DE3325503C2 - - Google Patents

Info

Publication number
DE3325503C2
DE3325503C2 DE19833325503 DE3325503A DE3325503C2 DE 3325503 C2 DE3325503 C2 DE 3325503C2 DE 19833325503 DE19833325503 DE 19833325503 DE 3325503 A DE3325503 A DE 3325503A DE 3325503 C2 DE3325503 C2 DE 3325503C2
Authority
DE
Germany
Prior art keywords
weight
dishwashing detergent
thixotropic
component
characterized
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.)
Expired - Fee Related
Application number
DE19833325503
Other languages
German (de)
Other versions
DE3325503A1 (en
Inventor
Michael Heusy Be Julemont
Maurice Angleur Be Marchal
Original Assignee
Colgate-Palmolive Co., New York, N.Y., Us
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US49761583A priority Critical
Application filed by Colgate-Palmolive Co., New York, N.Y., Us filed Critical Colgate-Palmolive Co., New York, N.Y., Us
Publication of DE3325503A1 publication Critical patent/DE3325503A1/en
Application granted granted Critical
Publication of DE3325503C2 publication Critical patent/DE3325503C2/de
Anticipated expiration legal-status Critical
Application status is Expired - Fee Related legal-status Critical

Links

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
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions; Pastes
    • 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
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid 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
    • C11D3/395Bleaching agents
    • C11D3/3958Bleaching agents combined with phosphates

Description

The invention relates to a hydrous, thixotropic dishwashing detergent, in particular for aromatic dishwashers.

Commercial detergents for household dishwashers in Powder form have the disadvantage that they are stored under moisture bake, and dust in dry form. liquid Dishwashing detergents, on the other hand, can be used in automated dishwashers because of the strong foaming that is extreme low viscosity and the excessively high alkalinity of this Use funds badly.

The previously known gel or thixotropic dishwashing detergents However, they were not suitable because of they are not sufficiently viscous to be in the dispensing container of the Dishwasher "anchored" to stay and beyond on dishes, Glassware or porcelain leave stained residues.

Ideally, thioxtrope detergents should be at rest be highly viscous or present in the plastic Bingham state and have relatively high flow values. Under shear load However, these products should quickly become liquid, for example when shaking in the container or during pressing through a nozzle, and in the absence of the applied shear force They should be fast in the high viscous or plastic state return to Bingham. Furthermore, these products must be considered in terms of Phase separation or exudation of constituents prolonged standing have sufficient stability.  

Such hitherto z. B. from DE-OS 31 38 425 known detergent for automatic dishwashers with the above mentioned Features result in standard household dishwashers to difficulties. These detergents generally contain Sodium tripolyphosphate (NaTPP) for softening the water, for binding the water hardness resulting salts and for emulsifying and / or for the peptization of dirt and also sodium silicate to achieve the desired alkalinity and protection for the glaze and decor of porcelain as well as in general only optional sodium carbonate to increase the alkalinity, further a chlorine releasing agent for better removal of Dirt stains or water stains and optionally a nonionic Surfactant.

Other washing agents of this type may eventually have a foam suppressant / surfactant included to reduce the foaming and thus the effectiveness of the machine cleaning process too support and ultimately the required cleaning effect to surrender, as stated in "SDA Detergents in Depth, Formulations Aspects of Machine Dishwashing "by Thomas Oberle (1974) is. Such as liquid or powder to gel products reformulated combinations are inappropriate,  which has led to considerable difficulties. In general in these agents, the hypochlorite bleach is omitted, as it is with other chemically active ingredients and in particular reacting with the surfactant and thereby the Suspending agent or the thixotropic agent decomposes and its effectiveness is impaired.

So be in US PS 41 15 308 thixotropic pastes for automatic dishwashers described that a suspending agent included, for. As carboxymethylcellulose, synthetic clays u. Like. And also inorganic salts such as silicates, phosphates, Polyphosphates, etc. as well as small amounts of a surfactant and have a foam suppressor. A bleach will but not described. From US-PS 41 47 650 is a similar product is known, optionally hypochlorite contains as bleaching agent, but no organic surfactant and no foam suppressant. The product is used as a detergent slurry described that no noticeable thixotropic Features.

