EP0326702B1 - Amine salts as stabilizers for the oil and water repellent finishing of fibre materials - Google Patents

Description

The present invention relates to the use of certain water-soluble amine salts as an additive to aqueous liquors in the context of the oil- and / or water-repellent finishing of fiber materials. The amine salts act as liquor stabilizers.

The stabilization of aqueous fleets in the oil and / or water repellent finish has long been known. It is necessary to prevent deposits from forming in the sensitive liquors, which lead to stains on the fiber materials to be finished. The use of emulsifiers alone is not possible by impairing the effects. Quaternary ammonium compounds, in particular octadecyloximethylpyridinium chloride, are recommended for this area of use according to the prior art. These compounds can only be obtained in a relatively cumbersome and therefore expensive manufacturing process and also have an unpleasant odor from case to case. The preferably used octadecyloximethylpyridinium chloride is also cumbersome to handle due to a higher solution temperature and can be classified as problematic in handling and processing by splitting off formaldehyde and pyridine.

From GB-A-602 109 it is known to use amine salts as emulsifiers for compositions which contain waxes, aluminum salts and fatty acids, the fatty acids being used as stabilizers.

The present invention has set itself the task for the oil and / or water-repellent finishing of fiber materials by means of aqueous liquors, which at least one silicone or an organic Contain fluorine compound as additives such liquor stabilizers that do not have the disadvantages shown. Surprisingly, it was found that selected amine salts, which are usually present in an aqueous medium, are extremely effective liquor stabilizers. These amine salts are dispersants for a wide variety of purposes, for example as anticoagulants (JP application 45/24710 ref. In Derwent CPI ref. No. 39182 Q) (see article "Study on Textile Dyeing Additives - Dyeing Additives for Polyester Fibers" , cited in CA 90 (18) 138.939 c) and pretreatment agent (FR-A 2 090 205), but it was in no way possible to infer the subject matter of the invention from these fields of application. According to claim 1, the object is therefore to use water-soluble salts of amines of the general formula (I)

In which R₁, R₂ and R₃ independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms is present and the sum of the carbon atoms in the alkyl radicals is at most 33, is preferably at most 22, An is an anion and x is an integer corresponding to the negative charges of the anion,
as an additive to aqueous liquors for the water- and / or oil-repellent finishing of fiber materials, the aqueous liquors containing at least one silicone or an organic fluorine compound.

Preferred embodiments of the invention are explained in subclaims 2 to 10.

zugrunde, wobei R₁, R₂ und R₃ unabhängig voneinander einen Alkylrest mit 1 bis 22 C-Atomen oder Wasserstoff bedeuten, mit der Maßgabe, daß mindestens 1 Alkylrest mit mindestens 8 C-Atomen zugegen und die Summe der C-Atome in den Alkylresten höchstens 33, vorzugsweise höchstens 22 ausmacht, sowie die Bedingung erfüllt ist, daß die daraus erhaltenen Stabilisatoren in Wasser löslich sind. Als Beispiele für derartige Amine seien genannt:
   Octylamin,
   Stearylamin,
   Behenylamin,
   Octadecyldimethylamin,
   Dodecyldiethylamin,
   Palmityldimethylamin,
   Dipalmitylmethylamin.The liquor stabilizers of the present invention are the amines of the formula (I a)

underlying, wherein R₁, R₂ and R₃ independently of one another are an alkyl radical having 1 to 22 carbon atoms or hydrogen, with the proviso that at least 1 alkyl radical having at least 8 carbon atoms and the sum of the carbon atoms in the alkyl radicals is at most 33 , preferably at most 22, and the condition is fulfilled that the stabilizers obtained therefrom are soluble in water. Examples of such amines are:
Octylamine,
Stearylamine,
Behenylamine,
Octadecyldimethylamine,
Dodecyldiethylamine,
Palmityldimethylamine,
Dipalmitylmethylamine.

Of course, technical mixtures of the present amines can also be used to prepare the liquor stabilizers. Amines have proven to be particularly effective in which R 1 is a saturated alkyl radical having 8 to 10 or 16 to 18 carbon atoms and R 2 and R 3 are hydrogen or the methyl radical. The stabilizers with C₈₋₁₀ alkyl residues are particularly soluble and low-foaming and those with C₁₆₋₁₈ alkyl residues are particularly effective. The liquor stabilizers which can be used according to the invention are prepared in aqueous solution by largely reacting the amines described with a slight excess of acids. In general, 1.1 to 1.45 equivalents of acid are reacted per mole of the amine. The following may be mentioned as acids: succinic acid, maleic acid, sulfuric acid, particularly monovalent acids such as propionic acid, formic acid, glycolic acid, lactic acid, hydrochloric acid, nitric acid and very particularly acetic acid. The acetates in particular have proven to be particularly effective as liquor stabilizers. The solutions of the liquor stabilizers are generally between 10 and 30, in particular 18 to 25,% by weight of amine salt. However, it is also possible to remove the water e.g. to obtain pulverulent liquor stabilizers by evaporation or by spray drying. However, this procedure is complex and the products obtained are sometimes less effective, so that the resulting aqueous formulations are preferably used immediately as such.

