EP1717303B1 - Liquid laundry detergent composition for low temperature programs and short programs - Google Patents

Abstract

Liquid detergent composition (I) comprises at least two liquid partial compositions, where the first liquid partial composition is a bleaching component containing a suspended organic peroxoacid and the second liquid partial composition is a detergent component containing at least an enzyme, where the detergent composition additionally contains nonionic surfactant such as at least one esterified fatty acid with polyethylene glycol exhibiting 5-15 ethoxy groups, and at least one etherified (ethoxylated) fatty alcohol with polyethylene glycol exhibiting 3-15 ethoxy groups.

Description

The present invention relates to a liquid detergent composition, in particular a detergent composition, which is composed of at least two separate liquid component compositions (components).

For detergents that are in liquid form, especially in aqueous detergents, it may cause incompatibilities between individual components of the detergent, resulting in insufficient storage stabilities, respectively. Deterioration of the washing result leads. A major incompatibility problem is e.g. between preferred bleaching agents and enzymes and / or surfactants.

To avoid such problems, it has already been proposed to store mutually reactive components separately and only directly before resp. during the washing process (see eg WO 2004/053042 ). The storage can take place in separate containers and subsequent dosing of these or - preferably - from two- or multi-chamber bottles or bags. Such containers are known (see WO 2004/053042 ).

Many liquid detergents are not suitable for very deep wash temperatures, in particular 20 to 30 ° C., and / or short programs, since they gel when added to cold water and therefore dissolve too little or too slowly. This gelling is at least in large part due to the nonionic surfactants which are used - since these are e.g. Remove the skin fat - would like to work in as high a concentration as possible.

The aim of the present invention was therefore to provide a liquid detergent, which gives good wash results even at low temperature and / or in the short program.

This object has been achieved by providing a liquid detergent according to claim 1, in particular a liquid detergent composition consisting of at least two partial liquid components, of which at least one partial liquid component is a bleaching component containing a suspended organic peroxyacid and at least one further liquid partial composition is a washing component containing at least one enzyme characterized in that the washing component additionally contains nonionic surfactants, at least a portion of the nonionic surfactants being selected from at least one fatty acid esterified with polyethylene glycol, the polyethylene glycol having 5-15 ethoxy groups, and at least one ethoxylated with polyethylene glycol Fatty alcohol, wherein the polyethylene glycol has 3-15 ethoxy groups. Specific embodiments are given in the dependent claims.

Preferably, the number of ethylene oxide groups in the fatty acid ester is 8-12 and in the etherified fatty alcohol is 5-9.

Surprisingly, it has been found that a very high proportion of nonionic surfactants can be achieved by using the surfactant system according to the invention without gelling the washing component when introduced into cold water and thus reducing the washing action. The ratio of fatty acid ester to ethoxylated fatty alcohol is usually from 1: 1 to 1: 4, in particular from 1: 1 to 1: 3, and the surfactant system is usually in amounts of 5 to 70 wt .-%, preferably from 15 to 60 wt .-%, in particular from 20 to 55 wt .-% based on the washing component used.

In addition to this special surfactant system, further nonionic and / or ionic and / or amphoteric surfactants may be present; in particular, anionic surfactants are also usually present. Preferred representatives are listed below.

Anionic surfactants are, for example, alkanesulfonates, fatty alkyl ether sulfates, alkylbenzenesulfonates, cumene sulfonate, olefinsulfonates, fatty alcohol sulfonates and mixtures thereof, in particular alkanesulfonates, fatty alkyl ether sulfates, alkylbenzenesulfonates, cumene sulfonate and mixtures thereof.

Nonionic surfactants are, for example, fatty alcohol ethoxylate, fatty acid polyglycol esters, sorbitan esters, alkylpolyglycoside, amine oxide and mixtures thereof, preferably fatty alcohol ethoxylate and / or fatty acid polyglycol ester.

Amphoteric surfactants are, for example, ampholytic surfactants and betaines.

The anionic surfactants are usually used in amounts ranging from 5 to 40 wt .-%, preferably 5 to 30 wt.% And in particular 10 to 15 wt .-% based on the weight of the total component, in addition to the inventive surfactant system at most additionally existing further nonionic surfactants are usually used in amounts ranging from 0 to 20 wt .-% and the amphoteric surfactants in the range of 1 to 20 wt .-%.

