DE1467614A1 - Detergent with a low foaming power - Google Patents

Description

I-ler ^ c. & Cie GmbH _{1 / ßl7} · Düsseldorf-Holthauseri, ίο. 8. 19 "

Patent department U 07 Q | 4 handle tr. 67

. Dr Wa / IP.

New patent application

D 3145

"Detergent with low foaming power"

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 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.

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BATH ORIGINAL

00980370993

One has already added non-ionic washing active substances, such as high molecular weight ethers and esters of polyglycol ethers, to the strongly foaming, anionic washing active substances of the sulfonate or sulfate type containing detergents to reduce foam formation. The foam-suppressing effect of nonionic surfactants is sufficient in this case. however, it is not sufficient for the mixtures to be used in drum washing machines at temperatures above 80 ° C. It is further known alkali soaps of fatty acids, in particular those having a chain length of C, to C ₂₂ g as a foam-suppressing substances to add the detergent. The effect of these substances, however, depends on the hardness of the water and is also limited to certain active washing substances. So it has not been possible hitherto 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 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.

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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 FRIEDL-CRAFTS synthesis or the by Alkyl sulfonates obtained from sulfochlorination can normally also contain these unsulfonated fractions from longer-chain ones Alkyl chlorides containing 8 to 18 carbon atoms exist. However, these accompanying substances reduce the foaming power the laundry raw materials do not; detergent compositions made from them foam in the absence of other foam, contraceptives in drum washing machines regularly at temperatures well below 80 C. The expert had to conclude from this that halogenated hydrocarbons are not suitable foam suppressants for synthetic detergent raw materials represent.

It has now been found, containing weakly foaming, powdery or granulated detergents at temperatures above 80 ° C water-soluble salts of anionic washing raw materials of the sulfonate or sulfonate type, saturated or unsaturated alkali soaps Fatty acids with 10 to 24 carbon atoms in the molecule and condensed alkali phosphates or organic ones, the hardness of lime

909803/0993

the water binding complex compounds, which are characterized in that they below 100 ⁰ C melting halogenated hydrocarbons having at least 10 carbon · atoms in the molecule in the form of finely divided particles contain 'which is mixed with the other detergent particles or with these agglomerates are present, wherein the weight ratio of washing-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, alicyclic, araliphatic, aromatic, straight-chain or branched and of a saturated or unsaturated nature and one halogen atom or several halogen atoms in the molecule contain. The non-cyclic halogenated hydrocarbons preferably contain at least 18, and the cyclic at least 12 carbon atoms in the molecule. Aliphatic chlorinated hydrocarbons containing more than 18 carbon atoms are particularly 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

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powder forms produced by spray drying or granulation Detergent mixtures mixed in in solid form or sprayed onto them in a liquid or molten state or be sprayed. You can also proceed in such a way that the halogenated hydrocarbons are initially only with one Mixed detergent component and this intermediate product is then incorporated into the detergent. The mixing can be continuous or discontinuous both at room temperature as well as at elevated temperature. Lunatic Interest in an even distribution of the substances recommends the. Use of conventional mechanical mixing or granulating devices. The halogenated hydrocarbons can, however also sprayed directly into the spraying chambers used to dry the detergent pastes with the aid of nozzles 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 halogenated hydrocarbon use. If necessary, can the halogenated hydrocarbons are previously dissolved in volatile solvents, but such a process is because of the systems required for the recovery of the solvent and the losses that are always associated with it are less expedient.

BATH

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The halogenated hydrocarbons added in the manner indicated are in a distribution state that is particularly favorable for effective foam suppression. This condition is characterized in that when solid halogenated hydrocarbons are used, the detergent and halogenated hydrocarbon particles are isolated next to each other or that both types of particles stick together to a greater or lesser extent or are fused or agglomerated. The liquid halogenated hydrocarbons are usually in the detergent particles, especially in the loose, absorbent "beads" or granules, in the form of microscopic 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 having 10 to 24 carbon atoms; however, those having 12 to 18 carbon atoms are preferably used because of their better detergency. They can be prepared in a known manner from naturally occurring, optionally hydrogenated fatty acid mixtures, such as coconut, palm oil, tallow, oil, tall oil or similar fatty acids. Even soaps synthetic fatty acids can be used.

