboxymethyl group were added as component (c). After the addition is complete, stirring is continued for a few minutes and then 187.5 g of 30% sodium hydroxide solution and then 225 g of deionized water are added with cooling and stirring. The mixture obtained has a pH of 8.

Verfährt man wie oben angegeben, verwendet jedoch die nachstehend aufgeführten Komponenten a), b) und c), in den in Tabelle I angegebenen Mengen, so erhält man gleichwertige Textilhilfsmittel.If the procedure is as described above, but using components a), b) and c) listed below in the amounts given in Table I, equivalent textile auxiliaries are obtained.

Komponente a)Component a)

  • (AA) Umsetzungsprodukt aus 1 Mol P₂O₅ und 3 Mol 2-Ethylhexanol bestehend aus 38 % Monoester und 62 % Diester;(AA) reaction product of 1 mol of P₂O₅ and 3 mol of 2-ethylhexanol consisting of 38% monoester and 62% diester;
  • (AB) Umsetzungsprodukt aus 1 Mol P₂O₅ und 3 Mol Hexanol;(AB) reaction product of 1 mol of P₂O₅ and 3 mol of hexanol;
  • (AC) Umsetzungsprodukt aus 1 Mol P₂O₅ und 3 Mol Decylalkohol (z.B. Victawet®58-B) und(AC) reaction product of 1 mol P₂O₅ and 3 mol decyl alcohol (e.g. Victawet®58-B) and
  • (AD) Umsetzungsprodukt aus 1 Mol P₂O₅ und 3 Mol eines technischen C₉-C₁₁-Alkanols.(AD) reaction product of 1 mole of P₂O₅ and 3 moles of a technical C₉-C₁₁ alkanol.
Komponente b)Component b)

  • (BA) Modifizierter polyethoxylierter geradkettiger Alkohol (z.B. Ukanil®190);(BA) Modified polyethoxylated straight chain alcohol (e.g. Ukanil®190);
  • (BB) Addukt aus 1 Mol Nonylphenol und 2 Mol Ethylenoxid;(BB) adduct of 1 mole of nonylphenol and 2 moles of ethylene oxide;
  • (BC) Addukt aus 1 Mol des technischen C₉-C₁₁-Alkanols, 5 Mol Ethylenoxid und 4 Mol Propylenoxid (z.B. Marlox®FK 4);(BC) adduct of 1 mole of the technical C₉-C₁₁ alkanol, 5 moles of ethylene oxide and 4 moles of propylene oxide (e.g. Marlox®FK 4);
  • (BD) Blockpolymer aus 30 Mol Propylenglykol und 4,5 Mol Ethylenoxid (z.B. Pluronic®C 61) und(BD) block polymer made from 30 mol propylene glycol and 4.5 mol ethylene oxide (e.g. Pluronic®C 61) and
  • (BE) Propoxiliertes Glycerin mit einem Mol.Gew. von 4200(BE) Propoxylated glycerol with one mol. from 4200
Komponente c)Component c)

  • (CA) Umsetzungsprodukt aus 1 Mol Laurylalkohol, 2,5 Mol Ethylenoxid und 1 Mol Chloressigsäure (z.B. Akypo®RLM 25);(CA) reaction product of 1 mol lauryl alcohol, 2.5 mol ethylene oxide and 1 mol chloroacetic acid (e.g. Akypo®RLM 25);
  • (CB) Umsetzungsprodukt aus 1 Mol Laurylalkohol, 5 Mol Ethylenoxid und 1 Mol Chloressigsäure (z.B. Sandopan®DTC);(CB) reaction product of 1 mol lauryl alcohol, 5 mol ethylene oxide and 1 mol chloroacetic acid (e.g. Sandopan®DTC);
  • (CC) Na-Lauryltriglykolethersulfat;(CC) Na lauryl triglycol ether sulfate;
  • (CD) Phosphorsäureester des Umsetzungsproduktes aus 1 Mol Nonylphenol und 9,5 Mol Ethylenoxid;(CD) phosphoric acid ester of the reaction product of 1 mol of nonylphenol and 9.5 mol of ethylene oxide;
  • (CE) Dinatrium-lauryl-sulfosuccinamat;(CE) disodium lauryl sulfosuccinamate;
  • (CF) Umsetzungsprodukt aus 1 Mol Nonylphenol, 7 Mol Ethylenoxid und 1 Mol Chloressigsäure und(CF) reaction product of 1 mol of nonylphenol, 7 mol of ethylene oxide and 1 mol of chloroacetic acid and
  • (CG) Ammoniumsalz des sauren Schwefelsäureesters des Adduktes aus 1 MOl Nonylphenol und 2 Mol Ethylenoxid.(CG) ammonium salt of the acid sulfuric acid ester of the adduct of 1 mole of nonylphenol and 2 moles of ethylene oxide.
Figure imgb0004
Figure imgb0004
 Beispiel 3:Example 3:

