EP0227720A1

EP0227720A1 - Washing agent for low washing temperatures

Info

Publication number: EP0227720A1
Application number: EP86903376A
Authority: EP
Inventors: Hans Andree; Horst Baumann; Manfred Biermann; Frantisek Jost; Horst-Jürgen KRAUSE; Fritz Lange; Herbert Leiter; Alfred Meffert; Uwe Ploog; Harald Schnegelberger; Eduard Smulders; Eric Sung; Andreas Syldatk; Günter Uphues; Günther VOGT
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1985-06-22
Filing date: 1986-06-16
Publication date: 1987-07-08
Also published as: WO1986007603A1; US4820436A

Abstract

L'agent de lavage à base de dérivés tensio-actifs anioniques et non ioniques comprend un composé aminé aliphatique comme additif renforçateur de lavage, qui est choisi de façon que sa valeur pKb soit au moins égale à 14, diminuée du pH de départ d'une solution aqueuse à 1% de l'agent de lavage contenant le composé amino. Des composés aminés renforçateurs de lavage qui sont choisis d'après la règle énoncée, sont certains ethers aminés, des composés amido-amines, des dérivés de glucamine ou des dérivés de morpholine.The washing agent based on anionic and nonionic surfactants comprises an aliphatic amine compound as wash-intensifying additive, which is chosen so that its pKb value is at least equal to 14, reduced by the starting pH of a 1% aqueous solution of the washing agent containing the amino compound. Wash-enhancing amine compounds which are chosen according to the stated rule are certain amine ethers, amido-amine compounds, glucamine derivatives or morpholine derivatives.

Description

"Detergent for low washing temperatures"

Due to the increasing popularity of easy-care textiles made of synthetic fibers, but also due to the constantly increasing energy costs associated with the growing environmental awareness of detergent users, the previously common cooked laundry has been increasingly replaced by washing at 60 ° C. With many detergents on the market, the usability for textile washing at 40 ° C or 30 ° C or. advertised at room temperature. In order to achieve a satisfactory washing result comparable to that of cooked laundry at such low temperatures, particularly high demands are placed on the composition of the low-temperature detergents. While you can remove the bleachable stains from the textiles with the usual cooking detergent with perborate or percarbonate or. In order to improve the washability of grease and pigment stains at temperatures around 60 ° C. and below, the washing liquor prepared in this way, adding a cold bleach activator, had to be strengthened by certain additives to increase the washing power of the surfactants previously used. For example, US Pat. No. 3,925,224 from 1975 already recommends adding water-insoluble surfactant types from the group of anionic, nonionic and amphoteric surfactants to customary detergent formulations based on water-soluble surfactants. The water-insoluble nonionic surfactants described also include ethoxylated alkylamines with C ₈ -C ₈ -alkyl chains and with 1 to 6 mol of added ethylene oxide, for example the coconut alkylamine reacted with 2 mol of ethylene oxide. In the German patent application 27 03 020 are reaction products of long chain epoxy alkanes with terminal or internal epoxy groups with monoethanolamine or diethanolamine or. described with aliphatic polyamines, where these reaction products can additionally be ethoxylated or propoxylated. Such hydroxyalkyla ines, which are also sparingly soluble in water, are recommended for strengthening the washing power of anionic, non-ionic and zwitterionic surfactants in detergent preparations, which are also suitable for washing at low temperatures. European patent application 112 593 discloses detergents containing ethoxylated mono- and diamines and ethoxylated polyethylene amines and polyethyleneimines, which are soluble in water due to an accumulation of polyglycol ether groups and the lack of long-chain hydrophobic residues. Detergents with the addition of these water-soluble ethoxylated amines are said to be distinguished by improved removal of clay-like pigments and by improved graying inhibition. In European patent application 121 949, among other things, tertiary amines with two C _u -C. ₀ -alkyl radicals and a third shorter alkyl or hydroxyalkyl radical and quaternary ammonium compounds derived therefrom are described as washing-strengthening additives for synthetic anionic surfactants. The two C _u -C_ alkyl radicals in the tertiary amine can be connected to the nitrogen atom via 1 to 3 ethyleneoxy bridges, it being understood that the pK value of the tertiary amine is at least about half a unit above the initial pH of the wash liquor lies.

From US 2,527,076 (German Patent P 3748) soap-containing detergents are known which contain surfactants of the sulfonate or sulfate type and alkyl-substituted fatty acid amides which act as lime soap dispersants. Nonionic surfactants, in particular those with low solubility in water, are in the Means not included. FR 1 1 18 024 discloses the use of fatty acid derivatives of aliphatic diamines and polyamines and their alkoxylates as cleaning enhancers in dry cleaning. According to US 3,454,494, the same compounds are used as finishing additives for textile detergents. Fatty acid derivatives of alkyl substituted diamines or. their mixtures with nonionic surfactants which are sparingly soluble in water are not mentioned in these documents.

Fatty acid amides of alkyl-substituted alkylenediamines, in particular N-lauroyl-N'-dimethyl-propylenediamine, are used in the form of their salts according to DE 23 38 386 as disinfectant active substances in hand disinfectants. However, the salt character and thus the disinfectant effect are lost in a customary, alkaline textile detergent. A teaching of the content of using these compounds in the form of the free amido amines in textile detergents with a surfactant component selected in a certain way is not disclosed in this literature.

From DE 22 26 925 - A1 (US 3 849 347) a gel-like agent is known with which the greasy textiles are pretreated. This agent contains a mixture of "oil-friendly" nonionic surfactants and anionic surfactants of the sulfate or sulfonate type, for example, lauryl alcohol / myristyl alcohol mixtures reacted with 3 moles of ethylene oxide or nonylphenol reacted with 5 moles of ethylene oxide The preferred anionic surfactant is linear alkylbenzenesulfonate, but the use is cumbersome and time-consuming since it requires the gel-like cleaning composition to be applied beforehand and the textile material to be left in the washing machine for up to 30 minutes before being placed in the washing machine Because of their gel-like character, the general-purpose detergents are usually difficult to incorporate. From US 3 925 224 it is known that the addition of a water-insoluble surfactant, which is referred to as an "additive", to detergents containing conventional water-soluble anionic, nonionic or zwitterionic surfactants leads to an increase in washing power. Examples of water-insoluble "additives" are ethoxylated alcohols with 12 to 15 carbon atoms or. Octylphenol with 3 glycol ether groups (EO), ethoxylated coconut amine with 2 EO groups, fatty acid diethanolamides, ethoxylated fatty acid amides and free fatty alcohols. Fatty acid amides that are free of hydroxyalkyl groups are not mentioned. The additives can be added to the detergents or the wash liquors in solid or liquid form. Celebrations, d. H . Powdery additives can be from 0.1 to 60% by weight additive or its mixture with water-soluble surfactants and from 99.9 to 40 cew. -% carrier material, such as builder salts, fillers, bleach or other detergent ingredients. The additives are added to these materials to avoid aerosol formation in the exhaust air from the spray towers (pluming) during spray drying. The additives mentioned are essentially oil-like substances which, owing to their tendency to stick, are difficult to obtain in larger, ie. H . Allow 5 - 8% excess amount to be incorporated into conventional washing powder and carrier materials, since they impair their flowability. No. 3,925,224 does not provide a suggested solution as to how larger amounts, in particular up to 60%, of these additives can be admixed with known powdered “builders” and fillers without losing their free-flowing properties.

The prior art proposals have several other disadvantages. For example, the ethoxylated fatty alkylamines have a more or less pronounced intrinsic odor that interferes with use in demanding branded laundry detergents and is neutralized by special perfuming measures got to. In the case of hydroxyalkylamines, which are derived from terminal and internal long-chain epoxyalkanes, their origin from petroleum as a non-renewable raw material is considered disadvantageous today. In the case of water-soluble ethoxylated amines, it is not always possible to recognize a contribution to improving the fat wash-out, which is problematic particularly when washing at low temperatures. Finally, tertiary amines, which are almost completely protonated, place narrow limits on practical use.

