DE1467615C3 - Low-foaming detergent - Google Patents

Description

1 467 al 5

3 4

sulfonic acid salt to soap to ester between 1: 2: 0.05. If necessary, the long-

and 10: 1: 2. chain esters beforehand in volatile solvents

Suitable esters are those from long-chain fatty acids, but this is because of such a process

acids and monohydric alcohols, in particular the equipment required for recovery, des

Fatty alcohols, fatty acid diesters of divalent Al solvents and the compounds always associated with them

alcohols, fatty acid diglycerides and triglycerides as well as sugar are less useful .. ·· .. ·. -, ·, (.-.. _{· ..- ,,:} ■ .-. .....

Fatty acid esters of other polyvalent alcohols or the esters added in the manner indicated

Sugars in which no or less than. a free one is in a distribution state suitable for a

Hydroxyl group is present per fatty acid unit, furthermore effective foam damping particularly. Cheap, jst.

Esters of long-chain fatty alcohols with monocarbons. This state is characterized by the fact that

acids, dicarboxylic acids or dimeric fatty acids, ester particles more or less strong, with the

in which no unesterified carboxyl groups are glued to detergent particles. merged. or ag-

lie,. as well as esters of monocarboxylic acids and di- glomerized or of, including them, are-.The

mer alcohols. .. .. ■ ..'-.,. Detergent and ester particles can also.

The effectiveness of the esters mentioned depends on 1.5 whether they are present side by side in isolation, provided that the chain length and the degree of saturation of the mix in the solid state took place.; .., ■. :; .- _; · -.>;..:; Alkyl chain. Such esters, especially triglycerides, are a prerequisite for -, the ... Occurrence of the ■ foam of natural ·. occurring fats and. Oils, in addition, is the presence of alkali soaps, more than 50 mol% of the alkyl chains of which are less suitable soaps; they differ from fatty acids. 10 as 18 carbon atoms, contain .or from unsaturated 20 to 24 carbon atoms; however, such C _llt residues will exist; are not effective enough. with 12 to 18 carbon atoms because of their better with increasing alkyl chain length and decreasing detergency _; used. You ^ can content of unsaturated, fractions increases the foam in a known manner, from., Naturally occurring, dampening effect of the ester, however, strongly increases, if necessary; Hydrogenated fatty acid mixtures, for example esters from monovalent coconut, palm oil, tallow, oil, tall oil, or similar carboxylic acids and monohydric alcohols, fatty acids are produced ... Also soaps, synthetic, the total number of carbon atoms at least 19 , table fatty acids can be used. ,., -,, ....; but preferably at least 22. Suitable more- Die .schaumdämpfende. Effect of the combination of valuable esters, such as di- or triglycerides, glycol esters from soap and finely divided ester particles or esters of dicarboxylic acids, contain, preferably at least two 'saturated radicals with 18 carbons from sulfate or on all known organic washing raw materials Sulfonate type. Examples of such material atoms or at least one saturated residue of washing raw materials are the water-soluble salts of 20 or more carbon atoms. Because free hy- primary and secondary. .. Älkylsulfaten ^ Alkylsulfpdroxylgruppen and others, the water solubility of naten, olefin, alkyl benzene and ester groups increasing reduce the effect, 35 · _{.K-Sulf.ofettsäureestern:} These compounds; In the form of compounds, preference is given to using compounds as salts, organic bases, in particular, from mono? which do not contain such gilips. The di- or trialkanoiamines mentioned. are present. -External anionic esters can in a known manner from, animal, see detergent active substances ".können, which contain pemic vegetable or fossil fats or waxes as well as nonionic detergent raw materials, so z. B. Synthetic Fettsäuien or "fatty alcohols overall 40 alkyl and Acylpolyglycoläther» · .. Allcyiphenolpolywonnen be; where necessary, a glycol ether or partially Amiqpxyde Die.Mitverwendung.der partly or fully removed or hydrogenation polyglycol be .zweckmäjJig _v. ννεπρ _Vu , which is carried out by unsaturated fractions. .... Cleaning power, still ^ .more, ^^ "increased: to be increased

