EP0213519A2 - Textile-treating composition - Google Patents

Abstract

A textile treatment composition comprising a mixture of (A) a dispersion accelerator selected from aldoses and ketoses; polyhydroxyl compounds obtained therefrom by hydrogenation; natural and synthetic hydrophilic polymers; and mixtures thereof; and (B) a fatty acid condensation product obtained by reacting aliphatic C8-C22 monocarboxylic acids or amide-forming derivatives thereof with polyamines and subsequent neutralization of unreacted amino groups; a process for producing such composition; and methods for its use. Preferably, the polyamines correspond to the formula <IMAGE> wherein: R is hydrogen, methyl, ethyl, or hydroxyethyl, R1 is hydrogen, methyl, ethyl, hydroxyethyl, or -(CH2)n-NHR, n is 2 to 4, and m is 1 to 4.

Description

The invention relates to textile treatment agents based on condensation products of carboxylic acids or carboxylic acid derivatives with polyamines, which are particularly well dispersible in water by the addition of dispersion accelerators, a process for their preparation and their use. In the context of this invention, textile treatment agents are understood to mean products which can be used in agents for finishing fibers and yarns, in detergents and in post-treatment agents for washed textiles.

For the treatment of textile fibers, yarns or fabrics, a large number of compounds or mixtures of substances are proposed which impart particularly valuable properties to the textiles treated therewith or which are components of agents for particularly effective textile care. Depending on the type of active ingredients used, the processing properties, the wearing properties of the textiles and their care can be improved. For example, U.S. Patent 2,340,881 describes condensation products made from a hydroxyalkyl polyamine and a fatty acid glyceride. These condensation products improve the lubricity and softness of the textiles treated with them. According to the teaching of this patent, the condensation products are used in the form of their aqueous dispersions. US Pat. No. 3,454,494 relates to fatty acid condensation products with an addition of dispersing polyoxyalkylene compounds. The German patent 19 22 046 describes detergents containing fatty acid condensation products from their manufacture hereby contain dispersing fatty acid glycerides; German patent specification 19 22 047 also describes these fatty acid condensation products as textile softeners for, in particular, liquid laundry aftertreatment agents. These and similar textile treatment agents can be dispersed in water by heating the water and usually using high shear forces, or by dispersing the condensation product, which has still been melted, in water. Because of the effort required, the manufacturer usually carries out the dispersion and delivers the dispersions to the user, which is associated with the transport of considerable amounts of water. There is therefore a need for textile treatment agents based on fatty acid condensation products with improved dispersibility in water, so that the user can easily carry out the dispersion of the textile treatment agents in water.

This object was achieved in that the fatty acid condensation products which are prepared by reacting a) aliphatic monocarboxylic acids having 8 to 22 carbon atoms or derivatives forming amides with b) polyamines and then neutralizing unreacted amino groups with lower carboxylic acids are dispersion accelerators which are produced from selects from the group of monosaccharides of the aldose and ketose type and the polyhydroxy compounds derived therefrom by hydrogenation and the natural and synthetic hydrophilic polymers, in amounts such that the textile treatment agents are quickly dispersible even in cold water in a short time.

Among the amide-forming derivatives of aliphatic monocarboxylic acids are the esters derived from natural or synthetic saturated or mono- or polyunsaturated, branched or unbranched fatty acids or fatty acid mixtures with lower alkanols, such as, for example To understand methanol or ethanol, the fatty acid glycerides and the fatty acid halides. For example, these are the derivatives derived from lauric acid, myristic acid, palmitic acid, stearic acid, coconut fatty acid, tallow fatty acid or rapeseed oil acid. The reaction products which can be produced from this by reaction with polyamines are referred to below as fatty acid condensation products.

Suitable polyamines correspond to the formula

In this formula, R = hydrogen, methyl, ethyl or hydroxyethyl, R = hydrogen, methyl, ethyl, hydroxyethyl or - (Ch ₂ ) _n -NHR, n means an integer between 2 and 4, m means an integer between 1 and 4. Suitable polyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, propylenediamine, di (trimethylene) triamine and in particular aminoethylethanolamine.

Lower carboxylic acids which are suitable for neutralizing unreacted amino groups are compatible, in particular low molecular weight organic mono- or polycarboxylic acids which are optionally substituted by hydroxyl groups, such as glycolic acid, citric acid, lactic acid or acetic acid, in the treatment environment.

