JPS61291698A - Thixotropic detergent composition for automatic tablewear washer improved in physical stability - 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 (Field of Application of the Invention) The present invention relates to an automatic dishwashing detergent having thixotropic properties and improved chemical and physical stability, which detergent is easily incorporated into the cleaning medium. Distributed into tableware, glassware,
Effectively cleans pottery etc.

BACKGROUND OF THE INVENTION Commercially available household dishwasher detergents are provided in powder form, but have several drawbacks. For example, the composition is not uniform,
Requires expensive operations to manufacture.

Tends to cake and form particles that are difficult to disperse when stored at high humidity; has a tendency to cake in the dishwasher dispenser; etc. Moreover, liquid compositions have a high degree of foaming, an unacceptably low viscosity, and an excessively high alkalinity, making them generally unusable.

Recent research and development efforts have focused on compositions in gel-like or "thixotropic" form, such as cleaning agents and automatic dishwashing wall products that have characteristics as thixotropic R-sts. Such dishwashing wall products are [anchored] within the dispenser cup of the dishwasher.
) The viscosity is insufficient to maintain the J state, and it is also disadvantageous in that it leaves stains on tableware, glassware, ceramics, etc. Ideally, a thixotropic cleaning composition has a high viscosity or Bingham plasticity at rest;
It must have a relatively high yield value. However, when subjected to shear stress such as when being shaken in a container or squeezed out of an orifice, it becomes fluidized rapidly, and once the application of shear stress is stopped, it rapidly becomes viscous/Bingham plastic. It must be something that returns to normal. Stability is likewise of primary importance. That is,
Shows significant signs of phase separation or interpolation after long-term storage7
must not.

Gel-form automatic dishwashing compositions having the above-mentioned properties have been problematic, especially as household automatic dishwashing machine compositions.For effective use, automatic dishwashing detergents (hereinafter referred to as A
(1) Sodium tripolyphosphate (NaTPP) to soften hard water, i.e. to bind its mineral content and to emulsify and/or thaw soil.

(2) Sodium silicate to provide the alkalinity necessary for effective cleaning and to preserve the glazes and patterns of fine pottery (31 Sodium carbonate (generally (considered to be an optional ingredient), +41 chlorine release agent to assist in detachment of soil particles that create water spots, and (5) defoamer/surfactant to reduce foaming, increase mechanical efficiency, and provide necessary detergent. It is generally recommended to include agents.

For example, SDA Detergents in Dept.
h, “Formulation Aspects o
f Machine DiahvraehingJ
(SDA Detergent Review, "Overview of Mechanical Dishwashing Formulations"), Thomas O'berle A/ (Thomas O'berle
) (1974). Cleaning agents close to the above-mentioned composition are mostly liquids or powders. It has proven difficult to combine such chain components in a gel form useful for use in home appliances. Such compositions generally omit hypochlorite bleach. Bleach tends to react with other chemically active ingredients, especially surfactants, thereby degrading the suspending or thixotropic agent and impairing its effectiveness. For example, U.S. Patent No. 4115.3
No. 08 is a thixotropic dishwashing machine containing suspending agents such as CMC, synthetic clay, inorganic salts including silicates, phosphates and polyphosphates, small amounts of surfactants and foam suppressants. is disclosed. However, bleach is not disclosed. U.S. Pat. No. 4,147.650 is somewhat similar and contains C/(hypochlorite) bleach as an optional ingredient, but no organic surfactants or foam suppressants. Furthermore, this product is described as a detergent slurry that does not have thixotropic properties.

U.S. Pat. No. 3,985,668 describes (1) a suspending agent, preferably clays of the smectite and attapulgite type, (2) an abrasive agent, such as silica sand or R-lite, and (3) a low density powder polymer. An abrasive cleaning cleaner having a gel-like consistency containing a filler such as expanded perlite is described, the abrasive having a bouyancy.

In addition to its function as a filler, it therefore has a stabilizing effect on the composition, thus displacing the unwanted supernatant layer water that forms due to leakage and phase destabilization. The above are essential ingredients. Optional ingredients include hypochlorite bleach,
There are bleach-stable surfactants and buffers such as silicates, carbonates and monophosphates. Builders such as NaTPP can also be included as additional optional ingredients to provide builder functions not provided by buffers or to supplement them. Such bil goo does not exceed 5 parts of the total composition in the present invention. Maintenance of the desired pH level (above 10) is achieved by buffer/builder components. A high pH is said to minimize chlorine bleach degradation as well as undesirable interactions between surfactants and bleach. NaTPP states that even if it exists, it is limited to 5 channels.

