DE3325503A1 - WATER-BASED, THIXOTROPICAL DISHWASHER FOR AUTOMATIC DISHWASHER - Google Patents

Description

description

The invention relates to a water-containing, thixotropic dishwashing detergent, in particular for automatic dishwashers, that is easily dispersible in the washing medium, making tableware, glassware, porcelain and others effective can be cleaned.

Commercially available detergents for household dishwashers are in powder form and have the disadvantage that they are composed unevenly, are relatively expensive to manufacture, when stored under moisture tend to cake together, resulting in the formation of difficult-to-disperse lumps that they are in dry form and thereby cause particular irritation in consumers suffering from allergies and that they tend to clump together in the dispenser of the dishwasher. Liquid dishwashing detergents In contrast, they can be used in automatic dishwashers because of the strong foam formation, the extremely low Use poor viscosity and the excessively high alkalinity of these agents.

Recent research and development has focused on gel or thixotropic mixtures, e.g. on abrasives and dishwashing detergents for automatic dishwashers in the form of thixotropic pastes.

However, these products are unsuitable as dishwashing detergents mainly because they are insufficient are viscous in order to remain "anchored" in the dispenser of the dishwasher, and furthermore, remain on Crockery, glassware, porcelain and other stained residues. Ideally, you want thixotropic detergents

be highly viscous in the resting state or in the plastic Bingham state are present and have relatively high flow values. Under shear stress, however, these products should become liquid quickly, for example when shaken in the container or when pressed through a nozzle, and

if the applied shear force ceases to exist, they should quickly change to the highly viscous or plastic state according to Bingham to return. Furthermore, the stability of these products with regard to phase separation or exudation of constituents - | 0 share of considerable importance when standing for a long time.

The detergents for automatic dishwashers which have hitherto been in gel form and have the properties mentioned above result in difficulties in particular in the case of conventional household dishwashers. It will be for such Automatic dishwashing detergents generally recommended that they contain sodium tripolyphosphate (NaTPP) for softening the water or for binding the salts that give the water hardness and for emulsifying and / or peptizing of dirt as well as sodium silicate to achieve the desired alkalinity for effective Cleaning and protection for the glaze and decor of porcelain and sodium carbonate, generally only optional, to increase the alkalinity, also a chlorine-releasing agent for better removal of dirt stains or water stains and finally a foam suppressor / surfactant to reduce foam formation and thus to support the effectiveness of the machine cleaning process and ultimately to achieve the required To give cleaning effect. This is for example in "SDA Detergents in Depth, Formulations Aspects of Machine Dishwashing "by Thomas Oberle (1974). Such a structured detergent are mostly liquids or Powder. The combination of these ingredients in gel form, which are suitable for household dishwashers,

has created considerable difficulties. In general, the hypochlorite bleaching agent is omitted from these agents, as it is with other chemically active ingredients

and in particular reacts with the surfactant and thereby the 5th

The suspending agent or the thixotropic agent decomposes and affects its effectiveness. So in US PS No. 4,115,308 thixotropic pastes for automatic dishwashers which contain a suspending agent contain, e.g. carboxymethyl cellulose, synthetic clays and the like and also inorganic salts such as silicates, phosphates, Polyphosphates, etc., and small amounts of a surfactant and a foam suppressor. A bleach will do but not described. From U.S. Patent 4,147,650

a similar product is known, the optional hypochlorite 15

as a bleaching agent, but does not contain any organic surfactant or foam depressant. The product is used as a detergent Described slurry that has no noticeable thixotropic properties.

