EP0420802A2 - Aqueous, storage stable, low foaming wetting agent - Google Patents

Aqueous, storage stable, low foaming wetting agent Download PDF

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Publication number
EP0420802A2
EP0420802A2 EP90810704A EP90810704A EP0420802A2 EP 0420802 A2 EP0420802 A2 EP 0420802A2 EP 90810704 A EP90810704 A EP 90810704A EP 90810704 A EP90810704 A EP 90810704A EP 0420802 A2 EP0420802 A2 EP 0420802A2
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European Patent Office
Prior art keywords
wetting agent
weight
hydrogen
carbon atoms
alkyl
Prior art date
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Granted
Application number
EP90810704A
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German (de)
French (fr)
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EP0420802A3 (en
EP0420802B1 (en
Inventor
Christian Guth
Albert Stehlin
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BASF Schweiz AG
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Ciba Geigy AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • 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
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
    • D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
    • 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
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
    • D06P1/6133—Addition products of hydroxyl groups-containing compounds with oxiranes from araliphatic or aliphatic alcohols
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/62—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/621—Compounds without nitrogen
    • D06P1/627—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing

Definitions

  • the present invention relates to a new aqueous, storage-stable, low-foaming wetting agent in use, and to its production and use in textile treatment.
  • the object of the present invention is to provide a wetting agent whose cloud point enables storage stability up to 40 ° C. and at the same time shows low-foaming behavior in use.
  • the substituent R in formula (1) advantageously represents the hydrocarbon radical of an unsaturated or saturated aliphatic monoalcohol with 8 to 22 carbon atoms.
  • the hydrocarbon radical can be straight-chain or branched.
  • R is preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.
  • natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C9-C11 oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). (“Alfol" is a registered trademark).
  • Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexanedecenyl alcohol or oleyl alcohol.
  • the alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups, which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.
  • Alkylene-O p chains are preferably of the ethylene glycol, ethylene propylene glycol or ethylene isopropylene glycol type; p is preferably 4 to 20.
  • nonionic surfactants are: - Addition products of preferably 4 to 20 moles of alkylene oxides, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as isopropylene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms.
  • non-ionic surfactants correspond to the formula in which one of Y1 and Y2 is methyl or ethyl and the other is hydrogen, n1 is an integer from 2 to 24 and ml is an integer from 0 to 15, the sum of m1 and n1 is a maximum of 24 and R and R1 have the meaning given in formula (1).
  • non-ionic surfactants of the formula wherein R2 C9 to C14 alkyl, R3 is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl, of Y3 and Y4 one residue is hydrogen or methyl and the other hydrogen, m2 is an integer from 4 to 8 and n2 is an integer from 4 to 8.
  • R2 has the meaning given in formula (3)
  • R4 is hydrogen, C1 to C4-alkyl or phenyl-lower alkyl, of Y5 and Y6 one residue is hydrogen and the other is ethyl
  • n3 is an integer from 4 to 8
  • m3 is an integer from 1 to 3.
  • the nonionic surfactants of the formulas (1) to (4) are prepared in a manner known per se, for example by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a short-chain, cycloaliphatic, fatty, phenyl-lower alkyl or styryl alcohol.
  • Particularly preferred hydrotroping agents of component (b) according to the invention are alkyl sulfates of the formula (5) R8O - SO3X, wherein R8 is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and X represents hydrogen, alkali metal or ammonium.
  • alkyl sulfate is in the form of a salt
  • sodium, potassium or ammonium salts can be used, for example.
  • the sodium salt is preferred.
  • Very particularly preferred hydrotroping agents of component (b) are alkyl sulfates in which the substituent R8 in formula (5) is the hydrocarbon radical of an aliphatic saturated monoalcohol having 4 to 24 carbon atoms.
  • the hydrocarbon residue can be straight-chain or branched.
  • Suitable aliphatic saturated monoalcohols are natural alcohols, such as lauryl, myristyl, cetyl, stearyl, arachnidyl or behenyl alcohol.
  • Preferred are compounds in which the substituent R8 is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, for example.
  • the alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.
  • alkyl sulfonates of formula (8) and their alkali metal or amine salts can also be used together with other compounds as hydrotroping agents, e.g. with polymerized acrylic acid, C1 to C10 - alkylphosphonic acid or C1 to C10 - alkylphosphonic acid esters.
  • alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.
  • the wetting agent according to the invention can additionally contain an optional component (c).
  • Non-polar organic solvents with a flash point above 65 ° C are suitable.
  • cyclic straight-chain or in particular branched alcohols are used, such as e.g. Cyclohexanol, methylcyclohexanol, tetralin, n-hexanol, 2-ethylhexanol-1, isooctyl alcohol, isononyl alcohol and especially trimethylhexanol-3,5,5.
  • esters such as tributyl citrate or tributyl phosphate can be used as non-polar organic solvents.
  • the new wetting agents can be prepared by simply stirring the components (a), (b) and, if appropriate, (c).
  • the preparation is preferably carried out by mixing components (a), (b) and optionally (c) with stirring and adding deionized water until a homogeneous solution is obtained.
  • Preferred wetting agents according to the invention particularly advantageously contain, based on the mixture as a whole, 15 to 60% by weight of component (a), 2 to 10% by weight of component (b), 0 to 4% by weight of component (c) and ad 100% water.
  • the new wetting agents are aqueous formulations with low foaming in use, which are characterized by a cloud point which is above 40 ° C. and which are stable up to 40 ° C.
  • wetting agents are used in textile treatment, especially in pretreatment, such as in long liquor bleaching or in chlorine and peroxide hot bleaching.
  • the amounts in which the wetting agent according to the invention is added to the treatment liquors are between 0.1 and 10, preferably 0.5 and 5 g per liter of treatment liquor.
  • the fleet can also contain other additives, e.g. 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, cellulose, 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 made of 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 10 to 60 ° C, but preferably at room temperature.
  • the cellulose material is optionally after intermediate drying, heat treatment, e.g. Subject to temperatures from 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 direct, i.e. without intermediate drying, by steaming at 95 to 120 ° C, preferably 100 to 106 ° C.
  • the heat treatment can take 30 seconds to 30 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 10 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, jet or reel runner. If necessary, however, the treatment can also be carried out up to 150 ° C., preferably 105 to 140 ° C., under pressure in so-called high-temperature apparatus (HT apparatus).
  • HT apparatus high-temperature apparatus
  • the fiber materials are washed with hot water at around 90 to 98 ° C and then with warm and finally with cold water rinsed thoroughly, neutralized if necessary and then dried preferably at elevated temperatures.
  • the main advantages of the wetting agents according to the invention are their good storage stability and their low-foaming behavior in use.
  • Formulations A, B, C and D are prepared by mixing the components listed in Table I according to their weight proportions with stirring until a homogeneous solution is obtained.
  • Table I A B C. D
  • Nonionic surfactant of formula (1) for example 15 moles of the ethylene / propylene oxide adduct with 1 mole of a C9 - C11 fatty alcohol 25th 25th 25th 25th 2-ethylhexanol sulfate sodium salt (40% solution) 9 9 3,5,5-trimethylhexanol 3rd 2nd Sodium cumene sulfonate 100% 10th 10th Isopropanol 5 water 66 63 63 60 Cloud point [° C] * 40.5 41.5 45.3 55.5 Foam height [ml] of 2 g / l of the formulation ** 70 50 50 80 * Cloud point of the formulation tel quel; ** Foam test based on DIN 53902
  • a raw cotton jersey is bleached in a ®AHIBA dyeing machine in a bath, which is per liter 2g of formulation B 0.2g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US-PS 4254063, Na-gluconate and magnesium chloride (ratio 2: 1: 1) 1g NaOH solid and Contains 5 ml H2O2 (35%).
  • the bleach bath is heated to 90 ° C. within 20 minutes and then held at this temperature for a further 30 minutes.
  • the substrate is then washed out hot and cold and neutralized. No disruptive foaming occurs during bleaching.
  • the result is a uniform degree of whiteness, which is increased from ⁇ 72 to 50 CIBA-GEIGY whiteness units.
  • a raw cotton jersey with a running weight of 80 g is passed through a chlorine bleaching bath per liter in a Galaxy system (Benninger, Switzerland) at a speed of 54 m / min 4g active chlorine 1.5g NaOH (100%) and Contains 2 g of formulation B.
  • the residence time is 15 minutes at 16 ° C.
  • the goods are evenly wetted and the chlorine bleach bath is foam-free.
  • the goods are squeezed and passed through an H2O2 bleaching bath, which is per liter 2 g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US Pat. No. 4,254,063, Na gluconate and magnesium chloride (ratio 2: 1: 1) 3g NaOH (100%) 3 ml water glass 38 ° Be 0.5 g of formulation B and Contains 15 ml H2O2 (35%).
  • the residence time is 35 minutes at 85 ° C. No annoying foam formation occurs in the peroxide bleaching bath either.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