The introduction of these compounds in the fine should .. Since they are in the agent according to the invention ¹ ? ;.H?' ^NEN teiligen- cleaning materials can be prepared for Schaumdämpfüng way in different 45 or only a small contribution, for example in the form that the supply, their presence is not erforder) I. Esters obtained by spray-drying or granulation. This is a particular advantage of the process of making powdered detergent mixtures, since polyglycol ethers are known to add the "neigy" in the form of fine flakes, shavings or powder. ~ Washing powder for - gluing: and agglutinating it, -mixing'or sprayed in a molten state 50 heights; ..,: r. ,, _T. ·, ·., - ■.: - "--.-.-.! Ί.! · ■■. ·, ··. ·: ■,. or be sprayed. One can also proceed as follows: The detergents contain up to ^ O .Gewientsprod that the esters are initially only mixed with a detergent cent of alkali salts. condensed .phosphates, component mixed and., this ,, intermediate product such as pyrophosphate, tri-.or. Tetrapolyphosphate, or, subsequently, in. .the detergent is incorporated ;; The Nfetaphosphate, The well-known phosphates: can be admixed, _L can be continuous or discontinuous 55 or completely or. t.eiiweise..by, organic ,, die, KaIksowohl -bej. . Room temperature · .als .also in, .erhöhter hardening of Wassers'bin.den.de: l ^ ^om P ^'s xWldner, ■ Terhperatu.r replaced effected: - | jn interest are a gieichmäßige, n. .Examples-;, for ... such 'compounds .sind distribution of the - substances are recommended ... the use of the alkali salts of nitrililotriacetic acid or of the usual mechanical mixing or granulating devices, diaminotetraacetic acid, furthermore; Organophosphorus compounds. The .Esters. Can. auch.mit'.Hilfe.ypn -So _bonds; like ·, aminoalkylenephosphonic acids and nozzles, immediately jn the. the drying of the washing hydroxyethane-rlJ -djphosphonsäur.e as well as their alkar medium pastes serving atomization chambers one Jisalze, - ■ _; ^; . ' ., - r - - ·, ".; ...: ■ be sprayed. rThis arrangement has the advantage that, in addition to the substances mentioned, the: .invention that the added substances are particularly uniform in the detergents produced according to the usual, onin with the detergent and contain a separate 65 construction and additives, such as alkalis, .new mixing equipment, .is saved , in particular magnesium silicate, guide for the detergent paste and the ester additives, water-soluble, cellulose ethers, visual appearance

lighter, fragrances and dyes. The additives have no effect on the foam behavior of the detergents. If the powdered agents are further processed into tablets, they can still dissolve them Means are added.

The amount of detergent sulfonic acids to be used Salts, soap and insoluble esters depend on the intended use of the detergent. Contains detergents that are equally suitable for machine pre-wash and hot wash 3 up to 20, preferably 5 to 15 percent by weight of anion-active compounds of the sulfate or sulfonate type and 0.5 to 20, preferably 1 to 10 percent by weight of soap. The one for effective foam suppression sufficient amounts of insoluble esters are between 0.05 and 2, preferably between 0.1 and 1 percent by weight, the required minimum amount with the content of the mixture in high-foaming detergent raw materials increases. An optimal effect occurs with a weight ratio from soap to ester from 1: 0.1 to 1: 1. A crossing the specified amount of ester is of course possible, but does not provide any advantages, as this does not improve the foam absorption, but the detergency increases Dimensions is affected.