Antifoaming agents are not disclosed.

Colgate-Palm
UK patent application GB 2,116.19
Nos. 9A and GB 2.140,450A contain desirable properties characterized by a thixotropic gel-type structure and each of the various components necessary for effective cleaning in automatic dishwashers. A liquid ADD composition is disclosed. Typical gel-like aqueous dishwasher detergent compositions with thixotropic properties contain the following chain components: (
(based on weight) (a) 5 to 3 grams of alkali gold salt of tripolyphosphate, (b
) Sodium silicate 2.5 to 20%.

(cl　alkaline carbonate gold acupuncture salt 0 to 9%.

(d) 0.1 to 5 g of a water-dispersible organic detergent active material that is stable to chlorine bleach; (el) 0 to 5 g of a chlorine bleach-stable foam suppressor.

(fl Chlorine bleach compound, in an amount to provide about 0.2 to 4 units of available chlorine; and (gl Thixotropic thickener 1) in an amount sufficient to provide a thixotropic index of about 2.5 to 10 for the composition.

The ADD compositions so formulated are low foaming, readily soluble in cleaning media, and most effective at optimal pH, i.e., pHI 0.5-13.5, leading to improved cleaning performance. . The composition typically has a gel consistency, ie, a highly viscous, opaque gelatinous material, and has a Bingham plasticity and therefore a relatively high yield value. Therefore, a certain shear force is required to initiate or increase flow, and such force will be obtained in the agitated distributor cup of an operating automatic dishwasher. Under appropriate conditions, the composition fluidizes rapidly and is easily dispersed. When the shear force is stopped,
The fluid composition rapidly returns to a high viscosity, Bingham plastic state close to its original consistency.

(Problems to be Solved by the Invention) The liquid ADD formulations disclosed so far do not have the above-mentioned disadvantages, or have only a few disadvantages, but in reality, the shelf life of the product is limited. Further improvements in physical stability are required in order to increase the stability and increase consumer acceptance.

Therefore, one object of the present invention is to provide a thixotropic liquid A with improved physical stability and rheological properties.
An object of the present invention is to provide a DD composition.

To provide a thixotropic liquid ADD composition that has reduced thixotropic thickener levels and still does not generally adversely affect the high viscosity at low shear rates and low viscosity at shear rates that are characteristic of the desired thixotropic properties. is also an object of the invention.

These and other objects will be more readily understood from the detailed description and preferred embodiments that follow. By adding a certain amount of long-chain fatty acid polyvalent metal salt, which is effective in preventing sedimentation of suspended particles! ll achieved.

SUMMARY OF THE INVENTION Accordingly, the present invention provides an aqueous automatic dishwashing bale detergent composition, typically gel-punch and thixotropic, containing the following in weight percentages:

(attriyt" alkali metal lyphosphate salt 5 to 35 parts, (bl sodium silicate 2.5 to 20 parts.

(C) Alkali metal carbonate 0 to 9φ, (al
0.1 to 5 grams of a water-dispersible organic detergent active material that is stable to chlorine bleach; (θ) 0 to 5 grams of a foam suppressor that is stable to chlorine bleach.

(fl Chlorine-whitening agent compound, amount to provide about 0.2 to 4φ available chlorine.

(g) An amount sufficient to impart a thixotropic index of about 2.0 to 10 to one set of thixotropic thickeners.

(h + Sodium hydroxide O to 30 T.

(1) long chain fatty acid polyvalent metal salt 1 in an amount effective to increase the physical stability of the composition, and (jl water, balance).

Another feature of the present invention is to provide a method of cleaning dishes in an automatic dishwasher with an aqueous water/bath containing the effective components of the liquid automatic dishwashing detergent (LADD) compositions described above. According to this feature of the invention, the LADD composition can be easily poured into the dispensing cup of an automatic dishwasher, and the composition rapidly thickens to its normal gel-like state within a few seconds and can be used for one dish wash. It will remain in the dispensing cup until the shear force is reapplied, such as by water spraying from the machine.

