JPS59226099A - Thixotropic composition containing chlorine bleaching agent for automatic dish washer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to automatic dishwashing detergent compositions with xyxotropic properties, improved chemical and physical stability, and which compositions are easily dispersed in cleaning media. Is it possible to effectively clean dishes, glass containers, ceramics, etc.? This is what we provide.

Commercially available household dishwashing detergents that come in powder form have several drawbacks. 1) Non-uniformity of composition, high cost of operations required for manufacturing, formation of lumps that are difficult to disperse, caking tendency during storage under humid conditions, and 7) dustiness, which is a special source of irritation for users suffering from allergies. 5 is prone to caking in dishwasher dispensing equipment; moreover, the liquid form of this building composition is generally susceptible to high foam levels 5 due to unacceptably low viscosity, and excessively high alkalinity. cannot be used in an automatic dishwasher.

Recent research and development efforts have focused on compositions of this type in the form of gels or "xixotropics," such as scouring cleansers and dishwashing products, which are formulated as xyxotropic pastes. Ta. Products for dishwashers are thus provided.

It is inherently unsatisfactory in that it has insufficient viscosity and remains in the dispensing equipment in the dishwasher, and also produces spot-like residues on dishes, glass containers, china, etc. It is. Ideally, the thixotropic cleansing composition should be highly viscous at rest, Bingham plastic in nature, and have a relatively high yield value. However, when subjected to shear stress such as shaking in a container and squeezing out of a pore, these compositions rapidly fluidize and enter a high viscosity/Bingham plastic state when the shear stress (o') application is discontinued. ), stability is also of primary importance, ie.

There should be no significant signs of phase separation or leaking after prolonged standing.

The provision of gel-like automatic dishwashing compositions having the aforementioned properties has heretofore been problematic, particularly for compositions for use in domestic dishwashing machines. To effectively use an automatic dishwashing detergent, this is henceforth dADD
They are also called (l) hard water minerals? Sodium tripolyphosphate (NaTPP) which softens and binds and emulsifies and/or sours dirt; (2) Alkalinity required for effective cleaning? Sodium silicate, which supplies and protects ceramic glazes and patterns; (3) Sodium carbonate, which enhances alkalinity, although generally considered an optional ingredient: (41
Chlorine release agent to help remove dirt spots that lead to water spotting: and (5) Foam? It is generally recommended to include suds suppressants/surfactants, which reduce and thereby increase machine efficiency and provide the required washability, e.g., SDA.
Detergpnts in Deptb, [Preparation status of machine dishwashing] (Thomas Opal) (197
4) A cleanser similar to the composition described in #iJ, which I want to see
Usually in liquid or powder form. It has proven difficult to combine such ingredients into a gel form that is useful for domestic mechanical delivery. Generally, such compositions omit hypochlorite cooling agents. it is,
The whitening agent reacts with other chemically active ingredients, especially surfactants.

This is because it tends to degrade the suspending agent or xyxotropic agent and impair its effectiveness. Such traps, U.S. Pat. No. 4,115,508, include anti-settling agents such as eMe, synthetic clay, etc.; inorganic salts including silicates, phosphates, polyphosphates, etc.; small amounts of surfactants and soap suds suppressors; Discloses a thixotropic base for automatic dishwashing comprising; No. 4,147,650, which does not disclose a whitening agent, is somewhat similar and includes a Gt-daughter whitening agent as an optional ingredient, but no organic surfactant or suds suppressant. Moreover, the product is described as a detergent slurry with no apparent thixotropic properties.

US%W! No. f 3.985.668 contains 11) anti-settling agents, preferably clays of the smectite and attapulgite types; (2) abrasive agents, such as silica sand or perlite; Has a stabilizing effect on the composition.

Thereby displacing water that would otherwise be utilized in the overlying layer, which is undesirable due to leakage and phase de-stabilization. Describes an abrasive cleaning cleanser with a gel-like consistency containing: low-density powdered polymers, expanded perlite, etc. Optional ingredients include a hypobitite bleach, a bleach-stable surfactant, and a buffer.

