EP0454741A1

EP0454741A1 - Textile conditioners.

Info

Publication number: EP0454741A1
Application number: EP90902188A
Authority: EP
Inventors: Guenter Uphues; Uwe Ploog; Klaudia Bischof
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1989-01-23
Filing date: 1990-01-15
Publication date: 1991-11-06
Anticipated expiration: 2010-01-15
Also published as: BR9007045A; WO1990008217A1; KR970011243B1; US5238586A; DE3901820A1; EP0454741B1; AU4951590A; JPH04503088A; ATE90120T1; EP0379923A1; ZA90445B; ES2044555T3; KR910700377A; TR25133A; CA2008361A1; DE59001626D1

Abstract

PCT No. PCT/EP90/00075 Sec. 371 Date Jul. 23, 1991 Sec. 102(e) Date Jul. 23, 1991 PCT Filed Jan. 15, 1990 PCT Pub. No. WO90/08217 PCT Pub. Date Jul. 26, 1990.Textile treatment preparations based on the condensates of aliphatic monocarboxylic acids or amide-forming derivatives thereof with optionally hydroxyl-substituted polyamines and an addition of dispersion accelerators from the group of certain monosaccharides and hydrogenation products thereof, polyols and natural and synthetic hydrophilic polymers show particularly good dispersibility, even in cold water, if the amino groups unreacted during the condensation reaction are only partly neutralized with low molecular weight, optionally hydroxyl-substituted mono- or polycarboxylic acids.

Description

"Textile treatment agent"

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. The invention further relates to a method for producing the textile treatment agents and their use. Textile treatment agents in the context of this invention are understood to mean products which can be used in agents for finishing fibers and yarns, in detergents and in aftertreatment agents for washed textiles.

For the treatment of textile fibers, yarns or fabrics, a large number of compounds or fabrics are proposed which impart desired properties to the textiles treated therewith or which are components of agents for 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, US Pat. No. 2,340,881 describes condensation products made from a hydroxyalyl polyamine and a fatty acid glyceride. These condensation products improve the lubricity and the 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 acting polyoxyalkylene compounds. The German patent 19 22 046 describes detergents containing fatty acid condensation products which contain fatty acid partial glycerides which have a dispersing action; In German patent specification 19 22 047 these fatty acid condensation products are also described as textile softeners for liquid laundry aftertreatment agents in particular. 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 was still melted during manufacture, in water. Because of the effort required, the manufacturer therefore usually carries out the dispersion and delivers the dispersions to the user, which is associated with the transport of considerable amounts of water. According to the teaching of German patent application DE 35 30 302, such active substances are added with hydrophilic dispersion accelerators in order to improve the dispersibility. The effect of the dispersion accelerator is particularly good if, according to the teaching of German patent application P 37 30 792.4, these substances are already present in the reaction mixture during the condensation reaction. However, there is still a need for textile treatment agents based on fatty acid condensation products with improved dispersibility, especially in cold water, so that the user can easily carry out the dispersion of the textile treatment agents himself.

This object was achieved by a textile treatment agent which can be prepared by reacting a) aliphatic monocarboxylic acids with 8 to 22 carbon atoms or derivatives forming amides with b) optionally hydroxyl-substituted polyamines and subsequent neutralization of unreacted amino groups, the textile treatment agent an addition of dispersion accelerators, selected from the group of monosaccharides of the aldose and ketose type and the polyhydroxy compounds derived therefrom by hydrogenation, the polyols, such as, in particular, pentaerythritol, dipentaerythritol, trimethylolpropane, the alkylglycosides and the sorbitan esters , to which ethylene oxide is added if desired, and which contains natural and synthetic hydrophilic polymers, characterized in that the unreacted amino groups are neutralized to 20 to 80 mol%, in particular 30 to 60 mol%. In contrast to the complete neutralization with stoichiometric or excess amounts of acids, this partial neutralization with inferior amounts of acid surprisingly brings about improved dispersibility in cold water and a lighter color of the reaction product.

Amide-forming derivatives of aliphatic monocarboxylic acids are understood to mean the esters derived from natural or synthetic fatty acids or fatty acid mixtures with lower alkanols such as, for example, 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 fatty acid. The reaction products which can be produced from this by reaction with polyamines are mentioned below as fatty acid condensation products, which also include idazolines in the case of • reaction of diethylenetriamine with 2 mol of fatty acid or fatty acid derivatives.