Ein rohes, mit Stärke geschlichtetes Baumwollgewebe wird mit einer Entschlichtungsflotte imprägniert, die im Liter
2 g des gemäss Beispiel 2 hergestellten Textilhilfmittels,
4 g einer stabilisierten Bakterienamylase und
3 g NaCl
enthält und eine Calciumwasserhärte von 10° dH aufweist und durch Abquetschen auf eine Flottenaufnahme von 100 % gebracht. Das imprägnierte Gewebe wird aufgerollt, mit einer Plastikfolie luft­dicht verpackt und während 24 Stunden bei Raumtemperatur (15-25°C) gelagert. Das Gewebe wird anschliessend zuerst mit heissem, 4 g/l festes NaOH enthaltendem Wasser (90-98°C) gewaschen, dann mit warmem und zuletzt mit kaltem Wasser gespült, neutralisiert und getrocknet.A raw, starch-sized cotton fabric is impregnated with a desizing liquor, which is in liters
2 g of the textile aid produced according to Example 2,
4 g of a stabilized bacterial amylase and
3 g NaCl
contains and has a calcium water hardness of 10 ° dH and brought to a liquor absorption of 100% by squeezing. The impregnated fabric is rolled up, packed airtight with a plastic film and for 24 hours at room temperature (15-25 ° C) stored. The fabric is then first washed with hot water (90-98 ° C.) containing 4 g / l solid NaOH, then rinsed with warm and finally with cold water, neutralized and dried.

Der nach der TEGEWA-Violettskala gemessene Entschlichtungsgrad beträgt Note 1 für das Rohgewebe und Note 7 für das mit dem erfin­dungsgemässen Hilfsmittel, gemäss Beispiel 1, behandelte Gewebe.The degree of desizing measured according to the TEGEWA violet scale is grade 1 for the raw fabric and grade 7 for the fabric treated with the aid according to the invention, according to example 1.

Verwendet man bei sonst gleichen Bedingungen ein anionaktives Waschmittel z.B. das Di-natriumsalz der 1-Benzyl-2-heptadecyl-benz­imidazol-disulfonsäure anstelle des erfindungsgemässen Hilfsmittels, so beträgt der Entschlichtungsgrad die Note 5 (Bereich der Skala 1-9).If an anionic detergent is used under otherwise identical conditions e.g. the disodium salt of 1-benzyl-2-heptadecyl-benzimidazole-disulfonic acid instead of the auxiliary according to the invention, the degree of desizing is 5 (range on the scale 1-9).

Beispiel 4:Example 4:

In einem Jet mit 3000 l Fassungsvermögen werden 600 l Wasser (5° dH) und 121 kg Rohbaumwoll-Tricot vorgelegt und auf 60°C aufgeheizt. Dann werden 0,7 ml/l des gemäss Beispiel 2 hergestellten Textil­hilfsmittels zugesetzt und der Tricot während 10 Minuten vorgenetzt. Dabei tritt kein störender Schaum auf. Anschliessend werden nachein­ander 0,5 ml/l eines Peroxidstabilisators, z.B. eine Mischung aus Natriumgluconat, Magnesiumchlorid und einem Gemisch von oligomeren Esterkondensaten der 1-Hydroxyethan-1,1diphosphonsäure 1,0 ml/l Natronlauge 45° Bé und 2,0 ml/l Wasserstoffperoxid 35 % zugesetzt und das Bad innerhalb 30 Minuten auf 90°C aufgeheizt. Bei dieser Temperatur wird während 45 Minuten gebleicht. Man lässt abkühlen und gibt dem Bad 3 g/l eines Reduktionsmittels, zur Zerstörung von Restsauerstoff zu und behandelt 15 Minuten lang. Das Bad wird abgelassen und das Färbebad eingefüllt. Die Vorbehandlung ergab ein gutes Basisweiss für die anschliessende Pastellfärbung.600 l of water (5 ° dH) and 121 kg of raw cotton tricot are placed in a jet with a capacity of 3000 l and heated to 60 ° C. Then 0.7 ml / l of the textile aid prepared according to Example 2 are added and the tricot is pre-wetted for 10 minutes. There is no annoying foam. Then 0.5 ml / l of a peroxide stabilizer, for example a mixture of sodium gluconate, magnesium chloride and a mixture of oligomeric ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, 1.0 ml / l 45 ° Bé sodium hydroxide solution and 2.0 ml / l Hydrogen peroxide 35% added and the bath heated to 90 ° C within 30 minutes. It is bleached at this temperature for 45 minutes. Allow to cool and add 3 g / l of a reducing agent to the bath to destroy residual oxygen and treat for 15 minutes. The bath is drained and the dye bath filled. The pretreatment resulted in a good basic white for the subsequent pastel coloring.