It must be regarded as surprising that the presence of finely divided particles of long-chain esters in amounts of less than 1% suppresses the foaming tendency of mixtures of high-foaming detergent raw materials and soaps at higher temperatures to such an extent that they can be used in drum washing machines. This was all the more surprising as the esters are ineffective if they are intensively mixed with the liquid or paste-form detergent concentrates, the so-called "slurries", analogously to the other detergent components, so that homogeneous, non-segregating dispersions are formed which are then sprayed or removed. be dried in other ways. Also surprising is the fact that foam suppression only occurs when a certain, synergistic amount of soap is present, but the effect is not linked to the presence of insoluble lime soaps. The foam properties of the agents according to the invention are thus largely independent of the degree of hardness of the tap water. Another advantage is fine that the foam development between 20 und'50 ⁰ C, that is "in the so-called fine-washing area, only moderately attenuated. Copious foam prevents a stronger mechaniche processing of the laundry and prevents characterized felting, creasing and damaging sensitive tissue in wool It is of particular importance that, within the specified concentration range, the added insoluble esters neither affect the cleaning properties nor the storage and pourability of the powder detergents Has unimpeded access to the detergent particles and the speed of dissolution is not impaired, even in the cold ser inevitable.

Examples

In the following examples, powder detergents produced by hot atomization were mixtures used. The foam behavior was tested under realistic conditions in a commercially available drum washing machine (series 4 from Schulthess, Zurich). For a filling were 14 1 detergent solution required. The fleet level and the

ίο The foam height was read through the sight glass, on which, starting at the height of the liquid level, there are six markings with the designations O to 5 were attached at the same intervals. The foam numbers given in the table below correspond to the height of the mark reached by the foam level. The number O means that none Foam development takes place; the rating 5 indicates that the drum, without over-foaming with foam is filled, while the number 6 indicates that the suds are foaming over. The application concentration of the detergent was 3.5 g / l in all examples. Unless otherwise stated, tap water was used with a degree of hardness of 16 ° dH are used. All of the percentages given below are percentages by weight.

Example e 1 to 7

'' A washing powder of the following composition was used:

8.0% Na dodecylbenzenesulfonate,

2.5% fatty alcohol polyglycol _{ether (C 18} -FeW alcohol, JZ = 50, 7 to 10 ethylene glycol groups),

1.5% Na cellulose glycolate,
25.0% pentasodium triphosphate,
23.0% tetrasodium pyrophosphate,
6.5% water glass,
15.0% sodium perborate,
6.5% sodium sulfate,
8.5% fragrances, optical brighteners, water.

In the comparative tests, the remaining 3.5% consisted of either soap powder or the in . Table 1 listed esters, in the examples according to the invention, however, from the mixtures of the two Fabrics. In Experiments B, C and D and Examples 1, 2, 5 and 6, the esters were in liquid or in the molten state, in the remaining examples in powder form in a granulating device mixed with the soap. The soap used consisted of 60% Na coconut soap and 40% Na TaIg soap.

The results of the foam measurement as a function of the temperature are compiled in Table 1, which also contains comparative tests A to D. Comparative experiments B, C and D show that the foam-suppressing effect of triglycerides made from unsaturated C ₁₈ fatty acids or C _u , g fatty acid mixtures and from fatty acid monoglycerides, i.e. typical dietary fats, is inadequate. Examples 1 and 2 show that hydrogenation of unsaturated fractions in a triglyceride which predominantly contains C, {, fatty acids leads to a considerable increase in activity. , Examples 1 to 7 and the comparative experiments in the absence of soap performed, so all the solutions foam already at a temperature of 50 ⁰ C.

