GB1601758A

GB1601758A - Fluid aqueous textile softener

Info

Publication number: GB1601758A
Application number: GB1956378A
Authority: GB
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1977-05-16
Filing date: 1978-05-15
Publication date: 1981-11-04
Also published as: DE2722079B2; CH638002A5; DE2722079C3; FR2391312A1; FR2391312B1; DE2722079A1

Abstract

The liquid aqueous textile softener contains as the active ingredient from 10 to 30 per cent by weight of condensates of 1 mol of a dialkylenetriamine or trialkylenetetramine, wherein the alkylene moieties have 2 to 3 carbon atoms, and from 1.8 to 2.9 mol of fatty acids of 16 to 18 carbon atoms in a solution that has been rendered acidic with a water-soluble acid. The textile softener additionally contains from 5 to 30 % by weight, based on said active ingredient, of compounds of the formula I. The substituents in the formula I have the meanings specified in Claim 1. The textile softener can be prepared by adding from 5 to 30 % by weight, based on said active ingredient, of a compound of the formula I to a textile softener that contains the abovementioned active ingredient. <IMAGE>

Description

(54) FLUID AQUEOUS TEXTILE SOFTENER (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:- The resent invention relates to the fluidizing of an inherently pasty aqueous textile softener based on a weakly acidic solution of a polyalkylene polyamine/fatty acid condensate.

It has long been conventional practice to finish cellulosic or synthetic fibers, filaments or yarns with a softener to enable them to be converted to woven or knitted fabrics, and also to treat textiles, after washing or dyeing, with a softener to give a smooth, pleasant hand. A large number of softeners has been disclosed. For example, an aqueous textile softener which contains, as the active softening ingredient, a condensate of 1 molar proportion of dialkylenetriamine or trialkylenetetramine and from 1.8 to 2.9 molar proportions of fatty acid (of which up to about one-third may be unsaturated) of 16 to 18 carbon atoms, in acid solution, has proved very effective. The condensate consists of a mixture of the corresponding amides and of cyclic compounds (imidazolines and tetrahydropyrimidines).On working such a condensate into a paste with boiling water in the presence of an inorganic or organic acid, an aqueous formulation is obtained which, if it contains from 10 to 30 percent by weight of active softening ingredient is a stiff paste at room temperature, ie. is highly viscous and not pourable, and cannot be diluted with cold water to the use concentration.

If an attempt is made to lower the viscosity of this stiff aqueous paste formulation by adding a surfactant, and thereby to make the formulation easier to handle, a certain effect is achieved only if a relatively large amount (from 30 to 50 percent by weight, based on active softener ingredient) of a non-ionic oxyalkylation product of the type of alcohols of 9 to 15 carbon atoms which have been subjected to mixed oxyethylation/oxypropylation with from 10 to 20 moles of alkylene oxide is used.~TIowever, the products, only some of which are initially pourable, tend to thicken on standing. Furthermore, the addition of the above non-ionic oxyalkylation product has an adverse effect on the excellent softening action of the said fatty acid/polyamine condensate on cellulosic and synthetic fibers.

The present invention seeks to provide a way of fluidizing the above softener without a substantial adverse effect on its softening action.

According to the present invention there is provided a fluid aqueous textile softener which contains, as the active softening ingredient, from 10 to 30 percent by weight of a condensate of 1 molar proportion of dialkylenetriamine of trialkylenetetramine (where alkylene is of 2 or 3 carbon atoms) with from 1.8 to 2.9 molar proportions of one or more fatty acids of 16 to 18 carbon atoms in a solution acidified with a water-soluble acid, wherein there is further present from 5 to 30 percent by weight, based on the active softening ingredient, of a compound of the formula

where n is an integer from I to 4, R1 and R2 independently of one another are methyl or ethyl, R3 is hydrogen or methyl, R4 is alkyl of 7 to 15 carbon atoms, with the main chain being of at least 7 carbon atoms, and X is one equivalent of the anion of a water-soluble inorganic or organic acid.