From US-PS 39 85 668 abrasives are gelatinous Consistency known to be a suspending agent, preferably smectite and attapulgite type, scouring agents, such as quartz sand or perlite, as well as fillers, such as powdered Low density polymers or expanded perlite, these fillers show a certain buoyancy and thus stabilize the mixture and additionally as Dietary fibers act while replacing water, otherwise an undesirable supernatant stratification due exudation or phase impairment would. In addition to these basic components such Abrasives still optional hypochlorite bleach, bleach-stable surfactants and buffer substances, eg. B. silicates, Carbonates, monophosphates, etc., included. Furthermore, can Also builders, such as NaTPP, may be present to aid the builder  to support the buffer substances. The amount such builders should 5 wt .-%, based on the Total composition, do not exceed. The maintenance of the desired pH above 10 by the buffer / builder components, the high pH is a decomposition of the chlorine bleach and a undesirable interaction between surfactant and bleach should be kept to a minimum. That if necessary existing NaTPP is limited to 5 wt .-%; foam suppressors are not included in these products.

The invention is based on the object, a dishwashing detergent to create for automatic dishwashers which has thixotropic properties and improved has chemical and physical stability and the easily and quickly disperse in the washing liquid lets, thus cleaning the porcelain, glass and dishes can be effectively done without any of the above Disadvantages occurs.

Further, it is an object of the present invention Dishwashing detergent with good physical stability to create, even after prolonged storage no shows significant phase separation. Furthermore, the new Dishwashing detergent should be constructed so that no or at least only significantly weakened unwanted interactions between the chemically active ingredients occur.

Another object of the invention is to provide a Dishwashing detergent for automatic dishwashers, the above-mentioned stability even at strong alkaline setting of the detergent used for the effective cleaning power is required has. Farther the dishwashing detergent should be better rheological Exhibit properties and at low shear rates  higher viscosities and at high shear rates have lower viscosities, so that it is advantageous used in the dispenser of the dishwasher can be. Finally, a dishwashing detergent be created with a low foam development, improved cleaning power and faster dispersibility in a dishwasher.

This object is achieved by a hydrous, thixotropic dishwashing detergent, in particular for automatic dishwashers, the is formulated according to the main claim.

The dishwashing detergent according to the invention for automatic Dishwashers have low foaming, are both chemically and physically stable, solve are quick in the wash and are special effective at pH levels, which improves cleaning efficiency at pH's in the range of 10.5 to 13.5. The mixtures of the invention are normally  a gel-like consistency, d. h., they are very viscous, opaque, gelatinous products with a Bingham elasticity and thus have relatively high flow values. Accordingly is a certain shearing force required, to cause or amplify the leakage, as well as you put them in a dispenser of a powered or has switched on automatic dishwasher. Under these conditions, the mixture according to the invention quickly brought into a fluid state and released easily. When the shear force is released, the fluid mixture returns quickly in their highly viscous state or in the plastic Bingham state back and almost takes their former Consistency again.

In general, the effectiveness of the invention Dishwashing detergent directly dependent on the available standing, chlorine content, alkalinity, solubility in the washing medium and the foam inhibition. The pH of the Dishwashing detergent according to the invention is preferably at least about 9.5, more preferably in the range from about 10.5 to 13.5, and most preferably at at least about 11.5. At relatively low pH is the dishwashing detergent according to the invention too viscous, d. H. almost solid, and settles under those in the dispenser prevailing shear forces no longer easily bring into a fluid state; such a means then loses most or even all of its thixotropic Eigenschaten one. The addition of NaOH is therefore often required to bring the pH to a value within increase the above range and the flow properties to improve. Also the presence of carbonate is often necessary, as it is the buffer substance Maintaining the desired pH range guaranteed. A difference in carbonate sol can be avoided since  otherwise form needle-like carbonate crystals that increase the stability, Thixotropy and / or cleaning power of the invention Dishwashing detergents impair. caustic Soda (NaOH) also serves to remove the existing foam suppressant, namely the phosphoric acid ester or phosphonic acid ester, to neutralize. The dishwashing detergent according to the invention contains usually about 0.5 to 3 wt .-% NaOH and about 2 to 9% by weight of sodium carbonate; it should, however, be noticed be that sufficient alkalinity also by the existing NaTPP and sodium silicate are ensured can.

