DE1467613A1 - Detergent with a low foaming power - Google Patents

Description

The invention relates to solid detergent compositions comprise a low foaming at temperatures above 8O ⁰ C.

Highly foaming detergents are known to be unsuitable for use in modern drum washing machines. A strong foaming leads, in particular at temperatures above 8O ⁰ C to a foaming over of the cleaning baths under considerable losses of washing active substance. It has also been shown that large amounts of foam dampen the mechanical processing of the items to be cleaned, which is why the detergents in the machines do not develop their full cleaning power.

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Nonionic active washing substances, such as high molecular weight ethers and esters of polyglycol ethers, have already been added to the high-foaming, anionic detergent active substances 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 8O ⁰ C. It is also known to add alkali soaps of fatty acids, in particular those with a chain length of C ^ q to Cp _2, as foam-suppressing substances to the detergents. The effect of these substances, however, depends on the hardness of the water and is also limited to certain active washing substances. Up to now it has not been possible to sufficiently reduce the foam development of alkyl sulfates and sulfofatty acid ester salts, which is why these detergent raw materials could not be used in machine detergents or could only be used 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.

BATH ORIGINAL 909803/0992

A powdery or granulated detergent which foams slightly above 80 C has now been found, containing water-soluble salts of anionic detergent raw materials from sulfate and / 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 by the fact that there are water-insoluble ketones or diketones with at least 18 carbon atoms in the molecule ^{that melt below 10O 0 C} Contains the form of distributed particles that are mixed with the other detergent particles or are agglomerated with them and the weight ratio of wash-active sulfonic acid salt to soap to keto compound is between 1: 2: 0.05 and 10: 1: 2.

The water-insoluble ketones or diketones, hereinafter referred to as "keto compounds" for short, can be aliphatic or alicyclic or araliphatic, straight-chain or branched and of a saturated or unsaturated nature and others, contain groups in the molecule that do not increase the solubility in water, e.g. ether or ester groups as well as halogen atoms. Suitable ketones are, for example, the monoketones of

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Series ^c _n ^H 2n ^ * ^{such as laurone} (di-n-undecyl ketone), myristone, palmitone and stearone and their mixtures, also ß-diketones of the formula ^G _n ^H pn-2 ⁰ 2 ^and esters of long-chain alcohols with ketocarboxylic acids or with ketodicarboxylic acids and long-chain fatty acids with hydroxyketones, whereby these compounds should, if possible, not contain any free hydroxyl or carboxyl groups which increase the water solubility. These compounds can be introduced into the finely divided detergents in various ways, for example in the form that the keto compounds are mixed in solid form with the detergent mixtures produced by spray drying or granulation or are sprayed or sprayed onto them in a molten state. One can also proceed in such a way that the keto compounds are initially mixed with only one detergent component and this intermediate product is then incorporated into the detergent. The admixing can take place continuously or discontinuously, both at room temperature and at elevated temperature. In the interest of an even distribution of the substances, the use of conventional mechanical mixing or granulating devices is recommended. The keto compounds can, however, also be sprayed directly into the atomization chambers used to dry the detergent pastes with the aid of nozzles

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will. This arrangement has the advantage that the added substances are distributed particularly evenly in the detergent and a separate mixing device is saved. A two-substance nozzle with a separate Find feed for the detergent paste and the keto compounds use. If necessary, the to be added Substances are previously dissolved in volatile solvents, but such a process is necessary because of the need Systems for the recovery of the solvent and the losses that are always associated with it are less expedient.

The keto compounds mixed in in the manner indicated are present in a distribution state that is effective. Foam attenuation is particularly favorable. This state is characterized in that the keto compounds, depending on whether they are introduced into the finely divided detergent in a solid or in a molten or dissolved state , are in the form of solid, isolated particles next to the detergent particles or are more or less glued to the latter, fused or are agglomerated.

