JPH0243300A - Aqueous thixotrope liquid composition - Google Patents

Abstract

The physical stability of liquid gel-like compositions based on montmorillonite, attapulgite, hectorite or other inorganic colloid-forming clay or other thixotropic thickener, and small amounts, such as 0.1 to 0.2 weight percent, of calcium, magnesium, aluminium or zinc stearate or other polyvalent metal salt of long chain fatty acid is greatly improved by increasing the alkalinity level to such an extent that when the composition is added to an aqueous wash bath at a concentration of about 10 grams per liter the pH of the wash bath becomes at least 11.2. The aqueous compositions preferably also includes chlorine bleach, and the chlorine-bleach loss with time is also reduced in the high alkalinity formulations. Use as liquid gel-like automatic dishwasher compositions are described.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a built-in aqueous liquid detergent composition for automatic dishwashing transport that has improved cleaning performance and physical stability.

More particularly, the invention describes the use of high alkalinity levels to improve the cleaning performance and rheological properties of concentrated liquid automatic dishwashing detergent compositions stabilized by long chain alkyl fatty acids (and their metal salts). Regarding.

BACKGROUND OF THE INVENTION The present invention particularly has thixotropic properties, improved chemical and physical stability and increased apparent viscosity.
The present invention relates to automatic dishwasher detergent compositions that are easily dispersed in cleaning media and exhibit improved cleaning performance for dishes, glassware, china, and the like.

Commercial household automatic dishwashing detergents, which are available in powder form, have, for example, a non-uniform composition; their production requires expensive operations; a tendency to cake during storage in high humidity conditions; It has disadvantages such as: it produces clumps that are difficult to disperse; it is dusty, a particular source of irritation for users with allergies, and it has a tendency to cake in the dishwasher dispenser. However, liquid forms of such compositions generally cannot be used in automatic dishwashers.

Recent research and development efforts have focused on compositions in gel or thixotropic form, such as, for example, abrasive cleansers and automatic dishwasher formulations featuring thixotropic pastes. The dishwasher formulation thus provided is
The first problem is that the viscosity is insufficient to "stagnate" in the dishwasher's dispensing cup. Thixotropic detersive compositions should ideally be highly viscous at rest, i.e. of Bingham plastic nature, and should have relatively high yield values, e.g. when shaken in a container. When subjected to shear stress, such as squeezing through an orifice, the composition rapidly fluidizes and quickly returns to its highly viscous/Bingham plastic state upon cessation of the applied shear stress. Stability is of fundamental importance as well, ie, there should be no significant signs of separation or leakage in the molds stored for long periods of time.

Automatic dishwashing compositions in the form of gels having the above-mentioned properties have therefore proven problematic, particularly for compositions used in domestic dishwashers. In order to effectively use automatic dishwasher detergent, hereinafter abbreviated as ADD, this (
1) Sodium tripolyphosphate to soften or bind hard water minerals and emulsify and/or decoagulate stains; 2) Provide the alkalinity necessary for effective cleaning and improve the luster and pattern of delicate porcelain. (3) Sodium carbonate, generally considered optional, to increase alkalinity; (4) Chlorine release agents useful in removing soil stains that result in water stain formation; and (5
) It is generally desirable to include an antifoam/surfactant to reduce foaming, thereby increasing dishwashing maneuverability and providing the necessary cleaning power. For example, Totus Opal (Tbo)
mas O1+erle)'s SDA detergent details, ``Dishwasher detergent problem<Formulati.

ns Aspect or Macl+ine
(1974), cleaning agents similar to the above compositions are mostly liquids or powders. It has proven difficult to combine such ingredients into a gel form that is effective for domestic dishwashers. Generally, such compositions do not use hypochlorite bleach because the bleach contains other chemically active ingredients,
This is because they tend to react particularly with surfactants.

Accordingly, U.S. Pat. No. 4,115,308 uses a suspending agent (
A thixotropic automatic dishwashing line paste is disclosed which contains: inorganic salts including silicates, phosphates and polyphosphates; small amounts of surfactants and foam suppressants. Bleach not disclosed, U.S. Pat.
No. 147,650 discloses a somewhat similar detergent that optionally contains Cβ-(hypochlorite) bleach but no organic surfactants or suds suppressants. Additionally, this formulation is described as a detergent slurry with no apparent thixotropic properties.