The efficacy of the liquor stabilizers which can be used according to the invention is broad. However, the effects can still be improved by adding the usual emulsifiers to the same, in amounts of 5 to 55% by weight, in particular 10 to 40% by weight, based on the amine salt. The emulsifiers used are known to the person skilled in the art. These are, in particular, nonionic and / or weakly cationic emulsifiers.

bis C₁₂-Alkylphenole, wobei die Anzahl der Ethylenoxideinheiten zwischen 6 und 30 liegt, geeignet. Als Beispiele für solche Emulgatoren seien genannt:
2,6,8-Trimethyl-4-Nonyloxihexaethylenoxiethanol, Isotridecylethoxilat mit durchschnittlich 8 Ethylenoxideinheiten, mit durchschnittlich 12 Mol Ethylenoxid ethoxilierter sekundärer Dodecylalkohol oder n-Decylalkohol und Nonylphenolpolyglykolether mit durchschnittlich 10 Ethylenoxideinheiten. Daneben sind in gleicher Weise auch stickstoffhaltige Emulgatoren, wie sie durch Ethoxilierung von Fettaminen oder Fettsäureamiden entstehen, geeignet, wobei diese Verbindungen durch Zugabe von Säuren auch in Salzform vorliegen können.
Als Beispiele, wiederum ohne Anspruch auf Vollständigkeit, seien folgende Verbindungen genannt:
Dodecyloxypropylamin ethoxiliert mit 12 bis 15 Mol Ethylenoxid in Form des Acetats, Stearylamin ethoxiliert mit durchschnittlich 20 Mol Ethylenoxid, Hexadecylamin ethoxiliert mit durchschnittlich 15 Mol Ethylenoxid in Form des Acetats und Stearinsäureamid ethoxiliert mit 25 Mol Ethylenoxid.Ethylene oxide adducts of fatty alcohols, in particular those of primary and / or secondary, linear to branched alcohols having 8 to 16 C atoms and ethoxylated C, are suitable as emulsifiers $\frac{}{\text{6}}$

to C₁₂ alkylphenols, the number of ethylene oxide units being between 6 and 30, suitable. Examples of such emulsifiers are:
2,6,8-Trimethyl-4-Nonyloxihexaethylenoxiethanol, Isotridecylethoxilat with an average of 8 ethylene oxide units, with an average of 12 moles of ethylene oxide ethoxylated secondary dodecyl alcohol or n-decyl alcohol and nonylphenol polyglycol ether with an average of 10 ethylene oxide units. In addition, nitrogen-containing emulsifiers, such as those formed by ethoxylation of fatty amines or fatty acid amides, are also suitable, it being possible for these compounds to be present in salt form by adding acids.
The following compounds are mentioned as examples, again without claim to completeness:
Dodecyloxypropylamine ethoxylates with 12 to 15 moles of ethylene oxide in the form of the acetate, stearylamine ethoxylates with an average of 20 moles of ethylene oxide, hexadecylamine ethoxylates with an average of 15 moles of ethylene oxide in the form of the acetate and stearic acid amide with 25 moles of ethylene oxide.

The liquor stabilizers which can be used according to the invention have a tendency to foam, and it has therefore proven expedient proven to add the same defoamer. As such, the commercially available products are suitable in commercially available amounts, silicone-free defoamers being preferred. Defoamers which are known to those skilled in the art, such as octadecanol, isotridecanol, tributyl phosphate, higher ketones and the usual defoamers based on silicones or mixtures of the various compounds, may be mentioned.

The liquor stabilizers which can be used according to the invention are used in the course of oil and / or water-repellent finishing of fiber materials. The various known chemicals based on organic fluorine compounds are used for the oil-repellent finish. The person skilled in the art knows the polymers or copolymers based on perfluoroalkyl acrylates and also the other compounds used for oil repellency, as described, for example, in EP-B-073 364, US Pat. No. 3,356,628, US Pat. No. 3,968,066 and US-A-4 054 592 and DE-A-34 35 618. In these publications, the extenders used together with the fluorochemicals are also described on a case-by-case basis (see also DE-PS-1 233 874). These oil-repellent agents are generally used in the form of aqueous emulsions, the emulsions generally containing 15 to 35% by weight of active substance. In addition to the extenders already mentioned, silicones are used for the water-repellent finish. These products or the dispersions used thereof are known to the person skilled in the art and he will have no trouble selecting the appropriate finishing agents.