In general, the effectiveness of ADD is determined by (a) effective chlorine water fishing, (b)
alkali metals, (61) dissolved in a cleaning medium, and (
a1 Directly related to foaming suppression. In the present invention, ADD i
Preferably, the pH of the parabolite is about 9.5 or higher, and about 1
More preferably 0.5 to 13.5, and most preferably about 11.5 or more. If the p,H values are relatively low, the ADD product will be too viscous, i.e., solid-like, and will not easily flow at the shear levels that occur in the distributor cup under normal machine operation and conditions. . In fact, the composition loses much, if not all, of its thixotropic properties. Therefore, in order to increase the pH to the above range and increase the fluidity, Na
Addition of OH is often required. The presence of carbonates is also frequently required in the present invention. This is because the carbonate acts as a buffer to maintain the desired pH level. However, excess carbonate must be avoided. This is because, if carbonate is present in excess, its needle-like crystals are formed, which impairs the stability, thixotropy and/or detergency of the ADD product. Caustic soda (NaOH) also has the additional function of neutralizing phosphoric acid or phosphate ester foam suppressants, if present. There is about 0.5 to 3 weight percent NaOH and about 2 to 9 weight percent sodium carbonate in the composition. The NaOH in the composition is about 0.
Typical amounts are 5 to 3% by weight, and sodium carbonate is typically about 2 to 9% by weight, but sufficient alkalinity can also be imparted by NaTPP and sodium silicate.

About 8 to 35% by weight, preferably about 20 to 30% by weight
N
The average hydration period of aTPP is about 1 or more or more than about 5, including a stable hexahydrate with a degree of hydration of 6, which corresponds to a water content of O to 2.7% by weight or about 18% by weight. te 16.5
% or more. In fact, an average of 0.3 to 1% moisture is believed to be very effective and aid in the formation of stable hexahydrate species. The hexahydrate promotes hydration and solubilization of the remaining NaTPP particles, on average NaTPP is about 5 to 15
It contains t% water by weight, which corresponds to an average hydration period of about 1 to 5%. If only hexahydrate is used, the detergent product will be liquid and will have little thixotropic properties.

If only anhydrous NaTPP is used, the product will be too thick and unsuitable. For example, anhydrous NaTPP: hexahydrate N
Effective compositions are obtained with weight ratios of aTPP of 0.5:1 to 2:1, with 'N ratios of about 1:1 being particularly preferred.

Inhibition of foaming is important for increasing the efficiency of dishwashers and for minimizing the destabilizing effects caused by the presence of excess foam in the dishwasher during use. Proper selection of the detergent active material, type and/or amount of the main foaming component will significantly reduce foaming. The degree of foaming is also somewhat related to the hardness of the wash water, so N has a water softening effect.
Proper adjustment of the proportion of aTPP helps achieve the desired degree of foam inhibition. However, it is generally preferred to include a stable foam suppressor or restrictor in the chlorine bleach.

For example, BASF-Wayandotte (PCUK
-PAE) and an alkylphosphonic acid ester with the chemical formula 0-P-ROR, and Ho
oksr (SAP) and Knapsack (LPK)
n-158), an alkyl phosphate partial ester having the chemical formula HO-P-OROR, is particularly effective. In the above formula, one or both R's in each type of ester independently represent a C2-2o alkyl group. mixtures of both types or other chlorine bleach-stable types;
Alternatively, mixtures of mono- and di-esters of the same type can also be used. Particularly preferred are mixtures of mono- and di-C16-18 argyl phosphoric acid partial esters, such as monostearyl/distearyl phosphate 1.2/1 (Knapsack). Typical proportions of foam suppressants used in the composition are from 0.1 to 5% by weight, preferably about 0.1% to 5% by weight.
1 to 0.5 weight-Itt%, detergent active ingredient (d)
7 The Keiyo ratio of the foam suppressor (e) is generally about 10/] to 1
/1, preferably about 4/1 to 1/1. Other antifoaming agents that can be used include, for example, known silicones.

Although any chlorine bleach compound such as dichloroisocyanurate, dichlorodimethylhydantoin or TSP chloride can be used in the compositions of the invention, alkaline hypochlorite salts such as potassium salts, lithium salts, magnesium salts, etc. Salt, especially sodium salt, is preferred. The composition must contain sufficient chlorine bleach to provide about 0.2 to 4.0 weight tons of available chlorine. The available chlorine is determined by acidifying, for example, 100 parts of the composition with excess hydrochloric acid. A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite will contain or provide about the same fraction of available chlorine. It is particularly preferred that the amount of available chlorine is about 0.8 to 1.6 weight. For example, available chlorine to 13% hypochlorous acid) IJ
Advantageously, Na0C1 is used in an amount of about 3 to 20 inches, preferably about 7 to 12 inches.