The in the dishwashing detergent according to the invention in a Amount in the range of about 8 to 35 wt .-%, preferably from about 20 to 30% by weight, present NaTPP should preferably be free of heavy metals as these become one Decomposition or inactivation of the preferably used Sodium hypochlorite and other chlorine bleach contribute. To improve and accelerate hydration and solubilization of NaTPP and avoidance of unwanted thickening of the dishwashing detergent can NaTPP has an average degree of hydration of less than about 1 or more than 5, which is a water content from 0 to 2.7% by weight or at least 16.5% by weight corresponds, including the stable hexahydrate (hydration degree of 6) corresponding to a water content of about 18% by weight or more. Actually, a humidification is on On average about 0.3 to 1 wt .-% water very effective and serves. To form germs of the stable hexahydrate, the hydration and solubilization of the remaining ones Promote NaTPP particles.  

The foam damping is important to the effectiveness of the Dishwasher to increase and destabilizing Effects due to excessive foaming may occur during use, to a minimum. The foam can be selected by appropriate choice the type as well as the amount of surfactants that are the main foam-producing component, sufficient be reduced. The extent of foam development also depends on the hardness of the washing water in the washing machine with a suitable Einregelurierung the shares NaTPP, which has a water softening effect, can contribute to the desired level of foam damping to reach. In general, however, it is preferred to use against chlorine bleach resistant foam breaker or insert damper. Particularly effective here are the Alkylphosphonic esters of the formula

the z. Available from BASF-Wyandotte (PCUK-PAE), and in particular the alkylphosphonic esters of the formula

the z. Available from Hooker (SAP) and Knapsack (LPKn-158) are one or both R groups in both ester types independently of one another alkyl groups with 12 to 20 Represent C atoms. It can also be mixtures of the two Ester types or other chlorine bleach resistant Species or mixtures of mono- and diesters of said Species are used. Particularly preferred is a Mixture of mono and di (C₁₆ to C₁₈ alkyl) phosphoric esters, for example, the monostearyl and distearyl phosphoric esters in the ratio 1.2: 1 (product of Knapsack). In general, the foam suppressant is in an amount of 0.1 to 5 wt .-%, preferably from 0.1 to 0.5 wt .-%, in the Dishwashing detergent used according to the invention, wherein the Weight ratio of surfactant (component d) to foam depressant (Component e) generally in the range of about 10: 1 to 1: 1, preferably in the range of 4: 1 to 1: 1, lies. Other foam depressors include, for. B. the known Silicones.

According to the invention are alkali metal hypochlorites, such as. Potassium, Lithium, magnesium and especially sodium hypochlorite used. The dishwashing detergents according to the invention are intended contain an amount of chlorine bleach that sufficient to provide about 0.2 to 4% by weight of active chlorine, such as by acidification of 100 parts of the dishwashing detergent determined with excess hydrochloric acid can be. A solution containing about 0.2 to 4% by weight of sodium hypochlorite contains, delivers or also contains about the same percentage of active chlorine. Especially preferred is a content of 0.8 to 1.6 wt .-% of active chlorine.  

The sodium silicate, which contributes to the alkalinity and protection of hard surfaces such as porcelain stains and Decor, contributes, is in the range of from about 2.5 to 20% by weight, preferably from about 5 to 15% by weight, used in the dishwashing detergent according to the invention. The sodium silicate is generally in the form an aqueous solution added and preferably has a Na₂O: SiO₂ ratio of about 1: 2.2 to 1: 2.8. Also most other ingredients of the invention Dishwashing detergents, in particular sodium hydroxide, sodium hypochlorite, Foam depressants and thixotropic thickener, are often in the form of previously prepared aqueous Dispersions or solutions used.

The used in the dishwashing detergents according to the invention surfactants be in amounts of about 0.1 to 5 wt .-%, and preferably from about 0.3 to 0.8 wt .-% used and are linear or branched alkali metal mono- and / or di-C₈-C₁₄-alkyldiphenyl dioxide monosulfonates and / or disulfonates, for example the commercially available DOWFAX 3B-2 products and DOWFAX 2A-1-WZ. In general, paraffin sulfonates tend to adversely affect the thixotropic properties or even destroy it, and it has been found that they cause an excessive viscosity increase, causing serious difficulties in terms of required high shear forces occur. The surfactants should further with other components of the invention Mixture be compatible.  

Thixotropic thickener, d. H. Thickener or suspending agent which thixotropes an aqueous medium Lend properties are already known and can organic or inorganic water-soluble, water-dispersible or colloid forming monomeric or polymeric products  which, of course, in the dishwashing detergents according to the invention are stable, d. H. resistant to higher Alkalinity and chlorine bleaches, such as. For example, sodium hypochlorite. The most preferred thickeners or Suspending agents are generally inorganic colloid-forming Clays of smectite and / or attapulgite type. These Substances are generally used in amounts of about 2 used to 5 wt .-%, wherein the amount in each case sufficient to give the product the desired Bingham plasticity to rent.