Beispiel 5:Example 5:

Ein Gewebe aus Polyester/Baumwolle 65/35 von 200 g/m² wurde auf einer Steepmaster-Kontinuebleichanlage gebleicht. Das mit einer Mischschlichte versehene Material wurde entschlichtet, gespült und nass-in-nass mit einem Bleichbad folgender Zusammensetzung imprägniert:
2 ml/l des gemäss Beispiel 2 hergestellten Textilhilfsmittels
8 ml/l einer Zusammensetzung aus Esterkondensaten der 1-Hydroxy­ethan-1,1-diphosphonsäure, Alkaligluconat und Magnesium­chlorid
15 ml/l Natronlauge 50° Bé
36 ml/l H₂O₂ (50 %)A fabric of polyester / cotton 65/35 of 200 g / m² was bleached on a Steepmaster continuous bleaching machine. The material with a mixed size was desized, rinsed and wet-on-wet impregnated with a bleaching bath of the following composition:
2 ml / l of the textile aid prepared according to Example 2
8 ml / l of a composition of ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, alkali metal gluconate and magnesium chloride
15 ml / l caustic soda 50 ° Bé
36 ml / l H₂O₂ (50%)

Das so imprägnierte Material durchläuft während 20 Minuten ein auf 60°C aufgeheiztes Bleichbad folgender Zusammensetzung:
2 ml/l des gemäss Beispiel 2 hergestellten Textilhilfsmittels
8 ml/l einer Zusammensetzung aus Esterkondensaten der 1-Hydroxy­ethan-1,1-diphosphonsäure, Alkaligluconat und Magnesium­chlorid
10,5 ml/l Natronlauge 50 %
18,0 ml/l H₂O₂ (50 %).
Nach dieser Behandlung, die ohne Schaumentwicklung durchgeführt werden kann, wird das Gewebe abgequetscht und anschliessend 2 Minuten mit Sattdampf gedämpft. Nachher wird gründlich heiss und kalt gespült. Das so behandelte Material weist einen Weissgrad (Filger 46) von 85 % auf, gemessen mit dem Elrepho-Gerät. Der DP-Wert der behandelten Ware betrug 2500, der Schädigungsfaktor s nach Eisenhut: 0,1, d.h. ungeschädigt.The material impregnated in this way runs through a bleaching bath heated to 60 ° C. of the following composition for 20 minutes:
2 ml / l of the textile aid prepared according to Example 2
8 ml / l of a composition of ester condensates of 1-hydroxyethane-1,1-diphosphonic acid, alkali metal gluconate and magnesium chloride
10.5 ml / l sodium hydroxide solution 50%
18.0 ml / l H₂O₂ (50%).
After this treatment, which can be carried out without foaming, the tissue is squeezed off and then steamed for 2 minutes with saturated steam. Afterwards it is rinsed thoroughly hot and cold. The material treated in this way has a whiteness (Filger 46) of 85%, measured with the Elrepho device. The DP value of the treated goods was 2500, the damage factor s according to Eisenhut: 0.1, ie undamaged.

