EP0118611A2 - Aqueous emulsions and process for the softening of fibrous material, in particular textile material - Google Patents

Aqueous emulsions and process for the softening of fibrous material, in particular textile material Download PDF

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Publication number
EP0118611A2
EP0118611A2 EP83112292A EP83112292A EP0118611A2 EP 0118611 A2 EP0118611 A2 EP 0118611A2 EP 83112292 A EP83112292 A EP 83112292A EP 83112292 A EP83112292 A EP 83112292A EP 0118611 A2 EP0118611 A2 EP 0118611A2
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Prior art keywords
diester
emulsion
softening
emulsions
polyethylene
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EP83112292A
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German (de)
French (fr)
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EP0118611B1 (en
EP0118611A3 (en
Inventor
Günter Pusch
Dieter Walz
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Chemische Fabrik Pfersee GmbH
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Chemische Fabrik Pfersee GmbH
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof

Definitions

  • the invention relates to aqueous emulsions for softening fiber material, in particular textile material.
  • emulsifier or emulsifier system they contain unsymmetrical diesters of certain dicarboxylic acids selected as softening agents.
  • These emulsions may additionally contain other soft-grip agents known for the treatment of fiber material, in particular polyethylene.
  • a process for softening fiber material using these emulsions is also claimed.
  • polyethylene emulsions belonging to the prior art still leave something to be desired, particularly with regard to the handle and the wet soiling.
  • the object of the present invention is to provide plasticizer emulsions for fiber material, in particular textile material, which do not show the disadvantages shown when they are used.
  • a method for softening fiber material, in particular textile material, with the emulsions according to the invention is also claimed.
  • the diesters as dicarboxylic acid are based on succinic, glutaric, adipic and fumaric and in particular maleic acid.
  • succinic, glutaric, adipic and fumaric and in particular maleic acid is particularly preferred for economic reasons, but in general the asymmetrical diesters can be produced particularly well from the anhydrides, which is why all acids forming an anhydride are of particular importance.
  • One acid residue of the dicarboxylic acid is esterified with a monohydric alcohol having 12 to 28 carbon atoms.
  • These alcohols can contain double bonds, such as for example with oleyl alcohol, but alcohols derived from saturated fatty acids are preferably used. Examples include: myristyl, palmityl, stearyl, arachyl -, behenyl alcohol and montan wax fatty alcohols.
  • the alcohols are preferably used in the form of their technical mixtures in the preparation of the esters, very particularly those technical mixtures of saturated fatty alcohols with 16 to 22 carbon atoms are to be emphasized.
  • the other acid residue of the dicarboxylic acid is esterified with a di- or trihydric alcohol, and the remaining hydroxyl groups can also be etherified.
  • Such alcohols - as can be seen from the formula scheme of the general formula (I) - are ethylene, 1,2-propylene and 1,2-butylene and 1,4-butylene and 1,6-hexylene glycol Consider, where the still free hydroxyl group can be etherified with a monohydric alcohol having 1 to 4 carbon atoms.
  • the di- and triethylene or propylene glycol and the glycerin are also suitable. Ethylene glycol and glycerin are particularly preferred as the second esterification component.
  • the asymmetrical diesters are prepared in a manner known per se by reacting the dicarboxylic acid or a derivative thereof, such as the acid chloride or - if accessible - the anhydride with the long-chain monohydric alcohol in a molar ratio of 1: about 1 and then further reacting in a known manner with the optionally diol or triol etherified on one side.
  • the corresponding alkylene oxides can also be used, as described, for example, in British Pat. No. 1,162,898. It is sufficient to drive the reaction to an acid number below 30 (including the small amount of esterification catalyst).
  • the production of the asymmetrical diester is particularly simple if one starts from the anhydrides, in particular the maleic anhydride, as far as is accessible, which is why these are preferred as the starting material for the production of the diesters.
  • the asymmetrical diesters thus produced are converted into aqueous emulsions individually, but also in a mixture with one another, using emulsifiers in a known manner.
  • Anionic, nonionic and cationic can be used as emulsifiers.
  • Nonionic and cationic, optionally in a mixture with one another, are preferably used, since emulsions prepared with the aid of such emulsifiers are generally compatible with other products known for textile finishing.
  • the emulsifiers are used in customary amounts of 4 to 30% by weight, in particular 8 to 25% by weight (calculated as solid substance based on the asymmetrical diester).
  • a particular embodiment of the invention consists in using these diester emulsions together with polyethylene.
  • the polyethylene emulsions known per se can be mixed with the diester emulsions insofar as the emulsifiers used in each case for producing the emulsions are compatible with one another.
  • secondary emulsions are mainly used in the textile industry; these are those obtained by emulsifying polyethylene containing reactive groups.
  • Anionic, nonionic or cationic emulsifiers for emulsifying the polyethylene in known amounts are also suitable, as reported for example by G. Louis and co-workers (Textilveredlung 2 (1967), page 400/401).
  • the joint emulsification of a melted mixture of diester and polyethylene is more advantageous than the subsequent mixing of the pre-formed diester and polyethylene emulsions. This shows that the melting point depression that occurs makes it much easier for the polyethylene in the mixture with the diester to emulsify than the polyethylene alone.
  • the sequential emulsification of the molten polyethylene and the molten diester is also very suitable.
  • the emulsions of the mixtures are less viscous than the emulsions of the pure diester at the same solids content, which is often desirable.
  • the use of the emulsions of the mixtures of diester and polyethylene has the advantage that the handle, the wet soiling and the "soil release" properties give the treated fiber material an improvement in tear and abrasion resistance as well as sewability.
  • the proportion of diester, based on the sum of diester and polyethylene, should, however, be at least 25% by weight, preferably at least 35% by weight, since otherwise significant losses in terms of the achievable positive properties have to be accepted.
  • the emulsions are usually prepared so that they have a solids content of this or of diesters and polyethylene of about 15 to 40% by weight.
  • the emulsions according to the invention can be used very universally for softening fiber material, in particular textile material, since - depending on the intended use - they can be adjusted anionically, cationically or nonionically. In this way, they can be combined with other products that are customary for the treatment of fiber material.
  • the fiber material to be treated and the treatment method approx. 10 g / 1 to 80 g / 1 of the emulsions according to the invention are used.
  • the individual treatment methods are familiar to the person skilled in the art; in addition to the usual padding process, they also include coating the Fiber material, optionally in a foamed form.
  • the treatment with the emulsions according to the invention is suitable for all types of fiber materials.
  • the fiber materials are leather, leather substitutes, paper made from the usual fiber materials and in particular textiles, the latter in the form of woven fabrics, knitted fabrics and optionally pre-consolidated nonwovens.
  • the textile material can consist of natural fibers such as those made of cellulose or wool or of synthetic fibers such as polyester, polyamide or polyacrylic fibers.
  • textile material made of natural and synthetic fibers can of course also be treated.
  • test specimens are treated for 20 minutes at 60 ° C. with constant agitation (liquor ratio 1:50), then rinsed once, half of the
  • the reaction product is a Has an acid number of 20 or lower, the reaction is terminated, which is the case after about 1 to 1 1/2 hours.
  • the resulting waxy, asymmetrical diester has a melting range of approx. 50 to 55 ° C.
  • the following are reacted with one another: 323.0 g of the technical fatty alcohol mixture mentioned in the preparation of diester I, 98.1 g of maleic anhydride and 150 g of triethylene glycol.
  • the diester obtained has a melting range from 48 to 53 ° C.
  • the waxy reaction product has a melting range of 50 to 55 ° C.
  • a waxy reaction product is obtained.
  • a waxy reaction product is obtained.
  • a wax-soft product is obtained.
  • Emulsion A Emulsion A
  • emulsion A The preparation of emulsion A is repeated. However, instead of the mixture of polyethylene wax and diester I, only 650 g of diester I are emulsified.
  • Emulsion C (comparison)
  • emulsion A The preparation of emulsion A is repeated. However, instead of the mixture of polyethylene wax and diester I, 650 g of polyethylene wax are emulsified alone. It is necessary to melt the polyethylene at a temperature of approx. 115 ° C.
  • the emulsion obtained has a diester III and polyethylene content of 29% by weight.
  • emulsion E The preparation of emulsion E is repeated, but 260 g of diester III alone are emulsified instead of the mixture of polyethylene and diester III.
  • emulsion G 3 The preparation for emulsion G 3 is repeated, but instead of the diester IV, the diesters V, VI and VII are emulsified (pH adjustment to about 7.0) and in the end only enough water is added that a 25% by weight emulsion (based on the sum of diester and polyethylene).
  • the finely divided additive emulsions obtained give them a soft to very soft feel when treating textiles, and the problem of wet soiling is also solved in a good sense.
  • the fabric is dried at 120 ° C for 5 minutes.
  • Example 1 is repeated, but the liquor additionally contains 110 g / l of a 50% solution of dimethyloldihydroxyethylene urea and 15 g / 1 magnesium chloride hexahydrate. (Examples 2 A, 2 B and 2 C). In addition, equipment is only carried out with synthetic resin and catalyst, that is to say without an ester emulsion (example 2D).
  • the tissue squeezed to a liquor absorption of 60% by weight is dried at 100 ° C. for 5 minutes and then condensed at 150 ° C. for 4 minutes.
  • Example 1 The cotton poplin mentioned in Example 1 is treated in the manner given there with a liquor which in each case contains 60 g / l of the emulsions G1 to G5.
  • Example 1 of US Pat. No. 4,102,840 is repeated, 3% by weight of emulsion E being used as a softening agent instead of the polyethylene emulsion mentioned therein.
  • this finish is characterized by a particularly smooth surface and a distinctly soft feel, reduced wet soiling and improved soil release properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Colloid Chemistry (AREA)