For example, silicates, carbonates, monophosphates? include.

Builders such as NaTPP can be included as yet another optional ingredient to supply or supplement builder functions not provided by the buffer, and such builder foods are included in the entire composition according to the present invention. This buffer/builder component makes it possible to maintain the desired pH level of >10, which does not exceed 5% of the total pH. The pH is said to minimize degradation of the chlorine-rich whitener and undesirable interactions between the surfactant and the whitener. Na
TPP states that GC, if present, is limited to 5%. Antifoaming agents are not disclosed.

It is therefore a principal object of the present invention to provide a thixotropic detergent composition which is advantageously adapted for use in automatic dishwashing machines and which does not suffer from one or more of the above-mentioned disadvantages.

Another object of the invention is to provide a composition of this type which has good physical stability without significant signs of phase separation after long periods of standing.

Another object of the present invention is to provide a composition of this invention in which the problems associated with undesirable interactions of the chemically active component σ) are eliminated or reduced (at least substantially reduced). A7)5 Yet another object of the present invention is to provide compositions of this citron that have the above-mentioned stability under highly alkaline conditions necessary for effective detergent performance.

Yet another object of the invention is to have rheological properties that exhibit a higher viscosity at low shear rates and a lower viscosity at high shear rates, so that they can be used in the dispensing cup of an automatic pan fk machine. Advantageously adapted for use. Yet another object of this invention would be to provide the composition of this invention with low foaming properties.

It is an object of this type to provide a composition of this type that has improved washability, is durable and can be easily dispersed in a washing machine.

Other objects and advantages of the invention will become apparent hereinafter.

The foregoing terms include (a) 8 to 55% alkali metal tripolyphosphate, approximately by weight;
bl 2.5 to 20 ti sodium silicate; (C)0
(d) 0.1 to 5 chlorine bleach-stable, water-dispersible organic detergent actives; (C) 0 to 5 chlorine bleach-stable foaming agents; Inhibitor; (
fl A chlorine bleaching compound in an amount to provide about 0.2 to 4% available chlorine; and (g) a xixotrobi index of about 2.5 to 10? A composition comprising: a thixotropic thickener in an amount sufficient to provide a composition comprising: a thickening agent; A generally gel-like aqueous automatic 111i machine washer cleaning composition with xyxotropic properties is achieved in accordance with the present invention in its broadest sense.

The combined ADI) composition is thus low foaming, chemically and physically stable, readily soluble in cleaning media, and has improved settling performance. The pH that best exhibits the effect is 10.5-16.5
be. These compositions usually have a gel-like consistency, ie, Bingham plastic properties, and therefore relatively high yield values.
It is a highly viscous, opaque jelly-like substance. Thus, as obtained in the agitated dispensing cup of a running automatic dishwasher.

A certain shear force is required to initiate or increase flow. Under these conditions, the 5 composition fluidizes rapidly and easily disperses. Upon discontinuation of the shear force, the fluid composition rapidly returns to a highly viscous Bingham plastic state approximating its initial consistency.

In general, the effectiveness of ADD tj (a) available chlorine level;
(b) Alkalinity, (C) Solubility in the Washing Medium, and (d) Directly Related to Foam Control. pH of ADD composition
is at least about 95. More preferably about 10.5 to 13
．． 5. Most preferably at least about 11.5 is preferred in this case. At relatively low pH values, AD
The D product is too viscous, ie, solid, and therefore does not readily flow under the shear forces created in the dispensing cup under normal wash-like operating conditions. Essentially, a composition loses much, if not all, of its thixotropic properties, so the addition of NaOH is often required to raise the pH to within the above range and increase flowability. The presence of carbonate is also often necessary here, since it acts as a loosening agent making it possible to maintain the desired pH level. However, excess carbonate should be avoided as it can cause the formation of carbonate needles, thereby impairing the stability, thixotropy and/or washability of the ADD product. Caustic soda (NaOH)tiphosphoric acid or phosphonic acid noester foam suppressants when present? About 0 of the 5 compositions also serve the function of neutralizing
．． 5 to 6% by weight NaOH and about 2 to 9% by weight sodium carbonate are typical. However, it should be recognized that sufficient alkalinity may be provided by 1j NaTPP, sodium silicate, and K.

