EP1282739B1 - Use of surfactant mixtures as high speed textile fibre preparations - Google Patents

Abstract

A composition containing a saponin present in an extract of an Argania spinosa plant.

Description

Field of the Invention

The invention is in the field of textile technology and relates to the use of certain Mixtures for the production of new high-speed staple fiber preparations.

State of the art

Precise control is required in both the manufacture and processing of synthetic fibers the forces acting on the fibers are extremely important. Basically the influencing factors can be divided into two groups: acceleration forces, for example transferred from rotating rollers to the fibers as well as friction forces caused by friction of the fibers on hard surfaces. About the friction, i.e. the thread break To counteract this, one of the tried and tested means is to thread the yarn with a so-called To treat spin fiber preparation, which is simplified to an aqueous preparation acts, which on the one hand has a lubricating effect and on the other hand the static charge both between the fibers and between thread and roll.

Although a large number of such preparations are known and known from the prior art the topic of avoiding friction related to yarn manufacturing numerous Articles and books have appeared, various problems have not yet been solved solved satisfactorily. A disadvantage of the known spun fiber preparations is for example in that it is sufficient in the medium speed range Develop a lubricating effect, but for modern high-speed processes in the range of 100,000 to 110,000 rpm are hardly suitable. Another disadvantage is that conventional Preparations can only be used for processing undyed fibers because they tend to dissolve dyes under the usual texturing conditions and so that the fiber bleed out. This is accompanied by an increase in deposits on the Roll.

In this connection, reference is made to WO 01/047489 A1 (Cognis), from which transparent softening agents are known which can contain esterquats, fatty acid amidoamines and, if appropriate, nonionic surfactants. From EP 0739976 A1 (Henkel) agents for finishing hair and textiles are known which contain ester quats together with fatty acid amides. EP 0786250 A1 (Henkel) also relates to hair-activating compositions which contain 0.01 to 30% by weight of esterquats and 0.01 to 30% by weight of alkylamidoamines. In US 5,747,109 (Colgate) textile softeners are proposed which contain a combination of cationic surfactants together with nonionic polymers. DE 4439090 A1 (Henkel) discloses a process for the preparation of esterquat dispersions in which the fatty acid alkanolamine esters are quaternized in the presence of nonionic surfactants. Finally, DE 19738303 A1 (Schwarzkopf) discloses agents which contain an active ingredient combination, for example of panthenol, esterquats and amidoamines.

The object of the present invention was therefore to create new spin fiber preparations to make available, which also enable the processing of colored fibers or yarns and are also suitable for high-speed processes.

Description of the invention

(a) Esterquats,

(b) Fettsäureamidoamine und

(c) ethoxylierte nichtionische Tenside

zur Herstellung von Hochgeschwindigkeits-Spinnfaserpräparationen.The invention relates to the use of mixtures containing

(a) esterquats,

(b) fatty acid amidoamines and

(c) ethoxylated nonionic surfactants

for the production of high-speed staple fiber preparations.

Surprisingly, it was found that the preparations to be used according to the invention not only significantly reduce the static charge, an excellent one Have a lubricating effect and in this way also the high-speed processing of Allow yarns without thread breaks or deposits on the reels, but also the undesired bleeding of dyed synthetic fibers or yarns, in particular based on polyacrylate or polyester fibers, reliably prevent.

esterquats

The term "esterquats" generally means quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to international patent application WO 91/01295 (Henkel), according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. German patent DE 4308794 C1 (Henkel) also discloses a process for the preparation of solid ester quats , in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic are, for example, by R.Puchta et al. in Tens.Surf.Det., 30 , 186 (1993), M.Brock in Tens.Surf:Det. 30 , 394 (1993), R. Lagerman et al. in J.Am. Oil.Chem. Soc., 71 , 97 (1994) and I. Shapiro in Cosm.Toil. 109 , 77 (1994) appeared.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden Fettsäuren mit 16 bis 22 Kohlenstoffatomen, insbesondere Stearinsäure, Behensäure sowie teilgehärtete C_16/18-Talgfettsäure eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18- Talg- bzw. Palmfettsäure (Iodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (I) als besonders vorteilhaft erwiesen, in der R'CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht. Entsprechende Produkte sind unter der Marke Dehyquart® AU (Cognis Deutschland GmbH) im Handel.The quaternized fatty acid triethanolamine ester salts follow the formula (I)