Smectite clays include u. a. Montmorillonite (bentonite), hectorite, Saponite u. Like. These products are among the Trade names "Thixogel No. 1" and "Gelwhite GP" from the Georgia Kaolin Company and are Montmorillonite. As Attapulgitton the under the trade name "Attagel", such as "Attagel 40", "Attagel 50" and "Attagel 150", from Engelhard Minerals and Chemicals Corporation are used. Also mixtures of smectite and attapulgite in weight ratios of 4: 1 to 1: 5 are suitable for this. Thickener or suspending agent of the aforementioned kind are well known and Z. As described in US-PS 39 85 668. Friction agent or Polishes should be avoided.

The containing in the dishwashing detergents according to the invention Amount of water should of course not be so high that the Product an excessively low viscosity and flowability but not so low that one excessively high viscosity and low flowability is caused, in each case the thixotropic Properties adversely affected or even destroyed become. The appropriate amount of water can be easily obtained by routine experimentation in each adjacent case, they are determined  is generally in the range of 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 Behavior, especially in terms of viscosity as a function of shear forces. The investigations confirm that the mixtures according to the invention have a higher Viscosity at low shear rate and a lower viscosity at a high shear rate and the results indicate that an effective Transfer to the fluid state and a more effective Gelation in the shear forces in dishwashers occur. That means in the Practice improved casting and processing properties of obtained products that are not undesirable the dispenser can escape, as in the usual liquid dishwashing detergents is the case.

At shear forces occurring at 3 to 30 rpm, Brookfield viscosities are obtained in a range of 15,000 to 30,000 cps to about 3,000 to 5,000 cps as measured at room temperature with an LVT Brookfield viscometer after 3 minutes a spindle speed of 7.4 sec -1 corresponds to about 3 spindle revolutions per minute. An approximately 10-fold increase in the shear rate gives about a 6- to 7-fold reduction in viscosity. In the known gelatinous dishwashing detergents, the corresponding viscosity reduction is only about 2 times. Moreover, at about 3 revolutions per minute, these known blends have an initial viscosity of only about 2500 to 2700 cP. The blends of the invention exhibit a threshold of fluidization at lower shear rates and to a significantly greater extent the proportionate increase in shear rate over the proportionate reduction in viscosity. This property of the products according to the invention is expressed by the thixotropic index (TI), which corresponds to the ratio of the actual viscosity at 3 revolutions per minute to the actual viscosity at 30 revolutions per minute. The mixtures according to the invention have a T I value of about 2.5 to 10 and preferably of 6 to 8. All the dishwashing detergents according to the invention which were tested showed a complete and rapid return to their previous resting state with corresponding consistency, when no shear forces were exerted were.

According to a preferred method for producing the Dishwashing detergents according to the invention are all first inorganic salts, d. H. Carbonate (if present), Silicate and tripolyphosphate, dissolved in the aqueous medium or dispersed. The thickener will last added. The foam breaker (if any) will advance prepared as an aqueous dispersion, as well as the thickener. The dispersion of the foam suppressant, the caustic Soda (if present) and the inorganic salts first at elevated temperatures in an aqueous medium (deionized Water) mixed and then under constant Stirring cooled. Bleach, surfactant and thickener dispersion from room temperature are subsequently added to the cooled (25 to 35 ° C) solution. If excluding the chlorine bleach, the total salt concentration is (NaTPP, sodium silicate and carbonate) in the mixture according to the invention generally about 20 to 50% by weight, preferably about 30 to 40% by weight.  

Other conventional ingredients may be included in the invention Dishwashing detergent in small quantities, in general less than about 3% by weight, for example Perfume, hydrotropic agents, e.g. For example, sodium benzenesulfonate, Sodium toluenesulfonate, sodium xylene sulfonate and sodium cumene sulphonate, and preservatives, Colorants and pigments u. Like., Of course, all be resistant to chlorine bleach and high alkalinity have to. For dyeing, the chlorinated ones are particularly preferred Phthalocyanines and polysulfides of aluminosilicates used, the pleasing green or blue shades result. Titanium dioxide can be used to lighten or neutralize Fehlfarben be used.