Sodium silicate, which provides alkalinity and protection for hard surfaces such as glazes and patterns on fine-grained pottery, is present in the composition from about 2.5 to 20%
Polydisperse is used, preferably in the range of about 5 to 15% by weight. Sodium silicate is generally an aqueous solution, preferably Na
The ratio of 2O:5102 is about 1:2.2 to 1:2.8
It is added in the form of an aqueous solution. At this point, the other ingredients of the composition, particularly NaOH.

Foam suppressants and thixotropic thickeners are also frequently added in the form of pre-prepared aqueous dispersions or solutions.

Detergent active materials useful in this invention must be stable in the presence of chlorine bleaches, especially hypochlorite WI bleaches, and also be organic anionic, amine oxide, phosphine oxide, sulfoxide or itine type water dispersions. It is preferable to contain a surfactant, and the anionic surfactant mentioned at the beginning is particularly preferable. The amount of detergent active material used is approx.
．． ranging from 1 to 5 inches, preferably about 0.5 to 2 inches.
．． 0%, more preferably in the range of about 0.3 to 0.8 inches.

Particularly suitable surfactants for the present invention are linear or branched mono- and/or di(C8-14')alkyldiphenyl oxides and/or alkali metal disulfate salts, where f'I is For example, DOWF'A
It is sold as 3 B-2 oxO-ft 7 ax 2A-1. in general.

Paraffin sulfonates have been found to have a tendency to impair, if not destroy, thixotropy and increase viscosity excessively, causing severe shear problems. In addition, the surfactant must be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfonates, alkyl sulfonates, alkylarylaryl sulfonates and secondary alkyl sulfates. An example is C□. -018 Sodium alkyl sulfate, such as sodium dodecyl sulfate and tallow (t
allOW) 7/l/: Sodium sulfate, C10'1g Sodium alkanesulfonate such as sodium hexadecyl-1-sulfonate and C1
An example of sodium 2-C18 alkylbenzenesulfonate is sodium dodecylbenzenesulfone. The corresponding potassium salts can also be used.

As other suitable surfactants or detergents, amine oxide surfactants having the structural formula R2R'NO are representative. In the above formula, R represents a lower alkyl group such as methyl, and R' represents a long chain alkyl group having 8 to 22 carbon atoms such as lauryl, myristyl.

Instead of the amine oxides representing valmityl or cetyl groups, the corresponding phosphine oxide R2R'PO or sulfoxide RR'SO surfactants can also be used.

The typical structural formula of betaine surfactant is R2R'N4-R
'ICOO-, and each R in the above formula represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants are lauryldimethylamineoxy, myristyldimethylamineoxide, the corresponding phosphine oxides and sulfoxides, and r-decyldimethylammonium acetate.

These include tetradecyl diethylammonium pentanoate and hexadecyl dimethyl ammonium hexanoate. To be biodegradable, the alkyl groups in the surfactant must be linear.

Such compounds are preferred.

Surfactants of the above type are all well known in the art, e.g. U.S. Pat.
．． No. 271.030.

Thixotropic thickeners, ie, daughtering agents or suspending agents that impart thixotropic properties to aqueous media, are known in the art and include organic or inorganic water-soluble, water-dispersible, or colloid-forming monomer or Although it is a polymer,
Of course, these compositions must be stable. It must be stable, for example, to alkalinity and chlorine bleach compounds such as sodium hypochlorite. Particularly suitable thixotropic thickeners are inorganic, colloid-forming clays, generally of the smectite and/or attapulgite type. In order to impart the desired thixotropy and Bingham plasticity to the ADD formulations disclosed by the applicant in GB 2.116.199A and GB 2.140,450A, supra, these materials generally contain about It is used in an amount of 1.5 to 11 f, preferably 2 to 5 f. It is an advantage of the ADD formulations of the present invention that the desired thixotropy as well as Bingham plasticity can be achieved with a reduced amount of thixotropic thickener in the presence of a fatty acid multivalent all-metal stabilizer. For example, when used in combination with physical stabilizers, the content of inorganic colloid-forming clays of the smectite and/or attapulgite type is about 0.0 to 3%, preferably 0.2 to 2.5%, particularly preferably 0.00% to 3%, preferably 0.2% to 2.5%, particularly preferably 0.00% to 3%, preferably 0.2% to 2.5%, particularly preferably 0.0% to 3%, preferably 0.2% to 2.5%, particularly preferably 0.0% to 3%, preferably 0.2% to 2.5%, particularly preferably 0% In the range of 5 to 2.2 inches.