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The presence of alkali soaps is also a prerequisite for foam dampening to occur. Suitable soaps derive from fatty acids with 10 to 24 carbon atoms; however, those with 12 to 18 carbon atoms become Preferably used because of their better washing power. You can in a known manner from naturally occurring, optionally hydrogenated fatty acid mixtures, such as coconut oil, palm oil, tallow, oil, tall oil or similar fatty acids getting produced. Soaps made from synthetic fatty acids can also be used.

The foam-suppressing effect of the combination of soap and finely divided keto compounds extends to everyone known organic washing raw materials of the sulfate or sulfate type. Examples of such detergent raw materials are the water-soluble salts of primary and secondary alkyl sulf " fates, alkyl sulfonates, olefin sulfonates, alkyl benzene sulfonates and ct-sulfo fatty acid esters. These connections can in the form of salts of organic bases, in particular of mono-, di- or trialkanolamines. Except anionic washing active substances The mixtures can also contain nonionic detergent raw materials, for example. B. alkyl and acyl polyglycol ethers,

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Alkyl phenol polyglycol ethers or amine oxides. The co-use the polyglycol ether can be useful if the cleaning power is to be increased even further. Since they are in the agents according to the invention make little or no contribution to foam suppression is their presence but not required. This is a particular advantage of the process, since polyglycol ethers are known increase the tendency of washing powders to stick and clump together.

The detergents contain up to 60 percent by weight of lisalts of condensed phosphates, such as pyrophosphate, Tri- or tetrapolyphosphate or metaphosphate. The condensed phosphates can also be wholly or partly by organic, Complexing agents binding the lime hardness of the water are replaced. Examples of such compounds are Alkali salts of nitrilotriacetic acid or ethylenediaminotetraacetic acid, also organophosphorus compounds, such as aminoalkylenephosphonic acids and hydroxyethane-l, l-diphosphonic acid and its alkali salts:

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In addition to the substances mentioned, the detergents produced according to the invention can contain customary builders and additives contain, such as alkalis, neutral salts, alkali

Silicates, per compounds and stabilizers, I

in particular magnesium silicate, also water-soluble

Cellulose ethers, optical brighteners, fragrances and dyes. ^:

The additives have no effect on the foam ratio

the detergent. Provided the powdered means

further processed into tablets, solution-based

demanding funds are added.

The amount of detergent sulfonic acids salts, soap and Keto compounds depend on the intended use of the detergent. For machine prewash and boil wash equally suitable detergents contain 3 to 20, preferably 5 to 15 percent by weight of anionic compounds of the sulfate or sulfonate type and 0.5 to 20, preferably 1 to 10 weight percent soap. The amounts of keto compounds sufficient for effective foam suppression are between 0.05 and 2, preferably between 0.1 and 1.5 percent by weight, the minimum amount required with the content of the mixture of high-foaming

OWQINAL INSPECTED

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Detergent raw materials increases. An optimal effect occurs with a weight ratio of soap to keto compound of 1: 0.1 to 1: 1. It is of course possible to exceed the specified additional quantities however, there are no advantages, as this reduces the foam not improved, but the detergency is increasingly impaired.

It must be regarded as surprising that the presence of finely divided particles of water-insoluble keto compounds in amounts of less than 1% suppresses the foaming tendency of mixtures of high-foaming washing raw materials and soaps at higher temperatures to such an extent that they can be used in drum washing machines. This was all the less to be expected, since the same keto compounds 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 and these subsequently sprayed or otherwise dried.

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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. It is also advantageous in that the foaming between 20 and 50 ⁰ C, is attenuated only moderately so in the so-called Peinwaschbereich. Abundant foam prevents heavy mechanical processing of the laundry and thus prevents matting, creasing and damage to sensitive fabrics made of wool, silk and synthetic fibers. It is of particular importance that, within the specified concentration range, the added keto compounds affect neither the cleaning properties nor the storage and pourability of the powder detergents. Also, the amounts of keto compounds used are so small that when the agents dissolve, the water has unimpeded access to the detergent particles and the speed of dissolution is not impaired, even in the cold. As there is only a certain amount of time available for the dissolving process in fully automatic drum washing machines, the detergent must be quickly and completely dissolved in cold water.

