EP0462059A2 - Low-foaming, silicone-free, aqueous textile auxiliaries, their preparation and their use - Google Patents

Low-foaming, silicone-free, aqueous textile auxiliaries, their preparation and their use Download PDF

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Publication number
EP0462059A2
EP0462059A2 EP19910810421 EP91810421A EP0462059A2 EP 0462059 A2 EP0462059 A2 EP 0462059A2 EP 19910810421 EP19910810421 EP 19910810421 EP 91810421 A EP91810421 A EP 91810421A EP 0462059 A2 EP0462059 A2 EP 0462059A2
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EP
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Prior art keywords
component
formula
nonionic surfactant
textile
carbon atoms
Prior art date
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Application number
EP19910810421
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German (de)
French (fr)
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EP0462059A3 (en
EP0462059B1 (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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic 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
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene 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
    • C11D1/72—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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/8305—Miscellaneous [e.g., treated surfaces, etc.]

Definitions

  • the present invention relates to low-foaming, silicone-free, aqueous textile auxiliaries, their production and multiple uses, e.g. as wetting agents, detergents, dispersants or as stabilizers in peroxide bleaching liquors.
  • 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.
  • Lower alkyl means hydrocarbon radicals which have 1 to 5, in particular 1 to 4, carbon atoms. Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl.
  • 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, hexadecenyl 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 derived from soybean 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 of component (a) 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 40, m1 represents an integer from 0 to 15, and R and R1 have the meaning given in formula (1).
  • Nonionic surfactants of the formula are of particular interest wherein R2 C9 to C14 alkyl, R3 is hydrogen, C1-C4alkyl, a cycloaliphatic radical with at least 6 C 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 10.
  • R2 has the meaning given in formula (3)
  • R4 is hydrogen, C1 to C4-alkyl or lower alkylphenyl, 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 reacting the corresponding alkylene oxide adducts with thionyl chloride and then reacting the chlorine compound formed with a short-chain, cycloaliphatic, fatty, lower alkylphenyl or Styryl alcohol.
  • Acidic water-solubilizing groups from which component (a) is obtained are e.g. Carbonyl and / or sulfonic acid groups.
  • Ethylenically unsaturated polymerizable carboxylic or sulfonic acids are suitable. Both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each having an ethylenically unsaturated aliphatic radical and preferably at most 7 carbon atoms, can be used.
  • the monocarboxylic acids are e.g. acrylic acid, methacrylic acid, ⁇ -haloacrylic acid, 2-hydroxyethylacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid and vinyl acetic acid.
  • Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid.
  • Maleic anhydride is particularly mentioned as the anhydride of these acids.
  • Suitable sulfonic acids are vinylsulfonic acid or 2-acryloamido-2-methylpropanesulfonic acid.
  • Monocarboxylic acids having 2 to 5 carbon atoms in particular methacrylic acid and especially acrylic acid, are preferred.
  • Practically important compounds corresponding to component (a) are those which have been obtained from 5 to 50% by weight of a nonionic surfactant of the formula (1) and 95 to 50% by weight of acrylic acid.
  • Particularly preferred among these products are those compounds which have been obtained from a nonionic surfactant of the formula (3).
  • the compounds of component (a) of the composition according to the invention are prepared by methods known per se, expediently such that the corresponding nonionic surfactant is first mixed with at least 20% by weight, based on the end product, of an ethylenically unsaturated compound which has acidic, water-solubilizing groups, such as, for example, matching carboxylic acids, their anhydrides or sulfonic acids, and subsequently carrying out the reaction in the presence of catalysts, expediently at a temperature of 60 to 100.degree.
  • Free radical-forming organic initiators are preferably used as catalysts.
  • Suitable initiators for carrying out the reaction are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methyl-valeronitrile, 1,1′-azo-bis-1-cyclo-hexanitrile and 2,2′-azo-bis-isobutyric acid alkyl esters, symmetrical diacyl peroxides, such as e.g.
  • Suitable peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate.
  • Another suitable compound is potassium persulfate, which is preferably used in the present invention.
  • the catalysts are generally used in amounts of 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the starting products.
  • reaction is advantageously carried out in an inert atmosphere, e.g. carried out in the presence of nitrogen.
  • nonionic surfactants used as component (b) of the composition according to the invention correspond to the nonionic surfactant of component (a) according to formulas (1) to (4).
  • 2-Ethylhexyl sulfate is particularly preferred.
  • component (a) a compound obtained from a nonionic surfactant of the formula (1) and acrylic acid, as component (b), a nonionic surfactant of the formula (1) and optionally as component ( c) contain 2-ethylhexyl sulfate.
  • textile auxiliaries which contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (2) and acrylic acid, as component (b) a nonionic surfactant of the formula (2) and optionally as component (c ) Contain 2-ethylhexyl sulfate.
  • textile auxiliary mixtures which contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (3) and as component (b) a nonionic surfactant corresponding to the formula (3).
  • the textile auxiliary mixtures according to the invention can be prepared by simply stirring components (a), (b) and optionally (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.
  • the new blends are low-foaming, APEO and silicone-free textile auxiliaries. They are easy to handle due to their liquid commercial form, which is why they are particularly suitable for modern dosing systems. You are universal can be used and can therefore be considered for various purposes.
  • they can be used as wetting agents, textile detergents, dispersants or as stabilizers in peroxide bleaching liquors.
  • the amounts used in which the textile auxiliary according to the invention is added to the treatment liquors are between 0.1 and 30, preferably 0.2 and 10 g per liter of treatment liquor.
  • These fleets can also contain other additives, e.g. Desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.
  • Possible fiber materials are: cellulose, especially 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 70 to 120% by weight.
  • the padding process is used in particular in the pad-steam process and pad-batch process.
  • the impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature.
  • the cellulose material is optionally subjected to a heat treatment, e.g. Subject at temperatures from 80 to 140 ° C.
  • the heat treatment is preferably carried out by steaming at 95 to 140 ° 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 60 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 be carried out in long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 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.
  • a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 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.
  • 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, hot Water from about 90 to 98 ° C and then rinsed thoroughly with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.
  • auxiliary mixtures A, B and C are prepared by stirring the components listed in the table below.
  • Formulation B of Example 1 is tested for its washability.
  • a mixed fabric made of polyester / cotton artificially soiled with carbon black and motor oil is washed using a ® AHIBA dyeing machine with a twist for 30 minutes at 40 ° C and a liquor ratio of 1:25.
  • the amount used is 1 g / l of active substance and the pH of the wash liquor is adjusted to 10 using NaOH.
  • the fabric is rinsed, dewatered and dried.
  • the color difference according to DIN 6174 between the washed sample and an unwashed sample is measured.
  • the reflection number of the washed sample is 18.5.
  • Formulations A, B and C of Example 1 are suitable for use in highly concentrated alkaline stock liquors up to 360 g / l NaOH. After dilution of the stock fleets to the application concentration, no loss of network capacity due to the alkali load can be determined.
  • the degree of whiteness is increased from -77 to 56 CIBA-GEIGY whiteness units.
  • formulation B causes a substrate with good absorbency after bleaching.

