EP2376615A1 - Color-protecting dishwasher detergent - Google Patents

Color-protecting dishwasher detergent

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Publication number
EP2376615A1
EP2376615A1 EP09748772A EP09748772A EP2376615A1 EP 2376615 A1 EP2376615 A1 EP 2376615A1 EP 09748772 A EP09748772 A EP 09748772A EP 09748772 A EP09748772 A EP 09748772A EP 2376615 A1 EP2376615 A1 EP 2376615A1
Authority
EP
European Patent Office
Prior art keywords
wt
particle diameter
preferably
average particle
particular
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09748772A
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German (de)
French (fr)
Other versions
EP2376615B1 (en
Inventor
Susanne Tondera
Reiner Schackmann
Cornelius Bessler
Thomas Eiting
Arnd Kessler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Priority to DE102009004524A priority Critical patent/DE102009004524A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PCT/EP2009/064571 priority patent/WO2010078979A1/en
Publication of EP2376615A1 publication Critical patent/EP2376615A1/en
Application granted granted Critical
Publication of EP2376615B1 publication Critical patent/EP2376615B1/en
Application status is Active legal-status Critical
Anticipated expiration legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite, attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides; Polyimides

Abstract

With dishwashers, discolorations can occur on plastic materials, resulting from food residue of color-intensive foods such as curry, paprika, tomatoes, red cabbage, ketchup or carrots that are introduced into the dishwasher with the dishes to be cleaned. The occurrence of said discolorations was to be reduced. This was substantially achieved by the use of porous polyamide particles and/or synthetic layered silicates.

Description

03/11/2009

"Color Protective dishwasher detergent"

The present invention relates to a dishwasher detergent comprising a color transfer inhibitor in the form of certain porous polyamide particles and / or synthetic layer silicate. It relates to uses of said color transfer inhibitors in the context of their use in an automatic dishwasher. It further relates to a method for automatic dishwashing.

If occur at plastic discoloration in the course of machine dishwashing, which comes mostly from very intensely colored foods such as curry, paprika, tomatoes, red cabbage, ketchup, carrots, etc., which are introduced in the form of food particles in the dishwasher. Discoloration of the plastic, such as plastic dishes, lead the consumer dissatisfaction, because although the plastic dishes in question remains on a purely functional level, unaffected, many consumers appear to be optically canceled, but interferes with at least the aesthetic sense.

The object of the present invention was to make it possible to reduce the occurrence of discoloration of plastics in the course of automatic dishwashing as a consequence of colored food residues, at least.

This object is achieved by the subject matter of the invention. The invention provides a dishwasher detergent comprising a color transfer inhibitor in the form of

(A) porous polyamide particles which

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or

(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium magnesium lithium silicate), preferably with an average particle size of 5 to 800 nm, advantageously from 25 to 500 nm, in particular from 100 to 400 nm.

The layered silicate is in particular a forming in water a colloidal gel layer silicate. According to the invention suitable layer silicates are commercially available, for example, is Laponite® RD (Rockwood Additives Limited, UK) is particularly suitable. It can also be used mixtures of the synthetic layer silicates. It has surprisingly been found that in particular the said porous polyamide particles allow a high degree of prevention or significant reduction in the discoloration of plastic materials during the automatic dishwashing process. The change of the color impression of plastic dishes at its cleaning in an automatic dishwashing machine can be avoided or at least reduced. The transfer of dyes, as a result of colored food residues on plastic dishes at its cleaning in an automatic dishwashing machine can be suppressed or at least reduced. Particularly effective the transfer of the following dyes can be inhibited or at least reduced: red to blue Anthocyanfarbstoffe such as cyanidin, such as cherries, bilberries, red betanidine, for example from beetroot, orange red carotenoids, such as lycopene or beta-carotene, for example, tomato, ketchup or

Carrots, yellow Curcumafarbstoffe, such as curcumin, for example from curry and mustard, brown tannins, for example from tea, fruit, red wine deep brown humic acid, such as coffee, tea, cocoa, green chlorophyll, for example, from green herbs.

It is conceivable that the polymer particles dye molecules contained in the cleaning liquor by their large surface area which may be formed dendritically in particularly preferred cases or has a fractal geometry, take up, they do not re-emit and thus prevent the deposition of the dyes to the plastic dishes or at least can reduce.

Also, the aforementioned synthetic phyllosilicate (preferably magnesium silicate) may enable preventing or reducing the discoloration of plastic materials during the automatic dishwashing process. In particular, white and light-colored plastic materials benefit from the invention.

The production of the porous polyamide particles can be generally prepared by mixing a solution of polyamide in a suitable solvent with a liquid phase, are insoluble in the polyamides. Typically, the liquid phase is water-based, it being achieved by suitable other solvent that during mixing of the fluids at first a clear solution forms, from which precipitate the polyamide particles. In the preparation have particular mixing ratios of polyamide solution to the liquid phase of from 1 to 999 to 300: 700, preferably from 2 to 998 to 250 to 750, proven. Polyamide solutions can for example with the solvents o-cresol, m-cresol, p-cresol, chlorophenol, phenol, or mixtures thereof are provided. Also formic acid has proven itself.