The invention is based on the object of finding substances which can be produced from renewable raw materials and which have no intrinsically odor which is disruptive to the application technology, and whose problem-free incorporation into detergents improves the washing action of these agents at low washing temperatures. It is an object of the invention to provide such washing-strengthening substances as amine derivatives of fat raw materials. It is a further object of the invention to find those amine derivatives which can be prepared from fats and which are already used in relatively small amounts, ie. H . in amounts which are clearly inferior to the actual surfactants, bring about an additive increase in activity at the lower washing temperatures. A further object of _^ the invention is to provide a granular detergent which avoids the disadvantages of the known agents and which is characterized by a high detergency, especially against fatty and oily stains. It should be incorporated in the detergent, the detergent strengthening, without the powder condition suffers or. there are undesirable exhaust air problems during spray drying during the preparation of the agents. A further, very essential object of the invention is to find a selection criterion for the amine compounds that can be used as detergency boosters, which makes it possible to provide detergents which are based on the pH of those produced therefrom Wash liquors are optimized with regard to their washing power-enhancing effect and to the lowest possible use amount, especially the amine compound.

Accordingly, the present invention consists in a detergent containing at least one synthetic anionic and / or nonionic surfactant and an aliphatic amine compound, the amine compound being selected so that its pK. -Value at least equal to 14, reduced by the starting pH of a 1% aqueous solution of the detergent. The pH value relates to a detergent which contains the amine compound mentioned. The pK. Value represents the negative decimal logarithm of the equilibrium constants for the aminic compound when the hydrolysis equilibrium is present:

K _b = (amine H ⁺ ) (OH ^" ) (1)

(Amine)

For the pK. -Value applies accordingly

pK _b + pK _a = 14 (2)

pK _b = 14 - pK _a (3)

The pK. -Value is determined by titration of an aqueous solution of the aminic compound with a strong acid. If the pH curve during the titration is plotted as a function of the amount of acid added, the relationship applies to the point on the curve where half of the aminic substance is in ported form

pK. = 14 - pH (4) These relationships are e.g. B. in R. B RDI CKA, Fundamentals of Physical Chemistry, 12th edition, pages 609 and 610, VEB German Publishing House of Sciences, Berlin 1973.

The pK. Value is a characteristic value for protonatable aminic compounds in the context of this invention, which as a selection criterion for suitable aminic compounds according to the relationship (5)

pK. is at least 14 minus the pH of a 1 wt. % aqueous solution of the detergent containing the amine compound,

serves. The pK. -Value is generally between 4 and 9.

The mentioned selection criterion makes it possible to make an optimal selection with regard to the suitable connection type and the required amount of use. In the mentioned pK. -Value range are particularly suitable substances strengthening the washing power those that have a low pK. -Have value . However, substances are also suitable in which the difference between the pK. - Value and pH of 1 wt. - Detergent solution is not less than about 1. This applies in particular to substances with approximately the same solubility in water. It is assumed that the detergents according to the invention have particularly good washing action at both low and high washing temperatures, because the type and amount of the amine compound which enhances the washing power optimally relates to the pH-buffering properties of the by using the teaching according to the invention - especially with regard to its builders component - different detergent compositions are coordinated. Typical detergents improved with regard to washing power contain at least one amine compound from the

a) ether amines of the general formula

R ¹ - (OCH ₂ CH ₂ ) _χ - NR ² R ³ (I)

in which R is an alkyl, hydroxyalkyl or alkenyl group

2 6 to 22 carbon atoms, x a numerical value from 1 to 10, R and

3 R independently of one another are aikyl groups with 1 to 4 C atoms, the group H f OCH-CH-) with y = 1 to 6 or together with the nitrogen atom form a 5- or 6-membered ring which is another nitrogen - or

2 can contain oxygen atom, or one of the radicals R or

R also represents hydrogen;

b) Amidoamines of the general formula

^' R ⁴ - CO - NR ⁵ - (CH ₂ ) - NR ⁶ R ⁷ (II)

wherein n = 2 to 4, R is an alkyl or alkenyl group with 9 to 17 carbon atoms, R, R and R ^{7 are} hydrogen or C _j - bis

C, -alkyl groups, with the proviso that at least

5 6 7 represents one of the groups R, R, R represents an alkyl group;

c) alkyl, alkenyl or hydroxyalkyl derivatives of glucamine in which the alkyl, alkenyl or hydroxyalkyl group has 6 to 22 carbon atoms;

d) alkyl, alkenyl or hydroxyalkyl derivatives of morpholine in which the alkyl, alkenyl or hydroxyalkyl group has 6 to 22 carbon atoms,

comprehensive group. The ether amines (a), in which R is an alkyl, hydroxyalkyl or alkenyl group, are described in the unpublished German patent application P 35 22 389; the amidoamines (b) are part of the detergents of the likewise unpublished German patent application P 36 06 828. In particular, the detergents according to the invention contain

3 to 40% by weight of anionic and / or nonionic surfactants 0.1 to 5% by weight -% amine compound

5 - 80 wt.% Water-soluble and / or insoluble inorganic and / or water-soluble organic builder salts 0 - 30 Cew. % inorganic per compounds which give off H_C in aqueous systems, preferably

Perborate remainder other ingredients common in detergents.

The ether amines described in the earlier application are above all those ether amines of the general formula I in which the substituent R is such alkyl or alkenyl groups as are obtainable from industrial fats and are present in the fatty alcohols which can be prepared therefrom. Particularly preferred are radicals R having essentially 10 to 20 carbon atoms, in particular having essentially 12 to 18 carbon atoms in the alkyl or. Alkenyl group. Those substances of the formula I are preferably used in which the

2 3

Substituents R and R both represent the ethoxy group

H (OCH CH_) mean. Also preferably used

Y 2 are compounds of the formula I in which one of the radicals R

3 or R has said ethoxy grouping and the other

Radical is a C. -C. alkyl group or hydrogen. Particularly preferred compounds of the formula I are those in which the sum of all the index numbers x and y present is between the number values 2 and 7 and in which the substituent R represents an alkyl or alkenyl group having essentially 12 to 18 carbon atoms . Optimum effectiveness is achieved at a ratio of the total number of ethoxy and hydroxyethyl groups to the number of alkyl, hydroxyalkyl or alkenyl carbon atoms in the ether amine of the formula I from 1/6 to 1/2, preferably 1/4 to 2/5 observed.

The substances of the formula I used according to the invention can be prepared in a manner known per se by reacting a corresponding fatty alcohol polyglycol ether sulfate with a primary one

2 3 or secondary, introducing the substituents R and R.

Amine can be produced (British patents 1,067,762 and 1,087,413). A carbon-nitrogen bond is formed in these alkylation reactions. Another production process (older German patent application P 35 04 242.7) describes the reaction of a fatty alcohol polyglycol ether sulfate with a tertiary amine which has at least one hydroxyalkyl substituent, for example triethanolamine, the alkylation on the hydroxyl group of the hydroxyalkyl radical with formation a carbon-oxygen bond takes place.

The compounds of the formula I thus prepared can optionally

2 3 at least on the substituents R and R, provided they have reactive hydrogens, are subsequently alkoxylated. In general, however, the polyglycol ether grouping in the fatty alcohol ether sulfate is selected in the direct preparation in such a way that it together with the ethoxy or. Hydroxyethyl residues lead to an optimal balance between hydrophobicity and hydrophilicity of the molecule for the use according to the invention. Part of the ethoxy or. Hydroxyethyl residues can also be replaced by isopropoxy or hydroxyisopropyl residues. Typical representatives of the compounds of formula I used according to the invention are, for example, the reaction products of fatty alcohol ether sulfates, which may have a different degree of ethoxylation, with primary amines, such as, for example, B. ethanolamine, a C.-C.-alkylamine such as methylamine, or with secondary amines, such as. As diethanolamine, morpholine, a dialkylamine with C _^ -C ^ alkyl groups such as. B. Diethylamine. In particular, these are the reaction products of the fatty alcohol ether sulfates with tertiary amines having at least one hydroxyethyl group, such as. B. triethanolamine, diethanol-methylamine. These substances include, for example, the compounds: C ₁₂ / C ₁₀ - (coconut) alkyl poly (3,6) oxyethyl hydroxyethylamine, C ₁ _ / C ₁ .- (coconut) alkyl di- ( oxyethyl) -hydroxyethyl-ethylamine, C ₁₂ / C _1ü - (coconut) -alkyl-di- (oxyethyl) -hydroxyethyl-methylamine, lauryl-di-oxyethyl-diethylamine, n-octyl-oxyethyldihydroxyethylamine, C _1? / C _1ü - (coconut) alkyl-di-oxyethyl-dihydroxyethylamine, Ole-y l-trioxyethyl-dihydroxyethyl amine, N-Laury loxyethy l-morphol in, C ₁₈ -alkyl-poly- (6) -oxyethyl-diethanolamine, C ₁₂ / C_ ₄ - (coconut) -alkyl- ^* poly- (3,6) -oxyethyl-hydroxyethyl-methylamine, C ._ / C ..., -alkyl-poly- (4,6) -oxyethyl-dihydroxyethyl -amin, C.- / C .-- (tallow) -alkyi / alkenyl-tri-oxyethyl-dihydroxyethyl-amine (iodine number of tallow alcohol 110 to 130). Reaction products of the fatty alcohol ether sulfate with a primary, secondary or tertiary amine with at least one hydroxyisopropyl group are also suitable.