Generally sufficient to achieve the desired thixotropy as well as Bingham plasticity.

Montmorillonite (pennite) for smectite,
Includes hectorite and sabonite. This type of material is Thixogl (registered trademark)/Vh
1 and gel white (Gelvhite, registered trademark)
Joshia Kaolin Co., Ltd. (with product names such as GP and H)
Georgia Kaolin Company)
(both are -T-7 morillonite). Attapulgite clay has Attagel (Att.
agel (registered trademark) or aftergel 40. Engelh Nort Minerals and Chemicals Co., Ltd.
ardMinerals and Chemicals
Corporation). Smectite and attapulgite type 4:l to 1
:5mJrt ratio mixtures are also useful in the present invention. Thickening or suspending agents of the above type are well known in the art;
See, for example, US Pat. No. 3,985,668, cited above.

The use of abrasive or abrasive agents should be avoided.

The amount of water contained in these compositions must, of course, not be so large as to result in excessively low viscosity and fluidity, nor so small as to result in excessively high viscosity and low fluidity. No. In either case, thixotropy is reduced or destroyed.

Such amounts are readily determined by routine experimentation in any particular case and generally range from about 45 to 75 mC11-1, preferably about 55 to 65% by weight. The water must be well deionized or softened.

The description of the ADD 6 products corresponds to the compositions disclosed in the aforementioned British patent publications GB 2.116.199A and GB 2.140.45OA, except where indicated otherwise.

These nine previously disclosed ADD products exhibit improved rheological properties when evaluated by testing product viscosity as a function of shear rate. shows low viscosity.

The data were sufficient to demonstrate effective fluidization and gluing within the range of shear forces remaining within the dishwasher. In practical terms, this means improved injectability and processing properties compared to prior art liquid or gel ADD products, and also less leakage in one machine dispenser cup. . With a shear rate corresponding to 3 to 30 rpm, LvT using a /f64 spindle
The corresponding viscosity after 3 minutes at room temperature on a Brookfield viscometer is approximately 15,000-30,000 cps to approximately 30
00 to 5000 cps. Shear rate 7.4
seconds corresponds to a spindle rotation speed of about 3 rpm. An approximately 10-fold increase in shear succession results in a 6- to 7-fold reduction in viscosity. For prior art ALID gels, the corresponding viscosity reduction was only about twice that. Further, such compositions have an initial viscosity of 2500-2700 at about 3 rpm.
It was just an ape. That is, the composition of the applicant's prior invention has a fluidization threshold at a low shear rate y, and the ratio of shear force increment to viscosity decrement is small υ. This property of the prior invention ADD product is measured by the thixotropic index (T). This thixotropic index is.

The ratio of the apparent viscosity at 3 rpm to the apparent viscosity at 30 rpm is 2.5 to 10 for the prior composition.

The ADD composition substantially and rapidly returned to its previous static consistency upon cessation of application of shear.

The present invention shows that the physical stability of these prior art aqueous liquid ADD compositions, that is, their resistance to phase separation, sedimentation, etc., is adversely affected by the addition of an effective small amount of a polyvalent metal salt of a long chain fatty acid. It is based on the discovery that the rheological properties can be significantly improved without any concomitant effects and, in some cases, have a beneficial influence on their rheological properties.

As an example of improved rheological properties, the addition of fatty acid metal salt stabilizers in amounts as low as 0.2% or less often reduces the apparent viscosity at low shear speeds, e.g., spindle speeds of about 3.
It was found that the amount increased by a factor of 3 to 3. At the same time, the physical stability is improved to the point where no phase separation is observed in the composition containing the metal salt stabilizer even after more than 6 weeks over a temperature range from near freezing to above 40°C.

Suitable long chain fatty acids have about 8 to about 22 carbon atoms, including the carboxyl group carbon atoms of the fatty acid, more preferably about 1 carbon atom.
Higher fatty acids having 0 to 20 carbon atoms, particularly preferably about 12 to 18 carbon atoms. Aliphatic groups may be saturated or unsaturated, and may be linear or branched. Mixed fatty acids derived from natural sources, such as beef tallow fatty acid and coconut fatty acid.

Soybean fatty acids and the like can also be used.

Examples of fatty acids that can form polyvalent metal salt stabilizers are, for example, tecanic acid, dodecanoic acid, palmitic acid, myristic acid,
These include a mixture of stearic acid, oleic acid, icosanoic acid, beef tallow fatty acid, coconut fatty acid, soybean fatty acid, and coconut acid. Stearic acid is preferred in terms of both commercial availability and effectiveness.