The liquid phase, in the polyamides are insoluble, is preferably miscible with the abovementioned solvents and in addition water-miscible. Preferred liquid phases are aliphatic alcohols, aliphatic ketones and mixtures thereof. , methanol, ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and mixtures of these have proved particularly suitable.

Preferably, mixtures of from 10 to 98 wt .-% of aliphatic alcohols and / or ketones having from 2 to 90 wt .-% of water can be used as a liquid phase from which the precipitate polyamide particles. For nucleation, the liquid phase of high molecular weight polyalkylene glycols, such as PEG or PPG, in amounts of for example 0.5 to 10 wt .-% (based on the liquid phase).

The sequence of mixing is not critical to the manufacturing process. In preferred processes,

- aliphatic alcohols and / or ketones and water are added simultaneously but separately to a polyamide solution or

- a previously prepared mixture of aliphatic alcohols and / or ketones and water is added to a polyamide solution or

- aliphatic alcohols and / or ketones are added to a polyamide solution, after which water is added or

- water is added to a polyamide solution, followed aliphatic alcohols and / or ketones are added, or

- a polyamide solution is added to a previously prepared mixture of aliphatic alcohols and / or ketones and water, or

- a polyamide solution is added to aliphatic alcohols and / or ketones and water and connecting the water added.

The formation of the porous polyamide particles by precipitate formation is generally carried out in periods of 1 second to 2 hours and may be assisted by stirring. Preferably, the mixing of the liquid and formation of the particles at temperatures of from 5 to 7O 0 C is carried out, particularly preferably at 15 to 6O 0 C. After the above time period, the polyamide particles can be easily separated by decanting, filtration or centrifugation from the solvent mixture. preferably it is followed by a washing with methanol and / or acetone and drying in vacuo.

Very particularly preferred process for preparing a use solution of polyamide 11 and / or polyamide 12 in phenol which, based on their weight 0.1 to 50 wt .-% Polymaid (e) contains. As a liquid phase in such a preferred method, a mixture of ethanol (preferably 50 to 90 wt .-%, based on the liquid phase), ethylene glycol (preferably 1 to 10 wt .-%, based on the liquid phase) and glycerol (preferably 1 to 12 wt .-% used, based on the liquid phase). The polyamide solution in phenol (preferably 30 to 70 wt .-%, based on the mixture), the liquid phase (preferably 40 to 65 wt .-%, based on the mixture) and polyethylene glycol and / or polypropylene glycol having molar masses of> 1000 daltons ( preferably 0.5 to 10 wt .-%, based on the mixture) are stirred into a mixture with one another, containing 0.05 to 20 wt .-% of polyamide (s). This mixture, which ideally has a viscosity below 200 Pas is stirred at 20 to 8O 0 C, preferably at 25 to 65 0 C for 30 to 60 minutes.

The spherical porous polyamide particles produced by the methods described above which are used in preferred embodiments of the invention usually have number-average particle diameter of 0.1 .mu.m to 100 .mu.m, preferably from 0.3 microns to 50 microns, especially 0.5 microns to 35 microns, such as 1 micron to 30 microns. The ratio of volumenmittlerem particle diameter (Dv) to number average particle diameter (Dn), which is also called particle size distribution index (PDI = Dv / Dn), is preferably in the range of from 1 0 to 1; 3.

The porous polyamide particles have a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more. According to the invention, particularly preferred particles have a BET specific surface area (according to DIN 66131) of 5 m 2 / g to 80 m 2 / g, preferably from 6 m 2 / g to 60 m 2 / g and in particular from 7.5 m 2 / g to 50 m 2 / g. Very particularly preferred embodiments of the invention are characterized in that the porous polyamide particles have a BET specific surface area (according to DIN 66131) of 6 m 2 / g or more, preferably 7 m 2 / g or more, particularly of 8 m 2 / g or more.

Preferred porous polyamide particles have a Porositätsind ex Rl (RI = S / S0, where SO, based is the specific surface area to the number average particle diameter, and by the formula S0 = 6 / (p * Dn) where p is density of the particles and Dn of is number average particle diameter, and wherein S is the BET specific surface area is) in the range of 3 to 100, in particular from 5 to 70. the porous polyamide particles have an average pore diameter of 0.01 .mu.m to 0.20 .mu.m, in particular from 0 , 02 .mu.m to 0.1 .mu.m, and a crystallinity (DSC measurement) of 40% or greater.

The standard enthalpy (or specific heat of fusion) of the porous polyamide particles is measured by means of DSC. Here, the sample is heated, starting with a temperature increase rate of 5 ° C / min under nitrogen atmosphere from room temperature (2O 0 C). The standard enthalpy is calculated from the area of the heat absorption peak between 120 0 C and 230 0 C. The crystallinity of the polyamide porous particle is the quotient of the measured specific heats of fusion and the standard enthalpy crystalline polyamide, the latter for polyamide about 209 J / g 12th

With respect to the oil absorption capacity of usable in the present invention means particle composition of the invention are preferred in which the porous polyamide particles have an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more, preferably 170 ml / 100 g or more have.

The preparation of porous polyamide particles is also disclosed, for example, in Japanese disclosure writing 2002-80629. Preferably, the porous polyamide particles are spherical.

