DK162657B - DETAILS WITH CHARACTERISTIC APPLICATION CHARACTERISTICS - Google Patents

Abstract

1. A detergent based on anionic and non-ionic surfactants that has fabric-softening properties, characterized in that it contains, as fabric softener, from 5 to 25 % by weight of a powdered fabric-softening agent consisting of A) from 60 to 80 % by weight of a fabric softener based on one or more nitrogenous cationic surface-active substances having at least one hydrocarbon group that is attached to the nitrogen atom and has at least 8 carbon atoms, which softener optionally contains conventional additives, wherein the surface-active substances consist of at least one of the following compounds : a) a quaternary ammonium compound of the formula see diagramm : EP0151936,P6,F1 wherein R**1 and R**2 are alkyl radicals having from 8 to 24 C-atoms, R**3 and R**4 are alkyl radicals having from 1 to 4 C-atoms, and A- is an anion, b) an alkylimidazolinium compound of the general formula see diagramm : EP0151936,P7,F2 wherein R**5 is an alkyl radical having from 1 to 4 C-atoms, R**6 is an alkyl radical having from 8 to 25 C-atoms, R**7 is an alkyl radical having from 1 to 4 C-atoms or is hydrogen, and R**8 is an alkyl radical having from 8 to 25 C-atoms, and A- is an anion, c) a quaternary ammonium compound of the general formula see diagramm : EP0151936,P7,F3 wherein R**9 and R**10 are alkyl radicals having from 8 to 24 C-atoms or are fatty acid amidoalkyl radicals, R**11 is an alkyl radical having from 1 to 4 C-atoms, R**12 is hydrogen or methyl, x is an interger from 1 to 5, and A- is an anion, and B) from 20 to 40 % by weight of a highly adsorbent silicic acid having a surface area of from approximately 250 to approximately 600 m**2/g, wherein component A) has been adsorbent onto component B).

Description

DK 162657 B

BACKGROUND OF THE INVENTION The present invention relates to a detergent based on anionic and non-ionic surfactant having laundry softening properties.

Drum washing machines of the type that are common in 5 European households usually wash in two workflows. During the main washing process, the laundry is first cleaned using a washing powder. Then follow several rinses. To the last rinse bath is added a laundry softener for finishing. This should give the laundry a soft, tenacious grip and give it comfortable carrying properties, even when the laundry must be dried under adverse conditions.

Numerous attempts have already been made to combine the two wash treatments into one wash process, ie. already adding the 15 softener to the washing powder.

The solutions proposed so far have the disadvantage that the softening effect is lost. This is because the cationic plasticizer softener forms heavily soluble salts 20 with the excess anionic surfactant present in the detergent and remains ineffective in the wash water. Thus, after the rinsing process that completes the washing process, a cationic plasticizer can hardly be detected at all on the fabric. Such products then also show only an extremely unsatisfactory softening effect.

Already the preparation of such a detergent containing a composition for softening laundry is problematic.

In the manufacture of washing powders, a liquid slurry is usually prepared, which is then subjected to spray drying. If the softener is already added to this preconcentrate, a salt with the anionic surfactants is formed already in the detergent preparation.

35 Thus, the desired delayed activity is obtained only when the cationic plasticizer is in powder form and later mixed in the washing powder. However, since the cationic plasticizer has a 2

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less crystallization tendency, the nebulization process is not applicable. Also the roll drying process presents considerable difficulties due to the slow crystallization and solidification of the product. In addition, considerable crystallization heat is released, which causes the finished powder to bake again together.

Thus, there is a need for a detergent with detergent softening properties, where a powdered plasticizer can be blended easily with conventional detergent powders and in which the desired softening properties are not lost during the washing process.

Such a detergent containing a powdery agent for softening laundry is provided by the present invention. The detergent according to the invention is peculiar to the part of claim 1.

As cationic surfactants, the quaternary ammonium compounds containing lipophilic groups and alkylimidazolinium compounds having surfactant properties can be used as 20 softeners for laundry. Such compounds are e.g. described in Chemistry and Industry, 1969, pages 893 and 894.