The monosaccharides of the aldose and ketose type or their hydrogenation products which can be used as dispersion accelerators have 4, 5 or in particular 6 carbon atoms in the molecule. Examples are fructose, sorbose and in particular glucose, sorbitol and mannitol, which are inexpensive and effective. Natural or synthetic hydrophilic polymers are also suitable as dispersion accelerators. A preferred one natural polymer of this class is gelatin. Mixtures of gelatin and monosaccharides or their hydrogenation products are particularly suitable. Other useful natural hydrophilic polymers are e.g. B. guar, dextrin, gum arabic, agar agar, casein. Of the synthetic hydrophilic polymers, homopolymers or copolymers based on polyvinyl alcohol, polyacrylic acid and polyvinylpyrrolidone should be mentioned in particular. The suitable polymers have in common that they are easily soluble or dispersible or swellable in water.

The additions of dispersion accelerators required to achieve rapid dispersibility in a short time are in particular in the range from 0.5 to 10% by weight, based on the amount of dispersion accelerator and fatty acid condensation product. The dispersion accelerators are particularly effective if they are present in an intimate mixture with the fatty acid condensation product and, if appropriate, further additives of the textile treatment agent. Any type of mixing technique that leads to an intimate mixture of different components is generally suitable; It has proven particularly useful, however, if the melt of the fatty acid condensation product is mixed with the dispersion accelerator. This mixture thus obtained is then, for example, converted into particle form. Textile treatment agents which contain monosaccharides and / or their hydrogenation products, in particular glucose, sorbitol, mannitol or mixtures thereof, preferably in amounts of 5 to 10% by weight, as well as textile treatment agents which contain 5 to 10% by weight of gelatin as dispersion accelerators contain, especially good properties. The same applies to agents containing mixtures of monosaccharides and / or their hydrogenation products with gelatin as dispersion accelerators. A short time is understood as the duration of the mixing process with water until a dispersion of 0.1 to 2% is achieved. This time requirement is 10 to 20 minutes with stirring.

In some cases, the presence of further dispersing agents, for example fatty alcohol alkoxylates or oxo alcohol alkoxylates with 10 to 20 carbon atoms in the alcohol component and with 2 to 50 moles of alkylene oxide, in particular ethylene oxide and / or propylene oxide, preferably tallow alcohol + 50 moles of ethylene oxide or coconut alcohol + 5 moles of ethylene oxide + 4 Moles of propylene oxide, partial fatty acid glycerides and / or water-miscible solvents such as propylene glycol or glycerin are useful. The amount of additional dispersing aids in the textile treatment agents according to the invention can make up 0.5 to 70% by weight of the textile treatment agent.

The present invention further relates to a method for producing the textile treatment agent. The process according to the invention is characterized in that the fatty acid condensation products are intimately mixed with the dispersion accelerator and, if appropriate, other auxiliaries, and the mixture is processed into powder or shaped articles, preferably into flakes. An intimate mixture of fatty acid condensation product and dispersion accelerator is obtained in particular if the molten fatty acid condensation product is mixed with the dispersion accelerator and, if appropriate, the other constituents, the mixture is allowed to cool and then further processed into powder or molded articles. In the production of the fatty acid condensation products known per se, for example, the fatty acid or the fatty acid derivative and the polyamine are used in a molar ratio of 1: 1 to 3: 1 (carboxylic acid to polyamine). The reaction components are heated with constant mixing until virtually all the fatty acid or the fatty acid derivative has been reacted. Then any unreacted amino groups are neutralized with low molecular weight organic carboxylic acids or hydroxycarboxylic acids, for example by mixing the melt of the fatty acid condensation product with the calculated amount of acid, or the amine salt is formed Dissolving or dispersing the reaction product in the organic acid or a solution of the organic acid. The acid used for salt formation is used in a stoichiometric amount or in an up to about 30% excess. In a preferred embodiment of the process, the fatty acid condensation product is mixed with the degree of conversion of at least 95%, in particular at least 99%, at 80 to 150 ° C. with the dispersion accelerator and optionally with other additives in the melt, the mixture with the low molecular weight organic carboxylic acid or hydroxycarboxylic acid neutralized and the neutralized fatty acid condensation product further processed into powder or moldings. Working in an inert gas atmosphere and / or the addition of a reducing agent in the condensation reaction leads to particularly light-colored products. Hypophosphorous acid has proven particularly useful as a reducing agent. The textile treatment agents according to the invention can easily be processed into stable dispersions in water, even in cold water. All you need to do is mix with water and then stir gently. The dispersions obtained are extremely stable and do not tend to separate. The dispersions of textile treatment agents are used in a variety of ways to treat fibers, yarns or fabrics. The treatment of fibers or yarns is carried out using methods that are customary in textile technology, such as pull-out, immersion centrifugal, foulard or spray processes.