Suitable enzymes in this washing component are all conventional enzymes, such as proteases, amylases, lipases, cellulases, glycosidases, in particular mannanases and glucosidases. These are usually used in amounts based on the total weight of the component of 1 to 10 wt .-% of conventional liquid goods, in particular from 2.5 to 5 wt .-%.

The washing component may contain soaps but does not have to. Suitable soaps are, for example, sodium and potassium soaps. These are usually used in amounts of from 0 to 20% by weight, in particular from 1 to 5% by weight, based on the total weight of the component.

Other substances included in the washing component are solvents such as glycols, polyglycols, Alcohols and water and mixtures thereof, preferably also defoamers, for example commercially available silicone defoamers. Also included may be phosphonates and cationic surfactants as well as substances selected from the group comprising organic and inorganic bases, optical brighteners, perfume oils, dyes, preservatives, opacifiers and thickeners. All these substances are commercially available and can be used in the appropriate quality.

Solvents, such as glycols, polyglycols and alcohols, are usually used in total amounts of from 0 to 40% by weight, in particular from 5 to 30% by weight, based on the total weight of the component, and water in amounts of from 5 to 60% by weight. %, in particular in amounts of 10 to 45 wt .-%. Usual amounts of defoamer are 0 to 3 wt .-%, in particular about 0 to 1.5 wt .-% and of phosphonates 0 to 1.5 wt .-%, in particular 0 to 0.75 wt .-%. Cationic surfactants are used in amounts of 0 to 5 wt .-%, in particular from 0 to 0.5 wt .-%. Other substances from the group comprising bases, optical brighteners, perfume oils, dyes, preservatives and opacifiers are usually present in total amounts of up to a maximum of about 1% by weight. A thickening agent, e.g. a polyacrylate can be used to adjust the viscosity of the wash component. A thickening agent is present, if at all, usually in amounts of from 0 to 5% by weight, preferably in amounts of from 0.5 to 1.5% by weight.

The washing component usually has a pH of from 3 to 11, preferably from 6 to 9.

The preferred washing component according to the invention is already very active in washing at temperatures of 20-30 ° C. and this also in the eco or short program. It can be used together with any bleaching component, but it is preferably used together with a special bleaching component, which is characterized in particular by high storage stability. Along with Such a bleaching component, which will be described below, gives an excellent washing result even after months of storage.

The bleaching component-containing bleaching component which is preferred according to the invention is characterized in that it contains (i) as bleaching agent an organic peracid, in particular phthalimido peroxohexanoic acid (PAP), and (ii) a sulfosuccinate, and optionally a phosphonate.

Preferably, the organic peracid is at least partially undissolved, in the form of small particles with particle sizes of 95% smaller than 50 microns. Especially preferred is the particle size of about 90% of the particles in the range of 5 to 10 microns. The use of small particles with as homogeneous as possible a size distribution on the one hand ensures their rapid dissolution during the washing process, on the other hand, the homogeneous size distribution contributes to the stabilization of size and morphology of the crystals.

An additional stabilizing effect is achieved when the suspension is added to a sulfosuccinate. It is believed - without being bound to this theory in any way - that the effect of this specific class of surfactants is based on the fact that it attaches to the surface of the suspended particles and thus on the one hand also stabilizes their size, on the other hand to a mutual repulsion of Particles leads and prevents agglomeration.

Preferred sulfosuccinates are sulfosuccinates, such as laureth-sulfosuccinate, di-2-ethylhexyl-sulfosuccinate, di-iso-decyl-sulfosuccinate, di-iso-octyl-sulfosuccinate, sulfosuccinates of fatty acid alkanolamines and mixtures of such succinates, especially laureth-sulfosuccinates, especially preferably laureth -3-sulfosuccinate. Preferred sulfosuccinates are the (di) sodium salts.

The positive influence on particle growth, resp. the prevention of such growth, is particularly beautiful when a composition according to the invention is subjected to a temperature swing test. Even at maximum temperatures of 40 ° C, as easily reached in the summer, there is a marked gain in stability.

An additional stabilizing gain as well as an improvement in the washing performance is obtained if, in addition to the sulfosuccinate, a phosphonate is added, in particular hydroxyethyl di-phosphonate (HEDP). This serves as a complexing agent for heavy metal ions, which can catalytically decompose the peracid, but also for the hardness formers Ca ²⁺ , Mg ²⁺ .