From US Pat. No. 3,985,668, abrasives with a gel-like consistency are known which are a suspending agent, preferably of the smectite and attapulgite type, also abrasives such as quartz sand or perlite, and fillers such as powdered ones

Low density polymers, or expanded perlite, contain-25

ten, whereby these fillers show a certain buoyancy and thus stabilize the mixture and additionally as Dietary fiber works and replaces water, which would otherwise result in unwanted protruding layers

of exudation or a phase impairment result 30th

would. In addition to these basic ingredients, such abrasives can also optionally be hypochlorite bleach, bleach-stable surfactants and buffer substances, e.g. silicates, Carbonates, monophosphates, etc. contain. Furthermore can

Builders, such as NaTPP, may also be present to make the Buil-35

to support the effect of the buffer substances. The amount Such builders should not exceed 5% by weight, based on the total composition. The maintenance the desired pH value to over 10 is carried out by the buffer / builder components, with the high pH value a decomposition of the chlorine bleach and a to reduce undesired interaction between surfactant and bleach to a minimum. That if necessary NaTPP present is limited to 5% by weight; Foam pressers ^ q · are not included in these products.

The invention is based on the object of creating a dishwashing agent for automatic dishwashers, which has thixotropic properties and an improved ^ 5 chemical and physical stability and that disperse easily and quickly in the washing liquid so that the cleaning of china, glass and dishes can be done effectively without any of the above Disadvantages occurs.

It is also an object of the present invention to provide a dishwashing detergent with good physical stability to create that shows no significant phase separation even after prolonged storage times. Furthermore, the new Dishwashing detergents be constructed so that no or at least only significantly weakened undesirable interactions occur between the chemically active components.

Another object of the invention is to provide a Dishwashing detergent for automatic dishwashers that has the aforementioned stability even with strong alkaline setting of the detergent, which is necessary for effective cleaning power. Further-

OK, the dishwashing detergent should be better rheological Show eicjonschaft and at low heavy-speed

Possibilities have higher viscosities and at high shear rates lower viscosities, so that it is advantageous used in the dispenser of the dishwasher

can be. Finally, a dishwashing detergent 5

are created with little foam development, improved cleaning power and faster dispersibility in a dishwasher.

This object is achieved according to the invention by a water-containing, thixotropic dishwashing detergent, in particular for automatic dishwashers, which is characterized is through a content

a) 8 to 35 wt.% Alkali metal tripolyphosphate with a

average degree of hydration less than 5

than 1 or more than 5,

b) 2.5 to 20% by weight sodium silicate,

c) 0 'to 9% by weight of water-soluble alkali metal carbonate,

d) 0.1 to 5% by weight of an organic which is dispersible in water and resistant to chlorine bleach Surfactants,

e) 0 to 5% by weight of a foam-inhibiting agent that is resistant to chlorine bleach,

f) Chlorine bleach in an amount equal to about 0.2

supplies up to 4% by weight of available chlorine, and 25

g) a thixotropic thickener in an amount

• which is sufficient for the composition to have a thixotropic index from about 2.5 to 10.

The dishwashing detergents according to the invention for automatic ^ O dishwashers produce little foam, are both chemically and physically stable, dissolve quickly in the washing liquid and are special effective at pH values that result in an improved cleaning effect, namely at pH values in the range of 10.5 to 13.5. The mixtures according to the invention have normal

have a gel-like consistency, i.e. they are highly viscous, opaque, gel-like products with a Bingham elasticity and thus have relatively high flow values. Accordingly, a certain shear force is required to cause or increase the outflow, as one would in a dispenser of an operated or has the automatic dishwasher turned on. Under these conditions, the mixture according to the invention -10 quickly brought into a fluid state and easily released. When the shear force is removed, the fluid mixture quickly returns to its highly viscous or plastic state Bingham condition and almost returns to its former consistency.

In general, the effectiveness is that of the invention Dishwashing detergent depends directly on the available chlorine content, the alkalinity, the solubility in the washing medium and the foam inhibition. The pH of the dishwashing detergents according to the invention is preferably at least about 9.5, particularly preferably in the range from about 10.5 to 13.5 and very particularly preferably at at least about 11.5. At relatively low pH values, the dishwashing detergent according to the invention is too viscous, i.e. almost solid, and no longer easily lifts under the shear forces prevailing in the dispenser bring into a fluid state; such an agent then forfeits most or even all of its thixotropic Properties a. The addition of NaOH is therefore often required to bring the pH to a value within to increase the range given above and the flow properties to improve. The presence of carbonate is also often required because it acts as a buffer substance Maintenance of the desired pH range ensured.