The porous polyamide particles are preferably introduced as part of an automatic dishwashing agent in the respective wash solution, however, the porous polyamide particles can also be added separately as part of an automatic dishwashing wash solution readily, for example, as an additive. The same applies to the usable synthetic sheet silicate.

An agent of the invention preferably contains 0.05 wt .-% to 30 wt .-%, particularly 0.5 wt .-% to 10 wt .-%, of the aforementioned porous polyamide particles.

The synthetic layer silicate (preferably magnesium silicate) is used, containing an agent of the invention is preferably 0.05 wt .-% to 30 wt .-%, particularly 0.5 wt .-% to 10 wt .-%, on the synthetic layer silicate.

In particular, it is possible and advantageous to use both the porous polyamide particles and the synthetic layer silicate.

An inventive agent may in addition to said active compounds, if desired, additionally a further, known color transfer inhibitor, these then preferably in amounts of 0.01 wt .-% to 5 wt .-%, particularly 0.1 wt .-% to 1 wt %, contain. In a preferred embodiment of the invention, for example, is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof can be used. Useful are both polyvinylpyrrolidones having molecular weights of 15,000 to 50,000 as well as polyvinylpyrrolidones having molecular weights of about one million, in particular from 1,500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on Acrylamidoalkenylsulfonsäuren.

but can also be used enzymatic systems, comprising a peroxidase and hydrogen peroxide or a hydrogen peroxide in water-Iiefernde substance. The addition of a mediator compound for the peroxidase, for example, an acetosyringone, a phenol derivative or a phenothiazine or phenoxazine, is preferred in this case, wherein additionally the above-mentioned conventional polymeric dye transfer inhibiting agents may be used.

Polyvinylpyrrolidone preferably has an average molecular weight in the range 10,000 to 60,000, in particular in the range from 25,000 to 50,000 for use in the inventive compositions. Among the copolymers, those of vinylpyrrolidone and of vinylimidazole in the molar ratio 5: 1 to 1: 1 preferably with an average molecular weight ranging from 5000 to 50,000, in particular 10,000 to 20,000.

The dishwashing detergents according to the invention, which may be solid or liquid and in particular as powdered solids, in post-compacted particles, as homogeneous solutions or suspensions may be present can in addition to the inventively used ingredients in principle contain any known and conventional in such compositions, wherein substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, perfumes and perfume carriers are particularly preferred. These and other preferred ingredients are described in more detail later in part.

Another object of the invention is the use of (a) porous polyamide particles which

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or

(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium

Magnesium lithium silicate), preferably machine having an average particle size of 5 to 800 nm, advantageously from 25 to 500 nm, in particular from 100 to 400 nm, for preventing the discoloration of plastic materials during the

Dishwashing process. , Prevention of the discoloration of plastic materials during the automatic dishwashing process here means that the degree of discoloration of

Plastic materials is at least reduced, at best, the discoloration of

Plastic materials is completely suppressed.

Another object of the invention is the use of

(A) porous polyamide particles which

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or

(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium magnesium lithium silicate), preferably with an average particle size of 5 to 800 nm, advantageously from 25 to 500 nm, in particular from 100 to 400 nm, to avoid the transfer of dyes, as a result of colored food residues on plastic dishes at its cleaning in an automatic dishwasher. , Prevention of transfer of dyes on plastic dishes as used herein means that the degree of transfer of dyes on plastic dishes at least reducing, the transfer of dyes in plastic dishes is completely suppressed in the best case.

Another object of the invention is the use of (a) porous polyamide particles which

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or 8

(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium magnesium lithium silicate), preferably with an average particle size of 5 to 800 nm, advantageously from 25 to 500 nm, in particular from 100 to 400 nm, to avoid the change of the color impression of plastic dishes with its cleaning in an automatic dishwasher. , Avoiding the change of the color impression of plastic dishes here means that the amount of change in the color impression is at least reduced, the change of the color impression is completely suppressed in the best case.

With respect to the porous polyamide particles can be used as well as the usable synthetic layered silicate are also the previous parts of the description for the aforementioned uses in the rest. This also applies to the method mentioned below.

Another object of the invention is a method of machine dishwashing using aqueous solutions, in which is used an aqueous solution containing

(A) porous polyamide particles which

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or

(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium magnesium lithium silicate), preferably with an average particle size of 5 to 800 nm, advantageously from 25 to 500 nm, in particular from 100 to 400 nm.

Below possible ingredients are described which can advantageously be used in the inventive dishwasher detergents.

Advantageously builders can be used. The builders include especially the zeolites, silicates, carbonates, organic cobuilders and where there are no ecological objections to their use, also the phosphates.

With preferred crystalline layered silicates of general formula NaMSi x O 2x + I y H 2 O can be used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20th The crystalline layered silicates of the formula NaMSi x O 2x + I y H 2 O, for example, from Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 x H 2 O, kenyaite), Na-SKS-2 (Na2 Sh 4 O 29 x H 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 Oi x 7 H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 x H 2 O, makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi x O 2x + 1 y H 2 O, in which x stands for 2 h. In particular, both .beta.- and δ-sodium Na 2 Si 2 O 5 y H 2 O, and further in particular Na-SKS-5 (Oc-Na 2 Si 2 O 5), Na-SKS-7 (.beta.-Na 2 Si 2 0 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 H 2 O), Na-SKS-10 (NaHSi 2 O 5 3 H 2 O, kanemite), Na-SKS-11 ( .-Na 2 Si 2 O 5) and Na-SKS-13 (NaHSi 2 O 5), but in particular Na-SKS-6 (5-Na preferably 2 Si 2 O 5).