U.S. Pat. No. 3,985,668 discloses the use of (1) suspending agents, preferably clays of the smectite and apurgite type; (2) abrasives such as silica and burlite; and (3) low density It is composed of a powdered polymer such as expanded perlite, which is buoyant and serves as a bulking agent, as well as having a stabilizing effect on the composition, thereby reducing the amount of water that can be used to form an undesirable supernatant layer due to leakage or phase instability. An abrasive cleanser with a gel-like consistency is described that alternatively contains fillers. Said ingredients are essential ingredients. Optional ingredients include hypochlorite bleaches, bleach-stable surfactants and buffers such as silicates, carbonates and -phosphates, and are not provided by buffers. Builders, such as NaTPP, may also be included as optional ingredients in the pond to provide or supplement detergency-enhancing functionality, and the amount of such builder may be, according to this patent,
Not more than 5% of the total composition. Preferred 9H10 level (
Maintenance of the above) is achieved by the M buffer/builder component. A high pH is said to minimize degradation of chlorine bleach and undesirable interactions between surfactants and bleach. If NaTPP is present, this amount is limited to 5% as described above. Antifoaming agents are not disclosed.

UK Patent Application Nos. 2.116.199A and 2.140
, No. 450A [Both Colgate Balmolib (Co
disclosed a liquid ADD composition having properties favorably characterizing a thixotropic gel-like structure and containing various components necessary for effective cleaning in automatic dishwashing machines. ing. Typical gel-like aqueous automatic dishwashing detergent compositions with thixotropic properties consist of the following components by weight: (a) 5-35% alkali metal tripolyphosphate; (b)
Sodium silicate 2.5-20%; (c) Alkali metal carbonate 0-9%: (cl> Chlorine bleach-stable, water-dispersible organic detergent active substance 0.1-5%; (e) Chlorine bleach stable foam inhibitor 0-5% (f)
a chlorine bleach compound in an amount capable of releasing about 0.2 to 4% available chlorine; (g) a thixotropic enhancer in an amount sufficient to give the composition a Chickentropy Index of about 2.5 to 10; Contains a viscous agent; (b) sodium hydroxide as needed to adjust pH; and (i) a remainder of water.

The ADD compositions formulated in this way have low foaming properties; they dissolve easily in the cleaning medium and are most effective at pH values that are most conducive to improving cleaning performance, i.e., pH 10.5-14. The material is usually a highly viscous, opaque, jelly-like material with a gel consistency, ie, Bingham plasticity and relatively high yield values. Therefore, a certain shear force is required to initiate or increase flow. Under such conditions, the composition fluidizes quickly and easily disperses. When the shear force is discontinued, the fluid composition quickly returns to a highly viscous Bingham plastic state that closely approximates its previous consistency.

U.S. Patent No. 4,511,487 (April 16, 1985)
(date) describes a low-foaming detergent paste for dishwashing lines. This patented thixotropic detergent was determined by a rotational viscometer at a spindle speed of 5 revolutions per minute.
It has a viscosity of at least 30 Pa,.S at 20°C. The composition comprises finely divided hydrated sodium metasilicate;
It is based on a mixture of active chlorine compounds and a thickening agent which is a thin layer silicate of the hectorite type. Small amounts of nonionic surfactants and alkali metal carbonates and/or hydroxides may also be used.

Although these hitherto disclosed liquid ADD compositions have none or only a mild degree of one or more of the above deficiencies,
In practical practice, it has been found necessary to further improve the physical properties in order to extend the shelf life of the formulation and thereby increase user acceptance.

In commonly assigned co-pending application no. 903,924, filed September 5, 1986, the disclosure of which is hereby incorporated by reference in its entirety, several of the inventors of the present Thixotropic aqueous liquid AD as main ingredient
In order to improve the physical stability and rheological properties of the D composition, the use of small amounts of fatty acid metal salts such as aluminum stearate as anti-settling agents is mentioned.

Although this prior application discloses alkalinity levels for providing LADD compositions having a pH value of at least 9.5, preferably at least 12.5, in actual practice the pH level of these compositions is For example, the compositions illustrated in the examples of patent application Ser. 2
．． 2% or 3.1% by weight caustic soda solution (50% by weight)
%NaOH). However, approximately 1
When added at a typical concentration level of 0 g//, the wash bath should have a pH below 11, such as 10.9.

While these prior art compositions have improved physical stability and acceptable cleaning performance, it was desired to have even improved cleaning performance.

To this end, the inventors determined the alkalinity level of liquid ADD compositions containing clay/fatty acid salts in Application No. 903.
As disclosed in No. 324, I thought of increasing it.

Quite surprisingly, it has been discovered that increasing the alkalinity not only favorably improves the cleaning performance, but also unexpectedly and significantly improves the stability of the rheological properties to changes over time. It has also been discovered that at high alkalinity levels the available chlorine loss of chlorine bleach-containing compositions is substantially reduced, which was also quite surprising.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide liquid ADD compositions with improved cleaning performance, physical stability and rheological properties.