Suitable polyamines are preferably derived from optionally hydroxyl-substituted ethylenediamine or diethylenetriamine, such as. B. of Dihydroxyethylenedia in, hydroxyethyldiethylenetriamine,

REPLACEMENT LEAF Hydroxypropyldiethylenetriamine, and in particular hydroxyethylethylenediamine. N, N-dimethyl-1,3-diaminopropane, triethylene tetramine or tetraethylene pentamine are also suitable.

For the neutralization of unreacted amino groups, lower carboxylic acids, in particular low-molecular organic mono- or polycarboxylic acids, optionally substituted by hydroxyl groups, such as glycolic acid, citric acid, lactic acid or acetic acid, are suitable. Also suitable are monobasic inorganic acids, such as. B. hydrochloric acid or sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid. In some cases it may be expedient to combine the reaction products according to the present invention with further textile treatment agents, for example with textile softeners. Particularly suitable as fabric softeners are the widely used dimethyl di (C8 to C22 alkyl / alkenyl) ammonium salts such as dimethyl ditallow alkyl amium chloride or dimethyl distearyl a monium chloride or methosulfate. It is then generally advantageous that the reaction products, in the partial neutralization of non-converted amino groups, are already present in a mixture with the other textile treatment active ingredients.

The monosaccharides of the Aldosen and Ketpsen 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. Polyols, such as, in particular, pentaerythritol, dipentaerythritol and trimethylolpropane are very suitable.

REPLACEMENT LEAF Suitable alkyl glycosides are obtained by the Fischer process by reacting monosaccharide with fatty alcohol in the presence of an acidic catalyst. Alkyl glycosides, the alkyl group of which contains up to 16 carbon atoms, have long been known as surfactants.

Suitable sorbitan esters are esters with saturated or unsaturated fatty acids with 10 to 20 carbon atoms, in particular sorbitan oleate. 2 to 20 moles of ethylene oxide can additionally be added to the sorbitan esters.

Natural or synthetic hydrophilic polymers are also suitable as dispersion accelerators. A preferred natural polymer in 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. Textile treatment agents which, as dispersion accelerators, monosaccharides and / or their hydrogenation products, in particular glucose, sorbitol, mannitol or mixtures thereof, preferably in Amounts of 2.5 to 10% by weight, just like textile treatment agents which contain 5 to 10% by weight of gelatin, have particularly good properties. The same applies to agents containing mixtures of monosaccharides and / or their hydrogenation products with gelatin as dispersion accelerators. Agents which contain 1 to 5% by weight of pentaerythritol as dispersion accelerators also have particularly good properties.

In some cases, the presence of further dispersants, 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, fatty acid partial glycerides and / or water-miscible solvents such as propylene glycol or glycerol are useful. The amount of additional dispersants 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 agents mentioned. The process according to the invention is characterized in that the unreacted amino groups are neutralized to 20 to 80 mol%, preferably to 30 to 60 mol%. In the production of the fatty acid condensation products known per se, for example, the fatty acid or the fatty acid derivative and the polya are used in a molar ratio of 1: 1 to 3: 1 (carboxylic acid to polyamine). The reaction components are heated, if appropriate in the presence of the dispersion accelerator, with constant mixing until virtually all the fatty acid or the fatty acid derivative is implemented. Then unreacted amino groups are neutralized with low molecular weight organic carboxylic acids or hydroxycarboxylic acids or monobasic inorganic 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 by dissolving or dispersing the reaction product in the organic acid or a solution of the organic acid. The acid used for salt formation is added according to the invention in such an amount as is necessary for the 20 to 80 mol%, preferably 30 to 60 mol% neutralization. If the dispersion accelerator has not already been added during the condensation reaction, the addition takes place after the neutralization. Working in an intergas 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 are obtained, for example, as powders, flakes or pellets and can easily be processed into stable dispersions in water, in particular also 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 the textile treatment agents are used in a variety of ways for the treatment of fibers, yarns or fabrics. The treatment of fibers or yarns is carried out according to methods customary in textile technology, such as pull-out, immersion centrifugal, padding or spraying methods.

