EP0342331B1 - Composition with absorption capacity for the treatment of polyester fibrous materials - Google Patents

Composition with absorption capacity for the treatment of polyester fibrous materials Download PDF

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Publication number
EP0342331B1
EP0342331B1 EP89104695A EP89104695A EP0342331B1 EP 0342331 B1 EP0342331 B1 EP 0342331B1 EP 89104695 A EP89104695 A EP 89104695A EP 89104695 A EP89104695 A EP 89104695A EP 0342331 B1 EP0342331 B1 EP 0342331B1
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Prior art keywords
substituted
alkyl group
unsubstituted
branched
linear
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German (de)
French (fr)
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EP0342331A2 (en
EP0342331A3 (en
Inventor
Wolfgang Becker
Günter Uphues
Uwe Dr. Ploog
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/295—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing polyglycol moieties; containing neopentyl moieties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/04—Polyester fibers

Definitions

  • the invention relates to mixtures which contain oxidized polyethylenes and selected quaternary ammonium phosphates, and to the use of these mixtures as drawable textile auxiliaries for the antistatic, smooth and / or plasticizing of polyester-containing fiber materials.
  • the Aviv für aqueezing is part of the textile finishing and should give the flake, the sliver, woven fabric, knitted fabric or nonwoven in particular such properties as feel, smoothness, antistatic and fullness, through which the appearance, saleability, fitness for purpose and processing properties are increased.
  • the textile auxiliaries used for finishing can, for example, be applied to textile fiber materials in a full bath (exhaust process).
  • the full bath treatment the textiles are wetted for a long time in a large liquor ratio and then dewatered by squeezing, suctioning or centrifuging.
  • the full bath treatment has the advantage that the treatment times and temperatures can be chosen and varied as desired (see, for example, W. Bernard: “Textile finishing", 2nd edition, page 257-258, Springer-Verlag 1967).
  • Fat-polyamine condensation products, fatty acid amide derivatives, paraffin emulsions and silicone derivatives are usually used as antistatic agents, smoothing agents and / or plasticizers in the exhaust process.
  • antistatic agents smoothing agents and / or plasticizers in the exhaust process.
  • polyester-containing fiber materials have no or only unsatisfactory antistatic properties, smoothness and / or softness after finishing with these known substances.
  • the object on which the invention is based was therefore to develop textile auxiliaries which have a high substantivity to polyester-containing fiber materials and which give these fiber materials excellent antistatic smoothing and / or softening properties.
  • blends containing oxidized polyethylenes and certain quaternary ammonium phosphates have a high affinity for polyester-containing fiber materials.
  • the weight ratio of components A: B in the mixtures according to the invention is preferably between 10: 1 and 1: 5, particularly preferably between 10: 3 and 1: 2.
  • mixtures containing anoxidized polyethylenes with average molecular weights between 3000 and 8000, acid numbers between 25 and 60, saponification numbers between 40 and 80 and densities between 0.94 and 1.09 g / cm3 and at least one quaternary ammonium phosphate from at least one of the groups (B) 1-3, as textile auxiliaries for antistatic, smoothing and / or softening polyester-containing fiber materials is therefore also an object of the invention.
  • Anoxidized polyethylenes with average molecular weights between 3500 and 5000 and densities between 0.98 and 1.00 g / cm3 are preferred in the mixtures according to the invention.
  • the mixtures according to the invention which are preferably in the form of dispersions or solutions, particularly preferably in the form of aqueous emulsions, preferably contain between 5 and 50% by weight, particularly preferably between 10 and 30% by weight of components A and B.
  • the dispersions or solutions, preferably aqueous emulsions are applied in a manner known per se in rinsing, washing or immersion baths or by spraying processes on polyester-containing fiber materials and dried between 80 and 160 ° C. by means of spinning, squeezing and temperature treatment.
  • the mixtures according to the invention are preferably applied in the exhaust process from aqueous liquors at liquor ratios between 1: 5 and 1:25 at liquor pH values between 4.0 and 7.0 and temperatures between 40 and 80 ° C. Since textile auxiliaries containing component A and component B according to the invention have a high affinity for polyester-containing fiber materials, a high level of exhaustion of the treatment liquors is achieved.
  • Polyethylene-containing fiber materials include pure polyester fibers and mixtures of polyester fibers and natural and / or synthetic fibers, for example mixtures of polyester fibers and cotton; Polyester fibers and polyamide fibers; Polyester fibers, cotton and polyamide fibers; Polyester fibers and polyacrylic fibers understood.
  • the textile fiber materials are in the form of a flake, sliver, yarn, knitwear, woven fabric or nonwoven, preferably a flake or sliver.
  • the material can be raw white, bleached or colored.
  • the anoxidized polyethylenes contained in the mixtures according to the invention are commercial products which are offered, for example, by Allied Corp., USA under the name A-C® polyethylenes.
  • amines, imidazolines and amino-functional polyesters and phosphoric acid partial esters required as starting materials for the production of quaternary ammonium phosphates can be obtained by processes known from the literature:
  • Amines which can be prepared, for example, by hydrogenation of fatty acid nitriles (Ullmann's Encyclopedia of Industrial Chemistry, Volume 11, pages 448-449, Verlag Chemie, Weinheim 1976) or directly from fatty alcohols and ammonia according to GB-A-1 074 603 are preferred if desired reacted with ethylene oxide and / or propylene oxide at temperatures between 130 and 180 ° C with the proviso that the polyalkyl ether chains of the tertiary amines formed consist of 1 to 5 ethylene oxide and / or propylene oxide units.
  • Cocosamine, oleylamine, tallow amine, cocoalkyl-di-2-hydroxyethyl-amine, dimethyl-laurylamine and N-C12 ⁇ 14-alkylmorpholine are examples of amines which are suitable for the preparation of quaternary ammonium phosphates.
  • An example of acylated amines is cocoylamidopropyldimethylamine.
  • the condensation is carried out at temperatures between 150 and 240 ° C., preferably between 150 and 200 ° C.
  • the molar ratio of carboxylic acid: diamine is preferably between 1: 1 and 1: 2.
  • the carboxylic acids can be used either individually or in a mixture to prepare the imidazolines.
  • fatty acid mixtures such as those that occur when natural fats and / or oils are split. Individual fractions of such fatty acid mixtures are also suitable for the preparation of the imidazolines.
  • the carboxylic acids used are preferably those of the general formula R4-COOH, in which the radical R4 is a straight-chain or branched-chain, substituted or unsubstituted, saturated alkyl group having 7 to 17 carbon atoms or for a straight-chain or branched-chain, substituted or unsubstituted, unsaturated alkyl group having 17 to 21 carbon atoms, for example caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolinic acid, gadoleic acid and / or ricinoleic acid.
  • 1-Hydroxyethyl-2-undecylimidazoline, 1-hydroxyethyl-2-heptadecenylimidazoline and 1-hydroxyethyl-2-heptylimidazoline are suitable imidazolines.
  • alkoxylated tertiary amines required for the production of amino-functional polyesters are derived from primary alkyl and / or alkenylamines, for example from methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, cetylamine, oleylamine, linoleylamine, coconut amine and / or tallow amine. Alkyl amines made from coconut oil or tallow are preferred.
  • Alkyl and / or alkenyl amines are alkoxylated in a manner known per se at from 130 to 180 ° C. with ethylene oxide and / or propylene oxide, with the proviso that the degree of alkoxylation (sum of a and b) is between 2 and 30.
  • Tallow polyester 5 ethylene oxide units (EO) and adipic acid, polyester from coconut amine. 2 EO and adipic acid, polyester from coconut amine. 5 EO and succinic acid and / or polyester from tallow amine. 10 EO and sebacic acid are examples of suitable amino-functional polyesters.
  • the phosphoric acid partial esters are prepared from straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted, optionally alkoxylated alcohols having 6 to 22 carbon atoms.
  • Straight or branched chain, substituted or unsubstituted, saturated, optionally alkoxylated alcohols having 8 to 18 C atoms and / or straight or branched chain, substituted or unsubstituted, unsaturated, optionally alkoxylated alcohols having 18 to 22 C atoms are used, for example 2-ethylhexanol, n-octanol, isononyl alcohol, decyl alcohol, dodecyl alcohol, isotridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol, eicosenyl alcohol, docosenyl alcohol.
  • alcohols are optionally reacted with 1 to 10 moles of ethylene oxide, propylene oxide and / or butylene oxide.
  • the optionally alkoxylated alcohols are phosphated in a manner known per se by reacting 3 mol of alcohol with 1 mol of phosphorus pentoxide at 50 to 80 ° C.
  • water is treated at 90 to 100 ° C. for several hours.
  • the mixtures according to the invention are used as textile auxiliaries for the antistatic, smoothing and / or softening of polyester-containing fiber materials, these mixtures are preferably in the form of dispersions or solutions, particularly preferably in the form of aqueous emulsions. These emulsions contain 2 to 20% by weight of nonionic, cationic and / or amphoteric dispersants.
  • Suitable nonionic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated fats, oils, fatty alcohols with 8 to 24 carbon atoms in the fat residue, fatty amines with 8 to 24 carbon atoms in the fat residue and / or C8 ⁇ 18 alkylphenols, for example ethoxylated castor oil, Oleyl alcohol. 5 EO, omelet acetyl alcohol. 5 EO, tallow alcohol. 14 EO, stearylamine. 2 EO, tallow amine. 2 EO, stearylamine. 10 EO and / or nonylphenol. 10 EO.
  • Suitable cationic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated, alkylamines having 10 to 20 carbon atoms in the form of their ammonium salts, for example stearylamine. 10 EO.
  • Suitable amphoteric dispersants are, for example, C8 ⁇ 22-alkyldimethylbetaines, N-C8 ⁇ 22-alkylamidobetaines and / or amphoteric surfactants derived from amino acids.
  • the solutions or dispersions can contain further smoothing agents, for example paraffins with softening points between 35 and 80 ° C, fatty acid esters with 12 to 24 C atoms both in the fatty acid residue and in the straight and / or branched chain, saturated and / or unsaturated alcohol residue such as isotridecyl stearate, stearyl stearate and / or behenyl behenate and / or silicones such as dimethylpolysiloxane, plasticizers such as fatty acid amidopolyamines and / or quaternary ammonium salts, for example dimethyldistearylammonium chloride, antioxidants, for example oxygen acids of phosphorus and / or alkali metal sulfides and carboxylic acids, for example C-regulating agents and / or contain C1 ⁇ 4-hydroxycarboxylic acids such as acetic acid and / or glycolic acid.
  • paraffins with softening points between 35 and 80 ° C saturated and
  • the proportion of optional components in aqueous dispersions and emulsions is between 2 and 20% by weight.
  • the dispersions and solutions, preferably the aqueous emulsions, which contain the mixtures according to the invention, are prepared in a manner known per se by mixing anoxidized polyethylenes, dispersants and optional constituents with water and stirring them in a pressure-resistant apparatus at from 130 to 170.degree. After cooling, finely divided, storage-stable emulsions are obtained, into which quaternary ammonium phosphates and optionally further dispersants are stirred.
  • the mixtures according to the invention are heat-resistant and do not cause discoloration of the fiber materials.
  • the polyester-containing fiber materials finished with the mixtures according to the invention show, in comparison to untreated, only with anoxidized polyethylene or only with quaternary Ammonium phosphates treated polyester-containing fiber materials significantly reduced anti-electrostatic charges, low static and dynamic fiber / fiber and fiber / metal friction, excellent smoothness and good soft feel.
  • the conveyor belts produced on the needle bar section were assessed according to the cohesion meter measuring method.
  • the measured values cN. tex ⁇ 1 represent the 1.25-fold forces that are required to change the length of the original material.
  • the measured values determined were processed statistically using a Rothschild F-Meter with the aid of a connected small computer.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Medical Uses (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Woven Fabrics (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Mixtures which contain oxidized polyethylenes and selected quaternary ammonium phosphates are used as textile drawing aids for rendering polyester-containing fiber materials antistatic, smooth and/or soft.