Furthermore, it is an object of the present invention to provide a chlorine bleach-containing liquid ADD composition with reduced loss of available chlorine over time.

More specifically, the cleaning performance and physical stability of aqueous liquid automatic dishwashing detergent pastes or gels containing suspended particles (e.g., builder salts, bleach, etc.), clay thickeners, and fatty acid metal salt stabilizers. It is an object of the present invention to improve.

(Means for Solving the Problems) As will be easily understood from the following detailed description of the present invention and its preferred embodiments, the object of the present invention is to provide a physical stabilizer that is a long chain fatty acid metal salt. a highly alkaline clay thickening builder-containing aqueous liquid automatic dishwasher containing an alkaline compound such that when the composition is added to the aqueous washing bath at a concentration of 10 g/l, the pH of the washing bath is at least 11.2. This is achieved by a machine detergent composition. In a preferred implementation R, the composition further includes a chlorine bleach compound, which reduces the loss of available chlorine during storage due to high alkalinity levels.

According to a particularly preferred embodiment of the invention, the invention comprises the following components by weight: (a) 5-35% alkali metal tripolyphosphate (b)
Alkali gold silicate 52.5-30%.

(c) 0-9% alkali metal carbonate; (d) 2-10% alkali metal hydroxide; (e) 0.1-5% chlorine bleach-stable, water-dispersible organic detergent active.
: <n chlorine bleach stable foam inhibitor 0-5%; (g)
Chlorine bleach compound in an amount releasing about 0.2-4% available chlorine: (h) 0.1-10% inorganic colloid-forming clay: (i>
a long chain fatty acid metal salt in an effective amount to enhance the physical stability of the composition; and (j) with a balance of water, (1+) sodium silicate, (c) an alkali metal carbonate, and (d) hydroxide. The pH of the aqueous wash bath is at least 1 when the alkali metal is diluted to a concentration of 10 g/l in the aqueous wash bath.
To provide a thickened aqueous automatic dishwasher detergent composition that provides a sufficiently high pH of 1.2.

The present invention also provides the liquid automatic dishwasher detergent (LAD) described above.
D) Providing a method of washing dishes in an automatic dishwasher with an aqueous wash bath containing an effective amount of the composition According to this aspect of the invention, the LADD composition is readily incorporated into the dispensing cup of an automatic dishwasher. It is pourable and sufficiently viscous to remain stagnant within the dosing cup until shear force is applied again, such as by water spray from a washer.

LADD effectiveness is directly related to (a) available chlorine level; (b) alkalinity; (C) solubility in the washing medium; and (d) suds control. Therefore, the pH of the LADD composition
is at least about 9.5, most preferably at least about 1
2.5. Prior application No. 903
, 924, about 0.5 NaOH in the LADD composition.
An amount of ~6% by weight and an amount of about 2-9% by weight of sodium carbonate has been suggested.

According to the present invention, the type and amount of the alkaline component is such that when the composition is added to the aqueous wash bath at a concentration of Composition 101F per wash bath 11, the pH of the wash bath is at least 11.2, preferably at least 11. .5, for example 11
．． By cleaning at such levels, which are higher than normal alkalinity levels, the cleaning performance is improved and at the same time the rheological Properties and especially physical stability are also improved. Additionally, preferred embodiments that include chlorine bleach compounds in LADD compositions also have the added benefit of reduced loss of available chlorine.

To obtain such high pH levels, it is necessary to increase the total concentration of alkaline components compared to the levels actually used in LADD compositions known in the prior art. Such a composition is shown as Example 4 of our prior application no.
T hermphos) NW Thermphos N 1lex
a Aluminum tristearate anhydrous sodium carbonate caustic soda solution (50$ Na0II) 0.16 2 0.36 12.0 12, O 5,0 3,1 Sodium hypochlorite solution (h$) 1.0 Water balance pH 13-13.4 In this Example 4, the amount of sodium hydroxide was 2.2% by weight.
(1,1 wt.% a,i,) to 6.2 wt.% (3,1 wt.% a,i,) and correspondingly reduced the amount of make-up water, increasing the sodium carbonate level and sodium metasilicate. 5, Oz and 15.74$ without changing the level respectively.
(7,48$a, i,).

Testing of cleaning performance and rheological behavior of Example 4 showed that these compositions of Example 4 were compared to the control composition (caustic soda solution 2).
．． 2% by weight). However, when tested for available chlorine content, the control composition was slightly better than the Example 4 composition. In contrast, when highly alkaline compositions according to the invention are prepared by reducing the sodium carbonate and increasing the caustic soda concentration, the cleaning performance and rheological properties are not only improved;
Available chlorine content loss was also substantially reduced compared to the control composition. Similarly, the use of additional alkali metal silicates in place of Na 2 CO 3 also reduced available chlorine loss, improved cleaning performance, and stabilized rheological properties.