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

Abstract

Low-foaming, silicone-free, aqueous textile auxiliaries are described which are characterised in that they comprise (a) a reaction product of a nonionic surfactant of the formula <IMAGE> in which R denotes an aliphatic radical having at least 8 carbon atoms, R1 denotes hydrogen, C1- to C8-alkyl, a cycloaliphatic radical having at least 5 C atoms, lower alkylphenyl or styryl, "Alkylen" denotes an alkylene radical of 2 to 4 carbon atoms and p denotes a number from 2 to 60, with a compound containing an acid water-solubilising group, (b) a nonionic surfactant of the formula (1) and, if desired, (c) a hydrotropic agent. The textile auxiliaries are suitable as dispersants and for the wetting and/or washing of fibre materials.

Description

Die vorliegende Erfindung betrifft schaumarme, silikonfreie, wässrige Textilhilfsmittel, ihre Herstellung und vielfache Verwendung z.B. als Netzmittel, Waschmittel, Dispergiermittel oder als Stabilisatoren in Peroxid-Bleichflotten.The present invention relates to low-foaming, silicone-free, aqueous textile auxiliaries, their production and multiple uses, e.g. as wetting agents, detergents, dispersants or as stabilizers in peroxide bleaching liquors.

Die erfindungsgemässen schaumarmen, silikonfreien, wässrigen Textilhilfsmittel sind dadurch gekennzeichnet, dass sie

  • (a) ein Umsetzungsprodukt aus einem nichtionogenen Tensid der Formel
Figure imgb0001
worin
R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens
5 C-Atomen, Niederalkylphenyl oder Styryl,
"Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
p eine Zahl von 2 bis 60 bedeutet
mit einer eine saure, wasserlöslich machende Gruppe aufweisenden Verbindung,
  • (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls
  • (c) ein Hydrotropiermittel
    enthalten.
The low-foam, silicone-free, aqueous textile auxiliaries according to the invention are characterized in that they
  • (a) a reaction product of a nonionic surfactant of the formula
Figure imgb0001
wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical with at least
5 carbon atoms, lower alkylphenyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p represents a number from 2 to 60
with a compound having an acidic, water-solubilizing group,
  • (b) a nonionic surfactant of formula (1) and optionally
  • (c) a hydrotrope
    contain.

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.

Niederalkyl bedeuten Kohlenwasserstoffreste, die 1 bis 5, insbesondere 1 bis 4 Kohlenstoffatome aufweisen. Beispiele für derartige Gruppen sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, tert.Butyl, Amyl, Isoamyl oder tert.Amyl.Lower alkyl means hydrocarbon radicals which have 1 to 5, in particular 1 to 4, carbon atoms. Examples of such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl.