The invention also provides a process for softening or reviving a textile by impregnating it with an aqueous softener solution and drying it, wherein impregnation is carried out with an aqueous solution which contains, as the softener, from 0.1 to 5 gfl of the active softening ingredient plus compound of the formula I as defined above.

The carboxylic acid component for the manufacture of the fluidizer of the formula I (i.e. the source of the radical R4CO-) may essentially consist of caprylic acid, pelargonic acid, capric acid, undecylic acid or tridecylic acid or, preferably lauric acid or myristic acid or mixtures of these, in particular coconut fatty acid. The fact that coconut fatty acid can be used shows that the presence of unsaturated acids and of acids of fewer than 8 or more than 16 carbon atoms does not interfere.

However, such acids contribute little of nothing to the fluidizing action.

The other starting component for the manufacture of the fluidizer of the formula I is an asymmetrically substituted alkylenediamine. Amongst these, dimethylaminopropylamine and diethylaminopropylamine are particularly preferred; they may be produced, for example, by adduct formation of dimethylamine or diethylamine with acrylonitrile, followed by hydrogenation of the nitrile group. Dialkylaminoethylamines can be prepared, for example, by reacting the dialkylamine with ethyleneimine. The corresponding reaction with propyleneimine gives the corresponding methyl derivative. A general method of obtaining unsymmetrically substituted alkylenediamines starts from the corresponding alkylenediamine, which is monoacylated, then dialkylated at the free amino group and thereafter hydrolyzed. These and other methods of preparation are prior art.

The condensation of the above components to form the compound of formula I may be carried out in the conventional manner with or without an acid catalyst, and with removal of the water of reaction. For example, the process may be carried out in a melt, in which case the- reaction mixture is heated to a sufficiently high temperature that the water formed in the reaction is easily removable. Preferred temperatures are from 120 to 2000C. The water of reaction may be removed by means of an inert gas or of an azeotrope-forming substance, for example an aromatic or aliphatic hydrocarbon, eg. benzene, xylene, toluene, cyclohexane or gasoline.

Water-soluble, preferably monobasic, inorganic or organic acids are employed for forming the salt I. For economic reasons, inexpensive industrially manufactured acids, eg. hydrochloric acid. formic acid and acetic acid, are preferred. The acid is suitably employed in such amount that a 2% by weight strength aqueous solution of the salt has a pH of from 2 to 7, preferably from 3 to 5.

At a higher pH, the fluidizing effect is substantially less, whilst a lower pH is unnecessary.

The amount of fluidizer of the formula I in the softener is from 5 to 30, preferably from 15 to 25, percent by weight based on the active softening ingredient of the softener. These relatively small amounts have little effect on the softening action.

The conventional softener solution, without the fluidizer according to the invention, can advantageously be prepared as follows: the condensate is fused, the acid is added, the mixture is worked into a paste with about 4 times its amount by weight of boiling water, and the mixture is stirred for 10 minutes at about 95"C and left to cool slowly, while stirring.

To produce the fluid textile softener of the invention, the active softener ingredient and the fluidizer I can simply be fused together and then treated further as described above. Of course, alternative methods can also be used, for example, it is possible to prepare the aqueous solutions of the salt separately and then mix them, but this is involved and offers no advantages.

Compared to the conventional softeners based on the same compounds, the formulations of the invention are distinguished by their fluid consistency, resulting in greater ease of handling and metering, and in solubility in cold water. This is a substantial advantage in textile processing.

The formulation may be used in the manner conventionally employed with softeners. For example, the textile can be treated with the aqueous formulation at a concentration of either from 0.1 to 0.5 g of active softening ingredient+fluidizer per litre, using a long liquor, or of from 0.5 to 5 g of active softening ingredient+fluidizer per litre, using a short liquor on a padder; the pH of the liquor is advantageously 7 or less, preferably from 7 to 4.

After treatment, the textile goods are spin-dried or squeezed off, and then dried in the conventional manner.