Table 1

soap additive % 30 ° C 50 ° C 70 ° C Foam count 90 ° C 95 ⁰ C 100 ° C % oleic acid triglyceride 4th 4th 1 80 ° C 5 6th 6th A. 3.5 0.35 4th 0.5 0.5 2 3 6th 6th B. 3.5 Coconut oil 0.7 4th 0.5 0.5 1 3 6th 6th 0.7 3 0.5 0.5 1 6th 6th 6th C. 3.5 Stearic acid 1.4 1.5 0.5 0.5 1 4th 6th 6th monoglyceride 1 D. 3.5 tallow 0.7 2 0.5 0.5 3 6th 6th 0.18 4th 0.5 0.5 1.5 3 6th 6th 1 3.5 0.35 0.5 0.5 0.5 0.5 2 5 5 0.7 0.5 0.5 0.5 0.5 1.5 1.5 5 Sebum, hydrogenated 1.4 0.5 0.5 0.5 0.5 1 1 3 0.18 4th 0.5 0.5 0.5 0.5 1 2 2 3.5 0.35 4th 0.5 0.5 0.5 0.5 0.5 0.5 until 0.5 Stearic acid 1.4 Capric ester 0.7 2 0.5 0.5 0.5 0.5 1.5 3 3.5 Stearyl stearate 1.4 1.5 0.5 0.5 0.5 0.5 0.5 0.5 0.35 4th 0.5 0.5 0.5 0.5 0.5 0.5 4th 3.5 until 0.5 C ₂₂ alcohol acetate 1.4 0.7 4th 0.5 0.5 1 0.5 1 5 3.5 until 0.5 spermaceti 1.4 0.35 4th 0.5 0.5 0.5 0.5 0.5 6th 3.5 until 0.5 1,3-butanediol 1.4 distearoyl ester 0.35 4th 0.5 0.5 0.5 0.5 1 7th 3.5 until 0.5 1.4

Examples 8 to 12

The structural substance of the detergents used below contained:

3.5 parts Na soap (60% coconut, 40% tallow),

1.5 parts of sodium ceilulose glycolate, 48.0 parts of pentasodium thiiphosphate, 21.0 parts of sodium perborate,

6.5 parts water glass,

optical brighteners, fragrances, water.

Examples 8 and 9 contained the mixers

8.0 parts sodium dodecylbenzenesulfonate, in example 10:

8.0 parts Na coconut fatty alcohol sulfate and in example 11:

8.0 parts of the sodium salt of a tallow fatty acid

produced a-sulfofatty acid methyl ester.

The mixtures in Examples 9, 10 and 11 also contained:

3.5 parts fatty alcohol polyglycol ether (such as
Example 1) (as in example 1).

In Example 8, the polyglycol ether was replaced by sodium sulfate.

In example 9 soft water of 4 ° dH was used, in the other examples tap water with 16 ° dH. In all four examples, acetyl stearate was sprayed onto the pulverulent mixtures. The results are shown in Table 2.

The examples show that the foam damping even in the absence of polyglycol ethers, in soft water and when using others active washing sulfonic acid salts occurs.

Tabel

example additive 30 ° C I 40 ° C 50 ° C Foam count 1 80 ° C I 90 ° C 95 ° C I. 100 ° C 8th % 4th 4th 0.5 70 ° C 0.5 0.5 0.5 0.5 9 0.35 3 3 1 0.5 4th 6th 6th 6th 0 2 3 0.5 1 1 1.5 1.5 2 10 1.0 4th 4th 4.5 0.5 0.5 0.5 0.5 0.5 11th 0.35 3.5 4th 3.5 0.5 0.5 5 6th 6th 0 3.5 4th 1.5 0.5 0.5 0.5 0.5 0.5 12th 0.35 3 3.5 2 0.5 3 6th 6th 6th 0 3 3.5 1 2 1 2 2 2.5 0.7 1

509607/282

Claims (7)