An excess of carbonate should be avoided because

otherwise needle-like carbonate crystals form, which increase the stability, Thixotropy and / or cleaning power of the invention Affect dishwashing detergent. Caustic tables

Soda (NaOH) is also used to remove the existing foam-5

pressure, namely the phosphoric acid ester or phosphonic acid ester to neutralize. The dishwashing detergent according to the invention Usually contains about 0.5 to 3% by weight NaOH and about 2 to 9% by weight sodium carbonate; it should be noticed however that sufficient alkalinity can also be guaranteed by the existing NaTPP and sodium silicate can.

In the dishwashing detergent according to the invention in one Amount in the range of about 8 to 35 wt.%, Preferably from about 20 to 30 wt.%, NaTPP present should preferably Be free of heavy metals, as these lead to a decomposition or inactivation of the preferred Sodium hypochlorite and other chlorine bleach contribute. To improve and accelerate hydration and solubilizing NaTPP and avoiding undesirable thickening of the dishwashing detergent can do this NaTPP have an average degree of hydration of less than about 1 or more than 5, indicating a water content from 0 to 2.7% by weight or from at least 16.5% by weight 25

, including the stable hexahydrate (degree of hydration of 6) corresponding to a water content of about 18% by weight or more. Indeed, a humidification is on on average about 0.3 to 1% by weight of water is very effective

and serves to nucleate the stable hexahydrate, 30

which promote hydration and solubilization of the remaining NaTPP particles.

The foam absorption is important to the effectiveness of the Dishwasher increase and destabilizing effects due to excessive foaming c- can occur in use, to a minimum. The foam can be formed by appropriately selecting both the type and the amount of the surfactants, which are the main ones represent foam-producing component, are sufficiently reduced. The extent of the foam development

- _{0 also} depends on the hardness of the washing water in the washing machine, whereby a suitable adjustment of the proportions of NaTPP, which has a water-softening effect, can help to achieve the desired degree of foam suppression. In general, however, it is preferred to use a

. foam suppressors resistant to chlorine bleach or insert damper. The alkylphosphonic acid esters of the formula are particularly effective here

O
H

HO-P-R

OR

which are available, for example, from BASF-Wyandotte (PCUK-PAE), you

and especially the alkyl phosphoric acid esters of the formula

HO-P- OR

OR

which are available e.g. from Hooker (SAP) and Knapsack (LPKn-158) are, where one or both R groups in both types of ester are independently alkyl groups with 12 to 20 Represent carbon atoms. Mixtures of the two types of esters or others resistant to chlorine bleach can also be used Types or mixtures of mono- and diesters of the types mentioned are used. One is particularly preferred Mixture of mono- and di- (C ,, - to C, "- alkyl) -phosphoric acid esters, for example the monostearyl and distearyl phosphate

'^ phosphoric acid ester in a ratio of 1.2: 1 (product of Knapsack). As a rule, the foam pusher is used in an amount from 0.1 to 5% by weight, preferably from 0.1 to 0.5% by weight, in the Dishwashing detergents according to the invention used, the weight ratio of surfactant (component d) to foam

'^ pusher (component e) generally in the range of about 10: 1 to 1: 1, preferably in the range from 4: 1 to 1: 1. Other foam pressers include, for example, those known Silicones.