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Fatty acids with 16 to 22 carbon atoms, in particular stearic acid, behenic acid and partially hardened C _16/18 tallow fatty acid, are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 - tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R'CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p are 0 and X is methyl sulfate. Corresponding products are on the market under the Dehyquart® AU brand (Cognis Deutschland GmbH).

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Finally, the quaternized ester salts of fatty acids with 1,2-dihydroacypropyl dialkylamines of the formula (III) should be mentioned as a further group of suitable ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und X für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Marke Incroquat® (Croda) im Markt erhältlich.Furthermore, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which, preferably based on diethylene triamine, follow the formula (IV)

in which R ¹ CO represents an acyl radical having 6 to 22 carbon atoms, R ^{2 represents} hydrogen or R ¹ CO, R ⁶ and R ⁷ independently of one another represent alkyl radicals having 1 to 4 carbon atoms and X represents halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.

in der R⁸CO für einen gesättigten und/oder ungesättigten ethoxylierten Hydroxyacylrest mit 16 bis 22, vorzugsweise 18 Kohlenstoffatomen sowie 1 bis 50 Oxyethyleneinheiten, A für einen linearen oder verzweigten Alkylenrest mit 1 bis 6 Kohlenstoffatomen, R⁹, R¹⁰ und R¹¹ unabhängig voneinander für Wasserstoff oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, R¹² für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder einen Benzylrest und X für Halogen, Alkylsulfat oder Alkylphosphat steht.Finally, suitable esterquats are also substances which are obtainable on the basis of ethoxylated castor oil or its hardening products and preferably follow the formula (V)

in which R ⁸ CO for a saturated and / or unsaturated ethoxylated hydroxyacyl radical with 16 to 22, preferably 18 carbon atoms and 1 to 50 oxyethylene units, A for a linear or branched alkylene radical with 1 to 6 carbon atoms, R ⁹ , R ¹⁰ and R ¹¹ independently one another represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ^{12 represents} an alkyl radical having 1 to 4 carbon atoms or a benzyl radical and X represents halogen, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for formula (I) also apply to the esterquats of the formulas (II) to (V).

Both fatty acids and the corresponding triglycerides can be used to prepare the esterquats of the formulas (I) to (V) . Such a method, which should be mentioned as representative of the corresponding prior art, is proposed in the European patent EP 0750606 B1 (Cognis). It is also possible to carry out the condensation of the alkanolamines with the fatty acids in the presence of defined amounts of dicarboxylic acids, such as, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid. This results in a partially oligomeric structure of the ester quats, which can have an advantageous effect on the clear solubility of the products, especially when adipic acid is also used. Corresponding products under the Dehyquart® D 6003 brand (Cognis Deutschland GmbH) are commercially available and are described, for example, in European Patent EP 0770594 B1 (Cognis). The esterquats are usually commercially available in the form of 50 to 90% by weight alcoholic solutions, which can be diluted with water if required.

fatty acid

The fatty acid amidoamines which can be considered as component (b) are known pseudo-cationic compounds which are condensation products of C ₁₂ -C ₂₂ fatty acids with ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, dipropylenetriamine and / or tripropylenetetramine. Typical examples are the reaction products of the di- or oligoamines mentioned with lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid and gadolic acid mixtures, and behenic acid mixtures, behenic acid, behenic acid , From an application point of view, the use of the condensation product of behenic acid with diethylenetriamine (DETA) is particularly preferred.