Abstract

1. Aqueous emulsions for softening fibrous material, in particular textile material, containing at least one emulsifying agent, at least one softening agent and additional conventional constituents, characterised in that the emulsion contains as a softening agent at least one asymmetrical diester of a dicarboxylic acid of the general Formula (I), ROOC-A-COOR' whereby A = -CH2 (CH2 )m -CH2 - or -CH = CH-, R = a saturated or unsaturated alkyl radical with 12 to 28, in particular 16 to 22 C-atoms, see diagramm : EP0118611,P9,F1 oder see diagramm : EP0118611,P9,F2 X = H, CH3 , C2 H5 or CH2 OH, Y = H or an alkyl residue with 1 to 4 C-atoms with the proviso that when X = CH2 OH Y = H, Z = H or CH3 , m = 0, 1 or 2 and n = 2 or 3.

Description

Die Erfindung betrifft wäßrige Emulsionen zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial. Sie enthalten außer einem Emulgator oder Emulgatorsystem als Weichgriffmittel ausgewählte, unsymmetrische Diester von bestimmten Dicarbonsäuren. Diese Emulsionen können zusätzlich noch andere, für die Behandlung von Fasermaterial bekannte Weichgriffmittel, insbesondere Polyethylen enthalten. Außerdem wird ein Verfahren zum Weichmachen von Fasermaterial unter Einsatz dieser Emulsionen beansprucht.The invention relates to aqueous emulsions for softening fiber material, in particular textile material. In addition to an emulsifier or emulsifier system, they contain unsymmetrical diesters of certain dicarboxylic acids selected as softening agents. These emulsions may additionally contain other soft-grip agents known for the treatment of fiber material, in particular polyethylene. A process for softening fiber material using these emulsions is also claimed.

Die Verwendung von Polyethylen-Emulsionen zur Textilbehandlung ist seit langem bekannt, wie z.B. aus der Veröffentlichung von F. Schrum und L.Quenn (Amer. Dyest.The use of polyethylene emulsions for textile treatment has long been known, e.g. from the publication by F. Schrum and L.Quenn (Amer. Dyest.

Rep. 56 (1967), Seite 924 bis 927) hervorgeht. Diese Emulsionen verleihen den damit behandelten Textilien, besonders bei ihrer gemeinsamen Anwendung mit die Knitterfestigkeit steigernden Produkten, eine verbesserte Einreiß- und Scheuerfestigkeit sowie Vernähbarkeit verbunden mit einem weichen Warengriff.Rep. 56 (1967), pages 924 to 927). These emulsions give the textiles treated with them, especially when used together with products that increase the creasing resistance, improved tearing and abrasion resistance and sewability tied with a soft handle.

Doch lassen die zum Stande der Technik gehörenden Polyethylen-Emulsionen insbesondere hinsichtlich des Griffes sowie der Naßanschmutzung noch zu wünschen übrig.However, the polyethylene emulsions belonging to the prior art still leave something to be desired, particularly with regard to the handle and the wet soiling.

Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Weichmacher-Emulsionen für Fasermaterial, insbesondere Textilmaterial, die die aufgezeigten Nachteile bei ihrer Anwendung nicht zeigen.The object of the present invention is to provide plasticizer emulsions for fiber material, in particular textile material, which do not show the disadvantages shown when they are used.

Die Aufgabe wird durch die Bereitstellung von wäßrigen Emulsionen zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial gelöst, die mindestens einen Emulgator, mindestens ein Weichgriffmittel und weitere übliche Bestandteile enthalten, das dadurch gekennzeichnet ist, daß die Emulsion als Weichgriffmittel mindestens einen Diester einer Dicarbonsäure der allgemeinen Formel (I)

Figure imgb0001
wobei

  • A = -CH2(CH2)m-CH2- oder -CH = CH-,
  • R = gesättigter oder ungesättigter Alkylrest mit 12 bis 28, insbesondere 16 bis 22 C-Atomen,
  • R' =
    Figure imgb0002
    -(CH2CH2)n-OY,
    Figure imgb0003
  • X = H, CH3, C2H5 oder CH2OH,
  • Y = H oder einen Alkylrest mit 1 bis 4 C-Atomen mit der Maßgabe, daß bei X = CH20H Y = H ist,
  • Z = H oder CH3,
  • m = 0, 1 oder 2 und
  • n = 2 oder 3

bedeuten, enthält.The object is achieved by the provision of aqueous emulsions for softening fiber material, in particular textile material, which contain at least one emulsifier, at least one softening agent and other customary constituents, which is characterized in that the emulsion as softening agent comprises at least one diester of a dicarboxylic acid of the general type Formula (I)
Figure imgb0001
 in which
  • A = -CH 2 (CH 2 ) m -CH 2 - or -CH = CH-,
  • R = saturated or unsaturated alkyl radical having 12 to 28, in particular 16 to 22, carbon atoms,
  • R '=
    Figure imgb0002
     - (CH 2 CH 2 ) n -OY,
    Figure imgb0003
  • X = H, CH 3 , C 2 H 5 or CH 2 OH,
  • Y = H or an alkyl radical with 1 to 4 C atoms with the proviso that when X = CH 2 0H Y = H,
  • Z = H or CH 3 ,
  • m = 0, 1 or 2 and
  • n = 2 or 3

mean contains.

Außerdem wird ein Verfahren zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial mit den erfindungsgemäßen Emulsionen beansprucht.A method for softening fiber material, in particular textile material, with the emulsions according to the invention is also claimed.