There is described an aqueous, storage-stable, low-foam wetting agent comprising a nonionic surfactant selected from the group of the partially end-capped alkoxylated fatty alcohols, characterised in that it comprises (a) from 10 to 80% of a nonionic surfactant of the general formula <IMAGE> where R is an aliphatic radical of at least 8 carbon atoms, R1 is hydrogen, C1-C8-alkyl, a cycloaliphatic radical of at least 5 carbon atoms, phenyl(lower alkyl) or styryl, "Alkylen" is an alkylene radical of 2 to 14 carbon atoms, and p is a number from 2 to 24, and (b) from 1 to 10% by weight of a hydrotrope. The novel wetting agent is used in textile treatment, in particular in pretreatment.

Description

Die vorliegende Erfindung betrifft ein neues wässriges, lagerstabiles, in der Anwendung gering schäumendes Netzmittel sowie seine Herstellung und Verwendung in der Textil­behandlung.The present invention relates to a new aqueous, storage-stable, low-foaming wetting agent in use, and to its production and use in textile treatment.

Es ist z.B. aus den DE-A 33 15 961 und 3625078 bekannt, bei der Behandlung von Textilien schaumarme Netzmittel einzusetzen, um die Behandlung in alkalischen Flotten zu verbessern. Die dabei vorgeschlagenen Netzmittel weisen allerdings einen niedrigen Trübungspunkt auf, der sich ungünstig auf deren Lagerstabilität auswirkt. Bei Tempe­raturen oberhalb des Trübungspunktes kommt es zur Phasentrennung, wodurch die Ver­wendung dieser Netzmittel nicht mehr möglich ist.It is e.g. known from DE-A 33 15 961 and 3625078 to use low-foaming wetting agents in the treatment of textiles in order to improve the treatment in alkaline liquors. However, the wetting agents proposed here have a low cloud point, which has an unfavorable effect on their storage stability. At temperatures above the cloud point, phase separation occurs, which means that the use of these wetting agents is no longer possible.

Die Aufgabe der vorliegenden Erfindung besteht darin, ein Netzmittel bereitzustellen, dessen Trübungspunkt eine Lagerstabilität bis 40°C ermöglicht und gleichzeitig ein schaumarmes Verhalten in der Anwendung zeigt.The object of the present invention is to provide a wetting agent whose cloud point enables storage stability up to 40 ° C. and at the same time shows low-foaming behavior in use.

Das erfindungsgemässe wässrige, lagerstabile, in der Anwendung gering schäumende Netzmittel, enthaltend ein nichtionogenes Tensid aus der Gruppe der teilweise end­gruppenverschlossenen alkoxylierten Fettalkohole ist dadurch gekennzeichnet, dass es

  • (a) 10 bis 80 Gew.% eines nichtionogenen Tensids der allgemeinen Formel
    (1) R-O(̵Alkylen-)̵
    Figure imgb0001
    R₁
    worin
    R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
    R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Phenylniederalkyl oder Styryl,
    "Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
    p eine Zahl von 2 bis 24 bedeuten und
  • (b) 1 bis 10 Gew.% eines Hydrotropiermittels
enthält.The aqueous, storage-stable, low-foaming wetting agent according to the invention, containing a nonionic surfactant from the group of partially end-capped alkoxylated fatty alcohols, is characterized in that it
  • (a) 10 to 80% by weight of a nonionic surfactant of the general formula
    (1) RO (̵alkylene-) ̵
    Figure imgb0001
    R₁
    wherein
    R is an aliphatic radical with at least 8 carbon atoms,
    R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
    "Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
    p is a number from 2 to 24 and
  • (b) 1 to 10% by weight of a hydrotroping agent
contains.