The substances used according to the invention have no intrinsic odor that is harmful to application technology and, with regard to their long-chain alkyl or alkenyl residues, can be produced from renewable fat raw materials. These compounds thus have at least two advantageous properties which, together, cannot be attributed to the substances known as washing-strengthening additives. Detergent mixtures which have been prepared using the ether amines of the formula I defined above have an improved fat and Pigment / fat washable; they achieve or exceed the properties of the known detergents containing comparable detergent-enhancing additives.

The etheramines used in accordance with the invention can be mixtures of substances owing to their method of preparation. Thus, fatty alcohol mixtures of certain cuts of chain lengths are regularly obtained by industrial distillation processes via the raw material fat; Ethoxylation mixtures with an average degree of ethoxylation are also known to be obtained in the ethoxylation of the fatty alcohols as a precursor for the production of fatty alcohol polyglycol ether sulfate. Finally, the reaction of the fatty alcohol ether sulfate with the amine by forming a C-N or C-O bond can also lead to mixtures if the amine has more than one reactive site, the bisalkylation product also being able to be formed in minor amounts.

In the following the pK. Values listed for some characteristic ether amines:

R ¹ - (OCH ₂ CH ₂ ) _χ - NR ² R ³

a) with R ¹ = C ₁ 2/1 ₄ -alkyl- / alkenyl-

X = 3.6 to 4.6

R ² = R ³ = -CH ₂ CH ₂ OH

= 7.5 ^K b

with R ² = -CH ₂ CH ₂ OH R ³ H

= 6, 7

P ^K b

c) with R ¹ =

^C 8 ^H 17 ~ R ² = R ³ = -CH ₂ CH ₂ OH pK. = 6.3

d) dto. with

R ² = R ³ = (-OCH ₂ CH ₂ ) ₂ H

_P κ _b = 6.5

e) with R ¹ = C- ₂ ... "- alkyl / alkenyl

X = 2

R ² = H

R ³ = -CH ₂ CH ₂ OH

= 6.6 ^pK b

f) with R ¹ = ^C 12 ^H 25 ~

X = 1

R ² - CH ₃ - R ³ -CH ₂ CH ₂ OH

_P κ _b __ 7.5

g) with R ¹ = ^C 12 ^H 25 ~

X = 1

R ² = R ³ = -CH ₂ CH ₂ OH

_P K _b = 8.0

In the detergent according to the invention, the surfactant combination of at least one surfactant from the group of anionic, nonionic and zwitterionic surfactants and the etheramine of the formula I is preferably present in such a ratio that the surfactant or surfactant mixture and etheramine of the formula I in quantitative terms in a ratio of 30: 1 to 2: 1 and in particular in a ratio of 10: 1 to 3: 1. Based on the total detergent, the etheramine of the formula I is accordingly preferably present in amounts of 0.2 to 10% by weight, preferably 0.5 to 3% by weight. Preferred detergents contain the combination of Surfactant or surfactant mixture and the etheramine of the formula I in amounts of 5 to 65% by weight, preferably 8 to 35% by weight, again based on the overall detergent formulation. It is noteworthy to note that the washing-strengthening effect of the ether amines of the formula I occurs both with the synthetic anionic surfactants and with the nonionic surfactants.

Otherwise, 95 to 35% by weight, preferably 92 to 65% by weight, of the detergent containing etheramines consists of at least one further washing and cleaning substance from the group of inorganic and / or organic builders, builders, foam inhibitors, Dirt carriers, optical brighteners, enzymes, dyes and fragrances as well as water and / or other liquid carriers. Bleaching detergents contain an additive of peroxy compound, stabilizer and optionally an activator for the peroxy compounds, in total in quantities of 10 to 40% by weight, in particular 15 to 35% by weight, based on. all the detergent.

Typical powder detergents containing etheramines according to the invention correspond to the following general formulation:

5-50, preferably 5-25% by weight of at least one surfactant from the group of the sulfonate and sulfate surfactants and the nonionic surfactants of the type of the alkanols or alkenols substituted with hydrophilic nitrogen-free groups, 0.3-5, preferably 0.5- 2.5% by weight of the ether amines of the formula I, the surfactants and the ether amines preferably being present in a ratio of 10: 1 to 3: 1,

0 - 8, preferably 0.2 to 5 wt .-% of a foam inhibitor from the group of alkali soaps with essentially C ₁₈ -C ₂₂ fatty acid esters and the non-surfactant foam inhibitors. 50-94.7, preferably 55 to 90% by weight of powdered organic and inorganic builders, optionally including a bleaching component, and 0-10, preferably 0.5 to 10% by weight of conventional additives for detergents from the group of optical brighteners, enzymes, dirt carriers, corrosion inhibitors, textile softeners, antimicrobial agents, dyes and fragrances.

Typical liquid detergents according to the invention containing etheramines differ from the powdered formulations in that they have an increased surfactant content and a reduced proportion of builders and the lack of a bleaching component. Such detergents correspond to the following general formula:

10 - 60, preferably 15 to 50% by weight of at least one surfactant from the group of the sulfonate and sulfate surfactants of the nonionic surfactants of the type of the alkanols or alkenols of C.sub .-- C.sub.3 substituted with hydrophilic nitrogen-free groups. Soaps with a predominant proportion of soaps of chain length C ₁₂ C., preferably a mixture of the synthetic anionic, nonionic and soap surfactants,

0.5-8, preferably 0.8 to 6% by weight of the ether amines of the formula I, the surfactants and the ether amines preferably being in a ratio of 20: 1 to 5: 1, 0-20, preferably 1 to 15 Wt. Organic and / or inorganic builders,

10-89.5, preferably 15 to 60% by weight of liquid carriers from the group of the water-soluble lower alcohols, diols and ether alcohols and water, and ι 0 - 1 Q, preferably 0.5 to 10% by weight of the usual additives already mentioned above for powder detergents.

In the typical pasty detergents containing etheramines according to the invention, the liquid fraction consists largely, preferably practically exclusively, of non-ionic surfactants, so that the proportion of liquid carriers is significantly reduced compared to the liquid detergents. Preferred paste-like formulations do not require liquid carrier substances, which themselves do not contribute to the washability, in particular these formulations contain practically no free water, including water amounts below 2% by weight which are not in any form used as water of hydration the individual components are bound, understand. A corresponding frame formulation for paste detergents has the following composition

30 to 60, preferably 35 to 55% by weight wholly or predominantly as such surfactants in liquid form, in particular nonionic surfactants of the type of the alkanols or alkenols substituted with hydrophilic nitrogen-free groups, 1-10, preferably 2 to 8% by weight. % of the ether amines of the formula I, the surfactants and the ether amines preferably being in a ratio of 20: 1 to 5: 1, 0-8, preferably 0.2 to 6% by weight of a foam inhibitor from the group of soaps , in particular the Kalisei¬ fen and in particular the C ^ -C. g-potash soaps, and the non-surfactant foam inhibitors, 10-69, preferably 20 to 50 wt. % organic and / or inorganic builders, optionally including a bleaching component, and 0-10, preferably 0.5 to 10% by weight of the usual detergent additives already mentioned for the other frame formulations.

A particularly preferred embodiment of the invention relates to a powder-form detergent for low washing temperatures, which preferably contains a bleaching component composed of peroxy compound, cold bleach activator and stabilizer and which, together with a low-phosphate or phosphate-free builder component, has a special surfactant combination. The use of this detergent results in excellent cleaning performance even at stubborn grease and fat / pigment stains on common textile fabrics, ie on cotton, polyester and blended fabrics, at low washing temperatures. This special combination of surfactants is based on a mixture of nonionic surfactants from at least 2 separately manufactured low ethoxylated C 1 -C 6 alkanols or. Alkenols. with a cloud point in the range 0 to 45, preferably 5 to 40 (measured in water). In addition to these relatively poorly soluble nonionic surfactants, at least one slightly water-soluble anionic sulfonate and / or sulfate surfactant is present in amounts which are inferior to those of the nonionic ethoxylates, so that, for example, 10% by weight. Parts of the nonionic surfactant mixture 3 to 9 parts by weight of the sulfonate or. Sulfate surfactants are coming. As a further constituent essential to the invention, this surfactant combination contains 1 to 5 parts by weight of an etheramine of the formula I, again based on 10 parts by weight of the nonionic surfactant mixture.