The softener of the invention can also be used conjointly with other non-ionic or cationic textile treatment agents, eg. with basic dyes for dyeing polyacrylonitrile fibers. In such cases, the conventional conditions of use of these conventional agents can as a rule be retained. Other assistants which may be employed simultaneously with the softeners according to the invention are, for example, levelling agents, wetting agents and resin finishes. These may be present in solution or dispersion. It is only anionic substances which as a rule cannot be employed in the same liquor.

In the Examples, percentages are by weight.

Tests: Storage at +100C: the sample is stored in a 50 ml bottle for 24 hours at +100C and is then tested as to whether it is still easily pourable at the same temperature.

Viscosity, measured after 24 hours storage at 2-0 C: 100 ml Ford cup, 4 mm nozzle, flow time in seconds.

Softening action: Greige high bulk polyacrylonitrile, Nm 28/2, shrunk and washed, or cotton yarn, Nm 34/2, kier-boiled and bleached, is treated for 15 minutes, using a liquor weight ratio of 30:1, with 1 g/l of the softener formulation shown in Table 1 or 2, at pH 5 and 45"C, then spin-dried to 50% by weight moisture content (for polyacrylonitrile) of 100% by weight moisture content (for cotton), dried at 800C and conditioned for 48 hours.

Active softener ingredients 1. Condensate of 2.2 moles of technical-grade stearic acid and 1 mole of diethylenetriamine; acid number=3.7 mg of KOH/I g of substance.

2. Condensate of 2.5 moles of technical-grade stearic acid and 1 mole of diethylenetriamine; acid number=16 mg of KOHIl g of substance.

3. Condensate of 2.8 moles of technical-grade stearic acid and 1 mole of diethylenetriamine; acid number=19.5 mg of KOHIl g of substance.

4. Condensate of 2.2 moles of technical-grade stearic acid and I mole of dipropylenetriamine; acid number=14.6 mg of KOH/I g of substance.

5. Condensate of 2.2 moles of technical-grade stearic acid and 1 mole of 3 (2 - aminoethyl) aminopropylamine; acid number=9.5 mg of KOH/1 g of substance.

6. Condensate of 2.9 moles of technical-grade stearic acid and 1 mole of N,N' - bis - (3 - aminopropyl) - ethylenediamine; acid number=12.5 mg of KOH/I g of substance.

7. Condensate of 2.2 moles of technical-grade stearic acid, 0.6 mole of oleic acid and I mole of diethylenetriamine; acid number=19 mg of KOH/I g of substance.

Fluidizer of the formula I a) 3-Dimethylaminopropylamide of hardened coconut fatty acid (composition of the fatty acid: C8 about 7%; C,0 about 7%; C12 about 48%; C,4 about 18%; C,6 about 8%; C,8 about 11%).

b) Lauric acid 3-dimethylaminopropylamide.

c) Myristic acid 3-dimethylaminopropylamide.

d) 3-Diethylaminopropylamide of hardened coconut fatty acid.

e) 4-Diethylamino-l-methylbutylamide of hardened coconut fatty acid.

TABLE 1 Examples according to the Invention

pH (10 g of softener Viscosity at Ford cup made up to l00ml +l00Cafter flow time

Example Softener composition with water) 24 hours at +20 C 1 20% of a) 3.9 easily pourable 35 seconds 2% of a) 1.5% of formic acid

76:5o:: of water 2 20% of 1) 3.4 easily pourable 27 seconds 3% of a) 2% of formic acid 75% of water 3 20% of 1) 3.7 easily pourable 17 seconds 4% of a) 2% of formic acid 74% of water 4 20% of 1) 3.9 easily pourable 18 seconds 4% of b) 2% of formic acid 74% of water 5 20% of 1) 3.5 easily pourable 45 seconds 4% of c) 2% of formic acid 74% of water 6 2% of 1) 3.8 easily pourable 42 seconds 4% of d) 2% of formic acid 74% of water 7 20% of 1) 3.7 easily pourable 19 seconds 4% of e) 2% of formic acid 74% of water 8 20% of 1) 3.9 easily pourable 32 seconds 4%ofa) 1.8% of concentrated HCI 74.2% of water 9 20% of 1) 4.2 easily pourable 27 seconds 4% of a) 3% of acetic acid 73% of water 10 20% of 2) 3.5 easily pourable 35 seconds 4% of a) 2% of formic acid 74% of water 11 20% of 3) 3.4 easily pourable 32 seconds 4% of a) 2% of formic acid 74% of water TABLE 1 (cont.) Examples according to the Invention