Der Substituent R in Formel (1) stellt vorteilhafterweise den Kohlenwasserstoffrest eines ungesättigten oder gesättigten aliphatischen Monoalkohols mit 8 bis 22 Kohlenstoff­atomen dar. Der Kohlenwasserstoffrest kann geradkettig oder verzweigt sein. Vorzugs­weise bedeutet R einen Alkyl- oder Alkenylrest mit 9 bis 14 C-Atomen.The substituent R in formula (1) advantageously represents the hydrocarbon radical of an unsaturated or saturated aliphatic monoalcohol with 8 to 22 carbon atoms. The hydrocarbon radical can be straight-chain or branched. R is preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.

Als aliphatische gesättigte Monoälkohole können natürliche Alkohole, wie z.B. Lauryl­alkohol, Myristylalkohol, Cetylalkohol oder Stearylalkohol, sowie synthetische Alkohole, wie z.B. 2-Ethylhexanol, 1,1,3,3-Tetramethylbutanol, Octan-2-ol, Isononylalkohol, Tri­methylhexanol, Trimethylnonylalkohol, Decanol, C₉-C₁₁-Oxoalkohol, Tridecylalkohol, Isotridecanol oder lineare primäre Alkohole (Alfole) mit 8 bis 18 Kohlenstoffatomen in Betracht kommen. Einige Vertreter dieser Alfole sind Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) oder Alfol (16-18). ("Alfol" ist ein eingetragenes Warenzeichen).As aliphatic saturated monoalcohols, natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁ oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). ("Alfol" is a registered trademark).

Ungesättigte aliphatische Monoalkohole sind beispielsweise Dodecenylalkohol, Hexan­decenylalkohol oder Oleylalkohol.Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexanedecenyl alcohol or oleyl alcohol.

Die Alkoholreste können einzeln oder in Form von Gemischen aus zwei oder mehreren Komponenten vorhanden sein, wie z.B. Mischungen von Alkyl- und/oder Alkenylgruppen, die sich von Soja-Fettsäuren, Palmkernfettsäuren oder Talg-Oelen ableiten.The alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups, which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.

(Alkylen-O)p-Ketten sind bevorzugt vom Ethylenglykol-, Ethylenpropylenglykol- oder Ethylenisopropylenglykol-Typus; p ist bevorzugt 4 bis 20.(Alkylene-O) p chains are preferably of the ethylene glycol, ethylene propylene glycol or ethylene isopropylene glycol type; p is preferably 4 to 20.

Als nichtionogene Tenside seien beispielsweise genannt:
- Anlagerungsprodukte von vorzugsweise 4 bis 20 Mol Alkylenoxiden, insbesondere Ethylenoxid, wobei einzelne Ethylenoxideinheiten durch substituierte Epoxide, wie Iso­propylenoxid und/oder Propylenoxid, ersetzt sein können, an höhere ungesättigte oder ge­sättigte Fettalkohle mit 8 bis 22 Kohlenstoffatomen.Examples of nonionic surfactants are:
- Addition products of preferably 4 to 20 moles of alkylene oxides, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as isopropylene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms.

Praktisch wichtige, nichtionogene Tenside entsprechen der Formel

Figure imgb0002
worin von Y₁ und Y₂ der eine Rest Methyl oder Ethyl und der andere Wasserstoff,
n₁ eine ganze Zahl von 2 bis 24 und
ml eine ganze Zahl von 0 bis 15 bedeutet,
wobei die Summe von m₁ und n₁ maximal 24 ist und
R und R₁ die in Formel (1) angegebene Bedeutung haben.Practically important, non-ionic surfactants correspond to the formula
Figure imgb0002
 in which one of Y₁ and Y₂ is methyl or ethyl and the other is hydrogen,
n₁ is an integer from 2 to 24 and
ml is an integer from 0 to 15,
the sum of m₁ and n₁ is a maximum of 24 and
R and R₁ have the meaning given in formula (1).

Von ganz besonderem Interesse smd nichtionogene Tenside der Formel

Figure imgb0003
worin
R₂ C₉ bis C₁₄-Alkyl,
R₃ Wasserstoff, Butyl, einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl,
von Y₃ und Y₄ der eine Rest Wasserstoff oder Methyl und der andere Wasserstoff,
m₂ eine ganze zahl von 4 bis 8 und
n₂ eine ganze Zahl von 4 bis 8 bedeuten.Of particular interest are non-ionic surfactants of the formula
Figure imgb0003
 wherein
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl,
of Y₃ and Y₄ one residue is hydrogen or methyl and the other hydrogen,
m₂ is an integer from 4 to 8 and
n₂ is an integer from 4 to 8.

Weitere wichtige nichtionogene Tenside entsprechen der Formel

Figure imgb0004
worin R₂ die in Formel (3) angegebene Bedeutung hat,
R₄ Wasserstoff, C₁ bis C₄-Alkyl oder Phenylniederalkyl,
von Y₅ und Y₆ der eine Rest Wasserstoff und der andere Ethyl,
n₃ eine ganze Zahl von 4 bis 8 und
m₃ eine ganze Zahl von 1 bis 3 bedeuten.Other important nonionic surfactants correspond to the formula
Figure imgb0004
 wherein R₂ has the meaning given in formula (3),
R₄ is hydrogen, C₁ to C₄-alkyl or phenyl-lower alkyl,
of Y₅ and Y₆ one residue is hydrogen and the other is ethyl,
n₃ is an integer from 4 to 8 and
m₃ is an integer from 1 to 3.

Die Herstellung der nichtionogenen Tenside der Formeln (1) bis (4) geschieht in an sich bekannter Weise, so z.B. durch Umsetzung der entsprechenden Alkylenoxidanlagerungs­produkte mit Thionylchlorid und nachfolgender Umsetzung der entstandenen Chlorver­bindung mit einem kurzkettigen, cycloaliphatischen, Fett-, Phenylniederalkyl- oder Styryl­alkohol.The nonionic surfactants of the formulas (1) to (4) are prepared in a manner known per se, for example by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a short-chain, cycloaliphatic, fatty, phenyl-lower alkyl or styryl alcohol.

