EP0227720A1 - Washing agent for low washing temperatures - Google Patents

Washing agent for low washing temperatures

Info

Publication number
EP0227720A1
EP0227720A1 EP19860903376 EP86903376A EP0227720A1 EP 0227720 A1 EP0227720 A1 EP 0227720A1 EP 19860903376 EP19860903376 EP 19860903376 EP 86903376 A EP86903376 A EP 86903376A EP 0227720 A1 EP0227720 A1 EP 0227720A1
Authority
EP
European Patent Office
Prior art keywords
wt
detergent
characterized
composition according
amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19860903376
Other languages
German (de)
French (fr)
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE19853522389 priority Critical patent/DE3522389A1/en
Priority to DE3522389 priority
Priority to DE3606828 priority
Priority to DE19863606828 priority patent/DE3606828A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0227720A1 publication Critical patent/EP0227720A1/en
Application status is Withdrawn legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/42Amino alcohols or amino ethers
    • C11D1/44Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/32Amides; Substituted amides

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. The washing agent based on anionic surfactants and nonionic derivatives comprises an aliphatic amine compound as cleaning enhancer additive which is selected so that its pKb value is at least equal to 14, less of the starting pH of an aqueous 1% solution of the detergent containing the amino compound. 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. Amine compounds washing enhancers which are selected according to the set rule, are some ethers amines, amido-amines compounds, glucamine derivatives or morpholine derivatives.

Description

"Detergents for low washing temperatures"

Due to the increasing popularity of iron fabrics of synthetic fibers, but also by the ever increasing Energie¬ cost associated with the growing environmental awareness of Ver¬ consumers of detergents, previously used hot wash has been increasingly replaced by washing at 60 ° C. In many detergents of the market and the usability for textile washing at 40 ° C or 30 ° C respectively. awarded at room temperature. In order to achieve a zufrieden¬ tory and the hot wash comparable washing result at such low temperatures are particularly high demands on the composition of the low-temperature tur detergent. While for better removal of bleachable soils from the textiles, or the usual cooking detergent with perborate or percarbonate. the thus prepared wash liquor zusetzte a Kaltbleichaktivator, it was to improve the Aus¬ washability of fat and Pigmentanschmutzungen out at temperatures of 60 ° C and below necessary to enhance the detergency of the surfactants previously used by certain additives. Thus in U.S. Patent 3, 925, 224 already recommended additions of water-insoluble surfactant from the group of anionic, nonionic and amphoteric surfactants from 1975 to conventional detergent formulations based on itself was¬ serlöslicher surfactants. To those described wasser¬ insoluble nonionic surfactants also include ethoxylated alkyl amines with C 8 -C _, - alkyl chains and ange¬ with 1 to 6 moles of ethylene oxide lagertem, for example, the reacted with 2 moles of ethylene oxide cocoalkylamine. In DE-OS 27 03 020, reaction products of long-chain alkanes or epoxy with monoethanolamine or diethanolamine with terminal or internal epoxy group. may be described amines with aliphatic poly-, said reaction products additionally ated ethoxy or propoxylated. Such hybrid droxyalkyla ine, which are sparingly soluble also in water are for enhancing the detergency of the anionic, nonionic and zwitterionic surfactants nicht¬ in Waschmittelzuberei¬ obligations that are also for washing at low temperatures geeig¬ net recommended. From the European patent application 112,593 detergents are ethyleneimines having a content of ethoxylated mono- and diamines and ethoxylated polyethylene amines and poly that pierungen by an accumulation of Polyglykolethergrup- and are soluble by the absence of long-chain hydrophobic residues in water are known. Detergent with an additive of these water soluble ethoxyl ierten amines should be characterized by improved removal of clay pigments as well as by improved redeposition. In the europä¬ regard Patent Application 121 949, inter alia tertiary amines with two C u -C be.0 alkyl and a third shorter Alkyi- or hydroxyalkyl radical, as well as quaternary ammonium compounds derived therefrom as described detergency boosting additives for synthetic anionic surfactants. The two C ü -C_ alkyl tertiary amine can be about 1 to 3 ethyleneoxy bridges connected to the nitrogen atom, to apply 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) are known soap-containing detergent containing surfactants of the sulfonate or sulfate type, and alkyl-substituted fatty acid amides which act as lime soap dispersants. Nonionic surfactants sondere insbe¬ those having low solubility in water, are not included in the media. From FR 1 1 18 024 the use of fatty derivatives of al iphatischen diamines and polyamines is so¬ as their alkoxylates cleaning as a cleaning booster in the chemical-known. The same compounds are aimed ver¬ as revitalizing additives to laundry detergents according to US 3,454,494. Fatty acid derivatives of alkyl-substituted diamines or. their mixtures with low solubility in water nonionic Ten¬ are Šiden not mentioned in these documents.

Fatty acid amides of alkyl-substituted alkylenediamines, more particularly sondere the N-lauroyl-N'-dimethyl-propylene diamine are in the form of their salts according to DE 23 38 386 as disinfecting substances Wirk¬ used in hand disinfectants. In a conventional alkaline laundry detergent, however, the hydrochloric character and thus the disinfecting effect is lost. A teaching of the contents of these compounds in the form of free amine amido in laundry detergents with a use in a particular way aus¬ selected surfactant component is not disclosed in this Litera¬ turstelle.

DE 22 26 925 - A1 (US 3849347) is a gel-like Mit¬ tel known with which the fat-soiled fabrics to be pretreated. This composition contains a mixture of "ölfreundl cozy" "or non-ionic surfactants and anionic surfactants of the Sulfat¬. Sulfonate type. Suitable nonionic component z. B. With 3 moles of ethylene oxide unreacted lauryl alcohol Myristylalkohol- mixtures or reacted with 5 moles of ethylene oxide ver¬ turns. the preferred anionic surfactant is linear alkyl benzene sulfonate. However, the application is cumbersome and time consuming because it requires a prior application of the gel-like cleaning compound and up to 30 minutes lasting leaving behind of the fabric before placing them in the washing machine. in a Übl iches, körni ¬ ges Al lzweckwaschmittel the agents can incorporate only with difficulty because of their gel¬ like character mostly. from US 3,925,224 it is known that the addition of a wasser¬ insoluble surfactant, which is referred to as "additive" to detergents containing to customary water-soluble an¬, nonionic or zwitterionic nonionic surfactants leads to an increase in detergency. As examples of was¬-insoluble "Additives" are respectively ethoxylated alcohols having 12 to 15 carbon atoms. Octylphenol with 3 glycol ether groups (EO), ethoxylated cocoamine having 2 EO groups, chain fatty acid ethanolamides, ethoxylated fatty acid amides and called free fatty alcohols. Fatty acid amides, which are free of hydroxyalkyl groups are not mentioned. The additives can be added in solid or liquid form, the detergents and the washing liquors. Fixed, d. H . powdery additives may be selected from 0, 1 to 60 wt -.% of additive or its mixture with water-soluble surfactants and from 99 9 to 40 Cew. - consist% carrier material such as builder salts, fillers, bleach or other detergent ingredients. The additives are mixed into these materials to avoid Aerosolbifdung in the exhaust air of the spray towers (pluming) in spray drying. It concerns with the ge called additives are essentially oil-like substances which, owing to their tendency to stick only with difficulty in larger, d. H . can be incorporated 8% increase in the amount in conventional washing powder and carrier materials because they impair their ability Riesel¬ - 5th One proposed solution, as larger quantities, in particular up to 60% of these additives known pulverulent "builders" and fillers are mixed kön¬ NEN, without that they lose their flow properties, the US can not be inferred 3,925,224.

The proposals of the prior art have some other disadvantages. So the ethoxyl ierten fatty alkyl amines have a more or less pronounced odor that interferes in an application in demanding brand detergents and must be neutralized by special Parfümierungsmaßnahmen. The hydroxyalkylamines, derived from terminal and internal long-chain epoxy alkanes, today their origin from petroleum is seen as a non-renewable resource to be disadvantageous. In the cozy Water soluble ethoxylated amines is not always a contribution to improving the grease to be washed out, which just structures when washing at low Tempera¬ is problematic to detect. Schl ießlich put tertiary amines, which are almost completely protonated, the practical application of strict limits.

The invention IEGT l based on the object can be produced from renewable resources, and not from an application stören¬ locate the odor containing substances whose pro¬ problem-free incorporation in detergents improves the washing effect of these agents at low wash temperatures. It is an object of the invention to provide such a detergency enhancing substances as the amine derivatives of fatty raw materials. Further, it is an object of the invention is to find those produced from fats Aminderi¬ derivatives, already in relatively small amounts, d. H . in relation to the actual surfactants significantly unter¬ schüssigen amounts cause a superadditive increase in action in the lower wash 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 thereby the detergency enhancing additives may be incorporated into the detergent without including powder property or suffering. it is used in the preparation of the compositions to undesirable exhaust gas problems during the spray drying. Another very important object of the invention is to find a selection criterion for the question as detergency boosters coming amine compounds, whereby it is possible, detergent bereit¬ zustel len that the pH of the wash liquors produced therefrom with respect to detergency enhancing activity and are optimized for the lowest possible amount used, bond especially the Aminver¬.