25

The powdery surfactant of component A) consists of at least one of the following compounds: a) quaternary ammonium compounds of formula 30 r2 + R1- N - R4 1 3 A-

R- * A

Wherein R * and R ^ are alkyl groups of 8-24 carbon atoms and R R and R4 are alkyl groups of 1-4 carbon atoms and A A is another

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ion, b) alkylimidazolium compound having the general formula: B6 0 "". r8 E5 - VT® - C2H4 '? Wherein R8 is an alkyl group of 1-4 carbon atoms, R8 is an alkyl group of 8-25 carbon atoms, R7 is an alkyl group of 1-4 carbon atoms or hydrogen, and R8 is an alkyl group of 8 - 25 carbon atoms and A- is an anion, e.g. methosulfate, ethosulfate or a halogen, or c) quaternary ammonium compounds of the general formula: - R9) 20 R10 - N - (CEL - CH - O) - Η A-11 R12 - wherein R9 and R1 are alkyl groups of 8- 24 carbons or 25 fatty acid amidoalkyl groups, is an alkyl group having 1-4 carbon atoms, r 2 is hydrogen or methyl, x is an integer from 1 to 5, and A- is an anion.

Particularly preferred here is 1-methyl-2-alkyl-3-fatty acid amido-ethylimidazole in methyl methosulfate.

As the groups R 1, R 2, R 6, R 8, R 9 and R 10, fatty acid alkyl groups are usually used, preferably having a carbon chain length of from 16 to 18 carbon atoms.

A number of compounds which may be further discussed are mentioned in EU Patent No. 406 and DE Patent No. 30 25 35 4

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369. In particular, mention must be made of: methyl bi ((talgamidoethyl) -2-hydroxypropyl ammonium methosulfate and N, N-dimethyl bis (isopropanol oil acid ester) ammon in ummethosul barrels.

In particular, non-ionic surfactants, such as e.g. those disclosed in DE Patent No. 30 25 369, in particular reaction products of fatty acid ethanolamide or fatty amines with ethylene oxide and / or propylene oxide which act as dispersing agents or emulsifiers and which may also have an additional softening effect .

Additional nonionic emulsifiers are those based on oxyalkylates, e.g. ethylene oxide reaction products with 15 alkyl phenols or fatty alcohols. Examples of such adjuvants include: oleyl alcohol polyglycol ether, nonyl phenol polyglycol ether or stearic acid monoglyceride polyglycol ether.

20 Common additives are in particular fragrances, dyes and optical brighteners.

As component B) is used a high absorbent silicic acid having a surface of 250 - 600 m2 / g, preferably 350 - 500 m2 / g (determined by BET).

Suitable, finely divided, high absorbency carrier silicas with the greatest possible surface area are produced by precipitation and spray drying and are commercially available.

30

A process for the preparation of powdered plasticizers for laundry is to apply 60 - 80 parts by weight of high absorbent silica to 60 to 80 parts by weight of a laundry softener based on one or more of the nitrogen-containing cationic surfactants according to claim 1. substances which, if desired, contain usual excipients with stabilizing or rewetting effect and / or additives

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additives, in a powder mixer, optionally together with excipients and / or scents.

Suitable mixers are e.g. the commercially available plow cutters-5 mixers.

The silicic acid is mixed with the cationic plasticizer, any of the above-mentioned quaternary imidazolinium and ammonium compounds can be used, regardless of the detailed structure available. Further, the properties of the plasticizer are not affected by the nature of the anion. It is thus also irrelevant whether the plasticizer is in liquid form or must first be melted to be mixed with the silicic acid in the form of a melt.

The commercially available quaternary plasticizers 15 additionally contain frequent solvent, in particular lower alcohols and glycols such as isopropanol, 1,2-propylene glycol or hexylene glycol. These solvents generally do not interfere, ie. that might as well e.g. mix a plasticizer with up to 25% isopropanol with silicic acid to a fine 20 powder.

However, during the further processing of the powder, similar safety measures must be taken because of the emerging solvent vapors.

25

Also, plasticizers negotiated dissolved in the above nonionic surfactants can be applied to the silicic acid in the form of such solutions. The non-ionic surfactants applied together with the cationic plasticizer do not, of course, interfere with the washing process.

The powdered plasticizers can be mixed with the conventional household detergents for universal washing (hot washing) and washing at 60 ° C without any problems.

In this way, it should be noted that the grain size of the washing powder and the softening powder must not be different, for 35 6

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thus avoiding a mix-up. Washing powder is mostly in a grain size range of 450 - 500 µ. A typical softening powder of Example 2 has a grain size distribution according to the following sieve analysis: 5 100 - 200 µm: 10.9% 200 - 300 µm: 47.2% 300 - 400 µm: 29.1% 400 - 500 µm: 12, 8% 10

This distribution is usually suitable. In order to achieve a better fit according to the grain size of the detergent, the softener in the ngs powder can be granulated by suitable control of the speed and temperature of the plow shear mixer. Thereby the grain size is increased to 15 double or triple.