Als Komponente (b) der erfindungsgemässen Zusammensetzung kommen folgende Verbindungen in Betracht:
- Einwertige C₄ bis C₁₈-aliphatische und monocyclische Alkohole, wie C₂-C₁₈-Alkanole, C₂-C₁₈-Alkenole und Terpenalkohole, z.B. Ethanol, Propanol, Isopropanol, Hexanol, cis-3-Hexen-1-ol, trans-2-Hexen-1-ol, 1-Octen-3-ol, Heptanol, Octanol, trans-2-cis­6-Nonadien- 1-ol, Decanol, Linanol, Geraniol, Dihydroterpinol, Myrcenol, Nopol und Terpineol;
- Aromatische Alkohole der Formel

Figure imgb0005
worin X -(CH₂)₁₋₆-, -CH=CH-CH₂- oder -O-(CH₂)₂₋₆- und
R₅, R₆ und R₇, unabhängig voneinander, Wasserstoff, Hydroxy, Halogen oder
C₁-C₆-Alkoxy bedeuten, wie z.B. Benzylalkohol, 2,4-Dichlorbenzylalkohol, Phenylethanol, Phenoxyethanol, 1-Phenoxy-2-propanol (Phenoxy-isopropanol) und Zimtalkohol;
- Sulfonate von Terpenoiden oder ein- oder zweikernigen aromatischen Verbindungen, z.B. die Sulfonate des Camphers, Toluols, Xylols, Cumols und Naphthols;
- Aliphatische gesättigte und ungesättigte C₁-C₁₁-Monocarbonsäuren, wie die Essig­säure, Propionsäure, Capronsäure, Undecylensäure;
- Gesättigte oder ungesättigte C₃-C₁₂-Di- oder Polycarbonsäuren, z.B. die Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Kork-, Azelain- und Sebacinsäure, die Undecan- und Dodecandicarbonsäure, die Fumar-, Malein-, Wein- und Apfelsäure sowie die Citronen- und Aconitsäure;
Alle erwähnten organischen Säuren können auch in Form ihrer wasserlöslichen Salze, wie der Alkalimetall-, insbesondere Natrium- oder Kaliumsalze oder der Aminsalze vorliegen.The following compounds are suitable as component (b) of the composition according to the invention:
- Monohydric C₄ to C₁₈ aliphatic and monocyclic alcohols, such as C₂-C₁₈ alkanols, C₂-C₁₈ alkenols and terpene alcohols, for example ethanol, propanol, isopropanol, hexanol, cis-3-hexen-1-ol, trans-2-hexene -1-ol, 1-octen-3-ol, heptanol, octanol, trans-2-cis6-nonadien-1-ol, decanol, linanol, geraniol, dihydroterpinol, myrcenol, nopol and terpineol;
- Aromatic alcohols of the formula
Figure imgb0005
 wherein X - (CH₂) ₁₋₆-, -CH = CH-CH₂- or -O- (CH₂) ₂₋₆- and
R₅, R₆ and R₇, independently of one another, hydrogen, hydroxy, halogen or
C₁-C₆-alkoxy such as benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenylethanol, phenoxyethanol, 1-phenoxy-2-propanol (phenoxy-isopropanol) and cinnamon alcohol;
- Sulfonates of terpenoids or mononuclear or dinuclear aromatic compounds, for example the sulfonates of camphor, toluene, xylene, cumene and naphthol;
- Aliphatic saturated and unsaturated C₁-C₁₁ monocarboxylic acids such as acetic acid, propionic acid, caproic acid, undecylenic acid;
- Saturated or unsaturated C₃-C₁₂-di- or polycarboxylic acids, such as the malonic, Succinic, glutaric, adipic, pimelic, cork, azelaic and sebacic acids, undecanoic and dodecanedicarboxylic acids, fumaric, maleic, tartaric and malic acids as well as citric and aconitic acids;
All of the organic acids mentioned can also be in the form of their water-soluble salts, such as the alkali metal, in particular sodium or potassium, salts or the amine salts.

Besonders bevorzugte erfindungsgemässe Hydrotropiermittel der Komponente (b) sind Alkylsulfate der Formel
(5)      R₈O - SO₃X,
worin
R₈ einen aliphatischen gesättigten, verzweigten oder geradkettigen Rest mit 4 bis 24 Kohlenstoffatomen und
X Wasserstoff, Alkalimetall oder Ammonium bedeutet.Particularly preferred hydrotroping agents of component (b) according to the invention are alkyl sulfates of the formula
(5) R₈O - SO₃X,
wherein
R₈ is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and
X represents hydrogen, alkali metal or ammonium.

Liegt das Alkylsulfat als Salz vor, so kommen beispielsweise Natrium-, Kalium- oder Ammoniumsalze in Betracht. Das Natriumsalz ist bevorzugt.If the alkyl sulfate is in the form of a salt, sodium, potassium or ammonium salts can be used, for example. The sodium salt is preferred.

Ganz besonders bevorzugte Hydrotropiermittel der Komponente (b) sind Alkylsulfate, bei denen der Substituent R₈ in Formel (5) den Kohlenwasserstoffrest eines aliphatischen ge­sättigten Monoalkohols mit 4 bis 24 Kohlenstoffatome bedeutet. Der Kohlenwasserstoff­rest kann geradkettig oder verzweigt sein.Very particularly preferred hydrotroping agents of component (b) are alkyl sulfates in which the substituent R₈ in formula (5) is the hydrocarbon radical of an aliphatic saturated monoalcohol having 4 to 24 carbon atoms. The hydrocarbon residue can be straight-chain or branched.