^ Although every chlorine bleach in the invention Dishwashing detergents can be used, such as dichloroisocyanurate, Dichlorodimethylhydantoin, chlorinated TSP and the like, are alkali metal hypochlorites such as potassium, Lithium, magnesium and especially sodium hypochlorite, preferred. The dishwashing detergents according to the invention should contain an amount of chlorine bleach sufficient to provide about 0.2 to 4% by weight of active chlorine, which is determined, for example, by acidifying 100 parts of the dishwashing detergent with excess hydrochloric acid can be. A solution that contains about 0.2 to 4% by weight of sodium hypochlorite provides or also contains about the same percentage of active chlorine. A content of 0.8 to 1.6% by weight of active chlorine is particularly preferred.

The sodium silicate, which contributes to the alkalinity and protection of hard surfaces such as porcelain glazes and decorations, is used in an amount in the range from about 2.5 to 20% by weight, preferably from about 5 to 15% by weight, in the Dishwashing detergents according to the invention used. The sodium silicate is generally added in the form of an aqueous solution and preferably has an Na ₂ O: SiO ₂ ratio of about 1: 2.2 to 1: 2.8. Most of the other constituents of the -IO dishwashing detergents according to the invention, in particular sodium hydroxide, sodium hypochlorite, foam depressors and thixotropic thickeners, are also frequently used in the form of previously prepared aqueous dispersions or solutions.

Those used in the dishwashing detergents according to the invention Surfactants must be stable in the presence of chlorine bleaches, especially hypochlorite bleaches and preferably represent organic anionic products, amine oxides, phosphine oxides, sulfoxides and betaines as water-dispersible Represent types of surfactants, the former being particularly preferred. They are used in amounts from about 0.1 to 5% by weight and preferably from about 0.3 to 0.8% by weight are used. Particularly preferred surfactants are linear or branched alkali metal mono- and / or -di-Cg-C,.-alkyldi-

phenyl oxide monosulfonates and / or disulfonates, for example the commercially available products DOWFAX 3B-2 and DOWFAX 2A-1. In general, paraffin sulfonates tend to be tends to adversely affect the thixotropic properties or even destroy them, which has been found to cause an excessive increase in viscosity, thereby creating serious difficulties in terms of the high shear forces required. The surfactants should also be compatible with other constituents of the mixture according to the invention. Other suitable surfactants are for example primary alkyl sulfates, alkyl sulfonates, alkyl

aryl sulfonates and sec-alkyl sulfates, such as sodium C, ₀ -C, g-alkyl sulfates, e.g. sodium dodecyl sulfate, sodium tallow alcohol sulfate, sodium C, "- C, g-alkanesulfonates, e.g. sodium hexadecyl-1-sulfonate, and sodium C, ~ -C, "kylbenzenesulfonates, such as, for example, sodium dodecylbenzenesulfonate. The corresponding potassium salts can also be used.

Other suitable surfactants are amine oxides of the general formula R "R NO, where each R radical is a lower alkyl radical,

1
for example methyl, while R is a long-chain alkyl radical with 8 to 22 carbon atoms, for example a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding phosphine oxide of the general formula can also be used

1 1

R ₉ R PO or a sulfoxide RR SO can be used. Surfactants

of the betaine type have the general formula R_R N R COO, where each R is a lower alkylene group having 1 to 5 carbon atoms. Suitable examples of these surfactants are Lauryl dimethylamine oxide, myristyl dimethylamine oxide, coconut di

methylamine oxide, hardened tallow dimethylamine oxide as well as' the corresponding phosphine oxides and sulfoxides and the corresponding betaines including dodecyl-dimethylammonium acetate, Tetradecyl diethylammonium pentanoate, hexadecyl dimethylammonium hexanoate and the like. With regard to the biological

In terms of biodegradability, the alkyl radicals in these surfactants should be linear, which is why they are preferred.