When the textile treatment agents according to the invention are used in detergents, they bring about an improved cleaning effect and / or a softening of the laundry washed therewith. Finally, the textile treatment agents according to the invention can also be used as components of aftertreatment agents for washed textiles, as a result of which the textiles become soft and antistatic. The aftertreatment of the washed textiles can usually be done in the last rinsing bath but also take place during drying in an automatic tumble dryer, either spraying the laundry with a dispersion of the agent during drying or using the agent, applied to a substrate, for example a flexible, textile fabric. Depending on the type of textile treatment, the products according to the invention can have different compositions, ie the fatty acid condensation products can contain a more or less large fatty acid component, or a fatty acid component with fatty acid residues of different lengths. For the treatment of fibers and yarns and for the aftertreatment of washed textiles, those products according to the invention which have a proportion of 0.7 to 1 fatty acid residue, which is preferably saturated, with essentially 16 to 22 carbon atoms on a functional group of the Have polyamines, that is, amino or hydroxyl group. The aftertreatment agents according to the invention are also excellently suitable for the production of aqueous textile softener concentrates which, instead of the usual active substance concentration of approximately 5% by weight, have an active substance concentration of 10 to approximately 50% by weight. For use in detergents, those products are preferably selected which have condensation products from shorter fatty acid residues, ie with essentially 8 to 18 carbon atoms and a proportion of 0.3 to 1, preferably 0.3 to 0.5, fatty acid residues per functional group of the polyamine . Particularly good results are obtained with reaction products of this type which are derived from coconut fatty acid and dimethylaminopropylamine.

Example example 1

A known fatty acid condensation product suitable for textile finishing was prepared by adding 405 g (1.5 mol) technical stearic acid and 104 g (1 mol) aminoethylethanolamine in a three-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and distillation head within 2.5 Heated to 200 ° C. under a nitrogen blanket, during which time water split off. The reaction was continued until approximately 99% of the stearic acid was converted. The conversion was monitored by determining an acid number (analogous to determining the acid number in fats and oils) by titration with potassium hydroxide. After an acid number of 1.5 was reached, the mixture was cooled to 90 ° C. and the free amino groups were neutralized with glacial acetic acid. The homogeneous melt could be converted on a scale roller into yellow, non-adhesive scales with a melting point of approx. 63 ° C.

Example 2

The procedure was as in Example 1, but the neutralized melt was mixed with 5% by weight of sorbitol before the formation of flakes.

Example 3

746.5 kg of technical stearic acid (2816 mol) were melted under nitrogen at 80 ° C. in an Edeista steel stirred tank. One after the other, 192.1 kg of aminoethylethanolamine (1847 mol) and 1 kg of 50% hypophosphorous acid as an antioxidant were stirred into the melt. The mixture was heated to 150 ° C. at which distillate formation began. The contents of the kettle were heated to 200 ° C. within 2.5 hours and 1 Stirred at 200 C for one hour. A total of 50 kg of distillate was obtained; the acid number of the reaction mixture was below 5. The mixture was cooled to 100 ° C. and the contents of the kettle were mixed first with 48.0 kg of sorbitol and then with 62.9 kg of concentrated acetic acid. When the mixture was homogeneous, the melt was scaled on a scale roller. Pale yellow scales were obtained.

Example 4

420 kg of technical stearic acid (1584 mol) were melted under nitrogen at 80 ° C. in a stainless steel stirred container. Then 108 kg of aminoethylethanolamine (1038 mol) and 0.5 kg of 50% hypophosphorous acid were first mixed with the stearic acid. After heating to 150 ° C, water separation began. The mixture was heated to 200 ° C. in the course of 2.5 hours and stirred at this temperature for 1 hour. 28 kg of distillate were obtained, the acid number of the reaction mixture was below 2. Then the mixture was cooled to 125 ° C. and 50 kg of C _12/14 fatty alcohol + 5 mol of ethylene oxide + 4 mol of propylene oxide, 50 kg of sorbitol and 366 kg of tallow alcohol were stirred in succession + 40 moles of ethylene oxide. After 15 hours the melt was homogeneous. The mixture was cooled to 100 ° C. and 34 kg of concentrated acetic acid were mixed with the melt, which was then shaped into light yellow scales on a scale roller.