Als aliphatische gesättigte Monoalkohole kommen dabei natürliche Alkohole in Betracht, wie z.B. Lauryl-, Myristyl-, Cetyl-, Stearyl-, Arachnidyl- oder Behenylalkohol. Bevorzugt sind Verbindungen, bei denen sich der Substituent R₈ von verzweigten aliphatischen synthetischen Alkoholen mit 4 bis 12, insbesondere 4 bis 8 Kohlenstoffatomen ableitet, z.B-. Isobutylalkohol, sek.Butanol, tert.Butanol, Isoamylalkohol, 2-Ethylbutanol, 2-Methylpentanol, 5-Methylheptan-3-ol, 2-Ethylhexanol, 1-1-3-3-Tetramethylbutanol, Octan-2-ol, Isononylalkohol, Trimethylhexanol, Trimethylnonylalkohol, Decanol oder C₉-C₁₁-Oxoalkohol. Die Alkylsulfate können dabei bereits in Form ihrer Salze vorliegen und allein oder als (technisches) Gemisch untereinander in dem erfindungsgemässen Netzmittel eingesetzt werden.Suitable aliphatic saturated monoalcohols are natural alcohols, such as lauryl, myristyl, cetyl, stearyl, arachnidyl or behenyl alcohol. Preferred are compounds in which the substituent R₈ is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, for example. Isobutyl alcohol, sec-butanol, tert-butanol, isoamyl alcohol, 2-ethylbutanol, 2-methylpentanol, 5-methylheptan-3-ol, 2-ethylhexanol, 1-1-3-3-tetramethylbutanol, octan-2-ol, isononyl alcohol, Trimethylhexanol, trimethylnonyl alcohol, decanol or C₉-C₁₁-oxo alcohol. The alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.

Die Alkylsulfonate der Formel (8) sowie ihre Alkalimetall- oder Aminsalze können auch zusammen mit anderen Verbindungen als Hydrotropiermittel eingesezt werden, z.B. mit polymerisierter Acrylsäure, C₁ bis C₁₀ - Alkylphosphonsäure oder C₁ bis C₁₀ - Alkylphos­phonsäureestern.The alkyl sulfonates of formula (8) and their alkali metal or amine salts can also be used together with other compounds as hydrotroping agents, e.g. with polymerized acrylic acid, C₁ to C₁₀ - alkylphosphonic acid or C₁ to C₁₀ - alkylphosphonic acid esters.

Die Herstellung dieser Alkylsulfate erfolgt nach an sich bekannter Weise durch Um­setzung der entsprechenden Alkohole mit z.B. Schwefelsäure, Oleum, Chlorsulfonsäure oder Schwefeltrioxid.These alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.

Das erfindungsgemässe Netzmittel kann zusätzlich eine fakultative Komponente (c) enthalten.The wetting agent according to the invention can additionally contain an optional component (c).

Es kommen dafür unpolare organische Lösungsmittel in Betracht, deren Flammpunkt oberhalb von 65°C liegt. Es können z.B. zyklische geradkettige oder insbesondere ver­zweigte Alkohole eingesetzt werden, wie z.B. Cyclohexanol, Methylcyclohexanol, Tetra­lin, n-Hexanol, 2-Ethylhexanol-1, Isooctylalkohol, Isononylalkohol und besonders Tri­methylhexanol-3,5,5. Ferner können als unpolare organische Lösungsmittel Ester einge­setzt werden, wie zum Beispiel Tributylcitrat oder Tributylphosphat.Non-polar organic solvents with a flash point above 65 ° C are suitable. For example, cyclic straight-chain or in particular branched alcohols are used, such as e.g. Cyclohexanol, methylcyclohexanol, tetralin, n-hexanol, 2-ethylhexanol-1, isooctyl alcohol, isononyl alcohol and especially trimethylhexanol-3,5,5. Furthermore, esters such as tributyl citrate or tributyl phosphate can be used as non-polar organic solvents.

Die neuen Netzmittel können durch einfaches Verrühren der genannten Komponenten (a), (b) und gegebenenfalls (c) hergestellt werden.The new wetting agents can be prepared by simply stirring the components (a), (b) and, if appropriate, (c).

Die Herstellung erfolgt vorzugsweise dadurch, dass man die Komponenten (a), (b) und gegebenenfalls (c) unter Rühren mischt und deionisiertes Wasser hinzugibt, bis eine homogene Lösung vorliegt.The preparation is preferably carried out by mixing components (a), (b) and optionally (c) with stirring and adding deionized water until a homogeneous solution is obtained.

Bevorzugte erfindungsgemässe Netzmittel enthalten insbesondere mit Vorteil, bezogen auf das gesamte Gemisch,
15 bis 60 Gew.% der Komponente (a),
2 bis 10 Gew.% der Komponente (b),
0 bis 4 Gew.% der Komponente (c) und
ad 100% Wasser.Preferred wetting agents according to the invention particularly advantageously contain, based on the mixture as a whole,
15 to 60% by weight of component (a),
2 to 10% by weight of component (b),
0 to 4% by weight of component (c) and
ad 100% water.

Die neuen Netzmittel stellen wässrige, in der Anwendung gering schäumende Formulier­ungen dar, die sich durch einen Trübungspunkt auszeichnen, der über 40°C liegt und die bis 40°C lagerstabil sind.The new wetting agents are aqueous formulations with low foaming in use, which are characterized by a cloud point which is above 40 ° C. and which are stable up to 40 ° C.

Sie finden Verwendung als Netzmittel in der Textilbehandlung, insbesondere in der Vor­behandlung, wie beispielsweise in der Langflottenbleiche oder in der Chlor- und Peroxid-­Heissbleiche.They are used as wetting agents in textile treatment, especially in pretreatment, such as in long liquor bleaching or in chlorine and peroxide hot bleaching.

Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Netzen von Fasermaterialien. Das Verfahren ist dadurch gekennzeichnet, dass man diese Materialien in Gegenwart eines Netzmittels behandelt, das

  • (a) 10 bis 80 Gew.% eines nichtionogenen Tensids der allgemeinen Formel
    (1)      R-O(̵Alkylen-O)̵
    Figure imgb0006
    R₁
    worin
    R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
    R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Phenylniederalkyl oder Styryl,
    "Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und p eine Zahl von 2 bis 24 bedeuten,
  • (b) 1 bis 10 Gew. % eines Hydrotropiermittels
  • (c) 0 bis 4 Gew.% eines unpolaren Lösungsmittels und ad 100 % Wasser
enthält.The present invention accordingly also relates to a method for wetting fiber materials. The process is characterized in that these materials are treated in the presence of a wetting agent which
  • (a) 10 to 80% by weight of a nonionic surfactant of the general formula
    (1) RO (̵alkylene-O) ̵
    Figure imgb0006
    R₁
    wherein
    R is an aliphatic radical with at least 8 carbon atoms,
    R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
    "Alkylene" means an alkylene radical of 2 to 4 carbon atoms and p is a number from 2 to 24,
  • (b) 1 to 10% by weight of a hydrotroping agent
  • (c) 0 to 4% by weight of a non-polar solvent and ad 100% water
contains.