This surfactant combination, which is particularly preferred according to the invention for etheramines containing detergents, can be present in amounts of about 8 to 30% by weight in a low-phosphate or phosphate-free detergent formulation, the term "low-phosphate" referring to the permissible maximum values of the applicable The maximum amount of phosphate is oriented, which currently corresponds to a total detergent formulation with customary metering regulations of about 25% by weight sodium tripolyphosphate based on the total powdered detergent, which value can also be higher with lower-dose detergent concentrates.

The foaming power of detergents of this type can be increased by adding a non-surfactant-like foam inhibitor in amounts of from 0.2 to 0.8% by weight or from 0.5 to 5% by weight. -% of an alkali soap from mostly C. gC- _Q fatty acids, or. a mixture of the non-surfactant-like foam inhibitor and the soap in an amount of 0.2 to 5% by weight, based in each case on the total detergent, are reduced so that when used in washing machines neither foaming nor difficulties in Rinse occur.

Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type. As surfactants of the sulfonate type, alkylbenzenesulfonates come with a

Cg, _ alkyl residue, olefin sulfonates, d. H . Mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as they -C ₂ _{1 8} monoolefins with terminal or internal double bond, for example, from C by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are the alkanesulfonates which consist of C _{1 2} -C. _g -alkanes can be obtained by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfofatty acids, e.g. B. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acidή. Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, i.e. H . from fatty alcohols, such as. B. Coconut fatty alcohols, taig fatty alcohols, Oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C _{1 Q} -C- ₀ -oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated with 1 to 6 moles of ethylene oxide. ethoxylated secondary alcohols are suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

Suitable anionic surfactants based on natural raw materials are in addition to the detergent soaps, i. H . The salts of the insbeson particular C ₁ -C ₂ _{1 8} fatty acids, the water-soluble salts of the acyl cyanamides of formula RCONH-CN, wherein R represents a Alkyi- or alkenyl group having 9 to 23, preferably 11 to 17 atoms Kohlenstoff¬. These anionic surfactants are in the form of their sodium, potassium or ammonium salts or in the form of the soluble salts with organic bases, in particular the mono-, di- or triethanolamine.

The addition products of 3 to 20 moles of ethylene oxide to primary are particularly important as nonionic surfactants. --C --- alcohols such as B. on coconut or tallow fatty alcohols, on oleyl alcohol, on oxo alcohols, or on secondary alcohols of this chain length. In addition to the water-soluble nonionics included here, they are not or. not completely water-soluble, low ethoxylated fatty alcohol polyglycol ether with 3 to 7 ethylene glycol ether residues in the molecule of particular interest, especially when they are used together with water-soluble nonionic or anionic surfactants.

In combination with the low ethoxylated fatty alcohol polyglycol ethers, the non-ionic surfactants also include the water-soluble adducts of ethylene oxide with polypropylene glycol, alkylenediamine and 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. polypropylene glycol and on alkyl polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain functions as a hydrophobic radical. Non-ionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide. Be¬ as part of the surfactant was also the wasser¬ soluble alkyl glucosides, whose hydrophobic C_-C _2n alkyl group is linked to a usually oligomeric hydrophilic glucoside suitable. The preferred nonionic surfactants are the alkanols or substituted with ethoxy groups as hydrophilic nitrogen - free groups. Alkenols. The expression “nonionic surfactants (nonionics)” therefore does not include the ether amines of the formula I used according to the invention.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduced foaming power of the wash liquor is usually desirable when working in machines. In the case of soaps, the foam attenuation increases with the degree of saturation and the C number of the fatty acid residue; Sei¬ the saturated C_ fen ₀ -C_ _above fatty acids are therefore be¬ Sonders as foam inhibitors for detergents based on sodium triphosphate as a builder, whereas in the predominantly zeolite-containing detergents already C. -C. »Soaps show good foam inhibition, especially at low washing temperatures. The non-surfactant-like foam inhibitors are generally water-soluble, mostly containing aliphatic C 1 -C 4 -hydrocarbon compounds. Corresponding foam inhibitors are e.g. B. N-alkylaminotriazines with sentlichen in we¬ 8 to 18 carbon atoms in the alkyl, aliphatic C _{1 0} -C., _N ketones such. B. Stearone, and in particular paraffins lo 4U and halogen paraffins with melting points below 100 ° C. and silicone oil dispersions based on organopolysiloxanes and microfine silica, which can optionally be silanated. Suitable organic and inorganic builders for detergents containing etheramines are preferably alkaline salts, in particular alkali salts, which are not only able to precipitate or bind complex calcium ions, but also, if possible, bring about a synergistic increase in washing power with the surfactants and have a dirt-carrying capacity. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, in particular pentasodium triphosphate, are still of particular importance. In addition to these phosphates, organic complexing agents for calcium ions and heavy metal ions can be present. These include compounds of the aminopolycarboxylic acid type, such as. B. Nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologues. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids, such as. B. the compounds methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, ethylenediamine tetramethylene tetraphosphonic acid, diethylene triamine pentamethylene pentaphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid,

2-phosphonobutane-1, 2, 4-tricarboxylic acid.

Of the organic framework substances, the N- and P-free polycarboxylic acids which form complex salts with calcium ions, including polymers containing carboxyl groups, are of particular importance. Low molecular weight compounds such as. B. Citric acid, 2, 2'-oxydisuccinic acid or carboxymethyloxysuccinic acid. Suitable polymeric polycarboxylic acids have a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000. B. Polyacrylic acid, poly-alpha Polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000. B. Polyacrylic acid, poly-alpha-hydroxyacrylic acid, polymaleic acid, and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as, for. B. Vinyl methyl ether. The water-soluble salts of polyglyoxylic acid can also be used.

Another component of the builders component consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid. Suitable copolymers are those of acrylic acid or methacrylic acid with maleic acid or. Copoly¬ mers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, further with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In such copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent. Copolymers of acrylic acid with maleic acid, as described in more detail for example in EP 25 551 -B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred. The molecular weight of the homopolymers or copolymers is generally 1,000 to 150,000, preferably 1,500 to 100,000. Another component of the builders component consists of sodium silicate with the composition Na ₂ O: Si0 ₂ = 1: 2 to 1: 3.5, preferably 1: 2.5 to 1: 3.3. Mixtures of silicates with different alkali contents can also be used, for example a mixture of Na ₂ 0: Si0 ₂ = 1: 2 and Na ₂ O: SiO ₂ = 1: 2.5 to 3.3.

Suitable water-insoluble inorganic builders are suitable substitute as the phosphate in the German patent application DE 24 12 837 described in more detail for detergents and cleaners finely divided synthetic, bound water-containing sodium umalumosilikate from ^'zeolite A type.

The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i.e. H. they have practically no particles larger than 30 microns and preferably consist of at least 80% particles smaller than 10 microns. Their calcium binding capacity, which is determined according to the information in DE 24 12 -837, is in the range from 100 to 200 mg CaO / g. The zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX.

Suitable inorganic, non-complexing salts are the bicarbonates, also known as "washing alkalis", carbonates, borates, sulfates or silicates of the alkalis.

Other builder substances that are mostly used in liquid media because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkane, benzene, toluene, Xylene or cumene sulfonic acids, sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid. Acetamide and urea are also suitable as solubilizers.

The zeolite content of the agents is 10 to 40% by weight, preferably 12 to 20% by weight. -%, of polymers or. copolymeric carboxylic acids or. their salts 0, 5 to 5, preferably 0, 8 to 4% by weight and sodium silicate 1 to 7% by weight, preferably 2 to 6% by weight.

Other suitable framework acids are sodium carbonate and - if there are no concerns about the sub-use of minor amounts of phosphates - polyphosphates, in particular pentasodium tripolyphosphate. Its proportion can be up to 25 wt. %, preferably 5 to 22% by weight. In cases where phosphates cannot be used, replacement by sodium nitrilotriacetate in proportions of, for example, 2 to 10% by weight is also possible. Other known water-soluble phosphate substitutes can optionally be used, for example polyacetals of glyoxylic acid in the form of sodium salts. ^"

The framework salts also include the sequestering agents from the classes of the aminopolycarboxylic acids and polyphosphonic acids, which are usually present in a comparatively ^" small amount ^" and act as so-called co-builders, stabilizers, precipitation preventers (threshold substances). The aminopolycarboxylic acids include ethylenediaminetetraacetic acid, which Diethylenetriaminepentaacetic acid and its higher homologs Suitable polyphosphonic acids are 1-hydroxyethane-1, 1-diphosphonic acid, aminotri- (methylenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and their higher homologs, such as diethylenetriamine tetra- (methylenephosphonic acid) The abovementioned polycarboxylic acids or polyphosphonic acids are usually used in the form of the sodium or potassium salts is generally 0.1 to 5% by weight, preferably 0.2 to 1% by weight.