When the textile treatment agents according to the invention are used in detergents, they bring about an improved cleaning action and / or a softening of the laundry washed therewith. The invented Finally, 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 carried out in the last rinsing bath but also during drying in an automatic tumble dryer, either by spraying the laundry with a dispersion of the agent during drying or by applying the agent to a substrate, for example flexible, textile fabric, applies. 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 0.5 to 1 fatty acid residue, which is preferably saturated, with essentially 16 to 22 carbon atoms have proven particularly useful. atoms on a functional group of the polyamine, that is, amino or hydroxyl group. The aftertreatment agents according to the invention are also excellently suitable for the production of aqueous fabric softener concentrates which, instead of the usual active ingredient concentration of about 5% by weight, have an active ingredient concentration of 10 to 50% by weight. For use in detergents, those products are preferably selected which contain condensation products from shorter fatty acid esters, ie with essentially 12 to 16 carbon atoms and a proportion of 0.3 to 1, preferably 0.3 to 0.5, fatty acid residues per functional Have group of hydroxyalkyl polyamine.

REPLACEMENT LEAF Examples

example 1

A fatty acid condensation product known per se suitable for textile finishing was produced by adding 1215 g (4.5 mol) technical stearic acid and 312 g (3 mol) A inoethylethanolamine in a three-necked flask provided with a stirrer, thermometer, gas inlet pipe and distillation attachment within heated from 2.5 hours to 200 ° C. under a nitrogen blanket and split off water. The reaction was continued until the acid number, determined by DGF method C-V 2, had dropped to a value of 2.0. The content of amine nitrogen still present, determined by titration with perchloric acid in acetic acid medium, was 1.65%. After cooling to 90 ° C., the melt was transferred on a flake roller into light yellow, non-adhesive flakes with a melting range of 64-67 ° C.

1 a.

250.0 g (0.293 equivalents of amine nitrogen) of the condensation product were melted and at 90-100 ° C. 6.2 g (0.102 mol) of acetic acid were added, followed by 10.7 g of sorbitol. The clear melt was then converted into light yellow, brittle flakes on a scale roller.

111

250.0 g (0.293 equivalents of amine nitrogen) of the condensation product were melted and mixed at 90-100 ° C. first with 11.1 g (0.102 mol) glycolic acid, 70%, and then with 10.9 g sorbitol puts. The clear melt was again converted into the scale form.

sl

250.0 g (0.293 equivalents of amine nitrogen) of the condensation product were melted and 11.3 g (0.1 mol) of lactic acid, 80%, and then 10.9 g of sorbitol were added at 90-100 ° C. The clear melt was again converted into the scale form.

1 d)

250.0 g (0.293 equivalents of amine nitrogen) of the condensation product were melted and, at 90-100 ° C., 10.1 g (0.102 mol) of hydrochloric acid, 37% and then 10.8 g of sorbitol were added. The clear melt was again converted into the scale form.

Example 2 (comparative example)

A product according to Example 1 was produced and further treated as follows:

250.0 g (0.293 equivalents of amine nitrogen) each of the condensation product were melted and mixed with the acids mentioned below and 10.8 g of sorbitol at 90-100 ° C. and then converted into the flake form.

2a) 17.8 g (0.293 mol) of acetic acid

2 b) 31.9 g (0.293 mol) glycolic acid, 70% 2 c) 32.5 g (0.293 mol) lactic acid, 80%

2 d) 29.0 g (0.293 mol) hydrochloric acid, 37%

Example 3 (comparative example)

250.0 g (0.293 equivalents of amine nitrogen) of a condensation product according to Example 1 were melted and at 90-100 ° C. only 11.1 g (0.102 mol) of 70% glycolic acid were added and then converted into the scale form.

Example 4

As described in Example 1, 351 g (1.3 mol) of technical stearic acid and 104 g (1 mol) of aminoethylethanolamine were reacted. After an acid number of 2.5 was reached, the reaction was terminated. The content of amine nitrogen still present was 2.31%. 250 g (0.413 equivalents of amine nitrogen) of the condensation product were mixed at 90-100 ° C. with 16.2 g (0.144 mol) of lactic acid, 80% and then with 11.1 g of sorbitol. The clear melt was converted into the scale form.

