EP0929632A1

EP0929632A1 - Washing or laundering post-treatment agents

Info

Publication number: EP0929632A1
Application number: EP97910299A
Authority: EP
Inventors: Michael Dehmer; Chris Schleinig; Thomas Merz; Frank Everts
Original assignee: Henkel Ecolab GmbH and Co KG
Current assignee: Ecolab GmbH and Co oHG
Priority date: 1996-09-26
Filing date: 1997-09-17
Publication date: 1999-07-21
Also published as: DE19639602A1; WO1998013456A1

Abstract

The invention relates to powder, pasty or liquid washing or laundering post-treatment agents containing cyclodextrin, cyclodextrin derivatives as additives and substances forming cyclodextrin or cyclodextrin derivatives or their mixtures in the rinsing liquid. The tenside residues on textile surfaces can be efficiently reduced by using said substances.

Description

Detergent or laundry treatment agent

The present invention relates to a powdery, pasty or liquid washing or laundry aftertreatment composition which contains cyclodextrin, and to a process for treating textiles.

In washing processes for washing textiles, these are rinsed with water in one or more rinse cycles after the washing process, in which a conventional detergent is used, in order to remove the detergents again. The individual detergent components cannot all be rinsed out to the same extent. The nonionic surfactants that settle on the textile fibers pose particular problems. A further problem in connection with such residues is foam formation in the rinse cycles, which is noticeably noticeable in household laundry and can lead to malfunctions in commercial laundry, in particular in continuously operating car washes.

In commercial laundries, acidifying agents and / or fabric softening or softening agents are generally added to the washing water in at least one rinse cycle, preferably in the last rinse cycle. Fabric softeners or softeners are also common in the rinsing process for mechanical household laundry.

Acidifying agents usually contain acids such as phosphoric acid, acetic acid, hydrochloric acid, glycolic acid, citric acid, lactic acid or formic acid and, due to the alkaline detergents, should lower the relatively high pH.

Fabric softeners or conditioners are said to improve the feel and appearance of the textiles and to give them antistatic properties. Such agents usually contain cationic surfactants, for example quaternary ones Ammonium compounds. These compounds settle on the textile surface, which changes the charge on the surface of the textiles and maintains the desired properties.

Usual textile softeners or anti-aging agents are, for example, compounds of the so-called esterquat type. These compounds are technically quaternized difatty acid trialkanolamine ester salts, which are usually obtained by reaction of trialkanolamines, such as triethanol or tripropanolamine, with fatty acids or fatty acid esters and subsequent reaction of the difatty acid esters formed with methyl chloride or dimethyl sulfate. They correspond to Formula I.

CH ₃

1 +

[R ² CO-O- (CH ₂ ) nN- (CH ₂ ) nO-COR ² ] X ^** (I)

(CH ₂ ) _π -OH

in which R ² CO represents an aliphatic acyl radical having 12 to 22 carbon atoms and 0.1, 2 or 3 double bonds, n represents 2 or 3 and X represents halide, methosulfate or methophosphate.

These compounds are widely used as finishing agents. For example, in international patent application WO 94/06899 liquid detergents are described which contain quaternary ammonium compounds of the formula I, alkyl glycosides and other surfactants as textile softeners. These agents can contain from 10 to 50% by weight, based on the agent, of a mixture of quaternary compounds of the formula I and alkyl glycosides. The quaternary ammonium compounds mentioned naturally tend to hydrolysis on the acyl radical in an aqueous medium. According to European patent application EP-A-239910, cationic plasticizers of the esterquat type, which are present in 0.5 to 1.5% by weight solution, show the optimum of hydrolysis stability in an aqueous medium at a pH between 2 , 5 and 4.2. Above and below this range the aqueous active ingredient dispersions become increasingly unstable with hydrolytic decomposition.

The aim is to keep the amount of residues from the detergents on the textiles as low as possible. Such residues include, for example, surfactants such as anionic and nonionic surfactants on the textile surfaces. In particular, the nonionic surfactants, however, also tend to form strong foams in very small amounts. Efforts are therefore made to minimize the residual content of nonionic surfactants and, if possible, to fall below a residual content of 200 ppm, based on the amount of laundry.

The object of the present invention was to provide a washing or laundry aftertreatment agent which significantly reduces the residual surfactant content on textiles, in particular the content of nonionic surfactants, preferably not exceeding a limit of 200 ppm, based on the amount of laundry should be.

The present invention accordingly relates to a powdery, pasty or liquid washing or laundry aftertreatment agent, characterized in that it contains cyclodextrin, cyclodextrin derivatives or substances or mixtures of the foregoing which form cyclodextrin or cyclodextrin derivatives in the rinsing liquid.