Beispiel 6:Example 6:

Ein rohes, geschlichtetes Baumwollgewebe von 208 g/m² wird mit einer Flotte, die im Liter 100 ml Natronlauge von 36° Bé enthält, imprägniert und auf eine Flottenaufnahme von 60 % abgequetscht. Anschliessend wird 10 Minuten lang mit Sattdampf bei 101°C gedämpft und danach heiss und kalt gespült. Anschliessend wird getrocknet und der CIBA-GEIGY-Weissgrad bestimmt, der -25 beträgt, (der des rohen, unbehandelten Gewebes -67). Gibt man dieser Flotte jedoch 10 g/l des gemäss Beispiel 2 hergestellten Textilhilfsmittels zu, so erhöht sich die Flottenaufnahme auf 95 % und der Weissgrad des behandelten Gewebes hat den Wert von +15.A raw, sized cotton fabric of 208 g / m² is impregnated with a liquor containing 100 ml of 36 ° Bé sodium hydroxide solution and squeezed to a liquor absorption of 60%. It is then steamed with saturated steam at 101 ° C for 10 minutes and then rinsed hot and cold. It is then dried and the CIBA-GEIGY whiteness is determined, which is -25, (that of the raw, untreated tissue -67). However, if 10 g / l of the textile aid prepared according to Example 2 are added to this liquor, the liquor absorption increases to 95% and the whiteness of the treated fabric has a value of +15.

Beispiel 7:Example 7:

Ein rohes Baumwollgewirke mit einem Flächengewicht von 285 g/m² wird auf einem Foulard bei 25°C mit einer Flotte, die im Liter
50 g des Farbstoffes der Formel

Figure imgb0005
5 g des gemäss Beispiel 2 hergestellten Textilhilfs­mittels
15 ml Natriumhydroxidlösung (30 %) und
75 ml Natronwasserglaslösung mit 26,3-27,7 % Silikatgehalt, enthält, imprägniert, worauf bei einer Tauchzeit von 1,0 Sekunden bei 2 Passagen und einem Walzendruck von 1,5 bar/cm² eine Flotten­aufnahme von 83 % (berechnet auf das Trockengewicht des Substrates) erzielt wird. Hiernach wird das Gewirke aufgerollt und 6 Stunden bei 25°C gelagert. Alsdann wird das Gewirke gespült und 20 Minuten bei Kochtemperatur mit einem nicht-ionogenen Waschmittel (0,5 g/l des Additionsproduktes von 9 Mol Ethylenoxid an 1 Mol Nonylphenol) in einem Flottenverhältnis von 1:40 nachgewaschen. Anschliessend wird das Substrat nochmals gespült und getrocknet.A raw knitted cotton fabric with a basis weight of 285 g / m² is placed on a padder at 25 ° C with a liquor in liters
50 g of the dye of the formula
Figure imgb0005
 5 g of the textile aid prepared according to Example 2
15 ml sodium hydroxide solution (30%) and
Contains 75 ml of soda water glass solution with 26.3-27.7% silicate content, impregnated, whereupon with a diving time of 1.0 seconds at 2 passages and a roller pressure of 1.5 bar / cm² a liquor absorption of 83% (calculated on the dry weight of the substrate) is achieved. The knitted fabric is then rolled up and stored at 25 ° C. for 6 hours. The knitted fabric is then rinsed and washed for 20 minutes at cooking temperature with a nonionic detergent (0.5 g / l of the addition product of 9 mol of ethylene oxide with 1 mol of nonylphenol) in a liquor ratio of 1:40. The substrate is then rinsed again and dried.

Man erhält eine farbstarke und brillante rote Färbung, die sich besonders durch ein ruhiges Warenbild auszeichnet.A strong, brilliant red color is obtained, which is particularly characterized by a calm product appearance.

Claims (13)