Accordingly, in a particularly preferred embodiment of the invention, the alkaline compound contains 3 to 20 ffij 1% of the alkali metal geate, 1% of the alkali metal hydroxide, on an activity basis based on the total group of acids.
．． 0 to 45% by weight and 0 to about 4% by weight of alkali metal carbonates.
provided that the total amount of alkali metal hydroxide and alkali metal carbonate is about 65% by weight or less, the total amount of alkali metal silicate and alkali metal carbonate is about 20% by weight or less, and the pH of the composition is is at least 12.8, and the pH of the aqueous cleaning bath 11 containing 10 g of the composition is at least 11.
．． In a clay-thickened, fatty acid salt-stabilized chlorine bleach-containing liquid automatic dishwashing detergent composition as in No. 5,
High alkalinity is obtained.

The alkali metal of the alkaline compounds, i.e. silicates, carbonates and hydroxides, is preferably sodium, although mixtures of the corresponding potassium or sodium salts can also be used.

Sodium silicate, which provides alkalinity and protects hard surfaces, such as the luster and patterns of delicate pottery, is about 2.5 to 2
0 weight? ≦, preferably used in the composition in an amount within the range of 5 to 15% by weight. Sodium silicate is Na2O:S
It is generally added as an aqueous solution with an iO2 ratio in the range of about 1 + 1.3 to 1:2.8, particularly preferably 1:20 to 1:2.6. In this regard, it should be mentioned that most of the other components of the invention, especially NaOH and sodium hypochlorite, are also often added as pre-prepared aqueous dispersions or solutions.

The liquid dishwasher detergent compositions of the present invention generally also include an alkali metal phosphate detergency enhancing builder, such as sodium tripolyphosphate (NaTPP), which also contributes to the pH of the composition.

Preferred NaTPP is used in the LADD composition in a range of about 8-35% by weight, preferably about 20-30% by weight, which does not degrade or inhibit the preferred sodium hypochlorite, other chlorine bleach compounds. Preferably, it does not contain heavy metals that tend to be activated. NaTPP is used as an anhydride or a hydrate including a stable hexahydrate, and the hexahydrate phase degree is approximately 10% by weight! ! It corresponds to a moisture content of 6 or more. Particularly preferred LAPP compositions are obtained, for example, when the weight ratio of anhydrous NaTPP to hexahydrate NaTPP is from 0.5:1 to 2=1, with values of about 1:1 being particularly preferred.

In addition to NaTPP detergency enhancement builder or NaTP
Other phosphorus or non-phosphorus inorganic or organic strong detersive builder salts may also be used in place of some or all of the P.

Examples of suitable detergency-enhancing builder sequestering agents are, for example, trisodium nitrilotriacetate, tetrasodium methylenediaminetetraacetate, sodium citrate, and their corresponding potassium salts. Tetrasodium birophosphate or tetrapotassium birophosphate may also be used. However, sodium tripolyphosphate 11 is particularly preferred where phosphorus-containing detergents are acceptable.

Foam suppression is important in order to increase the efficiency of a dishwasher and to minimize the destabilizing effects that can be created by the presence of excess foam within the dishwasher during use. By appropriate selection of the type and/or amount of the main foaming component of the detergent active, foam can be significantly reduced. Since the foaming degree depends to some extent on the hardness of the washing water in the washing machine, a preferable foaming suppression degree can be easily obtained by appropriately adjusting the proportion of NaTPP, which has a water softening effect.

However, it is preferred to include a stable suds suppressor in the chlorine bleach. Alkyl phosphonic R acid ester of the formula: 8O-P-It, and especially the formula: 110-P-011
Acidic R phosphate alkyl esters are particularly effective. In the above formula, one or both of the R groups of each type of ester independently represents a C12-C2° alkyl group.

It is also possible to use ethoxylated derivatives of the various types of esters, such as condensation products of 1 mol of ester with 1 to 10 mol, preferably 2 to 6 mol, particularly preferably 3 or 4 mol of ethylene oxide. Some examples of the above foam suppressants include, for example, the product S from Hooker.
There are also commercially available mixtures of both types or other chlorine bleach-stable types or warm mixtures of monoesters and diesters of the same type, such as the product LPKn 158 from AP and KN apsack. Can be used. Particularly preferred are mixtures of acidic mono-/di-C16C1B alkyl esters, such as, for example, acidic monostearyl/distearyl phosphate 1.2/1 esters and their condensation products with 3 to 4 mol of ethylene oxide.