Wie aus dem Formelschema der allgemeinen Formel (I) hervorgeht, liegen den Diestern als Dicarbonsäure die Bernstein-, Glutar-, Adipin- sowie die Fumar- und insbesondere die Maleinsäure zugrunde. Letztere ist aus wirtschaftlichen Überlegungen heraus besonders bevorzugt, doch lassen sich generell die unsymmetrischen Diester besonders gut aus den Anhydriden herstellen, weshalb allen ein Anhydrid bildenden Säuren besondere Bedeutung zukommt.As can be seen from the formula scheme of the general formula (I), the diesters as dicarboxylic acid are based on succinic, glutaric, adipic and fumaric and in particular maleic acid. The latter is particularly preferred for economic reasons, but in general the asymmetrical diesters can be produced particularly well from the anhydrides, which is why all acids forming an anhydride are of particular importance.

Der eine Säurerest der Dicarbonsäure ist mit einem einwertigen Alkohol mit 12 bis 28 C-Atomen verestert.Diese Alkohole können, wie z.B. beim Oleylalkohol, Doppelbindungenerthalten, bevorzugt werden jedoch Alkohole, die sich von gesättigten Fettsäuren ableiten, verwendet. Beispielhaft seien genannt: Myristyl-, Palmityl-, Stearyl-, Arachyl-, Behenylalkohol und Montanwachsfettalkohole. Vorzugsweise werden bei der Herstellung der Ester die Alkohole in Form ihrer technischen Mischungen eingesetzt, wobei ganz besonders die technischen Gemische von gesättigten Fettalkoholen mit 16 bis 22 C-Atomen hervorzuheben sind.One acid residue of the dicarboxylic acid is esterified with a monohydric alcohol having 12 to 28 carbon atoms. These alcohols can contain double bonds, such as for example with oleyl alcohol, but alcohols derived from saturated fatty acids are preferably used. Examples include: myristyl, palmityl, stearyl, arachyl -, behenyl alcohol and montan wax fatty alcohols. The alcohols are preferably used in the form of their technical mixtures in the preparation of the esters, very particularly those technical mixtures of saturated fatty alcohols with 16 to 22 carbon atoms are to be emphasized.

Der andere Säurerest der Dicarbonsäure ist mit einem zwei- oder dreiwertigen Alkohol verestert, wobei die verbleibenden HydroxyLgruppen auch verethert sein können. Als solche Alkohole kommen - wie aus dem Formelschema der allgemeinen Formel (I) ersichtlich - das Ethylen-, das 1,2-Propylen- und 1,2-Butylen- sowie das 1,4-Butylen-und 1,6-Hexylenglykol in Betracht, wobei die noch freie Hydroxylgruppe mit einem einwertigen Alkohol mit 1 bis 4 C-Atomen verethert sein kann. Darüber hinaus sind auch das Di- und Triethylen- bzw. -propylenglykol sowie das Glycerin geeignet. Besonders bevorzugt sind als zweite Veresterungskomponente das Ethylenglykol und das Glycerin.The other acid residue of the dicarboxylic acid is esterified with a di- or trihydric alcohol, and the remaining hydroxyl groups can also be etherified. Such alcohols - as can be seen from the formula scheme of the general formula (I) - are ethylene, 1,2-propylene and 1,2-butylene and 1,4-butylene and 1,6-hexylene glycol Consider, where the still free hydroxyl group can be etherified with a monohydric alcohol having 1 to 4 carbon atoms. In addition, the di- and triethylene or propylene glycol and the glycerin are also suitable. Ethylene glycol and glycerin are particularly preferred as the second esterification component.

Die Herstellung der unsymmetrischen Diester erfolgt in an sich bekannter Weise durch Umsetzung der Dicarbonsäure oder einem Derivat derselben, wie dem Säurechlorid oder - soweit zugänglich - dem Anhydrid mit dem langkettigen einwertigen Alkohol im Molverhältnis 1 : etwa 1 und anschließender weiterer Umsetzung in bekannter Weise mit dem gegebenenfalls einseitig veretherten Di- bzw. Triol. Anstelle der Polyole können auch die entsprechenden Alkylenoxide eingesetzt werden, wie es beispielsweise in der GB-PS 1 162 898 beschrieben ist. Es ist ausreichend, die Umsetzung soweit zu treiben, daß eine Säurezahl von unter 30 (einschließlich der geringen Menge an Veresterungskatalysator) erreicht wird.The asymmetrical diesters are prepared in a manner known per se by reacting the dicarboxylic acid or a derivative thereof, such as the acid chloride or - if accessible - the anhydride with the long-chain monohydric alcohol in a molar ratio of 1: about 1 and then further reacting in a known manner with the optionally diol or triol etherified on one side. Instead of the polyols, the corresponding alkylene oxides can also be used, as described, for example, in British Pat. No. 1,162,898. It is sufficient to drive the reaction to an acid number below 30 (including the small amount of esterification catalyst).

Besonders einfach gestaltet sich die Herstellung des unsymmetrischen Diesters, wenn man - soweit zugänglich - von den Anhydriden, insbesondere dem Maleinsäureanhydrid ausgeht, weshalb diese als Ausgangsmaterial für die Herstellung der Diester bevorzugt sind.The production of the asymmetrical diester is particularly simple if one starts from the anhydrides, in particular the maleic anhydride, as far as is accessible, which is why these are preferred as the starting material for the production of the diesters.

Die so hergestellten unsymmetrischen Diester werden einzeln aber auch in Mischung untereinander mit Hilfe von Emulgatoren in bekannter Weise in wäßrige Emulsionen überführt. Als Emulgatoren kommen anionische, nichtionische und kationische in Betracht. Bevorzugt werden nichtionische und kationische, gegebenenfalls in Mischung untereinander eingesetzt, da mit Hilfe solcher Emulgatoren hergestellte Emulsionen in der Regel mit anderen zur Textilveredelung bekannten Produkten verträglich sind.The asymmetrical diesters thus produced are converted into aqueous emulsions individually, but also in a mixture with one another, using emulsifiers in a known manner. Anionic, nonionic and cationic can be used as emulsifiers. Nonionic and cationic, optionally in a mixture with one another, are preferably used, since emulsions prepared with the aid of such emulsifiers are generally compatible with other products known for textile finishing.

Als Beispiele für Emulgatoren seien genannt:

  • Polyvinylalkohol in wäßriger Lösung, ethoxylierte Fettsäureamide, ethoxylierte Fettsäuren, ethoxylierte Fettalkohole und ethoxylierte Fettamine, letztere auch in Form ihrer Salze mit niedermolekularen organischen Säuren oder Mineralsäuren sowie quaternäre Ammoniumverbindungen wie Octadeyloxymethylpyridiniumchlorid oder Cetylbenzyldimethylammoniumehlorid. Ebenfalls als Emulgatoren geeignet sind Umsetzungsprodukte aus Epoxygruppen enthaltenden Verbindungen und Di- oder Polyaminen, wie sie z.B. in der US-PS 3 320 197 beschrieben sind, oder Kondensationsprodukte aus Harnstoff und seinen Derivaten mit Epoxygruppen enthaltenden Verbindungen und ausgewählten Aminen, wie sie in der US-PS 3 729 437 besehrieben sind. Besonders bewährt haben sich als Emulgatoren Polyglykoletherreste enthaltende Fettsäureamide, wie sie aus der US-PS 3 904 661 bekannt sind, da diese oberflächenaktiven Substanzen schwach kationaktive Eigenschaften mit nichtionischen Eigenschaften in sich vereinen.
Examples of emulsifiers are:
  • Polyvinyl alcohol in aqueous solution, ethoxylated fatty acid amides, ethoxylated fatty acids, ethoxylated fatty alcohols and ethoxylated fatty amines, the latter also in the form of their salts with low molecular weight organic acids or mineral acids as well as quaternary ammonium compounds such as octadeyloxymethylpyridinium chloride or cetylbenzyldimethylammonium chloride. Also suitable as emulsifiers are reaction products of compounds containing epoxy groups and di- or polyamines, as described, for example, in US Pat. No. 3,320,197, or condensation products of urea and its derivatives with compounds containing epoxy groups and selected amines, as described in the US -PS 3 729 437 are described. Fatty acid amides containing polyglycol ether residues, as are known from US Pat. No. 3,904,661, have proven particularly useful as emulsifiers, since these surface-active substances combine weakly cationic properties with nonionic properties.