Example 5

A 2.5 g sample of the flaky material from Examples 1 and 2 was stirred into a beaker with 500 ml of deionized water at 20 ° C. (blade stirrer, 150 revolutions per minute). The time to complete dispersion was over 90 minutes for the material from Example 1 and only 15 minutes for the material according to the invention from Example 2. The products from Examples 3 and 4 were completely dispersed in less than 15 minutes.

Example 6

₁₀ g of the product from Example 4 were poured over 90 g of water in a beaker and left to stand. After 6 hours, the mixture was stirred gently. A homogeneous, stable dispersion was formed in which no individual particles were visible to the naked eye. After filtration through a fine-mesh, black polyester fabric with a mesh size of approx. 0.1 mm, no visible residues remained.

Example 7

With a textile treatment liquor containing 30 g of a 10% stock liquor per liter of water, prepared by sprinkling the product of Example 2 in cold Ylasser and stirring for 30 minutes at room temperature, cotton terry toweling was used at 45 ° C for 20 minutes Liquor temperature (liquor ratio 1:20) treated in the drawing process and dried for 3 minutes at 120 ° C. Similarly, after the padding process, cotton-polyester fabric with a liquor; which, in addition to customary textile finishing agents, contained 60 g of a 10% stock liquor (produced as described above) of the product from Example 4, treated and dried per liter of water. In both cases, fabrics were obtained that were not discolored and had a pleasantly soft feel.

Example 8

5% by weight of mannitol was added to the neutralized melt of the fatty acid condensation product from Example 1 as a dispersion accelerator. The textile treatment agent according to the invention thus obtained had properties as shown in the Examples 6 and 7 were described for the products of Examples 2 and 4, respectively. If the same amount of glucose or gelatin was used as the dispersion accelerator, similar results were obtained.

Example 9

If 10% by weight of sorbitol, mannitol, glucose or gelatin was added to the condensation product of Example 1, the time for a complete dispersion of the textile treatment agent according to the test method given in Example 5 was less than 15 minutes.

Example 10

Condensation products which had been prepared according to Example 1, from stearic acid and an equimolar mixture of diethylenetriamine and triethylenetetramine and had been converted into an easily dispersible form by adding a dispersion accelerator according to Examples 2, 8 and 9, had properties comparable to those in Examples 5, 6 and 7 described on.

Example 11

As described in Example 3, a condensation product of hydrogenated tallow and aminoethylethanolamine was prepared in equimolar amounts. With 5 or 10 weight percent additions of sorbitol, mannitol, glucose, gelatin and with 1: 1 mixtures of gelatin with sorbitol, mannitol or glucose, textile treatment agents were obtained which behaved similarly to the textile treatment agents according to the invention described above.

Example 12

As described in Example 3, a condensation product was prepared from coconut oil and aminoethylethanolamine (molar ratio 0.5: 1). With 5 or 10 weight percent additions of sorbitol, mannitol, glucose, gelatin and with 1: 1 mixtures of gelatin with sorbitol, mannitol or glucose, textile treatment agents were obtained which behaved in terms of their dispersion rate as the textile treatment agents according to the invention described above.

Example 13

5% by weight of gelatin were added to a fatty acid condensation product according to Example 11. A textile treatment liquor was produced from the textile treatment agent thus obtained, according to Example 7, with which textiles from cotton terry toweling fabric were treated for 7 minutes at room temperature. After drying, non-discolored fabrics were obtained which had a pleasantly soft feel.

Example 14

wurden 3,0 Gew.-% eines erfindungsgemäßen Textilbehandlungsmittels, hergestellt durch Umsetzung von Kokosfettsäure (mindestens 50 % C₁₂/C₁₄-Fettsäure) mit N,N-Dimethylaminopropylamin (Molverhältnis 1 : 1) unter Zusatz von 5 Gew.-% Sorbit zugesetzt. Mit diesem Waschmittel wurden künstlich mit Makeup-Creme, Wimperntusche und Lippenstift angeschmutzte Baumwolltextilien zusammen mit Ballastwäsche gewaschen. Zum Vergleich wurde mit einem Waschmittel ohne Zusatz eines erfindungsgemäßen Textilbehandlungsmittels gewaschen. Die mit dem Waschmittel, welches den Zusatz des erfindungsgemäßen Textilbehandlungsmittels enthielt, gewaschenen Prüftextilien waren deutlich sauberer als die mit dem Waschmittel ohne Zusatz des erfindungsgemäßen Textilbehandlungsmittels gewaschenen Prüftextilien. Ähnliche Ergebnisse erhält man, wenn man dem Waschmittel 3 Gew.-% erfindungsgemäße Textilbehandlungsmittel mit 5 Gew.-% Sorbit auf der Basis von C₈- bis C10-Fettsäure, Ölsäure, hydrierter Talgfettsäure und Ricinolsäure mit Dimethylaminopropylamin bzw. mit Aminoethylethanolamin zusetzt.To a standard detergent (IEC test detergent with perborate, type 1 in the formulation from May 1976) with the following composition