The other usual detergent components include anti-graying substances, optical brighteners, enzymes, bleaching agents and bleach activators, foam inhibitors, colorants and fragrances, bioeides, neutral salts and substances which improve the powder quality.

Suitable anti-graying agents are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose, are also suitable.

Suitable optical brighteners are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-1, 3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure, the parts of the morpholino group carry a diethanolamino group, and brighteners of the substituted diphenylstyrene type, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4, are also suitable '-Bis- (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl-4' - (2-sulfostyryl) diphenyls.

Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be embedded in coating substances in order to protect them against premature decomposition.

The perhydrates and per-compounds commonly used in detergents and bleaches come in as bleaching components Question. The perhydrates preferably include sodium perborate, which can be present as a tetrahydrate or as a monohydrate, furthermore the perhydrates of sodium carbonate (sodium percarbonate), sodium pyrophosphate (perpyrophosphate), sodium silicate (persilicate) and urea. These perhydrates are preferably used together with bleach activators.

Sodium perborate tetrahydrate in combination with bleach activators is preferred as the bleaching component. The bleach activators include in particular N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are polyacylated alkylenediamines, such as tetraacetylmethylene diamine, tetraacetylethylenediamine and their higher homologues, and acylated glycolurils, such as tetraacetylglycoluril. Further examples are Na-cyanamide, N-alkyl-N-sulfonyl-carbonamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, cyanurates and imidazolines. In addition to carboxylic anhydrides such as phthalic anhydride and esters such as Na (iso) nonanoyl phenol sulfonate, in particular acylated sugars such as glucose pentaacetate are suitable as O-acyl compounds. Preferred bleach activators are tetraacetylethylene diamine and glucose pentaacetate. The bleach activators can also be coated with coating substances in order to avoid interactions with the per-compounds, especially during the storage of powdery mixtures.

Suitable foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica and saturated fatty acids with 18 to 24 carbon atoms or their alkali soaps. Mixtures of various foam inhibitors, e.g. B. from silicones and paraffins are useful. Neutral salts, in particular sodium sulfate, and magnesium silicate, which acts as a stabilizer for per compounds, can be considered as further constituents.

The other detergent ingredients can be present in amounts that are common in known detergent compositions. The proportion of graying inhibitors is generally 0.2 to 2% by weight, the proportion of optical brighteners 0.05 to 0.5% by weight. The proportion of enzymes depends primarily on their activity. Technical enzyme preparations, which are usually mixed with stabilizers, calcium salts and blending agents and adjusted to a specific activity, are usually used in proportions of 0.1 to 2% by weight. The proportion of perborate is usually 5 to 25% by weight. The amounts of bleach activators used are also based on their effectiveness. Highly effective activators, such as tetraacetylethylenediamine, are usually used in amounts of 0.5 to 5% by weight. This also applies analogously to foam inhibitors, the proportion of which can be generally 0.01 to 0.5% by weight in the case of highly effective silicone defoamers, or up to 2% by weight in the case of waxy or paraffinic substances or higher molecular weight fatty acids. The proportion of sodium suifate can be up to 25% by weight, or even more in special cases.

Further detergents according to the invention contain 1 to 5% by weight of amidoamine of the formula II, the amidoamine differing from fat

Derives acids whose acyl radical (R -CO-) has 12 to 18 carbon atoms, at least 50% by weight having 12 to 14 carbon atoms ζ fi 7 and the sum of the radicals in the radicals R, R , R and, in addition, water-insoluble to partially soluble polyglycol ether groups containing surfactants which are absorbed on and made from a granular carrier material (i) ethoxylated, linear or in the 2-position methyl branched, saturated or monounsaturated primary C _1g- C ₁₈ alcohols with an average of 4 to 6 glycol ether groups,

(ii) ethoxylated, saturated or in the 2-position methyl branched, saturated primary C _1Q -C. "-Alcohols with an average of 4 to 6 glycol ether groups exist,

wherein the weight ratio of (i): (ii): the amidoamine is 1: (2 to 6): (0.8 to 2.5) and the weight ratio of (i + ii + amidoamine): the base materials is 4: 1 is up to 1: 2, it also contains water-soluble surfactants of the sulfonate type and / or sulfate type.

The nonionic surfactants consist of a mixture of selected nonionic surfactants which, owing to their comparatively low degree of ethoxylation, are insoluble or only partially soluble in water, but are nevertheless dispersible. Their HLB values are below 12, mostly between 6 and 11.5.

The non-ionic surfactant listed under (i) is derived from primary fatty alcohols of natural or synthetic origin, which can be saturated, monounsaturated, linear or methyl-branched in the 2-position (oxo radical). Linear fatty alcohols are preferably used as starting materials, ie cetyl alcohol, stearyl alcohol, oleyl alcohol and mixtures thereof, e.g. B. Taig fatty alcohol. The average number of glycol ether groups is 4 to 6, in particular 5. Corresponding to the statistical distribution customary for polyglycol ethers, these are mixtures which can also contain portions with a lower and higher degree of ethoxylation. However, as indicated, the statistical maximum or the average degree of ethoxylation should be 4 to 6, preferably 5. The HLB value of the (i) fraction is between 7.5 and 10, preferably 8.2 to 9.3. The nonionic surfactant listed under (ii) is also derived from fatty alcohols or oxoalcohols with 10 to 14 carbon atoms. Linear alcohols with 12 to 14 carbon atoms are preferably used as starting materials, ie lauryl alcohol and myristyl alcohol and mixtures thereof. C - C obtained from coconut fatty alcohols are particularly useful. "-Alcohol mixtures, the proportion of shorter-chain alcohols expediently below

5 wt .-% is. The average number of ethylene polyglycol ether groups is 4 to 6, in particular 5. With regard to the statistical distribution of the glycol ether groups, what has been said in section (i) applies analogously. The HLB value of the (ii) fraction is between 8.5 and 12, preferably between 9 and 11.5.

The aminoamide is derived from saturated or monounsaturated fatty acids having 10 to 18, preferably 12 to 18, carbon atoms, with particular preference being given to those fatty acids whose acyl radicals are more than 50% by weight, in particular more than 65% by weight .-% consist of those with 12 to 14 carbon atoms. Mixtures obtained from coconut fatty acids are particularly suitable, from which the fraction with 10 and fewer carbon atoms has been largely separated. The diamine residue is derived from alkylated diamines, such as ethylenediamine, 1,3-propylenediamine and 1,4-butylenediamine. Methyl, ethyl, propyl or isopropyl groups are suitable as aikyl groups. Preferably the sum of the

5 7

Carbon atoms in the radical (H ₂ ) and the radicals R to R 4 to

6. Examples of such compounds are N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N-methyl-N-ethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-dimethylpropylenediamine, N-methyl-N '-ethyl-propylenediamine and mixtures of such alkylated alkylenediamines. Particularly preferred are compounds of the formula II in which R represents an alkyl radical having 9 to 1J C atoms, at least 50% of the radicals R having 11 to 13 C atoms, the radical R being H, R and R being methyl and / or represent ethyl groups and n = 3. The weight ratio (i): (ii): aminoamide is 1: (2-6): (0, 8-2, 5), preferably 1: (3-5): (1-2), being in the preferred range there is a particularly balanced ratio with regard to cleaning ability, in particular with respect to greasy and oily soiling. The aminoamide content of the agents is preferably 1 to 5% by weight.

As anionic surfactants of the suifonate type or. Sulfate types are suitable for the detergents already described for etheramines.

The weight ratio of the nonionic component (surfactants + aminoamide) to anionic component is 4: 1 to 1: 2, in particular 2: 1 to 1: 1. In this area, the washing power is particularly pronounced against both greasy and mineral soiling. The content of the agent in the aforementioned surfactants is a total of 10 to 25% by weight, preferably 12 to 20% by weight.

The substances already described for detergents containing etheramines serve as builders or builder salts.