Accordingly, the present invention is a detergent containing at least one synthetic anionic and / or nonionic surfactant and an aliphatic bond Aminver¬, wherein the amine compound is selected so that its pK. Value is at least equal to 14, reduced by the output-pH of a 1% aqueous solution of the detergent is. The pH refers to a detergent composition containing the amine compound ge called. The pK. Value lt stel the negative writing tive logarithm of the equilibrium constant for the amine compound in the presence of Hydrolysegleich¬ weight is:

K b = (amine + H) (OH ') (1)

(Amine)

For the pK. Value therefore applies

pK b + pK a = 14 (2)

pK b = 14 - pK a (3)

The pK. Value was determined by titration of an aqueous solution Lö¬ the amine compound with a strong acid. Plotting the pH profile during the titration as a function of the added amount of acid to, the following relationship applies for the point of the curve where half of the amine substance is in the form portonierter,

pK. = 14 - pH (4) These correlations are z. B. in R. B described RDI CKA, fundamentals of physical chemistry, 12th edition, pages 609 and 610, VEB German Academic Publishers, Berlin 1973.

The pK. is value for protonatable amine compounds within the scope of this invention, a characteristic value as a selection criterion for suitable amine compounds according to the relation (5)

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

serves. The pK. Value l IEGT generally 4 to 9

The selection criterion mentioned makes it possible to make a connection in terms of the appropriate type and the required amount used op¬ timale selection. In said pK. Value range are particularly suitable detergency enhancing substances those that have a low pK. -Have value . But there are also substances suitable in which the difference between the pK. - value and the pH of the 1 wt. - aqueous detergent solution is not less than about. 1 This is particularly true for substances with about the same solubility in water. It is believed that detergent according to the invention therefore particularly good Wasch¬ effective both at low and at high Waschtempera¬ structures have, because the type and amount of detergency ver¬ fortifying amine compound buffering in an optimal manner to the pH-value properties component particularly their Gerüststoff¬ - - through the application of the inventive teaching differnet I have voted together laws detergent ab¬. Typical I hinsichtl detergency improved detergents contain at least one amine compound selected 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 a Alkyi-, Hydroxyalkyi- or alkenyl group having

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

R 3 independently of one another Aikylgruppen having 1 to 4 C-Ato¬ men, mean the group H f OCH-CH-) with y = 1 to 6 or together with the nitrogen atom a 5- or 6-membered ring containing one additional nitrogen - or

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

R is also hydrogen;

b) amidoamines of the formula al lgemeinen

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

wherein n = 2 to 4, R is a Alkyi- or alkenyl group having 9 to 17 carbon atoms, R, R and R 7 is hydrogen or C j - to

C, mean -Aikylgruppen, with the proviso that at least

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

c) Alkyi-, alkenyl or hydroxyalkyl derivatives of glucamine, where the Alkyi-, alkenyl or hydroxyalkyl group having from 6 to 22 carbon atoms;

d) Alkyi-, alkenyl or hydroxyalkyl derivatives of morpholine in which the Alkyi-, alkenyl or hydroxyalkyl group having from 6 to 22 carbon atoms,

group comprising. The ether amines (a) in which R is a Alkyi-, hydroxyalkyl or alkenyl group, are in the non-prepublished deut¬'s patent application P 35 22 389.; the amido amines (b) are a component of the detergent which is also not vor¬ unpublished German Patent Application P 36 06 828. Insbe¬ sondere contain detergent according to the invention

3-40 wt -.% Anionic and / or nonionic surfactants 0, 1 - 5 wt. -% of amine compound

Range 5 - 80 wt -.% Of water-soluble and / or insoluble inorganic and / or organic water-soluble builder salts 0-30 Cew. -% inorganic, "releasing in aqueous systems H_C per compounds, preferably

Perborate radical other conventional ingredients in detergents.

The ether amines described in the prior application are in particular those ether amines of the general formula I, in which it is the substituent R are those Alkyi- or alkenyl groups, such as are available from industrial fats and are present in the resulting herstel lbaren fatty alcohols is. Particularly vorzugt R essentially containing 10 to 20 atoms Kohlen¬, in particular with substantially 12 to 18 lenstoffatomen Koh¬ are respectively in the Alkyi-. Alkenyl. Preferably, such substances of the formula I are used where

2 3

Substituents R and R both the Ethoxygruppierung

H (OCH CH_) mean. Also preferred are used

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

Or R 3 comprises said Ethoxygruppierung and the other

Residue means a C -C.-alkyl group or hydrogen. those compounds of formula I in which the sum of all existing index numbers x and y zwi¬ rule the numerical values ​​2 and 7 is particularly preferred, and where the substi- tuent R a Alkyi- or alkenyl group having essentially 12 to 18 carbon atoms , An optimum efficiency is at a RATIOS-is άer total number of ethoxy and hy- droxyethyl-Cruppen to the number of Alkyi-, hydroxyalkyl or -alkenyl-Al- carbon atoms in the ether amine of the formula I from 1 / 6-1 / 2 preferably 1/4 to 2/5 was observed.

The substances of the formula I according to the invention can be prepared by processes known per se by reacting an ent speaking Fettalkoholpolyglykolethersulfats with a primary

2 3 or the secondary, the substituents R and R importing

be prepared amine (British Patents 1,067,762 and 1,087,413). In these alkylation reactions is a Kohlen¬ material-nitrogen bond is formed. Another Herstellungsver¬ drive (earlier German patent application P 35 04 242.7) be¬ writes the reaction of a Fettalkoholpolyglykolethersulfats with a tertiary amine having at least one hydroxyalkyl substituent, that is, for example, triethanolamine, wherein the alkylation at the hydroxyl group of the hydroxyalkyl moiety to form a carbon-oxygen bond takes place.

The compounds of formula I thus prepared can gegebe-

2 3 be appropriate, alkoxylated or subsequently to the substituents R and R, provided that these have reak¬ tion capable hydrogens. In general, but is selected in the direct manufacture, the Polygfykolether moiety in the fatty alcohol ether sulfate such that it or, together with the optionally supplied via the amine einge¬ ethoxy. Hydroxyethyl radicals leads to optimal for the proper use he find balance between Hydro¬ phobia and hydrophilic properties of the molecule. A part of or ethoxy. Hydroxyethyl radicals may also be replaced by isopropoxy or hydroxy-isopropyl radicals. Typical representatives of the Verbindun¬ gene used in the invention of formula I are, for example, the reaction products of fatty alcohol ether sulfates which may have a different degree of ethoxylation, with primary amines, such. For example, ethanol amine, a C.-C.-alkylamine such as methylamine, or with se¬ ondary amines such. As diethanolamine, morpholine, a di- alkylamine with C ^ -C ^ alkyl such. As diethylamine. Insbe¬ sondere is the reaction products of fatty alcohol ether sulfates having tertiary, at least one hydroxyethyl group-containing amines such. amine as triethanolamine, diethanol-methyl. These substances include, for example, the gene Verbindun¬: C 12 / C lu - (coconut) alkyl poly (3.6) oxyethyl-hydroxyethylamine, C 1 _ / C 1 .- (coconut) alkyl-di- ( oxyethyl) -hydroxyethyI-ethylamine, C 12 / C 1R - (coconut) alkyl-di- (oxyethyl) -hydroxyethyl-methylamine di lauryl-oxyethyl-diethylamine, n-octyl-oxyethyldihydroxyethyl- amine, C 1? / C 1R - (coconut) alkyl-di-oxyethyl-dihydroxyethylamine, olefinsulfonates y l-trioxyethyl-dihydroxyethy lämin, 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 -amine, C. - / C .-- (tallow) -alkyi / alkenyl nyl-tri-oxyethyl-dihydroxyethyl-amine (tallow alcohol iodine value of the 110 to 130). Reaction products of fats Fettalkoholethersul- with a primary, secondary or tertiary amine having we¬ nigstens a hydroxyisopropyl group are suitable.

The substances used in the invention do not have an application an¬ technically disturbing odor and can be made from renewable raw materials with respect to their long-chain fatty Alkyi- or alkenyl radicals. So have these applications Verbin¬ least two beneficial properties that can be awarded collectively known as detergency boosting additives substances not. Detergent mixtures which have been prepared using the ether amines of the formula I as defined above, have an improved grease and pigment / grease-ness be washed; they reach or exceed the properties of the known fact, comparable detergency enhancing additives containing detergent.