pH (10 g of softener Viscosity at Ford cup made up to 100 ml +100C after flow time Example Softener composition with water) 24 hours at + 20 C 12 20% of 4) 3.8 easily pourable 22 seconds 4%ofa) 2% of formic acid 74% of water 13 20% of 5) 3.7 easily pourable 18 seconds 4% of a) 2% of formic acid 74% of water 14 20% of 6) 3.9 easily pourable 25 seconds 4% of a) 2% of formic acid 74% of water 15 20% of 7) 3.6 easily pourable 16 seconds 4%ofa) 2% of formic acid 74% of water TABLE 2 Compataive Examples

pH l l

(lOg of softener Viscosity at Ford cup Comparative made up to 100 ml +10 C after flow time Example Softener composition with water) 24 hours at +20 C

1 20% of 1) 3.8 stiff paste not measurable 1.2% of formic acid (paste) 78.8% of water 2 20% of 2) 3.4 stiff paste not measurable 1.2% of formic acid (paste) 78.8% of water 3 20% of 3) 3.8 stiff paste not measurable 1% of formic acid (paste) 79% of water 4 20% of 4) 3.9 soft, non- not measurable 1.2% of formic acid pourable paste (paste) 78.8% of water 5 20% of 5) 3.6 stiff paste not measurable 1.5% of formic acid (paste) 78.5% of water 6 20% of 6) 3.8 stiff paste not measurable 1.5% of formic acid (paste) 78.5% of water 7 20% of 7) 3.9 stiff paste not measurable 1% of formic acid (paste) 79% of water TABLE 2 (cont.) Comparative Examples

pH (10 g of softener Viscosity at Ford cup Comparative made up to 100 ml +l00C after flow time Example Softener composition with to water) 24 hours at +20 C 8 20% of 1) 4.1 stiff paste not measurable 2.5% of acetic acid (paste) 77.5% of water

9 20% of 1) 3.9 stiff paste not measurable 1% of concentrated (paste) MCI 79% water of water 10 20% of 1) 3.9 soft, non- not measurable 8% of a Cg,11 oxo- pourable paste (paste) alcohol reacted with 9 moles of ethylene oxide+7 moles of propylene oxide (used as the mixed oxide) 1.2% of formic acid 70.8% of water 11 20% of 1) 3.9 soft, non- not measurable 8% of a C1ar5 oxo- pourable paste (paste) alcohol reacted with 8 moles of ethylene oxide+4 moles of propylene oxide (used as the mixed oxide) 30 1.2% of formic acid 70.8% of water The first 9 formulations in Table 2 have an excellent softening and smoothing action both on polyacrylonitrile and on cotton. The effect is only very slightly reduced by adding the fluidizer to these formulations (resulting in the Examples according to the invention, in Table 1).The addition of an oxyalkylated fatty alcohol to the stearic acid/polyamine condensate (Comparative Examples 10 and 11 in Table 2) on the other hand very markedly worsens the hand of the yarns, which become rough, dull and straw-like.

WHAT WE CLAIM IS: 1. A fluid aqueous textile softener which contains, as active softening ingredient, from 10 to 30 percent by weight of a condensate of I molar proportion of dialkylenetriamine or trialkylenetetramine (where alkylene is of 2 or 3 carbon atoms) with from 1.8 to 2.9 molar proportions of one or more fatty acids of 16 to 18 carbon atoms in a solution acidified with a water-soluble acid, wherein there is further present from 5 to 30 percent by weight, based on the active softening ingredient, of a compound of the formula

where n is an integer from 1 to 4, R' and R2 independently of one another are methyl or ethyl, R3 is hydrogen or methyl, R4 is alkyl of 7 to 15 carbon atoms, with the main cham being of at least 7 carbon atoms, and X- is one equivalent of the anion of a water-soluble inorganic or organic acid.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