Suitable typical washing powder formulations having a similar frame recipe are e.g. described in Tensid-Taschenbuch, 2nd edition, Carl Hanser Verlag, Munich / Vienna and in "Waschmittelchemie", 20 HUthig-Verlag, Heidelberg (1976).

Such detergents are based on anionic or non-ionic surfactants and optionally antifoaming agents and contain the usual complexing agents, ion exchangers, bleaches, eg activators, stabilizers, gray inhibitors, enzymes, optical brighteners, corrosion inhibitors, fragrances, coloring agents and coloring agents. substances for setting certain properties of a product such as pH, water content, rice capacity, density, volume weight, etc.

30

Surprisingly, the detergents disclosed in the invention do not exhibit the aforementioned disadvantages of the previously known detergents to which plasticizers have been added. 1

The detergent according to the invention used for softening laundry can be prepared without problems and mixed as a powder with conventional detergent powder ingredients. One

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Complex formation between the cationic constituents of the softening agent and anionic surfactants does not occur. In addition, the crystalline structure of the plasticizer ensures a delayed solution of the cationic plasticizers, such that the dirt is detached from the fibers during the washing process by the easily soluble anionic surfactant and solubilized in the wash liquor thereby consuming the anionic surfactant. The cationic plasticizer that dissolves during delay can then unobstructedly settle on the fibers. The carrier silica acid contained in the detergent 10 according to the invention remains in the wastewater and can no longer be detected on the finished washed fabric. Negative impact on the washing process, laundry or washing machine could not be ascertained.

The following examples show the preparation of the detergent according to the invention.

As a starting washing powder, a common commercial detergent of the following composition was used: 20 anionic surfactant (mainly Na-alkylbenzenesulfonate) 15% pentane sodium pyrophosphate 30% sodium perborate 28% optical brightener 0.1% 25 carboxymethyl cellulose 0.5% water glass 3% foam inhibitor 2% perfume 0.1% dye 0.7% sodium sulfate and setting agent 17% water up to 100%

Example 1 30 parts by weight of silicic acid having a surface area of 500 m2 / g ("Sipernat" 50 S, Degussa) are placed in a Loedige mixer. Under 8

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still stirring slowly a mixture of 70 parts of dimethyl distearyl ammonium chloride is slowly added. The mixer is then set to optimum shear force. Afterwards stir for a further approx.

30 minutes and then a free flowing powder is obtained.

5

Example 2 28 parts by weight of silicic acid having a surface area of 450 m2 / g ("Siper-nat" 50, Degussa) are placed in a Loedige mixer under slow stirring and 72 parts by weight of a solution of 75% 1-methyl-2 tallow alkyl-3-talgamidoethylimidazolinium methosulfate in 25% isopropanol is sprayed onto the silicic acid with continuous mixer under a pressure of 3 bar using a suitable nozzle. The mixer is set to optimum shear force. Mix for a further 15 minutes. 20 minutes until a uniform, liquid, lump-free powder is obtained.

Example 3 20 In a plow shear mixer (Fa. Loedige), 24 parts by weight of carrier silicic acid are applied and with still stirring at a rate of 120 rpm. First, dilute 68 parts by weight of 1-methyl-2-oleylalkyl-3-amidoethylimidazolinium methosulfate.

Then 8 parts by weight of nonylphenol polyglycol ether (made with 9 moles of ethylene oxide) are similarly sprayed. The mixture is then adjusted to optimal shear force and run for 30 minutes with shear force until the grain size of the powder has stabilized. The powder is then finished for bottling.

Example 4

To prepare a softening wash powder, a 4.5-part carrier silica acid is first placed in a plow shear mixer (Fa. Loedige) and, while still mixing, 10.5 parts by weight of a melt of a mixture of 75% N, N- bis-talgamethiomethyl-N- (2-hydroxyethyl) -N-methylammonium methosulfate and 25% 1,2-propylene glycol. The mixing process is continued in succession.

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g for 30 minutes under optimal shear force until the grain size is adjusted to the grain size of the washing powder to be used.

Thereafter, at substantially no shear force, while still mixing, at approx. 100 rpm

85 parts by weight of a commercially available washing powder prepared by spray drying, and the mixing process is continued (about 20 minutes) until a homogeneous powder is formed.