The ether amines used in this invention may be due han¬ by their method of preparation substance mixtures spindles. So be obtained via the raw material fat regularly fatty alcohols hol mixtures of certain sections of chain lengths by gro߬ technical distillation process; also in the ethoxy-regulation of fatty alcohols as fatty alcohol polyglycol ether sulfate precursor for manufacturing ethoxy are known to be obtained lierungsgemische having an average degree of ethoxylation. Finally, the reaction of the fatty alcohol ether sulfate with the amine may be a weave CN or CO bond then lead to mixtures if the amine has more than one reactive site, which can result in minor amounts and the Bisalkylierungsprodukt.

The following are the pK be. Values ​​for some characteristic ether amines listed:

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

R 2 = -CH 2 CH 2 OH R 3 is H

= 6, 7

P K b

c) 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 b = 6.5 κ

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

X = 2

R 2 = H

R 3 = -CH 2 CH 2 OH

= 6.6 pK b

f) R 1 = C 12 H 25 ~

X = 1

R 2 - CH 3 - R 3 is -CH 2 CH 2 OH

P κ B __ 7.5

g) R 1 = C 12 H 25 ~

X = 1

R 2 = R 3 = -CH 2 CH 2 OH

P K b = 8.0

In the inventive detergent, the surfactant combination of at least one surfactant from the group of anionic, nonionic and zwitterionic surfactants, and the ether amine of the formula I is preferably in such an amount ratio before that surfactant or surfactant mixture and an ether amine of the formula I in terms of quantity in the ratio of 30: are 1: 1 to 2: 1 and in particular in a ratio of 10: 1 to. 3 Based on the total detergent, the ether amine of the formula I is accordingly preferably in amounts of 0.2 to 10 wt .-%, preferably 0.5 to 3 wt .-% exists. Preferred detergents contain the combination of surfactant or surfactant mixture and the ether amine of the formula I in amounts of from 5 to 65 wt .-%, preferably 8 to 35 wt .-%, again based on the total detergent formulation. Bemer¬ kenswert is the finding that the detergency enhancing effect of the ether amines of the formula I having both the rule syntheti¬ anionic surfactants as well as with the nonionic Ten¬ Šiden occurs.

In the other 95 are made to 35 wt .-%, preferably 92-65 wt .-% of the ether amines containing detergent from at least one further washing and cleaning active substance from the group of inorganic and / or organic Gerüstsub¬ punch (Builders), foam inhibitors, soil suspending agents, optical brighteners, enzymes, dyes and fragrances, water and / or other liquid carriers. A bleaching detergent containing an addition of peroxy compound, stabilizer, and optionally an activator .for the Peroxyyerbindungen, total quantities in 10 to 40 wt .-%, in particular 15 to 35 wt .-%, based on. the total detergent.

Typical of the present invention, ether amines containing powder detergent in accordance with the following basic formulation:

Of 5 - 50, preferably 5 - 25 wt .-% of at least one surfactant from the group of sulfonate and sulfate surfactants and the nonionic surfactants of the type substituted with hydrophilic nitrogen-free groups alkanols or alkenols, 0.3 - 5, preferably 0,5 - 2.5 wt .-% of the ether amines of the formula I, wherein the surfactants and the ether amines vor¬ preferably in a ratio of 10: 1 to 3: 1, respectively,

0-8, preferably 0.2 to 5 wt .-% of a foam inhibitor from the group of alkali metal soaps of substantially C 18 -C 22 fatty acid esters and the non-surfactant suds inhibitors. From 50 to 94.7, preferably 55 to 90 wt .-% powdered organic and inorganic builders, ge optionally including a bleaching component, and 0 - 10, preferably 0.5 to 10 wt .-% customary additives for detergents from the group of optical brighteners, enzymes, soil suspending agents, corrosion inhibitors, textile tilweichmacher, antimicrobial agents, dyes and fragrances.

Flüssigwasch¬ containing typical invention, etheramines medium different from the powdered formulations by increased surfactant and a reduced Gerüstsub¬ punch portion and the lack of a bleaching component. Such detergent in accordance with the following basic formulation:

10-60, preferably 15 to 50 wt .-% of at least one sids Ten from the group of sulfonate and sulfate surfactants of the nonionic surfactants of the type substituted with hydro¬ philic nitrogenous groups alkanols or alkenols the C .-- C ... soaps with a predominant proportion of soaps of the chain lengths C 12 C., preferred wise a mixture of synthetic anionic, nonionic and soap surfactants,

From 0.5 to 8, preferably 0.8 to 6 wt .-% of the ether amines of the formula I, wherein the surfactants and the ether amines vor¬ preferably in a ratio of 20: 1 to 5: 1 are present 0 - 20, preferably 1 to 15 by weight of organic and / or inorganic builders,

10 - hole 89.5, preferably 15 to 60 wt .-% liquid carrier materials from the group of water-soluble lower Alko¬, diols and ether alcohols and water, and ι 0 - 1 Q, preferably 0 5 to 10 wt -.% the usual, already mentioned above for powdered detergent Zu¬ rates.

In the typical invention, ether amines containing paste-detergents consists of substantially liquid portion, preferably substantially excl ießlich nicht¬ from nonionic surfactants, so that compared with the liquid detergent, the proportion of liquid carriers I Deutl is reduced. Preferred pasty formulations come without a liquid Trä¬ gerstoffe that even lei¬ not contribute to the detergency most from, in particular, these formulations contain virtually no free water, by which is weight water amounts below 2 -.%, Which does not in any way as water of hydration of the Einzel¬ are component-bound, of course. A framework recipe for paste detergent has the following composition Zu¬

30 - 60, preferably 35 to 55 wt -.% Wholly or mainly as such iegende in liquid form vorl surfactants, particularly non-ionic surfactants of the type substituted with hydrophilic nitrogen-free groups alkanols or alkenols, 1 - 10, preferably 2 to 8 wt. - % of ether amines of the For¬ mel I wherein vorzugs¬ the surfactants and the ether amines, in the ratio of 20: 1 are present, 0 - 8, preferably 0, 2 to 6 weight -% of a foam inhibitor from the group consisting of soaps 1 to fifth , in particular of the fen Kalisei¬ and in particular the C ^ -C. g potassium soaps, and the non-surfactant foam inhibitors, 10 - 69, preferably 20 to 50 wt. -% of organic and / or inorganic builders, optionally eventually ein¬ a bleaching component, and 0 - 10, preferably 0, 5 to 10 wt -.% Of the usual additives mentioned above for the other Formulation Examples Wasch¬.

A particularly preferred embodiment of the invention, be¬ arrives puiverförmiges detergent for lower temperatures Waschtempe¬ that preferably contains a bleaching component from Peroxyver- bond, Kaltbleichaktivator and stabilizer and which has a specific surfactant together with a low-phosphate or phosphate-free builder component. The use of this detergent leads at low wash temperatures even against stubborn fat and grease / pigment soil on conventional textile fabrics, ie cotton, Poly ester and blended fabrics to excellent cleaning performance. This particular surfactant is constructed on the basis of a mixture of nonionic surfactants from at least 2 separately produced low ethoxylated C ^ -C- g alkanols respectively. nolen alkenes. having a cloud point in .Bereich 0 to 45, preferably 5 to 40 (measured in water). In addition to these relatively schwerlös¬ union nonionic surfactants wasser¬ a slightly soluble anionic sulfonate and / or sulfate surfactant is at least in stoichiometric gegen¬ over the nonionic ethoxylates amounts vor¬ hands, so that by weight, for example, 10th Parts of the mixture Niotensid- 3 to 9 parts by wt. Of sulfonate or. Sulfate surfactant come. As a further essential to the invention part of this surfactant contains 1 to 5 parts by wt. Of an ether amine of the formula I, again based to 10 wt. Parts by the nonionic surfactant micro research.

This invention containing for etheramines detergent particularly preferred surfactant combination may be present in amounts of from about 8 to 30 -.% Component of a low-phosphate or its phosphate-free detergent formulation, which is oriented, the term "low phosphate" to the maximum permissible values ​​of the existing phosphate maximum quantity regulations, which at a Uπiversalwaschmittelformulierung with conventional proportioning an amount of about 25 wt regulations currently -. ° s Natriumtripoly- phosphate based on the entire powder detergent corresponds, which value medium concentrates at low dose Wasch¬ may also be higher.

The foaming power of such detergents can 5 percent to 5 by addition of a non-surfactant foam inhibitor in amounts of 0, 2 to 0.8 wt .-% or from 0. -% of an alkali soap usually C. gC Q fatty acids, respectively. a mixture of the nichttensid¬-like foam inhibitor and soap in an amount of 0, 2 to 5 wt -.%, each based on the total detergent, so re¬ be duced that when used in washing machines neither effervescence nor difficulty Rinse occur.