Als aliphatische gesättigte Monoalkohole 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, Hexadecenylalkohol oder Oleylalkohol.Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl 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, Palmkemfettsäuren 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 derived from soybean 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, aus denen die Komponente (a) hergestellt wird, seien beispielsweise genannt:

  • Anlagerungsprodukte von vorzugsweise 2 bis 60 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 from which component (a) is produced are:
  • Addition products of preferably 2 to 60 mol 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 der Komponente (a) 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 40,
m₁ eine ganze Zahl von 0 bis 15 bedeutet, und
R und R₁ die in Formel (1) angegebene Bedeutung haben.Practically important, nonionic surfactants of component (a) 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 40,
m₁ represents an integer from 0 to 15, and
R and R₁ have the meaning given in formula (1).

Von ganz besonderem Interesse sind nichtionogene Tenside der Formel

Figure imgb0003

worin
R₂ C₉ bis C₁₄-Alkyl,
R₃ Wasserstoff, C₁-C₄Alkyl, 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 10 bedeuten.Nonionic surfactants of the formula are of particular interest
Figure imgb0003
wherein
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, C₁-C₄alkyl, a cycloaliphatic radical with at least 6 C 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 10.

Weitere wichtige nichtinogene Tenside entsprechen der Formel

Figure imgb0004

worin R₂ die in Formel (3) angegebene Bedeutung hat,
R₄ Wasserstoff, C₁ bis C₄-Alkyl oder Niederalkylphenyl,
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 noninogenic surfactants correspond to the formula
Figure imgb0004
wherein R₂ has the meaning given in formula (3),
R₄ is hydrogen, C₁ to C₄-alkyl or lower alkylphenyl,
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-, Niederalkylphenyl- oder Styrylalkohol.The nonionic surfactants of the formulas (1) to (4) are prepared in a manner known per se, for example by reacting the corresponding alkylene oxide adducts with thionyl chloride and then reacting the chlorine compound formed with a short-chain, cycloaliphatic, fatty, lower alkylphenyl or Styryl alcohol.

Saure wasserlöslich machende Gruppen, aus denen die Komponente (a) erhalten wird, sind z.B. Carbonyl- und/oder Sulfonsäuregruppen. Geeignet sind ethylenisch ungesättigte polymerisierbare Carbon- oder Sulfonsäuren. Es können sowohl Monocarbonsäuren als auch Dicarbonsäwen und deren Anhydride sowie auch Sulfonsäuren, die jeweils einen ethylenisch ungesättigten aliphatischen Rest und vorzugsweise höchstens 7 Kohlenstoffatome aufweisen, in Betracht kommen. Bei den Monocarbonsäuren handelt es sich z.B. um die Acrylsäure, Methacrylsäure, α-Halogenacrylsäure, 2-Hydroxyethylacrylsäure, α-Cyanoacrylsäure, Crotonsäure und Vinylessigsäure. Ethylenisch ungesättigte Dicarbonsäuren sind vorzugsweise die Fumarsäure, Maleinsäure oder Itaconsäure, ferner die Mesaconsäure, Citraconsäure, Glutaconsäure und Methylmalonsäure. Als Anhydrid dieser Säuren sei insbesondere Maleinsäureanhydrid genannt.Acidic water-solubilizing groups from which component (a) is obtained are e.g. Carbonyl and / or sulfonic acid groups. Ethylenically unsaturated polymerizable carboxylic or sulfonic acids are suitable. Both monocarboxylic acids and dicarboxylic acids and their anhydrides as well as sulfonic acids, each having an ethylenically unsaturated aliphatic radical and preferably at most 7 carbon atoms, can be used. The monocarboxylic acids are e.g. acrylic acid, methacrylic acid, α-haloacrylic acid, 2-hydroxyethylacrylic acid, α-cyanoacrylic acid, crotonic acid and vinyl acetic acid. Ethylenically unsaturated dicarboxylic acids are preferably fumaric acid, maleic acid or itaconic acid, furthermore mesaconic acid, citraconic acid, glutaconic acid and methylmalonic acid. Maleic anhydride is particularly mentioned as the anhydride of these acids.

Als definitionsgemässe Sulfonsäuren kommen beispielsweise Vinylsulfonsäure oder 2-Acryloamido-2-methylpropansulfonsäure in Frage.Examples of suitable sulfonic acids are vinylsulfonic acid or 2-acryloamido-2-methylpropanesulfonic acid.

Vorzugsweise kommen Monocarbonsäuren mit 2 bis 5 Kohlenstoffatomen, insbesondere die Methacrylsäure und vor allem die Acrylsäure, in Betracht.Monocarboxylic acids having 2 to 5 carbon atoms, in particular methacrylic acid and especially acrylic acid, are preferred.

Praktisch wichtige, der Komponente (a) entsprechende Verbindungen sind solche, die aus 5 bis 50 Gewichtsprozent eines nichtionogenen Tensids der Formel (1) und 95 bis 50 Gew.-% Acrylsäure erhalten worden sind.Practically important compounds corresponding to component (a) are those which have been obtained from 5 to 50% by weight of a nonionic surfactant of the formula (1) and 95 to 50% by weight of acrylic acid.

Unter diesen Produkten besonders bevorzugt sind solche Verbindungen, die aus einem nichtionogenen Tensid der Formel (3) erthalten worden sind.Particularly preferred among these products are those compounds which have been obtained from a nonionic surfactant of the formula (3).