10

Example 5 In the same way as described in Examples 1-3, the plasticizers listed in Table 1 are prepared.

15

Table 1.

Preparation No. 123456 N, N-di-stearyl-N-methyl-N-2-hydroxy-2Q-ethyl-ammonium-methylsulfate-5-1-methyl-2-norstearyl-3-stearylamido-ethyl-imidazolinium methylsulfate-38- - 45 dicocodimethylammonium chloride - 53 methyl bis (oleylamidoethyl) -2-hydroxyethyl anunonium methyl sulphate - - 50 20 - 1,2-Ethanediyl bis (2-nor-tallow-1-methyl) -imidazolinium methyl sulfate - 30 - 10 isopropanol 21 15 17 - 1.2 - propylene glycol - - - 13 20 10 3Q lauryl alcohol, 3 moles eo - 4 - 2 7 silicic acid 28 28 30 35 35 28 35 10

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The mode of operation of the detergent containing the softener according to the invention is demonstrated by the following washing experiments. As a detergent, a commercially available product of the above formulation was used. The following commercially available quaternary ammonium compounds were used as plasticizers: 1. Di methyldistearyl ammonium chloride id.

2. 1-methyl-2-tallow alkyl-3-talgamidoethylimidazolinium methosulfate.

Both plasticizers contained approx. 25% isopropanol. In each case, 70 parts by weight of the plasticizer was adsorbed on 30 parts by 15 parts of precipitated carrier silica with a specific surface area of 450 m 2 / g (according to BET) in a plow shear mixer.

Washed with standard whitewash towel in a commercially available 10 gauge in household universal washing machine. The washing temperature was preferably 60 ° C. The softening effect was assessed using pairwise statistical comparisons with 25 subjects. For this test, 50 points = very soft and 0 points = raw material. The results are shown in the following table: 25 1 35 11

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Table 2.

5

Detergent Substance softness __ (α50} _

Untreated substance 3 1Q Commercially available universal detergent 10 Commercially available universal detergent + 10 g / 1 dispersion of dimethyldistearyl =. c ammonium chloride until the 3rd.

1 o rinsing 45 Commercially available universal detergent + 5% plasticizer 1 at SiC> 2 35 20 Commercially available universal detergent + 5% plasticizer 2 at SiC> 2 34 Commercially available universal detergent + 10% plasticizer 2 25 at Si02 39 Similarly detergents containing the plasticizers listed in Table 1 were tested for their softening effect, again using a commercially available universal detergent of the above composition. The results are shown in the following Table 3: 35

Claims (3)

20 A) 60-80% by weight of plasticizer based on one or more nitrogenous cationic surfactants having at least one hydrocarbon group attached to the nitrogen atom having at least 8 carbon atoms and optionally containing usual excipients, the surfactants consisting of at least one of the following 25 compounds: a) a quaternary ammonium compound of the formula R 2 is R 1 -N-R 4 i3 a- wherein R 1 and R 2 are alkyl groups of 8-24 carbon atoms and R 3 and R 4 are alkyl groups of 1-4 carbon atoms and A- is an anion, b) an alkylimidazolium compound. see with the general formula R6 ASN Il o 5 R - N, '©' N - C-H. - N - C - R8 \ A b wherein R5 is an alkyl group of 1-4 carbon atoms, R6 is an alkyl group of 8-25 carbon atoms, R7 is an alkyl group of 1-4 carbon atoms or hydrogen, and R8 is an alkyl group with 8 to 25 carbon atoms and A- is an anion, or c) a quaternary ammonium compound of the general formula R 9 - R 10 - N - (CH ~ - CH - O) - Η A-IZIW R 12 -1 20 where R 9 and R 8 is alkyl groups of 8-24 carbon atoms or fatty acid amidoalkyl groups, R 1 is an alkyl group of 1-4 carbon atoms, R 2 is hydrogen or methyl, x is an integer 25 from 1 to 5, and A- is an anion and 20 - 40 wt% silicic acid with high absorbency and with a surface of approx. 250 to approx. 600 m2 / g, with component A) being adsorbed on component B). Detergent according to claim 1, characterized in that the surfactant is 1-methyl-2-alkyl-3-fatty acid amido-ethylimidazolinium methosulfate. 35 Detergent according to claim 1 or 2, characterized in that component A) contains nonionic emulsifiers as auxiliaries.