Die Einsatzmengen, in denen das erfindungsgemässe Netzmittel den Behandlungsflotten zugesetzt wird, betragen zwischen 0,1 und 10, vorzugsweise 0,5 und 5 g pro Liter Behand­lungsflotte. Die Flotte kann noch weitere Zusätze enthalten, z.B. Entschlichtungsmittel, Farbstoffe, optische Aufheller, Kunstharze und Alkalien wie Natriumhydroxid.The amounts in which the wetting agent according to the invention is added to the treatment liquors are between 0.1 and 10, preferably 0.5 and 5 g per liter of treatment liquor. The fleet can also contain other additives, e.g. 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, Zellwolle, Viskose, Azetatreyon, native Cellulosefaser und besonders Rohbaumwolle, Wolle, Polyamid-, Polyacrylnitril- oder Polyesterfasermaterialien sowie Fasermischungen, z.B. solche aus Polyacrylnitril/Baumwolle oder Polyester/Baumwolle.The following are considered as fiber materials:
Cellulose, in particular untreated natural cellulose such as hemp, linen, jute, cellulose, 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 made of 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 10 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 30 Minuten dauern. Bei dem Pad-Batch-Verfahren wird die imprägnierte Ware ohne Trocknung aufgerollt und anschliessend gegebenenfalls mit eine Plastikfolie verpackt, und bei Raum­temperatur 1 bis 24 Stunden gelagert.The impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature. After impregnation and squeezing, the cellulose material is optionally after intermediate drying, heat treatment, e.g. Subject to temperatures from 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. Preferably the heat treatment is direct, i.e. 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 30 minutes. In the pad-batch 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 10 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, Jet 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 10 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, jet or reel runner. If necessary, however, the treatment can also be carried out up to 150 ° C., preferably 105 to 140 ° C., under pressure in so-called high-temperature apparatus (HT apparatus).

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 getrocknet.Then, if the process requires, the fiber materials are washed with hot water at around 90 to 98 ° C and then with warm and finally with cold water rinsed thoroughly, neutralized if necessary and then dried preferably at elevated temperatures.

Als wesentliche Vorteile der erfindungsgemässen Netzmittel sind neben ihrer ausgezeich­neten Netzwirkung ihre gute Lagerstabilität sowie ihr schaumarmes Verhalten in der An­wendung zu verzeichnen.The main advantages of the wetting agents according to the invention, in addition to their excellent wetting action, are their good storage stability and their low-foaming behavior in use.

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

Herstellungsbeispiele der FormulierungenManufacturing examples of the formulations Beispiel 1:Example 1:

Man stellt die Formulierungen A, B, C und D her, indem man die in Tabelle I aufgeführten Komponenten entsprechend ihrer Gewichts-Anteile unter Rühren mischt, bis eine homogene Lösung entsteht. Tabelle I: A B C D Nichtionogenes Tensid der Formel (1), z.B. 15 Mol des Ethylen/Propylenoxidadduktes an 1 Mol eines C₉ - C₁₁-Fettalkohols 25 25 25 25 2-Ethylhexanolsulfat-Natriumsalz (40%ige Lösung) 9 9 3,5,5-Trimethylhexanol 3 2 Natrium-Cumolsulfonat 100% 10 10 Isopropanol 5 Wasser 66 63 63 60 Trübungspunkt [°C]* 40,5 41,5 45,3 55,5 Schaumhöhe [ml] von 2 g/l der Formulierung** 70 50 50 80 *Trübungspunkt der Formulierung tel quel; ** Schaumprüfung in Anlehnung an DIN 53902 Formulations A, B, C and D are prepared by mixing the components listed in Table I according to their weight proportions with stirring until a homogeneous solution is obtained. Table I: A B C. D Nonionic surfactant of formula (1), for example 15 moles of the ethylene / propylene oxide adduct with 1 mole of a C₉ - C₁₁ fatty alcohol 25th 25th 25th 25th 2-ethylhexanol sulfate sodium salt (40% solution) 9 9 3,5,5-trimethylhexanol 3rd 2nd Sodium cumene sulfonate 100% 10th 10th Isopropanol 5 water 66 63 63 60 Cloud point [° C] * 40.5 41.5 45.3 55.5 Foam height [ml] of 2 g / l of the formulation ** 70 50 50 80 * Cloud point of the formulation tel quel; ** Foam test based on DIN 53902

ApplikationsbeispieleApplication examples Beispiel 2:Example 2:

Ein Roh-Baumwolltrikot wird in einem ®AHIBA-Färbeapparat in einem Bad gebleicht, welches pro Liter
2g der Formulierung B
0,2g des wässrigen Gemisches aus dem Oligomeren-Gemisch von Phosphor­säureestern gem. US-PS 4254063, Na-Gluconat und Magnesiumchlorid (Verhältnis 2:1:1)
1g NaOH fest und
5 ml H₂O₂ (35 %) enthält.A raw cotton jersey is bleached in a ®AHIBA dyeing machine in a bath, which is per liter
2g of formulation B
0.2g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US-PS 4254063, Na-gluconate and magnesium chloride (ratio 2: 1: 1)
1g NaOH solid and
Contains 5 ml H₂O₂ (35%).