Machine dishwashing detergents preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x O 2x + 1 y H 2 O from 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular 0, 4 to 10 wt .-%, each based on the total weight of these agents.

Other useful builders are amorphous sodium silicates with an Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and more preferably 1: 2 to 1: 2.6, which preferably dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In this invention is meant by the term "amorphous" means that the silicates do not produce sharp X-ray reflexes in X-ray diffraction experiments, as it is typical of crystalline substances, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle , cause.

Alternatively or in combination with the aforementioned X-ray amorphous sodium silicates, amorphous silicates can be used, the silicate particles in

provide electron diffraction experiments blurred or even sharp diffraction maxima. This may be interpreted so that the products have microcrystalline regions with a size ten to several hundred nm, values ​​up to max. 50 nm and especially up to max. 20 nm are preferable. Such X-ray amorphous silicates likewise have retarded dissolution compared with traditional water glasses. Particular preference is given to compressed / compacted amorphous silicates, compounded amorphous silicates and over dried X-ray amorphous silicates. 10

In the present invention, it is preferred that these (s) silicate (s), preferably alkali metal silicates, with particular preference crystalline or amorphous alkali metal, present in the agents in amounts of 3 to 60 wt .-%, preferably from 8 to 50th -% and in particular from 20 to 40 wt .-%, in each case based on the weight of the automatic dishwashing agent.

Of course, the widely known phosphates can also be used as builders providing their use should not be avoided for ecological reasons. Among the multitude of commercially available phosphates, the alkali metal phosphates are the most important with particular preference for pentasodium or Pentapotassium (sodium or potassium) in the detergents and cleaners industry.

Alkali metal phosphates is the collective term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which n and orthophosphoric acid H 3 PO may in addition to higher molecular weight representatives metaphosphoric acids (HPO 3). 4 The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime encrustations in fabrics, and furthermore contribute to cleaning performance.

Technically important phosphates are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate). According to the invention use the sodium potassium tripolyphosphates are.

Phosphates are used as washing- or cleaning-active substances in automatic dishwashing agents in the context of the present application, so these preferred compositions comprise (s) phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium ), in amounts of from 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the automatic dishwashing agent.

Further builders are the alkali carriers. As alkali carriers, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonate, said alkali metal silicates, alkali metal metasilicates and mixtures of the aforementioned substances are, with the purposes of this invention, preferably, the alkali metal carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate may be used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their in 1 1

Comparison with other builders low chemical compatibility with the other ingredients of machine dishwashing detergents, the optional alkali metal hydroxides are preferably used only in small quantities, preferably in quantities below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt % and particularly below 2 wt .-%, based in each case on the total weight of the automatic dishwashing agent. Particularly preferred are compositions which, based on its total weight less than 0.5 wt .-% and in particular not contain any alkali metal hydroxides.

Particularly preferred is the use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate, in amounts of from 2 to 50 wt .-%, preferably from 5 to 40 wt .-% and in particular 7.5 to 30 wt .-%, each based on the weight of the automatic dishwashing agent. Particularly preferred are compositions which, based on the weight of the automatic dishwashing agent less than 20 wt .-%, preferably less than 17 wt .-%, preferably less than 13 wt .-% and in particular less than 9 wt.% of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.

As organic cobuilders polycarboxylates / polymeric polycarboxylates, polyacetals, dextrins, other organic cobuilders and phosphonates are, in particular. These classes are described below.

Useful organic builders are, for example usable in the form of the free acid and / or their sodium salts, polycarboxylic acids, and such carboxylic acids are understood to polycarboxylic acids which carry more than one acid function. For example, this citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, fumaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic are (NTA), providing their use for environmental reasons is not objectionable, and mixtures thereof. The free acids Besides their builder effect also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH value of the automatic dishwashing detergent. Citric acid, succinic acid, adipic acid, gluconic acid and any mixtures thereof are particularly mentioned.

Be particularly advantageous for the cleaning and rinsing agents according to the invention, the use of citric acid and / or citrates to these agents has been shown. Therefore, According to the invention preferred machine dishwashing detergents, characterized in that the automatic dishwashing agent citric acid or a salt of citric acid contains, and the proportion by weight of citric acid or of the salt of citric acid, preferably more than 10 wt .-%, preferably more than 15 wt .-%, and in particular between 20 and 40 wt .-% is. 12

As builders, polymeric polycarboxylates are also suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.

At the indicated for polymeric polycarboxylates molecular weights are within the meaning of this specification, weight-average molecular weights Mw of the particular acid form which, basically, were determined by gel permeation chromatography (GPC) using a UV-detector. The measurement was made against an external polyacrylic acid standard, which owing to its structural similarity to the polymers under investigation, provides realistic molecular weight. These figures differ significantly from the molecular weights measured against polystyrene sulfonic acids as standard. The measured against polystyrenesulfonic acids are significantly higher than the molecular weights mentioned in this specification generally.

