DE1467613B2 - Low-foaming detergent - Google Patents

Description

The invention relates to solid detergent having a low foaming power in the temperature range above 80 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 80 ⁰ C to a foam over the cleaning liquors with 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.

One already has the highly foaming, anionic washing active substances of the sulfonate or sulfate type containing detergents to reduce the

ίο Foaming non-ionic washing active substances, such as high-molecular ethers and esters of polyglycol ethers, added. 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 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 acidic 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 washing raw materials that deserve special interest because of their favorable washing-active and physiological properties and their easy biodegradability.

It has now an above 8O found ⁰ C low-foaming powdered or granular detergents containing water-soluble salts of anionic detergent bases of the sulfate or sulfonate type, alkali soaps of saturated or unsaturated fatty acids having 10 to 24 carbon atoms in the molecule and condensed alkali metal phosphates, or organic, calcium hardness of the water binding complex compounds, which is 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 distributed particles, which are mixed with the remaining "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, alicyclic or araliphatic, straight-chain or branched and of a saturated or unsaturated nature and other groups which do not increase the water solubility, e.g. B. ether or ester groups as well as halogen atoms, contained in the molecule. Suitable ketones are, for example, the monoketones of the C _n H _2n O series, such as laurone (di-n-undecyl ketone), myristone, palmitone and stearone and mixtures thereof, and also β-diketones of the formula C _n H _2n - ₂ O ₂ and long-chain esters 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 cleaning agents in various ways, for example in the form that the keto compounds are incorporated into the detergent mixtures prepared by spray drying or granulation

3 4

mixed in solid form or in melted detergent powder for gluing and balling

stood on it to be sprayed or sprayed on. Man raise.

can also proceed in such a way that the keto compounds The detergents contain up to 60 per cent by weight only with a detergent component with a percentage of alkali salts of condensed phosphates, mixes and then converts this intermediate product into 5 such as pyrophosphate, tri- or tetrapolyphosphate or the detergent is incorporated. Mixing can be metaphosphates. The condensed phosphates can continuously or discontinuously, both at and completely or partially through organic, the lime room temperature as well as replacing binding complexing agents at elevated temperature hardness of the water take place. Be in the interest of an even distribution. Examples of such compounds are of the substances, the use of the usual alkali metal salts of nitrilotriacetic acid or ethylene mechanical mixing or granulating devices is recommended. The diaminotetraacetic acid, also organophosphorus keto compounds but can also with the help of bonds, such as aminoalkylenephosphonic acids and nozzles, directly into the drying of the washing hydroxyethane-l, l-diphosphonic acid and its alcohol pastes serving nebulization chambers one potash salts.

be sprayed. This arrangement has the advantage that 15 In addition to the substances mentioned, the inventions the added substances are particularly uniform according to the detergents produced and the usual structure distribute in the detergent and contain separate additives, such as alkalis, neutral salts, Mixing device is saved. A two-fluid nozzle with a separate medium, in particular magnesium silicate, and water supply can also be used as atomizing alkali metal silicates, per compounds and stabilizing nozzle for the detergent paste and the keto 20 soluble cellulose ethers, optical brighteners, fragrances and bindings are used. If necessary, dyes. The additives have no effect on that The substances to be added can previously be slightly foamed in the detergent. Unless the powder volatile Solvents can be dissolved, but is a shaped medium to be processed into tablets, Such a process because of the necessary equipment, solvent-promoting agents can also be added, to recover the solvent and the 25 The amount of washing-active sulfonic acid salts, always associated losses less expedient. Soap and keto compounds depend on that

The keto intended use of the detergent mixed in as indicated. For the machi-

Compounds are in a distributed state, quick prewash and hot wash equally

The detergents particularly suitable for effective foam suppression contain 3 to 20, preferably

is cheap. This state is characterized by 30 5 to 15 percent by weight of anion-active compounds

that the keto compounds, depending on whether they are used in solid fertilizers of the suff at or suffonate type and 0.5 to 20,

or in the molten or dissolved state in the preferably 1 to 10 percent by weight soap. The for

finely divided detergents are introduced, in the form of an effective foam dampening sufficient quantity

solid, isolated particles in addition to the detergent genes of keto compounds are between 0.05 and 2,

particles are present or more or less strongly with 35 preferably between 0.1 and 1.5 percent by weight,

the latter are glued, fused or agglomerated. taking the required minimum amount with the salary