About 8 to 65 weight percent, preferably about 20 to 50% by weight
The NaTPP used in the composition should preferably contain no heavy metals, as heavy metals tend to decompose or inactivate the preferred sodium hypochlorite and other chlorine bleach compounds. In order to improve and promote the hydration and solubilization of the NaTPP and to avoid undue thickening of the composition, the NaTPP must not be completely anhydrous and have an average degree of hydration of about 5 (trihydrate). It is preferred to humidify or hydrate to contain up to about 15 inches of water.

In practice, humidification to an average of about 0.5 to 1 inch of water is very effective, forming stable hydrochloric salt seeds that promote hydration and solubilization of the remaining NaTPP particles. useful for.

Suppression of foaming is important to increase dishwasher efficiency and to minimize destabilizing effects that may occur due to the presence of excess foam within the washer during use. Foam can be significantly reduced by appropriate selection of the type and/or amount of detergent actives, ie the main foam-forming components. The degree of foaming also depends somewhat on the hardness of the washing water in the machine, in which case
Appropriate adjustment of the proportion of NaTPP with a water softening effect helps provide the desired dust foaming control. However, it is generally preferred to include a chlorine bleach-stable suds suppressor or suds inhibitor; particularly effective are alkyl phosphates of the formula %, such as BASF-Wgandotte. ) (PCUK-PAE), and also in particular alkyl acid phosphoric acid esters of the formula
(SAP) and Knapsack (LPKn-158), one or both R groups in each type of ester are independent! IcC72-20 alkyl. Mixtures of either these two types or other chlorine bleach-stable types, or mono- and di-
Mixtures of esters may be used; particular preference is given to monostearyl/distearyl acid phosphates 1.2/1 (
Mono- and G-C16-1 such as Natpsack Co.)
It is a mixture of 8 alkyl acid phosphates. When used, from 0.1 to 5% by weight in one composition, preferably about 0.1
Foam suppressants in proportions of from to 0.5% by weight are typical;
The weight ratio of detergent active ingredient (d) to suds suppressant (e) generally ranges from about 10=1 to 1:1 and preferably from about 4=1 to 1:1. Other antifoaming agents are, for example, known silicones.

Alkali metals such as potassium, although any chlorine bleach compounds such as dichloro-in cyanurate, dichloro-dimethylhydantoin chlorinated TSP, etc. may be used in the compositions of the present invention.

Hypochlorite salts of lithium, magnesium and especially sodium are preferred, and the composition has a composition of about 0.2 to 4% by weight, as determined by acidifying, for example, 100 parts of the composition with an excess of hydrochloric acid. % available chlorine (enough to provide chlorine bleach stability). Approximately 0.
Solutions containing 2 to 4 weight percent sodium hypochlorite contain or provide approximately the same percentage of available chlorine.

Particularly preferred is about 0.8 to 1.6 weight percent available chlorine.

IJum is present in the composition in an amount ranging from about 2.5 to 20% by weight, preferably from about 5 to 15% by weight. used for. The sodium silicate is generally added in the form of an aqueous KU solution, preferably in a ratio of about 1:2.2 to 1:2.
At this point, most of the other components of the composition, especially N, have a Na20:St02 ratio of 8.
a0)l, sodium hypochlorite, antifoaming agents and xixotropic thickeners are also often added in the form of preformed aqueous dispersions or solutions.