Particularly suitable polymers are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molecular weights of 2,000 to 10,000 g / mol in this group may in turn, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Particularly suitable copolymers of acrylic acid with maleic acid which contain from 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% of maleic acid. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and especially 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of the automatic dishwashing detergent (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-% and in particular 3 to 10 wt .-%.

In order to improve the water solubility of the polymers can also contain allyl sulfonic acids such as allyloxybenzenesulfonic acid and methallyl sulfonic acid as monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain, as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives, or as monomers, salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives are , 13

Other preferred copolymers are those which contain as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Polymers effective as softeners are, for example, the sulfonic acid group-containing polymers which can be used with particular preference.

Particularly preferably used as a sulfonic acid group-containing polymers are copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid, and optionally further ionic or nonionic monomers.

With particular preference, include automatic dishwashing detergent methylglycinediacetic acid of the invention or a salt of methyl glycine diacetic acid, wherein the weight proportion of methylglycine diacetic acid or the salt of methylglycine diacetic acid is preferably between 0.5 and 15 wt .-%, preferably between 0.5 and 10 wt .-% and in particular between 0.5 and 6 percent by .-%.

In addition, all compounds which are capable of forming complexes with alkaline earth ions are used as builders can.

The inventive compositions may contain surfactants, which belong to the group of surfactants are the nonionic, anionic, cationic and amphoteric surfactants.

Suitable nonionic surfactants are all known in the art nonionic surfactants may be used. Suitable nonionic surfactants are, for example, methyl-branched aliphatic radical, the symbol are alkyl glycosides of the general formula RO (G) x, a primary straight-chain R or methyl-branched, especially in the 2-position having from 8 to 22 and preferably corresponds to 12 to 18 C-atoms and G is, which stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which glycosides the distribution of mono- and oligoglycosides, is any number between 1 and 10; x is preferably 1, 2 to 1; 4.

Another class of preferred suitable nonionic surfactants which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl ester, preferably having 1 to 4 carbon atoms in the alkyl chain. 14

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fat alcohols, especially not more than half of them.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula,

in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 represents hydrogen, an alkyl or hydroxyalkyl having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides are known substances which may normally be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid or a fatty acid chloride.

As the preferred low-foaming nonionic surfactants can be used. With particular preference, the dishwasher detergents containing nonionic surfactants from the group of alkoxylated alcohols. can be used as nonionic surfactants alcohol are preferably alkoxylated, advantageously ethoxylated, more especially primary alcohols preferably containing 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of used, in which the alcohol methyl-branched linear or preferably in the 2-position or linear and methyl-branched radicals may contain the mixtures typically present in oxoalcohol radicals. However, alcohol ethoxylates containing linear radicals of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol preferably. Preferred ethoxylated alcohols include, for example, C- |2 - 14 alcohols with 3 EO or 4 EO, C 9 .n alcohol containing 7 EO, C 3 .i 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 2 -i 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C- |2 - 14 alcohol with 3 EO and C | 2-18 alcohol with 5 EO. The degrees of ethoxylation indicated represent statistical averages, which can correspond to a specific product of a whole or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO may also be used. Examples are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO. 15

Especially preferred nonionic surfactants which have a melting point above room temperature are. Nonionic surfactant (s) (e) with a melting point above 2O 0 C, preferably above 25 0 C, more preferably between 25 and 6O 0 C and in particular from 26.6 to 43.3 0 C, is / are particularly preferred ,

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally complex, such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

Particularly preferred nonionic surfactants in the context of the present invention, low-foaming nonionic surfactants have been found to comprise alternating ethylene oxide and alkylene oxide units. Among these surfactants with EO-AO-EO-AO-blocks are preferred, wherein one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nichionische surfactants of the general formula

Ri-O- (CH 2 -CH 2 -O) - (CH 2 -C HO) - (CH 2 -CH 2 -O) - (CH 2 -C HO) -H

R2 R3

preferably, R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 represents alkyl or alkenyl; each group R is -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z is 2 and R 3 are independently selected from -CH 3, independently of one another are integers 1 to 6

The carbon chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants are statistical average values ​​which may be an integer or a fractional number for a specific product. Due to the manufacturing process do not exist commercial products of the cited formulas of an individual representative, but instead of mixtures, whereby not only the C-chain lengths and the degrees of ethoxylation or alkoxylation average values ​​and can thus be fractional numbers.

Anionic surfactants are used as a constituent of machine dishwasher detergents, is their content, based on the total weight of the agent is preferably less than 4 wt .-%, preferably less than 2 wt .-% and most preferably less than 1 wt .-%. Automatic dishwashing agents that contain no anionic surfactants are particularly preferred. 16

In place of the above-mentioned surfactants or in conjunction with them surfactants may also be used cationic and / or amphoteric. As cationic active substances, cationic compounds of the following formulas can be used:

Ri

Ri-N- (CH 2) n -T-R 2 (CH 2) n -T-R2

wherein each R 1 group is independently selected from C- |.6 alkyl, alkenyl or hydroxyalkyl groups; each R 2 group is independently selected from C 8-28 - alkyl or alkenyl groups; R 3 = R 1 or (CH 2) n -TR 2; R 4 = R 1 or R 2 or (CH 2) n -TR 2; T = -CH 2 -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing agents, the content of cationic and / or amphoteric surfactants is preferably less than 6 wt .-%, preferably less than 4 wt .-%, most preferably less than 2 wt .-% and in particular less than 1 wt %. Machine dishwashing detergents which contain no cationic or amphoteric surfactants are particularly preferred.