Description

Die Erfindung betrifft Mischungen, die anoxidierte Polyethylene und ausgewählte quartäre Ammoniumphosphate enthalten, sowie die Verwendung dieser Mischungen als ziehfähige Textilhilfsmittel zum Antistatisch-, Glatt- und/oder Weichmachen polyesterhaltiger Fasermaterialien.The invention relates to mixtures which contain oxidized polyethylenes and selected quaternary ammonium phosphates, and to the use of these mixtures as drawable textile auxiliaries for the antistatic, smooth and / or plasticizing of polyester-containing fiber materials.

Die Aviverung ist ein Teil der Textilveredlung und soll der Flocke, dem Kammzug, Gewebe, Gewirke oder Nonwovens insbesondere solche Eigenschaften wie Griff, Glätte, Antistatik und Fülle verleihen, durch die Aussehen, Verkaufsfähigkeit, Gebrauchstüchtigkeit und Verarbeitungseigenschaften erhöht werden. Die zur Avivierung verwendeten Textilhilfsmittel können beispielsweise auf Textilfasermaterialien im Vollbad (Ausziehverfahren) appliziert werden. Bei der Vollbadbehandlung werden die Textilien im großen Flottenverhältnis eine längere Zeit benetzt und anschließend durch Abquetschen, Absaugen oder Zentrifugieren entwässert. Im Vergleich zu anderen Behandlungsverfahren wie Foulardieren, Pflatschen, Rakeln, Besprühen, hat die Vollbadbehandlung den Vorteil, daß die Behandlungszeiten und -temperaturen beliebig gewählt und variiert werden können (siehe beispielsweise W. Bernard: "Appretur der Textilien", 2. Auflage, Seite 257-258, Springer-Verlag 1967).The Aviverung is part of the textile finishing and should give the flake, the sliver, woven fabric, knitted fabric or nonwoven in particular such properties as feel, smoothness, antistatic and fullness, through which the appearance, saleability, fitness for purpose and processing properties are increased. The textile auxiliaries used for finishing can, for example, be applied to textile fiber materials in a full bath (exhaust process). In the full bath treatment, the textiles are wetted for a long time in a large liquor ratio and then dewatered by squeezing, suctioning or centrifuging. Compared to other treatment methods such as padding, splashing, knife coating, spraying, the full bath treatment has the advantage that the treatment times and temperatures can be chosen and varied as desired (see, for example, W. Bernard: "Textile finishing", 2nd edition, page 257-258, Springer-Verlag 1967).

Das Ausziehverfahren ist jedoch nur dann wirtschaftlich, wenn Textilhilfsmittel zum Einsatz gelangen, die eine genügend hohe Substantivität zu Fasermaterialien aufweisen und damit eine gute Erschöpfung der Behandlungsflotten ermöglichen. Kationische Textilhilfsmittel, die Fasermaterialien antistatische und/oder weichmachende Eigenschaften verleihen, zeigen gegenüber natürlichen Fasern, beispielsweise Cellulose, Baumwolle und/oder Wolle eine hohe Substantivität, während die Affinität zu den meisten synthetischen Fasermaterialien, insbesondere Polyesterfasern, deutlich geringer ist (Chwala/Anger: "Handbuch der Textilhilfsmittel", Seiten 689-692, Verlag Chemie Weinheim 1967).However, the pull-out process is only economical if textile auxiliaries are used that have a sufficiently high substantivity to fiber materials and thus allow the treatment liquors to be well exhausted. Cationic textile auxiliaries which impart fiber materials with antistatic and / or softening properties show a high substantivity towards natural fibers, e.g. cellulose, cotton and / or wool, while the affinity for most synthetic fiber materials, especially polyester fibers, is significantly lower (Chwala / Anger: "Handbook of Textile Aids", pages 689-692, Verlag Chemie Weinheim 1967).

Üblicherweise werden Fett-Polyamin-Kondensationsprodukte, Fettsäureamidderivate, Paraffinemulsionen sowie Silikonderivate als Antistatika, Glättemittel und/oder Weichmacher im Ausziehverfahren verwendet. Nachteilig ist jedoch, daß diese Substanzen nur eine ungenügende Substantivität gegenüber polyesterhaltigen Fasermaterialien besitzen. Ferner weisen polyesterhaltige Fasermaterialien nach der Avivierung mit diesen bekannten Substanzen keine oder nur unbefriedigende Antistatik, Glätte und/oder Weichheit auf.Fat-polyamine condensation products, fatty acid amide derivatives, paraffin emulsions and silicone derivatives are usually used as antistatic agents, smoothing agents and / or plasticizers in the exhaust process. However, it is disadvantageous that these substances have an insufficient substantivity towards polyester-containing fiber materials. In addition, polyester-containing fiber materials have no or only unsatisfactory antistatic properties, smoothness and / or softness after finishing with these known substances.

Die der Erfindung zugrunde liegende Aufgabe bestand daher in der Entwicklung von Textilhilfsmitteln, die eine hohe Substantivität zu polyesterhaltigen Fasermaterialien besitzen und die diesen Fasermaterialien ausgezeichnete antistatische glatt- und/oder weichmachende Eigenschaften verleihen.The object on which the invention is based was therefore to develop textile auxiliaries which have a high substantivity to polyester-containing fiber materials and which give these fiber materials excellent antistatic smoothing and / or softening properties.

Es wurde gefunden, daß Mischungen, die anoxidierte Polyethylene und bestimmte quartäre Ammoniumphosphate enthalten, eine hohe Affinität zu polyesterhaltigen Fasermaterialien haben.It has been found that blends containing oxidized polyethylenes and certain quaternary ammonium phosphates have a high affinity for polyester-containing fiber materials.

Erfindungsgegenstand sind demgemäß Mischungen, enthaltend:

  • (A) anoxidierte Polyethylene mit mittleren Molekulargewichten zwischen 3000 und 8000, mit Säurezahlen zwischen 25 und 60, Verseifungszahlen zwischen 40 und 80 und Dichten zwischen 0,94 und 1,09 g/cm³ und
  • (B) mindestens ein quartäres Ammoniumphosphat aus mindestens einer der folgenden Gruppen:
    • 1.)
      Figure imgb0001
       worin
      R¹  eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 22 C-Atomen oder
      Figure imgb0002
      R²
      Figure imgb0003
        Methyl oder Ethyl
      R³
      Figure imgb0004
        Methyl oder Ethyl oder R² und R³ zusammen -CH₂CH₂-O-CH₂CH₂-,
      R⁴  eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 5 bis 21 C-Atomen,
      R⁵  H oder eine Alkylgruppe mit 1 bis 4 C-Atomen,
      R  eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 22 C-Atomen und
      A  eine Alkylenkette mit 2 bis 4 C-Atomen bedeutet,
      p  2 oder 3 und
      n  = 1, m = 2 oder n = 2, m = 1 ist,
    • 2.)
      Figure imgb0005
       worin
      R⁴
      eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstuierte Alkylgruppe mit 5 bis 21 C-Atomen,
      R⁶
      OH oder
      Figure imgb0006
      R
      eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 22 C-Atomen und
      A
      eine Alkylenkette mit 2 bis 4 C-Atomen bedeutet und
      n
      = 1, m = 2 oder n = 2, m = 1 ist,
    • 3.) quartäre Ammoniumphospate auf Basis aminofunktioneller Polyester, hergestellt durch Umsetzung von Dicarbonsäuren der allgemeinen Formel



              HOOC-R⁷-COOH



      in der
      R⁷
      einen aliphatischen, alicyclischen oder aromatischen, substituierten oder unsubstituierten Rest mit 1 bis 10 C-Atomen bedeutet,
      mit alkoxylierten tertiären Aminen der allgemeinen Formel
      Figure imgb0007
       in der
      R⁸
      einen gesättigten oder ungesättigten, gerad- oder verzweigtkettigen, substituierten oder unsubstituierten Alkylrest mit 1 bis 20 C-Atomen und
      A′
      eine Alkylenkette mit 2 bis 3 C-Atomen bedeutet,
      a und b
      Zahlen swischen 1 und 20 sind mit der Maßgabe, daß die Summe a + b 2 bis 30 ist und der Polymerisationsgrad der Polyester 2 bis 50 beträgt und
      anschließendes Mischen der erhaltenen aminofunktionellen Polyester in Gegenwart von Wasser bei 50 bis 80°C mit Mono-und/oder Dialkylphosphorsäureestern der allgemeinen Formeln
      Figure imgb0008
       in welchen
      R
      eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 22 C-Atomen und
      A
      eine Alkylenkette mit 2 bis 4 C-Atomen bedeutet, und
      Umsetzung mit Alkylenoxiden mit 2 bis 4 C-Atomen bei Drucken zwischen 1 und 5 bar und Temperaturen zwischen 80 und 100 °C mit der Maßgabe, daß die Polyalkyletherkette der quaternierten Aminfunktionen aus 1 bis 10 Alkylenoxideinheiten besteht.
Accordingly, the invention relates to mixtures comprising:
  • (A) Anoxidized polyethylenes with average molecular weights between 3000 and 8000, with acid numbers between 25 and 60, saponification numbers between 40 and 80 and densities between 0.94 and 1.09 g / cm³ and
  • (B) at least one quaternary ammonium phosphate from at least one of the following groups:
    • 1.)
      Figure imgb0001
       wherein
      R¹ is a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group having 6 to 22 carbon atoms or
      Figure imgb0002
      R²
      Figure imgb0003
       Methyl or ethyl
      R³
      Figure imgb0004
       Methyl or ethyl or R² and R³ together -CH₂CH₂-O-CH₂CH₂-,
      R⁴ is a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group with 5 to 21 C atoms,
      R⁵ H or an alkyl group with 1 to 4 carbon atoms,
      R is a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group having 6 to 22 carbon atoms and
      A represents an alkylene chain with 2 to 4 carbon atoms,
      p 2 or 3 and
      n = 1, m = 2 or n = 2, m = 1,
    • 2.)
      Figure imgb0005
       wherein
      R⁴
      a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group with 5 to 21 carbon atoms,
      R⁶
      OH or
      Figure imgb0006
      R
      a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group having 6 to 22 carbon atoms and
      A
      is an alkylene chain with 2 to 4 carbon atoms and
      n
      = 1, m = 2 or n = 2, m = 1,
    • 3.) Quaternary ammonium phosphates based on amino-functional polyester, produced by reacting dicarboxylic acids of the general formula



