EP0462059B1 - 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
EP0462059B1
EP0462059B1 EP19910810421 EP91810421A EP0462059B1 EP 0462059 B1 EP0462059 B1 EP 0462059B1 EP 19910810421 EP19910810421 EP 19910810421 EP 91810421 A EP91810421 A EP 91810421A EP 0462059 B1 EP0462059 B1 EP 0462059B1
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EP
European Patent Office
Prior art keywords
component
textile auxiliary
auxiliary composition
acid
weight
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EP19910810421
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German (de)
French (fr)
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EP0462059A2 (en
EP0462059A3 (en
Inventor
Christian Guth
Albert Stehlin
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BASF Schweiz AG
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding 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.
  • EP-A-0,360,736 discloses a wetting and washing agent which comprises (a) a mixture of monomeric and oligomeric phosphoric acid esters, (b) a copolymer of monomeric carboxylic or sulfonic acids and polyalkylene oxide adducts, (c) a nonionic surfactant and (e) a Contains antifoam as an optional component. It is used in textile pretreatment.
  • EP-A-0,299,691 discloses a stable composition which contains (a) an emulsion stabilizer which is prepared by the polymerization of an unsaturated carboxylic acid such as acrylic acid in the presence of a water-soluble nonionic surfactant and (b) a free nonionic surfactant, and as suitable hydrotrope diisonaphthalene monosulfonate.
  • the composition is used in textile treatment to remove hydrocarbonaceous dirt.
  • the low-foaming, silicone-free, aqueous textile auxiliaries according to the invention are characterized in that they contain components (a), (b) and optionally (c) listed in claim 1.
  • 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.
  • aliphatic saturated monoalcohols natural alcohols, such as, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and synthetic alcohols, such as, for example, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol
  • Decanol, C 9 -C 11 oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms can be used. 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 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.
  • the nonionic surfactants of the formulas (1) and (4) are prepared in a manner known per se, for example by reacting the corresponding alkylene oxide addition products with thionyl chloride and then reacting the chlorine compound formed with a short-chain, cycloaliphatic, fatty, lower alkylphenyl or Styryl alcohol.
  • Acid 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 of which has 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-acrylamido-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 (4) and 95 to 50% by weight of acrylic acid or methacrylic acid.
  • 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 then 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-methylvaleronitrile, 1,1'-azo-bis-1-cyclo-hexanitrile and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, 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.
  • the reaction is advantageously carried out in an inert atmosphere, for example in the presence of nitrogen.
  • Optional component (c) is 2-ethylkenyl sulfate.
  • 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 mixtures are low-foaming, APEO and silicone-free textile auxiliaries. Due to their liquid commercial form, they are easy to handle, which is why they are particularly suitable for modern dosing systems. You are universal can be used and can therefore be considered for various applications.
  • they can be used as wetting agents, textile detergents, dispersants or as stabilizers in peroxide bleaching liquors.
  • 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 batchwise 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 required by the process, with hot Water from about 90 to 98 ° C and then thoroughly rinsed with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.

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 EP-A-0,360,736 offenbart ein Netz- und Waschmittel, das (a) ein Gemisch aus monomeren und oligomeren Phosphorsäureestern, (b) ein Mischpolymerisat aus monomeren Carbon- oder Sulfonsäuren und Polyalkylenoxidaddukten, (c) ein nichtionogenes Tensid und (e) ein Antischaummittel als fakultative Komponente enthält. Es findet Verwendung in der Textilvorbehandlung.EP-A-0,360,736 discloses a wetting and washing agent which comprises (a) a mixture of monomeric and oligomeric phosphoric acid esters, (b) a copolymer of monomeric carboxylic or sulfonic acids and polyalkylene oxide adducts, (c) a nonionic surfactant and (e) a Contains antifoam as an optional component. It is used in textile pretreatment.