When a foam inhibitor is used in the composition, the ratio is typically 0.1 to 5% by weight, preferably 0.1 to 0.5% by weight, and the detergent active ingredient (d)/foam inhibitor (e ) generally from about 10:1 to 1:1, preferably from about 5=1 to 1
・The range is up to 1. Other antifoam agents that can be used are the known silicones, such as those available from Dow Chemical.

Furthermore, it is an advantage of the present invention that many of the stabilizer salts, such as stearates (eg, aluminum stearate), are also effective as antifoam agents.

Compositions of the invention include, for example, dichloroiso-cyanurate, dichlorodimethyl handantoin or chlorinated TS.
Although chlorine bleaches such as P can be used, hypochlorites of alkali or supra-alkali metals such as potassium, lithium, magnesium and especially sodium are preferred. The composition may be modified, e.g. by excess hydrochloric acid, from composition 1.
Sufficient chlorine bleach should be included to release about 0.02 to 4.0% by weight of available chlorine, as measured by acidifying 0.00 parts. Sodium hypochlorite approximately 0.2-4
．． Solutions containing 0% by weight contain or release approximately the same percentage of available chlorine. Available chlorine approximately 0.8-1.6ffi%
is particularly preferred. For example about 3-20%, especially about 7-12%
It is advantageous to use a sodium hypochlorite (N ao Cf) solution containing from about 11 to about 13% available chlorine in an amount of %.

Detergent actives useful here must be stable in the presence of chlorine bleaches, especially hypochlorite bleaches, and must be organic anionic, water-dispersible amine oxides, phosphine oxides, sulfoxides or betaines. Detergent actives of the surfactant type are preferred, the first-mentioned anionic actives being most preferred. These are about 0.1-5%, preferably about O
1-2. It is used in amounts within the range of Oz. The most preferred surfactants in this case are linear or branched mono- and/or di-(C11-C1,) Alkyl, diphenyl oxide sulfate and/or diTiRM alkali metal.

Additionally, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include primary alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates and secondary alkyl sulfates, for example sodium dodecyl sulfate and sodium tallow alcohol sulfate. , C1,) to C5, sodium alkyl sulfates: C, -''-C, such as e.g. sodium hexadecyl-1-sulfonate, sodium alkanesulfonates and C12 to C1s alkylbenzene sulfones such as e.g. sodium dodecylbenzenesulfonate. The corresponding potassium salt is also used.

Amine oxide surfactants as other suitable surfactants or detergents typically have the structure R2R'N-0. In the formula, each R represents a lower alkyl group such as methyl,
R1 represents a long-chain alkyl group with 8 to 22 carbon atoms, such as a lauryl, myristyl, palmityl or heptyl group; instead of the amine oxide, the corresponding surfactant phosphine oxide R2RI PO:if,) 'r
SYF RR' SO can be used. Betaine surfactants are typically
Specific examples of these surfactants include lauryl dimethylamine oxide, myristyl dimethylamine oxide, the corresponding phosphine oxy The alkyl groups of these surfactants are readily available for biodegradability, including trichloride and sulfoxide, and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldiethylammonium 11-pentanoate, hexadecyldimethylammonium hexanoate, etc. It is calm,
Such compounds are preferred.

Surfactants of the above type, all of which are well known in the art, are described, for example, in U.S. Pat.
It is stated in No. 30.

Thixotropic thickeners, i.e., suspending agent thickeners that impart thixotropic properties to aqueous media, are well known in the art and can be organic or inorganic water-soluble or water-dispersible or colloid-forming, monomeric or polymeric. , should of course be stable in these compositions, e.g. to high alkalinity and to chlorine bleaches such as e.g. sodium hypochlorite. Particularly preferred thickeners generally include inorganic colloid-forming clays of the smectite and/or attapulgite type. These materials are generally used in amounts of about 0.1 to 10% by weight, preferably 1 to 5% by weight to provide the desired thixotropy and Bingham plasticity. However, in the presence of fat/metal salt stabilizers, the desired thixotropy and Bingham plasticity can be obtained by the presence of small amounts of thixotrope thickeners, e.g. 0.1-3%, preferably 0.1-0. .5%
, Special G, :10.1~2! Amounts of inorganic colloid-forming clays of the smectite and/or attapulgite type within the range of are generally sufficient to obtain thixotropic properties and Bingham plasticity when used in combination with physical stabilizers.