      HOOC-R⁷-COOH



      in the
      R⁷
      represents an aliphatic, alicyclic or aromatic, substituted or unsubstituted radical having 1 to 10 C atoms,
      with alkoxylated tertiary amines of the general formula
      Figure imgb0007
       in the
      R⁸
      a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl radical having 1 to 20 C atoms and
      A ′
      is an alkylene chain with 2 to 3 carbon atoms,
      a and b
      Numbers between 1 and 20 are provided that the sum a + b is 2 to 30 and the degree of polymerization of the polyester is 2 to 50 and
      subsequent mixing of the amino-functional polyesters obtained in the presence of water at 50 to 80 ° C. with mono- and / or dialkylphosphoric esters of the general formulas
      Figure imgb0008
       in which
      R
      a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group having 6 to 22 carbon atoms and
      A
      is an alkylene chain having 2 to 4 carbon atoms, and
      Reaction with alkylene oxides with 2 to 4 carbon atoms at pressures between 1 and 5 bar and temperatures between 80 and 100 ° C with the proviso that the polyalkyl ether chain of the quaternized amine functions consists of 1 to 10 alkylene oxide units.

In den erfindungsgemäßen Mischungen liegt das Gewichtsverhältnis der Komponenten A : B vorzugsweise zwischen 10 : 1 und 1 : 5, besonders bevorzugt zwischen 10 : 3 und 1 : 2.The weight ratio of components A: B in the mixtures according to the invention is preferably between 10: 1 and 1: 5, particularly preferably between 10: 3 and 1: 2.

Aus der japanischen Patentanmeldung JP 59/47478 ist bereits bekannt, quartäre Ammoniumphosphate der allgemeinen Formel

Figure imgb0009

in welcher

R₁
eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen,
Figure imgb0010
 oder β-Hydroxyalkyl bedeutet,
R₂ und R₃
unabhängig voneinander eine Alkyl- oder Alkenylgruppe mit 1 bis 22 C-Atomen, eine Benzylgruppe oder
Figure imgb0011
 bedeutet oder R₂ und R₃ -CH₂CH₂-O-CH₂CH₂- bedeuten,
R₄
(OCH(R₆)CH₂)l-OH,
R₅
eine Alkyl- oder Alkenylgruppe mit 7 bis 21 C-Atomen,
R₆
H oder eine Alkylgruppe mit 1 bis 18 C-Atomen,
X⁻
das Anion eines organischen Phosphorsäureesters der allgemeinen Formel
Figure imgb0012
R₇
eine Alkyl- oder Alkenylgruppe mit 8 bis 22 C-Atomen,
A und A′
eine Alkylengruppe mit 2 bis 4 C-Atomen bedeutet,
m
1 bis 3,
n
1 bis 20,
l
1 bis 5,
p
0 bis 20 und
q
1 oder 2 ist,
als Antistatika für synthetische Textilfasern, beispielsweise Polyesterfasern zu verwenden.Quaternary ammonium phosphates of the general formula are already known from Japanese patent application JP 59/47478
Figure imgb0009
in which
R₁
an alkyl or alkenyl group with 8 to 22 carbon atoms,
Figure imgb0010
 or β-hydroxyalkyl means
R₂ and R₃
independently of one another an alkyl or alkenyl group having 1 to 22 carbon atoms, a benzyl group or
Figure imgb0011
 means or R₂ and R₃ mean -CH₂CH₂-O-CH₂CH₂-,
R₄
(OCH (R₆) CH₂) l -OH,
R₅
an alkyl or alkenyl group with 7 to 21 C atoms,
R₆
H or an alkyl group with 1 to 18 carbon atoms,
X⁻
the anion of an organic phosphoric acid ester of the general formula
Figure imgb0012
R₇
an alkyl or alkenyl group with 8 to 22 carbon atoms,
A and A ′
represents an alkylene group with 2 to 4 carbon atoms,
m
1 to 3,
n
1 to 20,
l
1 to 5,
p
0 to 20 and
q
Is 1 or 2,
to be used as antistatic agents for synthetic textile fibers, for example polyester fibers.

Die Verwendung von anoxidierten Polyethylenen in Glättemitteln ist aus der EP-A-108 925 bekannt.The use of anoxidized polyethylene in smoothing agents is known from EP-A-108 925.

Durch Kombination bestimmter quartärer Ammoniumphosphate (Komponente (B) 1 - 3) mit anoxidierten Polyethylenen (Komponente A) wird nun überraschenderweise sowohl die antistatische Wirkung als auch die Glätte polyesterhaltiger Fasermaterialien deutlich verbessert. Des weiteren verleihen die erfindungsgemäßen Mischungen polyesterhaltigen Fasermaterialien ein gutes Griffgefühl.By combining certain quaternary ammonium phosphates (component (B) 1-3) with anoxidized polyethylene (component A), both the antistatic effect and the smoothness of polyester-containing fiber materials are now surprisingly improved. Furthermore, the mixtures according to the invention give polyester-containing fiber materials a good feel.

Die Verwendung von Mischungen, enthaltend anoxidierte Polyethylene mit mittleren Molekulargewichten zwischen 3000 und 8000, Säurezahlen zwischen 25 und 60, Verseifungszahlen zwischen 40 und 80 und Dichten zwischen 0,94 und 1,09 g/cm³ und mindestens ein quartäres Ammoniumphosphat aus mindestens einer der Gruppen (B) 1 - 3, als Textilhilfsmittel zum Antistatisch-, Glatt- und/oder Weichmachen polyesterhaltiger Fasermaterialien ist daher ebenfalls Erfindungsgegenstand.The use of mixtures containing anoxidized polyethylenes with average molecular weights between 3000 and 8000, acid numbers between 25 and 60, saponification numbers between 40 and 80 and densities between 0.94 and 1.09 g / cm³ and at least one quaternary ammonium phosphate from at least one of the groups (B) 1-3, as textile auxiliaries for antistatic, smoothing and / or softening polyester-containing fiber materials is therefore also an object of the invention.

Anoxidierte Polyethylene mit mittleren Molekulargewichten zwischen 3500 und 5000 und Dichten zwischen 0,98 und 1,00 g/cm³ werden in den erfindungsgemäßen Mischungen bevorzugt.Anoxidized polyethylenes with average molecular weights between 3500 and 5000 and densities between 0.98 and 1.00 g / cm³ are preferred in the mixtures according to the invention.

Als Komponente B gelangen vorzugsweise solche quartären Ammoniumphosphate der allgemeinen Formeln zu (B) 1 - 3 zum Einsatz, in denen die Reste folgende Bedeutung haben:

R¹
eine gesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 8 bis 18 C-Atomen, eine ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 18 bis 22 C-Atomen oder
Figure imgb0013
R⁴
eine gesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 7 bis 17 C-Atomen oder eine ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 17 bis 21 C-Atomen,
R⁶
OH,
R₈
eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 20 C-Atomen,
R
eine gesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 8 bis 18 C-Atomen oder eine ungesättigte gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 18 bis 22 C-Atomen und
A
Ethylen- und/oder Isopropylengruppen.
As component B, preference is given to using quaternary ammonium phosphates of the general formulas (B) 1-3 in which the radicals have the following meaning:
R¹
a saturated, straight or branched chain, substituted or unsubstituted alkyl group with 8 to 18 C atoms, an unsaturated, straight or branched chain, substituted or unsubstituted alkyl group with 18 to 22 C atoms or
Figure imgb0013
R⁴
a saturated, straight or branched chain, substituted or unsubstituted alkyl group with 7 to 17 C atoms or an unsaturated, straight or branched chain, substituted or unsubstituted alkyl group with 17 to 21 C atoms,
R⁶
OH,
R₈
a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group with 6 to 20 C atoms,
R
a saturated, straight or branched chain, substituted or unsubstituted alkyl group having 8 to 18 C atoms or an unsaturated straight or branched chain, substituted or unsubstituted alkyl group having 18 to 22 C atoms and
A
Ethylene and / or isopropylene groups.

Die erfindungsgemäßen Mischungen, die vorzugsweise in Form von Dispersionen oder Lösungen, besonders bevorzugt in Form wäßriger Emulsionen vorliegen, enthalten vorzugsweise zwischen 5 und 50 Gew.-%, besonders bevorzugt zwischen 10 und 30 Gew.-% der Komponenten A und B. Die Dispersionen oder Lösungen, vorzugsweise wäßrigen Emulsionen, werden in an sich bekannter Weise in Spül-, Wasch- oder Tauchbädern oder durch Sprühprozesse auf polyesterhaltige Fasermaterialien appliziert und mittels Schleudern, Abquetschen und Temperaturbehandlung zwischen 80 und 160 °C getrocknet. Vorzugsweise erfolgt die Applikation der erfindungsgemäßen Mischungen im Ausziehverfahren aus wäßrigen Flotten bei Flottenverhältnissen zwischen 1 : 5 und 1 : 25 bei Flotten-pH-Werten zwischen 4,0 und 7,0 und Temperaturen zwischen 40 und 80 °C. Da Textilhilfsmittel, enthaltend erfindungsgemäß Komponente A und Komponente B, eine hohe Affinität zu polyesterhaltigen Fasermaterialien haben, wird eine hohe Auszehrung der Behandlungsflotten erreicht.The mixtures according to the invention, which are preferably in the form of dispersions or solutions, particularly preferably in the form of aqueous emulsions, preferably contain between 5 and 50% by weight, particularly preferably between 10 and 30% by weight of components A and B. The dispersions or solutions, preferably aqueous emulsions, are applied in a manner known per se in rinsing, washing or immersion baths or by spraying processes on polyester-containing fiber materials and dried between 80 and 160 ° C. by means of spinning, squeezing and temperature treatment. The mixtures according to the invention are preferably applied in the exhaust process from aqueous liquors at liquor ratios between 1: 5 and 1:25 at liquor pH values between 4.0 and 7.0 and temperatures between 40 and 80 ° C. Since textile auxiliaries containing component A and component B according to the invention have a high affinity for polyester-containing fiber materials, a high level of exhaustion of the treatment liquors is achieved.