Das Bleichbad wird innerhalb von 20 Minuten auf 90°C aufgeheizt und dann weitere 30 Minuten bei dieser Temperatur gehalten. Anschliessend wird das Substrat heiss und kalt ausgewaschen und neutralisiert. Während der Bleiche tritt keine störende Schaum­bildung auf. Es resultiert ein gleichmässiger Weissgrad, der von ⁻72 auf 50 CIBA-GEIGY-Weisseinheiten angehoben wird.The bleach bath is heated to 90 ° C. within 20 minutes and then held at this temperature for a further 30 minutes. The substrate is then washed out hot and cold and neutralized. No disruptive foaming occurs during bleaching. The result is a uniform degree of whiteness, which is increased from ⁻72 to 50 CIBA-GEIGY whiteness units.

Beispiel 3:Example 3:

Ein rohes Baumwolltrikot mit einem Laufmetergewicht von 80 g wird in einer Galaxy-Anlage (Firma Benninger, Schweiz) bei einer Geschwindigkeit von 54 m/min durch ein Chlor-Bleichbad geführt, das pro Liter
4g Aktiv-Chlor
1,5g NaOH (100%) und
2 g der Formulierung B enthält. Die Verweilzeit beträgt 15 Minuten bei 16°C.
Die Ware wird gleichmässig benetzt und das Chlor-Bleichbad ist schaumfrei. Nach einem Spülprozess wird die Ware abgequetscht und durch ein H₂O₂-Bleichbad geleitet, das pro Liter
2 g des wässrigen Gemisches aus dem Oligomeren-Gemisch von Phosphor­säureestern gem. US-PS 42 54 063, Na-Gluconat und Magnesiumchlorid (Verhältnis 2:1:1)
3g NaOH(100%)
3 ml Wasserglas 38°Be
0,5 g der Formulierung B und
15 ml H₂O₂ (35 %) enthält.A raw cotton jersey with a running weight of 80 g is passed through a chlorine bleaching bath per liter in a Galaxy system (Benninger, Switzerland) at a speed of 54 m / min
4g active chlorine
1.5g NaOH (100%) and
Contains 2 g of formulation B. The residence time is 15 minutes at 16 ° C.
The goods are evenly wetted and the chlorine bleach bath is foam-free. After a rinsing process, the goods are squeezed and passed through an H₂O₂ bleaching bath, which is per liter
2 g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US Pat. No. 4,254,063, Na gluconate and magnesium chloride (ratio 2: 1: 1)
3g NaOH (100%)
3 ml water glass 38 ° Be
0.5 g of formulation B and
Contains 15 ml H₂O₂ (35%).

Die Verweilzeit beträgt 35 Minuten bei 85°C. Auch im Peroxid-Bleichbad tritt keine störende Schaumbildung auf. Es resultiert ein hoher gleichmässiger Weissgrad von R 46 = 86.2 (gemessen mit dem Elrephogerät).The residence time is 35 minutes at 85 ° C. No annoying foam formation occurs in the peroxide bleaching bath either. The result is a high, uniform whiteness of R 46 = 86.2 (measured with the Elrepho device).

Claims (14)