In addition, the bleaching component may contain a thickening agent, e.g. a thickening agent selected from the group of hydrocolloids such as xanthan or soluble cellulose derivatives and mixtures thereof.

The peroxy acid is used (based on the total weight of the bleaching component) usually in amounts of 1 to 17 wt .-%, preferably from 2 to 7 wt .-%, particularly preferably from 3 to 6 wt .-%, and the sulfosuccinate usually in Amounts of 0.1 to 5 wt .-%, preferably 0.25 to 3 wt .-%, in particular from 0.5 to 2 wt .-%. Usual amounts of phosphonate are from 0.1 to 2.5 wt .-%, preferably 0.3 to 2 wt .-%, in particular from 0.5 to 1.5 wt .-%. The thickener is used in such amounts that, measured at 25 ° C with a Brookfield viscometer with a cylindrical spindle, a viscosity in the range of 300-1500 mPas, preferably 600-1000 mPas results.

The pH of the bleaching component is usually 1.5 to 6.5, in particular 2.5 to 4.5.

In addition to water as a common "solvent" resp. liquid carrier, the bleaching component or other solvents resp. liquid carriers, for example the preferred propylene glycol. Usual water contents are in the range of 50 to 95 wt .-% and conventional amounts of propylene glycol in the range of 0 to 10 wt .-%.

In addition, the bleaching component may contain other substances, such as other surfactants, e.g. Na alkanesulfonate, amine oxide, alkyl polyglycoside, fatty alcohol ethoxylate and mixtures thereof.

A bleaching component with this composition is suitable for use in combination with any washing component, e.g. in the ratio 1: 1 to 1: 4 (bleaching component: washing component).

The bleaching component can be prepared by simply mixing the ingredients in the desired amounts, using a thickening agent such as xanthan to pre-swell in water, then adding the remaining ingredients in any order. The preparation of the washing component is not critical; It can be made by simply mixing the ingredients in the desired tightness.

The liquid detergent according to the invention can be packaged in separate containers, eg as a kit, but preferably in portioned two-chamber containers, eg bags which dissolve without residue in the washing machine or can be used in an applicator in which the casing is pierced, for example in rupturable 2-chamber containers or - especially preferred - in 2- or multi-chamber bottles. Suitable containers are known (see WO 2004/053042 , in particular S. 3, 3. Abs. to S. 5 middle).

The invention will be explained in more detail below with reference to some examples.

Example 1:

Washing components which are suitable for use together with the bleaching component likewise according to the invention can be obtained by simply mixing the ingredients be prepared in the desired amounts. Examples of compositions of washing components according to the invention are given in Table 1 below. <b> Table 1: </ b> T1 T2 T3 T4 T5 T6 alkylbenzenesulfonate 15 - - - - - Na-alkanesulfonate - 15 10 7 8th - Fatty alcohol ethoxylates 6-7 EO 20 20 22 20 25 25 Fatty acid polyglycol ester 10 EO 5 8th 12 15 18 25 betaine - 4 1 1 5 5 Na / K-cumene - - 2.4 2.6 2 - Enzymes (protease, amylase, lipase, cellulase and mannanase as usual commodity) 3.5 3 4 4 3 4 Soap 15 6 3 - - 5 Wacker S167 silicone anti-foaming agent - - - 0.5 0.5 - Alkylhydroxyethyl-di-methyl ammonium chloride - - - - 12:02 - propylene glycol 25 9 5 5 25 20 Na salt of diethylenetriaminepentamethylenephosphonic acid 0.2 0.2 - 0.4 0.4 0.4 alcohol 1 2.5 - - 2 3 optical brightener, perfume oils, dyes, preservatives, opacifiers as common commercial goods 1 0.5 1 1 1 0.5 demineralized water 14.3 31.8 39.6 43.5 8.10 12.1

Example 2:

By simply mixing the ingredients shown in Table 2 below in the indicated amounts in weight percent, the bleaching components B1 to B7 were prepared, with the xanthan being pre-swelled in water, after which the other ingredients were added. <b> Table 2: </ b> B1 B2 B3 B4 B5 B6 B7 PAP suspension (% by weight referred to 17% commercial product) * 6 12 18 24 29 35 41 Disodium Laureth-3 sulfosuccinate 0.5 0.6 2 0.5 1 3 0.1 amine oxide 0.2 - - - - - 0.3 alkylpolyglycoside - 0.4 0.5 - - 0.5 - Fatty alcohol ethoxylate 3-8 EO 1 0.5 - 0.5 - - 1 Hydroxyethyl di-phosphonate 0.4 0.6 0.6 0.8 0.6 0.8 1 xanthan 0.1 0.2 0.3 0.3 0.3 0.4 - propylene glycol 4 3 3 3 3 5 6 water 87.8 82.7 75.6 70.9 66.1 55.3 50.6 * Product Eureco from Solvay, optimized for particle size distribution

Example 3: Storage Tests of the Bleaching Component

The bleaching components were subjected to a temperature swing test. Each 500 ml of the bleaching components were stored over a period of 3 months in a climatic cabinet, which changes its temperature from 4 ° C to 40 ° C and vice versa every 12 hours. During the period the samples were visually assessed and at the end additionally the content of PAP was determined.

The particular bleaching component B5 was compared with a conventional bleaching component of the following composition (in% by weight):

29% by weight of PAP suspension (17% commercial product), 0.6% by weight of hydroxyethyl di-phosphonate, 0.3% by weight of xanthan, 3% by weight of propylene glycol and 67.1% by weight of water.

The results with bleaching component B5 and the conventional bleaching agent described above are shown in Table 3. <b> Table 3: </ b> Bleaching component B5 conventional bleaching component after 1 month the suspension is stable Separation of 1 mm at the surface after 2 months the suspension is stable Separation of 5 mm at the surface, larger crystals have settled on the bottom after 3 months the suspension is stable the suspension has collapsed Stability of the PAP after 3 months (in% by weight) 0% dismantled 12% mined

Example 4 : Washing Tests in the Washing Machine

The experiments were carried out in a Miele washing machine (Novotronic W300-75CH) with the 30 ° C temperature short program (main wash and staged spin) using 4 kg fiber and 2 pieces WFK dirt ballast fabric. The washing effect was measured as a remission increase on the test soils pigment / skin fat, soot / mineral oil, used motor oil, aged yolk and starch / pigment on WFK cotton. In each case 75 ml of the washing component were used per wash.

The special washing component T4 was compared with a conventional washing component of the following composition (in% by weight):

7 wt .-% sodium alkanesulfonate, 35 wt .-% Lutensol A07 (conventional nonionic surfactant), 1 wt .-% betaine, 2.6 wt .-% Na / K-cumene sulfonate, 4 wt .-% enzymes, 0.5 wt. % Wacker S167 silicone antifoaming agent, 5% by weight of propylene glycol, 0.4% by weight of sodium salt of diethylenetriaminepentamethylenephosphonic acid and a total of max. 1% by weight of other ingredients, namely optical brightener, perfume oils, Dyes, preservatives and opacifiers (all handmade), demineralized water to 100% by weight.

The results are shown in Table 4 <b> Table 4: </ b> dirt Washing component T4 conventional washing component Pigment / sebum 67 63 Russ / mineral oil 41 36 used motor oil 57 51 aged egg yolk 76 74 Starch / Pigment 46 43

Claims (15)

1. Liquid detergent composition comprising at least two liquid sub-compositions,

   - of which at least one liquid sub-composition is a bleaching component containing a suspended organic peroxide acid and

   - of which at least one further liquid sub-compositions is a washing component containing