The agents according to the invention are in the form of granular powders or powder mixtures which can be obtained in a suitable manner by granulating, spray drying, spray mixing, homogenizing or by a combination of these procedures. Since the non-ionic surfactants and the aminoamides consist of liquid compounds which tend to stick and which, owing to their tendency to "pluming", are only suitable to a limited extent for spray drying, it is often necessary for them to be adsorbed onto a carrier substance is. Suitable carriers are the builders, in particular zeolite, phosphates, silicates, nitrilotriacetate and their mixtures, and also spray-dried mixtures of skeletal salts, anionic surfactants and other constituents, insofar as these are stable under the conditions of spray drying. Carrier substances consisting of skeletal salts can also contain neutral salts, such as sodium sulfate, graying inhibitors, Mg silicate and additional adsorbents, such as finely divided silica, finely divided aluminum oxide, smectite clays, layered silicates and bentonites. Instead of spray-dried mixtures, it is also possible to use skeleton salt mixtures prepared by build-up granulation as the carrier substance for the nonionic surfactants and the aminoamides. After the liquid components have been applied to these carrier materials, the granules can also be provided with adsorbent coatings which prevent sticking, which can be done, for example, by powdering with the aforementioned fine-particle adsorbents.

A particularly preferred embodiment of the invention is that 30 to 100% by weight of the anionic surfactants are present in the form of granules containing the zeolite, the salt of the polymeric or. copolymers' carboxylic acid and the sodium silicate or. part of the total sodium silicate present. Suitable granules have the following composition (in% by weight, based on the granulate):

60-80%, especially 65-75% zeolite, 3-20, especially 4-15% polycarboxylic acid salt, 0.1-2%, especially 0.15-1% sodium silicate, 8-18 I, especially 10-16 % Water, which at a

Drying temperature of 145 ° C is removable, 0, 5 - 5, preferably 2 - 4% dispersion stabilizer.

Dispersion stabilizers are to be understood as meaning compounds which are used to stabilize aqueous or pasty zeolite slurries. They are generally added to these slurries during their manufacture or to moist filter cakes and also remain in the process. Processing in the zeolites. For this purpose, reference is made to DE 25 27 388. Examples of such stabilizers are neutral salts, such as sodium sulfate, nonionic surfactants from the class of ethoxylated fatty alcohols with 12 to 18 carbon atoms and 3 to 10 glycol ether groups, and polymeric and copolymeric carboxylic acids. Preferably, the dispersion stabilizer consists of the nonionic surfactant or. part of the same.

The granulate, which is preferably produced by spray drying and is described in more detail in patent application P 34 44 960 (D 7180), has an average grain size of 0.2 to 1.2 mm and contains less than 2% by weight. in dusty parts (grain size less than 0.05 mm) and not more than 5% by weight of coarse parts (grain size more than 2 mm). Its bulk density is 400 to 700 g / l. It is characterized by a very high adsorption capacity for liquid or paste-like substances and is therefore particularly suitable as a carrier for the nonionic surfactants.

In a further preferred embodiment, the agent according to the invention is therefore present as a mixture of several partial powders. The following are possible as partial powder:

(A) A partial powder consisting of the granules of zeolite described above, (co) polymeric carboxylic acid salt, sodium silicate, water, the nonionic dispersion stabilizer and the nonionic surfactant component adsorbed on these granules and the amidoamine.

(B) A partial powder consisting of the anionic surfactant component, the skeletal salts not contained in the granules and further detergent components, insofar as these are suitable spray drying is suitable. These include complexing agents, graying inhibitors, optical brighteners, neutral salts.

(C) One or more partial powders which contain such constituents which, for reasons of stability, should not be brought into direct contact with the constituents of the partial powders (A) and (B) or should not be spray-dried. These ingredients include bleach, bleach activators, foam inhibitors, enzymes, fragrances, and bioeids. These substances are generally prepared separately or converted into a suitable powder or granulate form and mixed with the other partial powders. Liquid components, such as perfume oils, can also be applied to other granular partial powders, e.g. B. the perborate, sprayed on and added to the mixture together with this. The foam inhibitors are also preferably applied to an adsorbent carrier substance or embedded in a water-soluble coating material in order to protect them against interactions with other powder constituents and the resulting loss of activity.

The invention further relates to a process for the production of the detergents containing amidoamines according to the invention. This method consists in that a granulate of the composition (in% by weight)

60-80%, in particular 65-75%, zeolite, 3-20%, in particular 4-15% polycarboxylic acid salt, 0.1-2%, in particular 0.15-1% sodium silicate, 8-1 8%, in particular 10 - 16% water, which at a

Drying temperature of 145 ° C is removable, 0.5 - 5%, preferably 2 - 4% dispersion stabilizer by spray drying, the granules are impregnated with a mixture of the nonionic surfactants and the aminoamide, and the partial powder (A) obtained is mixed with a spray-dried partial powder (B) according to the composition given above and further partial powders (C) according to the composition given above.

When producing the partial powder (A), care must be taken to ensure that its sodium silicate content is limited. If the content of sodium silicate in the detergent is substantially higher for technical reasons, the excess portion should be added to the other partial powders, in particular the spray-dried partial powder (B). Higher proportions of sodium silicate in these granules than specified increase its disintegration time or impair its solubility in the wash liquor. This delays the release of the nonionic surfactant, which can lead to a deterioration in the washing result. This subdivision of the total sodium silicate present into two different partial powders is a further aspect of the invention.

Further information on the production of the granules and their impregnation with nonionic surfactants can be found in DE 34 44 960 (D 7180), to which reference is expressly made here.

The compositions of the invention are characterized by a high detergency power supply in particular by an excellent Reini¬ against persistent ^* greasy stains, such as those made of food and sauces residues, skin fat, lipstick and mascara from. Despite their comparatively high content of liquid non-ionic surfactants, they are extremely pourable and free-flowing and do not tend to grease cardboard packaging. Provided that after the preferred procedure, d. H . Adsorbing the non-ionic surfactant on the previously prepared granules of zeolite, polymeric acid and sodium silicate completely avoids the formation of aerosols in the exhaust air from the spray towers.

B e i s p i e l e

example 1

This example shows the increase in the primary washing power on pigment / grease stains and on bleachable stains under the conditions of machine washing. The tests were carried out at 40 ° C. and 60 ° C. in a Miele W 433 washing machine. Further test information: 1 -Lye program, liquor ratio 1: 5, 6 at approx. 20 liters of washing liquor; Detergent concentration 6.9 g / l; Water hardness 16 ° d; 3-fold determination using 3.6 kg clean filling laundry, each with 2 rags (sewn on the filling laundry) of the test soils specified below. The following were used as pigment / grease stains: dust-wool grease on unrefined cotton; Dust-skin fat on refined cotton and dust-skin fat on cotton / polyester blend. Bleachable stains were used with red wine, blackberry, tea and coffee.

Test detergent formulation: 4% by weight alkylbenzenesulfonate,

5, .5 wt -.% Ethoxylated C_ ₂ -C _{1 8} coconut oil fatty alcohol with 5 moles of

Ethylene oxide

20 wt. -% sodium tripoly phosphate

20% by weight sodium perborate tetrahydrate

15% by weight of zeolite A

5% by weight of water glass Na ₂ O '3, 35 SiO-

3.0% by weight of amine compound remainder up to 100 cew. -%: Perborate stabilizer, dirt carrier, silicone foam brake, sodium sulfate and water. The pH of a 1 wt. % aqueous solution of this detergent was 9.9.

As amine compound is an ether amine of the formula IC was ₁ _l ₄ -Kokosalkyl- (OCH ₂ CH ₂₎ used ₂ / C ₃ H ₆ -NH-CH ₂ CH ₂ 0H; the pK. -Value of this etheramine is 6.7. A comparison was made with the well-known detergent boosters Kokosamin + 2 EO. Result :

The mean values from the individual reflectance values (Φ% R) were determined. In the 40 ° C wash, the pigment / grease stains were found to have a value of 63.8% R for the etheramine formulation and 62.9 for the known detergent booster. In the case of the bleachable soiling, corresponding reflectance values 61, 9 for the recipe according to the invention and 60, 8 for the known detergent booster were found. In the 60 ° C wash, the corresponding reflectance values were 69, 4 and 69, 0 (pigment / fat). and 68, 6 and 67, 8 (bleachable stains).

In addition, the two test detergents in this example were subjected to an odor test by a group of 3 experienced persons and compared with the detergent without a detergent-enhancing additive. For the recipe according to the invention with the etheramine of the composition specified above, only a weak intrinsic odor was found, which was considerably less than the odor of the recipe with coconut amine + 2 EO.