The silicones are primarily dispersions of known polydimethylsiloxanes and hydrogen methylpolysiloxane cans are mainly used for economic reasons, but other known silicones can also be used within the scope of the invention.

The amounts of oleophobicizing or hydrophobicizing agents which can be used in the context of the invention are within the scope known to the person skilled in the art.

Of course, as is known to the person skilled in the art, the finishing liquors can contain customary additives, in particular crease-free agents and fillers, e.g. Softening agents and the associated catalysts are added in customary amounts.

It is surprising and was by no means apparent from the prior art that excellent liquor stabilizers can be provided by using these simple amine salts. These compounds are characterized by simple and therefore inexpensive production, are almost odorless and easy to handle due to the lower solution temperature. It should be particularly emphasized, however, that disruptive fission products do not occur when these products are used, and consequently significant ecological progress is achieved through the use of these simple compounds.
However, the effectiveness is fully available. In this way, the otherwise sensitive fleets remain stable for several hours, which is particularly important under the harsher conditions in practice. In addition, the addition of the amine salts as liquor stabilizers according to the invention largely prevents roller coatings without having a negative influence on the finishing effects can be observed. Roll coverings cause stains on the finished goods, so that the use of liquor stabilizers for the oil- and / or water-repellent finish is unavoidable.

The invention is illustrated by the following examples. In these examples,% = percent by weight and parts = parts by weight.

example 1

1300 g of water, 138 g of 60% acetic acid and 34 g of a commercially available silicone defoamer (active substance 40% by weight) are brought to 85 ° C. in a 4 liter 4-necked flask (1st vessel) with an effective stirrer, internal thermometer and reflux condenser warmed up.
In a second vessel 265 g (1 mol) of hydrogenated tallow fatty amine (dest .; 98% primary amine of the following composition: 5% C₁₄, 32% C₁₆, 60% C₁₈, 3% unsaturated C₁₈, amine number 208-223) are melted and also heated to 85 ° C. After removing the heating source, the molten amine is added to the 1st vessel in a thin stream with vigorous stirring in such a way that the temperature is between 85 and 95 ° C. After the amine addition has ended, the mixture is stirred for a further 10 minutes at the temperature mentioned and then bottled. The product solidifies into a transparent, highly viscous mass at room temperature. The viscosity of a 1:10 dilution with water of this mass is 720 mPa.s (at 20 ° C). The pH of the 20% solution is approximately 4.9 (= product 1).

Example 2

500 g of fatty amine acetate solution according to Example 1, in which the silicone defoamer was replaced by 19 g of tributyl phosphate, are heated to 80 ° C. with 20 g of emulsifier (dodecyloxypropylamine ethoxylated with 12 to 15 mol of ethylene oxide in the form of the acetate), with stirring, for 15 minutes at this temperature held and then bottled. The product, which is thin at 80 ° C (pH 4.5), solidifies on cooling to a pasty mass. The viscosity of this solution after dilution 1:10 is 600 mPa.s (= product 2).

The products from Examples 1 and 2, as the following equipment examples show, are outstandingly suitable for stabilizing equipment fleets.

Example 3

In the manner described in Example 1, the following liquor stabilizers are prepared in aqueous medium by converting 1 mol of the amines with 1.25-1.3 mol of the corresponding acids (concentration of amine salt approx. 18%):
Octadecyldimethylammonium formate,
Hexadecylammonium lactate,
Octyldiethylammonium glycolate and
Behenylammonium chloride.

The described emulsifier can easily be replaced by 15 g of stearyl alcohol polyglycol ether (ethoxylated with an average of 15 moles of ethylene oxide per mole of alcohol). Instead of the defoaming agents mentioned, 25g®FUMEXOL B from CIBA-GEIGY AG are also suitable.
As in Example 1, these liquor stabilizers are outstandingly suitable for stabilizing liquors for oil- and / or water-repellent finishing, whereby the inexpensive stabilizers, which can be produced in a simple manner, are easy to process and do not cause any odor nuisance, and also during drying and condensation of the treated fiber materials no adverse fissile materials occur.

Example 4

1 mol of n-decylamine and 1 mol of succinic acid are reacted in 765 g of water at 70 ° C. while increasing the temperature to give a water-clear, low-viscosity solution (pH 4.3), which solidifies on cooling to a crystalline, white mass with good water solubility.