Preferred polyvalent metals are aluminum and zinc, but also other polyvalent metals, especially [A] of the Periodic Table of the Elements.

l1lA, +1. IA, VA, 輛■A, jiB
, IIB, ■B.

Metals from groups VB and II can also be used. Specific examples of such other polyvalent metals include k(Ft, C(L, Ti
.

Zr, V, Na, Mn, Fe, Co,
Nx, Ca, Sn.

Includes Sb, Bt, etc. Preferably, the metal salt is used in its highly oxidized state.

Many of these metal salts are commercially available.

For example, aluminum salts can be used in their diacid acid salt forms such as aluminum tristearate-Al (C17H35C0
It is available as aluminum stearate such as 0)3. Monosates of these metals, such as +3 valent kl, such as aluminum monostearate, AJ(O
H)2(C17H35C00), diacid salts such as aluminum distearate), AJ(OH)(C.

It is also possible to use mixtures of two or three of HCOO)2 and -, di- and diacids, for example mixtures of - and diacids for +2-valent Zn. Most preferably, diacid acid salts of +2 valent metals, diacid acid salts of +3 valent metals, and tetraacid salts of +4 valent metals are used in combination. For example, it is preferred that at least 30 Ti, preferably at least 50 Ti, particularly preferably from 80 to 100 Ti, of all metal salts are in the highest possible oxidation state, i.e. each possible valence site is occupied by a fatty acid residue. .

The above-mentioned metal salts are generally commercially available, but they can be prepared by saponifying animal fat, fatty acids such as stearic acid, or corresponding fatty acid esters, and then preparing hydroxides or oxides of polyvalent metals, such as aluminum salts. It can also be easily produced by treating with alum, alumina, etc.

Aluminum stearates, such as aluminum tristearate, and zinc stearates, such as zinc distearate, are suitable polyvalent fatty acid salt stabilizers.

The amount of fatty acid salt stabilizer to achieve the desired physical stability depends on the nature of the fatty acid salt, the nature and nature of the thixotropic agent, detergent active compounds, inorganic salts especially TPP, other ingredients and the expected This will relate to storage and shipping conditions.

However, generally the amount of polyvalent gold or tetrasate stabilizer is reduced to about 0.
．． A range of 0.02% to 1%, preferably about 0.06% to 0.8%, particularly preferably about 0.08% to 0.4%, provides long-term stability and is required for commercially acceptable products. It is made of resin and does not undergo phase separation during storage or transportation at both low and high temperatures.

One preferred method for making these compositions is to first dissolve or disperse all inorganic salts, carbonates (if used), silicates, and tolipoIJ+J phosphates in an aqueous medium. The solubilizer is added last. The antifoam agent (if used), like the thickening agent, is prepared as a preswaged aqueous dispersion. First, the anti-foaming dispersion, caustic powder (if used), and no fNm are mixed in ion-exchanged water at elevated temperature to form an aqueous solution, which is then cooled with continued stirring.

A room temperature dispersion of bleach, surfactant, fatty acid salt, stabilizer and thickener is then added to the cooled (25-35°C) solution. Excludes chlorine bleach compounds.

The total mK (NaTPP, silicate, sodium carbonate) is generally about 20 to 5% of the composition.

Preferably it is about 30 to 40% by weight.

Fragrances, hydrotropic agents such as benzene, toluene,
Other conventional ingredients, such as sodium quince and cumene sulfonates, preservatives, dyes and pigments, are also included in the compositions in small amounts, generally less than about 3 parts by weight. Of course, all of these other conventional ingredients must be stable to chlorine bleaching compounds and high alkalinity. Chlorinated phthalocyanine and aluminosilicate phorisulfides are particularly suitable colorants, imparting crisp green and blue shades, respectively. TiO□ is used for whitening or neutralizing and removing dark shadow areas.

The liquid ADD compositions of the present invention are readily used in known manner for cleaning dishes and other kitchen utensils in a wash water bath containing an effective amount of the compositions in an automatic dishwasher equipped with a suitable detergent dispensing agent. be done.

Although the invention can be practiced in a variety of ways, a number of specific embodiments are described in the Examples below to illustrate the invention.

The amounts and proportions stated in this application apply to 11% of the composition unless otherwise specified.
The quantity is a fake.

Example 1 To demonstrate the effectiveness of metal salt stabilizer liquid ADD formulations, a stabilizer and a thixotropic thickener were prepared. First, add the following ingredients to Gulsti.
The mixture was mixed using a mixer at 9-ω°C.