Die Herstellung der Verbindungen der Komponente (a) der erfindungsgemässen Zusammensetzung erfolgt nach an sich bekannten Methoden, zweckmässig in der Weise, dass man zunächst das entsprechende nichtionogenes Tensid mit mindestens 20 Gew.-%, bezogen auf das Endprodukt, einer ethylenisch ungesättigten Verbindung, die saure, wasserlöslich machende Gruppen aufweist, wie z.B. entsprechende Carbonsäuren, deren Anhydride oder Sulfonsäuren, zusammenbringt und anschliessend in Gegenwart von Katalysatoren, zweckmässig bei einer Temperatur von 60 bis 100°C die Umsetzung durchführt.The compounds of component (a) of the composition according to the invention are prepared by methods known per se, expediently such that the corresponding nonionic surfactant is first mixed with at least 20% by weight, based on the end product, of an ethylenically unsaturated compound which has acidic, water-solubilizing groups, such as, for example, matching carboxylic acids, their anhydrides or sulfonic acids, and subsequently carrying out the reaction in the presence of catalysts, expediently at a temperature of 60 to 100.degree.

Als Katalysatoren werden vorzugsweise freie Radikale bildende organische Initiatoren verwendet. Geeignete Initiatoren zur Durchführung der Umsetzung sind z.B. symmetrische aliphatische Azoverbindungen wie Azo-bis-isobuttersäurenitril, Azo-bis-2-methyl-valeronitril, 1,1′-Azo-bis-1-cyclo-hexanitril und 2,2′-Azo-bis-isobuttersäurealkylester, symmetrische Diacylperoxide, wie z.B. Acetyl-, Propionyl- oder Butyrylperoxid, Benzoylperoxid, brom-, nitro-, methyl- oder methoxy-substituierte Benzoylperoxide sowie Lauroylperoxid; symmetrische Peroxydicarbonate, wie z.B. Diethyl-, Diisopropyl-, Dicyclohexyl-, sowie Dibenzylperoxidicarbonat; tert.-Butylperoctoat, tert.-Butylperbenzoat oder tert.-Butylphenylperacetat sowie Peroxidcarbamate wie tert.-Butyl-N-(phenylperoxi)-carbamat oder tert.-Butyl-N-(2,3-dichlor- oder -4-chlorphenyl-peroxid)-carbamat. Weitere geeignete Peroxide sind: tert.-Butylhydroperoxid, Di-tert.-butylperoxid, Cumolhydroperoxid, Di-cumolperoxid und tert.-Butylperpivalat. Eine weitere geeignete Verbindung ist Kaliumpersulfat, das bei der vorliegenden Erfindung bevorzugt eingesetzt wird.Free radical-forming organic initiators are preferably used as catalysts. Suitable initiators for carrying out the reaction are e.g. symmetrical aliphatic azo compounds such as azo-bis-isobutyronitrile, azo-bis-2-methyl-valeronitrile, 1,1′-azo-bis-1-cyclo-hexanitrile and 2,2′-azo-bis-isobutyric acid alkyl esters, symmetrical diacyl peroxides, such as e.g. Acetyl, propionyl or butyryl peroxide, benzoyl peroxide, bromo, nitro, methyl or methoxy substituted benzoyl peroxides and lauroyl peroxide; symmetrical peroxydicarbonates, e.g. Diethyl, diisopropyl, dicyclohexyl and dibenzyl peroxidicarbonate; tert-butyl peroctoate, tert-butyl perbenzoate or tert-butylphenyl peracetate and peroxide carbamates such as tert-butyl-N- (phenylperoxi) -carbamate or tert-butyl-N- (2,3-dichloro- or -4-chlorophenyl- peroxide) carbamate. Other suitable peroxides are: tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, di-cumene peroxide and tert-butyl perpivalate. Another suitable compound is potassium persulfate, which is preferably used in the present invention.

Die Katalysatoren werden in der Regel in Mengen von 0,1 bis 10 Gew.-%, vorzugsweise 0,5 bis 2 Gew.-%, bezogen auf die Ausgangsprodukte, eingesetzt.The catalysts are generally used in amounts of 0.1 to 10% by weight, preferably 0.5 to 2% by weight, based on the starting products.

Die Umsetzung wird vorteilhafterweise in inerter Atmosphäre, z.B. in Gegenwart von Stickstoff durchgeführt.The reaction is advantageously carried out in an inert atmosphere, e.g. carried out in the presence of nitrogen.

Die als Komponente (b) der erfindungsgemässen Zusammensetzung verwendeten nichtionogenen Tenside entsprechen dem nichtionogenen Tensid der Komponente (a) gemäss den Formeln (1) bis (4).The nonionic surfactants used as component (b) of the composition according to the invention correspond to the nonionic surfactant of component (a) according to formulas (1) to (4).