Die Emulgatoren werden dabei in üblichen Mengen von 4 bis 30, insbesondere 8 bis 25 Gewichts-% (gerechnet als Festsubstanz bezogen auf den unsymmetrischen Diester) eingesetzt.The emulsifiers are used in customary amounts of 4 to 30% by weight, in particular 8 to 25% by weight (calculated as solid substance based on the asymmetrical diester).

Wie schon erwähnt, besteht eine besondere Ausgestaltung der Erfindung darin, diese Diester-Emulsionen zusammen mit Polyethylen einzusetzen. Dabei können die an sich bekannten Polyethylenemulsionen mit den Diester-Emulsionen vermischt werden, soweit die jeweils zur Herstellung der Emulsionen verwendeten Emulgatoren miteinander verträglich sind.As already mentioned, a particular embodiment of the invention consists in using these diester emulsions together with polyethylene. The polyethylene emulsions known per se can be mixed with the diester emulsions insofar as the emulsifiers used in each case for producing the emulsions are compatible with one another.

In der Textilindustrie werden vor allem sogenannte Sekundäremulsionen eingesetzt; das sind solche, die durch Emulgierung von Polyethylen, das reaktive Gruppen enthält, erhalten werden. Dabei kommen ebenfalls anionische, nichtionogene oder kationische Emulgatoren zur Emulgierung des Polyethylens in bekannten Mengen in Betracht, wie beispielsweise von G. Louis und Mitarbeiter (Textilveredlung 2 (1967), Seite 400/401) berichtet wird.So-called secondary emulsions are mainly used in the textile industry; these are those obtained by emulsifying polyethylene containing reactive groups. Anionic, nonionic or cationic emulsifiers for emulsifying the polyethylene in known amounts are also suitable, as reported for example by G. Louis and co-workers (Textilveredlung 2 (1967), page 400/401).

Vorteilhafter als die nachträgliche Vermischung der vorgebildeten Diester- und Polyethylen-Emulsionen ist die gemeinsame Emulgierung einer aufgeschmolzenen Mischung aus Diester und Polyethylen. Hierbei zeigt sich, daß sich durch die eintretende Schmelzpunktsdepression das Polyethylen in der Mischung mit dem Diester wesentlich leichter emulgieren läßt als das Polyethylen allein. Ebenfalls sehr gut geeignet ist die aufeinanderfolgende Emulgierung des geschmolzenen Polyethylens und des geschmolzenen Diesters. Die Emulsionen der Mischungen sind bei gleichem Feststoffgehalt weniger viskos als die Emulsionen des reinen Diesters, was häufig erwünscht ist.The joint emulsification of a melted mixture of diester and polyethylene is more advantageous than the subsequent mixing of the pre-formed diester and polyethylene emulsions. This shows that the melting point depression that occurs makes it much easier for the polyethylene in the mixture with the diester to emulsify than the polyethylene alone. The sequential emulsification of the molten polyethylene and the molten diester is also very suitable. The emulsions of the mixtures are less viscous than the emulsions of the pure diester at the same solids content, which is often desirable.

Die Anwendung der Emulsionen der Mischungen aus Diester und Polyethylen hat den Vorteil, daß ohne nennenswerte Beeinträchtigung des Griffes, der Naßanschmutzung und der "Soil-Release"-Eigenschaften dem behandelten Fasermaterial gleichzeitig eine Verbesserung der Reiß- und Scheuerfestigkeit sowie der Vernähbarkeit verliehen wird.The use of the emulsions of the mixtures of diester and polyethylene has the advantage that the handle, the wet soiling and the "soil release" properties give the treated fiber material an improvement in tear and abrasion resistance as well as sewability.

Der Anteil an Diester, bezogen auf die Summe von Diester und Polyethylen, sollte jedoch mindestens 25 Gewichts-%, bevorzugt mindestens 35 Gewichts-% betragen, da anderenfalls nennenswerte Einbußen hinsichtlich der erzielbaren positiven Eigenschaften hinzunehmen sind.The proportion of diester, based on the sum of diester and polyethylene, should, however, be at least 25% by weight, preferably at least 35% by weight, since otherwise significant losses in terms of the achievable positive properties have to be accepted.

Die Emulsionen werden dabei in der Regel so hergestellt, daß sie einen Feststoffgehalt an Dieser bzw. an Diester und Polyethylen von ca. 15 bis 40 Gewichts-% aufweisen.The emulsions are usually prepared so that they have a solids content of this or of diesters and polyethylene of about 15 to 40% by weight.

Die erfindungsgemäßen Emulsionen können zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial sehr universell eingesetzt werden, da sie - je nach dem vorgesehenen Verwendungszweck - anionisch, kationisch oder nichtionisch eingestellt werden können. So können sie mit anderen zur Behandlung von Fasermaterial üblichen Produkten kombiniert werden. Besonders hervorgehoben sei für den Bereich der Behandlung von Textilmaterial die Kombination mit Produkten, die die Knitterfestigkeit verbessern, Produkten zur Erzielung einer Wasser- und bzw. oder Ölabweisung und Produkten zum Flammhemmendmachen, wobei hierzu selbstverständlich auch die entsprechenden Katalysatoren zu zählen sind.The emulsions according to the invention can be used very universally for softening fiber material, in particular textile material, since - depending on the intended use - they can be adjusted anionically, cationically or nonionically. In this way, they can be combined with other products that are customary for the treatment of fiber material. For the treatment of textile material, special mention should be made of the combination with products that improve the creasing resistance, products for achieving water and / or oil repellency and products for flame retardancy, which of course also includes the corresponding catalysts.

Von den erfindungsgemäßen Emulsionen kommen in Abhängigkeit der Konzentration, des zu behandelnden Fasermaterials und der Behandlungsmethode jeweils ca. 10 g/1 bis 80 g/1 zum Einsatz. Die einzelnen Behandlungsmethoden sind dem Fachmann geläufig; sie umfassen neben dem üblichen Foulardverfahren auch das Beschichten des Fasermaterials, gegebenenfalls in verschäumter Form.Depending on the concentration, the fiber material to be treated and the treatment method, approx. 10 g / 1 to 80 g / 1 of the emulsions according to the invention are used. The individual treatment methods are familiar to the person skilled in the art; in addition to the usual padding process, they also include coating the Fiber material, optionally in a foamed form.

