DE1467614B2 - Low-foaming detergent - Google Patents

Description

The halogenated hydrocarbons can ali-; phatic, alicyclic, 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. Particularly 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 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 use. If necessary the halogenated hydrocarbons can be dissolved beforehand in volatile solvents, but is such a process because of the facilities required to recover 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 solid halogenated hydrocarbons are used 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 -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 when 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 completely or partially replaced by organic complexing agents that bind the hardness of the water. 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 retention of the detergents. If the powder detergents are further processed into tablets, dissolving 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 the foam suppression only occurs when a certain, synergistic amount of soap occurs, but the effect is not related to its presence insoluble lime soap is bound. 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 ° C, i.e. in the so-called delicate wash range, is only moderately steamed. Abundant foam prevents heavy mechanical processing of the laundry and prevents it thereby matting, creasing and damaging sensitive fabrics made of wool, silk and synthetic fibers. It is of particular importance that within the specified concentration range the added Halocarbons neither the cleaning properties nor the storage and pourability of powder detergents. Also are the amounts used Halocarbons are so low that when the agents dissolve, the water has unimpeded access the detergent particles and does not affect the dissolution speed even in the cold will. Since in fully automatic drum washing machines only a certain time for the solution 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 practical conditions in a commercially available 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 affixed at equal intervals was. The foam numbers given in the table below 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.

Exampleelto3

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 mixtures of these, which were combined with Soap-fed granulating device by spraying in the liquid or mixing in the powdery Chlorinated hydrocarbons had been produced. 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 ° 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.

B e i s ρ i e 1 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 control agent used.

Table 1

example soap
% additive
% 30 ° C 50 ° C NS
70 ° C lum number
80 ° C 90 ° C 95 ° C 100 ° C _ 3.5 O 4th 5 1 1.5 6th 6th 6th 1 3.15
2.45
O 0.35
1.05
3.5 4th
4.5
4th 5
4.5
6th 0.5
0.5
6th 0.5
0.5
6th 0.5
0.5
6th 0.5
0.5
6th 1
1
6th 2 3.15 0.35 5 5 0.5 0.5 0.5 0.5 1 3 3.15 0.35 4th 4th 0.5 1 1 1.5 3 4th 3.5
3.5
O 0
0.35
3.5 3.5
3.5
4th 3.5
4th
4th 0.5
0.5
6th 1
0.5
6th 5
0.5
6th 6th
0.5
6th 6th
0.5
6th 5 3.5
O 1.4
3.5 2
3 1
6th 0.5
6th 1
6th 1.5
6th 1.5
6th 2
6th 6th 3.5
O 0.7
3.5 4th
4th 4th
6th 0.5
6th 0.5
6th 0.5
6th 0.5
6th 0.5
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 _{: 8} 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

at
game additive 20 ° C Fore
30 ° C i walk
40 ° C 50 ° C Foam number
40 ° CI 60 ° C 2
0 Hauptwi
80 ° C ischgang
90 ° C 95 ° C 99 ° C 7th O
1.4 2
1 2
2 2
0.5 0 3.5
0.5 2
0.5 3
0.5 6th
1 6th
2 6th
4.5 8th O
1.4 2
2 2
3 2
0.5 3
0.5 3.5
1 3
1 6th
1.5 6th
3 6th
4th

409520/372

Claims (9)