Surprisingly, it was found that the content of surfactant residues, in particular nonionic surfactants, on textiles can be significantly reduced by using the agent according to the invention.

The use of cyclodextrins in the field of detergents and cleaning agents is already known from the prior art. In international patent application WO94 / 10280 a cleaning agent is described which contains at least one cyclodextrin or cyclodextrin derivative as an active cleaning component. The agent described is especially for removal of oils, fats, aliphatic and aromatic hydrocarbons, acids, esters and ethers from any surface.

International patent application WO93 / 05136 describes a process for the production of solid particles from water-sensitive materials, in which particulate complexes of cyclodextrins and perfumes are provided with a protective cover.

Cyclodextrins, also called cycloglucans, are formed during the breakdown of starch by Bacillus macerans or B. circulans under the action of cyclodextrin glycosyltransferase. The cyclodextrins generally consist of 6.7 or 8 α-1,4-linked glucose units. The use of cyclodextrins or their derivatives as active cleaning components is described, for example, in international patent application WO 94/10280. Surprisingly, it has now been found that the addition of cyclodextrins or their derivatives or of substances which form these compounds in situ in the rinsing liquid can inhibit the deposition of nonionic surfactants on the textile surface.

The agent according to the invention can contain any cyclodextrin monomers, for example α-, β- or γ-cyclodextrin. All cyclodextrin derivatives, such as, for example, cyclodextrin carbonates, ethers or polyethers, or cyclodextrin derivatives in which one or more of the hydroxyl groups are substituted by functional radicals, are also suitable. Such functional residues include, for example, C- alkyl, especially methyl or ethyl, hydroxyethyl, hydroxypropyl or acetyl groups. Those radicals by which the water solubility of the cyclodextrin is increased are particularly suitable. Any mixtures of cyclodextrin and several and / or cyclodextrin derivatives can also be used.

Substances which form cyclodextrin or cyclodextrin derivatives in situ in the rinsing liquid can be substances which form cyclodextrins in the presence of cyclodextrin glycosyltransferase. A combination of Cyclodextrin glycosyl transferase and amylose have proven to be particularly advantageous since amylose is an inexpensive and ecologically harmless substance.

The cyclodextrins can be contained in the agents according to the invention in an amount of 0.5% by weight to 10% by weight, in particular 0.5 to 5% by weight, based on the agent. The agents according to the invention are preferably metered into the washing or rinsing liquid in such a way that the cyclodextrins, cyclodextrin derivatives or the substances forming these compounds are present in an amount of 0.1 to 5% by weight, preferably 1 to 2% by weight, based on the amount of textiles to be rinsed. The substances can be added at any time in the washing or rinsing process, for example at the beginning or during the process. In commercial washing processes, the agent according to the invention is preferably added at the beginning of the last rinsing bath.

If the agent according to the invention is in liquid form, it preferably contains water as the main solvent, which can be present in amounts between 40 and 90% by weight, preferably between 60 and 90% by weight.

The pH of a liquid agent according to the invention is generally between 1 and 13, in the case of laundry aftertreatment agents according to the invention in particular between 1 and 7.5, preferably above 4.5 and particularly preferably between 5.5 and 6.5. The pH under the conditions of use of agents according to the invention corresponds approximately to this. If an agent according to the invention is used as a detergent, the pH is generally in the alkaline range, while when used as a laundry aftertreatment agent, a pH in the acidic to neutral range is preferred. To set a low pH, customary acids such as phosphoric acid, hydrochloric acid, glycolic acid, citric acid, lactic acid and formic acid and mixtures of the above can be used in this field. The proportion of the acids is usually determined by the desired pH of the agent or the intended use. The agents according to the invention can contain conventional substances known in this field, preferably in amounts between 0.5 and 15% by weight, preferably between 1.5 and 5.5% by weight, based on the finished agent, as auxiliary agents.

Aviva active ingredients with the formula I are preferred

CH ₃ l +

[R ² CO-O- (CH ₂ ) nN- (CH ₂ ) nO-COR ² ] X ^** (I),

(CH ₂ ) _n -OH

in which R ² CO represents an aliphatic acyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, n represents 2 or 3 and X represents halide, methosulfate or methophosphate.

Typical examples of the acyl radical R ² CO are derived from fatty acids, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, petroseline acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures. Ester quats based on stearic or hardened tallow fatty acid in the form of their chlorides or methosulfates are preferred.

Furthermore, the agents according to the invention can also contain other customary components and additives which are usually contained in washing or laundry aftertreatment agents. Examples of these are builders, enzymes, inorganic salts, such as carbonates, hydrogen carbonates, sulfates and silicates, softening agents, colorants and fragrances, pearlescent agents, solvents, such as, for example, ethanol, propylene glycol or glycol ethers, soil repellents, thickeners and / or optical brighteners. The above-mentioned solid components, such as builders and inorganic salts, are particularly contained in the agent according to the invention if it is in particle form.