Detergent active materials useful herein must be stable in the presence of chlorine bleaches, particularly hypochlorite bleaches, and are preferably organic anionic amine oxides, phosphine oxides, sulfoxides and betaines. Of the moisture-friendly surfactant types, the former being the most prevalent, they are used in a range of about 0.1 to 5%, preferably about 0.6% to 0.8%. Particularly preferred surfactants herein are commercially available as 1, such as Dowfax 6B-2 and Dowfax 2-1. Linear or branched alkyl metal mono- and/or diC
8-14 alkyl diphenyl oxide mono- and/
or a di-sulfonate. In general, paraffin sulfonates have been found to tend to lose, if not destroy, thixotropy, unduly increasing viscosity and causing severe shear problems. Additionally, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants are primary alkyl sulfates, alkyl sulfonates, 1-alkylaryl sulfonates, and secondary alkyl sulfonates. include. Examples are sodium dodecyl sulfate and tallow alcohol fJAt, sodium 010-018 alkyl sulfate like sodium hexadecyl-1-sulfonate, C10'+8 sodium alkanesulfonate like sodium salt and C1 like sodium dodecylbenzenesulfonate. □-G1B sodium alkylbenzene sulfonate. Equivalent potash 9
Mug salt may also be used.

As other suitable surfactants or detergents, amine oxide surfactants typically have a structure of R2R'NO, in which each Rfl lower alkyl group is methyl, and R' is 8 to 22 long-chain alkyl groups with 5 carbon atoms, such as lauryl, myristyl-palmityl or cetyl groups.Instead of the amine oxides, the corresponding surfactants phosphine oxides R2R'PO or sulfoxides F (R'5O-i The betaine surfactant is typically SEIZO R2F ('N+
PiC001 and in this formula each R has 1 to 5 carbon atoms? It is a lower alkylene group with Specific examples of these surfactants are lauryl-dimethylamine oxide, myristyl dimethylamine oxide, coco dimethylamine oxide, hydrogenated cow oil dimethylamine oxide, the corresponding phosphine oxides and sulfoxides, and dodecyldimethylammonium acetate, tetradecyl - Corresponding betaines including diethylammonium pentanoate, hexatecyldimethylammonium hexanoate, etc. K because it is biodegradable.

The alkyl in these surfactants should and is preferably linear.

Other types of surfactants all well known in Chinese cabbage are e.g. U.S. Pat.
271.01.

Thixotropic thickeners, i.e. thickening agents or suspending agents that provide aqueous media with thixotropic properties, are known in Chinese cabbage and are organic or inorganic water-soluble, water-dispersible or colloid-forming agents. well, and may be monomeric or polymeric, and of course should be stable in these compositions, e.g. stable to high alkalinity and chlorine entertainment compounds such as sodium hypochlorite. Particularly preferred are inorganic colloid-forming clays, generally of the smectite and/or attapulgite type. These materials are generally used in amounts of about 2 to 5% by weight, but in any case in amounts sufficient to provide the desired thixotropic properties and Pingham plastic properties.

This type of material, which includes smectite clays such as hamonthorionite (bentonite), hectorite, saponite, etc.
It is available under trade names such as 1 and 5 and Gel White GP (both of which are montmorillonites). Attapulgite clays are manufactured by Engelhardt Minerals and Chemicals under the trade name Akgel or Ryotagel 40. Also useful herein are mixtures of smectite and acpulgite in a 4:1 p) to 1:5 weight ratio, including materials commercially available as Ryotagel 50 and Akugel 150. Other AT class thickeners or anti-settling agents are well known in Chinese cabbage1, e.g. referenced U.S. Pat. No. 3.98.
5.668. Abrasives and polishing should be avoided.

The fFi of water contained in these compositions should of course not be so great as to result in unreasonably low viscosity and fluidity;
Nor should it be so small as to give rise to unduly high viscosities and low flow properties, in which case the thixotropic properties would be reduced or destroyed; easily determined by 45 to 75 weights, preferably about 5
k) In the range from 5 to 65% by weight, the water should also preferably be deionized or softened.