Unter "polyesterhaltige Fasermaterialien" werden reine Polyesterfasern sowie Mischungen aus Polyesterfasern und Natur-und/oder Synthesefasern, beispielsweise Mischungen aus Polyesterfasern und Baumwolle; Polyesterfasern und Polyamidfasern; Polyesterfasern, Baumwolle und Polyamidfasern; Polyesterfasern und Polyacrylfasern verstanden. Die Textilfasermaterialien liegen als Flocke, Kammzug, Garn, Wirkware, Gewebe oder Nonwovens, vorzugsweise als Flocke oder Kammzug vor. Das Material kann rohweiß, gebleicht oder gefärbt sein."Polyester-containing fiber materials" include pure polyester fibers and mixtures of polyester fibers and natural and / or synthetic fibers, for example mixtures of polyester fibers and cotton; Polyester fibers and polyamide fibers; Polyester fibers, cotton and polyamide fibers; Polyester fibers and polyacrylic fibers understood. The textile fiber materials are in the form of a flake, sliver, yarn, knitwear, woven fabric or nonwoven, preferably a flake or sliver. The material can be raw white, bleached or colored.

Die in den erfindungsgemäßen Mischungen enthaltenen anoxidierten Polyethylene sind handelsübliche Produkte, die beispielsweise von Allied Corp., USA unter dem Namen A-C® Polyethylene angeboten werden.The anoxidized polyethylenes contained in the mixtures according to the invention are commercial products which are offered, for example, by Allied Corp., USA under the name A-C® polyethylenes.

Die Herstellung der in den erfindungsgemäßen Mischungen enthaltenen quartären Ammoniumphosphate erfolgt nach dem in JP 59/47478 beschriebenen Verfahren, indem man Amine, Imidazolin und/oder aminofunktionelle Polyester, erhalten gemäß DE-A-30 32 216 durch Kondensation alkoxylierter tertiärer Amine mit Dicarbonsäuren, mit Phosphorsäureestern der allgemeinen Formeln

Figure imgb0014

worin

R
eine gesättigte oder ungesättigte, gerad- oder verzweigtkettige, substituierte oder unsubstituierte Alkylgruppe mit 6 bis 22 C-Atomen und
A
eine Alkylenkette mit 2 bis 4 C-Atomen bedeutet,
bei 50 bis 80 °C mischt und anschließend diese Mischungen im Autoklaven bei 80 bis 100 °C mit Alkylenoxiden mit 2 bis 4 C-Atomen umsetzt, mit der Maßgabe, daß die Polyalkyletherkette der quaternierten Aminfunktionen aus 1 bis 10 Alkylenoxideinheiten besteht.The quaternary ammonium phosphates contained in the mixtures according to the invention are prepared by the process described in JP 59/47478 by using amines, imidazoline and / or amino-functional polyesters obtained according to DE-A-30 32 216 by condensation of alkoxylated tertiary amines with dicarboxylic acids Phosphoric acid esters of the general formulas
Figure imgb0014
wherein
R
a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl group having 6 to 22 carbon atoms and
A
is an alkylene chain with 2 to 4 carbon atoms,
mixes at 50 to 80 ° C and then reacting these mixtures in an autoclave at 80 to 100 ° C with alkylene oxides having 2 to 4 carbon atoms, with the proviso that the polyalkyl ether chain of the quaternized amine functions consists of 1 to 10 alkylene oxide units.

Die als Edukte zur Herstellung quartärer Ammoniumphosphate benötigten Amine, Imidazoline und aminofunktionellen Polyester sowie Phosphorsäurepartialester sind nach literaturbekannten Verfahren zugänglich:
   Amine, die beispielsweise durch Hydrierung von Fettsäurenitrilen (Ullmann's Encyclopädie der technischen Chemie, Band 11, Seite 448 - 449, Verlag Chemie, Weinheim 1976) oder direkt aus Fettalkoholen und Ammoniak gemäß GB-A-1 074 603 hergestellt werden können, werden gewünschtenfalls vorzugsweise mit Ethylenoxid und/oder Propylenoxid bei Temperaturen zwischen 130 und 180 °C umgesetzt mit der Maßgabe, daß die Polyalkyletherketten der gebildeten tertiären Amine aus 1 bis 5 Ethylenoxid- und/oder Propylenoxideinheiten bestehen. Kokosamin, Oleylamin, Talgamin, Kokosalkyl-di-2-hydroxyethyl-amin, Dimethyl-laurylamin und N-C₁₂₋₁₄-Alkylmorpholin sind Beispiele für Amine, die sich zur Herstellung quartärer Ammoniumphosphate eignen. Als Beispiel für acylierte Amine ist Kokoylamidopropyl-dimethyl-amin zu nennen.The amines, imidazolines and amino-functional polyesters and phosphoric acid partial esters required as starting materials for the production of quaternary ammonium phosphates can be obtained by processes known from the literature:
Amines which can be prepared, for example, by hydrogenation of fatty acid nitriles (Ullmann's Encyclopedia of Industrial Chemistry, Volume 11, pages 448-449, Verlag Chemie, Weinheim 1976) or directly from fatty alcohols and ammonia according to GB-A-1 074 603 are preferred if desired reacted with ethylene oxide and / or propylene oxide at temperatures between 130 and 180 ° C with the proviso that the polyalkyl ether chains of the tertiary amines formed consist of 1 to 5 ethylene oxide and / or propylene oxide units. Cocosamine, oleylamine, tallow amine, cocoalkyl-di-2-hydroxyethyl-amine, dimethyl-laurylamine and N-C₁₂₋₁₄-alkylmorpholine are examples of amines which are suitable for the preparation of quaternary ammonium phosphates. An example of acylated amines is cocoylamidopropyldimethylamine.

Die als Ausgangsstoffe zur Herstellung quartärer Imidazoliniumphosphate benötigten Imidazoline können durch Kondensation von Carbonsäuren, Carbonsäureestern oder Carbonsäurechloriden mit Diaminverbindungen hergestellt werden (G. Gawalek: "Tenside", S. 305 - 306, Akademie Verlag, Berlin 1975). Vorzugsweise erfolgt die Herstellung der Imidazoline gemäß der deutschen Offenlegungsschrift DE-A-36 18 944 durch Kondensation von Carbonsäuren der allgemeinen Formel R⁴-COOH, in der R⁴ eine gerad- oder verzweigtkettige, gesättigte oder ungesättigte, substituierte oder unsubstituierte Alkylgruppe mit 5 bis 21 C-Atomen bedeutet, mit Diaminen der allgemeinen Formel H₂N-CH₂CH₂-NH-CH₂CH₂R⁶, in der

R⁶
OH oder
Figure imgb0015
 bedeutet.
The imidazolines required as starting materials for the production of quaternary imidazolinium phosphates can be prepared by condensation of carboxylic acids, carboxylic acid esters or carboxylic acid chlorides with diamine compounds (G. Gawalek: "Tenside", pp. 305-306, Akademie Verlag, Berlin 1975). The imidazolines are preferably prepared by condensation in accordance with German Offenlegungsschrift DE-A-36 18 944 of carboxylic acids of the general formula R⁴-COOH, in which R⁴ is a straight or branched chain, saturated or unsaturated, substituted or unsubstituted alkyl group having 5 to 21 carbon atoms, with diamines of the general formula H₂N-CH₂CH₂-NH-CH₂CH₂R⁶, in which
R⁶
OH or
Figure imgb0015
 means.

Die Kondensation wird bei Temperaturen zwischen 150 und 240 °C, vorzugsweise zwischen 150 und 200 °C durchgeführt. Das Molverhältnis Carbonsäure : Diamin liegt vorzugsweise zwischen 1 : 1 und 1 : 2.The condensation is carried out at temperatures between 150 and 240 ° C., preferably between 150 and 200 ° C. The molar ratio of carboxylic acid: diamine is preferably between 1: 1 and 1: 2.

Zur Herstellung der Imidazoline können die Carbonsäuren sowohl einzeln als auch im Gemisch eingesetzt werden. Von besonderer Bedeutung ist der Einsatz von Fettsäuregemischen, wie sie bei der Spaltung natürlich vorkommender Fette und/oder Öle anfallen. Einzelne Fraktionen solcher Fettsäuregemische eignen sich ebenfalls zur Herstellung der Imidazoline. Als Carbonsäuren werden vorzugsweise solche der allgemeinen Formel R⁴ - COOH eingesetzt, in der der Rest R⁴ für eine gerad- oder verzweigtkettige, substituierte oder unsubstituierte, gesättigte Alkylgruppe mit 7 bis 17 C-Atomen oder für eine gerad- oder verzweigtkettige, substituierte oder unsubstituierte, ungesättigte Alkylgruppe mit 17 bis 21 C-Atomen steht, beispielsweise Caprylsäure, Caprinsäure, Laurinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Linolsäure, Linolinsäure, Gadoleinsäure und/oder Rizinolsäure.The carboxylic acids can be used either individually or in a mixture to prepare the imidazolines. Of particular importance is the use of fatty acid mixtures, such as those that occur when natural fats and / or oils are split. Individual fractions of such fatty acid mixtures are also suitable for the preparation of the imidazolines. The carboxylic acids used are preferably those of the general formula R⁴-COOH, in which the radical R⁴ is a straight-chain or branched-chain, substituted or unsubstituted, saturated alkyl group having 7 to 17 carbon atoms or for a straight-chain or branched-chain, substituted or unsubstituted, unsaturated alkyl group having 17 to 21 carbon atoms, for example caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolinic acid, gadoleic acid and / or ricinoleic acid.