Smectite clay is montmorillonite (bentonite)
, including hectorite, smectite, sabonite, etc.
Preferred is montmorillonite clay, which is a thixogel (
TI+ixogel (registered trademark) No. 1 and Gelwhite (registered trademark) G P
,H.

etc. under the product name of Josiah Kaolin Company (G
Eorgia Kaolin Company) and Rutherne Clay Products (Luthern Clay Products) under the trade names ECCAGUM® GP, H, etc.
available from ClayProdncts). Attapulgite clay has the trade name Attagel (A t
tagelH (registered trademark)), that is, aftergel 40. Attagel 50 and Attagel 150 are manufactured by Engelhard Minerals and Gercals Corporation.
nd Cl+emicals Corporation
). Mixtures of smectite and attapulgite types in weight ratios from 4.1 to 1.5 are also useful in this case. Abrasives or eluents are used for delicate tableware,
Since there is a risk of leaving an island on the surface of the crystal, etc., use LA.
Its use in DD should be avoided.

Preferred long-chain fatty acids have about 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, including the carbon of the carboxyl group of the fatty acid.
Especially preferred are higher aliphatic fatty acids having 12 to 18 carbon atoms. Aliphatic radicals can be saturated or unsaturated and straight or branched. Straight chain saturated fatty acids are preferred.

For example, fatty acids of natural origin, such as tallow fatty acids, coconut oil fatty acids, soybean fatty acids, etc., or fatty acid mixtures, such as fatty acids of natural origin obtainable from industrial manufacturing processes, can be used.

Therefore, examples of fatty acids from which polyvalent metal salt stabilizers can be prepared include, for example, decanoic acid, dodecanoic acid, valmitic acid,
These include acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut oil fatty acid, and mixtures of these acids. Stearic acid and mixed fatty acids are preferred.

Preferred metals are those of Group 11A of the Periodic Table of the Elements, such as magnesium, calcium, aluminum and zinc;
Polyvalent metals of Group 1 IB and Group 11 [B, but
Polyvalent metals can also be used, including Group 1IA, Group 1VA, Group VA, Group 1B, Group 1VB, Group VB, Group VIB, Group IB, and Group 1 metals.

Special examples of such polyvalent metals are Ti, Zr, V, Nb
Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi
etc.

Finally, metals exist in divalent to pentavalent states. It is preferred to use metal salts with their high oxidation potential. L.A.D.D.
For compositions and for applications such as those that come into contact with objects used in the handling, storage or presentation of food or that come into contact with or are consumed by people or animals, metal salts may be used to reduce the toxicity of the metal. should be selected taking into consideration. For this application, calcium and magnesium salts are particularly preferred as generally safe food additives.

Many of these metal salts are commercially available. For example, aluminum salt is aluminum tristearate Al<C17H
6-acid salts (e.g. aluminum stearate), diacid salts (e.g. aluminum nistearate) or ~ acid salts, diacid salts and 2-) or a mixture of three diacids is used as a metal such as A[ having a valence of +3; It is used as km such as Preference is given to using major amounts of diacids of divalent metals, diacids of trivalent metals, tetraacids of +4 metals and diacids of +5 metals.

The above metal salts are generally commercially available, but include, for example, the generation of fatty acids (e.g., tallow fatty acids), treatment with hydroxides or oxides of polyvalent metals, and treatment with alum, alumina, etc. in the case of aluminum salts. or by reaction of soluble metal salts and soluble fatty acid salts.

Calcium stearate, or calcium nistearate, magnesium stearate, or magnesium nistearate: Aluminum stearate, or aluminum tristearate, and zinc stearate, or zinc nistearate, are the preferred polyvalent metal fatty acid salt stabilizers.

Naturally occurring acids, such as coconut oil acid, as well as mixed fatty acid metal salts, such as mixed fatty acids resulting from commercial manufacturing processes, are also advantageously used as inexpensive and readily available sources of long chain fatty acids.

The properties of fatty acid salt stabilizers that favorably enhance physical stability are determined by the properties of the fatty acid salts, the properties of the fatty acid salts, the detergent actives, the inorganic salts, the NaTPP, the nature and amount of the LADD components, and the expected It depends on factors such as storage and transportation.

However, in general, the polyvalent metal fatty acid salt stabilizer is about 0.02~
U, preferably in the range from about 006 to 0.8z, particularly preferably from about 008 to 0.4 or ensure that there is no phase separation during transport.

Depending on the amount, proportion and type of physical stabilizer and thixotropic agent, the addition of fatty acid salts not only increases the physical stabilizer but also increases the apparent viscosity at the same time. Fatty acid salt approx. 0
．． 08-0.4 weight 1% and thixotropic agent about 1-2.5
Since a ratio of fatty acid salt/thixotropic agent within a weight percent range is usually sufficient to provide these simultaneous benefits, the use of these ingredients in such a ratio is most preferred.