ADD products of the present invention exhibit improved rheological properties when evaluated by testing product viscosity and shear rate as a function of shear rate; our results show that the composition has greater viscosity at lower shear rates and higher shear rates. The data shows effective fluidization and gelling within the shear rates encountered in dishwashers; σ) Compared to the ADDi product, the viscosity (Pluck Fee) v 53 to 5 (for an applied shear rate corresponding to 1 rpm) means improved pouring and processing properties and less leakage in the dispensing cup of the machine. A4 by LVT Brookfield viscometer at room temperature
When measured after 6 minutes using the spindle, approximately 15,
0DD-40,000 centiboise to about 6,000-
5. This corresponds to the range of ODD centiboise. 7.4
A shear rate of sec-1 corresponds to a spindle rpm of about 6. An increase in shear rate of about 10 times - 16 times to a 7 times decrease in viscosity occurs. In the case of current ADDs, the corresponding viscosity reduction is only a factor of 2; moreover, for this type of composition, the initial viscosity taken at about 5 rpm is only about 2
It is 500-2700 centipoise. The compositions of the present invention thus exhibit a significantly greater degree of initial flow χ at lower shear rates and in terms of shear rate increase versus viscosity decrease. ), which is the apparent viscosity (a) at 5 rpm vs. 50 rpm.
In.

The ratio of the apparent viscosity of the composition of the present invention is measured from 2.5 to 10. Each of the ADD compositions tested, preferably having a Tl value of #-t6 to 8, substantially and rapidly returns to its initial resting state consistency when shear is discontinued? Indicated.

According to one preferred method of dispensing these compositions:
All inorganic salts, carbonates (if used), silicates and tripolyphosphates, should be dissolved or dispersed in the aqueous medium first, and the thickener added last. The foam suppressor (if used), like the thickener, is prepared in advance as an aqueous dispersion. This foam suppressant dispersion, caustic soda (
(if used) and inorganic salts are first dissolved in water (desalinated water).
The mixture was mixed at an elevated temperature in a vacuum chamber, and then cooled with gradual stirring. Room temperature bleach, surfactant and thickener are then added to this cooled (25-559C) solution. Excluding chlorine bleach compounds, the total salt concentration (NaTPP, sodium silicate and sodium carbonate) is generally about 20 to 50% by weight in the composition.

Preferably it is 50 to 40% by weight.

Other conventional ingredients may be included in the composition in amounts generally less than about 6% by weight, such as perfumes: hydrotropes such as benzene-toluene-xylene, oyohycumene-sodium sulfonate. Agents: Preservatives: Dyes and pigments, etc.

Of course all are stable to chlorine bleach compounds and high alkalinity (properties for all components).

Particularly preferred for coloring are polysulfides of chlorinated phthalocyanines and aluminosilicates.

They give off pleasant green and blue hues, respectively.

TiO□ may be used for whitening or neutralizing color shifts from the standard.

The liquid ADD composition of the present invention can be washed by washing dishes, other kitchen utensils, etc. in an aqueous washing bath containing an effective amount of the composition in an automatic dishwasher equipped with a suitable detergent sugar dispensing device. can be easily used in known ways.

Preferred embodiment for the following examples? They are illustrative only and should not be considered limiting.

All amounts and proportions referred to herein are by weight of the composition unless otherwise specified.

Example 1 A pre-dispersion of a suds suppressant in 0.16 PY65' water of a 2=1 mixture of heptano and di-(C16-C,8) alkyl esters of phosphoric acid was introduced into a disc impeller y (
and mixed for 30 minutes at 60°C.

This dispersion is called Part 1.

A pre-dispersion of Gel White (hydrated) thickener 51 in water 171 is made by mixing for 10 minutes at 70°C using a z-blade mixer.

This dispersion? Call it Part 1.

With the following ingredients 'Y50-60'C, Giu
sti) Miki f-medium te mixture j 7:h.

% A1%2 Deionized water 16.9 Part 1
6.16 0.16 caustic soda solution・
49t NaOH2,401,2 Sodium Carbonate
ZOO7,0 Sodium silicate 47.5 solution 313.74:6. The mixture is cooled to 25-50°C with continued stirring and added to the following ingredients at room temperature.

Part 2 (Dispersion using high speed turbine) 20,00 3.0
Dowfax 5B-250,800,561, Natpsack LPKn 153.

Z active ingredient.

6, NazO:5tC)z = 1: 2.44,
i.e. moisture content 0-5%, especially 6%.