TABLE 2 (cont.) Comparative Examples

pH (10 g of softener Viscosity at Ford cup Comparative made up to 100 ml +l00C after flow time Example Softener composition with to water) 24 hours at +20 C 8 20% of 1) 4.1 stiff paste not measurable 2.5% of acetic acid (paste) 77.5% of water

9 20% of 1) 3.9 stiff paste not measurable 1% of concentrated (paste) MCI 79% water of water 10 20% of 1) 3.9 soft, non- not measurable 8% of a Cg,11 oxo- pourable paste (paste) alcohol reacted with 9 moles of ethylene oxide+7 moles of propylene oxide (used as the mixed oxide) 1.2% of formic acid 70.8% of water 11 20% of 1) 3.9 soft, non- not measurable 8% of a C1ar5 oxo- pourable paste (paste) alcohol reacted with 8 moles of ethylene oxide+4 moles of propylene oxide (used as the mixed oxide) 30 1.2% of formic acid 70.8% of water The first 9 formulations in Table 2 have an excellent softening and smoothing action both on polyacrylonitrile and on cotton. The effect is only very slightly reduced by adding the fluidizer to these formulations (resulting in the Examples according to the invention, in Table 1).The addition of an oxyalkylated fatty alcohol to the stearic acid/polyamine condensate (Comparative Examples 10 and 11 in Table 2) on the other hand very markedly worsens the hand of the yarns, which become rough, dull and straw-like.

WHAT WE CLAIM IS:

1. A fluid aqueous textile softener which contains, as active softening ingredient, from 10 to 30 percent by weight of a condensate of I molar proportion of dialkylenetriamine or trialkylenetetramine (where alkylene is of 2 or 3 carbon atoms) with from 1.8 to 2.9 molar proportions of one or more fatty acids of 16 to 18 carbon atoms in a solution acidified with a water-soluble acid, wherein there is further present from 5 to 30 percent by weight, based on the active softening ingredient, of a compound of the formula

where n is an integer from 1 to 4, R' and R2 independently of one another are methyl or ethyl, R3 is hydrogen or methyl, R4 is alkyl of 7 to 15 carbon atoms, with the main cham being of at least 7 carbon atoms, and X- is one equivalent of the anion of a water-soluble inorganic or organic acid.

2. A fluid aqueous textile softener as claimed in claim 1 wherein in the formula

I R4C(O) is the acyl radical of lauric or myristic acid.

3. A fluid aqueous textile softener as claimed in claim 1 wherein in the formula I R2~NH(R')(CH2)nCH(R3)NH is the amino radical of dimethylaminopropylamine or diethylaminopropylamine.

4. A fluid aqueous textile softener as claimed in claim 1, wherein the compound of the formula I is produced from 1 mole of dimethylaminopropylamine and 1 mole of coconut fatty acid.

5. A fluid aqueous textile softener as claimed in any of claims 1 to 4, wherein such an amount of water-soluble acid is employed in the manufacture of the compound of the formula I that a 2% by weight strength aqueous solution of the compound has a pHof from 2 to 7.

6. A fluid aqueous textile softener as claimed in claim I and described in any of the Examples in the foregoing Table 1.

7. A process for fluidizing an aqueous textile softener which contains, as the active softening ingredient, from 10 to 30 percent by weight of a condensate of 1 molar proportion of dialkylene-triamine or trialkylenetetramine (where alkylene is of 2 or 3 carbon atoms) with from 1.8 to 2.9 molar proportions of one or more fatty acids of 16 to 18 carbon atoms in a solution acidified with a water-soluble acid, wherein fluidizing is effected by adding from 5 to 30 percent by weight, based on the active softening ingredient, of a compound of the formula I defined in claim 1.

8. A process for softening or reviving a textile by impregnating it with an aqueous softener solution and drying it wherein impregnation is carried out with an aqueous solution which contains, as the softener, from 0.1 to 5 g/l of the active softening ingredient plus compound of the formula I as defined in any of claims 1 to 6.

9. Textile material which has been treated by a process as claimed in claim 8.