1 2 development leads, in particular at temperatures, claims: above 800C to an over-foaming of the cleaning liquor with considerable losses of washing 1. Powdered or granulated, at tempe- active substance. It has also been found, temperatures above 80 ⁰ C low foaming 5 that large amounts of foam tung the mechanical machining-duty detergents containing water-soluble salts of arrival attenuate to be cleaned, and therefore the ionic detergent bases of the sulfate or. SuIf onat detergents in the machines do not develop their full type, alkaline soaps, saturated or unsaturated fat cleaning power. acids with 10 to 24 carbon atoms in the molecule One already has the strongly foaming, anionic and condensed alkali phosphates or organic washing active substances of the sulphonate or sulphate type, detergents containing the lime hardness of the water to reduce the complex compounds, thereby known foaming nonionic washing active substances , records that it is below 100 ⁰ C melting as high molecular ethers and esters of polyglycol halogenated hydrocarbons with at least 10 ethers added. The foam-suppressing effect of lenstoffatomen in the molecule in the form of finely divided 15 nonionic surfactants is sufficient in this case, however, contains particles that are mixed with the other detergents for use of the mixtures in drum particles or with these agglomerated washing machines are at temperatures above 80 ⁰ C, the weight ratio from not from. It is also known that alkali soaps can be converted from sulfonic acid salt into soap, especially those with a halogenated hydrocarbon chain length of between 1: 2: 0.05 and 20 C ₁₈ to C ₂₂ as foam-suppressing substances with a washing ratio of 10: 1: 2. add funds. The effect of these substances is 2. Means according to claim 1, characterized, however, depending on the hardness of the water and " distinguishes that it is aliphatic chlorinated hydrocarbons, and is limited to certain active detergents With at least 18 carbon atoms and substances. So it was previously not possible to foam several Contains chlorine atoms in the molecule. 35 development of. Alkyl sulfates and sulfo fatty acids 3. Means according to claim 1, characterized by reducing ester salts to a sufficient extent, records that there are cyclic halogenated hydrocarbons, which is why these washing raw materials have so far been used in machine fabrics With at least 12 carbon atoms and detergents not or only in minor contains several halogen atoms in the molecule. Dimensions could be used. Just this one 4. Agent according to claims 1 to 3, characterized in that 30 washing raw materials deserve, because of their favorable character, that it contains soaps of chain length C _{12 with} active washing and physiological properties up to C ₁₈ . such as their easy biodegradability, 5. Means according to claims 1 to 4, thereby their interest. characterized in that the weight ratio is known to contain synthetic detergent raw materials Soap to halogenated hydrocarbons 1: 0.1 to 1: 1 35 of the sulfate or sulfonate type, mostly small amounts amounts to. unreacted starting material. In case of , 6. Means according to claims 1 to 5, characterized by the Friedel-Crafts synthesis alkyl characterized in that it contains 5 to 15 percent by weight of benzenesulfonates or by sulfochlorination! of anion-active compounds from sulfate or obtained alkyl sulfonates, these can be unsulfo- ^! Sulfonate type, 1 to 10 percent by weight soap and 40 nated fractions also consist of longer-chain, normally up to 60 percent by weight of alkali salts of 8 to 18 carbon atoms containing alkyl condensed phosphates and 0.1 to 1.5 Ge chlorides. These accompanying substances reduce the percentage by weight of halogenated hydrocarbons. - however, the foaming power of the washing raw materials 7. Process for the preparation of the means according to not; detergent compositions made from it -, according to claims 1 to 6, characterized in that 45 foam in the absence of other foaming agents the halogenated hydrocarbons are already included in the precautionary agent in drum washing machines Partial detergent or part of the same to- Temperatures' Well below 80 ° C regularly over, mixes. "" --- The expert had to conclude that halogen 8. The method according to claim 7, characterized in that the hydrocarbons are not suitable for foam dampening, that the halogenated hydrocarbons 50 fenden means for synthetic detergent raw materials therein that of drying the detergent pastes. sprayed serving atomization chambers. There were now at temperatures above 80 ° C 9. The method according to claim 7, characterized by low foaming, powdery or granulated draws that the addition of the halogenated detergent found containing water-soluble salts Hydrogen during the granulation of the detergent anionic detergent raw materials from the sulphate or sulphonate agent he follows. 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 60 bonds, which are characterized in that they contain halogenated hydrocarbons which melt below 100 ° C with at least 10 carbon atoms in the molecule in The invention relates to solid detergents which contain in the form of finely divided particles with the Temperature range above 8O ⁰ C a small amount of remaining detergent particles mixed or with Have foaming power. 65 these are agglomerated, with the weight Highly foaming detergents are known to have a ratio of active sulfonic acid salt to detergent for use in modern drum soap to halogenated hydrocarbons between 1: 2: 0.05 washing machines not suitable. A strong foam and 10: 1: 2 lies.