Zur Erzielung der erwünschten Effekte genügt es, das behandelte Fasermaterial bei etwa 70°C bis 1200C zu trocknen, sofern nicht die kombiniert mit angewandten Produkte ein höheres Erhitzen erfordern. Bei solchen zusätzlich angewandten Produkten, sei es zur Verbesserung der Knitterfestigkeit, der Hydrophobierung und der Flammfestigkeit, sind in der Regel für 1 bis 8 Minuten Temperaturen von 130°C bis 170°C erforderlich.To achieve the desired effects, it is sufficient to dry the treated fiber material at about 70 ° C to 120 0 C, provided that the combined require products with applied a higher heating. With such additionally used products, be it to improve the creasing resistance, the hydrophobization and the flame resistance, temperatures of 130 ° C. to 170 ° C. are generally required for 1 to 8 minutes.

Die Behandlung mit den erfindungsgemäßen Emulsionen ist für Fasermaterialien aller Art geeignet. Als Fasermaterialien sind Leder, Lederersatzstoffe, Papier aus den üblichen Fasermaterialien und insbesondere Textilien zu nennen, letztere in Form von Geweben, Gewirken und gegebenenfalls vorverfestigten Faservliesen. Das Textilmaterial kann dabei aus natürlichen Fasern wie solchen aus Cellulose oder Wolle oder aus Synthesefasern, wie aus Polyester-, Polyamid- oder Polyacryl-fasern, bestehen. Daneben kann selbstverständlich auch Textilmaterial behandelt werden, das aus natürlichen und synthetischen Fasern hergestellt worden ist.The treatment with the emulsions according to the invention is suitable for all types of fiber materials. The fiber materials are leather, leather substitutes, paper made from the usual fiber materials and in particular textiles, the latter in the form of woven fabrics, knitted fabrics and optionally pre-consolidated nonwovens. The textile material can consist of natural fibers such as those made of cellulose or wool or of synthetic fibers such as polyester, polyamide or polyacrylic fibers. In addition, textile material made of natural and synthetic fibers can of course also be treated.

In den folgenden Beispielen werden zur Beurteilung der Effekte folgende Testmethoden angewandt:

  • Naßanschmutzung nach folgender Methode:
    • 0,5 g Farbruß und 0,3 g ethoxyliertes Nonylphenol (9 Mol Ethylenoxyd je Mol Nonylphenol) werden dick angeteigt und dann unter Rühren auf 1 Liter mit Wasser verdünnt.
In the following examples, the following test methods are used to assess the effects:
  • Wet soiling using the following method:
    • 0.5 g of carbon black and 0.3 g of ethoxylated nonylphenol (9 moles of ethylene oxide per mole of nonylphenol) are made into a thick paste and then diluted to 1 liter with water while stirring.

In dieser Schmutzflotte werden die Prüflinge 20 Minuten bei 600C unter dauernder Bewegung (Flottenverhältnis 1 : 50) behandelt, dann einmal gespült, die Hälfte desIn this dirty liquor, the test specimens are treated for 20 minutes at 60 ° C. with constant agitation (liquor ratio 1:50), then rinsed once, half of the

Prüflings mit 3 g/1 eines handelsüblichen Waschmittels während 20 Minuten gekocht (Baumwolle) bzw. bei 60°C gewaschen (Synthetic und Cellulose/Synthetic-Mischungen), kurz gespült und dann visuell beurteilt (Noten 5 bis 1, wobei Note 5 unmerklich und Note 1 stark angeschmutzt bedeutet). Die angegebene Note gibt den Mittelwert aus ungewaschenem und gewaschenem Muster an. Soil-Release-Eigenschaften nach dem sogenannten "Lanolin-Test" (Siehe DE-AS 17 19 359, Beispiel 1).Test piece with 3 g / 1 of a commercial detergent boiled for 20 minutes (cotton) or washed at 60 ° C (synthetic and cellulose / synthetic blends), briefly rinsed and then assessed visually (marks 5 to 1, marks 5 imperceptible and Grade 1 means heavily soiled). The grade given gives the mean of the unwashed and washed pattern. Soil release properties according to the so-called "lanolin test" (see DE-AS 17 19 359, example 1).

Griff nach Bewertungsstufen:

  • 5 = oberflächenglatter, sehr weicher Griff
  • 4 = weicher Griff
  • 3 = wenig weicher Griff
  • 2 = trockener, etwas fülliger Griff
  • 1 = trockener, fülliger Griff
Grip by rating levels:
  • 5 = smooth, very soft handle
  • 4 = soft handle
  • 3 = little soft grip
  • 2 = dry, somewhat full handle
  • 1 = dry, plump handle

Herstellung der unsymmetrischen DiesterProduction of the asymmetrical diesters Diester IDiester I

In einem 1 Liter-Dreihalskolben mit Rührer, Thermometer und absteigendem Kühler werden 323,0 g (1 Äquivalent) eines Fettalkoholgemisches mit einem überwiegenden Anteil der Fettalkohole mit 20 und 22 C-Atomen (Hydroxylzahl des Gemisches 173,3) bei einer Temperatur von 70°C aufgeschmolzen und mit 98,1 g ( 1 Mol) Maleinsäureanhydrid versetzt. Anschließend wird auf 130 bis 1350C erhitzt und diese Temperatur für 3 Stunden eingehalten. Danach werden 77,5 g (1,25 Mol) Ethylengly kol und 1,8 g Schwefelsäure (96%ig) zugefügt und die Temperatur auf 145°C gesteigert. Bei dieser Temperatur destilliert langsam Wasser ab. Sobald das Reaktionsprodukt eine Säurezahl von 20 oder niedriger aufweist, wird die Reaktion beendet, was nach ca. 1 bis 1 1/2 Stunden der Fall ist. Der entstandene wachsartige, unsymmetrische Diester hat einen Schmelzbereich von ca. 50 bis 55°C.In a 1 liter three-necked flask with stirrer, thermometer and descending condenser, 323.0 g (1 equivalent) of a fatty alcohol mixture with a predominant proportion of the fatty alcohols with 20 and 22 C atoms (hydroxyl number of the mixture 173.3) are at a temperature of 70 ° C melted and mixed with 98.1 g (1 mol) of maleic anhydride. The mixture is then heated to 130 to 135 ° C. and this temperature is maintained for 3 hours. Then 77.5 g (1.25 mol) of ethylene glycol and 1.8 g of sulfuric acid (96%) are added and the temperature is increased to 145 ° C. Water slowly distills off at this temperature. As soon as the reaction product is a Has an acid number of 20 or lower, the reaction is terminated, which is the case after about 1 to 1 1/2 hours. The resulting waxy, asymmetrical diester has a melting range of approx. 50 to 55 ° C.

Diester IIDiester II

In der oben angegebenen Weise werden miteinander umgesetzt: 323,0 g des bei der Herstellung von Diester I genannten technischen Fettalkoholgemisches, 98,1 g Maleinsäureanhydrid und 150 g Triethylenglykol. Der erhaltene Diester hat einen Schmelzbereich von 48 bis 530C.The following are reacted with one another: 323.0 g of the technical fatty alcohol mixture mentioned in the preparation of diester I, 98.1 g of maleic anhydride and 150 g of triethylene glycol. The diester obtained has a melting range from 48 to 53 ° C.

Diester IIIDiester III

In der oben angegebenen Weise werden miteinander umgesetzt: 323,0 g des bei der Herstellung von Diester I genannten technischen Fettalkoholgemisches, 98,1 g Maleinsäureanhydrid und 92,1 g Glycerin (vorher sorgfältig entwässert).The following are reacted with one another: 323.0 g of the technical fatty alcohol mixture mentioned in the preparation of diester I, 98.1 g of maleic anhydride and 92.1 g of glycerol (previously carefully dewatered).

Das wachsartige Reaktionsprodukt hat einen Schmelzbereich von 50 bis 55°C.The waxy reaction product has a melting range of 50 to 55 ° C.