Prerequisite for the occurrence of the foaming of the mixture of high-foaming washing raw materials Attenuation is also the presence of alkali soaps. increases. An optimal effect occurs with a weight suitable Soaps are derived from fatty acids with a ratio of 10 to a ratio of soap to keto compound of 1: 0.1 24 carbon atoms; however, those with 40 to 1: 1 up. Exceeding the specified To-12 up to 18 carbon atoms because of their better set quantities is of course possible, yields Detergency used preferably. However, they have no advantages, since they do not improve the foam known from naturally occurring damping, but the washing does not improve hydrogenated fatty acid mixtures, as like, is increasingly impaired. Coconut, palm oil, tallow, oil oil, tall oil or the like 45 It must be regarded as surprising that Fatty acids. Soaps are also synthesized due to the presence of finely divided particles More fatty acids can be used. ---- water-insoluble keto compounds in amounts of

The foam-suppressing effect of the combination is less than 1% and the tendency to foam of mixtures of soap and finely divided keto compounds extends from high-foaming detergent raw materials and soaps to all known organic washing raw materials 50 at higher temperatures, of the sulfate or suffonate type. Examples of such that their use in drum washing machines washing raw materials are the water-soluble salts of is possible. This was all the less to be expected since primary and secondary alkyl sulfates, alkyl sulfates - the same keto compounds are ineffective if naten, olefin sulfonates, alkylbenzenesulfonates and Λ-sulfofatty acid esters analogous to the other detergent components. These compounds can be present with the liquid or paste-form detergents as salts of organic bases, in particular of mono-, concentrates, the so-called "slurries", intensive di- or trialkanolamines. Except anion-mixed, so that homogeneous, non-segregating niche active washing substances, the mixtures can form dispersions and then contain non-ionic detergent raw materials, e.g. B. sprays or otherwise dries.
Alkyl and acyl polyglycol ethers, alkylphenol poly- 60 It is also surprising that the glycol ethers or amine oxides. The use of foam dampening only in the presence of a certain polyglycol ether can be useful if the th, synergistic amount of soap occurs, the cleaning power is further increased, but the effect is not insoluble. Since it is not bound to any licher lime soaps in the agents according to the invention. The foaming properties or only a small contribution to foam dampening of the agents according to the invention are thus provided, but their presence is not required. largely independent of the degree of hardness of the tap water, a particular advantage of the method is too dependent on this. Another advantage is that the foam appears, since polyglycol ether is known to have a tendency of the winding between 20 and 50 ° C, so in the so-called

Delicates area, only moderately steamed. Abundant foam prevents a stronger mechanical Processing of the items to be washed, thereby preventing matting, creasing and damage being more sensitive Fabrics made from wool, silk and synthetic fibers. It is of particular importance that within the specified Concentration range, the added keto compounds neither the cleaning properties nor impair the shelf life and pourability of powder detergents. Also are the applied ones Amounts of keto compounds are so small that the water is unhindered when the agents dissolve Has access to the detergent particles and the dissolution speed does not even in the cold is affected. Since in fully automatic drum washing machines only a certain time for the Dissolution process is available, is a quick and complete dissolution of the detergent in cold Water inevitable.

Examples

In the following examples, powdery detergent mixtures produced by hot atomization were used used. The foam behavior was tested under realistic conditions in a commercial drum washing machine. 141 washing lye were required for one filling. Of the The liquor level and the foam height were read through the sight glass, on which, starting at the level of the Liquid level, six markings with the designations 0 to 5 at equal intervals, were appropriate. The foam numbers given in the following table correspond to the height of the Foam levels reached mark. The number 0 means that there is no foam development; the number 5 indicates that the drum is filled with foam without foaming over, while the number 6 indicates that the suds are foaming over. The use concentration of the detergent was in all examples 3.5 g / l. Unless otherwise stated, tap water with a degree of hardness of 16 ° dH was used used. All of the percentages given below are percentages by weight.

Examples 1 to 5

A washing powder with the following composition was used:

12.0% sodium dodecylbenzenesulfonate, 1.5% fatty alcohol _{polycol ether (C 18} fatty alcohol, ao JZ = 50, 7 to 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 3.5% in the comparative tests consisted of either soap powder or those in Table 1 listed ketones, in the examples according to the invention, however, from the mixtures of the two substances. the The soda soap used was made using 60% coconut fatty acids and 40% tallow fatty acids been. All detergent ingredients were intimately mixed in a mixing drum.

The results of the foam measurement as a function of the temperature are summarized in Table 1, which also contains the comparison tests.