The liquid dishwashing detergents according to the invention can in a known manner for washing dishes or other Kitchen appliances u. Like. In automatic dishwashers, with a suitable detergent dispenser are lightly bathed in an aqueous bath be used in effective amounts.

The invention will be further understood from the following examples explained. All quantities are by weight unless otherwise expressly understood is specified.

Example 1

It was first a predispersion I with a foam depressor prepared a 2: 1 mixture of mono- and Di (C₁₆ to C₁₈) alkyl esters of phosphonic acid (LPKn 158 from Knapsack) in an amount of 0.16 g in 6 g of water with the dispersion passing through 30 minutes Mixing with a disc stirrer at 60 ° C was obtained.  

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

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

This mixture was heated to 25 to 24 hours with constant stirring Cooled to 30 ° C and then at room temperature the following Added ingredients:

The surfactant was a 45% aqueous solution of sodium monodecyl-diphenyloxide disulfonate and sodium dodecyl diphenyloxide disulfonate used.

An opaque gel-like mixture containing about 40% active ingredient was obtained which had a T I value of about 7 and an actual viscosity of 28,000 cP at 3 revolutions per minute and 4,000 cP at 30 revolutions per minute. When tested in an automatic dish-washing machine with dispenser, the mixture according to the invention showed an excellent cleaning performance, whereby it was released easily and quickly. The dishwashing detergent according to the invention was satisfactorily non-foaming. After prolonged storage of the product in a closed container, virtually no or only insignificant phase separation was observed. The pH of the detergent was 11.6 in a 1% aqueous solution. The behavior under shear conditions was excellent; After the shear forces were removed, the product very quickly returned to the consistency of the previous resting state, indicating that the yield value would not be appreciably adversely affected if the stresses were within the shear limits set forth above, which correspond at least approximately to those in a switched on automatic dishwasher occur. There were also no discernible differences in the delivery of the product from a tube as compared to the delivery from a dispenser of a dishwasher.

Example 1

Example 1, in which the effect of a Dishwashing detergent with a combination of polyphosphate, Carbonate and silicate in a total concentration  was shown by about 37% was repeated with the Difference that the total concentration of these salts was varied within the limits specified above.

The best results were with a total concentration of these combined salts of at least 30% and in particular with a NaTPP concentration of at least about 20% received. Higher silicate concentrations that are desired are to protect the porcelain glaze and decor, also give a higher alkalinity by a suitable Reduction of sodium hydroxide concentration and / or Regulation of sodium carbonate concentration compensated can be. The results show that these mixtures very sensitive to changes in NaTPP concentration (the higher concentration range is more effective) and the Hydrogenation grade react. Changes in the surfactant concentration generally require a corresponding and direct change in the concentration of the foam depressant, to the desired low foam development to reach.

A lowering of the pH of the mixture of Example 1 to less than about 10.5 causes a significant decrease the efficiency of this mixture and a corresponding Lowering the flowability.  

example 3

The following ingredients were added with stirring in the Order in which the ingredients are listed below are fed to a mixing vessel and to the finished Homogenization mixed.

Chemical and physical. Properties of the mixture obtained: 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, Spindle No. 5, 20 rpm at 25 ° C). 9250 ± 3250 cP

Claims (12)