Als fakultative Komponente (c) der erfindungsgemässen Zusammensetzung kommen folgende Verbindungen in Betracht:

  • Alkalimetall- und Aminsalze von C₁-C₁₀-Alkylphosphorsäureestern.
  • Diole, z.B. Hexylenglykol
  • Sulfonate von Terpenoiden oder ein- oder zweikemigen aromatischen Verbindungen, z.B. die Sulfonate des Camphers, Toluols, Xylols, Cumols und Naphthols;
  • Alkalimetall- und Aminsalze von gesättigten oder ungesättigten C₃-C₁₂-Di- oder Polycarbonsäuren, z.B. von der Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Kork-, Azelain-und Sebacinsäure, von der Undecan- und Dodecandicarbonsäure, von der Fumar-, Malein-, Wein- und Apfelsäure sowie der Citronen- und Aconitsäure;
The following compounds are suitable as optional component (c) of the composition according to the invention:
  • Alkali metal and amine salts of C₁-C₁₀ alkyl phosphoric acid esters.
  • Diols, e.g. hexylene glycol
  • Sulfonates of terpenoids or mono- or di-core aromatic compounds, for example the sulfonates of camphor, toluene, xylene, cumene and naphthol;
  • Alkali metal and amine salts of saturated or unsaturated C₃-C₁₂-di- or polycarboxylic acids, for example of malonic, succinic, glutaric, adipic, pimelin, cork, azelaic and sebacic acid, of undecanoic and dodecanedicarboxylic acids, from fumaric, maleic, tartaric and malic acid as well as citric and aconitic acid;

Besonders bevorzugt ist 2-Ethylhexylsulfat.2-Ethylhexyl sulfate is particularly preferred.

Im Vordergrund des Interesses stehen Textilhilfsmittel, die als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (1) und Acrylsäure erhalten worden ist, als Komponente (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls als Komponente (c) 2-Ethylhexylsulfat enthalten.The focus of interest is on textile auxiliaries which, as component (a), a compound obtained from a nonionic surfactant of the formula (1) and acrylic acid, as component (b), a nonionic surfactant of the formula (1) and optionally as component ( c) contain 2-ethylhexyl sulfate.

Von besonderem Interesse sind Textilhilfsmittel, die als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (2) und Acrylsäure erhalten worden ist, als Komponente (b) ein nichtionogenes Tensid der Formel (2) und gegebenenfalls als Komponente (c) 2-Ethylhexylsulfat enthalten.Of particular interest are textile auxiliaries which contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (2) and acrylic acid, as component (b) a nonionic surfactant of the formula (2) and optionally as component (c ) Contain 2-ethylhexyl sulfate.

Als weitere wichtige Textilhilfsmittelgemische kommen solche in Betracht, die als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (3) erhalten worden ist, und als Komponente (b) ein nichtionogenes Tensid entsprechend Formel (3) enthalten.Further important textile auxiliary mixtures are those which contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (3) and as component (b) a nonionic surfactant corresponding to the formula (3).

Die erfindungsgemässen Textilhilfsmittelgemische können durch einfaches Verrühren der Komponenten (a), (b) und gegebenenfalls (c) hergestellt werden.The textile auxiliary mixtures according to the invention can be prepared by simply stirring components (a), (b) and optionally (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 Textilhilfsmittel enthalten insbesondere mit Vorteil, bezogen auf das gesamte Gemisch,

  • 2 bis 22 Gew.-% der Komponente (a),
  • 10 bis 95 Gew.-% der Komponente (b),
  • 0 bis 15 Gew.-% der Komponente (c) und
  • ad 100 % Wasser.
Preferred textile auxiliaries according to the invention contain, particularly advantageously, based on the mixture as a whole,
  • 2 to 22% by weight of component (a),
  • 10 to 95% by weight of component (b),
  • 0 to 15% by weight of component (c) and
  • ad 100% water.

Die neuen Gemische stellen schaumarme, APEO- und silikonfreie Textilhilfsmittel dar. Sie zeichnen sich auf Grund ihrer flüssigen Handelsform durch einfache Handhabung aus, weshalb sie besonders für moderne Dosiereinrichtungen geeignet sind. Sie sind universell einsetzbar und können daher für verschiedene Anwendungszwecke in Betracht kommen.The new blends are low-foaming, APEO and silicone-free textile auxiliaries. They are easy to handle due to their liquid commercial form, which is why they are particularly suitable for modern dosing systems. You are universal can be used and can therefore be considered for various purposes.

Beispielsweise können sie als Netzmittel, Textilwaschmittel, Dispergiermittel oder als Stabilisator in Peroxid-Bleichflotten eingesetzt werden.For example, they can be used as wetting agents, textile detergents, dispersants or as stabilizers in peroxide bleaching liquors.