The group of polymers includes in particular the washing or cleaning action Poylmere, for example rinsing and / or polymers active as softeners. Generally, cationic, anionic and amphoteric polymers are used in automatic dishwashing agents in addition to non-ionic polymers.

"Cationic polymers" in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized ammonium groups or other positively charged groups for example, present in the polymer chain (alkyl). Particularly preferred cationic polymers derived from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups of the cationic guar derivatives, the 17 polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinyl pyrrolidone-methoimidazolinium chloride - copolymers, quaternized polyvinyl alcohols or of the polymers indicated under the INCI designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27th

"Amphoteric polymers" for the purposes of the present invention, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units. These groups can be, for example carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred usable amphoteric polymers derive from the group of alkyl acrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methyl methacrylic acid copolymers, alkylacrylamide / acrylic acid / alkyl amino alkyl (meth) acrylic acid copolymers, alkylacrylamide / methacrylic acid / alkylamino - alkyl (meth) acrylic acid copolymers, alkylacrylamide / methyl methacrylic acid / alkyl amino alkyl (meth) acrylic acid copolymers, alkylacrylamide / Alkymethacrylat / Alkylaminoethylmethacryl- at / alkyl methacrylate copolymers as well as copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Preferably usable zwitterionic polymers derive from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium / methacrylic acid copolymers and their alkali and ammonium salts, and methacroylethylbetaine / methacrylate copolymers.

In a particularly preferred embodiment of the present invention, the polymers are present in pre-assembled form. For fabrication of the polymers, among others, the encapsulation of the polymers by means of water-soluble or water-dispersible coating agent is thereby, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; Encapsulation of the polymers by water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 3O 0 C; the co-granulation of the polymers with inert carriers, preferably with carrier materials from the group of washing or cleaning-active substances, more preferably from the group of builders (builders), or co-builder. 18

Machine dishwashing detergents containing the above-mentioned cationic and / or amphoteric polymers in quantities of between 0.01 and 10 wt .-%, each based on the total weight of the automatic dishwashing agent. However, such machine dishwashing detergents, where the proportion by weight of cationic and / or amphoteric polymers is between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, preferably between 0, are preferred in the context of the present application 01 and 4 wt .-%, more preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing agent.

The bleaching agents are usable with particular preference washing or cleaning substance. Among the compounds used as bleaching agents in water H 2 O 2 compounds, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H2 O2 -yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or Phthaloiminopersäure. Furthermore, bleaching agents from the group of organic bleaches can be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxy acids being mentioned in particular as examples the alkyl and aryl peroxyacids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε- phthalimidoperoxycaproic acid [Phthaliminoperoxyhexansäure (PAP)] , o- Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinates, and (c) aliphatic and araliphatic icarbonsäuren peroxide, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1, 4 diacid, N, N terephthaloyl di (6-aminopercaproic acid).

As bleaching agents and chlorine or bromine-releasing substances may be used. Suitable chlorine- or bromine-releasing materials, for example, heterocyclic N-bromo and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric, dibromoisocyanuric and / or dichloroisocyanuric come (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1, 3-dichloro-5,5-dimethylhydantoin are also suitable. 19

According to the invention machine dishwashing detergents are preferably containing 1 to 35 wt .-%, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate , contain.

The active oxygen content of the dishwasher detergents, all based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular 0.6 to 5 wt %. Particularly preferred compositions have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1, 0 wt .-% to.

Bleach activators are used in machine dishwashing detergents, for example, in order to achieve cleaning at temperatures of 60 0 C and below, an improved bleaching effect. Suitable bleach activators are compounds which, under perhydrolysis conditions produce aliphatic peroxocarboxylic acids preferably containing 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances which carry O- and / or N-acyl groups of said number of carbon atoms and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso- NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy 2,5-dihydrofuran, n-methyl morpholinium acetonitrile methyl sulfate (MMA) and acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose and acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam , Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators may be used. These bleach activators are preferably used in amounts to 10 wt .-%, particularly 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-%, and particularly preferably 2 to 6 wt .-%, each on the total weight of the bleaching activator.

To increase the washing or cleaning performance of machine dishwashing detergents use enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; starting from the 20 natural molecules are available for use in machine dishwashing detergents improved variants are available that can be preferably used accordingly. Machine dishwashing detergents contain enzymes preferably in total amounts of 1 x 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method and the biuret method.

The enzymes may be used in any well-established in the prior art form. These include, for example, obtained by granulation, extrusion or lyophilization or solid preparations, in particular in liquid or gel form, solutions of the enzymes, advantageously highly concentrated, water and / or mixed with stabilizers.