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

Cg, _ alkyl, olefin, 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 alkane sulfonates obtainable from C 1 -C 2. g alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition onto olefins are available, as well as the esters of alpha-sulfofatty acids, for example. B. the alpha-suifonierten methyl or ethyl esters of hydrogenated coconut, palm kernel or Talgfettsäureή. Suitable surfactants of the sulfate type are the Schwefelsäuremonoester of primary alcohols nat cozy or synthetic origin, i. H . of fatty alcohols such. B. Coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or C 1 -C- Q 0 oxo alcohols, and those se-ondary alcohols of this chain length. or the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide aliphatic primary alcohols. ethoxylated secondary alcohols are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides.

Suitable anionic surfactants to nat Icher raw materials in addition to the active washing soaps, d. 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- atoms or alkenyl group having 9 to 23, preferably 11 to 17 Kohlenstoff¬. These anionic surfactants l ying in the form of their sodium, potassium or ammonium salts or in the form of soluble salts with organic bases, in particular the mono-, di- or triethanolamine before.

The nonionic surfactants which are particularly important Anlage¬ addition products of from 3 to 20 moles of ethylene oxide to primary. --C --- alcohols such. B. on coconut or tallow fatty on Oleyl¬ alcohol, oxoalcohols or secondary alcohols of this chain length. Besides this included water-soluble nonionics are not respectively. not completely water-soluble, low-ethoxylated fatty alcohol polyglycol ether having 3 to 7 ethylene glykoletherresten in the molecule of particular interest, especially when they are used together with water-soluble nonionic or anionic surfactants.

I n combination with the low-ethoxylated fatty alcohol polyglycol are glycol ethers, as nonionic surfactants, the wasser¬ soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing adducts of ethylene oxide with polypropylene glycol, polypropylene glycol, alkylenediamine and Alkylpolypropylenglykole having 1 to 10 carbon atoms in the alkyl chain useful in which the polypropylene glycol chain as a hydrophobic residue acts. Also nicht¬ ionic surfactants of the amine oxide or sulfoxide ver¬ reversible, for example the compounds N-cocoalkyl-N, N-di- methyl amine oxide, N-TalgaIkyl-N, N-dihydroxyethylamine. Be¬ as the surfactant was in part are also suitable soluble wasser¬ the alkyl glucosides, the hydrophobic C_-C 2n alkyl group is linked to a usually oligomeric hydrophilic glucoside. The preferred nonionic surfactants are the respectively with ethoxy groups as hydrophilic nitrogen-free group-substituted alkanols. Alkenols. The term "nonionic surfactants (nonionics)" includes therefore not Ether¬ used in the invention of the formula I amine.

The foaming power of the surfactants can be increased by combining ge appropriated surfactant or decrease. Usually a reduced foaming of the wash liquor while working in the machine is desired. In soaps the foam suppression increases with the degree of saturation and the number of carbon atoms of the fatty acid residue; Sei¬ fen saturated C_ 0 -C_ above fatty acids are therefore suitable be¬ Sonders as foam inhibitors for detergents based on sodium triphosphate as a builder, while containing predominantly in the zeolite detergents already C. -C. "Soaps good Schaumin- show hibierung, especially at low wash temperatures. The non-surfactant foam inhibitors are generally water-soluble, mostly aliphatic C "-C -_- hydrocarbon radicals containing compounds. Appropriate foam inhibitors are for. 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 and lo 4U haloparaffins having melting points below 100 ° C and silicone oil dispersions based on organopolysiloxanes and microfine silica, which may optionally be silanized. Suitable organic and inorganic builders are suitable for ether amines containing detergent preferably alkaline salts, particularly alkali metal salts, not only precipitate calcium ions or bind complex, but possible also effect with the surfactants a synergistic increase in detergency and a Schmutztragever¬ may possess. Of the inorganic salts, the wasser¬ soluble alkali metaphosphates or alkali polyphosphates, particularly pentasodium triphosphate, are still of particular importance. In addition to these phosphates organic complexing agent for calcium ions and heavy metal ions may be present. These include compounds of the type of aminopolycarboxylic such. B. Nitrilotriacetic acid, amine-pentaacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine and higher homologs. Suitable phosphorus-containing organic complexing agents are water-soluble salts of alkane polyphosphonic acids, amino and Hydroxyalkanpolyphos- phonsäuren and phosphonopolycarboxylic acids such. B. the Ver¬ compounds methanediphosphonic acid, dimethyl aminomethane-1, 1-di- phosphonic acid, Aminotrimethylentriphosphonsäure, tetramethylentetraphosphonsäure ethylenediamine, diethylenetriamine pentaphosphonsäure, 1-hydroxyethane-1, 1-diphosphonic acid,

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

Among the organic builders are the N and P-freely-, with calcium ion complex salts polycarboxylic acids, including polymers containing carboxyl groups, are of particular importance. Suitable low molecular weight Verbindun¬ are gen such. B. boxymethyloxybernsteinsäure citric acid, 2, 2'-oxydisuccinic acid or carboxylic. Suitable polymeric Polycarbonsäu¬ ren have a molecular weight of 350 to about 1 500 000 in the form of water-soluble salts. Particularly preferred polymeric polycarboxylates have to include a molecular weight ranging from 500 to 175,000, and especially in the range from 10000 to 100 000. Da¬ compounds such. B. Polyacrylic acid, poly-alpha- polycarboxylates have to include a molecular weight ranging from 500 to 175,000, and especially in the range from 10000 to 100 000. Da¬ compounds such. B. Polyacrylic acid, poly-alpha- hydroxyacryisäure, polymaleic acid, and copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such. B. Vinylmethyl¬ ether. Further useful are the water-soluble salts of the polyglyoxylic acid.

Another component of the builder component consists of a homopolymeric and / or copolymeric carboxylic acid or its sodium or potassium salt, the sodium salts are preferred. -suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acrylic. Suitable copolymers are those of acrylic or methacrylic acid or with maleic acid. Copolyvidone mere ethers of acrylic acid, methacrylic acid or maleic acid with vinyl, such as vinyl methyl ether or Vinylethy, further comprising Vinylestern such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide as well as with ethylene, propylene or styrene. In such copolymeric acids in which one of the components has no Säure¬ function whose proportion is in the interest of aus¬ reaching water solubility not more than 70 mole percent, vor¬ preferably less than 60 mole percent. Particularly suitable copolymers of acrylic acid with maleic acid, as characterized 25551 -B1 detail for example in EP. These are copolymers which 40 to 90 wt -.% Of acrylic acid or methacrylic acid and 60 to 10 wt -.% Contained maleic acid. Especially preferred are those copolymers in which are present wt .-% acrylic acid and 55 to 15 wt .-% of maleic acid 45 to 85 are. The molecular weight of the homo- or Copolyme¬ ren is in general from 1000 to 150,000, preferably 1500 to 100 000. A further component of the builder component consists of sodium silicate having 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 content can 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 used in the usual hydrated, finely crystalline form, ie they have virtually no particles greater than 30 microns and preferably consist of at _ least 80% of particles of a size less than 10 microns. Their calcium binding capacity, as determined in accordance with DE 24 12 -837, is in the range of 100 to 200 mg CaO / g. Also useful is particularly zeolite NaA, and also the zeolite NaX and NaA and NaX mixtures.

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

Other builders, are usually employed in liquid compositions, the properties due to their hydrotropic Eigen¬ are the salts of the capillary, 2 to 9 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic acids, for example the alkali metal salts of alkane, benzene, toluene, xylene or cumene sulphonic acids, the sulfobenzoic acid, sulfophthalic acid, sulfo acid, sulfosuccinic acid and salts of acetic acid or lactic acid. As solubilizers acetamide and urea are suitable.

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

Other suitable Gerüstsaize are sodium and - if minor amounts of phosphates to stand against the concomitant use of no concern - polyphosphates, particularly penta tripolyphosphate. Its proportion may be present under the conditions specified above to 25th -, preferably 5 wt% to 22 -. Amounted%. In cases where phosphates are not used nen kön¬, also a replacement by sodium nitrilotriacetate in An¬ comes to share, for example, 2 to 10 wt -.% In question. Other known water-soluble phosphate substitutes can optionally be used ", for example polyacetals of glyoxylic acid in the form of sodium salts.

