DE1467614C3 - 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. In particular at temperatures above 80 ° C., excessive foam development leads to the cleaning liquor foaming over with considerable loss of detergent 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.
You already have the highly foaming, anionic one

ίο Washing active substances of the sulfonate or sulfate type containing detergents to reduce foam formation non-ionic washing active substances, such as high molecular weight 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. Add alkali soaps of fatty acids, in particular those with a chain length of C ₁ 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 synthetic detergent raw materials of the sulfate or sulfonate type usually contain small amounts of unreacted starting material. In the case of the alkylbenzenesulfonates produced by Friedel-Crafts synthesis or the alkylsulfonates obtained by sulfochlorination, these unsulfonated fractions can also consist of longer-chain alkyl chlorides normally containing 8 to 18 carbon atoms. However, these accompanying substances do not reduce the foaming power of the washing raw materials; Detergent compositions produced therefrom foam in the absence of other anti-foaming agent in drum washing machines at temperatures far below 8O ⁰ C regularly. The person skilled in the art had to conclude from this that halogenated hydrocarbons are not suitable foam-suppressing agents for synthetic detergent raw materials.

Weakly foaming, powdery or granulated detergents have now been found at temperatures above 80 ° C., 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, the hardness of lime of the water-binding complex compounds, which are characterized in that they ^{contain below 100 0} C melting halogenated hydrocarbons with at least 10 carbon atoms in the molecule in the form of finely divided particles, which are mixed with the other detergent particles or are present agglomerated with them, the weight ratio of wash-active sulfonic acid salt to Soap to halogenated hydrocarbons is between 1: 2: 0.05 and 10: 1: 2.

The halogenated hydrocarbons can be aliphatic, aiicyclic, araliphatic, aromatic, straight-chain or branched and of a saturated or unsaturated nature and a halogen atom or contain several halogen atoms in the molecule. The non-cyclic halogenated hydrocarbons preferably contain at least 18, the cyclic at least 12 carbon atoms in the molecule. Especially Aliphatic chlorinated hydrocarbons containing more than 18 carbon atoms are effective as well as contain several chlorine atoms in the molecule. The introduction of these compounds into the finely divided Cleaning agents can be done in various ways, for example in the form that the halogenated hydrocarbons the powder detergent mixtures produced by spray drying or granulation mixed in solid form or sprayed onto it in a liquid or molten state or be sprayed on. One can also proceed in such a way that the halogenated hydrocarbons are initially only mixed with a detergent component and then this intermediate product into the detergent incorporated. The admixing can be continuous or discontinuous both at room temperature as well as 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 halogenated hydrocarbons but can also be used directly in the drying of the detergent pastes with the aid of nozzles Serving atomization chambers are sprayed. This arrangement has the advantage that the added substances are distributed particularly evenly in the detergent and a separate one Mixing device is saved. A two-substance nozzle with a separate feed can also be used as an atomizing nozzle for the detergent paste and the halogenated hydrocarbon Find use. If necessary, the halogenated hydrocarbons can beforehand in Volatile solvents can be dissolved, 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 halogenated hydrocarbons added in the manner indicated are in a distribution state that is necessary for effective foam suppression is particularly cheap. This condition is characterized by the fact that when using solid halogenated hydrocarbons the detergent and halogenated hydrocarbon particles are present in isolation next to one another or that both types of particles are more or less strongly bonded or fused to one another, or are agglomerated. The liquid halogenated hydrocarbons are usually in the detergent particles, especially in the loose, absorbent "beads" or granules, in the form of microscopic ones Droplets, lamellae or other inclusions and agglomerates.

The presence of alkali soaps is also a prerequisite for foam dampening to occur. Suitable soaps are derived from fatty acids containing 10 to 24 carbon atoms; however, there will be with 12 to 18 carbon atoms are preferably used because of their better detergency. You can in known way from naturally occurring, optionally hydrogenated fatty acid mixtures, such as coconut, Palm oil, tallow, oil, tall oil or similar fatty acids are produced. Also synthetic soaps Fatty acids can be used.

The foam-suppressing effect of the combination of soap and finely divided halogenated hydrocarbon particles extends to all known organic washing raw materials of the sulfate or sulfonate type. Examples for such washing raw materials are the water-soluble salts of primary and secondary alkyl sulfates, Alkyl sulfonates, olefin sulfonates, alkyl benzene sulfonates and x-sulfo fatty acid esters. These connections can, in particular, as salts of sodium, potassium and ammonium or as salts of organic bases of mono-, di- or trialkanolamines are present. In addition to anionic washing active substances, the Mixtures also contain nonionic detergent raw materials, such. B. alkyl and acyl polyglycol ethers, Alkyl phenol polyglycol ethers or amine oxides. The use of polyglycol ethers can be useful if the cleaning power is to be increased even further. Since they are in the inventive Agents make little or no contribution to foam suppression is their presence but not required. This is a particular advantage of the process, as polyglycol ether known to increase the tendency of washing powder to stick and agglomerate.