Ethoxylated nonionic surfactants

Addition products of an average of 20 to 150, preferably 30 to 100 and in particular 40 to 75 moles of ethylene oxide with primary C ₈ -C ₂₂ alcohols or C ₈ -C ₂₂ triglycerides come in as ethoxylated nonionic surfactants which form component (c) Question. The ethoxylates can be prepared in a known manner, that is to say by base-catalyzed addition of ethylene oxide to the hydroxyl group of the alcohols or by hydrotalcite-catalyzed insertion of ethylene oxide into the carbonyl ester group and have both a conventionally broad and a narrowed homolog distribution.

Typical examples are the adducts of an average of 20 to 150, preferably 30 to 100 and in particular 40 to 75 mol of ethylene oxide over fatty alcohols or oxo alcohols with 8 to 22, preferably 12 to 18 carbon atoms, such as capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, Capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, Palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, Gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical Mixtures. The addition products are particularly preferred from an average of 40 to 75 moles of ethylene oxide in stearyl alcohol, tallow fatty alcohol and behenyl alcohol.

Further typical examples are the adducts of an average of 20 to 150, preferably 30 to 100 and in particular 40 to 75 moles of ethylene oxide to synthetic or natural triglycerides represents which of fatty acids with 8 to 22 and in particular 12 to 18 carbon atoms derived. Typical examples of suitable vegetable oils or animal fats are Palm oil, palm kernel oil, coconut oil, olive oil or beef tallow. However, the is particularly preferred Use of adducts of an average of 20 to 300, preferably 50 to 250 and in particular 100 to 200 moles of castor oil and hardened castor oil; here the attachment takes place in the essentially to the secondary hydroxyl group in the fat chain.

Industrial applicability

(a) 40 bis 65, vorzugsweise 45 bis 55 Gew.-% Esterquats

(b) 10 bis 20, vorzugsweise 12 bis 18 Gew.-% Fettsäureamidoamine und

(c) 15 bis 50, vorzugsweise 30 bis 40 Gew.-% ethoxylierte nichtionische Tenside

mit der Maßgabe enthalten, dass sich die Mengenangaben, gegebenenfalls zusammen mit weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen. Als Hilfsmittel können beispielsweise Antistatika, Fadenschlußmittel, pH-Regulantien, Bakterizide und/oder Korrosionsinhibitoren enthalten sein. In der Regel beträgt die Menge an Additiven - bezogen auf die Präparationen - insgesamt bis zu 15 Gew.-%, vorzugsweise liegt der Anteil aber bei 1 bis 10 Gew.-%.With regard to the production of high-speed staple fiber preparations, which are notable for particularly little deposits on the rolls, such preparations have proven themselves

(a) 40 to 65, preferably 45 to 55% by weight of ester quats

(b) 10 to 20, preferably 12 to 18 wt .-% fatty acid amidoamines and

(c) 15 to 50, preferably 30 to 40% by weight of ethoxylated nonionic surfactants

with the proviso that the amounts, if necessary together with other auxiliaries and additives, add up to 100% by weight. Antistatic agents, thread closure agents, pH regulators, bactericides and / or corrosion inhibitors can be included as auxiliaries. As a rule, the amount of additives, based on the preparations, is up to 15% by weight in total, but the proportion is preferably 1 to 10% by weight.

For the purposes of the invention, the preparations are preferably in the form of aqueous emulsions used, which can contain 1 to 30 wt .-%, preferably 15 to 25 wt .-% of the preparation. These emulsions can be prepared in the usual way, for example using godets (so-called lick-rolls) or dosing pumps and application pens applied to the fibers or yarns become. Another form of application can be the fibers or yarns to lead through immersion baths. The preparations can be made at various points in the yarn production or yarn equipment are used, i.e. both immediately after extrusion, when texturing or winding. In this context, the term spun fiber preparation synonymous to Teoturierhilfsmittel or rinsing oil.