1-Hydroxyethyl-2-undecylimidazolin, 1-Hydroxyethyl-2-heptadecenylimidazolin und 1-Hydroxyethyl-2-heptylimidazolin sind geeignete Imidazoline.1-Hydroxyethyl-2-undecylimidazoline, 1-hydroxyethyl-2-heptadecenylimidazoline and 1-hydroxyethyl-2-heptylimidazoline are suitable imidazolines.

Aminofunktionelle Polyester werden gemäß DE-OS 30 32 216 durch Kondensation alkoxylierter tertiärer Amine der allgemeinen Formel

Figure imgb0016

in der

R⁸
einen gesättigten oder ungesättigten, gerad- oder verzweigtkettigen, substituierten oder unsubstituierten Alkylrest mit 1 bis 20 C-Atomen und
A′
eine Alkylenkette mit 2 bis 3 C-Atomen bedeutet,
a und b
Zahlen zwischen 1 und 20 sind mit der Maßgabe, daß die Summe von a und b 2 bis 30 ist,
mit Dicarbonsäuren der allgemeinen Formel HOOC-R⁷-COOH, in welcher der Rest
R⁷
einen aliphatischen, alicyclischen oder aromatischen, substituierten oder unsubstituierten Rest mit 1 bis 10 C-Atomen bedeutet,
bei Temperaturen zwischen 180 und 260 °C, gegebenenfalls in Gegenwart von mit Wasser nicht mischbaren organischen Lösungsmitteln, beispielsweise Xylol oder Toluol, zur azeotropen Entfernung von Reaktionsnebenprodukten unter Ausschluß von Luftsauerstoff erhalten. Die aminofunktionellen Polyester besitzen Polymerisationsgrade zwischen 2 und 50, wenn pro Mol alkoxyliertem, tertiärem Amin 0,8 bis 1,1 Mol Dicarbonsäure eingesetzt werden. Als aliphatische, alicyclische und/oder aromatische, gegebenfalls substituierte Dicarbonsäuren kommen beispielsweise Malonsäure, Maleinsäure, Fumarsäure, Bernsteinsäure, Hydroxymalonsäure, Äpfelsäure, Chlorethandicarbonsäure, Oxalsäure und/oder Terephthalsäure in Frage. Im Falle der Oxalsäure verschwindet R⁷ in der allgemeinen Formel. Besonders geeignete aliphatische Dicarbonsäuren sind Säuren mit 6 bis 10 C-Atomen, wie Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure und/oder Sebazinsäure.Amino-functional polyesters are according to DE-OS 30 32 216 by condensation of alkoxylated tertiary amines of the general formula
Figure imgb0016
in the
R⁸
a saturated or unsaturated, straight or branched chain, substituted or unsubstituted alkyl radical having 1 to 20 C atoms and
A ′
is an alkylene chain with 2 to 3 carbon atoms,
a and b
Numbers between 1 and 20 are provided that the sum of a and b is 2 to 30,
with dicarboxylic acids of the general formula HOOC-R⁷-COOH, in which the rest
R⁷
represents an aliphatic, alicyclic or aromatic, substituted or unsubstituted radical having 1 to 10 C atoms,
at temperatures between 180 and 260 ° C, optionally in the presence of water-immiscible organic solvents, for example xylene or toluene, for azeotropic removal of reaction by-products with the exclusion of atmospheric oxygen. The amino-functional polyesters have degrees of polymerization between 2 and 50 if 0.8 to 1.1 mol of dicarboxylic acid are used per mole of alkoxylated, tertiary amine. Examples of suitable aliphatic, alicyclic and / or aromatic, optionally substituted dicarboxylic acids are malonic acid, maleic acid, fumaric acid, succinic acid, hydroxymalonic acid, malic acid, chloroethane dicarboxylic acid, oxalic acid and / or terephthalic acid. In the case of oxalic acid, R⁷ disappears in the general formula. Particularly suitable aliphatic Dicarboxylic acids are acids with 6 to 10 carbon atoms, such as adipic acid, pimelic acid, suberic acid, azelaic acid and / or sebacic acid.

Anstelle der freien Säuren können mit gleichem Ergebnis auch Derivate dieser Säuren, beispielsweise Anhydride, Halogenide, Dimethylester in äquimolaren Mengen eingesetzt werden. Vorzugsweise werden jedoch die freien Dicarbonsäuren verwendet. Die zur Herstellung aminofunktioneller Polyester benötigten alkoxylierten tertiären Amine leiten sich von primären Alkyl-und/oder Alkenylaminen ab, beispielsweise von Methylamin, Ethylamin, Butylamin, Octylamin, Decylamin, Dodecylamin, Cetylamin, Oleylamin, Linoleylamin, Kokosamin und/oder Talgamin. Alkylamine, die aus Kokosöl oder Talg hergestellt werden, werden bevorzugt. Alkyl- und/oder Alkenylamine werden in an sich bekannter Weise bei Temperaturen zwischen 130 und 180 °C mit Ethylenoxid und/oder Propylenoxid alkoxyliert mit der Maßgabe, daß der Alkoxylierungsgrad (Summe von a und b) zwischen 2 und 30 liegt.Instead of the free acids, derivatives of these acids, for example anhydrides, halides, dimethyl esters, can be used in equimolar amounts with the same result. However, the free dicarboxylic acids are preferably used. The alkoxylated tertiary amines required for the production of amino-functional polyesters are derived from primary alkyl and / or alkenylamines, for example from methylamine, ethylamine, butylamine, octylamine, decylamine, dodecylamine, cetylamine, oleylamine, linoleylamine, coconut amine and / or tallow amine. Alkyl amines made from coconut oil or tallow are preferred. Alkyl and / or alkenyl amines are alkoxylated in a manner known per se at from 130 to 180 ° C. with ethylene oxide and / or propylene oxide, with the proviso that the degree of alkoxylation (sum of a and b) is between 2 and 30.

Polyester aus Talgamin . 5 Ethylenoxideinheiten (EO) und Adipinsäure, Polyester aus Kokosamin . 2 EO und Adipinsäure, Polyester aus Kokosamin . 5 EO und Bernsteinsäure und/oder Polyester aus Talgamin . 10 EO und Sebazinsäure sind Beispiele für geeignete aminofunktionelle Polyester.Tallow polyester. 5 ethylene oxide units (EO) and adipic acid, polyester from coconut amine. 2 EO and adipic acid, polyester from coconut amine. 5 EO and succinic acid and / or polyester from tallow amine. 10 EO and sebacic acid are examples of suitable amino-functional polyesters.

Die Herstellung der Phosphorsäurepartialester geht aus von gerad- oder verzweigtkettigen, gesättigten oder ungesättigten, substituierten oder unsubstituierten, gegebenenfalls alkoxylierten Alkoholen mit 6 bis 22 C-Atomen. Vorzugsweise werden gerad- oder verzweigtkettige, substituierte oder unsubstituierte, gesättigte, gegebenenfalls alkoxylierte Alkohole mit 8 bis 18 C-Atomen und/oder gerad- oder verzweigtkettige, substituierte oder unsubstituierte, ungesättigte, gegebenenfalls alkoxylierte Alkohole mit 18 bis 22 C-Atomen eingesetzt, beispielsweise 2-Ethylhexanol, n-Octanol, Isononylalkohol, Decylalkohol, Dodecylalkohol, Isotridecylalkohol, Tetradecylalkohol, Hexadecylalkohol, Octadecylalkohol, Octadecenylalkohol, Eicosenylalkohol, Docosenylalkohol. Diese Alkohole werden gegebenenfalls mit 1 bis 10 Mol Ethylenoxid, Propylenoxid und/oder Butylenoxid umgesetzt. Die Phosphatierung der gegebenenfalls alkoxylierten Alkohole erfolgt in an sich bekannter Weise, indem bei 50 bis 80 °C 3 Mol Alkohol mit 1 Mol Phosphorpentoxid umgesetzt werden. Zur Hydrolyse von Polyphosphorsäureverbindungen wird mehrere Stunden bei 90 bis 100 °C mit Wasser behandelt.The phosphoric acid partial esters are prepared from straight-chain or branched-chain, saturated or unsaturated, substituted or unsubstituted, optionally alkoxylated alcohols having 6 to 22 carbon atoms. Straight or branched chain, substituted or unsubstituted, saturated, optionally alkoxylated alcohols having 8 to 18 C atoms and / or straight or branched chain, substituted or unsubstituted, unsaturated, optionally alkoxylated alcohols having 18 to 22 C atoms are used, for example 2-ethylhexanol, n-octanol, isononyl alcohol, decyl alcohol, dodecyl alcohol, isotridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol, eicosenyl alcohol, docosenyl alcohol. These alcohols are optionally reacted with 1 to 10 moles of ethylene oxide, propylene oxide and / or butylene oxide. The optionally alkoxylated alcohols are phosphated in a manner known per se by reacting 3 mol of alcohol with 1 mol of phosphorus pentoxide at 50 to 80 ° C. For the hydrolysis of polyphosphoric acid compounds, water is treated at 90 to 100 ° C. for several hours.