Equipment example

A polyester jacketed poplin (approx. 200 g / m²) is padded with the following liquors (liquor absorption 55 to 60%) and completed by drying (10 minutes at 110 ° C) and condensation (5 minutes at 150 ° C). The following fleets were used for the equipment:

A) Fluorocarbon equipment

20 g / l of an approximately 70% aqueous solution of dimethylol dihydroxyethylene urea etherified with methanol (contains approximately 6% alkali metal chloride) (component 1),
5 ml / l of an aqueous, approx. 55% zinc chloride solution (pH approx. 2.2) (component 2), 2 ml / l acetic acid 60%, 30 g / l of a commercially available extender (approx. 12 % fat-modified hexamethylolmelamine methyl ether, approx. 1% emulsifier, approx. 5% propylene glycol),
25 g / l of a commercially available approx. 20% oleophobicizing agent (®SCOTCHGARD FC 251 from the 3 M company)

B) silicone equipment

20 g / l

Component (1),

5 ml / l

Component (2),

2 ml / l

60% acetic acid

20 g / l

a commercially available, aqueous, weakly cationic, approx. 40% hydrogen methyl polysiloxane emulsion and

15 g / l

a commercially available, aqueous, weakly cationic, approx. 25% dimethylpolysiloxane emulsion.

3 g / l and 5 g / l of the products according to Example 1 and Example 2 are added to each of these liquors A and B to stabilize the liquors. For comparison, 3 g / l or 5 g / l of a commercially available stabilizing agent (approx. 20% octadecyloximethylpyridinium chloride; comparative product) are also added to the individual liquors. The equipment obtained with these fleets are summarized in the table below (water repellency test according to DIN 53888 or the spray test according to AATCC 22-1974 and oil repellency according to AATCC 118-1972): Water repellency Spray test Oil repellency a b Fleet A) 8.5 5 3 X 100 4th 5 5 - and 3 g / l product (1) 7.6 5 3 X 100 4th 5 5 - and 5 g / l product (1) 7.3 5 3 X 100 4th 5 5 - and 3 g / l product (2) 9.1 5 3 X 100 4th 4th 4th - and 5 g / l product (2) 9.1 5 3 X 100 4th 5 4th - and 3 g / l comparative product 7.6 5 3 X 100 4th 5 5 - And 5 g / l comparative product 6.4 5 3 X 100 4th 5 5 a = water absorption in%; b = beading effect Water repellency Spray test Oil repellency a b Fleet B) 5.3 4th 3 X 100 - 4th 4th - and 3 g / l product (1) 6.0 4th 3 X 100 - 4th 4th - and 5 g / l product (1) 6.0 4th 3 X 100 - 4th 4th - and 3 g / l product (2) 5.7 4th 3 X 100 - 4th 4th - and 5 g / l product (2) 6.7 4th 3 X 100 - 4th 4th - and 3 g / l comparative product 8.0 4th 3 X 100 - 4th 4th - And 5 g / l comparative product 7.5 4th 3 X 100 - 4th 4th

The overall results of the equipment example show that the liquor stabilizers according to the invention have no negative influence on the hydrophobizing and oleophobicizing effects and are also highly effective, because even under extreme operating conditions, the finishing liquors are stable for at least 8 hours.

Claims (10)

1. Use of water-soluble salts of amines of the general formula (I)

   

   in which R₁, R₂ and R₃ independently of one another denote an alkyl radical having 1 to 22 C atoms or hydrogen, with the proviso that at least one alkyl radical having at least 8 C atoms is present and the total of the C atoms in the alkyl radicals is not more than 33, preferably not more than 22, An denotes an anion and x denotes an integer corresponding to the negative charges of the anion, as an addition to aqueous liquors for water-and/or oil-repellant treatment of fibre materials, the aqueous liquors containing at least one silicone or one organic fluorine compound.
2. Use according to Claim 1, characterised in that the salts are employed in amounts of 1 to 10, in particular 2 to 6 g/l.
3. Use according to Claim 1 or 2, characterised in that R, denotes an alkyl radical having 8 to 10 or 16 to 18 C atoms and R₂ and R₃ denote hydrogen or the methyl radical.
4. Use according to one or more of Claims 1 to 3, characterised in that An denotes a monovalent anion and x accordingly denotes 1.
5. Use according to one or more of Claims 1 to 4, characterised in that An denotes formate, glycolate, lactate, chloride, nitrate or, in particular, acetate.
6. Use according to one or more of Claims 1 to 5, characterised in that stearylammonium acetate, octylammonium acetate, tallow fat-ammonium acetate and/or octadecyldimethylammonium acetate is used as the amine salt.
7. Use according to one or more of Claims 1 to 6, characterised in that the salts are employed in the form of aqueous solutions which contain 10 to 30, in particular 18 to 25% by weight of amine salt (calculated as the solid).
8. Use according to one or more of Claims 1 to 7, characterised in that the liquors additionally contain customary emulsifiers, in particular non-ionic and/or weakly cationic emulsifiers.
9. Use according to Claim 8, characterised in that the emulsifiers have been added in amounts of 10 to 40% by weight, based on the amine salt.
10. Use according to one or more of Claims 1 to 9, characterised in that the liquors additionally contain customary foam suppressants in the customary amounts.