Gegenstand der vorliegenden Erfindung ist demnach auch ein Verfahren zum Netzen und/oder Waschen von Fasermaterialien. Das Verfahren ist dadurch gekennzeichnet, dass man diese Materialien in wässrigem Medium in Gegenwart eines Textilhilfsmittelgemisches, das

  • (a) ein Umsetzungsprodukt aus einem nichtionogenen Tensid der Formel
Figure imgb0005
worin
R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens
5 C-Atomen, Niederalkylphenyl oder Styryl,
"Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
p eine Zahl von 2 bis 60 bedeutet mit einer eine saure, wasserlöslich machende Gruppe aufweisenden Verbindung,
  • (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls
  • (c) ein Hydrotropiermittel
    enthält, behandelt.
The present invention accordingly also relates to a method for wetting and / or washing fiber materials. The process is characterized in that these materials are mixed in an aqueous medium in the presence of a textile auxiliary mixture
  • (a) a reaction product of a nonionic surfactant of the formula
Figure imgb0005
wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical with at least
5 carbon atoms, lower alkylphenyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p denotes a number from 2 to 60 with a compound having an acidic, water-solubilizing group,
  • (b) a nonionic surfactant of formula (1) and optionally
  • (c) a hydrotrope
    contains, treats.

Die Einsatzmengen, in denen das erfindungsgemässe Textilhilfsmittel den Behandlungsflotten zugesetzt wird, betragen zwischen 0,1 und 30, vorzugsweise 0,2 und 10 g pro Liter Behandlungsflotte. Diese Flotten können 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 30, preferably 0.2 and 10 g per liter of treatment liquor. These fleets 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.Possible fiber materials are: cellulose, especially 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 verschiedenen 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 von 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 70 bis 120 Gew.% beträgt. Das Foulardierverfahren kommt insbesondere beim Pad-Steam-Verfahren 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 70 to 120% by weight. The padding process is used in particular in the pad-steam process and 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 einer Hitzebehandlung, z.B. bei Temperaturen von 80 bis 140°C unterworfen. Vorzugsweise erfolgt die Hitzebehandlung durch Dämpfen bei 95 bis 140°C, vorzugsweise 100 bis 106°C. je nach Art der Hitzeentwicklung und des Temperaturbereiches kann die Hitzebehandlung 30 Sekunden bis 60 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 the impregnation and squeezing, the cellulose material is optionally subjected to a heat treatment, e.g. Subject at temperatures from 80 to 140 ° C. The heat treatment is preferably carried out by steaming at 95 to 140 ° 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 60 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 langen Flotten bei einem Flottenverhältnis von z.B. 1:3 bis 1:100, vorzugsweise 1:4 bis 1:25 und bei 10 bis 100, vorzugsweise 60 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 be carried out in long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 4 to 1:25 and at 10 to 100, preferably 60 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. 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 getrocknet.The fiber materials are then, if the process so requires, hot Water from about 90 to 98 ° C and then rinsed thoroughly with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.

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 TextilhilfsmittelgemischeProduction examples of the textile auxiliary mixtures Beispiel 1:Example 1:

Die Hilfsmittelgemische A, B und C werden durch Verrühren der in untenstehender Tabelle aufgeführten Komponenten hergestellt.

Figure imgb0006
The auxiliary mixtures A, B and C are prepared by stirring the components listed in the table below.
Figure imgb0006

ApplikationsbeispieleApplication examples Beispiel 2:Example 2:

Die Formulierung B von Beispiel 1 wird auf ihr Waschvermögen geprüft. Dazu wird ein mit Russ und Motorenöl künstlich angeschmutztes Mischgewebe aus Polyester/Baumwolle mittels eines ® AHIBA-Färbeapparates mit Drall 30 Minuten bei 40°C und einem Flottenverhältnis von 1:25 gewaschen. Die Einsatzmenge beträgt 1g/l Wirksubstanz und der pH-Wert der Waschflotte wird mit NaOH auf 10 eingestellt. Nach Beendigung des Waschvorganges wird das Gewebe gespült, entwässert und getrocknet.Formulation B of Example 1 is tested for its washability. For this purpose, a mixed fabric made of polyester / cotton artificially soiled with carbon black and motor oil is washed using a ® AHIBA dyeing machine with a twist for 30 minutes at 40 ° C and a liquor ratio of 1:25. The amount used is 1 g / l of active substance and the pH of the wash liquor is adjusted to 10 using NaOH. At the end of the washing process, the fabric is rinsed, dewatered and dried.

Zur Bestimmung des Waschvermögens wird die Farbdifferenz nach DIN 6174 zwischen der gewaschenen Probe und einem ungewaschenen Muster gemessen. Je höher die Reflexionszahl, desto besser ist der Wascheffekt. Die Reflexionszahl der gewaschenen Probe beträgt 18,5.To determine the washability, the color difference according to DIN 6174 between the washed sample and an unwashed sample is measured. The higher the reflection number, the better the washing effect. The reflection number of the washed sample is 18.5.

Beispiel 3:Example 3:

Die Formulierungen A, B und C von Beispiel 1 sind geeignet für die Anwendung in hochkonzentrierten alkalischen Stammflotten bis 360 g/l NaOH. Nach der Verdünnung der Vorratsflotten auf Anwendungskonzentration ist keine Einbusse des Netzvermögens durch die Alkalibelastung feststellbar.Formulations A, B and C of Example 1 are suitable for use in highly concentrated alkaline stock liquors up to 360 g / l NaOH. After dilution of the stock fleets to the application concentration, no loss of network capacity due to the alkali load can be determined.