1. Lagerstabiles, hartwasserbeständiges, wässeriges Textilhilfs­mittel, dadurch gekennzeichnet, dass es mindestens (a) einen Phosphorsäureteilester, (b) ein nicht-ionogenes Tensid, (c) ein anionisches Tensid und (d) ein Alkalimetallhydroxyd enthält. 1. Storage-stable, hard water-resistant, aqueous textile auxiliary, characterized in that it is at least (a) a partial phosphoric acid ester, (b) a non-ionic surfactant, (c) an anionic surfactant and (d) contains an alkali metal hydroxide. 2. Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass die Komponente a) ein aus der Umsetzung von 1 Mol P₂O₅ mit 3 Mol eines C₆-C₁₀-Alkanols gebildeter Teilester ist.2. Textile auxiliary according to claim 1, characterized in that component a) is a partial ester formed from the reaction of 1 mole of P₂O₅ with 3 moles of a C₆-C₁₀ alkanol. 3. Textilhilfsmittel gemäss Anspruch 2, dadurch gekennzeichnet, dass die Komponente a) in Form eines Salzes vorliegt.3. Textile auxiliary according to claim 2, characterized in that component a) is in the form of a salt. 4. Textilhilfsmittel gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Komponente b) ein nicht-ionogenes Alkylen­oxidanlagerungsprodukt von 1 bis 100 Mol Alkylenoxid an 1 Mol eines aliphatischen Monoalkohols mit mindestens 4 C-Atomen ist.4. Textile auxiliary according to one of claims 1 to 3, characterized in that component b) is a non-ionic alkylene oxide addition product of 1 to 100 moles of alkylene oxide to 1 mole of an aliphatic monoalcohol with at least 4 carbon atoms. 5. Textilhilfsmittel gemäss Anspruch 4, dadurch gekennzeichnet, dass die Komponente b) ein teilweise endständig, mit C₁-C₃-Alkyl blockiertes Anlagerungsprodukt von 1 bis 100 Mol Ethylenoxid und/oder Propylenoxid an 1 Mol eines aliphatischen Monoalkohols mit 8 bis 22 C-Atomen ist.5. Textile auxiliary according to claim 4, characterized in that component b) is a partially terminal, with C₁-C₃-alkyl blocked adduct of 1 to 100 moles of ethylene oxide and / or propylene oxide to 1 mole of an aliphatic monoalcohol with 8 to 22 carbon atoms is. 6. Textilhilfsmittel gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Komponente c) ein anionisches Tensid der Formel
R―O―(CH₂CH₂O-
Figure imgb0006
-X
ist, worin R Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, Alkylphenyl mit 4 bis 16 C-Atomen im Alkylteil oder o-Phenylphenyl, X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure oder den Rest einer organischen Säure und m 2 bis 30 bedeuten, und das Tensid als freie Säure, Natrium- oder Ammoniumsalz vorliegt.6. Textile auxiliary according to one of claims 1 to 5, characterized in that component c) is an anionic surfactant of the formula
R ― O― (CH₂CH₂O-
Figure imgb0006
-X
is where R is alkyl or alkenyl with 8 to 22 C atoms, alkylphenyl with 4 to 16 C atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid or the rest of an organic acid and m 2 to 30 mean, and the surfactant is present as a free acid, sodium or ammonium salt. 7. Textilhilfsmittel gemäss Anspruch 6, dadurch gekennzeichnet, dass die Komponente (c) ein anionisches Tensid der Formel
R-O-(CH₂CH₂O-
Figure imgb0007
-X₁
ist, worin R Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, X₁ Carboxy­alkyl mit 1 bis 3 C-Atomen im Alkylteil und m 2 bis 30 bedeuten.7. Textile auxiliary according to claim 6, characterized in that component (c) is an anionic surfactant of the formula
RO- (CH₂CH₂O-
Figure imgb0007
-X₁
is in which R is alkyl or alkenyl having 8 to 22 carbon atoms, X₁ carboxyalkyl having 1 to 3 carbon atoms in the alkyl part and m are 2 to 30. 8. Textilhilfsmittel gemäss einem der Ansprüche 2 bis 7, dadurch gekennzeichnet, dass die Komponente (a) der Teilester aus der Umsetzung von 1 Mol P₂O₅ und 3 Mol 2-Ethylhexanol, die Kompo­nente (b) teilweise endständig mit einer Methylgruppe blockierte Anlagerungsprodukt von 5 Mol Ethylenoxid und 8 Mol Propylenoxid an 1 Mol eines C₉-C₁₁-Alkanols und die Komponente (c) das Natriumsalz eines endständig mit einer Carboxymethylgruppe blockierten Anlage­rungsproduktes von 2,5 Mol Ethylenoxid an 1 Mol Laurylalkohol ist.8. Textile auxiliaries according to one of claims 2 to 7, characterized in that component (a) of the partial ester from the reaction of 1 mol of P₂O₅ and 3 mol of 2-ethylhexanol, component (b) partially with a methyl group blocked adduct of 5 Moles of ethylene oxide and 8 moles of propylene oxide to 1 mole of a C₉-C₁₁ alkanol and component (c) is the sodium salt of an addition product of 2.5 moles of ethylene oxide which is blocked with a carboxymethyl group and 1 mole of lauryl alcohol. 9. Textilhilfsmittel gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es, bezogen auf das Mittel
5 bis 45 Gew.% der Komponente (a),
3 bis 27 Gew.% der Komponente (b),
0,8 bis 7 Gew.% der Komponente (c),
1,2 bis 19 Gew.% der Komponente (d) und
2 bis 90 Gew.% deionisiertes Wasser
enthält.9. Textile aid according to one of claims 1 to 8, characterized in that it is based on the agent
5 to 45% by weight of component (a),
3 to 27% by weight of component (b),
0.8 to 7% by weight of component (c),
1.2 to 19% by weight of component (d) and
2 to 90% by weight of deionized water
contains. 10. Verwendung des Textilhilfsmittels gemäss einem der Ansprüche 1 bis 9 als Netz- und Entlüftungsmittel für Fasermaterialien.10. Use of the textile auxiliary according to one of claims 1 to 9 as a wetting and deaerating agent for fiber materials. 11. Verfahren zum Netzen und Entlüften von Fasermaterialien, dadurch gekennzeichnet, dass man diese Materialien in wässerigem Medium in Gegenwart eines wässerigen Hilfsmittelgemisches behandelt, das mindestens
(a) einen Phosphorsäureteilester,
(b) ein nicht-ionogenes Tensid,
(c) ein anionisches Tensid und
(d) ein Alkalimetallhydroxyd
enthält.11. A method for wetting and deaerating fiber materials, characterized in that these materials are treated in an aqueous medium in the presence of an aqueous auxiliary mixture which at least
(a) a partial phosphoric acid ester,
(b) a non-ionic surfactant,
(c) an anionic surfactant and
(d) an alkali metal hydroxide
contains. 12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass man das Textilhilfsmittel in einer Menge von 0,1 bis 20 g, vorzugsweise 0,5 bis 10 g pro Liter Flotte einsetzt.12. The method according to claim 11, characterized in that the textile auxiliary is used in an amount of 0.1 to 20 g, preferably 0.5 to 10 g per liter of liquor. 13. Verfahren gemäss einem der Ansprüche 11 und 12, dadurch gekenn­zeichnet, dass das Fasermaterial kontinuierlich oder diskontinuier­lich in wässriger Flotte behandelt wird.13. The method according to any one of claims 11 and 12, characterized in that the fiber material is treated continuously or discontinuously in an aqueous liquor.
EP87810711A 1986-12-08 1987-12-02 Aqueous storage-stable auxiliary textile agent resistant to hard water Expired - Lifetime EP0274350B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87810711T ATE74386T1 (en) 1986-12-08 1987-12-02 STORAGE STABLE, HARD WATER RESISTANT, WATER-BASED TEXTILE AID.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH488686 1986-12-08
CH4886/86 1986-12-08
CH2914/87 1987-07-30
CH291487 1987-07-30