Examples Examples 1 and 2, comparative examples V1 and V2

Red-dyed polyacrylic fibers were passed through immersion baths at 68 ° C which contained 1% by weight aqueous solutions of various spin fiber preparations. The fibers were then subjected to high-speed texturing at a roll speed of 100,000 rpm over a period of 6 hours. The thread break was examined (+ = less than 1, o = 1 to 5, - = greater than 5), the formation of residues on the rolls (+ = residue-free, o = small residues, - = strong residues) and the bleeding of the fibers (+ = no bleeding, o = slight bleeding, - = heavy bleeding). The results are summarized in Table 1. Examples 1 and 2 are according to the invention, examples V1 and V2 serve for comparison. Composition and application results of the spin finishes Composition / performance 1 2 V1 V2 Cetyl phosphate potassium salt - - 80 - Esterquat I - - - 80 Esterquat II 50 70 - - Condensation product of behenic acid with diethylenetriamine 15 10 20 20 Castor oil + 200EO 35 20 - - Application results - Thread break + + O O - residue formation + O O - - Bleed out + + - -

Claims (12)

1. The use of mixtures containing

   (a) esterquats,

   (b) fatty acid amidoamines and

   (c) ethoxylated nonionic surfactants

   for the production of high-speed spin finishes.
2. The use claimed in claim 1, characterized in that esterquats corresponding to formula (I):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² and R³ independently of one another represent hydrogen or have the same meaning as R¹CO, R⁴ is an alkyl group containing 1 to 4 carbon atoms or a (CH₂CH₂O)_qH group, m, n and p together stand for 0 or numbers of 1 to 12, q is a number of 1 to 12 and X is halide, alkyl sulfate or alkyl phosphate, are used as component (a).
3. The use claimed in claim 1, characterized in that esterquats corresponding to formula (II):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴ and R⁵ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used as component (a).
4. The use claimed in claim 1, characterized in that esterquats corresponding to formula (III):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁴, R⁶ and R⁷ independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or numbers of 1 to 12 and X stands for halide, alkyl sulfate or alkyl phosphate, are used as component (a).
5. The use claimed in claim 1, characterized in that esterquats corresponding to formula (IV):

   

   in which R¹CO is an acyl group containing 6 to 22 carbon atoms, R² is hydrogen or has the same meaning as R¹CO, R⁶ and R⁷ independently of one another are alkyl groups containing 1 to 4 carbon atoms and X is halide, alkyl sulfate or alkyl phosphate, are used as component (a).
6. The use claimed in claim 1, characterized in that esterquats corresponding to formula (V):

   

   in which R⁸CO is a saturated and/or unsaturated ethoxylated hydroxyacyl group containing 16 to 22 and preferably 18 carbon atoms and 1 to 50 oxyethylene units, A is a linear or branched alkylene group containing 1 to 6 carbon atoms, R⁹, R¹⁰ and R¹¹ independently of one another represent hydrogen or a C_1-4 alkyl group, R¹² is a C_1-4 alkyl group or a benzyl group and X is halogen, alkyl sulfate or alkyl phosphate, are used as component (a).
7. The use claimed in at least one of claims 1 to 6, characterized in that esterquats are derived from C_16-22 fatty acids are used as component (a).
8. The use claimed in at least one of claims 1 to 7, characterized in that condensation products of C_12-22 fatty acids with ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, dipropylenetriamine and/or tripropylene tetramine are used as component (b).
9. The use claimed in at least one of claims 1 to 8, characterized in that behenic acid/diethylenetriamine condensates as used as component (b).
10. The use claimed in at least one of claims 1 to 9, characterized in that products of the addition of on average 20 to 300 mol ethylene oxide onto primary C_8-22 alcohols or triglycerides are used as component (c).
11. The use claimed in at least one of claims 1 to 10, characterized in that products of the addition of on average 50 to 200 mol ethylene oxide onto castor oil are used as component (c).
12. The use claimed in at least one of claims 1 to 11, characterized in that mixtures containing

    (a) 40 to 65% by weight esterquats,

    (b) 10 to 20% by weight fatty acid amidoamines and

    (c) 15 to 50% by weight ethoxylated nonionic surfactants,

    with the proviso that the quantities shown add up to 100% by weight, optionally together with other auxiliaries and additives, are used.