The detergents contain up to 60 percent by weight of alkali salts of condensed phosphates, such as pyrophosphate, tri- or tetrapolyphosphate or metaphosphates. The condensed phosphates can also be wholly or partially replaced by organic complexing agents that bind the hardness of the water in the lime. Examples of such compounds are the alkali metal salts of nitrilotriacetic acid or ethylenediaminotetraacetic acid, and also organophosphorus compounds such as aminoalkylenephosphonic acids and hydroxyethane-l, l-diphosphonic acid and their alkali metal salts.
In addition to the substances mentioned, the detergents produced according to the invention can contain customary builders and additives, such as alkalis, neutral salts, alkali silicates, per compounds and stabilizers, in particular magnesium silicate, water-soluble cellulose ethers, optical brighteners, fragrances and dyes. The additives have no effect on the foam behavior of the detergents. Provided that the powder detergents are processed into tablets

^r , solubilizing agents can also be added.

The amount of detergent sulfonic acid salts, soap and halogenated hydrocarbons depends on the intended use of the detergent. For machine prewash and hot wash alike 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 percent by weight of soap. The sufficient quantities of halogenated hydrocarbons for effective foam suppression are between 0.05 and 2, preferably between 0.1 and 1.5 percent by weight, the minimum amount required increases with the content of the mixture of high-foaming detergent raw materials. An optimal one The effect occurs at a weight ratio of soap to halogenated hydrocarbon of 1: 0.1 to 1: 1. Exceeding the specified amount of halogen compounds is of course possible, it brings however, no advantages, as this neither reduces the foam

attenuation and the washing power can be improved.

It must be regarded as surprising that, due to the presence of finely divided particles Halogenated hydrocarbons in amounts of less than 1% greatly reduce the foaming tendency of mixtures foaming detergent raw materials and soaps at higher temperatures is so suppressed that their Use in drum washing machines is possible. This was all the more surprising as the halogenated hydrocarbons are ineffective if they are used as unsulfonated ingredients together with the detergent raw materials be introduced into the mixture or if they are analogous to the other detergent components with the liquid or paste-like detergent concentrates, the so-called "slurries", intensively mixed, so that homogeneous, non-segregating dispersions are formed.

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 that the foam development between 20 and 50 ⁰ C, that is in the so-called delicate wash range, is only moderately attenuated. 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 halogenated hydrocarbons neither affect the cleaning properties nor the storage and pourability of the powder detergents. The quantities of halogenated hydrocarbons used are also 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. Since there is only a certain amount of time available for the dissolving process in fully automatic drum washing machines, it is essential that the detergent dissolves quickly and completely in cold water.

Examples ---

In the following examples, powdery detergent mixtures produced by hot atomization were used used. The foam behavior was tested under practical conditions in a commercially available drum washing machine. 14 l of washing liquor were required for one filling. 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 affixed at equal intervals was. 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 is filled with foam without over-foaming, while the Number 6 indicates that the suds are foaming over. The concentration of the detergent used was sufficient in all examples 3.5 g / l. Unless otherwise stated, tap water was the hardness grade 16 ° dH used. All of the percentages given below are percentages by weight.

Examples 1 to 3

A detergent of the composition was used

8.0% Na dodecylbenzenesulfonate,

1.5% fatty alcohol polyglycol _{ether (C 18} , JZ = 50, 7 to 10 ethylene glycol groups),

1.5% Na cellulose glycolate,
30.0% pentasodium triphosphate,
16.0% tetrasodium pyrophosphate,
18.0% sodium perborate,

6.0% sodium sulfate,

6.5% water glass,

9.0% dyes and fragrances, water.

The remaining 3.5% consisted of soda soap (60% coconut, 40% tallow soap), chlorinated hydrocarbons or from their mixtures, which are sprayed into a granulator loaded with soap the liquid or admixture of the powdery chlorinated hydrocarbons have been produced was. The following chlorinated hydrocarbons were used:

Example 1:

Chlorinated paraffin liquid with more than 18 carbon atoms and 50% Cl.

Example 2:

Chlorinated paraffin solid with more than 18 carbon atoms and 70% Cl (melting range 80 to 90 ⁰ C).

Example 3:

Chlorinated diphenyl with 58% Cl (melting range 60 to 70 ⁰ C).

The results are shown in Table 1.

Example 4

A detergent with the following composition was used:

8.0% Na coconut fatty alcohol sulfate,

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

2.5% fatty alcohol polyglycol ether
(like examples 1 to 3),

1.5% Na cellulose glycolate,
48.0% pentasodium triphosphate,
21.0% sodium perborate,

6.5% water glass,

8.65% dyes and fragrances,

optical brighteners, water onto which 0.35% of the chlorinated paraffin used in Example 1 was sprayed. The foam numbers shown in the table show that the effect also applies to fatty alcohol sulfates occurs.