Example 5

As described in Example 1, 459 g (1.7 mol) of technical stearic acid and 104 g (1 mol) of aminoethylethanolamine were reacted. After an acid number of 4 had been reached, the reaction was terminated. The content of amine nitrogen still present was 1.17%. 250 g (0.209 equivalents of amine nitrogen) of the condensation product were mixed with 11.8 g (0.105 mol) of milk at 90 - 100 ° C. acid, 80% and then mixed with 10.9 sorbitol. The clear melt was converted into the scale form.

Example 6

175 g (0.205 equivalents of amine nitrogen) of the condensation product according to Example 1 were at 90-100 ° C. with 8.1 g (0.072 mol) of lactic acid, 80%, with 7.6 g of sorbitol and then with 81.7 distearyldimethylarnmonium chloride transferred. After a clear melt had formed, it was converted into the scale form.

Example 7

In a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and an inlet pipe for inert gas, 255.6 g (0.3 mol) of hardened beef tallow with a saponification number of 197.5 were melted and at 85 ° C with 31.2 g (0.3 MoT) aminoethyl ethanolamine and 16.0 g sorbitol. The mixture was stirred at 105.degree. C. while introducing nitrogen until the amine nitrogen content was 1.0%. The contents of the flask were now neutralized by adding 12.1 g of lactic acid, 80% (0.11 mol) to approximately 50 mol%. The melt, which was clear at 85 ° C., was converted into the scale form.

Example 8

Example 7 was repeated. Finally, about 24% (0.22 mol) of lactic acid, 80 H, was neutralized to about 100 mol%.

Example 9

In a three-necked flask equipped with a stirrer, a thermometer, a distillation head and an inlet tube for inert gas, 830.7 g (0.98 mol) of hardened beef tallow with a saponification number of 197.5 were melted and at 80 ° C. with 533.0 g of a commercially available distearyldimethylammonium chloride, which contained about 14% isopropanol and 11% water, 72.8 g of sorbitol and 101.4 g (0.98 mol) of aminoethylethanolamine were added. While introducing nitrogen, the temperature was raised to 100 ° C. and slowly evacuated to a pressure of 20 mbar in accordance with the distillate formation. After an amine nitrogen content of 0.83% had been reached, the reaction was terminated and the clear melt was converted into the flake form.

300 g of the product obtained were melted and neutralized with 10.0 g (0.090 mol) of lactic acid, 90%, to 50 mol% and then converted into the flake form.

Example 11

1100 g (4 mol) of technical stearic acid were melted in an apparatus according to Example 9, and 206 g (2 mol) of diethylenetriamine were added at 90 ° C. The temperature was raised to 210.degree. C. in the course of 2 hours and the mixture was stirred for 1 hour. 85 g of distillate were formed. It was then evacuated to 25 mbar and stirred at 210 ° C. for a further 1.5 hours. After cooling to 90 ° C., the product was converted into the flake form. The UV spectroscopic analysis showed an imidazoline content of 98.5%. 250 g (0.38 mol) of the product obtained were melted, 6.9 g (0.115 mol) of glacial acetic acid and 10.7 g of sorbitol were added and the mixture was stirred at 95-100 ° C. until a clear melt had formed, which then followed was converted into the scale form.

Example 12

Testing dispersibility

5 g of the products of Examples 1 to 11 were poured into a 125 ml wide-mouth bottle with 95 g of tap water (16 ° dH, 12 ° C) or deionized water (18 ° C) and left to stand for 15 minutes. The swelling behavior was then assessed. The mixture was then stirred with a magnetic stirrer for 2 minutes and the degree of dispersity was assessed visually. Further assessments were made after 1 and 24 hours. The degree of dispersity was assessed as follows and converted into numerical values:

Grading characteristics

Swelling: 1 = homogeneous, single phase

2 = homogeneously dispersed upper phase

3 = swollen scale structure clearly recognizable

4 = slightly wetted scales as sediment

5 = scales remain unchanged on the surface

After stirring: 1 = homogeneous, finely divided, weak translucency

2 = homogeneous, fine lig, no translucency

3 = homogeneous with coarse particles

4 = dispersion with gel-like particles

5 = little changed dandruff

The results can be found in Table 1 below. Table 1

Assessment of the degree of dispersity

Product swelling after stirring after 1 hour after 24 hours

LW ve LW ve LW ve LW ve

2 2 2 2 1/2 1 1 1

2 2 2/3 2 2 1 1 1

2 2 1/2 1/2 1 1 1 1

3 3 3 3 2/3 2 2 1

3 3/4 3 3 2 2 2 1/2

4 3/4 3/4 3/4 3 3 2/3 2

3 3 2/3 3 2 2/3 1 1

5 4/5 3/5 3/5 3/5 3/5 3 3 4/5 5 3/5 3/5 3/4 3/4 3/4 3/4 2/3 2/3 2/3 2 / 3 2 2 1/2 1/2