Diester IVDiester IV

In der oben angegebenen Weise werden miteinander umgesetzt: 260,0 g (1 Äquivalent) eines technischen Fettalkoholgemisches auf Basis von Fettalkoholen mit im wesentlichen 16 und 18 C-Atomen (Hydroxylzahl des Gemisches 215,4), 100,1g(1 Mol) Bernsteinsäureanhydrid und 77,5gEthylenglykol.The following are reacted with one another: 260.0 g (1 equivalent) of a technical fatty alcohol mixture based on fatty alcohols with essentially 16 and 18 carbon atoms (hydroxyl number of the mixture 215.4), 100.1 g (1 mol) of succinic anhydride and 77.5g ethylene glycol.

Der Schmelzbereich dieses Produktes liegt bei ca. 59°C.The melting range of this product is approx. 59 ° C.

Diester VDiester V

In der oben angegebenen Weise werden miteinander umgesetzt: 323,0 g (1 Äquivalent) des bei der Herstellung von Diester I genannten Fettalkoholgemisches, 98,1 g (1 Mol) Maleinsäureanhydrid und 140 g Diethylenglykolmonoethylether.The following are reacted with one another: 323.0 g (1 equivalent) of the fatty alcohol mixture mentioned in the preparation of diester I, 98.1 g (1 mol) of maleic anhydride and 140 g of diethylene glycol monoethyl ether.

Man erhält ein wachsartiges Reaktionsprodukt.A waxy reaction product is obtained.

Diester VIDiester VI

In der oben angegebenen Weise werden miteinander umgesetzt: 1 Mol Myristylalkohol, 1 Mol Maleinsäureanhydrid und 1,1 Mol 1,4-Butylenglykol.The following are reacted with one another: 1 mol of myristyl alcohol, 1 mol of maleic anhydride and 1.1 mol of 1,4-butylene glycol.

Man erhält ein wachsartiges Reaktionsprodukt.A waxy reaction product is obtained.

Diester VIIDiester VII

In der oben angegebenen Weise werden miteinander umgesetzt: 260 g des C 16 bis 18-Fettalkohols (siehe Diester IV), 1 Mol Adipinsäureanhydrid und 1 Mol Glycerin.The following are reacted with one another: 260 g of the C 16-18 fatty alcohol (see Diester IV), 1 mol of adipic anhydride and 1 mol of glycerol.

Man erhält ein wachsweiches Produkt.A wax-soft product is obtained.

Herstellung der EmulsionenPreparation of the emulsions Emulsion AEmulsion A

350 g Polyethylenwachs (oxydiertes Polyethylen mit einem mittleren Molekulargewicht von etwa 4 000 und einer Säurezahl von ca. 23) und 300 g des Diesters I werden zusammen aufgeschmolzen und ca. 32 g Triethanolamin zugefügt. Zu der Schmelze fügt man unter Rühren 55 g eines Fettalkoholpolyglykolethers (40 Mol Ethylenoxyd je Mol C 16-18-Fettalkohol) hinzu und läßt diese auf ca. 90 bis 95°C erwärmte Mischung unter kräftigem Rühren in eine ebenfalls auf ca. 90 bis 95°C erwärmte Lösung von 400 g des nach Beispiel 1 der US-PS 3 904 661 hergestellten Emulgators (60 % Aktivsubstanzgehalt) in 720 g Wasser einlaufen. Die so hergestellte Voremulsion wird homogenisiert und auf einen Gehalt von 35 Gewichts-% an Diester und Polyethylen eingestellt. Gegebenenfalls ist es erforderlich, den pH-Wert durch Zugabe von alkalisch reagierenden Substanzen, wie Natronlauge oder Triethanolamin, auf ca. 6,5 bis 7,5 einzuregulieren.350 g of polyethylene wax (oxidized polyethylene with an average molecular weight of about 4,000 and an acid number of about 23) and 300 g of diester I are melted together and about 32 g of triethanolamine are added. 55 g of a fatty alcohol polyglycol ether (40 moles of ethylene oxide per mole of C 16-18 fatty alcohol) are added to the melt with stirring and the mixture is left on about 90 to 95 ° C heated mixture with vigorous stirring in a likewise heated to about 90 to 95 ° C solution of 400 g of the emulsifier prepared according to Example 1 of US Pat. No. 3,904,661 (60% active substance content) in 720 g of water break in. The pre-emulsion thus produced is homogenized and adjusted to a content of 35% by weight of diester and polyethylene. It may be necessary to adjust the pH to about 6.5 to 7.5 by adding alkaline substances such as sodium hydroxide solution or triethanolamine.

Emulsion BEmulsion B

Die Herstellung der Emulsion A wird wiederholt. Es werden jedoch anstelle des Gemisches aus Polyethylenwachs und Diester I nur 650 g Diester I emulgiert.The preparation of emulsion A is repeated. However, instead of the mixture of polyethylene wax and diester I, only 650 g of diester I are emulsified.

Emulsion C (Vergleich)Emulsion C (comparison)

Die Herstellung der Emulsion A wird wiederholt. Es werden jedoch anstelle des Gemisches aus Polyethylenwachs und Diester I 650 g Polyethylenwachs allein emulgiert. Dabei ist es erforderlich, das Polyethylen bei einer Temperatur von ca. 115°C aufzuschmelzen.The preparation of emulsion A is repeated. However, instead of the mixture of polyethylene wax and diester I, 650 g of polyethylene wax are emulsified alone. It is necessary to melt the polyethylene at a temperature of approx. 115 ° C.

Emulsion DEmulsion D

In eine auf ca. 70°C erwärmte Lösung von 18 g Polyvinylalkohol (Verseifungszahl 140, Viskosität einer 4%igen Lösung 25 mPa-s) in 400 g Wasser läßt man 300 g des geschmolzenen Diesters II unter kräftigem Rühren langsam einlaufen. Anschließend wird diese Voremulsion homogenisiert und auf einen Estergehalt von 40 Gewichts-% eingestellt.In a solution of 18 g polyvinyl alcohol (saponification number 140, viscosity of a 4% solution 25 mPa-s) in 400 g water heated to approx. 70 ° C., 300 g of the melted diester II are slowly run in with vigorous stirring. This pre-emulsion is then homogenized and adjusted to an ester content of 40% by weight.

Emulsion EEmulsion E

In 320 ml einer auf 70°C erwärmten wäßrigen, essigsauren Lösung, deren Herstellung im Beispiel 13 der GB-PS 1 071 162 beschrieben ist, läßt man unter kräftigem Rühren eine aufgeschmolzene Mischung aus 160 g des Diesters III und 150 g Polyethylen (Daten siehe Emulsion A) langsam einlaufen, verdünnt mit 420 ml heißem Wasser, säuert mit 5 ml konzentrierter Ameisensäure an und homogenisiert anschließend in üblicher Weise.In 320 ml of an aqueous, acetic acid solution heated to 70 ° C., the preparation of which is described in Example 13 of British Patent 1,071,162, a melted mixture of 160 g of diester III and 150 g of polyethylene is left under vigorous stirring (for data, see Emulsion A) run in slowly, diluted with 420 ml of hot water, acidified with 5 ml of concentrated formic acid and then homogenized in the usual way.

Die erhaltene Emulsion hat einen Gehalt an Diester III und Polyethylen von 29 Gewichts-%.The emulsion obtained has a diester III and polyethylene content of 29% by weight.