5. 45% aqueous solution of monodecyl/didecyl diphenyl oxide sodium disulfonate.

5 compositions/ri of about 7 'I'i according to the method described above, resulting in an opaque composition with a gel-like consistency t (about 401 AI)
Y: Mochi, apparent viscosity value of 28,000 centivoise at 5 rpm and 5 Q rpm, and 4.
000 rpm K based. When tested in an automatic dishwasher equipped with a suitable dispensing cup, the composition provides excellent cleaning performance and is easily and quickly dispensed. Little or no phase separation is observed even after long periods of standing in a closed container.

The p) of the composition measured as a 100% solution in water is 111.6. When performing a shear test evaluation, a composition returns rapidly to its initial resting consistency, within the limits mentioned above, i.e. at a shear force limit less than (approximately) that encountered inside an automatic dishwasher during operation. No difference was observed when dispensing the ADD product with a squeeze tube rather than with a dispensing cup, which showed no appreciable reduction in yield value when tested in the test tube.

Example 2 Polyphosphate Carbonate Silicate 9 Example 1 is repeated in which the combined concentration is about 67 salts, except that the total linearity of such salts is varied within the limits previously given.

Best results are obtained at a combined concentration of at least 50%, especially when the sodium tripolyphosphate concentration is at least about 20%
%. High silicic acid and salt concentrations (and therefore high alkalinity), which are desirable to protect ceramic glazes and patterns, are compensated for by appropriately reducing the caustic soda concentration and/or adjusting the sodium carbonate (buffer) concentration. This composition can contain Na
It appears to be very sensitive to variations in TPP concentration (higher concentrations are more effective) as well as its degree of hydration. Does variation in surfactant concentration generally affect the desired low foaming level? To achieve this requires a corresponding and direct variation in the suds suppressant concentration.

Lowering the pH' of the example compositions by about 10.5 JJ causes a significant decrease in the effectiveness of the compositions, accompanied by a corresponding decrease in flowability.

Example 6 Example! Repeat the procedure, except that the corresponding ingredients are added to the alkyl fIIt salt surfactant, such as coconut oil sodium alkyl sulfate, attapulgite clay, such as Akugel 50. and montmorillonite and acgel 50 2:
Similar results are obtained when replacing with one mixture. The chlorinated phthalocyanine and aluminosilicate dyes are each added to the composition of Example 1 in small amounts, e.g. 0.002-0.0.
Addition of 0596 (-gK included in the pre-thickener dispersion or added later to the cooling solution) yields pleasantly colored green and blue compositions, respectively.

Example 4 In this example, the ingredients are sequentially added to a mixing vessel with stirring in the order listed and finally homogenized.

parts (weight) deionized water 59.4!
+62q6 green solution 0
．． 175 Attagel 50 Clay Thickener'
3.575 Titanium dioxide-anatase
0.575N a s T P P O-5% moisture (half of the total) 11.558 Natupuzatsuk LPK
n1582 0.16016% hypochlorous acid) IJium bath solution 9.250 Sodium carbonate 3.0004v, s
qbmts sodium m liquid' 17.89
549 Sodium hydroxide solution'i 2
．． 60ON a s T P P (J, 5 qbk
Minutes 11.558 Dowfax 5B
-250,800 11 Total moisture 59.5% Available chlorine 1.21 no 0.1% silicate 8.5 chips)]
12.8 +/-0,5 specific gravity 1.65 min. 20 revolutions at 25°C) 4'1, attapulgite 2, foam suppressor 6, approximately available chlorine 15 t4, Na2O: Sin□= 1: 2.45,
Detergent Active Surfactants Although this invention has been disclosed in terms of preferred embodiments, it is understood that modifications and variations thereof that are obvious to those skilled in the art are included within the spirit and scope of this application and the claims. will be done.

Procedural Amendment Written by Kazuo Wakasugi, Commissioner of the Patent Office, August 3, 1982. Thixotropic composition combined with chlorine bleach for automatic dishwashers 6
, Relationship with the case of the person making the amendment Patent applicant address name Colgate Palmoliff Company No. 4,
Agent 5, [Claims] and [Detailed Description of the Invention] columns of the specification to be amended (attachment) (1) The statement in [Claims] will be corrected as follows.