Alternatively, the enzymes can be encapsulated for both the solid and the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzyme is embedded in a solidified gel or those of the core-shell type in which an enzyme-containing core with a water, air and / or chemical-impermeable protective layer is coated. In superimposed layers further active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents or dyes may be applied in addition. Such capsules are applied by known methods, for example by shaking or rolling granulation or in fluid bed processes. Advantageously, such granules, for example, by applying a polymeric film former, and stable in storage due to the coating. Furthermore, it is possible to formulate two or more enzymes together, so that a single granule has a plurality of enzymatic activities. Preferably, one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations can, in amounts of from 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and are used in particular from 0.4 to 4 wt .-%, each based on the whole composition containing enzyme.

Glass corrosion inhibitors prevent the occurrence of cloudiness, streaks and scratches as well as iridescence of the glass surface of machine washed glassware. Preferred glass corrosion inhibitors originate from the group of magnesium and zinc salts as well as the magnesium and zinc complexes. In the present invention, the content of zinc salt in machine dishwashing compositions is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular from 0.4 to 3 wt .-%, or ., the content of zinc in oxidized form (calculated as Zn 2+) is between 0.01 to 1 wt .-%, preferably from 0.02 to 0.5 wt .-% and especially between 0.04 to 0.2 by weight %, each based on the total weight of the glass corrosion inhibitor-containing agent. 21

In order to facilitate the disintegration of prefabricated shaped bodies, it is possible disintegration aids, so-called tablet disintegrators, may be incorporated in the means in order to shorten the disintegration times. Tablet disintegrants or disintegration accelerators are auxiliaries which provide for the rapid disintegration of tablets in water or other media and for the speedy release of the active ingredients. Preferably disintegration aid can be used in amounts of 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%, each based on the total weight of the disintegration aid-containing agent may be used.

Suitable perfume oils or fragrances in the context of the present invention include individual perfume compounds, for example synthetic products are used of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Preferably, however, mixtures of different odorants, which together produce a pleasing fragrance note. Such perfume oils may also contain natural odorant mixtures, as are accessible from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.

The assembly according to the invention of dishwasher detergents can be done in different meadow. The agents may be present in solid or liquid as well as a combination of solid and liquid forms. Suitable solid forms, in particular powders, granules, extrudates, compactates, particularly tablets are suitable. The liquid forms based on water and / or organic solvents may be thickened, in the form of gels. Agents of the invention may be formulated in the form of single-phase or multi-phase products. in particular machine dishwashing detergents with one, two, three or four stages are preferred. Machine dishwashing detergents, characterized in that it is in the form of a prefabricated dispensing unit with two or more phases, are particularly preferred. The individual phases of multi-phase compositions may have the same or different states of aggregation. in particular machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one solid phase are preferred.

Inventive automatic dishwashing agents are preferably preformulated as dispensing units. These dosage units preferably comprise the necessary for a cleaning operation amount of washing or cleaning-active substances. Preferred dispensing units have a weight 12 to 30 g, preferably 14 to 26 g and especially 16 to 22 g. In order to achieve an optimal cleaning and final rinse, such machine dishwashing detergents are preferably present in the form of a pre-metering unit and between 0.001 and 1 g, preferably between 0.01 and 0.1 g, more preferably between 0.01 and 0 07 g and in particular between 0.01 and 0.05 g of the polymer a), or between 0.1 and 2.5 g, preferably between 0.2 and 2.2 g, more preferably 22 between 0.3 and 1, 9 g, more preferably between 0.4 and 1, 5 g of nonionic surfactant (s) (e) b). The volume of the aforesaid dispensing units and their spatial shape are chosen with particular advantage that a metering of the pre-assembled units can be of the dispensing chamber of a dishwasher. therefore, the volume of the dosing unit is preferably between 10 and 35 ml, preferably between 12 and 30 ml.

The automatic dishwashing agents according to the invention, in particular the prefabricated dispensing units, particularly preferably have a water-soluble coating.

The present application further provides a process for cleaning dishes in a dishwasher, in which means of the invention during the passage of a dishwashing program before the start of the main wash or in the course of the main is metered into the interior of a dishwasher. Dispensing or entry of the agent into the interior of the dishwasher can be performed manually, preferably but the agent is metered by the metering chamber in the interior of the dishwasher.

A typical Rahmenzeptur for a preferably usable dishwasher detergent, for example in tablet form, the following substances includes:

Na-tripolyphosphate 20-50 wt .-%

Sodium carbonate 10-30 wt .-%

5-18 wt .-% sodium

Bleach activator 0.5-5 wt .-%

Wt .-% bleach catalyst 0.01-1

Sulfopolymer 2.5-15 wt .-%

Polycarboxylate 0.1-10 wt .-%

Nonionic surfactant 0.5-10 wt .-%

Phosphonate 0.5-5 wt .-%

Amylase 0.1-5 wt .-%

Protease 0.1-5 wt .-%

Wt .-% each based on the total agent.

Instead of the sodium tripolyphosphate can be used wt .-% citrate in the formulation, in particular 10-50. 23 Example:

Dishwasher detergent comprising the following substances:

Citrate 36 wt .-%

Sodium carbonate 10-30 wt .-%

5-18 wt .-% sodium

Bleach activator 0.5-5 wt .-%

Wt .-% bleach catalyst 0.01-1

Sulfopolymer 2.5-15 wt .-%

Polycarboxylate 0.1-10 wt .-%

Nonionic surfactant 0.5-10 wt .-%

Phosphonate 0.5-5 wt .-%

Amylase 0.1-5 wt .-%

Protease 0.1-5 wt .-%

Wt .-% each based on the total agent.