Publications (2)

Publication Number Publication Date
EP0274350A1 true EP0274350A1 (en) 1988-07-13
EP0274350B1 EP0274350B1 (en) 1992-04-01

Family

ID=25691721

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87810711A Expired - Lifetime EP0274350B1 (en) 1986-12-08 1987-12-02 Aqueous storage-stable auxiliary textile agent resistant to hard water

Country Status (7)

Country Link
US (1) US4844710A (en)
EP (1) EP0274350B1 (en)
KR (1) KR880007851A (en)
BR (1) BR8706579A (en)
CA (1) CA1340335C (en)
DE (1) DE3777990D1 (en)
ES (1) ES2030759T3 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
EP0716180A1 (en) * 1994-12-08 1996-06-12 Ciba-Geigy Ag Wetting agent for mercerizing
US5741783A (en) * 1994-12-22 1998-04-21 Ciba Specialty Chemicals Corporation N-cyanomethylated chitosans and hydrolysates thereof
DE102004042738A1 (en) * 2004-09-03 2006-03-23 Cht R. Beitlich Gmbh Essential neutral textile additives, useful during textile improvement treatment and coloring e.g. cotton, comprises reactive products of phosphorus pentoxide or polyphosphoric acid with alcohols and carbonic acid and/or its derivative