Such surfactants are well known and are disclosed, for example, in U.S. Patent

3,985,668 and 4,271,030. 30th

Thixotropic thickeners, i.e. thickeners or suspending agents which are thixotropic in an aqueous medium Give properties, are already known and can organic or inorganic water-soluble, water-dispersible

yogable or colloid-forming monomeric or polymeric product

te be of course in the dishwashing detergents according to the invention are stable, i.e. resistant to high alkalinity and chlorine bleaching agents such as sodium hypochlorite. The particularly preferred thickeners or 5

Suspending agents are generally inorganic colloid-forming clays of the smectite and / or attapulgite type. These Substances are generally used in amounts of about up to 5% by weight, the amount in each case

should be sufficient to give the product the desired Bingham-Pla-10

to give sticity.

Smectite clays include montmorillonite (bentonite), hec- · torite, saponite, etc. These products are among the

Trade names "Thixogel No. 1" and "Gelwhite GP" sold by Georgia Kaolin Company and are montmorillonites.

As attapulgite clays under the trade name "Attagel", such as "Attagel 40", "Attagel 50" and "Attagel 150", used by Engelhard Minerals and Chemicals Corporation. Also mixtures of smectite

and attapulgite in weight ratios of 4: 1 to 1: 5 are suitable for this. Thickening agents or suspending agents of the aforementioned type are well known and are described, for example, in U.S. Patent 3,985,668. Friction means or

Polishing agents should be avoided. 25th

Those contained in the dishwashing detergents according to the invention The amount of water should of course not be so high that the product has an excessively low viscosity and flowability receives, but also not be so low that a

excessively high viscosity and low flowability

is caused, in each case the thixotropic Properties are adversely affected or even destroyed. The appropriate amount of water can easily be determined through routine experimentation be determined in each particular case, they 35

is generally in the range from about 45 to 75% by weight, preferably from about 55 to 65% by weight. The used Water is preferably deionized or plasticized.

The product according to the invention shows an improved rheological one Behavior, especially with regard to viscosity as a function of shear forces. The research confirms that the mixtures of the invention have a higher viscosity at low shear rate and a have lower viscosity at a high shear rate, and the results indicate that an effective Conversion into the fluid state and a more effective gelation with the shear forces, which in dishwashing machines

-I5 machines occur, is made possible. That means in the Practice improved casting and processing properties of the products obtained, which are not undesirable can escape from the dispensing device, as is the case with conventional liquid dishwashing detergents.

With the shear forces that occur at 3 to 30 revolutions per Minute occur, Brookfield viscosities are in a range from 15,000 to 30,000 cP to about 3000 to 5000 cP obtained, measured at room temperature with an LVT Brookfield viscometer after 3 minutes with a Spindle No. 4. A shear rate of 7.4 sea corresponds to about 3 spindle revolutions per minute. One about A 10 fold increase in shear rate results in an approximately 6 to 7 fold decrease in viscosity. Both known gel-like dishwashing detergents, the corresponding reduction in viscosity is only about 2 times Value. In addition, these known mixtures have an initial viscosity of only about 3 revolutions per minute about 2500 to 2700 cP. The mixtures according to the invention show a threshold fluidization at lower

Shear rates and, to a significantly greater extent, the proportional increase in the shear rate compared to the proportional reduction in viscosity. This property of the products according to the invention is expressed by the Thixotropy Index (TI), which is the ratio of the actual viscosity at 3 IM rotations per minute corresponds to the actual viscosity at 30 revolutions per minute. The mixtures according to the invention have a T'I of about 2.5 to 10 and preferably from 6 to 8. All dishwashing detergents according to the invention that were tested showed complete and rapid Return to their previous resting state with appropriate consistency when no more shear forces have been applied.

According to a preferred method for producing the dishwashing detergents according to the invention, all inorganic salts, i.e. carbonate (if present), silicate and tripolyphosphate, dissolved in the aqueous medium or dispersed. The thickener is added last. The foam pusher (if present) is used beforehand produced as an aqueous dispersion, as well as the thickener. The dispersion of the foam pusher, the caustic Soda (if present) and the inorganic salts are first treated at elevated temperatures in an aqueous medium (deionized Water) and then cooled with constant stirring. Bleach, surfactant and thickener dispersion from room temperature are then added to the cooled (25 to 35 ° C) solution. If apart from the chlorine bleach, the total salt concentration (NaTPP, sodium silicate and carbonate) is in of the mixture according to the invention generally about 20 to 50% by weight, preferably about 30 to 40% by weight.