1. Water-containing, thixotropic dishwashing detergent, in particular for automatic dishwashers, having a pH of about 10.5 to 13.5 containing
  • a) from 8 to 35% by weight of alkali metal tripolyphosphate having an average degree of hydration of less than 1 or more than 5,
  • b) 2.5 to 20% by weight of sodium silicate,
  • c) 0 to 9% by weight of water-soluble sodium carbonate,
  • d) 0.1 to 5 wt .-% of water-dispersible, chlorine bleach resistant organic surfactant of the group of linear and branched alkali metal mono- and / or di-C₈- to C₁₄-alkyldiphenyloxid monosulfonates and / or disulfonates,
  • e) from 0.1 to 5% by weight of chlorine bleach-resistant antifoaming agent of the group consisting of alkylphosphonic acid esters and acidic alkylphosphoric acid esters,
  • f) Sodium hypochlorite in an amount that provides about 0.2 to 4% by weight of available chlorine,
  • g) a thixotropic thickener in an amount sufficient that the composition has a thixotropic index of about 2.5 to 10, and
  • h) water in an amount which does not affect the desired thixotropic properties.
2. Dishwashing detergent according to claim 1, characterized in that that the surfactant is a mixture of alkali metal mono- and di- (C₈- to C₁₄-alkyl) -diphenyloxidmono- and disulfonates.
3. Dishwashing detergent according to claim 2, characterized in that that it contains as surfactant 0.5 to 2 wt .-% of a mixture of Sodium salts of mono- and di- (C₈- to C₁₄-alkyl) -diphenyloxidsulfonsäuren contains.
4. Dishwashing detergent according to one or more of the preceding Claims, characterized in that the thickening agent is a smectite and / or attapulgite clay.
5. Dishwashing detergent according to one or more of the preceding Claims, characterized in that the foam-braking Average alkyl phosphate ester and / or alkylphosphonic acid ester comprising 1 to 2 C₁₂ to C₂₀ alkyl groups.
6. Dishwashing detergent according to one or more of the preceding claims, comprising
  • a) from 20 to 30% by weight of sodium tripolyphosphate having an average degree of hydration of less than 1 or more than 5,
  • b) 2.5 to 20% by weight of sodium silicate,
  • c) 2 to 9% by weight of sodium carbonate,
  • d) 0.3 to 0.8% by weight of surfactant,
  • e) from 0.1 to 0.5% by weight of foam inhibitor,
  • f) Sodium hypochlorite in an amount sufficient to provide about 0.8 to 1.6% by weight of available chlorine,
  • g) from 1.5% to 10% by weight of a thixotropic smectite and / or attapulgite clay as thickening agent, sufficient to provide the composition with a thixotropic index of about 2.5 to 10, and
  • h) water in an amount which does not affect the desired thixotropic properties.
7. Dishwashing detergent according to one or more of the preceding Claims, characterized in that it as Thickener 2 to 5 wt .-% thixotropic montmorillonite clay contains.
8. Dishwashing detergent according to one or more of the preceding Claims, characterized in that it as Thickener 2 to 5% by weight of thixotropic attapulgite clay contains.
9. Dishwashing detergent according to one or more of the preceding Claims, characterized in that the thixotropic index has a value of 6 to 8.
10. Dishwashing detergent according to the preceding claims, characterized by a content of 55 to 65 wt .-% water.
11. A process for producing a dishwashing detergent according to to claims 1 to 10, characterized in that first an aqueous dispersion of the foam-braking Prepared by means of (component e), the obtained Dispersion with alkali metal tripolyphosphate (component a), Sodium silicate (component b) and alkali metal carbonate (Component c) is mixed in water, whereupon these obtained mixture with a surfactant (component d), a Chlorine bleach (component f) and a previously prepared aqueous dispersion of a thixotropic thickener (Component g) is mixed.  
12. A process for the preparation of an agent according to claim 1 to 10, characterized in that the Mixture by adding the ingredients in water in the Order component (g), then half the amount of Component (a), then each of components (e) and (f), then each of components (c) and (b), then the other half amount of component (a) and finally the component (d) is produced.
DE19833325503 1983-05-24 1983-07-15 Expired - Fee Related DE3325503C2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US49761583A true 1983-05-24 1983-05-24

Publications (2)

Publication Number Publication Date
DE3325503A1 DE3325503A1 (en) 1984-11-29
DE3325503C2 true DE3325503C2 (en) 1992-06-11

Family

ID=23977588

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19833325503 Expired - Fee Related DE3325503C2 (en) 1983-05-24 1983-07-15

Country Status (13)

Country Link
JP (1) JPS59226099A (en)
AU (1) AU565792B2 (en)
CA (1) CA1222426A (en)
CH (1) CH655325A5 (en)
DE (1) DE3325503C2 (en)
DK (1) DK159555C (en)
FR (1) FR2546527B1 (en)
GB (1) GB2140450B (en)
HK (1) HK84790A (en)
NZ (1) NZ204916A (en)
SE (1) SE459660B (en)
SG (1) SG45990G (en)
ZA (1) ZA8305186B (en)