"1. On an approximate weight basis: (a) an alkali metal tripolyphosphate having an average degree of hydration of less than about 1 or greater than about 5 from 8 to 65%; fb) from 2.5 to 20% sodium silicate; ( c)
0 to 9% alkali metal carbonate; (aj 0.1 to 5% chlorine bleach-stable water-dispersible organic detergent active; (e) 0 to 5% chlorine bleach-stable suds suppressor; (f) an amount of a chlorine bleach compound to provide about 0.2 to 4% available chlorine; and (g) an amount sufficient to provide a composition with a thixotropy:r! number of about 2.5 to 10. Thixotropic Thickener: An aqueous cyxotropic composition for automatic dishwashing machines comprising: thixotropic thickener;

2. The composition of claim 1, wherein the detergent active is selected from the group consisting of organic anionic amine oxide, phosphine oxide, sulfo oxide and betaine surfactants and mixtures thereof.

3. A composition according to claim 1, wherein the detergent active is an organic anionic alkali metal sulfate or sulfonate.

4. The composition according to claim 1, wherein the detergent active substance is an alkali metal C3-C□4 alkyl diphenyl oxide sulfonate.

5. The composition of claim 1, wherein the chlorine bleach compound is hypochlorous acid.

6. Claim 1, wherein the thickener is smectite or adapulgite clay or a mixture thereof.
The composition described in Section.

7. The composition of claim 1 comprising about 9% by weight of sodium carbonate.

8. At least about 0.1% by weight of the suds suppressant selected from the group consisting of acidic phosphoric acid alkyl esters and phosphonic acid alkyl esters containing one or two C12-20 alkyl groups, and mixtures thereof. A composition according to claim 1, comprising:

9.10. The composition of claim 1 having a pH of from '5 to about 16.5.

10. On an approximate weight basis: (a) sodium tripolyphosphate having an average degree of hydration of less than about 1 or greater than about 5 from 8 to 65%; (b) sodium silicate from 2.5 to 20%; (C) 2 to 9% sodium carbonate; (d) 0.1 to 5% chlorine bleach-stable, water-dispersible organic detergent active; (e) 0 to 5% chlorine bleach-stable suds suppressor; (f) sodium hypochlorite in an amount to provide about 0.2 to 2% available chlorine; (g) 1.5 to 10 chloride sufficient to give a composition with a thixotropic index of about 2.5 to 10; % of a thixotropic smectite and/or acpulgite clay thickener; and 1,+(h) sodium hydroxide in an amount sufficient to obtain a composition having a pH of about 10,5 to 16,5; An aqueous thixotropic composition for automatic washing machines.

A composition according to claim 1Q containing from about 0.5 to 2% of said detergent active which is a mixture of sodium mono- and di-C alkyl diphe-14 nyl oxide sulfonates.

12. The composition of claim 11 containing about 0.1 to 0.5% of the suds suppressant which is a mixture of mono- and di-C16-18 alkyl acidic phosphate esters.

13. The composition of claim 12, comprising about 20 to 3% sodium tripolyphosphate.

14. The composition of claim 13 comprising about 2 to 5% of a cyquintropic montmorillonite clay thickener.

15. The composition of claim 16, comprising about 2 to 5% thixotropic attapulgite clay thickener.

16° First, prepare an aqueous dispersion of any of the components (e) to be used, and use this dispersion to prepare the components (a) and (b) to be used.
) and any (c) with water, and then mixing the resulting mixture with a preformed aqueous dispersion of component (dj, (f)) and component (g), A method for producing the composition according to claim 1.

17° Component (g'), component (a) of 4-1 (
e), (f) any (c), (b), component (a)
4-1 and finally (tl) in water in this order.

1B. A method comprising washing dishes in an automatic dishwasher with an aqueous washing bath containing an effective amount of the composition of claim 1.