Beispiel 4:Example 4:

Ein Rohbaumwolltrikot wird zum Bleichen während 30 Minuten bei 90°C in einem Bleichbad behandelt, das folgende Bestandteile enthält:

  • 2 g/l der Formulierung B
  • 1g/l NaOH 100% und
  • 5 ml/l H₂O₂ 35%.
A raw cotton jersey is treated for bleaching for 30 minutes at 90 ° C in a bleaching bath containing the following ingredients:
  • 2 g / l of formulation B
  • 1g / l NaOH 100% and
  • 5 ml / l H₂O₂ 35%.

Während der Bleiche tritt kein störender Schaum auf. Nach dem Bleichen wird das Gewebe heiss ausgewaschen und neutralisiert.No disruptive foam occurs during bleaching. After bleaching, the fabric is hot washed out and neutralized.

Der Weissgrad wird von -77 auf 56 CIBA-GEIGY Weisseinheiten angehoben.The degree of whiteness is increased from -77 to 56 CIBA-GEIGY whiteness units.

Der Zusatz der Formulierung B bewirkt, dass nach der Bleiche ein Substrat mit guter Saugfähigkeit vorliegt.The addition of formulation B causes a substrate with good absorbency after bleaching.

Claims (20)

Schaumarme, silikonfreie, wässrige Textilhilfsmittel, dadurch gekennzeichnet, dass sie (a) ein Umsetzungsprodukt aus einem nichtionogenen Tensid der Formel
Figure imgb0007
 Worin
R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens
5 C-Atomen, Niederalkylphenyl oder Styryl,
"Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
p eine Zahl von 2 bis 60 bedeutet,
mit einer eine saure, wasserlöslich machende Gruppe aufweisenden Verbindung, (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls (c) ein Hydrotropiermittel
enthalten. Low-foaming, silicone-free, aqueous textile auxiliaries, characterized in that they (a) a reaction product of a nonionic surfactant of the formula
Figure imgb0007
 Wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical with at least
5 carbon atoms, lower alkylphenyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p represents a number from 2 to 60,
with a compound having an acidic, water-solubilizing group, (b) a nonionic surfactant of formula (1) and optionally (c) a hydrotrope
contain. Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass das nichtionogene Tensid der 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 40,
m₁ eine ganze Zahl von 0 bis 15 bedeutet, und
R und R₁ die in Formel (1) angegebene Bedeutung haben.Textile auxiliaries according to claim 1, characterized in that the nonionic surfactant of 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 40,
m₁ represents an integer from 0 to 15, and
R and R₁ have the meaning given in formula (1). Textilhilfsmittel gemäss Anspruch 2, dadurch gekennzeichnet, dass das nichtionogene Tensid der Komponente (a) der Formel
Figure imgb0009
 entspricht, worin
R₂ C₉ bis C₁₄-Alkyl,
R₃ Wasserstoff, C₁-C₄Alkyl, 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 10 bedeuten.Textile auxiliaries according to claim 2, characterized in that the nonionic surfactant of component (a) of the formula
Figure imgb0009
 corresponds to what
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, C₁-C₄alkyl, a cycloaliphatic radical with at least 6 C 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 10. Textilhilfsmittel gemäss Anspruch 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 Niederalkylphenyl,
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.Textile auxiliaries according to claim 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 lower alkylphenyl,
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. Textilhilfsmittel gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die saure, wasserlöslich machende Gruppe der Komponente (a) aus einer ethylenisch ungesättigten polymerisierbaren Sulfonsäure oder Carbonsäure oder deren Anhydrid entstammt.Textile auxiliary according to one of claims 1 to 4, characterized in that the acidic, water-solubilizing group of component (a) comes from an ethylenically unsaturated polymerizable sulfonic acid or carboxylic acid or its anhydride. Textilhilfsmittel gemäss Anspruch 5, dadurch gekennzeichnet, dass in Komponente (a) die ethylenisch ungesättigten Carbonsäuren Monocarbonsäuren mit 2 bis 5 Kohlenstoffatomen und vorzugsweise Methacrylsäure oder Acrylsäure bedeuten.Textile auxiliary according to claim 5, characterized in that in component (a) the ethylenically unsaturated carboxylic acids are monocarboxylic acids having 2 to 5 carbon atoms and preferably mean methacrylic acid or acrylic acid. Textilhilfsmittel gemäss Anspruch 6, dadurch gekennzeichnet, dass in Komponente (a) als Monocarbonsäure Acrylsäure verwendet wird.Textile auxiliaries according to claim 6, characterized in that acrylic acid is used as the monocarboxylic acid in component (a). Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass die Komponente (a) aus 5 bis 50 Gew.-% eines nichtionogenen Tensids gemäss Formel (1) und 95 bis 50 Gew.