If the agent according to the invention is in pasty form, it usually also contains builders and inorganic salts and thickeners in addition to water and solvents.

The known zeolites, crystalline sheet silicates and salts of polycarboxylic acids, such as citrates and / or (co) polymeric polycarboxylates, are particularly suitable as builders.

Suitable enzymes are those from the class of proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtiiis, Bacillus licheniformis, Streptomyces griseos and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.

The agents according to the invention can be added to the rinsing liquid directly during the washing process or in a rinse cycle after washing, preferably in the last rinse cycle.

The present invention furthermore relates to the use of cyclodextrin, cyclodextrin derivatives or substances or mixtures forming cyclodextrin or cyclodextrin derivatives in the rinsing liquid to improve the solubility of nonionic surfactants, in particular to avoid settling of the nonionic surfactants on the detergent treated with them Textile. The substances described above are added during the wash as an additive or in a rinse after washing. They are both in washing or washing detergents suitable for use in the household as well as for commercial laundries.

Yet another object of the present invention is a process for treating textiles, which is characterized in that during the washing process or in a rinsing step after washing the washing or rinsing liquid, cyclodextrin, cyclodextrin derivatives or in the washing or rinsing liquid cyclodextrin or cyclodextrin derivatives forming substances or mixtures of the above are added.

Examples

A commercial washing machine (E-Lux, FLE 120 MP) was loaded with 8.5 kg of filling laundry. Cotton beaver (Hohenstein test fabric) was used as the test fabric. The laundry was washed for 10 minutes at 70 ° C. with Pur Compactat® (commercial product from the applicant) as a detergent in a concentration of 10 g of detergent per kilogram of laundry. The liquor ratio (weight ratio of laundry to water) was 1: 5. The laundry was then rinsed twice with cold, soft water and once with cold, hard water (laundry: water = 1: 7) each for 3 minutes. Cyclodextrin was added to the last rinse at a concentration of 3 g / l.

The residual surfactant content remaining on the wash was 134 ppm.

In a comparative experiment, no cyclodextrin was added to the rinse cycle. The residual surfactant content was 209 ppm.

The reduction in the residual surfactant content in the example according to the invention compared to the comparative test was 36%. It is clear from the examples that the addition of cyclodextrin to the last rinse cycle significantly reduces the surfactant residues on the textiles.

Claims

claims

1. Powdery, pasty or liquid washing or laundry aftertreatment agent, characterized in that cyclodextrin, cyclodextrin derivatives, in the rinsing liquid cyclodextrin or cyclodextrin derivative-forming substances or mixtures of the above are contained as an additive.

2. Composition according to claim 1, characterized in that α-, β- and / or γ- cyclodextrins or cyclodextrin derivatives are used.

3. Composition according to claim 1 or 2, characterized in that cyclodextrin, cyclodextrin derivatives or in the rinsing liquid cyclodextrin, cyclodextrin derivative-forming substances or mixtures of the above in an amount of 0.1 to 5 wt .-%, based on the weight of the cleaning or rinsing textiles.

4. Composition according to one of claims 1 to 3, characterized in that it has a pH between 1 and 13.

5. Composition according to one of claims 1 to 4, characterized in that quaternary ammonium compounds of formula I as finishing agents

CH ₃ l +

[R ² CO-O- (CH ₂ ) nN- (CH ₂ ) _n -O-COR ² ] X ^** (I)

(CH ₂ ) _n -OH

6. Composition according to one of claims 1 to 5, characterized in that the compounds of formula I in an amount of 0.5 wt .-% to 15 wt .-%, preferably from 1.5 wt .-% and 5.5 % By weight are included.

7. Agent according to one of claims 1 to 5, characterized in that the agent contains further ingredients usual in washing or laundry post-treatment agents, such as builders, enzymes, inorganic salts, acids, pearlescent agents, solvents, dyes and fragrances and / or optical brighteners .

8. Use of the agent according to one of claims 1 to 7 as laundry aftertreatment agent in the household and / or in commercial laundries.

9. Use of cyclodextrin, cyclodextrin derivatives or substances forming the cyclodextrin or cyclodextrin derivatives or mixtures of the foregoing to improve the solubility of nonionic surfactants, in particular to avoid settling of the nonionic surfactants on the textiles treated with a detergent containing them.

10. A method for treating textiles, characterized in that during the washing process or in a rinsing step after washing the rinsing liquid, cyclodextrin, cyclodextrin derivatives or in the rinsing liquid, cyclodextrin or cycloxextrin derivative-forming substances or mixtures of the above are added.