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The foam-suppressing effect of the combination of soap and finely divided halogenated hydrocarbon particles extends to all known organic washing raw materials from the sulphate or sulfonate type. Examples of such washing raw materials are the water-soluble salts of primary and secondary Alkyl sulfates, alkyl sulfonates, olefin sulfonates, alkylben- ■ zene sulfonates and 06 sulfo fatty acid esters. These connections can be used as salts of sodium, potassium and ammonium or as salts of organic bases, in particular of mono-, di- or Trialkanolamines are present. In addition to anionic washing active substances, the mixtures can also contain nonionic washing raw materials included, so z. B. alkyl and acyl polyglycol ethers, alkylphenol polyglycol ethers or amine oxides. The use of polyglycol ethers can be useful if the cleaning ability should be increased even further. Since they are in the inventive Agents provide little or no contribution to foam suppression, but their presence is not required. This is a particular advantage of the process, since polyglycol ethers are known to have the tendency of washing powders raise to glue and clump together.

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The detergents contain up to 60 percent by weight of alkali salts of condensed phosphates such as pyrophosphate, trioder 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 the alkali salts nitrilotriacetic acid or ethylenediaminotetraacetic acid, and also organophosphorus compounds such as aminoalkylenephosphonic acids and hydroxyethane-l, l-diphosphonic acid and their alkali. salts.

In addition to the substances mentioned, those prepared according to the invention can be used Detergents contain common 'build-up and' additives, such as alkalis, neutral salts, alkali silicates, per compounds and stabilizers, especially magnesium silicate, water-soluble cellulose ethers, optical brighteners, fragrances and dyes. The additives have no effect on the foam behavior of the detergents. Unless the powder detergent To be processed into tablets, dissolving agents can also be added.

The amount of detergent sulfonic acids salts, soap and halogenated hydrocarbons depends on the intended use of the detergent. For machine pre-wash and hot wash the same

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Suitable detergents contain 5-20, 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 one for effective foam suppression sufficient amounts of halogenated hydrocarbons are between 0.05 and 2, preferably between 0.1 and 1.5 Percentage by weight, the required minimum amount with the content of the mixture of "high-foaming detergent raw materials increases. An optimal effect occurs with 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, but does not provide any advantages, as this neither does the foam attenuation nor the detergency can be improved.

It must be seen as surprising that by the presence finely divided particles of halogenated hydrocarbons in amounts of less than 1 $ the foaming tendency of mixtures high-foaming detergent raw materials and soaps at higher temperatures is suppressed to the extent that their use in drum washing machines is possible. This was all the more surprising than the halogenated hydrocarbons are ineffective if they are used as unsulfonated components together with the washing raw materials in the

Mixture are introduced or if they are analogous to the other detergent components with the liquid or pasty Detergent concentrates, the so-called "slurries", are mixed intensively so that homogeneous, non-separating dispersions are produced.

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Also surprising is the fact that the foam suppression only occurs in the presence of a specific, synergistic effect Soap amount occurs, but the effect is not linked to the presence of insoluble lime soaps. The foam properties the agents according to the invention are thus largely independent of the degree of hardness of the tap water. Advantageous is also that the foam development between 20 and 50 ° C, so in the so-called delicate wash range, is only moderately attenuated will. Abundant foam prevents heavy mechanical processing of the laundry and thus prevents matting, Creasing and damaging delicate woolen fabrics', 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 the powdery ones Affect detergent. Also, the amounts of halogenated hydrocarbons used are so small that when they dissolve the agent, the water has unimpeded access to the detergent particles and the speed of dissolution as well is not affected in the cold. Since in fully automatic drum washing machines only a certain time for the solution process is available, a quick and complete dissolution of the detergent in cold water is essential.

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Examples

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). 14 liters of washing liquor were required for one filling. 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 affixed at equal intervals. 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 foaming over, while the number 6 indicates that the detergent solution is foaming over. The use concentration of the detergent in all examples was 3 * 5 g / l. Unless otherwise stated, tap water with a degree of hardness of 16 ° dH was used. All percentages given below are percentages by weight.

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Examples 1-3

A detergent with the composition 8.0 % Na dodecylbenzenesulfonate 1.5 # fatty alcohol polyglycol ether (C ₁ Q, JZ «50,

7-10 ethylene glycol groups) 1.5 % Na cellulose glycolate

50.0 % 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 baking soda (60 # coconut, Tallow soap), chlorinated hydrocarbons or from their

Mixtures in a granulator loaded with mib soap by spraying in the liquid or mixing in the powdered chlorinated hydrocarbons was. The following chlorinated hydrocarbons were used:

Example 1: Liquid chlorinated paraffin with more than 18 carbon atoms and 50 # Cl

Example 2: Chlorinated paraffin solid with more than 18 carbon atoms and

10% 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.