Among the builder salts also include the most "small quantities present in relatively, co-builders as so-called, capacitors Stabili¬, Fällungsverhüter (threshold substances) acting Se¬ questrierungsmittel from the class of aminopolycarboxylic acids and polyphosphonic. The aminopolycarboxylic acids include ethylenediaminetetraacetic that Diethylentriaminpentaessig- acid and their higher homologs. Suitable Polyphosphonsäu¬ ren are 1-hydroxyethane-1, 1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and higher homologs thereof such. B. diethylenetriaminetetra- (methylenephosphonic ). the above-mentioned polycarboxylic acids or polyphosphonic acids are usually used in the form of Na¬ trium- or potassium salts. I hre use amount is generally from 0.1 to 5 wt !, preferably 0.2 to 1 wt .-%.

Among the other usual detergent ingredients include comparable grauungsverhütende materials, optical brighteners, enzymes, Bleich¬ agents and bleach activators, foam inhibitors, dyes and Duft¬ materials, biocides, neutral salts and substances which improve the texture Pulver¬.

Suitable Vergrauungsverhüter are cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses, and mixed ethers, such as methylhydroxyethylcellulose, hydroxypropylcellulose methylhydroxy- and methyl Carbpxymethylcellulose. Also suitable are mixtures of different cellulose ethers, particularly Ge mix of carboxymethylcellulose and methylcellulose.

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 similar structure, an¬ the steep of the morpholino carry a diethanolamino group. Furthermore, as come brightener of the type substituted diphenyl styryls in question, e.g., alkali metal salts of 4,4'-bis- (2-sulfo styryl) -diphenyls, 4.4 '-bis- (4-chloro-3-sulfostyryl) and 4- (4-chlorostyryl-4' - (2-sulfostyryl).

Suitable enzymes are those from the class of proteases, lipases and amylases and mixtures thereof in question. are particularly suitable from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus recovered ene zymatische agents. The enzymes can be embedded in coating substances ein¬ sien, to protect them against premature decomposition.

As a bleaching component perhydrates and per compounds normally used in detergents and bleaches in question. Among the preferred perhydrates are sodium perborate, which may be present as tetrahydrate or the monohydrate, the perhydrates of sodium carbonate (sodium percarbonate), the Natriumpyrophosphats (perpyrophosphate), the sodium silicate (persilicate) and of urea. This perhydrates come vorzugt together with bleach activators used.

Preferably sodium tetrahydrate is used in combination with bleach activators as bleaching component in question. Among the Bleich¬ activators include, in particular N-acyl compounds and O-acyl compounds. Examples of suitable N-acyl compounds are multiply acylated alkylenediamines such as tetraacetyl, tetraacetylethylenediamine and higher homologs thereof, and acy¬ profiled glycolurils, such as tetraacetyl. Further examples are sodium cyanamide, N-alkyl-N-sulfonyl-carboxamides, N-acylhydantoins, N-acylated cyclic hydrazides, triazoles, urazoles, perazine Diketopi-, sulfuryl, cyanurates and imidazolines. As O-acyl compounds are in addition carboxylic, such as phthalic anhydride and esters, such as sodium (iso) -nonanoyl-phenolsulfonate, especially acylated sugars, such as glucose in question. Preferred bleach activators are tetraacetylethylenediamine and glucose pentaacetate. The bleach activators in order to avoid interaction with the per compounds, especially during storage of powdery mixtures, be coated with coating substances.

Suitable foam inhibitors are, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silicic acid, paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica, and saturated fatty acids having 18 to 24 carbon atoms or their alkali soaps. Mixtures of various foam inhibitors, for example. B. silicones and paraffins are useful. Other suitable constituents neutral salts, in particular triumsulfat Na¬ as well as acting as a stabilizer for per compounds magnesium silicate into consideration.

The other detergent ingredients can be present in amounts which are common in known detergent compositions. The proportion of graying inhibitors are generally employed is from 0.2 to 2 by weight, the proportion of the optical brightener 0.05 to 0.5 wt .-%. The proportion of enzymes depends primarily on their activity. Technical enzyme preparations mixed üb¬ SHORT- with stabilizers, calcium salts and diluents and are adjusted to a specific activity, typically come set to Ein¬ in proportions of 0.1 to 2 wt .-%. The percentage of perborate is usually 5 to 25 wt .-%. The amounts of bleach activators also focuses on their effectiveness. Highly effective activators, such as tetraacetylethylenediamine, are usually used in amounts of 0.5 to 5 wt .-%. This applies analogously also for bitoren Schauminhi¬, whose proportion in the case of highly effective silicone antifoam generally 0.01 to 0.5 parts by weight, waxy in the case or may be pa¬ raffinischer substances or high molecular weight fatty acids to 2 wt .-%. The proportion of Natriumsuifat can wt .-% to 25 even be even more in special cases.

Other detergent according to the invention contain 1 to 5 wt .-% amidoamine of the formula II, wherein the amidoamine from fat

Ü derived acids, the acyl group (R-CO-) has 12 to 18 carbon atoms auf¬, wherein at least 50 wt .-% 12 to 14 C atoms ζ fi 7 and the sum of the in the radicals R, R , R and außer¬ which insoluble in water to partially soluble polyglycol-containing surfactants, which are absorbed on a granular material and ethoxylated Träger¬ from (i) linear or branched in the 2-position methyl ether groups, saturated or monounsaturated primary C 1g -C 18 - alcohols with an average of 4 to 6 glycol ether groups,

(ii) ethoxylated, linear or methyl-branched in the 2-position, saturated primary C -C 1Q. "Alcohols with an average of 4 to 6 glycol ether groups exist,

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

The nonionic surfactants consist of a mixture ausgewähl¬ ter nonionic surfactants which are not or only partially soluble, probably are dispersible but because of their comparatively low degree of ethoxylation in water. Their HLB values ​​are below 12, usually 6 to 11.5.

The listed under (i) nonionic surfactant derived from primary fatty alcohols of natural or synthetic origin, which may be monounsaturated, linear or methyl-branched in the 2-position (oxo radical) saturated. Preferably, starting from linear fatty alcohols, that is to say cetyl alcohol, stearyl alcohol, oleyl alcohol and mixtures thereof, z. As tallow. The average number of glycol ether is from 4 to 6, in particular 5. According to the chen Usually, for at polyglycol statistical distribution is mixtures which can ent also hold shares with lower and higher degrees of ethoxylation. However, the statistical maximum or the degree of ethoxylation should durchschnitt¬ Liche as indicated, will be 4 to 6, preferably at the 5th The HLB value of (i) fraction is between 7.5 and 10, preferably 8.2 to 9.3. The listed under (ii) nonionic surfactant derived from appropriate fatty alcohols or oxo alcohols containing 10 to 14 carbon atoms likewise. Preferably, linear alcohols having 12 to 14 carbon atoms are used as starting materials, ie, lauryl alcohol and myristyl alcohol and mixtures thereof. Are useful in particular from coconut fatty alcohols derived C .-- C. "-alcohol, wherein the proportion of shorter chain alcohols, advantageously with

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

The aminoamide derived from saturated or mono-saturated fatty acids with ungesät¬ 10 to 18, preferably 12 to 18 carbon atoms, from where such fatty acids are particularly preferred whose acyl groups composed of more than 50 wt .-%, in particular more than 65 .-% of those having 12 to 14 carbon atoms are made. Especially suitable are mixtures derived from coconut fatty acids, of which the fraction having 10 or less carbon atoms has been largely ab¬ separated. The diamine residue derived from amines alkylated Di¬ such as ethylenediamine, 1, 3-propylene and 1,4-butylene diamine from. As Aikylgruppen methyl, ethyl, propyl or isopropyl groups come into question. Preferably, the sum should the

5 7

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

6, respectively. Examples of such compounds are N, N-di- methylethylenediamine, N, N-dimethylpropylenediamine, N-methyl-N-ethyl-ethylenediamine, N, N'-dimethyl-ethylenediamine, N, N'-dimethylpropylenediamine, N-methyl-N 'ethyl-propylene and mixtures of such alkylated alkylenediamines. Particularly forthcoming Trains t are compounds of formula II, in which R represents an alkyl radical having from 9 to 1J carbon atoms, wherein at least 50% of the radicals R have 11 to 13 carbon atoms, R is H, R and R is methyl and / or representing 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), where in the preferred range a particularly balanced Verhält¬ nis is imposed detergency, especially against greasy and oily stains. The content of the means at the aminoamide is preferably 1 to 5 wt .-%.

or as the anionic surfactants of the sulfonate type. Sulfate type are those described previously in the ether amines containing detergents suitable.

The weight ratio of nonionic component (surfactants + aminoamide) to anionic component is from 4: 1 to 1: 2, in particular 2: 1 to 1: 1. In this area the Wasch¬ is strong against both greasy as mineral Verschmut¬ tongues particularly pronounced. The content of the agent to the vor¬ surfactants mentioned amounts to a total of 10 to 25 wt .-%, preferably 12 to 20 wt -.%.

As builders or builder salts, the substances described above containing already in the ether amines detergents are used.