Ion exchange water 41.10
=', -7-X caustic soda solution (50% NaOH)
1.00 anhydrous sodium carbonate
5.00 Sodium silicate Na20:Sioz ratio = 1:2.4
47.5% solution of 1574 Sodium TPP (substantially anhydrous, i.e. moisture 0-5%) (Thsrmphos Nw)
12.00 Sodium TPP (hexahydrate) (Thermphos N hexa)
12.00 mixture 25-30
The mixture was cooled to 0.degree. C., stirring was continued for 1 hour, and the following ingredients at room temperature were added.

Sodium hypochlorite solution (available chlorine 1.14')
9.00 Monostearyl phosphate
0.16DOWFAX3B-2 (Na monotecyl/didecyl 0.80 diphenyl oxyto 1 disulfonate 45% aqueous solution) Al tristearate or Zn distearate
XGe'1
White H2,oo-y monostearyl phosphate foam suppressant and Dowfax (D
owfax) 3 B 2 Detergent active compound total, Aluminum tristearate) 4 Just before addition of zinc distearate stabilizer or gel white) (Gelwhite)
It was added to the mixture just before adding the Ha agent.

As shown in Table 1, the density M of each liquid ADD formulation obtained was
, CDR (capillary drainage rate, Capillar7Dra
inase Rate), 3 and 3Q rpm
The appearance, viscosity, and physical stability (phase separation) during storage and shipping tests were measured. The results are also shown.
Shown below.

From the data in Table I the following conclusions are reached.

When 0.2 parts of Al stearate is added to a formulation containing 1.5% or 1 part of Gel White H, as well as 2%
Gel Why) Al stearate 0 in the formulation containing H
．． When adding 1 t or 0.1 t of zinc stearate,
Physical stability and apparent viscosity increase simultaneously6 (Table 1.
Experiment J (control), 2.3°6 and 9) Addition of 0.1% AI stearate to a formulation containing 1-line Gel White H, addition of 0.1% AI stearate to a formulation containing 0.5% Gel White H.
The addition of 2% Al stearate and the addition of 0.3 or 0.41 Al stearate to formulations containing 0.25 Excellent Gel White H increases physical stability without severe viscosity increases. (Table ■, Real Ml (scorching light), 4, 7, 1
0 and 11).

0.1% Al stearate and 0.5 width gel white H (
When experiment 8) is combined, the apparent viscosity remains at an acceptable level, but the physical stability may be improved.

Note to Table I) Place 6.4 m of round No. 1 filter paper (Whatman, Wh
atman).

A plastic tube with a length of 6.4 mm and a diameter of 3.4 mm is placed in the center of the nucleus. Fill tube with liquid ADD composition sample (1
after leaving it in the sun). Measure the time it takes for the solvent to seep out of the tube and reach the end of the circle. Time measurements are taken at three side points of the circle and averaged. The short time means that the gel is the solvent (water)
This means that it was not held well and leaked onto the F paper. 5
A time greater than minutes is considered good. A time of 4 to 5 minutes is considered unstable but acceptable.

(Measured after 3 minutes on spindle 4 for 2124 hours 1 day sample.

(3) Depends on height.

(4) Based on weight.

(5) Inside the glass bottle at 4℃, room temperature (20±2℃)%3
At 5°C and 43°C.

(6) 61 after 6 weeks and after transporting 3000 axes in a passenger car
11. Constant liquid separation.

(by weight in plastic bottle).

Example 2 Attagel-50 (Attapulgite clay) 2% or Bentone 7 was used instead of Gel White H as a thixotropic thickener.
) Example 1 and Example 1, except that 0.4% KW (specially treated hectorite clay) was used with (experiments 2 and 4) or without (control experiments 1 and 3) aluminum tristearate. The same composition as well as method of preparation was used. Apparent clay and physical stability were determined as described in Example 1. The results are shown in Table ■.

The results shown in Table 1 show that small amounts of aluminum stearate are equally effective in improving the physical stability of liquid thixotropic dishwasher detergent compositions based on attapulgite and hectorite clays.

Example 3 In this example, Al2O3, ZnSO4 and Al2(
Inorganic aluminum and zinc salts and monovalent metal salts of fatty acids, including SO4)3, are liquid thixotropic AD
This shows that composition D does not improve the stability of buried tubes. Example 1 Using the same formulation as Experiment 6, A12o3, ZnSO instead of 0.1% aluminum stearate
4, Al2(SO4)3 and sodium stearate were used at 0.1% each. The results of measuring the appearance and physical stability are shown in Table m.