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555360A (en) * 1984-06-22 1985-11-26 The Procter & Gamble Company Mild detergent compositions
NZ212920A (en) * 1984-08-13 1989-04-26 Colgate Palmolive Co Thixotropic automatic dishwasher detergent compositions containing polymeric carboxylic acid
NZ212921A (en) * 1984-08-13 1988-06-30 Colgate Palmolive Co Process for the manufacture of thixotropic detergent compositions
DE3440848C2 (en) * 1984-11-08 1988-07-14 Hans 8900 Augsburg De Biermaier
NZ216342A (en) * 1985-06-14 1989-08-29 Colgate Palmolive Co Aqueous thixotropic dishwasher compositions containing fatty acid metal salts as stabiliser
US5413727A (en) * 1985-06-14 1995-05-09 Colgate Palmolive Co. Thixotropic aqueous compositions containing long chain saturated fatty acid stabilizers
US5427707A (en) * 1985-06-14 1995-06-27 Colgate Palmolive Co. Thixotropic aqueous compositions containing adipic or azelaic acid stabilizer
US5057237A (en) * 1985-06-14 1991-10-15 Colgate Palmolive Co. Thixotropic liquid automatic dishwasher detergent composition with improved physical stability
US4752409A (en) * 1985-06-14 1988-06-21 Colgate-Palmolive Company Thixotropic clay aqueous suspensions
GR862954B (en) * 1986-01-07 1987-05-08 Colgate Palmolive Co Thixotropic aqueous suspensions
US4801395A (en) * 1986-08-07 1989-01-31 Colgate-Palmolive Company Thixotropic clay aqueous suspensions containing long chain saturated fatty acid stabilizers
EP0264975A1 (en) * 1986-08-18 1988-04-27 THE PROCTER & GAMBLE COMPANY Thickened aqueous dishwashing compositions
US4857226A (en) * 1986-10-29 1989-08-15 Colgate-Palmolive Company Thixotropic clay aqueous suspensions containing polyacrylic acid polymer or copolymer stabilizers
GB8719776D0 (en) * 1987-08-21 1987-09-30 Unilever Plc Machine dishwashing compositions
ZA8805894B (en) * 1987-08-21 1990-04-25 Colgate Palmolive Co Thixotropic clay aqueous suspensions containing polycarboxylic acids and metal salts thereof stabilizers
US4836946A (en) * 1987-08-21 1989-06-06 Colgate-Palmolive Company Thixotropic clay aqueous suspensions containing alkali metal fatty acid salt stabilizers
NZ226174A (en) * 1987-09-23 1991-03-26 Colgate Palmolive Co Aqueous cleaning composition; no- or low-phosphorus built mixture
NZ226289A (en) * 1987-09-29 1990-09-26 Colgate Palmolive Co Gel-like aqueous dishwashing composition with sodium silicate and silica anti-filming agent
GB8726308D0 (en) * 1987-11-10 1987-12-16 Unilever Plc Machine dishwashing composition
ZA8808457B (en) * 1987-11-12 1990-07-25 Unilever Plc Physical stability of liquid automatic dishwashing detergent
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US5141664A (en) * 1987-12-30 1992-08-25 Lever Brothers Company, A Division Of Conopco, Inc. Clear detergent gel compositions having opaque particles dispersed therein
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
DE3800483A1 (en) * 1988-01-11 1989-07-20 Henkel Kgaa Stable chlorine defoamer for active chlorine-containing detergent, more particularly dishwashing detergents
US4867896A (en) * 1988-02-17 1989-09-19 Lever Brothers Company Cleaning compositions containing cross-linked polymeric thickeners and hypochlorite bleach
GB2219596A (en) * 1988-06-09 1989-12-13 Procter & Gamble Liquid automatic dishwashing compositions having enhanced stability
US4859358A (en) * 1988-06-09 1989-08-22 The Procter & Gamble Company Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
US4988452A (en) * 1988-06-09 1991-01-29 The Procter & Gamble Company Liquid automatic dishwashing detergent compositions containing bleach-stable nonionic surfactant
US4950416A (en) * 1988-10-19 1990-08-21 Vista Chemical Company Liquid dishwasher detergent composition
US4971717A (en) * 1989-04-28 1990-11-20 Colgate-Palmolive Co. Aqueous liquid automatic dishwashing detergent composition with improved anti-filming and anti-spotting properties
US5064553A (en) * 1989-05-18 1991-11-12 Colgate-Palmolive Co. Linear-viscoelastic aqueous liquid automatic dishwasher detergent composition
EP0407187A3 (en) * 1989-07-07 1991-07-17 Unilever Plc Aqueous thixotropic cleaning composition
US5169552A (en) * 1989-10-04 1992-12-08 The Procter & Gamble Company Stable thickened liquid cleaning composition containing bleach
US5185096A (en) * 1991-03-20 1993-02-09 Colgate-Palmolive Co. Aqueous liquid automatic dishwashing detergent composition comprising hypochlorite bleach and bleach stabilizer
DE19730648A1 (en) * 1997-07-17 1999-01-21 Henkel Kgaa Use of electrolyte mixtures as sequestering agents