The compositions of the invention are available as granular powders or powder mixtures, which are available in a suitable manner by granulation, spray drying, spray mixing, homogenizing or a combination of these procedures. Since the nicht¬ ionic surfactants and the aminoamides are liquid, tending to stick compounds, due to their Nei¬ supply to the "pluming" only limited suitability for spray drying are suitable, it is often I required, that they sorbed ad¬ to a carrier substance is. As a carrier, the builders, more particularly zeolite, phosphates, silicates, nitrilotriacetate, and mixtures thereof are suitable, salt further spray-dried mixtures of Gerüst¬, anionic surfactants and other components, provided that they are stable under the conditions of spray-drying. From builder salts existing carrier substances can also Neutral salts such as sodium sulfate, Vergrauungsverhüter, Mg-silicate as well as additional adsorbent such as contained feintei celled silica, finely divided alumina, smectite clays, layered silicates and bentonites. Instead of spray-dried mixtures Gerüstsalz¬ prepared mixtures can serve as a carrier for the nonionic surfactants and the aminoamides also by build-up. After applying the liquid components to this there are suitable carrier materials, the granules still with adsorbent, the sticking preventing coatings be ver¬ see what can be done for example by powdering with vorgenann¬ th finely divided adsorbents.

A particularly preferred embodiment of the invention consists of the fact that 30 to 100 wt -.% Of the anionic surfactants in the form of granules vorl ying containing respectively zeolite, the salt of the polymer. copolymeric 'carboxylic acid and the Natriumsi¬ LIKAT respectively. a portion of the sodium silicate present in total. Suitable granules have the following composition (in weight -%, based on granules.):

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, 8-18 I, in particular 10-16 % water, at a

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

Among the dispersion stabilizers are meant compounds that are used to stabilize aqueous slurries or pasty zeolite. They are generally added to these slurries during their manufacture or moist filter cake and also remain during further processing in the zeolite. Reference is made to this DE 25 27 388th Examples of such stabilizers are neutral salts such as sodium sulphate, nonionic surfactants from the class of ethoxylated fatty alcohols having 12 to 18 carbon atoms and 3 to 10 glycol ether groups and polymers and copolymers carboxylic acids. Preferably the dispersion stabilizer is selected from the listed under non-ionic surfactant is or. of the same part.

The granulate is preferably produced by spray drying and be¬ detail in the patent application P 34 44 960 (D 7180) is written, has an average grain size of 0, 2 to 1, 2 mm and contains less than 2 wt -.% by weight, of dust-like fractions (particle size less than 0, 05 mm) and not more than 5 -.% of coarse particles (particle size about 2 mm). Its bulk density is 400 to 700 g / I. It is characterized by a very high adsorption capacity for liquid or pasty substances and is therefore particularly suitable as a carrier for the nonionic surfactants.

Therefore, in a further preferred embodiment, the invention is present as a mixture of several part powder. As part of powder are:

(A) A part of powder consisting of the above-described Gra¬ granulate of zeolite, (co) polymeric carboxylic acid salt, Na¬ triumsilikat, water, sator the nonionic Dispersionsstabili¬ and the adsorbed onto these granules nicht¬ nonionic surfactant component and the amidoamine.

(B) A portion of powder component consisting of the anionic Tensidkompo¬, the builder salts is not contained in the granules, and other detergent components, to the extent these are suitable for spray drying. These include complexing agents, graying inhibitors, optical brighteners, neutral salts.

(C) One or more part powders ent hold such ingredients that not brought reasons of stability, in direct contact with the constituents of the powder part (A) and (B) or are not to be spray-dried. These ingredients include bleaching agents, bleach activators, foam inhibitors, enzymes, perfumes and biocides. These materials are generally prepared separately and transferred to a suitable powder or granule form and mixed with the rest of powders. Liquid ingredients, such as perfume oils, can also go to other granular part powder such. B. the perborate be sprayed and added together with this to the mixture. Also, the foam inhibitors are preferably applied to a substance adsorbing acting Träger¬ or embedded in a water-soluble .Hüllmaterial in order verbestandteilen against interactions with other Pul¬ and to protect the resulting Wirkungs¬ loss.

The invention further provides a process for the production development of the amidoamines of the present invention containing detergent. This method consists in that a granulate of the composition Zu¬ (wt in -.%)

60-80%, in particular 65-75% zeolite, 3-20%, in particular 4-15% polycarboxylic acid salt, 0, 1 - 2%, in particular 0, 15-1% of sodium silicate, 8 - 1 8%, in particular 10 - 16% water at a

is drying temperature removable from 145 ° C, 0, 5-5%, preferably 2 - produces 4% dispersion stabilizer by spray drying, impregnating the granules with a mixture of nonionic surfactants and the aminoamide and the part obtained powder (A) with a spray-dried Teil¬ powder mixed (B) according to the above specified composition, and further part of powders (C) above-mentioned composition.

In the preparation of part of the powder (A) is important to ensure that its content is limited to sodium silicate. is provided from an¬ application for technical reasons, the content of sodium silicate in the detergent significantly higher, the excess portion should be added to the rest of powders, in particular the part sprühgetrock¬ Neten powder (B). Higher proportions of Natriumsiiikat in these granules as specified increase its disintegration or deterioration of its solubility and in the washing liquor. Thus, the release of the nonionic surfactant, which can lead to a deterioration of the washing result is delayed. This division of the 'Na¬ total triumsilikats present in two different partial powder is a further aspect of the invention.

More details about the preparation of the granulate and its impregnation with nonionic surfactants can be found in DE 34 44 960 (D 7180), is applied to the here expressly incorporated genom¬ men.

The compositions of the invention are characterized by a high detergency, in particular by an excellent Reini¬ purification capacity versus * persistent fatty stains, for example those from food and sauces residues, skin fat, lipstick and mascara from. In spite of their relatively high content of liquid nonionic surfactants, they are outstandingly pourable and free-flowing and do not tend to carry fats of Kartonageverpackungen. If they are prepared according to the preferred procedure, d. H . Adsorbing the nonionic surfactant of the previously prepared granules of zeolite, polymeric acid and sodium silicate, the formation of aerosols in the exhaust air of the spray towers is completely avoided.

EXAMPLES

example 1

This example shows the increase in the wash cycle of Pig¬ management / greasy stains as well as bleachable stains under the terms of machine wash. The tests wur¬ the carried out at 40 ° C and 60 ° C in a washing machine Miele W 433rd Further experimental data: 1 -Laugenprogramm, liquor ratio 1: 5, 6 at approx. 20 liter wash liquor; Detergent concentration 6, 9 g / l; Water hardness 16 ° d; 3-fold determination using 3, 6 kg of clean ballast washing, with in each case 2 tabs (sewn onto the ballast washing) of the test stains below. dirt as a pigment / Fettan¬ were used: dust-wool grease of unprocessed cotton; Dust sebum on refined cotton and dust sebum on cotton / polyester blend. were dirt as bleachable An¬ those used with red wine, blackberry, tea and coffee.

Formulation of the test detergent: 4 wt -% alkyl benzene sulfonate.

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

ethylene oxide

20 wt. -% Natriumtripoly phosphate

20 wt -.% Sodium perborate tetrahydrate

15 wt -.% Zeolite A

5 wt -.% Water glass Na 2 O '3 SiO- 35

3, .0 wt -.% Amine compound residue to 100 Cew. -% Perboratstabilisator, soil suspending agents, Sili¬ kon foam brake, sodium sulfate and water. The pH of a 1 wt. -% aqueous solution of this Wasch¬ means was 9. 9

As amine compound is an ether amine of the formula was used IC l 2 / C 1 4 -Kokosalkyl- (OCH 2 CH 2) 3 6 -NH-CH 2 CH 2 0H; the pK. Value of this ether amine is 6. 7 was compared with the known detergency boosters coconut amine + 2 EO. Result :

The mean values ​​from the individual reflectance values ​​(% Φ R) have been identified. the value of 63, 8% Φ R and for the known detergency booster, the value 62 found 9 fatty soils for the etheramine formulation, - at the 40 ° C wash were performed on the pigment /. In the case of the bleachable stains were as ent speaking reflectance values ​​61, 9 zeptur or for the inventive Re¬ 60, 8 gefun¬ for the known detergency booster. In the 60 ° C wash, the corresponding values ​​were Remissions¬ at 69, 4 and 69, 0 (pigment / fat). and at 68, 6 and 67, 8 (bleachable stains).

In addition, the two test detergent of this example were subjected by a panel of three experienced persons to an odor test and compare with the detergent without waschkraftver¬ strengthening additive. For the inventive formulation with the ether amine of the composition given above only faint odor was found, which was significantly ge ringer than the smell of the recipe with coconut amine + 2 EO.