Other conventional ingredients can generally be used in small amounts in the dishwashing detergents according to the invention less than about 3% by weight, for example perfume, hydrotropes, for example sodium benzene-5

sulfonate, sodium toluene sulfonate, sodium xylene sulfonate and sodium cumene sulfonate, as well as preservatives, dyes and pigments and the like, all of which, of course, must be resistant to chlorine bleach and high alkalinity. ^{Chlorinated y} are particularly preferred for dyeing

th phthalocyanines and polysulphides from aluminosilicates are used, which produce pleasing green and blue shades. Titanium dioxide can be used to lighten or neutralize false colors.

The liquid dishwashing detergents according to the invention can in a known way for washing dishes or other kitchen appliances and the like in automatic dishwashers, which are equipped with a suitable dispenser for detergent, easily in a water-containing washing bath be used in effective amounts.

The invention is further illustrated by the following examples. All quantities are given as weights

to be understood, unless expressly stated otherwise 25

is specified.

example 1

First a predispersion I with a foam-30

made a push-button, which contained a 2: 1 mixture of mono- and di- (C, _fi - to C, Q-) alkyl esters of phosphoric acid (LPKn 158 from Knappsack) in an amount of 0.16 g in 6 g of water, with the dispersion for 30 minutes

Mixing with a disk stirrer at 60 C was obtained.

COPY

Another predispersion II was prepared from a smectite (GELWHITE GP) in an amount of 3 g in 17 g of water, mixing for 10 minutes at a temperature of 70 C with a Z-paddle mixer.

The following ingredients were mixed in a Giusti mixer at 50 to 60 C:

'. Weight%

Components

Deionized water dispersion I

¹⁵ NaOH solution (49%)

sodium

Sodium silicate solution (47.5%) (Na _{2 OiSiO 2} = 1: 2.4)

NaTPP (anhydrous) ²⁰ NaTPP (hexahydrate)

The anhydrous NaTPP contained about 0-2.7 wt% moisture.

This mixture was cooled to 25 to 30 ° C. with constant stirring and then
Components added:

Weight% active ingredients 16.9 6.16 0.16 2.40 1.2 7.00 7.0 13.74 6.5 12.00 11.54 12.00 9.36

Cooled 30 ° C and then the following at room temperature

Wt.% Wt.% Act. Components

Sodium hypochlorite solution
with 13% by weight active chlorine 7.615 1.0

Dispersion II 20.00 3.0

Surfactant 0.80 0.36

35 r

A 45% strength aqueous solution of sodium monodecyl diphenyloxide disulfonate was used as the surfactant and sodium didecyl diphenyl oxide disulfonate are used.

An opaque gel-like mixture with about 40% active ingredients was obtained, which had a T ¹ I value of about 7 or an actual viscosity of 28,000 cP at 3 revolutions per minute and 4,000 cP at 30 revolutions per minute.

-10 pointed. When tested in an automatic dishwasher with a dispensing device, the mixture according to the invention exhibited excellent resistance to disintegration, with it was delivered easily and quickly. The inventive Dish detergent was unsatisfactory

"15 foaming. After prolonged storage of the product in In a closed container, practically no or only an insignificant phase separation was observed. The pH of the detergent in a 1% strength aqueous solution was 11.6. The behavior under shear conditions was excellent; after releasing the shear forces, the product very quickly returned to the consistency of the previous one State of rest, showing that the flow value is not noticeably adversely affected when the stresses lie within the limit values of the shear force given above, which at least approximately correspond to those that occur in an automatic dishwasher that is switched on. There were also no discernible ones Differences in the delivery of the product from a tube compared to the delivery from a dispenser a dishwasher.