19. A method comprising washing dishes in an automatic dishwasher with an aqueous medium containing an effective amount of the composition of claim 16.

20. The composition of claim 16 having a Shkintropy Index of about 6 to 8. (2) Specification No. 1
The statement in lines 7 to 10 on page 5 is corrected as follows.

"is an average degree of hydration less than about 1 or greater than about 5,
That is, at least 16.5% water by weight is served, including stable filtrate with a degree of hexahydration corresponding to 0 to 2.7% by weight or more than about 18% by weight water. In reality, it humidifies to about 0.3 to 1% moisture on average.''

Claims (1)

[Claims] 1. On a dog weight basis. (a) 8 to 55-alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate; (C)
0 to 9% alkali metal carbonate; (diO,1 to 5-chlorine bleach-stable water-dispersible organic detergent active; (e) 0 to 5% chlorine-bleach-stable suds suppressor; (f) an amount of a chlorine bleach compound to provide an available chlorine of from about 0.2 to 4 t; and (g) an amount of a thixotropy compound sufficient to provide a composition Y having a thixotropy index t of from about 2.5 to 10. an aqueous thixotropic composition for automatic dishwashing machines consisting of a viscous agent; 2. a group consisting of amine oxide, phosphine oxide, sulfo oxide and betaine surfactants and mixtures thereof, wherein the detergent active substance is organic anionic; 6. The composition according to claim 1, wherein the detergent active substance is an organic anionic alkali metal sulfate or sulfonate. 4. The detergent active substance is alkali gold 111CL801
4-alkyl diphenyl oxide sulfonate. A composition according to claim 1. 5. The above chlorine bleach compound is hypochlorous acid. A composition according to claim 1. 6. The thickener is smectite or attapulgite clay or a mixture thereof. Claim 1
The composition described in Section. Z. The composition of claim 1 comprising about 0 to 9% by weight sodium carbonate. 8. A small amount (about 0.1 % by weight. 9. The composition of claim 1 having a pHt of from 10.5 to about 13.5. 10. Approximately by weight. (a) 8 to 55% sodium tripolyphosphate: (b)
2.5 to 20% sodium silicate: (C) 2 to 9-sodium carbonate; (d) 0.1 to 5% chlorine-extreme white stability, water dispersion 1
1 Ω organic detergent active: (e) 0 to 5 chlorine bleach-stable foam suppressor: (fl Sodium hypochlorite in an amount to give about 0.2 to 2% available chlorine: (g ) to obtain a composition with a thixotropic index of about 2.5 to 10, sufficient smectite lead and/or attapa/gite clay thickeners of 1.5 to 101; and a water-based autoclave. A thixotropic composition for dishwashing machines containing from about 0.5 to 2 hours of the detergent actives described above, which is a mixture of mono- and di-C8-14 alkyl diphenyl oxide sulfonic acids. A composition according to claim 10. 12, about 0.1 to 0.5% of the suds suppressant described above, which is a mixture of mono- and di-C16-18 alkyl acidic phosphate esters. A composition according to claim 11. 16. The composition of claim 12, comprising about 20 to 60% sodium tripolyphosphate. 17. The composition of claim 16, comprising about 2 to 5 thixotropic monmorillonite clay thickeners. 15. Comprising about 2p-La 5% xixotropic attapulgite clay thickener.
4. The composition according to 4. 16 First, prepare an aqueous dispersion of any of the components (e) to be used, and then apply this dispersion to the components (a) and (b) to be used.
) and any (C) 't' containing water, and then the resulting mixture is mixed with an aqueous dispersion of components (d) and (f) - and any (C) 't' beforehand. A method for producing a composition according to claim 1. Any (C), (b), the other of component (a), and finally K (d), χ in this order. 18.% effective ti of the composition as claimed in claim 1.
A method consisting of washing dishes in an automatic dishwasher with an aqueous washing bath containing Lv. 19. A method comprising washing dishes in an automatic dishwasher with an aqueous medium containing an effective amount of the composition of claim 16. 20, with approximately 6 to 8 sychintropic fingers av. A composition according to claim 16.