Example 5

Example 1 was repeated in soft tap water of 4 ° dH.

Example 6

In Example 1, the polyglycol ether was replaced by sodium sulfate.

The results in Table 1 show the effectiveness of the foam regulating agent used.

Table 1

Rf * i ^ n if * ϊ soap additive O 30 ° C 50 ° C Foam number 80 ° C 90 ° C 95 ° C 100 ° C % % 0.35 4th 5 70 ° C 1.5 6th 6th 6th 3.5 1.05 4th 5 1 0.5 0.5 0.5 1 1 3.15 3.5 4.5 4.5 0.5 0.5 0.5 0.5 1 2.45 0.35 4th 6th 0.5 6th 6th 6th 6th O 0.35 5 5 6th 0.5 0.5 0.5 1 2 3.15 0 4th 4th 0.5 1 1 1.5 3 3 3.15 0.35 3.5 3.5 0.5 1 5 6th 6th 4th 3.5 3.5 3.5 4th 0.5 0.5 0.5 0.5 0.5 3.5 1.4 4th 4th 0.5 6th 6th 6th 6th O 3.5 2 1 6th 1 1.5 1.5 2 5 3.5 0.7 3 6th 0.5 6th 6th 6th 6th O 3.5 4th 4th 6th 0.5 0.5 0.5 0.5 6th 3.5 4th 6th 0.5 6th 6th 6th 6th O 6th

Examples 7 and 8

A detergent mixture was used, consisting of:

8.0% Na dodecylbenzenesulfonate, 3.5% Na soap (60% coconut, 40% tallow),

2.5% fatty alcohol polyglycol ether (as in Example 1),

1.5% Na cellulose glycolate,
30.0% pentasodium triphosphate,
18.0% tetrasodium pyrophosphate, 15.0% sodium perborate,

6.0% sodium sulfate,

6.5% water glass,

The rest of the optical brighteners, fragrances, water.

The following halogenated hydrocarbons were added in a mixing drum:

Example 7:
1.4% cyclododecane dibromide.

Example 8:

1.0% alkyl chloride C ₁₈ to C ₂₀ .

The washing machine was loaded with 2 kg of laundry and the foaming behavior of the lye (lye concentration 3.5 g / l) in the course of a two-stage washing process, followed by in the main wash cycle Pumping off the pre-wash liquor, fresh wash liquor was used. The results are in Table 2 compiled.

Table 2

additive 20 ° C Prewash 40 ⁰ C 50 ° C Foam number 6O ⁰ C Main wash 90 ° C 95 ° C 99 ° C at 2 30 ° C. 2 • 3 --- 2 80 ° C 6th 6th 6th game % 1 2 0.5 0 0 3 1 2 4.5 0 2 2 2 3 40 ° C 2 0.5 6th 6th 6th 7th 1.4 2 2 0.5 0.5 3.5 0.5 3 1.5 3 4th 0 3 0.5 1 8th 1.4 3.5 1

409 650/238

Claims (9)

Patent claims: 1. Powdery or granulated ^{detergent which foams slightly at temperatures above 80 °} C. and contains water-soluble salts of anionic detergent raw materials from sulfate or. , That it contains sulfonate 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, characterized in that below 100 ⁰ C melting halogenated hydrocarbons having at least 10 carbon atoms in the molecule in the form of finely divided particles, which are mixed with or agglomerated with the other detergent particles, the weight ratio of detergent sulfonic acid salt to soap to halogenated hydrocarbon being between 1: 2: 0.05 and 10: 1: 2. 2. Composition according to claim 1, characterized in that it is aliphatic chlorinated hydrocarbons contains at least 18 carbon atoms and several chlorine atoms in the molecule. 3. Composition according to claim 1, characterized in that it is cyclic halogenated hydrocarbons contains at least 12 carbon atoms and several halogen atoms in the molecule. 4. Agent according to claims 1 to 3, characterized in that it contains soaps of chain length C ₁₂ to C ₁₈ . 5. Composition according to claims 1 to 4, characterized in that the weight ratio of Soap to halogenated hydrocarbon is 1: 0.1 to 1: 1. 6. Agent according to claims 1 to 5, characterized in that it is 5 to 15 percent by weight of anion-active compounds of the sulfate or sulfonate type, 1 to 10 percent by weight soap and up to 60 percent by weight of alkali salts of condensed phosphates and 0.1 to 1.5 percent by weight Contains halogenated hydrocarbons. 7. Process for the preparation of the agent according to Claims 1 to 6, characterized in that that the halogenated hydrocarbons are mixed with the finely divided detergent or part of the same. 8. The method according to claim 7, characterized in that the halogenated hydrocarbons sprayed into the spraying chambers used to dry the detergent pastes. 9. The method according to claim 7, characterized in that the addition of the halogenated hydrocarbons takes place during the granulation of the detergent.