Example 2

Example 1, in which the effect of a Dishwashing detergent with a combination of polyphosphate, carbonate and silicate in one total concentration

of about 37% was shown, was repeated with the difference that the total concentration of these salts was varied within the limits given above.

The best results have been obtained with a total concentration of these combined salts of at least 30% and in particular obtained with a NaTPP concentration of at least about 20%. Higher silicate concentrations that are desirable are to protect the porcelain glaze and the decor, also result in a higher alkalinity, which by a suitable Reduction of the sodium hydroxide concentration and / or regulation of the sodium carbonate concentration compensated can be. The results show that these mixtures are very sensitive to changes in the NaTPP concentration 5

(the higher concentration range is more effective) and the degree of hydrogenation. Changes in surfactant concentration generally also require a corresponding and direct change in the concentration of the foam pusher, in order to achieve the desired low foam development.

Lowering the pH of the mixture from Example 1 to below about 10.5 causes a considerable decrease the efficiency of this mixture and a corresponding reduction in flowability.

Example 3

Similar results are obtained when the process according to Example 1 is repeated with the difference that that certain components are replaced by corresponding other components, namely the alkyl sulfate surfactant, e.g. by sodium coconut alkyl sulfate, and attapulgite clay, e.g. with Attagel 50 or a mixture of Montmoril "ionite and Attagel 50 in a ratio of 2: 1. The addition is lower

Amounts, e.g., 0.002 to 0.05% by weight, of a chlorinated one Phthalocyanine and an aluminosilicate dye to the Mixture according to Example 1 (including the predispersion

the thickener or the subsequent addition to the 5th

chilled solution) results in mixtures of more pleasant green or blue color.

Example 4

The following ingredients were added with stirring in the order in which the ingredients are listed below are fed to a mixing vessel and mixed until the homogenization is complete.

Components parts by weight

:

deionized water 39,436

green color solution (2%) 0.173

Attapulgite clay 3.375

Titanium dioxide 0.375

NaTPP with 0.5% moisture

(half of the total) 11,558

x)
Foam press 0.16 0

13% sodium hypochlorite solution

(with about 13 wt% active chlorine) 9.230

Sodium carbonate 3,000

47.5% sodium silicate solution

(with Na ₂ OtSiO ₂ = 1: 2.4) 17.895

49% sodium hydroxide solution 2,600

NaTPP with 0.5% moisture 11,558

Surfactant ^XX) 0.800

2: 1 mixture of mono- and di- (C, _fi = -bis C, "" ~) alkyl esters

. of phosphoric acid.

45% aqueous solution of sodium monodecyl and sodium didecyl diphenyl oxide disulfonates.

Chemical and physical properties of the obtained Mixture:

Total moisture content 59.5%

active chlorine 1.2 +/- 0.1%

Silicates' 8.5%

pH 12.8 +/- 0.3

Density 1.35 min.

Viscosity (Brookfield RVF Viscometer, ο

Spindle No. 5, 20 rpm at 25 ^U C). 9250 +/- 3250 cps

sy / do 15

Claims (18)