The amount of water included in these compositions should of course not be so high as to cause unduly low viscosity and flowability, nor so high that either shrinkage or decomposition results in unduly high viscosity, low flowability and thixotropy. Such an amount should not be lower, and is easily calculated by routine experimentation where ↑ν is - most preferably about 30-75% by weight, preferably tL< about 3
It is 5 to 65% by weight. The water should preferably be deionized or softened.

According to a preferred method of preparing these compositions, first all inorganic salts, namely carbonates (if used), silicates and tripolyphosphates, are dissolved or dispersed in an aqueous medium.Finally, the thickener is added. The foam inhibitor (if used) is prepared in advance as an aqueous dispersion, as is the thickener.

Foam suppressant molecule j! Bleach, surfactant, Add the fatty acid metal salt stabilizer and thickener dispersion to the cooled solution (25-35°C).

Total salt concentration (NaTPP, excluding chlorine bleach.

Sodium silicate and sodium carbonate) generally comprise about 20 to 50% by weight, preferably about 30 to 40% by weight of the composition.
%.

Another highly preferred method of mixing the components of the LADD'fJ agent is to first form a mixture of water, suds suppressor, detergent, physical stabilizer (fatty acid salt) and thixotrope 7FIJ (eg, clay). These components are mixed together under high shear conditions, preferably at room temperature with stirring, to form a homogeneous dispersion. The pond components are introduced into this premix section under low shear mixing conditions. For example, add the required amount of premix to a low shear moisture automachine and then add the remaining ingredients sequentially or simultaneously while mixing. Although it is preferred to add the ingredients continuously, it is unnecessary/necessary to complete the addition of the entire first portion before beginning the addition of the next ingredient. Furthermore, one or more ingredients are divided into small amounts,
Can be added at different times.

The remaining ingredients are combined in the following order: sodium hydroxide, alkali metal carbonate, sodium silicate, alkali metal ribolyphosphate (water-damaged), alkali metal tripolyphosphate (anhydrous or up to 3% water), bleach (preferably Good results have been obtained by adding sodium chlorite) and sodium hydroxide in this order.

Other conventional ingredients, such as perfumes; hydrotropes such as sodium benzene, toluene, xylene and cumene-sulfonates, preservatives, dyes, pigments, etc., generally in small amounts, generally less than about 3% by weight; can be included in these compositions, all of which are naturally stable to chlorine bleach and high alkalinity (the nature of all ingredients).

Chlorinated phthalocyanines and aluminosilicate polysulfides, which give the preferred green and blue tints, respectively, are particularly preferred as colorants; TiO□ can be used to neutralize whitening or color shifts.

The liquid LADD #1 compositions of the present invention can be used in a suitable manner using an aqueous wash bath containing an effective amount of the composition, generally sufficient to fill or partially fill the self-dosing cup of the particular dishwasher being used. In an automatic dishwasher with a detergent dispenser, it can be easily used in a known manner for washing dishes and other kitchen utensils alike.

Although the invention can be carried out in various ways, it will be illustrated by some specific embodiments with reference to the following examples.

All proportions stated herein are by weight of the composition unless otherwise indicated.

Takumi-1 Liquid LAD stabilized with fatty acid metal salts and thickened with clay
To demonstrate the effect of alkalinity in Composition D, the compositions shown in Table 1 are prepared with varying amounts of alkaline compounds.

In making these compositions, add the monostearyl phosphate foam suppressor and Dowfax 3B-2 detergent active to the warm just before adding the Pharmaglu H clay thickener; add all NaOH after the clay. .

Cleaning performance of the produced liquid LADD composition shown in Table 1 (1st
Table), density and physical stability (phase separation) during storage and transport tests. The results are shown in Table III.

1) Commercially available powder ADD, pl-1=12.22)
A plate with rice adhered to it and a cutter with rice and borage adhered to it (the control composition and the compositions of Run No. 3. No. 5 were heated at 4°C.
Aging at room temperature (RT), 35°C or 43°C;
Measure the viscosity of each sample in a plastic bottle.1.4.
Brookfield LVT after 6 and 12 weeks storage
Measured with a viscometer at 3 rpn using a No. 54 spindle. The results are shown in Table IV.

Concave-1 Control composition, compositions of runs No. 3 and No. 5, and a reference example in which the aluminum stearate of the control composition was omitted and the clay amount was increased to 2% were tested and kept at room temperature for 10 days. Q. The rheological properties were measured after standing for 6 weeks and 3 months, and the results are shown in Table V.

Residual available chlorine levels after storage for 2, 4° or 12 weeks at room temperature, 35°C and 43°C using the Shin-2 V control composition and the composition of Run No. 1.3.5. It was measured.