3.0 wt .-% of a textile treatment agent according to the invention, prepared by reacting coconut fatty acid (at least 50% C ₁₂ / C ₁₄ fatty acid) with N, N-dimethylaminopropylamine (molar ratio 1: 1) with the addition of 5 wt .-% sorbitol added. This detergent was used to wash cotton fabrics soiled artificially with makeup cream, mascara and lipstick together with ballast laundry. For comparison, washing was carried out with a detergent without the addition of a textile treatment agent according to the invention. The test textiles washed with the detergent which contained the addition of the textile treatment agent according to the invention were significantly cleaner than the test textiles washed with the detergent without addition of the textile treatment agent according to the invention. Similar results are obtained if 3% by weight of textile treatment agent according to the invention with 5% by weight of sorbitol based on C ₈ to C 10 fatty acid, oleic acid, hydrogenated tallow fatty acid and ricinoleic acid are added to the detergent with dimethylaminopropylamine or with aminoethylethanolamine.

Example 15

Zur llerstellung dieses Mittels vermischte man die Feststoffe bei ₈₀ °C in der Schmelze und rührte die Schmelze in Wasser vun 80 °C ein. Nach dem Abkühlen der gebildeten Dispersion fügte man den Duftstoff zu.This example describes the composition of a laundry aftertreatment agent.

To prepare this agent, the solids were mixed in the melt at ₈₀ ° C. and the melt was stirred into water at 80 ° C. After the dispersion formed had cooled, the fragrance was added.

To use the aftertreatment agent, the washed textiles were treated in a liquor which contained 3 g of the aftertreatment agent per liter of water. After drying, the textiles had a pleasant fragrance and a full, soft feel.

Claims (10)

_1st Textile treatment agents can be produced by reacting a) aliphatic monocarboxylic acids with 8 to 22 carbon atoms or their amide-forming derivatives with b) polyamines and subsequent neutralization of unreacted amino groups, characterized by the addition of dispersion accelerators, selected from the group of monosaccharides of the aldose and ketose type and the polyhydroxy compounds derived therefrom by hydrogenation and the natural and synthetic hydrophilic polymers in such amounts that the textile treatment agent can be dispersed rapidly in cold water in a short time. 2. Textile treatment agent according to claim 1, characterized in that the addition is 0.5 to 10 wt .-% dispersion accelerator, based on the amount of dispersion accelerator and fatty acid condensation product. 3. Textile treatment agent according to one of claims 1 or 2, characterized in that it contains the dispersion accelerator and optionally other additives in an intimate mixture. 4. Textile treatment agent according to one of claims 1 to 3, characterized in that it contains monosaccharides and / or their hydrogenation products, in particular glucose, sorbitol, mannitol or mixtures thereof, preferably in amounts of 5 to 10% by weight as dispersion accelerators. 5. Textile treatment agent according to one of claims 1 to 3, characterized in that it contains gelatin as a dispersion accelerator, preferably in amounts of 5 to 10% by weight. 6. Textile treatment agent according to one of claims 4 or 5, characterized in that it contains mixtures of monosaccharides and / or their hydrogenation products with gelatin as dispersion accelerators. 7. A process for the preparation of textile treatment agents according to one of claims 1 to 6, characterized in that the fatty acid condensation products are mixed intimately with dispersion accelerators, preferably in the melt, and the mixture is further processed into powder or molded articles, preferably into flakes. 8. Use of textile treatment agents according to one of claims 1 to 6 for finishing fibers, yarns or fabrics. 9. Use of textile treatment agents according to one of claims 1 to 6 in the washing of textiles. 10. Use of textile treatment agents according to one of claims 1 to 6 for the aftertreatment of washed laundry.