White plastic boards were in an automatic dishwashing machine (BOSCH SGS 57M82EU / 80) rinsed with the aforementioned automatic dishwashing agents with the addition of 50 g of Ketchup with and without the porous polyamide particles at 7O 0 C. The porous polyamide particles (10 g per run) had the following properties:

- a number-average particle diameter of 0.1 to 100 microns,

- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,

- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,

- a crystallinity (DSC measurement) of 40% or greater, and

- a quotient of volumenmittlerem particle diameter to number average particle diameter of from 1 0 to 1; 5.

The boards from the dishwashing test with the addition of porous polyamide particles showed a significantly lower red color as the boards from the dishwashing test without adding porous polyamide particles on visual evaluation.

Claims

24 claims:
1. dishwasher detergent comprising a color transfer inhibitor in the form of
(A) porous polyamide particles which
- a number-average particle diameter of 0.1 to 100 microns,
- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,
- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,
- a crystallinity (DSC measurement) of 40% or greater, and
- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or
(B) synthetic phyllosilicate (preferably magnesium silicate, in particular sodium magnesium lithium silicate).
2. Composition according to claim 1, characterized in that it includes 0.05 wt .-% to 30 wt .-%, particularly 0.5 wt .-% to 10 wt .-%, of the porous polyamide particles.
3. Composition according to claim 1 or 2, characterized in that it contains .-% to 30 wt .-%, containing 0.05 wt .-% in particular from 0.5 to 10 wt .-%, of synthetic layer silicate.
4. A composition according to any one of claims 1-3, characterized in that the porous polyamide particle number-average particle diameter of 0.3 microns to 50 microns, preferably of from 0.5 .mu.m to 30 .mu.m, in particular from 1 .mu.m to 30 .mu.m.
5. A composition according to any one of claims 1-4, characterized in that, in the porous polyamide particles, the ratio of volumenmittlerem particle diameter (Dv) to number average particle diameter (Dn), which is also called particle size distribution index (PDI = Dv / Dn) ranging from 1, from 0 to 1, is located. 3
6. A composition according to any one of claims 1-5, characterized in that the porous polyamide particles have a BET specific surface area (according to DIN 66131) of 5 m 2 / g to 80 m 2 / g, preferably from 6 m 2 / g to 60 having m 2 / g and in particular from 7.5 m 2 / g to 50 m 2 / g.
7. The composition according to any one of claims 1-6, characterized in that the porous polyamide particles have a porosity index Rl in the range of 3 to 100, in particular in the range of 5 to 70 wt. 25
8. A composition according to any one of claims 1-7, characterized in that the porous polyamide particles (an average pore diameter of 0.01 .mu.m to 0.20 .mu.m, in particular from 0.02 microns to 0.1 microns, and a crystallinity DSC measurement) have 40% or greater.
9. A composition according to any one of claims 1 to 8, characterized in that it additionally contains a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
10. Use of
(A) porous polyamide particles which
- a number-average particle diameter of 0.1 to 100 microns,
- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,
- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,
- a crystallinity (DSC measurement) of 40% or greater, and
- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or
(B) synthetic phyllosilicate (preferably magnesium silicate), for preventing the discoloration of plastic materials during the automatic dishwashing process.
11. Use of
(A) porous polyamide particles which
- a number-average particle diameter of 0.1 to 100 microns,
- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,
- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,
- a crystallinity (DSC measurement) of 40% or greater, and
- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or
(B) synthetic phyllosilicate (preferably magnesium silicate), for preventing the transfer of dyes resulting from colored food residues on plastic dishes at its cleaning in an automatic dishwasher.
12. Use of
(A) porous polyamide particles which 26
- a number-average particle diameter of 0.1 to 100 microns,
- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,
- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,
- a crystallinity (DSC measurement) of 40% or greater, and
- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or
(B) synthetic phyllosilicate (preferably magnesium silicate) in order to avoid the change of the color impression of plastic dishes at its cleaning in an automatic dishwasher.
13. A method for automatic dishwashing with aqueous solutions, characterized in that use is an aqueous solution containing
(A) porous polyamide particles which
- a number-average particle diameter of 0.1 to 100 microns,
- a BET specific surface area (according to DIN 66131) of 5 m 2 / g or more,
- an oil absorption capacity (boiled linseed oil) of 160 ml / 100 g or more,
- a crystallinity (DSC measurement) of 40% or greater, and
- a quotient of volumenmittlerem particle diameter to number average particle diameter of 1, having from 0 to 1, 5, and / or
(B) synthetic phyllosilicate (preferably magnesium silicate).
EP09748772.2A 2009-01-09 2009-11-04 Automatic dishwashing detergent composition protecting colour Active EP2376615B1 (en)

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DE102009004524A DE102009004524A1 (en) 2009-01-09 2009-01-09 Color Protective dishwasher detergent
PCT/EP2009/064571 WO2010078979A1 (en) 2009-01-09 2009-11-04 Color-protecting dishwasher detergent

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