Summary: The reflectance values of the formulation according to the invention are slightly but significantly above the values of the comparative detergent. The inherent smell of etheramine is considerably less than that of coconut amine + 2 EO, which is of great importance in the perfuming of such a washing powder as is required by the market. i

Analogous results are also obtained if the above-mentioned ether amine of the formula I is replaced by one of the following ether amines: C- ₂ -. "-Co-alkyl-di-oxyethyl-dihydroxyethylamine; C. _ _/ , "-Cocoalkyl-di-oxyethyl-hydroxyethyl-methylamine; ^ ₁ 2/1 ~ cocoalkyl-di-oxyethyl-N-morpholine; C. -, _ _8- tallow alkyl-tetra-oxy-ethyl-dihydroxyethylamine. The pK. -Values of these compounds were all above 4.5.

Example 2

According to the specifications of patent DE 33 44 960 (D 7180), an absorbent granulate of the following composition was produced by spray drying (GT = parts by weight): 46.7 GT Zeolite NaX (based on anhydrous substance)

5.0 GT copolymer (sodium salt)

0.14 GT sodium silicate

1, 56 pbw of ethoxylated tallow alcohol (part of component (i))

0, 6 pbw sodium sulfate 13, 6 pbw water, of which 8, 9 pbw removable at 145 ° C

67.6 GT

The zeolite used had a particle size of 1 to 8 microns, the proportion over 8 microns being 6% by weight. There were no portions above 20 microns. A copolymer of acrylic acid and maleic acid with an average molecular weight of 70,000 (Sokalan CP5 ^ ') in the form of the sodium salt was used as the polycarboxylic acid. A tallow alcohol reacted with 5 mol ethylene oxide (EO) (30% cetyl alcohol, 70% stearyl alcohol) was used as the ethoxylated fatty alcohol (corresponds to part of component (i)).

The grain spectrum determined by sieve analysis gave the following weight distribution: mm from to to to to below

1.6 0.8 0.4 0.2 0.1 0.1

% By weight 0 1 37 53 9 0

The liter weight was 550 g / l.

67.6 parts by weight of the granules were sprayed with a molten mixture of the nonionic surfactant and the aminoamide described in more detail below in a spray mixing apparatus consisting of a cylindrical drum (LÖDIGE mixer) equipped with mixing elements and spray nozzles inclined to the horizontal. The temperature of the granules was 20 ° C, that of the surfactant melt 50 ° C. The surfactant mixture consisted of 4.1 parts by weight of tallow alcohol with 5 EO (remaining part of component (i), 20 parts by weight of a lauryl alcohol-myristyl alcohol mixture (2: 1) with 5 EO (component (ii)) and 8, 3 parts by weight of the amino amide N-cocosacyl-N'-dimethylpropyiendiamine, in which the acyl radical is a C.sub .-- C. mixture with a mean chain length of C._ _ The pK. Value of the amino ¬ amides is 5.9 After cooling, a non-adhesive, granular product was obtained, the flowability of which was excellent, despite a total content of 34% by weight of liquid nonionic surfactant, and the bulk density was 740 g / l.

30 parts by weight of the granules impregnated with the nonionic surfactant and the amino amide (partial powder A) were mixed with 54.7 parts by weight of a mixture of a spray-dried powder (partial powder B) and sodium sulfate (as a weight compensation). The spray powder contained sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium ethylenediaminetetra-methylene phosphate (EDTMP), cellulose ether, sodium silicate, optical brighteners and a further proportion of sodium sulfate. Granulated enzymes of granulated silicon foaming agent, sodium perborate and granulated tetraacetyl ethylenediamine (TAED) added. These pulverulent or granular constituents are summarized under the term "partial powder C", the proportion of which is a total of 15.3 parts by weight.

The composition of the agent and other agents produced in the same way are listed in Table 1 (in% by weight).

table

C.g-C.g alcohol

+ 5 EO 1.7 1.4 1.5 1.4

C ₁₂ -C ₁₄ -A! Alcohol

+ 5 EO 6.0 4.5 5.0 4.5

N-acyl-N'-dimethyl-propylenediamine 2.5 3.0 3.0 2.0

Na dodecylbenzene sulfonate 6.0 8.0 7.0 7.0

Zeolite (anhydrous) 14.0 14.0 14.0 14.0

Acrylic acid-maleic acid copol. 1.5 1.5 1.5 1.5

Na tripoly phosphate 20.0 20.0 20.0 20.0

EDTMP 0.3 0.3-0.3 0.3

Sodium silicate

(of which 0.04% in

Granules) 4.0 4.0 4.0 4.0

Cellulose ether 0.5 0.5 0.5 0.5 optical brightener 0.2 0.2 0.2 0.2

Enzyme 0.5 0.5 0.5 0.5

Defoamer granules

(Silicone content 30%) 0.3 0.3 0.3 0.3

Sodium perborate 12.0 12.0 12.0 12.0

TAED 2.5 2.5 2.5 2.5

Sodium sulfate 17.5 16.8 17.1 16.8

Water rest rest rest rest

The pH of 1% by weight aqueous solutions of these detergents was 10.5. Comparative tests with artificially soiled textile samples were carried out. The soiling applied to cotton textiles under reproducible conditions consisted of make-up cream, mascara and lipstick. The samples were placed together with 3 kg of ballast laundry in commercially available household washing machines (absorption capacity 4 kg of dry laundry) and washed at a temperature of 60 ° C. (easy care program with 20 minutes of prewash at 25 ° C.). The washing time including heating in the main wash cycle was 40 minutes, the detergent concentration 7.5 g / l, the ratio of the amount of textile (in kg) to the wash liquor (in liters) was 1:10, the water hardness of the tap water was 16 dH (160 mg CaO per liter). After rinsing three times, the product was spun, dried and the reflectance value of the samples was determined photometrically. The results (Table III) are mean values from 5 washing tests, each with 6 samples.

For comparison, detergents were used which contained the following surfactants with the same composition as Example 2 (see Table II):

Table II

-

_β attempt

1 2 3

Na dodecylbenzenesulfonate 7.0 5.0 10.2

Tallow alcohol + 5 EO 6.0 2.0 3.0

Tallow alcohol + 15 EO 2.2 7.2 -

Coconut alkylamine + 2 EO - - 2.0

The qualitative and quantitative composition of the tallow alcohol or coconut alkyl residues was identical to that used in the example. The compositions experiment 1 and 2 correspond to the surfactant compositions of commercially available high-performance detergents. Experiment 3 corresponds to agents according to US 3 925 224. The results show the superiority of the agents according to the invention.

table

Make-up lipstick Wim ipern- middle pen ink worth

Example 1 60 57 50 56

Example 2 65 60 52 59

Example 3 64 60 54 59

Example 4 56 57 54 56

Trial 1 35 52 33 40

Trial 2 40 44 34 39

Trial 3 42 45 41 43

Example 3

in a detergent of the composition

2 wt. - alkylbenzenesulfonate

3 wt. -% soap based on hydrogenated tallow fatty acid

10% by weight of C _{1 3} , ₅ -oxoalcohol + 5 moles of ethylene oxide

20% by weight of zeolite NaA

20% by weight sodium tripolyphosphate

5 wt. - water glass 1: 3, 35

20% by weight sodium perborate

10% by weight sodium sulfate

Rest: water 2.5 and 5 wt .-% sodium sulfate were replaced by the same amount of different N-alkylmorpholines. With the morpholine-containing detergents, washing tests were carried out in the launderometer at 40 ° C., 30 minutes, textile / alkali ratio 1:30 with 6.6 g detergent per liter at a water hardness of 16 ° d. The test textiles were artificially soiled with grease. The washing power of the morpholine-containing detergents was checked with that of the morphol-free detergents by measuring the reflectance on the washed textiles. The following results were shown in Table IV:

Table IV

% Remission

Detergent without additives 45.9

Detergent + 2.5% by weight N-hexylmorpholine 54.6

Detergent + 5.0% by weight N-hexylmorpholine 55.1

Detergent + 2.5% by weight ^' N-octylmorpholine 54.9

Detergent + 5.0% by weight N-octylmorpholine 55.8

Detergent + 2.5% by weight N-dodecylmorpholine 54.3

Detergent + 5.0% by weight N-dodecalmorpholine 54.7

One recognizes the washing-strengthening effect of the N-alkylmorpholines.