Die EP-A-0,299,691 offenbart eine stabile Zusammensetzung, die (a) einen Emulsionsstabilisator enthält, der hergestellt wird durch die Polymerisation einer ungesättigten Carbonsäure, wie z.B. Acrylsäure, in Anwesenheit eines wasserlöslichen nichtionogenen Tensids und (b) eines freien nichtionogenen Tensids, und als geeignetes Hydrotropiermittel Diisonaphthalinmonosulfonat. Die Zusammensetzung findet Verwendung in der Textilbehandlung zur Entfernung von kohlenwasserstoffhaltigem Schmutz.EP-A-0,299,691 discloses a stable composition which contains (a) an emulsion stabilizer which is prepared by the polymerization of an unsaturated carboxylic acid such as acrylic acid in the presence of a water-soluble nonionic surfactant and (b) a free nonionic surfactant, and as suitable hydrotrope diisonaphthalene monosulfonate. The composition is used in textile treatment to remove hydrocarbonaceous dirt.

Die erfindungsgemässen schaumarmen, silikonfreien, wässrigen Textilhilfsmittel sind dadurch gekennzeichnet, dass sie die in Ansprüch 1 aufgeführten Komponenten (a), (b) und gegebenenfalls (c) enthalten.The low-foaming, silicone-free, aqueous textile auxiliaries according to the invention are characterized in that they contain components (a), (b) and optionally (c) listed in claim 1.

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, for example, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and synthetic alcohols, such as, for example, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol Decanol, C 9 -C 11 oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms can be used. 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, 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 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, aus denen die Komponente (a) hergestellt wird, seien die Tenside der Formel

Figure imgb0001
   worin

  • R2 C9 bis C14-Alkyl,
  • R4 Wasserstoff, C1 bis C4-Alkyl oder C1-C5-Alkylphenyl,
  • 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,
genannt.The non-ionic surfactants from which component (a) is produced are the surfactants of the formula
Figure imgb0001
 wherein
  • R 2 C 9 to C 14 alkyl,
  • R 4 is hydrogen, C 1 to C 4 alkyl or C 1 -C 5 alkylphenyl,
  • of Y 5 and Y 6 one is hydrogen and the other is ethyl.
  • n 3 is an integer from 4 to 8 and
  • m 3 is an integer from 1 to 3,
called.

Die Herstellung der nichtionogenen Tenside der Formeln (1) und (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) and (4) are prepared in a manner known per se, for example by reacting the corresponding alkylene oxide addition products 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 Dicarbonsäuren 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.Acid 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 of which has 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-Acrylamido-2-methylpropansulfonsäure in Frage.Examples of suitable sulfonic acids are vinylsulfonic acid or 2-acrylamido-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 (4) und 95 bis 50 Gew.-% Acrylsäure oder Methacrylsäure 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 (4) and 95 to 50% by weight of acrylic acid or methacrylic acid.

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 then 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-methylvaleronitrile, 1,1'-azo-bis-1-cyclo-hexanitrile and 2,2'-azo-bis-isobutyric acid alkyl ester; symmetrical diacyl peroxides, 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, for example in the presence of nitrogen.

Als fakultative Komponente (c) kommt 2-Ethylkenylsulfat in Betracht.Optional component (c) is 2-ethylkenyl sulfate.

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 particularly advantageously contain, 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 mixtures are low-foaming, APEO and silicone-free textile auxiliaries. Due to their liquid commercial form, they are easy to handle, which is why they are particularly suitable for modern dosing systems. You are universal can be used and can therefore be considered for various applications.