Summary: The reflectance values ​​of the recipe according to the invention are slightly but significantly above the values ​​of the comparative detergent. The smell of ether amine is we¬ sentlich lower than that of coconut amine + 2 EO, which is in the Par¬ fümierung of such washing powder, as required by the market, of great importance. i

Analogous results are also obtained when amine replaces the ether amine above ge called the formula I by one of the following Ether¬: C 2 -. "-Kokosalkyl-di-oxyethyl dihydroxyethylamine; C. _ /, "-Kokosalkyl-di-oxyethyi-hydroxyethyl-methylamine; ^ 1 2.1 ~ coco-di-oxyethyl-N-morpholino; C. -, _ 8 -Talgalkyl tetra-ethyl-oxy dihydroxyethylamine. The pK. Values ​​of these compounds were all- over 4.5.

example 2

According to the patent specification DE 33 44 960 (D 7180) was prepared by spray-drying an absorbent granules of the following Zusam¬ mensetzung prepared (GT = parts by weight): 46, 7 GT NaX zeolite (based on anhydrous substance)

5, 0 GT copolymer (sodium salt)

0, 14 GT sodium silicate

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

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

67, 6 GT

The zeolite used had a particle size of 1 to 8 microns, wherein the proportion of about 8 microns 6 wt -.% Was. Larger than 20 microns were not available. As the polycarboxylic acid is a copolymer of acrylic acid and maleic acid having an average molecular weight of 70,000 (Sokalan CP5 ^ ') in the form of Na¬ was brought into use triumsalzes. As an ethoxylated fatty alcohol with 5 moles of ethylene oxide (EO) was reacted tallow alcohol (30% cetyl alcohol, 70% stearyl alcohol) was used (corresponding to a part of the component (i)).

The particle size distribution determined by sieve analysis revealed the following weight distribution: mm over to to to to under

1.6 0.8 0.4 0.2 0.1 0.1

Wt .-% 0 1 37 53 9 0

The weight per liter was 550 g / I.

67.6 parts by weight of the granules were apparatus in a Sprühmisch¬, comprising a relative to the horizontal inclined, equipped with mixing elements and spray nozzles cylindrical drum (Lödige mixer) with a molten mixture of the nonionic surfactant and the Aminoamidsbesprüht described in more detail below. The temperature of the granules was 20 ° C, the Tensidschmelze of 50 ° C. The surfactant mixture consisted of 4.1 parts by weight of tallow alcohol with 5 EO (remaining there are suitable proportion of component (i), 20 parts by weight of lauryl-myristyl alkohoI mixture (2: 1) with 5 EO (component (ii)) and 8, 3 parts by weight parts of the amino amide N-N'-Cocosacyl- dimethylpropyien- diamine wherein the acyl radical is a C .-- C. --Gemisch with a mitt¬ sized chain length of c._ _. the pK. value of the amino ¬ amide is 5.9. After cooling, a non-adhesive, granular product was obtained, the flowability was excellent, despite a content of 34 wt .-% liquid nonionic surfactant. the bulk density was 740 g / I.

30 parts by weight of the amide impregnated with the nonionic surfactant and the amino granulate (powder part A) were mixed with 54.7 Ge weight parts of a mixture of a spray-dried powder (Part B powder) and sodium sulfate (as weight compensation) mixed ver¬. The spray powder containing sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium ethylenediamine tetra-methylenphos- phosphate (EDTMP), cellulose ethers, sodium silicate, optical brightening agents and a further proportion of sodium sulfate. granulated enzymes were granulated silicon konentschäumer verbestandteilen to further Pul¬ admixed sodium perborate and granulated Tetraacetyl¬ ethylenediamine (TAED). This powdery or gra¬ nulären ingredients are summarized under the term "part powder C" zu¬, which accounts for a total of 15, 3 parts by weight.

The composition of the agent as well as other, produced in the same manner agent (wt in. -%) listed in Table 1.

table

Cg-Cg 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-propylene diamine 2.5 3.0 3.0 2.0

Na dodecyl benzene 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

(From 0.04% in the

Granules) 4.0 4.0 4.0 4.0

Cellulose ether 0.5 0.5 0.5 0.5 0.2 0.2 0.2 0.2 optical brighteners

Enzyme 0.5 0.5 0.5 0.5

Defoamer

(Silicone content 30%) 0.3 0.3 0.3 0.3

Sodium 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 Balance Balance Balance Balance

The pH value of 1 wt .-% aqueous solutions of these washes was 10.5. There were conducted tilproben with artificially soiled textile comparative experiments. The applied under reproducible conditions Baumwolitextilien soils consisted of make-up cream, mascara and lipstick. The samples were, together with 3 kg of ballast laundry in commercial Haus¬ retaining washers (Capacity 4 kg of dry laundry) put ein¬ and washed at a temperature of 60 ° C (slightly Pflege¬ program with 20 minutes of pre-wash at 25 C). The Wasch¬ duration including heating in the main wash was 40 Mi¬ grooves, the detergent concentration (in liters) was 7.5 g / I, the ratio of textile amount (in kg) to wash liquor 1: 10, the water hardness of tap water 16 dH (160 mg CaO per liter). After three times of rinsing was spun, dried and the reflectance value of the sample is determined photometrically. The Er¬ results of (Table III) are average values ​​from 5 washing experiments with 6 samplings.

For comparison detergents were used, containing the following surfactants with an otherwise identical composition as Example 2 (see Table II):

table II

-

β test

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 -

Cocoalkylamine + 2 EO - - 2.0

The tallow alcohol or cocoalkyl were identical with respect to their qualitative and quantitative composition with the game used in Bei¬. The compositions of Experiment 1 and 2 correspond to the surfactant compositions of commercially available high-performance detergent. Experiment 3 corresponds agents according to US 3 925 224. The results show the superiority of he find proper means.

table

Makeup Lippen¬ Wim ipern- Central pin mascara 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

Experiment 1 35 52 33 40

Experiment 2 40 44 34 39

Experiment 3 42 45 41 43

example 3

in a detergent of the composition

2 wt. - alkylbenzenesulfonate

3 wt. -% soap based on hydrogenated tallow

10 wt -.% C 1 3, 5 -OxoaIkohol + 5 moles of ethylene oxide

20 wt -.% Zeolite NaA

20 wt -.% Sodium tripolyphosphate

5 wt - water glass. 1: 3, 35

20 wt -.% Sodium perborate

10 wt -.% Sodium sulphate

Remainder: water, 2.5 and 5 wt .-% of sodium sulfate is replaced by the same amount of different N-alkylmorpholines. With morpholine haitigen detergents fabric / liquor ratio 1 were Launderometer washing tests at 40 ° C, 30 minutes: 30 with 6.6 g detergent per liter at a water hardness of 16 ° d durch¬ performed. The test fabrics were artificially soiled with grease. The detergency of the detergent was examined with the morpholinic the morphological infreien detergent by measuring the reflectance of the washed fabrics. following, listed in Table IV results were obtained:

table IV

% Remission

Detergent without additional 45.9

Detergent + 2.5 wt .-% N-hexylmorpholine 54.6

Detergent + 5.0 wt .-% N-hexylmorpholine 55.1

Detergent + 2.5 wt .-% 'N-octyl morpholine 54.9

Detergent + 5.0 wt .-% N-octyl morpholine 55.8

Detergent + 2.5 wt .-% N-dodecyl morpholine 54.3

Detergent + 5.0 wt .-% N-Dodecalmorpholin 54.7

One recognizes the detergency enhancing effect of N-AIkylmorpholine.

A 1 part by weight of the detergent celled solution had a pH-value between 9.5 and 10. The pK. Values ​​of the morpholine derivatives be for N-hexylmorpholine 6.3

N-octyl morpholine 7.4

N-dodecylmorpholine 8.7 Example 4

A heavy-duty detergent of the following composition:

5.0 wt .-% alkyl benzene sulfonate

4.6 wt .-% of a mixture of 8 parts c._, 18 - fatty alcohol + 5 moles of ethylene oxide and 2 parts

C 12 / C 14 ~ Fettalkoho1 Mo1 + 3 ethylene oxide

0.8 wt -.% Tallow alcohol + 5 moles of ethylene oxide

0.3 wt -.% Tallow alcohol + 14 moles of ethylene oxide

21.3 percent -.% Phosphate Natriumtripoly

13.9 wt -.% Zeolite A

0.25 wt -.% Ethylene diamine

1.20 wt -.% Polycarboxylate

0.5 wt -.% Cellulose

4.6 wt -% water glass, Na.O. SiO_ = 1: 3.35

0.1 wt -.% - Magnesium silicate

22.2 wt -.% Sodium perborate

1.6 wt -.% Tetraacetylethylenediamine

8.3 wt -% of sodium carbonate residue. Water, dye, perfume

was compared in its washing performance with an inventive detergent that instead of 4.6 wt .-% of the above-mentioned fatty alcohol ethoxylate mixture only 2 wt .-% of said fatty alcohol ethoxylate, this but in addition 2 wt .-% Wasch¬ booster in the form of 4- (2-hydroxydodecyl) morpholine (pK b value 7.8) was obtained. As Prüftextil served with wool fat artificially soiled cotton Wäschereiforschungs¬ institute Krefeld. was washed in an automatic washing machine Haus¬ halt at 90 C wash temperature. The pH value of a 1 wt .-% aqueous solution of Waschmit¬ means of the present invention was 9.9. The reflectance of the washed with the detergent erfindungsge¬ MAESSEN Pruftextils was significantly by 4 units higher than the reflectance value of the ge with the tensidreicheren but detergency booster-free detergent washed Pruftextils.