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In the following examples, powdered detergent mixtures prepared by hot atomization were used. The foam behavior was tested under practical conditions in a commercially available drum washing machine (series 4 from SCHULTHESS, Zurich). For a filling suds were needed lh first The liquor level and the foam height were read through the sight glass, on which, beginning at the height of the liquid level, six markings with the designations 0 to 5 were made at equal intervals. The foam numbers given in the following table correspond to the height of the mark reached by the foam level. The number 0 means «that there is no foam development; The rating 5 indicates that the drum can be filled with foam without foaming over, while the number 6 indicates that the washing liquor is foaming over. The use concentration of the detergent was 3 * 5 ß / ¹ in all examples. Unless otherwise stated, tap water with a degree of hardness of 16 ° dH was used. All of the percentages given below are percentages by weight.

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Examples 1-5 , "

A washing powder of the following composition was used: 12.0 % Na dodecylbenzenesulfonate

1.5 % fatty alcohol polyglycol ether (Cjp fatty alcohol, JZ = 50, 7-10 ethylene glycol groups) 1.5 % Na cellulose glycolate

25.0 % pentasodium triphosphate

20.0 % tetrasodium pyrophosphate

4.5 % water glass

15.0 % sodium perborate

8.5 % sodium sulfate

8.5 % fragrances, optical brighteners, water

The remaining 2> 5 $ in the comparative tests consisted either of soap powder or the ketones listed in Table 1, whereas in the examples according to the invention *, they consisted of mixtures of the two substances. The soda soap used was made using 60 # coconut fatty acids and kO% tallow fatty acids. All detergent ingredients were intimately mixed in a mixing drum.

The results of the foam measurement as a function of the temperature are compiled in Table 1, which also includes the comparative experiments contains.

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Ex. soap Ketone - Show number
30 ° 40 ° 50 ° 70 ° 80 ° 90 ° 95 ° 100 ° - 3.5 - 0.35
0.7
1.05
1.75
2.45
3.5 4 4 0.5 1 2 6 6 6 1 3.15
2.80
2.45
1.75
1.05
0 Nonadecanedione-2,4 0.35
0.7
3.5 4 4.5 3. 0.5 0.5 0.5 · 0.5 3
4 4 2 0.5 0 0.5 1 2
3.3 1 00 0.5 1 2
4 3 0.5 0 0 0. 12
1 1 0.5 0 0 0 0 1
5 5 6 6 6 6 6 6 2 3.5
3.5
3.5
0 Lauron 0.35
0.7-1.4 3 1 ° »5 0.5 0.5 1 2 3
2.5 0.5 0.5 0 0 1 1.5 "2
1 0.5 0.5 0 0 0.5 1 1.5
55 6 6 6 6 6 6 3 3.5 Dotria contandion 0.35
0.7-1.4 H- VjI
η- ro
te
VJi
O O
te te
Ui Ui
O O
te te
Ul ul
O O
te te
Ui Ui
O O
te te
UI ul
O O
te te
Ui Ui
O H-
te te
Ul ul k 3.5 Tricosandione '0.35
1.05
3.5 3 2 0.5 0.5 0.5 0.5 1 3
0.5 0.0 0 0 0 0 2 ' 5 3.5
2.45
0 Distearoylacetone
dicarboxylic acid ester 4 ^ 4.5 0.5 0.5 1 2 3
5 5 4 0.5 0.5 0.5 0.5 0.5
5 6 6 6 6 6 6 6

Table 1

1.5 Parts 48.0 It 15.0 ti 10.0 dd 6.5 Il

Examples 6 "- Q

The structural substance of the detergents used below contained:

Na cellulose glycolate

Pentasodium triphosphate

Sodium perborate ■ Sodium sulfate water glass

optical brighteners, fragrances, water

In Examples 6 and 7 the mixtures contained:

8.0 parts sodium dodecylbenzenesulfonate, in example 8:

8.0 parts Na coconut fatty alcohol sulfate and in example 9:

8.0 parts of the sodium salt of an oc-sulfofatty acid methyl ester prepared from tallow fatty acids.