Example 4 Following the same general method as in Example 1, the following gel-like tigisotropic liquid ADD was prepared.

Ingredients t(A, Engineering, Sodium silicate (NazO:5iO2=1:
2.4 475% solution of 7.48) Monostearyl phosphate 0.16
Dowfax 3B-20,37 Thermphos NW
12jDThermphos N hexa
12.0 Aluminum tristearate 0.1 Anhydrous sodium carbonate
4.9 Caustic soda solution (381NaOH
) 3.0Pharma1qel Ex
Uroclay (Silicon #Mg7'Al clay)
1.25 Sodium hypochlorite solution (1
1ch) 1.0 water
Remaining pH = 12.5-12.9 Small amounts of perfumes, colorants, etc. may also be added to the formulation.

Claims (22)

[Claims] (1) Approximately by weight: (a) 5 to 35% alkali metal tripolyphosphate; (b) 2.5 to 20% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) A water-dispersible organic detergent active material that is stable to 0.1 to 5% chlorine bleach. (e) 0 to 5% of a chlorine bleach stable foam suppressor; (f) a chlorine bleach compound in an amount to provide about 0.2 to 4% available chlorine; (g) about 2 to 10% of a chlorine bleach compound present in the composition; (h) 0 to 3% sodium hydroxide; (i) an amount effective to increase the physical stability of the composition; 1. An aqueous thixotropic automatic dishwasher composition comprising: a polyvalent metal salt of a long-chain fatty acid as a chemical stabilizer; (j) the balance being water. 2. The composition of claim 1, wherein the physical stabilizer (i) is a polyvalent metal salt of a fatty acid of about 8 to 22 carbon atoms. 3. The composition of claim 2, wherein the acid has about 12 to 18 carbon atoms. (4) Polyvalent metals are IIA, IIIA, and IVA of the periodic table of elements.
3. The composition of claim 2, wherein the metal is a metal selected from any of Groups VIII, VA, VIIA, IIB, IIIB, IVB, VB and VIII. (5) Polyvalent metal is Mg, Ca, Ti, Zr, V, Nb
, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi,
5. The composition of claim 4, wherein the composition is selected from the group consisting of Al and Zn. (6) The composition according to claim 2, wherein the physical stabilizer (i) is an aluminum or zinc salt of the acid. (7) The composition according to claim 1, wherein the physical stabilizer (i) is aluminum tristearate. (8) The composition according to claim 1, wherein the physical stabilizer (i) is zinc distearate. (9) The amount of physical stabilizer (i) present is about 0.02 to 1
%. (10) The composition of claim 1, wherein the amount of physical stabilizer (i) present is about 0.06 to 0.8%. (11) The composition of claim 1, wherein the amount of physical stabilizer (i) present is about 0.08 to 0.4%. (12) The composition of claim 1, wherein the thixotropic thickener (g) is an inorganic colloid-forming clay. (13) The composition according to claim 12, wherein the clay is montmorillonite clay, attapulgiaite clay, hectorite clay or smectite clay. 14. The composition of claim 12, wherein the amount of clay thickener ranges from about 0.1 to 3%. 15. The composition of claim 12, wherein the amount of clay thickener ranges from about 0.5 to 2.2%. (16) Claims containing about 0.1 to 0.2% physical stabilizer (i) and about 0.5 to 2% by weight inorganic colloid-forming clay as thixotropic thickener (g) Composition according to item 6. (17) about 0.3 to 0.4% physical stabilizer (i) and about 0.25% thixotropic thickener (g);
Claim 6 contains an inorganic colloid-forming clay of
The composition described in Section. (18) The composition according to claim 1, wherein the chlorine bleach compound (f) is sodium hypochlorite. (19) The composition according to claim 1, which contains about 0.1% by weight or more of a foam inhibitor. (20) Foaming inhibitor is 1 or 2 C_1_2_
The composition according to claim 19, which is a phosphoric acid partial alkyl ester or alkylphosphonic acid ester containing -_2_0 alkyl groups or a mixture thereof. (21) The composition according to claim 1, which has a pH of about 10.5 to about 13.5. (22) Cleaning soiled dishes in an automatic dishwashing machine comprising contacting the soiled dishes in an automatic dishwashing machine with an aqueous cleaning bath in which an effective amount of the composition according to claim 1 is dispersed. how to.