Tabel!

at
game soap
O/
/O Ketone % 30 ° C 40 ° C 50 ° C look
70 ° C number
80 ° C 90 ° C 95 ° C 100 ° C 3.5 4th 4th 0.5 1 2 6th 6th 6th 1 3.15
2.80
2.45
1.75
1.05
0 Nonadecanedione-2,4 0.35
0.7
1.05
1.75
2.45
3.5 4th
4th
3
4th
1
5 4.5
4th
3
3
1
5 3
2
1
0.5
0.5
6th 0.5
0.5
0
0
0
6th 0.5
0
0
0
0
6th 0.5
0.5
0.5
0
0
6th 0.5
1
1
1
0
6th 3
2
2
2
1
6th 2 3.5
3.5
3.5
0 Lauron 0.35
0.7
1.4
3.5 3
2.5
1
5 1
0.5
0.5
5 0.5
0.5
0.5
6th 0.5
0
0
6th 0.5
0
0
6th 1
1
0.5
6th 2
1.5
1
6th 3
2
1.5
6th 3 3.5 Dotria contandion 0.35
0.7 to 1.4 3
1 2
1.5 0.5
0.5 0.5
0.5 0.5
0.5 0.5
0.5 0.5
0.5 1.5
0.5 4th 3.5 Tricosandione 0.35
0.7 to 1.4 3
0.5 2
0 0.5
0 0.5
0 0.5
0 0.5
0 1
0 3
2 5 3.5
2.45
0 Distearoylactone
dicarboxylic acid ester 0.35
1.05
3.5 4th
5
5 4th
5
6th 4.5
4th
6th 0.5
0.5
6th 0.5
0.5
6th 1
0.5
6th 2
0.5
6th 3
0.5
6th

Examples 6 to 9

The structural substance of the detergents used below contained:

1.5 parts of sodium cellulose glycolate, 48.0 parts of pentasodium triphosphate, 15.0 parts of sodium perborate,
10.0 parts of sodium sulfate,

6.5 parts water glass,

optical brighteners, fragrances, water.

In Examples 6 and 7 the mixtures contained: 8.0 parts of sodium dodecylbenzenesulfonate,

in example 8:

8.0 parts sodium coconut fatty alcohol sulfate,

and in example 9:

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

The mixtures in Examples 7 to 9 also contained:

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

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

On the detergent mixed with varying amounts of sodium soap made from 60% coconut and 40% tallow fatty acids melted palmiton was sprayed on in a granulator.

The drum washing machine already described served as the foam measuring device. In Example 7, soft water was used of 4 ° dH is used, in the other examples tap water with 16 ° dH. The results are in Table 2 reproduced. 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 opposite Examples 8 and 9 show that fatty alcohol sulfates and sulfoester salts are effective.

soap Ketone 30 ° C 50 ° C Table 2 Foam number 90 ° C 95 ° C 100 ° C at % . % 4th 4.5 80 ° C 5 6th 6th game 3.5 0 3.5 4th 70 ° C ' 1 0.5 0.5 0.5 6th 3.5 0.35 3 2 0.5 0.5 6th 6th 6th 3.5 0 2 0.5 0.5 4th 1.5 1.5 1.5 7th 3.5 1.4 3.5 3.5 1 1 5 6th 6th 3.5 0 3.5 1.5 0.5 0.5 0.5 0.5 0.5 8th 3.5 0.35 2 2 0.5 0.5 6th 6th 6th 3.5 0 1.5 1 0.5 5 1.5 2 2.5 9 3.5 0.7 3 1 1

409519/393

Claims (10)

Patent claims: 1. At temperatures above 8O ⁰ C foaming powdered or granular detergents containing water-soluble salts of anionic detergent bases of the sulfate or sulfonate type, alkali soaps weak saturated or unsaturated fatty acids having 10 to 24 carbon atoms in the molecule and condensed alkali metal phosphates or organic binding the calcium 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 is between 1: 2: 0.05 and 10: 1: 2. 2. Agent according to claim 1, characterized in that it contains ketones of the general formula C _m H ₂ "O". 3. Composition according to claim 1, characterized in that it contains / 3-diketones of the general formula C _n H _2n -SO ₂ . 4. Composition according to claim 1, characterized in that it has higher molecular weight ketocarboxylic acid esters contains. 5. Composition according to claim 1 to 4, characterized in that it contains soaps of chain length C ₁₂ to C ₁₈ . 6. Composition according to claim 1 to 5, in which the weight ratio of soap to keto compounds 1: 0.1 to 1: 1. 7. Composition according to claim 1 to 6, 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 soap, up to to 60 percent by weight of alkali salts of condensed phosphates and 0.1 to 1.5 percent by weight of water-insoluble keto compounds. 8. A method for producing the agent according to claim 1 to 7, characterized in that the keto compounds are mixed with the finely divided detergent or part of it .. 9. The method according to claim 8, characterized in that the keto compounds in die'der Sprayed drying of the detergent pastes serving atomization chambers. 10. The method according to claim 8, characterized in that the addition of the keto compounds takes place during the granulation of the detergent.