The mixtures in Examples 7 to 9 also contained 5.5 parts of fatty alcohol polyglycol ether (as in Example 1)

In Example 6, this ingredient was replaced by sodium sulfate. . replaced.

In a granulating device, melted palm clay was sprayed onto the detergent mixed with varying amounts of sodium soap made from 60 % coconut and 40 % tallow fatty acids.

The drum washing machine already described served as the foam measuring device. In example 7 soft water of 4 ° dH was used, in the other examples tap water with 16 ° dH. The result

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Table 2 shows the results. Example 6 shows the effectiveness of the additive in the absence of polyglycol ethers, on Example 7 which show in soft water. That the finely divided ketones also compared to petalcohol sulfates and sulfoester salts are effective, goes from the examples 8 and 9.

Ex. soap
% Ketone
% T he number
50 ° 50 ° 70 ° 80 ° 90 ° 95 ° 100 ⁰ C 6th 5.5
5.5 O
0.55 ^ 4.5 0.5 15 6 6
5.5 4 0.5 0.5 0.5 0.5 0.5 7th 5.5
5.5 Ό
1.4 5 2 14 6 6 6
2 0.5 0.5 1 1.5 1.5 1.5 8th 5.5
5.5 O
0.55 5.5 5.5 0.5 0.5 5 6 6
5.5 1.5 0.5 0.5 0.5 0.5 0.5 9 5.5
5.5 0
0.7 2255666
1.5 1 ■ 1 1 1.5 2 2.5

Table 2

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Claims (1)

Claims 1. At temperatures above 80 ° 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 ones that bind the hardness of the water Complex compounds, characterized in that it contains ^{water-insoluble ketones or diketones which melt below 100 0} C and have at least 18 carbon atoms in the molecule in the form of finely divided particles, which are mixed with the other detergent particles or are agglomerated with them and the weight ratio of wash-active sulfonic acid salt to soap increases Keto compound between 1; 2: 0.05 and 10: 1: 2. 2. Composition according to claim 1, characterized in that it contains ketones of the general formula ^c _n ^H 2 _n °. J.'Mittel according to claim 1, characterized in that ß-diketones of the general formula ^C _n ^H 2n-2 # 2 ^{ENTN 'Senior Citizen} · - 17 - Νβυβ documents (Ail7i1Ab «.2Nr.1Setz3elMAn <ter _un0e0M .v.4.9.tir ' 909803/099? At 4. Smock according to claim 1, characterized in that it contains iiohermolecular ketocarboxylic acid esters. 5. A composition according to, claim 1 to 4, characterized in that it contains up C ₁ Q containing soaps having a chain length C _12th 6. Composition according to claim 1 to 5, in which the weight ratio from soap to keto compounds is 1: 0.1 to 1: 1. ·. 7. Composition according to claim 1 to 6, characterized in that there are 5 to 15 percent by weight of detergent compounds of the sulfate or sulfohate type, 1 to 10 percent by weight soap, up to 60 percent by weight of alkali salts. condensed phosphates ■ ·· ■ ····· "· and 0.1 to 1.5 percent by weight of ... water-insoluble Contains Xeto compounds. 3. / experienced for the preparation of the agent according to claim 1 to 7, / characterized in that the xeto compounds are dem Γ · ε · in-part detergent or part of the same. - "18 - ' BAD ORIGJNAL 909803/0992 H67613 j --ie. ir 9. The method according to claim 8, characterized in that the keto compounds in the drying of the washing " sprayed in spray chambers serving medium pastes. 10. The method according to claim 8, characterized in that
the addition of the keto compounds takes place during the granulation of the detergent. 11. Composition according to claim 1 to 10, characterized in that the finely divided detergent is converted into tablet form. 1.' 908803/0992