Werden die erfindungsgemäßen Mischungen als Textilhilfsmittel zum Antistatisch-, Glatt- und/oder Weichmachen von polyesterhaltigen Fasermaterialien verwendet, liegen diese Mischungen vorzugsweise in Form von Dispersionen oder Lösungen, besonders bevorzugt in Form wäßriger Emulsionen, vor. Diese Emulsionen enthalten 2 bis 20 Gew.-% an nichtionischen, kationischen und/oder amphoteren Dispergatoren. Geeignete nichtionische Dispergatoren sind alkoxylierte, vorzugsweise ethoxylierte und/oder propoxylierte Fette, Öle, Fettalkohole mit 8 bis 24 C-Atomen im Fettrest, Fettamine mit 8 bis 24 C-Atomen im Fettrest und/oder C₈₋₁₈-Alkylphenole, beispielsweise ethoxyliertes Rizinusöl, Oleylalkohol . 5 EO, Oleylacetylalkohol . 5 EO, Talgalkohol . 14 EO, Stearylamin . 2 EO, Talgamin . 2 EO, Stearylamin . 10 EO und/oder Nonylphenol . 10 EO. Als kationische Dispergatoren kommen alkoxylierte, vorzugsweise ethoxylierte und/oder propoxylierte Alkylamine mit 10 bis 20 C-Atomen in Form ihrer Ammioniumsalze in Frage, beispielsweise Stearylamin . 10 EO. Als amphotere Dispergatoren eignen sich beispielsweise C₈₋₂₂-Alkyldimethylbetaine, N-C₈₋₂₂-Alkylamidobetaine und/oder von Aminosäuren abzuleitende Amphotenside.If the mixtures according to the invention are used as textile auxiliaries for the antistatic, smoothing and / or softening of polyester-containing fiber materials, these mixtures are preferably in the form of dispersions or solutions, particularly preferably in the form of aqueous emulsions. These emulsions contain 2 to 20% by weight of nonionic, cationic and / or amphoteric dispersants. Suitable nonionic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated fats, oils, fatty alcohols with 8 to 24 carbon atoms in the fat residue, fatty amines with 8 to 24 carbon atoms in the fat residue and / or C₈₋₁₈ alkylphenols, for example ethoxylated castor oil, Oleyl alcohol. 5 EO, omelet acetyl alcohol. 5 EO, tallow alcohol. 14 EO, stearylamine. 2 EO, tallow amine. 2 EO, stearylamine. 10 EO and / or nonylphenol. 10 EO. Suitable cationic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated, alkylamines having 10 to 20 carbon atoms in the form of their ammonium salts, for example stearylamine. 10 EO. Suitable amphoteric dispersants are, for example, C₈₋₂₂-alkyldimethylbetaines, N-C₈₋₂₂-alkylamidobetaines and / or amphoteric surfactants derived from amino acids.

Als fakultative Bestandteile können die Lösungen oder Dispersionen weitere Glättemittel, beispielsweise Paraffine mit Erweichungspunkten zwischen 35 und 80 °C, Fettsäureester mit 12 bis 24 C-Atomen sowohl im Fettsäurerest, als auch im gerad- und/oder verzweigtkettigen, gesättigten und/oder ungesättigten Alkoholrest wie Isotridecylstearat, Stearylstearat und/oder Behenylbehenat und/oder Silicone wie Dimethylpolysiloxan, Weichmacher wie Fettsäureamidopolyamine und/oder quartäre Ammoniumsalze, beispielsweise Dimethyldistearylammoniumchlorid, Antioxidantien, beispielsweise Sauerstoffsäuren des Phosphors und/oder Alkalidisulfite und pH-Wert-Regulantien, beispielsweise C₁₋₄-Carbonsäuren und/oder C₁₋₄-Hydroxycarbonsäuren wie Essigsäure und/oder Glykolsäure enthalten. Der Anteil der fakultativen Bestandteile liegt in wäßrigen Dispersionen und Emulsionen zwischen 2 und 20 Gew.-%. Die Herstellung der Dispersionen und Lösungen, vorzugsweise der wäßrigen Emulsionen, die die erfindungsgemäßen Mischungen enthalten, erfolgt in an sich bekannter Weise, indem anoxidierte Polyethylene, Dispergatoren und fakultative Bestandteile mit Wasser gemischt und in einer druckfesten Apparatur bei 130 bis 170 °C gerührt werden. Nach dem Abkühlen werden feinteilige, lagerstabile Emulsionen erhalten, in die quartäre Ammoniumphosphate und gegebenenfalls weitere Dispergatoren eingerührt werden.As optional components, the solutions or dispersions can contain further smoothing agents, for example paraffins with softening points between 35 and 80 ° C, fatty acid esters with 12 to 24 C atoms both in the fatty acid residue and in the straight and / or branched chain, saturated and / or unsaturated alcohol residue such as isotridecyl stearate, stearyl stearate and / or behenyl behenate and / or silicones such as dimethylpolysiloxane, plasticizers such as fatty acid amidopolyamines and / or quaternary ammonium salts, for example dimethyldistearylammonium chloride, antioxidants, for example oxygen acids of phosphorus and / or alkali metal sulfides and carboxylic acids, for example C-regulating agents and / or contain C₁₋₄-hydroxycarboxylic acids such as acetic acid and / or glycolic acid. The proportion of optional components in aqueous dispersions and emulsions is between 2 and 20% by weight. The dispersions and solutions, preferably the aqueous emulsions, which contain the mixtures according to the invention, are prepared in a manner known per se by mixing anoxidized polyethylenes, dispersants and optional constituents with water and stirring them in a pressure-resistant apparatus at from 130 to 170.degree. After cooling, finely divided, storage-stable emulsions are obtained, into which quaternary ammonium phosphates and optionally further dispersants are stirred.

Es entstehen lagerstabile, flüssige, milchig-weiße Emulsionen mit Feststoffgehalten von 5 bis 50 Gew.-%. Durch Zusatz von Säuren, vorzugsweise Essigsäure, Glykolsäure oder Milchsäure, wird ein pH-Wert von 3,0 - 6,0 eingestellt.Storage-stable, liquid, milky white emulsions with solids contents of 5 to 50% by weight are formed. By adding acids, preferably acetic acid, glycolic acid or lactic acid, a pH of 3.0-6.0 is set.

Die erfindungsgemäßen Mischungen sind hitzebeständig und bewirken keine Verfärbungen der Fasermaterialien. Die mit den erfindungsgemäßen Mischungen ausgerüsteten polyesterhaltigen Fasermaterialien zeigen im Vergleich zu unbehandelten, nur mit anoxidierten Polyethylenen oder nur mit quartären Ammoniumphosphaten behandelten polyesterhaltigen Fasermaterialien deutlich reduzierte antielektrostatische Aufladungen, niedrige statische und dynamische Faser/Faser-und Faser/Metall-Reibungen, eine hervorragende Glätte sowie einen guten Weichgriff.The mixtures according to the invention are heat-resistant and do not cause discoloration of the fiber materials. The polyester-containing fiber materials finished with the mixtures according to the invention show, in comparison to untreated, only with anoxidized polyethylene or only with quaternary Ammonium phosphates treated polyester-containing fiber materials significantly reduced anti-electrostatic charges, low static and dynamic fiber / fiber and fiber / metal friction, excellent smoothness and good soft feel.

Beispiele:Examples: 1. Herstellung stabiler, wäßriger Emulsionen, die anoxidierte Polyethylene (Komponente A) enthalten.1. Preparation of stable, aqueous emulsions containing anoxidized polyethylenes (component A).

  • 1.1
    5,0 g Oleylcetylalkohol . 5 EO
    8,1 g anoxidiertes Polyethylen (mittleres Molekulargewicht = 4000, Säurezahl (SZ) = 28, Verseifungszahl (VZ) = 45, Dichte = 0,99 g/cm³)
    2,6 g Paraffin (Schmelzpunkt = 52 bis 54 °C)
    1,7 g Stearinsäure-isotridecylester
    2,4 g Stearylamin . 2 EO
    0,2 g Natriumbisulfit
    11,9 g Essigsäure, 60 gewichts-%ig
    63,1 g Wasser
    Die aufgeführten Einsatzstoffe wurden bei 155 bis 165 °C unter Rühren in einer Druckapparatur gemischt. Es wurden 95 g einer feinteiligen Emulsionen mit einem pH-Wert von 4,1 erhalten.    1.1
    5.0 g oleyl acetyl alcohol. 5 EO
    8.1 g of anoxidized polyethylene (average molecular weight = 4000, acid number (SZ) = 28, saponification number (VZ) = 45, density = 0.99 g / cm³)
    2.6 g paraffin (melting point = 52 to 54 ° C)
    1.7 g stearic acid isotridecyl ester
    2.4 g stearylamine. 2 EO
    0.2 g sodium bisulfite
    11.9 g acetic acid, 60% by weight
    63.1 g water
    The starting materials listed were mixed at 155 to 165 ° C. with stirring in a printing apparatus. 95 g of a finely divided emulsions with a pH of 4.1 were obtained.
  • 1.2
    5,0 g Oleylcetylalkohol . 5 EO
    10,9 g anoxidiertes Polyethylen (mittleres Molekulargewicht = 4500, SZ = 30, VZ = 45, Dichte = 1,00 g/cm³)
    3,1 g Stearylamin . 10 EO
    0,3 g Natriumbisulfit
    11,9 g Essigsäure, 60 gewichts-%ig
    58,8 g Wasser
    Aus den Einsatzstoffen wurden analog 1.1 90 g einer feinteiligen Emulsion hergestellt, deren pH-Wert 3,9 betrug.    1.2
    5.0 g oleyl acetyl alcohol. 5 EO
    10.9 g of oxidised polyethylene (average molecular weight = 4500, SZ = 30, VZ = 45, density = 1.00 g / cm³)
    3.1 g stearylamine. 10 EO
    0.3 g sodium bisulfite
    11.9 g acetic acid, 60% by weight
    58.8 g water
    Analogously to 1.1, 90 g of a finely divided emulsion, the pH of which was 3.9, were prepared from the starting materials.
  • 1.3
    5,0 g Oleylalkohol . 5 EO
    6,5 g anoxidiertes Polyethylen analog 1.1
    1,7 g Fettsäureamidopolyamin aus 2 Mol Behensäure und 1 Mol Tetraethylenpentamin
    0,7 g Talgalkohol . 14 EO
    0,8 g Dimethylpolysiloxan (Viskosität = 12 500 cSt)
    12,0 g Essigsäure, 60 gewichts-%ig
    1,5 g Stearylamin . 5 EO
    0,2 g Natriumbisulfit
    51,6 g Wasser
    Aus den Einsatzstoffen wurden analog 1.1 80 g einer feinteiligen Emulsion hergestellt, deren pH-Wert 4,1 betrug.    1.3
    5.0 g oleyl alcohol. 5 EO
    6.5 g of anoxidized polyethylene analog 1.1
    1.7 g of fatty acid amidopolyamine from 2 moles of behenic acid and 1 mole of tetraethylene pentamine
    0.7 g of tallow alcohol. 14 EO
    0.8 g dimethylpolysiloxane (viscosity = 12 500 cSt)
    12.0 g acetic acid, 60% by weight
    1.5 g stearylamine. 5 EO
    0.2 g sodium bisulfite
    51.6 g water
    Analogously to 1.1, 80 g of a finely divided emulsion, the pH of which was 4.1, were prepared from the starting materials.
2. Herstellung quartärer Ammoniumphosphate (Komponente B)2. Preparation of Quaternary Ammonium Phosphates (Component B)