-% Acrylsäure oder Methacrylsäure erhalten worden ist.Textile auxiliaries according to claim 1, characterized in that component (a) has been obtained from 5 to 50% by weight of a nonionic surfactant according to formula (1) and 95 to 50% by weight of acrylic acid or methacrylic acid. Textilhilfsmittel gemäss Anspruch 8, dadurch gekennzeichnet, dass das nichtionogene Tensid der Komponente (a) der Formel (3) entspricht.Textile auxiliaries according to claim 8, characterized in that the nonionic surfactant of component (a) corresponds to formula (3). Textilhilfsmittel gemäss einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Komponente (b) dem nichtionogenen Tensid der Komponente (a) entspricht.Textile auxiliary according to one of claims 1 to 9, characterized in that component (b) corresponds to the nonionic surfactant of component (a). Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass als fakultative Komponente (c) 2-Ethylhexylsulfat verwendet wird.Textile auxiliary according to claim 1, characterized in that 2-ethylhexyl sulfate is used as optional component (c). Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass sie als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (1) und Acrylsäure erhalten worden ist, als Komponente (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls als Komponente (c) 2-Ethylhexylsulfat enthalten.Textile auxiliary according to claim 1, characterized in that it contains as component (a) a compound obtained from a nonionic surfactant of the formula (1) and acrylic acid, as component (b) a nonionic surfactant of the formula (1) and optionally as Component (c) contain 2-ethylhexyl sulfate. Textilhilfsmittel gemäss Anspruch 12, dadurch gekennzeichnet, dass sie als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (2) und Acrylsäure erhalten worden ist, als Komponente (b) ein nichtionogenes Tensid der Formel (2) und gegebenenfalls als Komponente (c) 2-Ethylhexylsulfat enthalten.Textile auxiliaries according to claim 12, characterized in that they contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (2) and acrylic acid, as component (b) a nonionic surfactant of the formula (2) and optionally as Component (c) contain 2-ethylhexyl sulfate. Textilhilfsmittel gemäss Anspruch 12, dadurch gekennzeichnet, dass sie als Komponente (a) eine Verbindung, die aus einem nichtionogenen Tensid der Formel (3) erhalten worden ist, und als Komponente (b) ein nichtionogenes Tensid entsprechend Formel (3) enthalten.Textile auxiliaries according to claim 12, characterized in that they contain as component (a) a compound which has been obtained from a nonionic surfactant of the formula (3) and as component (b) a nonionic surfactant corresponding to formula (3). Textilhilfsmittel gemäss Anspruch 1, dadurch gekennzeichnet, dass sie, bezogen auf das Mittel,
   2 bis 22 Gew.-% der Komponente (a),
   10 bis 95 Gew.-% der Komponente (b),
   0 bis 15 Gew.-% der Komponente (c) und
   ad 100 % Wasser
   enthalten.Textile auxiliaries according to claim 1, characterized in that, based on the agent, they
2 to 22% by weight of component (a),
10 to 95% by weight of component (b),
0 to 15% by weight of component (c) and
ad 100% water
contain. Verwendung des Textilhilfsmittels gemäss einem der Ansprüche 1 bis 15 als Netzmittel, Textilwaschmittel, Dispergiermittel oder als Stabilisatoren in den Peroxid-Bleichflotten.Use of the textile auxiliary according to one of claims 1 to 15 as a wetting agent, textile detergent, dispersant or as stabilizer in the peroxide bleaching liquors. Verfahren zum Netzen und/oder Waschen von Fasermaterialien, dadurch gekennzeichnet, dass man diese Materialien in wässrigem Medium in Gegenwart eines Textilhilfsmittelgemisches, das (a) ein Umsetzungsprodukt aus einem nichtionogenen Tensid der Formel
Figure imgb0011
 worin
R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens
5 C-Atomen, Niederalkylphenyl oder Styryl,
"Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
p eine Zahl von 2 bis 60 bedeutet mit einer eine saure, wasserlöslich machende Gruppe aufweisenden Verbindung, (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls (c) ein Hydrotropiermittel
enthalten, behandelt. Process for wetting and / or washing fiber materials, characterized in that these materials in an aqueous medium in the presence of a mixture of textile auxiliaries, the (a) a reaction product of a nonionic surfactant of the formula
Figure imgb0011
 wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical with at least
5 carbon atoms, lower alkylphenyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p denotes a number from 2 to 60 with a compound having an acidic, water-solubilizing group, (b) a nonionic surfactant of formula (1) and optionally (c) a hydrotrope
included, treated. Verfahren gemäss Anspruch 17, dadurch gekennzeichnet, dass man das Texblhilfsmittel in einer Menge von 0,1 bis 30 g pro Liter Flotte einsetzt.A method according to claim 17, characterized in that the textile auxiliary is used in an amount of 0.1 to 30 g per liter of liquor. Verfahren gemäss Anspruch 17 oder 18, dadurch gekennzeichnet, dass das Fasermaterial kontinuierlich oder diskontinuierlich behandelt wird.A method according to claim 17 or 18, characterized in that the fiber material is treated continuously or discontinuously. Das gemäss einem der Ansprüche 1 bis 19 behandelte Fasermaterial.The fiber material treated according to one of claims 1 to 19.
EP19910810421 1990-06-11 1991-06-04 Low-foaming, silicone-free, aqueous textile auxiliaries, their preparation and their use Expired - Lifetime EP0462059B1 (en)

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