A 1% by weight solution of the detergent had a pH between 9.5 and 10. The pK. -Values of the morpholine derivatives are 6.3 for N-hexylmorpholine

N-octylmorpholine 7.4

N-dodecylmorpholine 8.7 Example 4

A heavy-duty detergent with the following composition:

5.0% by weight alkyl benzene sulfonate

4.6% by weight of a mixture of 8 parts of C., ₁₈ fatty alcohol + 5 moles of ethylene oxide and 2 parts

^C 12 ^{/ C} 14 ~ ^{fatty alcohol + 3 Mo1} ethylene oxide

0.8% by weight tallow alcohol + 5 moles of ethylene oxide

0.3% by weight tallow alcohol + 14 moles of ethylene oxide

21.3% by weight sodium tripoly phosphate

13.9% by weight of zeolite A

0.25% by weight of ethylenediaminetetramethylenephosphonic acid

1.20% by weight polycarboxylate

0.5% by weight cellulose ether

4.6% by weight of water glass, Na.O: SiO_ = 1: 3.35

0.1% by weight magnesium silicate

22.2% by weight sodium perborate

1.6% by weight tetraacetylethylenediamine

8.3% by weight sodium carbonate Remainder: water, dye, fragrances

was compared in its washing performance with a detergent according to the invention which, instead of 4.6% by weight of the above-mentioned fatty alcohol-ethoxylate mixture, only 2% by weight of this fatty alcohol-ethoxylate, but in addition 2% by weight of detergent booster in the form of 4- (2-hydroxydodecyl) morpholine (pK _b value 7.8). Cotton from the laundry research institute in Krefeld, artificially soiled with wool fat, served as the test textile. Was washed in an automatic household washing machine at 90 C washing temperature. The pH of a 1% by weight aqueous solution of the detergent according to the invention was 9.9. The reflectance value of the test textile washed with the detergent according to the invention was significantly around 4 Units higher than the reflectance value of the test textile washed with the surfactant-rich but detergent-free detergent.

Claims

Patent claims

1. Detergent containing at least one synthetic anionic and / or nonionic surfactant and an aliphatic amine compound, characterized in that the amine compound is selected so that its pk. -Value at least equal to 14, reduced by the starting pH of a 1% aqueous solution of the detergent, is.

2. Detergent according to claim 1, characterized in that there is at least one amine compound from the

a) ether amines of the general formula

R ¹ - (OCH ₂ CH ₂ ) _χ - NR ² R ³ (I)

in which R is an alkyl, hydroxyalkyl or alkenyl group having 6 to 22 carbon atoms, x is a numerical value of

2 3

1 to 10, R and R independently of one another are aikyl groups with 1 to 4 carbon atoms, the group H (OCH-CH-) with y = 1 to 6 or together with the nitrogen atom form a 5- or 6-membered ring , which is another nitrogen or oxygen atom

2 3 eenntthhaalltteenn kkaannnn ,, ooddeerr one of the radicals R or R is also hydrogen;

b) Amidoamines of the general formula

R ⁴ - CO - NR ⁵ - (CH ₂ ) _n - R ⁶ R ⁷ (II)

4 wherein n = 2 to 4, R is an alkyl or alkenyl group

5 6 7 with 9 to 17 carbon atoms, R, R and R are hydrogen or

C. to C. alkyl groups, with the proviso that that at least one of the groups R, R, R represents an alkyl group;

d) alkyl, alkenyl or hydroxyalkyl derivatives of morpholine in which the alkyl, alkenyl or hydroxyalkyl group has 5 to 22 carbon atoms,

comprehensive group contains.

3. Detergent according to one of claims 1 or 2, characterized in that

3 - 40% by weight anionic and / or nonionic

Surfactants

0.1-5% by weight amine compound

5 to 80% by weight of water-soluble and / or insoluble inorganic and / or water-soluble organic builder salts

0 - 30 wt .-% inorganic, in aqueous systems

H_0_ releasing per compounds, preferably perborate

The rest of the other usual components in the detergent

contains.

4. Detergent according to one of claims 1 to 3, characterized ge indicates that it contains ether amines of the general formula I, in which the substituent R is such alkyl or alkenyl groups as they are from technical fats are available and are present in the fatty alcohols that can be produced from them.

5. Agent according to one of claims 1 to 4, characterized gekenn¬ characterized in that the substituent R in the ether amine of formula I is an alkyl or. Alkenyl group with essentially 10 to 20, in particular 12 to 18 carbon atoms.

6. Composition according to one of claims 1 to 5, characterized gekenn¬ characterized in that the ether amines of formula I as substituents

2 3

R and R in each case denote the ethoxy group H (OCH ₂ CH ₂ ) or one of these two substituents mean this ethoxy group and the other is a C. -C “alkyl group or hydrogen.

7. Detergent according to one of claims 1 to 6, characterized ge indicates that in the ether amines of the formula I the sum of all existing index numbers x and y is between the numerical values 2 and 7 and as a substituent R an alkyl or alkenyl group with im represents essentially 12 to 18 carbon atoms.

8. Detergent according to one of claims 1 to 7, characterized ge indicates that in the ^' etheramine of formula I the ratio of the total number of ethoxy and hydroxyethyl groups to the number of alkyl or. Alkenyl carbon atoms is 1/6 to 1/2.

9. Detergent according to one of claims 1 to 8, characterized ge indicates that the surfactant system from at least one surfactant from the group of anionic and / or non-ionic surfactants and the etheramine of formula I in a ratio of 30: 1 to 2: 1 and in particular 10: 1 to 3: 1 is present.

10. Detergent according to one of claims 1 to 9, characterized ge indicates that the etheramine of formula I, based on the detergent, in an amount of 0, 2 to 10 wt.%, Preferably 0, 5 to 3 % By weight is present.

1 1. Detergent according to one of claims 1 or 2, characterized in that it contains 1 to 5% by weight of amidoamine of the general formula II, the amidoamine being derived from fatty acids whose acyl radical (R - CO-) 12 to 18 carbon atoms, at least 50% by weight of 12 to 14 carbon atoms

5 6 and have the sum of the residues R, R,

R and (CH ₂ ) - contained C atoms 4 to 6 is that it also contains water-insoluble to partially soluble polyglycol ether groups containing nonionic surfactants which are adsorbed on a granular carrier material and from

(i) ethoxylated, linear or. in 2-methyl¬ abutment condition branched, saturated or monounsaturated primary C. _fi -C _{1 8} alcohols with an average of 4 to 6 Glykoiethergrjuppen,

(ii) ethoxylated, linear or saturated primary C.-C. "-Alcohols with an average of 4 to 6 glycol ether groups exist,

contains that the weight ratio of (i): (ii): the amidoamine is equal to 1: (2 to 6): (0.8 to 2.5) and the weight ratio of (i + ii + amidoamine): the aminic Surfactants is 4: 1 to 1: 2 and that it contains water-soluble surfactants of the suifonate type and / or sulfate type.

12. Detergent according to one of claims 1 or 2 or 11, characterized in that 30 to 100 wt .-% of the Gerüst¬ substances are in the form of a granulate, which consists of 60 to 80 parts by weight of finely crystalline, synthetic zeolite NaA and / or NaX, 0.1 to 2 parts by weight of sodium silicate of the composition a ^ O: SiO- equal to 1: 2 to 1: 3.5, 3 to 20 parts by weight of a copolymer. (Meth) acrylic acid and maleic acid, 8 to 18 parts by weight of water which can be removed at 145 ° C. and 0.5 to 5 parts by weight of a dispersion stabilizer.

13. Detergent according to one of claims 1 or 2 or 11 or

12, characterized in that the nonionic surfactant and the amidoamine are adsorbed on the granules according to claim 17.

14. Detergent according to one of claims 1 or 2 or 10 to

13, characterized in that it consists of a mixture of several partial powders, one partial powder (A) consisting of the granules with the nonionic surfactants and amidoamines adsorbed thereon, a spray-dried partial powder (B) consisting of the water-soluble surfactants of the suifonate type and / or sulfate type, the builders, insofar as they are not already part of the granulate, and other detergent components capable of spray drying, and that at least one partial powder (C) is present which comprises the other detergent components which are not suitable for spray drying .

15. Detergent according to one of claims 1 or 2 or 10 to

14, characterized in that it contains up to 25% by weight, preferably 5 to 22% by weight, of sodium tripolyphosphate, which is part of the partial powder (B).

16. A process for the preparation of a detergent according to claims 1 or 2 or 10 to 15, characterized in that the nonionic surfactants and the amidoamines are adsorbed on a granulate produced by spray drying, the partial powder (A) thus obtained. with a partial powder (B) produced by spray drying, which contains the anionic surfactant component, the builders not contained in the granules, and further other detergent components suitable for spray drying, and also mixes with the remaining constituents which count as other detergent components.