  • 2.1
    127,4 g (0,47 Mol) Kokosalkyl-di-2-hydroxyethyl-amin wurden zusammen mit 80,0 g Wasser und 88,4 g (0,47 Säureäquivalente) eines Gemisches aus Mono- und Di-2-Ethylhexylphosphorsäureester im Gewichtsverhältnis 4 : 3 in einem Autoklaven vorgelegt und innerhalb von 4 h mit 104,0 g (2,35 Mol) Ethylenoxid bei 80 °C/3 bar zur Reaktion gebracht. Es wurden 392 g einer niedrigviskosen, ohne Gelbildung mit Wasser verdünnbaren Flüssigkeit erhalten.    2.1
    127.4 g (0.47 mol) of cocoalkyl-di-2-hydroxyethylamine were combined with 80.0 g of water and 88.4 g (0.47 acid equivalents) of a mixture of mono- and di-2-ethylhexylphosphoric acid esters in Weight ratio 4: 3 placed in an autoclave and reacted within 4 h with 104.0 g (2.35 mol) of ethylene oxide at 80 ° C / 3 bar. 392 g of a low-viscosity liquid which could be diluted with water without gel formation were obtained.
  • 2.2
    126 g (0,47 Mol) 1-Hydroxyethyl-2-undecylimidazolin wurden zusammen mit 80,0 g Wasser und 88,4 g (0,47 Säureäquivalente) eines Gemisches aus Mono- und Di-2-Ethylhexylphosphorsäureester im Gewichtsverhältnis 4 : 3 in einem Autoklaven vorgelegt und innerhalb von 4 h mit 103,4 g (2,35 Mol) Ethylenoxid bei 80 °C/3 bar zur Reaktion gebracht. Es wurden 395 g einer gelben, niedrigviskosen, ohne Gelbildung mit Wasser verdünnbaren Flüssigkeit erhalten.    2.2
    126 g (0.47 mol) of 1-hydroxyethyl-2-undecylimidazoline were mixed with 80.0 g of water and 88.4 g (0.47 acid equivalents) of a mixture of mono- and di-2-ethylhexylphosphoric acid esters in a weight ratio of 4: 3 placed in an autoclave and reacted within 4 h with 103.4 g (2.35 mol) of ethylene oxide at 80 ° C / 3 bar. 395 g of a yellow, low-viscosity liquid which could be diluted with water without gel formation were obtained.
  • 2.3
    125,1 g (0,44 Mol) Kokosalkyl-di-2-hydroxyethyl-amin, 80,0 g Wasser und 97,3 g (0,44 Säureäquivalente) eines Gemisches aus Mono- und Didodecylphosphat (molares Verhältnis 1,5 : 1) wurden analog 2.1 mit 97,6 g (2,22 Mol) Ethylenoxid umgesetzt. Es wurden 395 g einer mittelviskosen, hellbraunen Flüssigkeit erhalten, die leicht mit Wasser zu einer wenig getrübten Lösung verdünnbar war.    2.3
    125.1 g (0.44 mol) cocoalkyl-di-2-hydroxyethylamine, 80.0 g water and 97.3 g (0.44 acid equivalents) of a mixture of mono- and didodecyl phosphate (molar ratio 1.5: 1) were reacted analogously to 2.1 with 97.6 g (2.22 mol) of ethylene oxide. 395 g of a medium-viscosity, light brown liquid were obtained, which was easily dilutable with water to give a slightly cloudy solution.
3. Herstellung wäßriger Emulsionen, die die erfindungsgemäßen Mischungen (Komponente A und B) enthalten3. Preparation of aqueous emulsions containing the mixtures according to the invention (components A and B)

  • 3.1
    11,9 g quartäres Ammoniumphosphat 2.1 wurden mit 25.6 g Wasser verdünnt und anschließend mit 5,4 g eines mit 5 Mol Ethylenoxid alkoxyliertem Oleyl/Cetylalkoholgemisches versetzt. Durch Zugabe von 9,5 g 40 gewichts-%iger Essigsäure wurde ein pH-Wert von 5,2 eingestellt und mit 47,6 g der wäßrigen Emulsion 1.1 gemischt. Es entstand eine lagerstabile flüssige, milchig-weiße Emulsion mit einem Feststoffgehalt von 25 Gew.-% und einem pH-Wert von 4,5.    3.1
    11.9 g of quaternary ammonium phosphate 2.1 were diluted with 25.6 g of water and then 5.4 g of an oleyl / cetyl alcohol mixture alkoxylated with 5 mol of ethylene oxide were added. A pH of 5.2 was set by adding 9.5 g of 40% by weight acetic acid and mixed with 47.6 g of the aqueous emulsion 1.1. A storage-stable liquid, milky white emulsion with a solids content of 25% by weight and a pH of 4.5 was obtained.
  • 3.2
    11,9 g quartäres Ammoniumphosphat 2.2 wurden mit 25,6 g Wasser verdünnt und mit 5,4 g eines mit 5 Mol Ethylenoxid alkoxylierten Oleyl/Cetylalkoholgemisches versetzt. Durch Zugabe von 9,5 g 40 gewichts-%iger Essigsäure wurde ein pH-Wert von 5,2 eingestellt und mit 47,6 g der wäßrigen Emulsion 1.2 gemischt. Es entstand eine lagerstabile flüssige, milchig-weiße Emulsion mit einem Feststoffgehalt von 25 Gew.-% und einem pH-Wert von 4,5.    3.2
    11.9 g of quaternary ammonium phosphate 2.2 were diluted with 25.6 g of water and 5.4 g of an oleyl / cetyl alcohol mixture alkoxylated with 5 mol of ethylene oxide were added. A pH of 5.2 was set by adding 9.5 g of 40% by weight acetic acid and mixed with 47.6 g of the aqueous emulsion 1.2. A storage-stable liquid, milky white emulsion with a solids content of 25% by weight and a pH of 4.5 was obtained.
  • 3.3
    11,9 g quartäres Ammoniumphosphat 2.3 wurden mit 25,6 g Wasser verdünnt und mit 5,4 g eines mit 5 Mol Ethylenoxid alkoxylierten Oleyl/Cetylalkoholgemisches versetzt. Durch Zugabe von 9,5 g 40 gewichts-%iger Essigsäure wurde ein pH-Wert von 5,2 eingestellt und mit 47,6 g der wäßrigen Emulsion 1.1 gemischt. Es entstand eine lagerstabile flüssige, milchig-weiße Emulsion mit einem Feststoffgehalt von 25 Gew.-% und einem pH-Wert von 4,5.    3.3
    11.9 g of quaternary ammonium phosphate 2.3 were diluted with 25.6 g of water and 5.4 g of an oleyl / cetyl alcohol mixture alkoxylated with 5 mol of ethylene oxide were added. A pH of 5.2 was set by adding 9.5 g of 40% by weight acetic acid and mixed with 47.6 g of the aqueous emulsion 1.1. A storage-stable liquid, milky white emulsion with a solids content of 25% by weight and a pH of 4.5 was obtained.
4. Vergleichsprodukt Fettalkylamidoamin auf Basis von gehärtetem Rindertalg und Aminoethylethanolamin (Belfasin® 44, Henkel KGaA)4. Comparative product fatty alkylamidoamine based on hardened beef tallow and aminoethylethanolamine (Belfasin® 44, Henkel KGaA) 5. Applikation im Ziehverfahren5. Application in the drawing process

  • 5.1 Polyesterstapelfaser
    Gefärbtes und reduktiv nachbehandeltes Polyesterstapelfaser-Material (1.7 dtex/40 mm) wurde bei einem Flottenverhältnis von 1 : 10 20 Minuten bei einer Temperatur von 60 bis 70 °C mit einer essigsauren wäßrigen Lösung behandelt, die, berechnet auf das Warengewicht, jeweils 2 Gew.-% der unter 1., 2., 3. oder 4. genannten Mischungen enthielt. Im Anschluß an die Applikation wurde das Material geschleudert und bei 80 °C 2 h getrocknet.
    Die Messung des elektrostatischen Effektes wurde auf einer Laborkarde nach einer 24 h Klimatisierung (22 °C, 62 bis 65 % relative Luftfeuchte) des Fasermaterials mit einem Eltex-Gerät nach der Induktionsstrommethode (Meßabstand 100 mm) durchgeführt.
    Figure imgb0017
    5.1 polyester staple fiber
    Dyed and reductively aftertreated polyester staple fiber material (1.7 dtex / 40 mm) was treated at a liquor ratio of 1:10 for 20 minutes at a temperature of 60 to 70 ° C. with an acetic acidic aqueous solution, which, calculated on the weight of the goods, was 2 wt .-% of the mixtures mentioned under 1., 2., 3. or 4. contained. Following the application, the material was spun and dried at 80 ° C for 2 hours.
    The measurement of the electrostatic effect was carried out on a laboratory card after a 24 h air conditioning (22 ° C., 62 to 65% relative air humidity) of the fiber material with an Eltex device using the induction current method (measuring distance 100 mm).
    Figure imgb0017
  • 5.2 Polyester-Kammzug
    Ein gefärbter und reduktiv nachbehandelter Polyester-Kammzug (20 g/m; 6.7 dtex/80 mm) wurde bei einem Flottenverhältnis von 1 : 15 20 minuten bei einer Temperatur von 60 bis 70 °C mit einer essigsauren wäßrigen Lösung behandelt, die, berechnet auf das Warengewicht, jeweils 2 Gew.-% der unter 1., 2., 3. oder 4. beschriebenen Mischungen enthielt. Nach Beendigung der Avivierung wurde der Kammzug geschleudert und 2 h bei 80 °C getrocknet.    5.2 Polyester sliver
    A colored and reductively aftertreated polyester sliver (20 g / m; 6.7 dtex / 80 mm) was treated with a liquor ratio of 1:15 for 20 minutes at a temperature of 60 to 70 ° C. with an acetic acidic aqueous solution, calculated on the product weight contained 2% by weight of the mixtures described under 1, 2, 3 or 4. After the finishing, the comb was spun and dried at 80 ° C for 2 h.

Die Messung der elektrostatischen Aufladung wurde auf einer Doppelnadelstabstrecke während der Verstreckung (Liefergeschwindigkeit V = 150 m/min) nach der Induktionsstrommeßmethode zwischen Streckwerkausgang und Coilereinlauf im Abstand von 100 mm durchgeführt.