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462059B1 (en) * 1990-06-11 1997-07-02 Ciba SC Holding AG Low-foaming, silicone-free, aqueous textile auxiliaries, their preparation and their use
DE4202720A1 (en) * 1991-05-02 1992-11-05 Henkel Kgaa IMPROVEMENT OF THE SPRAYING ORDER OF WAESSER TREATMENT BOOTS ON TEXTILE MATERIAL
DE69100809T2 (en) * 1991-06-14 1994-05-19 The Procter & Gamble Co., Cincinnati, Ohio Stable bleaching compositions containing hydrogen peroxide.
US5711764A (en) * 1996-10-03 1998-01-27 Wasinger; Eric M. Composition and process for decolorizing and/or desizing garments
EP1149945A1 (en) * 2000-04-29 2001-10-31 Ciba Spezialitätenchemie Pfersee GmbH Composition for the pretreatment of fibrous materials

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DE730015C (en) * 1938-01-07 1943-01-06 Sandoz Ag Process for mercerizing
BE698817A (en) * 1967-05-22 1967-11-03
DE2164235A1 (en) * 1971-12-23 1973-06-28 Hoechst Ag STRONG ALKALINE ALLOY AND MERCERIZING SOLUTIONS
GB1445716A (en) * 1973-04-24 1976-08-11 Diversey Ltd Cleaning compositions
DE2659705A1 (en) * 1976-12-31 1978-07-06 Huels Faserwerke Preparations for synthetic fibres - contg. mineral oil, higher alcohol, phosphate ester and amine
US4106901A (en) * 1976-08-31 1978-08-15 Star Chemical, Inc. Emulsifier-solvent scour composition and method of treating textiles therewith
DE3230101A1 (en) * 1981-08-22 1983-03-10 Sandoz-Patent-GmbH, 7850 Lörrach Alkali-dry process for natural cellulose fibres and their blends with synthetic fibres
EP0102930A1 (en) * 1982-09-08 1984-03-14 Ciba-Geigy Ag Wetting agent and its use as mercerising aid

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DE1245898C2 (en) * 1964-10-23 1973-01-25 Hoechst Ag Low-foaming, leveling wetting agent
FR2551474B1 (en) * 1983-09-01 1986-12-05 Sandoz Sa PROCESS FOR TREATING CELLULOSIC TEXTILE MATERIALS

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DE730015C (en) * 1938-01-07 1943-01-06 Sandoz Ag Process for mercerizing
BE698817A (en) * 1967-05-22 1967-11-03
DE2164235A1 (en) * 1971-12-23 1973-06-28 Hoechst Ag STRONG ALKALINE ALLOY AND MERCERIZING SOLUTIONS
GB1445716A (en) * 1973-04-24 1976-08-11 Diversey Ltd Cleaning compositions
US4106901A (en) * 1976-08-31 1978-08-15 Star Chemical, Inc. Emulsifier-solvent scour composition and method of treating textiles therewith
DE2659705A1 (en) * 1976-12-31 1978-07-06 Huels Faserwerke Preparations for synthetic fibres - contg. mineral oil, higher alcohol, phosphate ester and amine
DE3230101A1 (en) * 1981-08-22 1983-03-10 Sandoz-Patent-GmbH, 7850 Lörrach Alkali-dry process for natural cellulose fibres and their blends with synthetic fibres
EP0102930A1 (en) * 1982-09-08 1984-03-14 Ciba-Geigy Ag Wetting agent and its use as mercerising aid

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420802A2 (en) * 1989-09-26 1991-04-03 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
EP0420802A3 (en) * 1989-09-26 1991-05-15 Ciba-Geigy Ag Aqueous, storage stable, low foaming wetting agent
EP0716180A1 (en) * 1994-12-08 1996-06-12 Ciba-Geigy Ag Wetting agent for mercerizing
US5709810A (en) * 1994-12-08 1998-01-20 Ciba Specialty Chemicals Corporation Mercerization wetting agent compositions
US5741783A (en) * 1994-12-22 1998-04-21 Ciba Specialty Chemicals Corporation N-cyanomethylated chitosans and hydrolysates thereof
DE102004042738A1 (en) * 2004-09-03 2006-03-23 Cht R. Beitlich Gmbh Essential neutral textile additives, useful during textile improvement treatment and coloring e.g. cotton, comprises reactive products of phosphorus pentoxide or polyphosphoric acid with alcohols and carbonic acid and/or its derivative

Also Published As

Publication number Publication date
BR8706579A (en) 1988-07-12
US4844710A (en) 1989-07-04
CA1340335C (en) 1999-01-26
KR880007851A (en) 1988-08-29
ES2030759T3 (en) 1992-11-16
EP0274350B1 (en) 1992-04-01
DE3777990D1 (en) 1992-05-07

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