Claims

P atentanspr ü che
1. detergents comprising at least one synthetic an¬ ionic and / or nonionic surfactant and are aliphatic amine compound, characterized in that the amine compound is selected so that the pk. Value min¬ least equal to 14, reduced by the initial pH value of a 1% aqueous solution of the detergent, is.
2. A detergent composition according to claim 1, characterized in that it comprises at least one amine compound selected 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 a Alkyi-, hydroxy-alkyl or alkenyl group having 6 to 22 carbon atoms, x has a numerical value of
2 3
1 to 10, R and R independently of one another Aikyl¬ groups having 1 to 4 carbon atoms, are the group H (OCH-CH-) with y = 1 to 6 or together with the nitrogen atom a 5- or 6-membered ring , of a further nitrogen or oxygen atom
2 3 eenntthhaalltteenn kkaannnn ,, ooddeerr one of R or R is also hydrogen;
b) amido amines 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 alkenyl group or Alkyi-
5 6 7 having 9 to 17 carbon atoms, R, R and R is hydrogen or
C.- mean to C. alkyl groups, with the proviso that at least one of the groups R, R, R represents an alkyl group;
c) Alkyi-, alkenyl or hydroxyalkyl derivatives of Gluc amine, in which the Alkyi-, alkenyl or hydroxycarboxylic alkyl group has 6 to 22 carbon atoms;
d) Alkyi-, alkenyl or hydroxyalkyl derivatives of Mor¬ pholin in which the Alkyi-, alkenyl or hydroxycarboxylic alkyl group has 5 to 22 carbon atoms,
contains full group.
3. A detergent composition according to any one of claims 1 or 2, characterized in that
3-40 wt -.% Anionic and / or nonionic
surfactants
0, 1 - 5 wt -.% Of amine compound
Range 5 - 80 wt -.% Of water-soluble and / or insoluble inorganic and / or organic builder salts wasserlös¬ Liche
0-30 wt .-% of inorganic, in aqueous systems,
H_0_ releasing peroxy compounds, preferably perborate
Rest other customary constituents in Waschmittein
contains.
4. A detergent composition according to any one of claims 1 to 3, characterized ge features that it contains ether amines of the general formula I, in which it is the substituent R to such Alkyi- or alkenyl groups, such as are available from commercial fats and in the it be produced fatty alcohols is.
5. A composition according to any one of claims 1 to 4, characterized gekenn¬ characterized in that the substituent R or a Alkyi- in the ether amine of formula I. Means alkenyl group having from substantially 10 to 20, especially 12 to 18 carbon atoms.
6. A composition according to any one of claims 1 to 5, characterized gekenn¬ characterized in that the ether amines of the formula I as substituents
2 3
R and R are each the Ethoxygruppierung H (OCH 2 CH 2), or one of these two substituents pierung this Ethoxygrup¬ and the other is C. -C "alkyl group or hydrogen.
7. A detergent composition according to any one of claims 1 to 6, characterized denotes ge, that lies with the ether amines of the formula I the sum of all existing I ndexzahlen x and y between the numerical values ​​of 2 and 7, and as the substituent R is a Alkyi- or alkenyl group having in is substantially 12 to 18 carbon atoms.
8. A detergent composition according to any one of claims 1 to 7, characterized denotes ge that or the ratio of the total number of the ethoxy and hydroxyethyl groups to the number of Alkyi- in 'ether amine of formula I. Alkenylkohlenstoffatome at 1 / 6-1 / 2.
9. A detergent composition according to any one of claims 1 to 8, characterized ge denotes that the surfactant system of at least one surfactant from the group of anionic and / or nonionic surfactants nicht¬ and the ether amine of the formula I in a ratio of 30: 1 to 2: 1 1 is present: and in particular 10: 1 to. 3
10. A detergent composition according to any one of claims 1 to 9, characterized denotes ge that the ether amine of the formula I, based on the detergent, in an amount of 0, 2 to 10 wt -.%, Preferably vor¬ 0, 5-3 wt -.% is present.
1. 1 Detergent according to one of claims 1 or 2, characterized ge features that it contains 1 to 5 -.% Amidoamine corresponding to general formula II contains my, wherein the amidoamine is derived from fatty acids, the acyl group (R - CO-) 12 to 18 C-Ato¬ me, wherein at least 50 wt .-% 12 to 14 C-atoms
have 5 and 6 wherein the sum of in the radicals R, R,
R and (CH 2) - C-atoms 4 to 6 is contained in that it further into water-insoluble or partially soluble poly containing nonionic surfactants which are adsorbed on a granular carrier material and of glycol ether
(I) ethoxylated or linear. 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 branched methyl¬ in the 2-position, saturated primary C. --C. "Alcohols with an average of 4 to 6 glycol ether groups are be¬,
, in that the weight ratio of (i): (ii): the amidoamine equal to 1: (2 to 6): (0, 8 and 2, 5) and the Ge weight ratio of (i + ii + amidoamine): the amine surfactant equal to 4: 1 to 1: 2, and that it keeps wasser¬ soluble surfactants of the sulfonate type and / or sulfate type ent.
12. A detergent composition according to any one of claims 1 or 2 or 11, da¬ by in that 30 to 100 wt .-% of Gerüst¬ materials in the form of granules are present, the weight of 60 to 80 wt. Parts by finely crystalline, synthetic zeolite NaA . SiO- equal to 1: 2 to 1:. and / or NaX, from 0.1 to 2 parts by sodium silicate of the composition Zu¬ a ^ O 3.5, 3 to 20 parts by weight of a copolymer. (Meth) acrylic acid and maleic acid, 8 to 18 wt. Parts by at 145 ° C entfern¬ bares water and 0.5 to 5 wt. Parts by a Dispersions¬ stabilizer consists.
13. A detergent composition according to any one of claims 1 or 2 or 11 or
12, characterized in that the nonionic surfactant and the amidoamine to the granules according to claim 17 are sorbed ad¬.
14. A detergent composition according to any one of claims 1 or 2 or 10 to
13, characterized in that it consists of a mixture meh¬ of exemplary portion of powder, wherein a part of the powder (A) consisting of the granules with the adsorbed thereon nonionic surfactants, and amidoamines, a spray-dried portion of powder (B) of the water-soluble surfactants of the sulfonate type and / or sulfate type, builders, provided these are not already part of the granules, and sprühtrock¬ voltage capable of other detergent ingredients, and in that at least part of powder is present (C) containing the son¬ Stigen, not suitable for spray-drying Waschmittel¬ ingredients comprising ,
15. A detergent composition according to any one of claims 1 or 2 or 10 to
14, characterized in that it contains up to 25 wt .-%, wt .-% of sodium tripolyphosphate vor¬ ent keeps preferably 5 to 22, which is a part of the constituent part of the powder (B).
16. A method for producing a Waschmitteis according to An¬ reflection of 1 or 2 or 10 to 15, characterized in that granulate at one prepared by spray-drying Gra¬ sorbed the nonionic surfactants and the amidoamines ad¬, the part thus obtained powder (A) a product obtained by spray-drying part of powder (B) comprising the anionic surfactant component which does not enthal¬ requested builders and other geeig¬ for spray drying items other detergent ingredients contains the granulate and mixed with the remaining, to the other detergent ingredients zäh¬ lumbar components.
EP19860903376 1985-06-22 1986-06-16 Washing agent for low washing temperatures Withdrawn EP0227720A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE19853522389 DE3522389A1 (en) 1985-06-22 1985-06-22 Granular detergent with improved cleaning power
DE3522389 1985-06-22
DE3606828 1986-03-03
DE19863606828 DE3606828A1 (en) 1986-03-03 1986-03-03 Detergent for low washing temperatures

Publications (1)

Publication Number Publication Date
EP0227720A1 true EP0227720A1 (en) 1987-07-08

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ID=25833339

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Country Status (3)

Country Link
US (1) US4820436A (en)
EP (1) EP0227720A1 (en)
WO (1) WO1986007603A1 (en)

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