Emulsion FEmulsion F

Die Herstellung der Emulsion E wird wiederholt, wobei jedoch anstelle der Mischung aus Polyethylen und Diester III 260 g Diester III allein emulgiert werden.The preparation of emulsion E is repeated, but 260 g of diester III alone are emulsified instead of the mixture of polyethylene and diester III.

Emulsion GEmulsion G

In einem absperrbaren Glasbehälter werden 700 g Polyethylen (siehe Emulsion A) bei etwa 110 bis 1150C aufgeschmolzen, dann 32 g erwärmtes Triethanolamin und 710 g auf ca. 60°C erwärmter Emulgator (siehe Beispiel 1 der US-PS 3 904 661) zugegeben, der Behälter verschlossen und die Innentemperatuur auf 105 bis 110°C gebracht.In a closable glass vessel, 700 g of polyethylene (see Emulsion A) was melted at about 110 to 115 0 C, then 32 g heated triethanolamine and 710 g to about 60 ° C heated emulsifier (see Example 1 of U.S. Patent No. 3,904,661) added, the container closed and the internal temperature brought to 105 to 110 ° C.

Bei dieser Temperatur werden 1 650 ml Wasser unter Rühren zugesetzt, kurz nachgerührt, die Temperatur auf ca. 950C gesenkt und weitere 32 g Triethanolamin von 60°C eingerührt. Danach werden 588 g einer erwärmten Mischung aus 80 Gewichts-% Diester IV und 20 Gewichts-% nichtionogenem Emulgator (siehe Emulsion A) zugegeben und abschließend 2 310 ml Wasser und 90 g Harnstoff langsam eingerührt. Man erhält eine feinteilige Additivemulsion, die 40 Gewichts-% Diester (bezogen auf die Summe von Diester und Polyethylen) enthält (Emulsion G 3).At this temperature, 1650 ml of water are added with stirring, stirred briefly, the temperature to about 95 0 C lowered and stirred an additional 32 g of triethanolamine of 60 ° C. 588 g of a heated mixture of 80% by weight of diester IV and 20% by weight of nonionic emulsifier (see emulsion A) are then added, and finally 2 310 ml of water and 90 g of urea are added slowly stirred in. A finely divided additive emulsion is obtained which contains 40% by weight of diester (based on the sum of diester and polyethylene) (emulsion G 3).

In analoger Weise (pH-Werteinstellung auf 6,5 bis 7,5) werden weitere Additivemulsionen folgender Zusammensetzung hergestellt:

Figure imgb0004
In an analogous manner (pH adjustment to 6.5 to 7.5), further additive emulsions of the following composition are prepared:
Figure imgb0004

Emulsion HEmulsion H

Die Herstellungsweise für Emulsion G 3 wird wiederholte wobei aber anstelle des Diesters IV die Diester V, VI und VII emulgiert werden (pH-Werteinstellung auf ca. 7,0) und am Schluß nur soviel Wasser zugesetzt wird, daß eine 25-gewichts-%ige Emulsion (bezogen auf die Summe von Diester und Polyethylen) entsteht.The preparation for emulsion G 3 is repeated, but instead of the diester IV, the diesters V, VI and VII are emulsified (pH adjustment to about 7.0) and in the end only enough water is added that a 25% by weight emulsion (based on the sum of diester and polyethylene).

Die erhaltenen feinteiligen Additivemulsionen verleihen bei der Behandlung von Textilien denselben einen weichen bis sehr weichen Griff und auch das Problem der Naßanschmutzung ist in gutem Sinne gelöst.The finely divided additive emulsions obtained give them a soft to very soft feel when treating textiles, and the problem of wet soiling is also solved in a good sense.

Behandlung des FasermaterialsTreatment of the fiber material Beispiel 1example 1

Mit einer Flotte, die 30 g/1 der Emulsion A (Beispiel 1 A) bzw. der Emulsion B (Beispiel 1 B) bzw. der Emulsion C (Beispiel 1 C) enthält, wird am Foulard ein Baumwoll-Popeline (120 g/m2) auf eine Flottenaufnahme von 60 Gewichts-% abgequetscht.With a liquor containing 30 g / 1 of emulsion A (example 1 A) or emulsion B (example 1 B) or emulsion C (example 1 C), a cotton poplin (120 g / m 2 ) squeezed to a liquor intake of 60% by weight.

Das Gewebe wird 5 Minuten bei 120°C getrocknet.The fabric is dried at 120 ° C for 5 minutes.

Die Ergebnisse der technologischen Prüfung sind in der Tabelle I zusammengefaßt:

Figure imgb0005
The results of the technological test are summarized in Table I:
Figure imgb0005

Beispiel 2Example 2

Das Beispiel 1 wird wiederholt, wobei jedoch die Flotte zusätzlich noch 110 g/l einer 50%igen Lösung von Dimethyloldihydroxyethylenharnstoff und 15 g/1 Magnesiumchlorid-Hexahydrat enthält. (Beispiele 2 A, 2 B und 2 C). Außerdem wird noch eine Ausrüstung nur mit Kunstharz und Katalysator, also ohne Ester-Emulsion durchgeführt (Beispiel 2 D).Example 1 is repeated, but the liquor additionally contains 110 g / l of a 50% solution of dimethyloldihydroxyethylene urea and 15 g / 1 magnesium chloride hexahydrate. (Examples 2 A, 2 B and 2 C). In addition, equipment is only carried out with synthetic resin and catalyst, that is to say without an ester emulsion (example 2D).

Das auf eine Flottenaufnahme von 60 Gewichts-% abgequetschte Gewebe wird in diesem Falle 5 Minuten bei 100°C getrocknet und anschließend 4 Minuten bei 150°C kondensiert.In this case, the tissue squeezed to a liquor absorption of 60% by weight is dried at 100 ° C. for 5 minutes and then condensed at 150 ° C. for 4 minutes.

Die Ergebnisse der technologischen Prüfung sind in der Tabelle II zusammengefaßt:

Figure imgb0006
The results of the technological test are summarized in Table II:
Figure imgb0006

Beispiel 3Example 3

Mit einer Flotte, die jeweils 60 g/1 der Emulsionen G1 bis G5 enthält, wird der im Beispiel 1 genannte Baumwollpopeline in der dort angegebenen Weise behandelt.The cotton poplin mentioned in Example 1 is treated in the manner given there with a liquor which in each case contains 60 g / l of the emulsions G1 to G5.

Die Ergebnisse der technologischen Prüfung sind in der Tabelle III zusammengefaßt:

Figure imgb0007
The results of the technological test are summarized in Table III:
Figure imgb0007

Beispiel 4Example 4

Die Ausrüstung des Beispiels 1 der US-PS 4 102 840 wird wiederholt, wobei anstelle der dort genannten Polyethylenemulsion 3 Gewichts-%der Emulsion E als Weichgriffmittel zum Einsatz kommen.The equipment of Example 1 of US Pat. No. 4,102,840 is repeated, 3% by weight of emulsion E being used as a softening agent instead of the polyethylene emulsion mentioned therein.

Diese Ausrüstung zeichnet sich bei sonst vergleichbaren technologischen Eigenschaften durch einen besonders oberflächenglatten und ausgeprägt weichen Griff, verringerte Naßanschmutzung und verbesserte Soil-Release-Eigenschaften aus.With otherwise comparable technological properties, this finish is characterized by a particularly smooth surface and a distinctly soft feel, reduced wet soiling and improved soil release properties.