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Example 4 '■■ * ■

A detergent with the following composition was used:

8.0 % Na coconut fatty alcohol sulfate 3.5% Na soap (βθ # coconut, 40 # tallow) 2.5 # petroleum alcohol polyglycol ether (as in examples 1 -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 to the $ 0.35 of the chlorinated paraffin used in Example 1 were inflated. The foam numbers given in the table show that the effect also occurs with fatty alcohol sulfates.

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 one used Foam control agent.

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$ 09803/0993

Ex. 1 1 soap additive t
Foam number
30 ° 50 ° 70 ° 80 ° 90 ° 95 ° 100 ° C 2
j 3.5 O 4 5 1 1.5 6 6 6 3 3.15
2.45
O 0.35
1.05
3.5 4 5 0.5 0.5 0.5 0.5 1
4.5 4.5 0.5 0.5 0.5 0.5 1
4 6 6 6 6 6 6 4th 3.15 0.35 ' 5 5 0.5 0.5 0.5 0.5 1 5 3.15 0.35 4 4 0.5 1 1 1.5 '3 6th 3.5
3.5
O 0
0.35
3.5 3.5 3.5 0.5 1 5 6 6
3.5 4 0.5 .0.5 0.5 0.5 0.5
4 4 6 6 6 6 6 3.5
O 1.4
3.5 2 1 0.5 1 1.5 1.5 2
3 6 6 6 6 6 6 3.5
O 0.7 ■
3.5 4 4 0.5 0.5 ' 0.5 0.5' .0.5
h 6 6 6 6 6 6

Table 1

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Examples 7 and 8

A detergent mixture was used, consisting of:

8.0 $ Na dodecylbenzenesulfonate

2.5 # Na soap (60 # JCokos, 4056 tallow)

2.5 # petroleum alcohol polyglyc ether (as in example 1)

1.5 # Na cellulose glycolate

30.0 % pentasodium triphosphate

1810 % tetranatriuraphosphate

15 # 0 % sodium perborate

$ 6.0> Sodium Sulphate

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 ₁ Q - 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 Followed the course of a two-stage washing process, with fresh ones in the main wash after pumping off the pre-wash liquor Wash liquor was used. The results are summarized in the table.

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Ex. additive Prewash • 30th ο _4o o Foam number 3 40 ° Main gear 80 ° 90 ° 95 ° 99 ° C • 20 ° 2 2 0 , 5 60 ° 3- β .6 6th 2 2 0.5 50 ° C , 5 2 0.5 1 2 4.5 7th O 1 2 2 3 1
* , 5 0 3 6th β 6th 1, 2 0.5 0 2 1 1.5 3 4 ■ 8th O 2 3. 0.5 ι, 0.5 Table 2 , 4 4th

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Claims (1)

Patent Department _ ΐγ '_ D 3145 Claims 1. A powdery or granular, low foaming at temperatures above 8O ⁰ C detergents containing water-soluble salts of anionic WaschrohstQffe 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, die.Kalkhärte of Water-binding complex compounds, characterized in that it contains halogenated hydrocarbons which melt below 100 C and have 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 agglomerated with them, the weight ratio of wash-active sulfonic acids! Salt to soap to halogenated hydrocarbon is between 1: 2: 0.05 and 10: 1: 2, 2. Means according to claim 1-, characterized in that there are aliphatic chlorinated hydrocarbons with at least 18 Contains carbon atoms and several chlorine atoms in the molecule. 18 - 909803/0993 New Untwtaeen H 6 76 U 5. Means according to claim 1, characterized in that it is cyclic halogenated hydrocarbons with at least 12 carbon atoms and several halogen atoms in the molecule contains. 4. Agent according to claim 1 to ~ 5, characterized in that it contains soaps of chain length C, p to C, o. 5. Composition according to claim 1 to 4, characterized in that the weight ratio of soap to halogenated hydrocarbon 1: 0.1 to 1: 1. 6. Means according to claim 1 to 5 * characterized in that that there are 5 to 15 percent by weight of anionic compounds of the sulfate or sulfonate type, 1 to 10 percent by weight of soap and up to 60 percent by weight of alkali salts of condensed phosphates and 0.1 to 1.5 percent by weight of halogenated hydrocarbons. 7. Process for the preparation of the agent according to Claim 1 to 6, characterized in that the halogenated hydrocarbons are used mixed with the finely divided detergent or part of the same. . - 19 - 909803/0993 8. The method according to claim 7, characterized in that the halogenated hydrocarbons are sprayed into the * the drying of the detergent pastes serving atomization chambers. 9. The method according to claim 7, characterized in that the addition of the halogenated hydrocarbons during the Granulating the detergent takes place. 10. Further development of the method according to claim 1 to 9 »characterized in that the finely divided detergent is converted into tablet form. ^! : 909803/0993