Claims Water-based, thixotropic dishwashing detergent, especially for automatic dishwashers, characterized by a content of a) 8 to 35% by weight of alkali metal tripolyphosphate with an average degree of hydration of less than 1 or more than 5, b) 2.5 to 20% by weight sodium silicate, c) 0 to 9% by weight of water-soluble alkali metal carbonate, d) 0.1 to 5% by weight of an organic which is dispersible in water and resistant to chlorine bleach Surfactants, e) 0 to 5% by weight of a foam-inhibiting agent that is resistant to chlorine bleach, f) chlorine bleach in an amount which provides about 0.2 to 4% by weight of available chlorine, and g) a ^m thixotropic thickener in an amount sufficient that the composition has a thixotropic tropie index of about 2.5 to 10. 2. Dishwashing detergent according to claim 1, characterized in that the surfactant is an organic anionic amine oxide, Is phosphine oxide, sulfoxide and / or betaine. 3. Dish washing agent according to claim 1, characterized in that the surfactant is an organic anionic alkali metal sulfate or sulfonate. _v 4. Dishwashing agent according to claim 1, characterized in that the surfactant is an alkali metal (Cg to C ₁₄ alkyl) diphenyl oxide sulfonate. 5. Dishwashing agent according to claim 1, characterized in that the chlorine bleach is sodium hypochlorite is. 6. dishwashing agent according to claim 1, characterized in that the thickener is a smectite and / or attapulgite clay. 7. dishwashing agent according to claim 1, characterized in that that it contains 0 to 9% by weight of sodium carbonate. 8. dishwashing detergent according to claim 1, characterized in that it contains at least about 0.1% by weight of the foam contains retarding agent, wherein the foam retarding agent consists of alkyl phosphate esters and / or alkyl phosphonic acid esters with 1 or 2 C ₁₂ - to C _2Q- alkyl groups. COPY 9. dishwashing detergent according to claim 1, characterized in that the pH is 10.5 to about 13.5. 10. Water-based, thixotropic dishwashing detergent, especially for automatic dishwashers, marked by a content of a) 8 to 35% by weight of sodium tripolyphosphate with an average degree of hydration of less than 1 or more than 5 _; b) 2.5 to 20% by weight sodium silicate, c) 2 to 9% by weight sodium carbonate, d) 0.1 to 5% by weight of a water-dispersible surfactant resistant to chlorine bleach, e) 0 to 5% by weight of a chlorine bleach resistant antifoam agent, f) Sodium hypochlorite in a sufficient amount, to provide about 0.2 to 2% by weight of available chlorine, g) 1.5 to 10% by weight of a thixotropic smectite and / or attapulgite clay as a thickening agent, which is sufficient that the composition has a thixotropy index of about 2.5 to 10, and h) sodium hydroxide in an amount sufficient to give the composition a pH of about 10.5 to 13.5. 11. Dishwashing agent according to claim 10, characterized in that it is about 0.5 to 2% by weight of a surfactant; Mixture of sodium salts of the mono- and di- (C ₀ - bis) ο j C 1 -C alkyl) -diphenyloxidsulfonic acids contains. 12. Dishwashing agent according to claim 11, characterized in that it is used as a foam inhibiting agent for example Contains 0.1 to 0.5% by weight of a mixture of mono- and di- (C ,, - to C ,, - alkyl) phosphate esters. GOFT 13. Dishwashing detergent according to claim 12, characterized in that it contains about 20 to 30% by weight of sodium tripolyphosphate contains. 14. Dishwashing agent according to claim 13, characterized in that it is about 2 to as a thickener Contains 5% by weight of thixotropic montmorillonite clay. 15. Dishwashing detergent according to claim 13, characterized in that it is about 2 to as a thickener Contains 5% by weight of thixotropic attapulgite clay. 16. Dishwashing detergent according to claim 13, characterized in that the thixotropy index has a value of 6 to 8 has. 17. A method for producing a dishwashing detergent according to claims 1 to 16, characterized in that initially an aqueous dispersion of the foam-retarding By means of (component e) is prepared, the dispersion obtained with alkali metal tripolyphosphate (component a), sodium silicate (component b) and alkali metal carbonate (component c) is mixed in water, whereupon this mixture obtained with a surfactant (component d), a chlorine bleach (component f) and a previously prepared aqueous dispersion of a thixotropic thickener (component g) is mixed. 18. The method according to claim 17, characterized in that the mixture by adding the ingredients in Water in the order component (g), then the half the amount of component (a), then each of the components (e) and (f), then each of components (c) and (b), then the other half amount of component (a) and finally component (d) is produced.