   o at least one enzyme and additionally

   o nonionic surfactants, of which at least one part of the nonionic surfactants is selected from at least one with polyethylene glycol esterified fatty acid having 5-15 ethoxy groups, and at least one with polyethylene glycol etherified (ethoxylated) fatty alcohol having 3-15 ethoxy groups.
2. Liquid detergent composition according to claim 1, characterised in that the fatty acid is esterified with a polyethylene glycol with 8-12 ethoxy groups and wherein the fatty alcohol is etherified (ethoxylated) with a polyethylene glycol with 5-9 ethoxy groups.
3. Liquid detergent composition according to any one of the preceding claims, characterised in that the ratio of fatty acid ester to ethoxylated fatty alcohol is from 1:1 to 1:4, in particular from 1:1 to 1:3.
4. Liquid detergent composition according to any one of the preceding claims, characterised in that as its solvent, the washing component contains a solvent selected from the group comprising glycols, polyglycols, alcohols, water and mixtures thereof.
5. Liquid detergent composition according to any one of the preceding claims, characterised in that the washing component additionally contains at least one substance selected from the group consisting of further anionic and/or nonionic and/or amphoteric surfactants, soaps, antifoaming agents, bases, phosphonates, cationic tensides, perfume oils, dyes, optical brighteners, preservatives and opacifiers.
6. Liquid detergent composition according to any one of the preceding claims, characterised in that the enzyme is present in amounts of 1 to 10 % wt. of common liquid merchandise, in particular of 2.5 to 5 % wt., and/or the fatty acids being esterified with polyethylene glycol and the fatty alcohols being etherified (ethoxylated) with polyethylene glycol are present in amounts of 5 to 70 % wt., preferably 15 to 60 % wt. and in particular 20 to 55 % wt.
7. Liquid detergent composition according to any one of the preceding claims, characterised in that further ingredients are present in the following amounts:

   - anionic surfactants: 5 to 40 % wt., preferably 5 to 30 % wt. and in particular 10 to 15 % wt.

   - further non-ionic surfactants: 0 to 20 % wt.

   - amphoteric surfactants: 1 to 20 % wt.

   - soaps: 0 - 20 % wt., preferably 1 - 5 % wt.

   - antifoaming agents: 0 - 3 % wt., preferably 0 to 1.5 % wt.

   - phosphonates: 0 - 1.5 % wt., preferably 0 - 0.75 % wt.

   - cationic tensides: 0 - 5 % wt., preferably 0 - 0.5 % wt.

   - perfume oils, dyes, optical brighteners, preservatives and opacifiers: maximum approximately 1 % wt.

   - solvents: (except for water) 0 - 40 % wt., preferably 5 - 30 % wt.,

   - water: 5 -60 % wt., preferably 10 -45 % wt.,

   - thickener: 0 - 5 % wt., preferably 0.5 - 1.5 % wt.
8. Liquid detergent composition according to any one of the preceding claims, characterised in that the washing component has a pH of 3-11, preferably of 6-9.
9. Liquid detergent composition according to any one of the preceding claims, characterised in that the bleaching component contains at least one sulfosuccinate.
10. Liquid detergent composition according to any one of the preceding claims, characterised in that the bleaching component contains at least one, and preferably one, phosphonate.
11. Liquid detergent composition according to claim 9 or 10, characterised in that the sulfosuccinate is selected from the group consisting of laureth sulfosuccinates, di-2-ethylhexyl sulfosuccinate, diisodecyl sulfosuccinate, disiooctyl sulfosuccinate, sulfosuccinates of fatty acid alkanolamines and mixtures of such succinates, in particular laureth sulfosuccinates, more particularly disodium laureth-3-sulfosuccinat and/or in that the phosphonate is hydroxyethylene diphosphonate (HEPD) and/or in that the peroxy acid is phtalimido-peroxyhexanoic acid (PAP).
12. Liquid detergent composition according to any one of the preceding claims, characterised in that the peroxy acid is present in the form of particles with a particle size of 95% < 50 µm, preferably 90 % of the particles having sizes of between 5 and 10 µm.
13. Liquid detergent composition according to any one of the preceding claims, characterised in that at least one of the following substances, in particular all substances, are present in the bleaching component in the following amounts expressed in terms of the total weight of the component:

    - phosphonate: 0.1 to 2.2 % wt., preferably 0.3 to 2 % wt., in particular 0.5 to 1.5 % wt.

    - organic peracid: 1-17 % wt., preferably 2-7 % wt., in particular 3-6 % wt.,

    - sulfosuccinate: 0.1-5 % wt., preferably 0.25-3 % wt., in particular 0.5-2 % wt.
14. Liquid detergent composition according to any one of the preceding claims, characterised in that the bleaching component comprises a thickener, in particular a thickener selected from the group consisting of hydrocolloids, such as xanthan or water-soluble cellulose ethers and mixtures thereof, in particular in amounts such that the viscosity of the bleaching component (measured at 25°C) lies in the range of 300-1500 mPas, preferably in the range of 600-1000 mPas.
15. Liquid detergent composition according to any one of the preceding claims, characterised in that the pH of the bleaching component lies in the range of 1.5 to 6.5, in particular in the range of 2.5 to 4.5.