3 2/3 2/3 2/3 2 1/2 1 1

2 2 2 2 1 1 1 1 2/3 3 3 2/3 2/3 2 2 1/2 3/4 4 4 3/4 3/4 3/4 3 2/3

2 1/2 3 2/3 2/3 2 2 1 3/4 3 3/4 3 3 3 2/3 2/3 2/3 2/3 2 2 1 1 1 1

LW = tap water ve = demineralized water Example 13

Softening test

Hardened terry toweling (approx. 60 g / sample) was treated in a wacker vessel on a roller bench with a liquor which contained the products in Table 2 in the form of 5% dispersions. The same standard conditions were chosen for all tests:

Water hardness: approx. 16 ° dH

Fleet ratio: 1:10

Amount used: 0.15% active ingredient based on tissue

Temperature: 15 ° C

Treatment time: 5 minutes

After the treatment, the tissue samples were dewatered in a household centrifuge and air-dried. The softening of 6 people was then assessed independently of one another. Grades from 1 = hard, rough to 4 = soft, pleasant are the standard of value. The numbers listed in Table 2 each represent the mean values of the grades found by the six individual persons.

Table 2

* Dispersion took place at 70 ° C.

It can be seen from Table 1 that the dispersibility of the products according to the invention is better than that of the non-inventive products of Comparative Examples 2, 3, 8 and 10.

From Table 2 it can be seen that the improvement in the cold water dispersibility is not associated with a loss of plasticizing effect.

Claims

Patent claims

1. Textile treatment agent can be produced by reacting a) aliphatic monocarboxylic acids with 8 to 22 carbon atoms or derivatives forming amides thereof with b) optionally hydroxyl-substituted polyamines and subsequent neutralization of unreacted amino groups, the textile treatment agent being an addition of dispersion accelerators selected from the Group of monosaccharides of the Aldosen and Ketosen type and the polyhydroxy compounds derived therefrom by hydrogenation, the polyols such as in particular pentaerythritol, dipentaerythritol, trimethylolpropane, the alkylglucosides, the sorbitan esters to which ethylene oxide is attached, if desired, and the natural and contains synthetic hydrophilic polymers, characterized in that the unreacted amino groups are neutralized to 20 to 80 mol%.

2. Textile treatment agent according to claim 1, characterized gekennzeich¬ net that the unreacted amino groups are neutralized to 30 to 60 mol%.

3. Textile treatment agent according to claim 1 or 2, characterized in that the reaction products in the partial neutralization of unreacted amino groups in a mixture with other textile treatment agents, in particular textile softeners of the dimethyl-di- (C8-C22-alkyl / alkenyl) type ) - ammonium salt are present.

4. A process for the preparation of a textile treatment composition according to any one of claims 1 to 3, by reacting a) aliphatic monocarboxylic acids having 8 to 22 carbon atoms or derivatives forming amides thereof with b) optionally hydroxyl-substituted polyamines and subsequent neutralization of unreacted Amino groups, the dispersion accelerator selected from the group of monosaccharides of the aldose and ketose type and the polyhydroxy compounds derived therefrom by hydrogenation, the polyols such as, in particular, pentaerythritol or trimethylolpropane, the alkylglucosides, the sorbitan esters, being attached to the desired ethylene oxide, if desired, in the textile treatment agent , and the natural and synthetic polymers, characterized in that the unreacted amino groups are neutralized to 20 to 80 mol%, preferably to 30 to 60 mol%.

5. Use of textile treatment agents according to one of claims 1 to 3 for finishing fibers, yarns or fabrics.

6. Use of textile treatment agents according to one of claims 1 to 3 in the washing of textiles.

7. Use of textile treatment agents according to one of claims 1 to 3 for the aftertreatment of washed laundry.