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1571501A (en) * 1976-01-23 1980-07-16 Unilever Ltd Detergent compositions
DE2750528A1 (en) * 1976-11-15 1978-05-24 Procter & Gamble A method for keeping a toilet bowl clean
US4116849A (en) * 1977-03-14 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
US4116851A (en) * 1977-06-20 1978-09-26 The Procter & Gamble Company Thickened bleach compositions for treating hard-to-remove soils
DE3138425A1 (en) * 1981-09-26 1983-04-14 Henkel Kgaa "Using a paste cleanser in Dish"
NZ203036A (en) * 1982-01-18 1986-04-11 Colgate Palmolive Co Aqueous automatic dishwasher composition with thixotropic properties

Also Published As

Publication number Publication date
CA1222426A1 (en)
GB8319158D0 (en) 1983-08-17
CA1222426A (en) 1987-06-02
AU565792B2 (en) 1987-10-01
CH655325A5 (en) 1986-04-15
AU1679383A (en) 1984-11-29
NZ204916A (en) 1985-11-08
DK159555C (en) 1991-04-02
FR2546527A1 (en) 1984-11-30
DK328083D0 (en) 1983-07-15
DK159555B (en) 1990-10-29
FR2546527B1 (en) 1987-09-04
DE3325503A1 (en) 1984-11-29
DK328083A (en) 1984-11-25
GB2140450B (en) 1987-07-01
JPS59226099A (en) 1984-12-19
ZA8305186B (en) 1985-02-27
GB2140450A (en) 1984-11-28
SG45990G (en) 1990-08-17
SE459660B (en) 1989-07-24
SE8303996D0 (en) 1983-07-15
SE8303996L (en) 1984-11-25
HK84790A (en) 1990-10-25

Similar Documents

Publication Publication Date Title
JP5426519B2 (en) Composition for washing dishes
US3741911A (en) Phosphate-free detergent composition
US4071463A (en) Stable cleaning agents of hypochlorite bleach and detergent
US4240919A (en) Thixotropic abrasive liquid scouring composition
US4610799A (en) Washing additive in paste form containing an activator for per compounds, and package therefor
AU697043B2 (en) Peroxygen bleach composition
CA1092476A (en) Detergent composition and its use in a dishwashing machine
US4859358A (en) Liquid automatic dishwashing compositions containing metal salts of hydroxy fatty acids providing silver protection
CA1120370A (en) Liquid bleaching compositions
DK168300B1 (en) A process for the preparation of solid detergent compositions and solid detergent compositions
US4933101A (en) Liquid automatic dishwashing compositions compounds providing glassware protection
US3936386A (en) Dishwashing compositions containing chlorinated isocyanurate
AU718606B2 (en) Stable bleach-containing cleansing compositions with soft abrasives
EP0720646B1 (en) Making thickened aqueous abrasive cleanser with improved rinsability
EP0120659B1 (en) Detergent compositions
US3390092A (en) Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US4469605A (en) Fabric softening heavy duty liquid detergent and process for manufacture thereof
FI91275B (en) The aqueous thixotropic automatic dishwashing liquid detergent mixture
US6017864A (en) Alkaline solid block composition
KR920000112B1 (en) Liquid detergent compositions
US5229026A (en) Linear viscoelastic aqueosous liquid automatic dishwasher detergent composition
US5731276A (en) Thickened aqueous cleaning composition and methods of preparation thereof and cleaning therewith
US4906396A (en) Protected enzyme systems
DE3300243C2 (en) dishwashing detergent
CA1151808A (en) Liquid, thickened chlorine bleaching composition

Legal Events

Date Code Title Description
8110 Request for examination paragraph 44
D2 Grant after examination
8328 Change in the person/name/address of the agent

Free format text: STOLBERG-WERNIGERODE, GRAF ZU, U., DIPL.-CHEM. DR.RER.NAT. SUCHANTKE, J., DIPL.-ING. HUBER, A., DIPL.-ING. KAMEKE, VON, A., DIPL.-CHEM. DR.RER.NAT., PAT.-ANWAELTE, 2000 HAMBURG

8364 No opposition during term of opposition
8339 Ceased/non-payment of the annual fee