1. Wässriges, lagerstabiles, in der Anwendung gering schäumendes Netzmittel, enthaltend ein nichtionogenes Tensid aus der Gruppe der teilweise endgruppenverschlossenen alkoxylierten Fettalkohole, dadurch gekennzeichnet, dass es
(a) 10 bis 80 Gew.% eines nichtionogenen Tensids der allgemeinen Formel
(1)      R-O(̵Alkylen-O)̵
Figure imgb0007
R₁
worin
R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Phenylniederalkyl oder Styryl,
"Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
p eine Zahl von 2 bis 24 bedeuten und
(b) 1 bis 10 Gew.% eines Hydrotropiermittels
enthält.1. Aqueous, storage-stable, low-foaming wetting agent in use, containing a nonionic surfactant from the group of partially end-capped alkoxylated fatty alcohols, characterized in that it
(a) 10 to 80% by weight of a nonionic surfactant of the general formula
(1) RO (̵alkylene-O) ̵
Figure imgb0007
R₁
wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p is a number from 2 to 24 and
(b) 1 to 10% by weight of a hydrotroping agent
contains. 2. Netzmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass die Komponente (a) der Formel
Figure imgb0008
 entspricht, worin von Y₁ und Y₂ der eine Rest Methyl oder Ethyl und der andere Wasserstoff,
n₁ eine ganze Zahl von 2 bis 24,
m₁ eine ganze Zahl von 0 bis 15 bedeuten,
wobei die Summe von ml und n₁ maximal 24 ist und
R und R₁ die in Formel (1) angegebene Bedeutung haben.2. Wetting agent according to claim 1, characterized in that component (a) of the formula
Figure imgb0008
 corresponds to, in which one of Y₁ and Y₂ is methyl or ethyl and the other is hydrogen,
n₁ is an integer from 2 to 24,
m₁ is an integer from 0 to 15,
the sum of ml and n₁ is a maximum of 24 and
R and R₁ have the meaning given in formula (1). 3. Netzmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das nichtionogene Tensid der Komponente (a) der Formel
Figure imgb0009
 entspricht, worin
R₂ C₉ bis C₁₄-Alkyl,
R₃ Wasserstoff, Butyl, einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl,
von Y₃ und Y₄ der eine Rest Wasserstoff oder Methyl und der andere Wasserstoff,
m₂ eine ganze zahl von 0 bis 8 und
n₂ eine ganze Zahl von 4 bis 8 bedeuten.3. wetting agent according to claim 1, characterized in that the nonionic surfactant component (a) of the formula
Figure imgb0009
 corresponds to what
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl,
of Y₃ and Y₄ one residue is hydrogen or methyl and the other hydrogen,
m₂ is an integer from 0 to 8 and
n₂ is an integer from 4 to 8. 4. Netzmittel gemäss einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das nichtionogene Tensid der Komponente (a) der Formel
Figure imgb0010
 entspricht, worin
R₂ C₉ bis C₁₄-Alkyl,
R₄ Wasserstoff, C₁ bis C₄-Alkyl oder Phenylniederalkyl,
von Y₅ und Y₆ der eine Rest Wasserstoff und der andere Ethyl ist, n₃ eine ganze zahl von 4 bis 8 und
m₃ eine ganze Zahl von 1 bis 3 bedeuten.4. Wetting agent according to one of claims 1 or 2, characterized in that the nonionic surfactant of component (a) of the formula
Figure imgb0010
 corresponds to what
R₂ C₉ to C₁₄ alkyl,
R₄ is hydrogen, C₁ to C₄-alkyl or phenyl-lower alkyl,
of Y₅ and Y₆ one is hydrogen and the other is ethyl, n₃ is an integer from 4 to 8 and
m₃ is an integer from 1 to 3. 5. Netzmittel gemäss Anspruch 1, dadurch gekennzeichnet dass es 1 bis 10 Gew.% eines Alkylsulfates der Formel
(5)      R₈O-SO₃X,
worin
R₈ einen aliphatischen gesättigten, verzweigten oder geradkettigen Rest mit 4 bis 24 Kohlenstoffatomen und
X Wasserstoff, Alkalimetall oder Ammonium bedeutet, enthält.5. wetting agent according to claim 1, characterized in that it is 1 to 10 wt.% Of an alkyl sulfate of the formula
(5) R₈O-SO₃X,
wherein
R₈ is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and
X represents hydrogen, alkali metal or ammonium. 6. Netzmittel gemäss Anspruch 5, dadurch gekennzeichnet, dass R₈ einen aliphatischen verzweigten Rest von 4 bis 12 Kohlenstoffatomen bedeutet.6. wetting agent according to claim 5, characterized in that R₈ is an aliphatic branched radical of 4 to 12 carbon atoms. 7. Netzmittel gemäss einem der Ansprüche 5 oder 6, dadurch gekennzeichnet, dass R₈ einen aliphatischen verzweigten Rest von 4 bis 8 Kohlenstoffatomen bedeutet.7. Wetting agent according to one of claims 5 or 6, characterized in that R₈ is an aliphatic branched radical of 4 to 8 carbon atoms. 8. Netzmittel gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es zusätzlich als fakultative Komponente (c) ein unpolares Lösungsmittel enthält.8. Wetting agent according to one of claims 1 to 7, characterized in that it additionally contains a non-polar solvent as an optional component (c). 9. Netzmittel gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es, bezogen auf das Mittel
(a) 15 bis 60 Gew.% der Komponente (a),
(b) 2 bis 10 Gew.% der Komponente (b),
(c) 0 bis 4 Gew.% der Komponente (c) und
ad 100% Wasser
enthält.9. wetting agent according to one of claims 1 to 8, characterized in that it, based on the agent
(a) 15 to 60% by weight of component (a),
(b) 2 to 10% by weight of component (b),
(c) 0 to 4% by weight of component (c) and
ad 100% water
contains. 10. Verwendung des Netzmittels gemäss einem der Ansprüche 1 bis 9 als Netzmittel in der Textilvorbehandlung.10. Use of the wetting agent according to one of claims 1 to 9 as a wetting agent in textile pretreatment. 11. Verfahren zum Netzen von Fasermaterialien, dadurch gekennzeichnet, dass man diese Materialien in wässrigem Medium in Gegenwart eines Netzmittels behandelt, das
(a) 10 bis 80 Gew. % eines nichtionogenen Tensids der in Anspruch 1 definierten Formel (1)
(b) 1 bis 10 Gew. % eines Hydrotropiermittels und
(c) 0 bis 4 Gew.% eines unpolaren Lösungsmittels
enthält.11. A process for wetting fiber materials, characterized in that these materials are treated in an aqueous medium in the presence of a wetting agent which
(a) 10 to 80% by weight of a nonionic surfactant of the formula (1) defined in claim 1
(b) 1 to 10% by weight of a hydrotroping agent and
(c) 0 to 4% by weight of a non-polar solvent
contains. 12. Verfahren gemäss Anspruch 11, dadurch gekennzeichnet, dass man das Netzmittel in einer Menge von 0,1 bis 10 g, vorzugsweise 0,5 bis 5 g pro Liter Flotte einsetzt.12. The method according to claim 11, characterized in that the wetting agent is used in an amount of 0.1 to 10 g, preferably 0.5 to 5 g per liter of liquor. 13. Verfahren gemäss einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, dass das Fasermaterial kontinuierlich oder diskontinuierlich behandelt wird.13. The method according to any one of claims 11 or 12, characterized in that the Fiber material is treated continuously or discontinuously. 14. Das gemäss einem der Ansprüche 12 bis 13 behandelte Fasermaterial.14. The fiber material treated according to one of claims 12 to 13.
EP90810704A 1989-09-26 1990-09-17 Aqueous, storage stable, low foaming wetting agent Expired - Lifetime EP0420802B1 (en)

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DE19500842A1 (en) * 1995-01-13 1996-07-18 Henkel Kgaa Process for the preparation of end-capped nonionic surfactants
US6028229A (en) * 1995-01-13 2000-02-22 Henkel Kommanditgesellschaft Auf Aktien Process for producing end-group-locked non-ionic tensides
EP0742309A1 (en) * 1995-05-10 1996-11-13 Hoechst Aktiengesellschaft Surfactant mixture
US5776206A (en) * 1995-05-10 1998-07-07 Hoechst Aktiengesellschaft Surfactant mixture for textile treatment
DE19920559A1 (en) * 1999-05-05 2000-11-16 Cognis Deutschland Gmbh Process for the preparation of alkyl-terminated alkyl and / or alkenyl ethers
WO2011071492A1 (en) 2009-12-09 2011-06-16 Dow Global Technologies Llc Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof

Also Published As

Publication number Publication date
EP0420802A3 (en) 1991-05-15
CA2026039A1 (en) 1991-03-27
JP2763190B2 (en) 1998-06-11
BR9004788A (en) 1991-09-10
PT95351B (en) 1997-06-30
DD298062A5 (en) 1992-02-06
AR247433A1 (en) 1994-12-29
MX173539B (en) 1994-03-14
DK0420802T3 (en) 1995-09-18
CA2026039C (en) 1998-02-03
PT95351A (en) 1991-08-14
ZA907642B (en) 1991-05-29
ATE126289T1 (en) 1995-08-15
JPH03123634A (en) 1991-05-27
US5484553A (en) 1996-01-16
ES2075891T3 (en) 1995-10-16
EP0420802B1 (en) 1995-08-09
DE59009494D1 (en) 1995-09-14

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