Patent claims: 1. At temperatures above 8O ⁰ C weakly foaming powdery or granulated detergent, containing water-soluble salts of anionic washing raw materials of the sulfate or sulfonate type, alkali soaps of saturated or unsaturated fatty acids ^ with 10 to, 24 carbon atoms in the molecule and; condensed alkali phosphates, or organic! Complex compounds binding the lime hardness of water, characterized in that it contains finely divided, mixed with the other detergent particles or agglomerated with them, of those water-insoluble esters in which at least one saturated alkyl radical of 18 or more. Carbon atoms is contained and in which at most 50 mol percent of the alkyl radicals are unsaturated or have fewer than 18 carbon atoms, the weight ratio of detergent sulfonic acid salt to soap to ester between 1: 2: 0.05 and 10: 1: 2. 2. Means according to claim 1, characterized in that; that there are esters of long-chain fatty acids and monohydric alcohols. Fatty acid diesters of dihydric alcohols, fatty acid diglycerides and triglycerides or fatty acid esters of other polyvalent alcohols or sugars in which there is no or less than one free hydroxyl group per fatty acid unit. ^1: ■ · ' 3. Composition according to claim 1, characterized in that it contains esters of long-chain fatty alcohols Monocarboxylic acids, dicarboxylic acids or dimeric fatty acids in which no unesterified carboxyl groups present, or contains esters of monocarboxylic acids and dimeric alcohols. 4. Means according to claim 1 to 3, characterized in that es.Seifen contains the: chain length C ₁₂ to C _liä . 5. The method according to claim 1 to 4, characterized in that the weight ratio of Soap to ester is 1: 0.1 to 1: 1. 6. Composition according to claim 1 to 5, characterized in that it is 5 to 15 percent by weight detergent compounds of the sulfate or sulfonate type, 1 to 10 percent by weight T5eife, and up to 60 percent by weight of alkali salts of condensed phosphates and 0.2 to 1 percent by weight of water-insoluble esters. 7. A method for producing the agent according to claim 1 to 6, characterized in that the esters are mixed with the finely divided detergent or part of the same. S. The method according to claim 7, characterized in that the water-insoluble esters sprayed into the spray chambers used to dry the detergent pastes. *). Method according to claim 7, characterized in that that the addition of the water-insoluble esters during the granulation of the detergent success. The invention relates to solid detergents which have a low foaming power ^{in the temperature range "'above 80 ° C.} Highly foaming "detergents are known for use in modern drum washing machines not suitable. A strong foam development leads in particular at temperatures above 80 ° C to a foaming of the cleaning liquor with considerable loss of detergent ίο substance. It has also been shown that large Foam quantities the mechanical processing of the too :. items to be cleaned, which is why the detergents in the machines do not have their full cleaning power to develop. . ': Nonionic active washing substances such as high molecular weight ethers and esters of polyglycol ethers have already been added to the high-foaming detergents containing anionic detergents of the sulphonate or sulphate type in order to reduce foam formation. However, the foam-damping effect of nonionic surfactants is not sufficient in this case for use of the mixtures in drum washing machines at temperatures above 80 ° C ■. It is also known to add alkali soaps of fatty acids, in particular those with a chain length of C ₁₈ to C _{22, to} the detergents as foam-suppressing substances. The effect of these substances, however, depends on the hardness of the water and is also limited to certain active washing substances. So it was not previously possible to reduce the foam development of alkyl sulfates and sulfofatty acid ester salts to a sufficient extent, which is why these detergent raw materials could not be used in machine detergents or only to a minor extent. However, it is precisely these detergent raw materials that deserve special interest because of their favorable washing-active and physiological properties and their easy biodegradability. It is known that in dishwashing the fat and oil residues washed off the plates in low-foaming, nonionic cleaning substances and soap-containing detergents cause foam reduction. This knowledge cannot be generalized. It has been shown that when using highly foaming detergent substances of the sulfate or sulfonate type, the usual edible fats do not develop an adequate "" effect, especially at temperatures between 80 and 100 ^° C., as are commonly used in modern drum washing machines. It has now a low-foaming at temperatures above 8O ⁰ C powdered or granulated laundry center! found, containing water-soluble salts of anionic washing raw materials from sulfate or. Sulfonate type, alkali soaps of saturated or unsaturated fatty acids with 10 to 24 carbon atoms in the molecule and condensed alkali phosphates or organic complex compounds that bind the hardness of the water, which are characterized in that they contain finely divided, mixed with the other detergent particles or agglomerated particles of such water-insoluble esters , in which at least one saturated alkyl radical with 18 or more carbon atoms is contained and in which at most 50 mol percent of the alkyl radicals are unsaturated or have fewer than 18 carbon atoms, the weight ratio of detergent