Figure imgb0018
The measurement of the electrostatic charge was carried out on a double-needle bar section during drawing (delivery speed V = 150 m / min) using the induction current measurement method between the drafting device outlet and the coil inlet at a distance of 100 mm.
Figure imgb0018

Die auf der Nadelstabstrecke hergestellten Streckenbänder wurden nach der Cohesionmetermeßmethodik beurteilt. Die Meßwerte cN . tex⁻¹ repräsentieren die bei einem Verzug von 1,25fach auftretenden Kräfte, die benötigt werden, um eine Längenänderung des Vorlagematerials herbeizuführen. Die ermittelten Meßwerte wurden über ein Rothschild F-Meter unter Zuhilfenahme eines angeschlossenen Kleincomputers statistisch aufbereitet.

Figure imgb0019
The conveyor belts produced on the needle bar section were assessed according to the cohesion meter measuring method. The measured values cN. tex⁻¹ represent the 1.25-fold forces that are required to change the length of the original material. The measured values determined were processed statistically using a Rothschild F-Meter with the aid of a connected small computer.
Figure imgb0019

Claims (9)

  1. Mixtures containing
    A) partly oxidized polyethylenes having average molecular weights of 3,000 to 8,000, acid values of 25 to 60, saponification values of 40 to 80 and densities of 0.94 to 1.09 g/cm³ and
    B) at least one quaternary ammonium phosphate from at least one of the following groups:
    1.)
    Figure imgb0029
     in which
    R¹   is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₆₋₂₂ alkyl group or
    Figure imgb0030
    R²
    Figure imgb0031
       methyl or ethyl,
    R³
    Figure imgb0032
       methyl or ethyl or R² and R³ together represent -CH₂CH₂-O-CH₂CH₂-,
    R⁴   is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₅₋₂₁ alkyl group,
    R⁵   is H or a C₁₋₄ alkyl group,
    R   is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₆₋₂₂ alkyl group and
    A   is a C₂₋₄ alkylene chain,
    p   is 2 or 3 and
    n   is 1 and m is 2 or n is 2 and m is 1,
    2.)
    Figure imgb0033
     in which
    R⁴   is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₅₋₂₁ alkyl group,
    R⁶   is OH or
    Figure imgb0034
    R   is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₆₋₂₂ alkyl group and
    A   is a C₂₋₄ alkylene chain and
    n   is 1 and m is 2 or n is 2 and m is 1,
    3.) quaternary ammonium phosphates based on aminofunctional polyesters having degrees of polymerization of 2 to 50 prepared by condensation of dicarboxylic acids corresponding to the following general formula:



            HOOC-R⁷-COOH



    in which
    R⁷ is an aliphatic, alicyclic or aromatic, substituted or unsubstituted C₁₋₁₀ radical,
    with alkoxylated tertiary amines corresponding to the following general formula:
    Figure imgb0035
     in which
    R⁸ is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₁₋₂₀ alkyl group and
    A' is an ethylene and/or isopropylene group and
    a and b are numbers of 1 to 20, with the proviso that the sum of a+b is 2 to 30,
    reaction with mono- and/or dialkylphosphoric acid esters corresponding to the following general formulae:
    Figure imgb0036
     in which
    R is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₆₋₂₂ alkyl group and
    A is a C₂₋₄ alkylene chain,
    in the presence of water at 50 to 80°C
    and subsequent reaction with C₂₋₄ alkylene oxides under pressures of 1 to 5 bar and at temperatures of 80 to 100°C, with the proviso that the polyalkyl ether chain of the quaternized amine functions is made up of 1 to 10 alkylene oxide units.
  2. Mixtures as claimed in claim 1, characterized in that the ratio by weight of component A to component B is between 10:1 and 1:5 and preferably between 10:3 and 1:2.
  3. Mixtures as claimed in one or both of claims 1 and 2, characterized in that the partly oxidized polyethylenes have average molecular weights of 3,500 to 5,000 and densities of 0.98 to 1.00 g/cm³.
  4. Mixtures as claimed in one or more of claims 1 to 3, characterized in that, in the general formulae for component B.1.) to 3.),
    R¹ is a saturated, linear or branched, substituted or unsubstituted C₈₋₁₈ alkyl group, an unsaturated, linear or branched, substituted or unsubstituted c₁₈₋₂₂ alkyl group or
    Figure imgb0037
     R⁴ is a saturated, linear or branched, substituted or unsubstituted C₇₋₁₇ alkyl group or an unsaturated, linear or branched, substituted or unsubstituted c₁₇₋₂₁ alkyl group,
    A represents ethylene and/or isopropylene groups,
    R⁶ is OH,
    R⁸ is a saturated or unsaturated, linear or branched, substituted or unsubstituted C₆₋₂₀ alkyl group and
    R is a saturated, linear or branched, substituted or unsubstituted C₈₋₁₈ alkyl group or an unsaturated, linear or branched, substituted or unsubstituted c₁₈₋₂₂ alkyl group.
  5. Mixtures as claimed in one or more of claims 1 to 4, characterized in that they are present in the form of solutions or dispersions and preferably in the form of aqueous emulsions.
  6. Mixtures as claimed in claim 5, characterized in that the content of components A and B in aqueous emulsions is between 5 and 50% by weight and preferably between 10 and 30% by weight.
  7. Mixtures as claimed in one or both of claims 5 and 6, characterized in that the emulsions contain 2 to 20% by weight nonionic, cationic and/or amphoteric dispersants.
  8. Mixtures as claimed in one or more of claims 5 to 7, characterized in that the mixtures contain alkoxylated fats, oils, fatty alcohols containing 8 to 24 carbon atoms in the fatty part, fatty amines containing 8 to 24 carbon atoms in the fatty part and/or C₈₋₁₈ alkyl phenols.
  9. The use of the mixtures containing component A and component B claimed in one or more of claims 1 to 8 as textile auxiliaries for the antistatic treatment, smoothing and/or softening of polyester-containing fibre materials.
EP89104695A 1988-03-24 1989-03-16 Composition with absorption capacity for the treatment of polyester fibrous materials Expired - Lifetime EP0342331B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89104695T ATE95855T1 (en) 1988-03-24 1989-03-16 PULLABLE COMPOSITION FOR THE TREATMENT OF FIBER MATERIALS CONTAINING POLYESTER.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3809928 1988-03-24
DE3809928A DE3809928A1 (en) 1988-03-24 1988-03-24 TOWABLE TEXTILE TOOLS FOR POLYESTER CONTAINING FIBER MATERIALS

Publications (3)

Publication Number Publication Date
EP0342331A2 EP0342331A2 (en) 1989-11-23
EP0342331A3 EP0342331A3 (en) 1991-11-21
EP0342331B1 true EP0342331B1 (en) 1993-10-13

Family

ID=6350572

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89104695A Expired - Lifetime EP0342331B1 (en) 1988-03-24 1989-03-16 Composition with absorption capacity for the treatment of polyester fibrous materials

Country Status (8)

Country Link
US (1) US4975091A (en)
EP (1) EP0342331B1 (en)
JP (1) JPH01314783A (en)
AT (1) ATE95855T1 (en)
AU (1) AU614045B2 (en)
BR (1) BR8901358A (en)
DE (2) DE3809928A1 (en)
ES (1) ES2059597T3 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ235490A (en) * 1989-10-16 1993-08-26 Colgate Palmolive Co Fabric-softening compositions
JPH03174067A (en) * 1989-11-30 1991-07-29 Kao Corp Oil for high speed spinning
JPH0441776A (en) * 1990-06-01 1992-02-12 Kao Corp Liquid soft finishing agent
US5282983A (en) * 1990-08-22 1994-02-01 Kao Corporation Fabric softener composition and ammonium salt
US5182033A (en) * 1991-06-14 1993-01-26 Sherex Chemical Company, Inc. Polyamide salts
US5491004A (en) * 1994-05-26 1996-02-13 Henkel Corporation Process for applying a low soiling fiber finish
US5789373A (en) * 1996-01-31 1998-08-04 Baker; Ellen Schmidt Laundry additive compositions including dispersible polyolefin
US5830843A (en) * 1996-01-31 1998-11-03 The Procter & Gamble Company Fabric care compositions including dispersible polyolefin and method for using same
US5728673A (en) * 1996-01-31 1998-03-17 The Procter & Gamble Company Process for making a fluid, stable liquid fabric softening composition including dispersible polyolefin
US6140413A (en) * 1999-03-29 2000-10-31 Henkel Corporation Silicone softener viscosity reducer
WO2002079364A1 (en) * 2001-03-30 2002-10-10 Ciba Specialty Chemicals Holding Inc. Softener compositions and their use

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3390184A (en) * 1965-06-01 1968-06-25 Jefferson Chem Co Inc Production of primary amines by ammonolysis
US3984335A (en) * 1975-01-16 1976-10-05 Basf Wyandotte Corporation Compositions for souring and softening laundered textile materials and stock solutions prepared therefrom
DE3007930A1 (en) * 1980-03-01 1981-09-24 Henkel KGaA, 4000 Düsseldorf NEW POLYESTER COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A TEXTILE SOFTENER
DE3032216A1 (en) * 1980-08-27 1982-04-08 Henkel KGaA, 4000 Düsseldorf Hair shampoo and cosmetic compsn. - contg. polyester prepd. by condensing di:carboxylic acid and alkoxylated tert. amine and opt. neutralising with acid
JPS5947478A (en) * 1982-09-06 1984-03-17 花王株式会社 Spinning oil for synthetic fiber
DE3238395A1 (en) * 1982-10-16 1984-04-19 Henkel KGaA, 4000 Düsseldorf SMOOTHING AGENT FOR TEXTILE FIBER MATERIAL
JPS61108767A (en) * 1984-10-31 1986-05-27 竹本油脂株式会社 Antistatic agent for synthetic fiber
JPS61289182A (en) * 1985-06-14 1986-12-19 竹本油脂株式会社 Antistatic agent for synthetic fiber
DE3618944A1 (en) * 1986-06-05 1987-12-10 Henkel Kgaa QUARTAERE 2-ALKYLIMIDAZOLINIAL SALTS, METHOD FOR THE PRODUCTION AND USE THEREOF
US4698391A (en) * 1986-07-30 1987-10-06 Eastman Kodak Company Crosslinked polymers with lowered resistivity and materials and methods for their preparation

Also Published As

Publication number Publication date
JPH01314783A (en) 1989-12-19
ATE95855T1 (en) 1993-10-15
ES2059597T3 (en) 1994-11-16
AU3170289A (en) 1989-09-28
DE3809928A1 (en) 1989-10-05
BR8901358A (en) 1989-11-07
AU614045B2 (en) 1991-08-15
EP0342331A2 (en) 1989-11-23
EP0342331A3 (en) 1991-11-21
US4975091A (en) 1990-12-04
DE58905875D1 (en) 1993-11-18

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