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 (4) mit einer eine saure, wasserlöslich machende Gruppe aufweisenden Verbindung
  • (b) ein nichtionogenes Tensid der Formel (1) und gegebenenfalls
  • (c) 2-Ethylhexylsulfat als Hydrotropiermittel
enthält, behandelt, wobei
die Einsatzmengen, in denen das erfindungsgemässe Textilhilfsmittel den Behandlungsflotten zugesetzt wird, zwischen 0,1 und 30, vorzugsweise 0,2 und 10 g pro Liter Behandlungsflotte betragen. Diese Flotten können noch weitere Zusätze enthalten, z.B. Entschlichtungsmittel, Farbstoffe, optische Aufheller, Kunstharze und Alkalien wie Natriumhydroxid.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 (4) with a compound having an acidic, water-solubilizing group
  • (b) a nonionic surfactant of formula (1) and optionally
  • (c) 2-ethylhexyl sulfate as a hydrotrope
contains, treats, being
the amounts 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 liquors can also contain other additives, for example desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.

Als Fasermaterialien kommen in Betracht: Cellulose, insbesondere unvorbehandelte natürliche Cellulose wie z.B. Hanf, Leinen, Jute, 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 batchwise 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 einer 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 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 required by the process, with hot Water from about 90 to 98 ° C and then thoroughly rinsed with warm and finally with cold water, neutralized if necessary and then preferably dried at elevated temperatures.

Claims (10)

  1. A low-foam, silicone-free aqueous textile auxiliary composition which comprises
    (a) a reaction product of a nonionic surfactant of the formula
    Figure imgb0004
     wherein
    R2 is C9-C14alkyl,
    R4 is hydrogen, C1-C4alkyl or C1-C5alkylphenyl,
    one of Y5 and Y6 is hydrogen and the other is ethyl,
    n3 is an integer from 4 to 8, and
    m3 is an integer from 1 to 3,
    with a compound which contains an acidic water-solubilising group,
    (b) a nonionic surfactant of the formula

            (1)    R-O―(-alkylene-O-)p-R1,

    wherein
    R is an aliphatic radical of at least 8 carbon atoms,
    R1 is hydrogen, C1-C8alkyl, a cycloaliphatic radical of at least 5 carbon atoms, lower alkylphenyl or styryl,
    "alkylene" denotes an alkylene radical of 2 to 4 carbon atoms, and
    p is a number from 2 to 60; and, optionally,
    (c) 2-ethylhexyl sulfate as hydrotropic agent.
  2. A textile auxiliary composition according to claim 1, wherein the acidic water-solubilising group of component (a) is from an ethylenically unsaturated polymerisable sulfonic acid or carboxylic acid or the anhydride thereof.
  3. A textile auxiliary composition according to claim 2, wherein the ethylenically unsaturated carboxylic acid in component (a) is a monocarboxylic acid of 2 to 5 carbon atoms and is preferably methacrylic acid or acrylic acid.
  4. A textile auxiliary composition according to claim 3, wherein the monocarboxylic acid used in component (a) is acrylic acid.
  5. A textile auxiliary composition according to claim 1, wherein component (a) has been obtained from 5 to 50 % by weight of a nonionic surfactant of formula (4) and 95 to 50 % by weight of acrylic or methacrylic acid.
  6. A textile auxiliary composition according to claim 1, which comprises, based on said composition,
    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
    water to make up 100 %.
  7. Use of the textile auxiliary composition according to one of claims 1 to 6 as wetting agent, textile detergent, dispersant or as stabiliser in the peroxide bleach liquors.
  8. A process for wetting and/or washing fibre materials, wherein said materials are treated in aqueous medium in the presence of a textile auxiliary composition which comprises
    (a) a reaction product of a nonionic surfactant of the formula (4) with a compound which contains an acidic, water-solubilising group,
    (b) a nonionic surfactant of the formula (1), and, optionally,
    (c) 2-ethylhexyl sulfate as hydrotropic agent,
    the textile auxiliary composition being employed in an amount of 0.1 to 30 g per litre of liquor.
  9. A process according to claim 8, wherein the fibre material is treated continuously or batchwise.
  10. The fibre material treated in accordance with one of claims 8 or 9.
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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CH194590 1990-06-11
CH709/91 1991-03-08
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