Claims (5)

1. Wäßrige Emulsionen zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial, enthaltend mindestens einen Emulgator, mindestens ein Weichgriffmittel und weitere übliche Bestandteile, dadurch gekennzeichnet, daß die Emulsion als Weichgriffmittel mindestens einen unsymmetrischen Diester einer Dicarbonsäure der allgemeinen Formel (I)
Figure imgb0008
wobei A = -CH2(CH2)m-CH2- oder -CH = CH-, R = gesättigter oder ungesättigter Alkylrest mit 12 bis 28, insbesondere 16 bis 22 C-Atomen, R' =
Figure imgb0009
-(CH2CH2)n-OY,
Figure imgb0010
 X = H, CH3, C2H5 oder CH2OH, Y = H oder einen Alkylrest mit 1 bis 4 C-Atomen mit der Maßgabe, daß bei X = CH20H Y = H ist, Z = H oder CH3, m = 0,1 oder 2 und n = 2 oder 3 bedeuten, enthält. 1. Aqueous emulsions for softening fiber material, in particular textile material, containing at least one emulsifier, at least one softening agent and other conventional constituents, characterized in that the emulsion as softening agent comprises at least one asymmetrical diester of a dicarboxylic acid of the general formula (I)
Figure imgb0008
 in which A = -CH 2 (CH 2 ) m -CH 2 - or -CH = CH-, R = saturated or unsaturated alkyl radical having 12 to 28, in particular 16 to 22, carbon atoms, R '=
Figure imgb0009
 - (CH 2 CH 2 ) n -OY,
Figure imgb0010
 X = H, CH 3 , C 2 H 5 or CH 2 OH, Y = H or an alkyl radical with 1 to 4 C atoms with the proviso that when X = CH 2 0H Y = H, Z = H or CH 3 , m = 0.1 or 2 and n = 2 or 3 mean contains. 2. Wäßrige Emulsionen nach Patentanspruch 1, dadurch gekennzeichnet, daß der Diester der allgemeinen Formel
Figure imgb0011
entspricht, wobei R1 einen Alkylrest mit 16 bis 22 C-Atomen bedeutet.2. Aqueous emulsions according to claim 1, characterized in that the diester of the general formula
Figure imgb0011
 corresponds, where R 1 is an alkyl radical having 16 to 22 carbon atoms. 3. Wäßrige Emulsionen nach Patentanspruch 1, dadurch gekennzeichnet, daß der Diester der allgemeinen Formel
Figure imgb0012
entspricht, worin R1 die in Patentanspruch 2 angegebene Bedeutung hat.3. Aqueous emulsions according to claim 1, characterized in that the diester of the general formula
Figure imgb0012
 corresponds, wherein R 1 has the meaning given in claim 2. 4. Wäßrige Emulsion nach den Patentansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Emulsion als Weichgriffmittel zusätzlich Polyethylen enthält.4. Aqueous emulsion according to claims 1 to 3, characterized in that the emulsion additionally contains polyethylene as a softening agent. 5. Verfahren zum Weichmachen von Fasermaterial, insbesondere von Textilmaterial durch Behandeln mit wäßrigen Emulsionen von Weichgriffmitteln und anschließendem Erhitzen, dadurch gekennzeichnet, daß man eine Emulsion gemäß Patentansprüchen 1 bis 4 in üblicher Weise aufbringt.5. A process for softening fiber material, in particular textile material by treatment with aqueous emulsions of softening agents and subsequent heating, characterized in that an emulsion according to claims 1 to 4 is applied in a conventional manner.
EP83112292A 1982-12-22 1983-12-07 Aqueous emulsions and process for the softening of fibrous material, in particular textile material Expired EP0118611B1 (en)

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AT83112292T ATE42978T1 (en) 1982-12-22 1983-12-07 AQUEOUS EMULSIONS AND PROCESSES FOR SOFTENING FIBROUS MATERIAL, ESPECIALLY TEXTILE MATERIAL.

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DE19823247407 DE3247407A1 (en) 1982-12-22 1982-12-22 AQUEOUS EMULSIONS AND METHOD FOR SOFTENING FIBER MATERIAL, ESPECIALLY TEXTILE MATERIAL
DE3247407 1982-12-22

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EP0118611A3 EP0118611A3 (en) 1986-12-30
EP0118611B1 EP0118611B1 (en) 1989-05-10

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989001541A1 (en) * 1987-08-19 1989-02-23 Commonwealth Scientific And Industrial Research Or Treatments to improve the properties of keratinous textiles
US5562847A (en) * 1995-11-03 1996-10-08 The Procter & Gamble Company Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity
US5652205A (en) * 1994-07-19 1997-07-29 The Procter & Gamble Company Perfumes for laundry and cleaning compositions
US5721202A (en) * 1995-11-03 1998-02-24 The Procter & Gamble Company Perfumes for laundry and cleaning composition
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
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1162898A (en) * 1966-12-19 1969-08-27 Balm Paints Ltd Production of Hydroxy-Alkyl Esters of Ethylenically Unsaturated Dicarboxylic Acids
US3679719A (en) * 1970-03-12 1972-07-25 American Cyanamid Co Non-yellowing softening agent for cotton and rayon textiles
FR2119010A1 (en) * 1970-12-22 1972-08-04 Sandoz Sa
US4026915A (en) * 1975-08-27 1977-05-31 S. C. Johnson & Son, Inc. Di-mixed alky aspartate salts
DE3046713A1 (en) * 1979-12-14 1981-09-17 CIBA-GEIGY AG, 4002 Basel Antistatic finishing of synthetic textile, esp. polyamide carpet - using aq. film-forming compsn. contg. acid di:carboxylic ester of aliphatic diol

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3651102A (en) * 1967-05-01 1972-03-21 Exxon Research Engineering Co Preparation of diesters

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1162898A (en) * 1966-12-19 1969-08-27 Balm Paints Ltd Production of Hydroxy-Alkyl Esters of Ethylenically Unsaturated Dicarboxylic Acids
US3679719A (en) * 1970-03-12 1972-07-25 American Cyanamid Co Non-yellowing softening agent for cotton and rayon textiles
FR2119010A1 (en) * 1970-12-22 1972-08-04 Sandoz Sa
US4026915A (en) * 1975-08-27 1977-05-31 S. C. Johnson & Son, Inc. Di-mixed alky aspartate salts
DE3046713A1 (en) * 1979-12-14 1981-09-17 CIBA-GEIGY AG, 4002 Basel Antistatic finishing of synthetic textile, esp. polyamide carpet - using aq. film-forming compsn. contg. acid di:carboxylic ester of aliphatic diol

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989001541A1 (en) * 1987-08-19 1989-02-23 Commonwealth Scientific And Industrial Research Or Treatments to improve the properties of keratinous textiles
US5652205A (en) * 1994-07-19 1997-07-29 The Procter & Gamble Company Perfumes for laundry and cleaning compositions
US5744435A (en) * 1994-07-19 1998-04-28 The Procter & Gamble Company Perfumes for laundry and cleaning compositions
US5756827A (en) * 1994-07-19 1998-05-26 The Procter & Gamble Company Manufacture of perfumes for laundry and cleaning compositions
US5562847A (en) * 1995-11-03 1996-10-08 The Procter & Gamble Company Dryer-activated fabric conditioning and antistatic compositions with improved perfume longevity
US5721202A (en) * 1995-11-03 1998-02-24 The Procter & Gamble Company Perfumes for laundry and cleaning composition
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
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

Also Published As

Publication number Publication date
ES8503755A1 (en) 1985-03-16
ATE42978T1 (en) 1989-05-15
EP0118611B1 (en) 1989-05-10
DE3379844D1 (en) 1989-06-15
ES528280A0 (en) 1985-03-16
EP0118611A3 (en) 1986-12-30
DE3247407A1 (en) 1984-06-28

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