The results are shown in Table ■.

Claims (1)

[Claims] 1. An aqueous solution containing water, a clay thixotropic agent, an effective amount of at least one long chain fatty acid metal salt to enhance the physical stability of the composition, an organic detergent, a chlorine bleach, and a detergent builder. a thixotropic liquid composition, the composition comprising about 10
A composition comprising an alkali metal component and an alkaline earth metal component in an amount sufficient to provide a pH of at least 11.2 when added to 1 liter of water. 2. The metal salt is a polyvalent metal salt of a long-chain fatty acid with 8 to 22 carbon atoms or a mixture of two or more types of such fatty acids of a metal from Group II, Group III, or Group IV of the Periodic Table of the Elements. A composition according to claim 1. 3. The composition according to claim 1, wherein the polyvalent metal is aluminum, zinc, calcium or magnesium. 4. The composition according to claim 1, wherein the fatty acid metal salt is calcium stearate or magnesium stearate. 5. The following components (wt%): (a) Alkali metal tripolyphosphate 5-35%; (b)
2.5-30% alkali metal silicate; (c) 0-9% alkali metal carbonate; (d) 2-10% alkali metal hydroxide; (e) chlorine bleach-stable, water-dispersible organic (f) 0-5% chlorine bleach-stable foam suppressor; (g) chlorine bleach in an amount to release about 0.2-4% available chlorine; ( h) 0.1 to 10% of an inorganic colloid-forming clay; (i) a long chain fatty acid metal salt as a physical stabilizer in an amount effective to increase the physical stability of the composition; and (j) water. , the total amount of components (b), (c) and (d) is 10% of the composition.
An aqueous thixotropic dishwasher composition in an amount that provides a pH of the composition such that when diluted to a g/l concentrate, the pH of the water is at least 11.2. 6. The composition of claim 5, wherein the physical stabilizer (i) is a polyvalent metal salt of an aliphatic fatty acid having about 12 to 18 carbon atoms. 7. Polyvalent metal is Mg, Ca, Ti, Zr, V, Nb, M
n, Fe, Co, Ni, Cd, Sn, Sb, Bi, Al
7. The composition of claim 6, wherein the composition is a metal selected from the group consisting of Zn and Zn. 8. The composition according to claim 5, wherein the physical stabilizer (i) is an aluminum salt, zinc salt, magnesium salt or calcium salt of stearic acid. 9. The composition of claim 5, wherein the physical stabilizer is present in an amount of about 0.02-1%. 10. The composition according to claim 5, wherein the clay (h) is attapulgite clay or smectite clay. 11. The composition of claim 10, wherein the amount of clay (h) is within the range of about 0.1-3%. 12. The composition of claim 10, comprising about 0.1-0.5% by weight of the physical stabilizer (i) and 0.1-2% by weight of the colloid-forming clay (h). 13. The composition according to claim 5, wherein the chlorine bleach (f) is sodium hypochlorite. 14. The composition of claim 5, comprising at least about 0.1% by weight of suds suppressor (e). 15. The composition according to claim 14, wherein the foam suppressor is an acidic alkyl phosphoric ester, an alkylphosphonic ester having one or two C_1_2 to C_2_0 alkyl groups, an ethoxylation product thereof or a mixture thereof. 16. The amounts of components (b), (c) and (d) are such that when the composition is diluted to 10 g/l, the pH of the diluted composition is about 11.
6. The composition of claim 5, wherein the amount is such that the amount is between 5 and 13.5. 17. Contacting the soiled dishes with an aqueous wash bath having an effective amount of the composition of claim 5 dispersed therein in an amount sufficient to form a wash bath with a pH of at least about 11.2 in an automatic dishwasher. How to wash dirty dishes in an automatic dishwasher, consisting of: 18. In a method for improving the phase separation stability of a composition comprising a gel-like aqueous dispersion of at least one water-insoluble, finely divided detergent builder material, the dispersion comprises about 1 to 2.5 weights of a smectite clay thickener. % and Periodic Table of Elements Group IIA, I
Group IIA, Group IVA, Group VA, Group IB, Group IIB,
Long chain C_1_2 of polyvalent metal selected from Group IIIB, Group IVB, Group VB, Group VIB, Group VIIB and Group VIII
By adding about 0.08 to 0.4% by weight of the C_1_8 fatty acid metal salt, the composition has a viscosity at low shear of about 2 to 0.4% by weight, which is lower than the viscosity under low shear conditions of the composition without the long chain fatty acid metal salt. The viscosity of the composition under high shear conditions is approximately 1/2 to 1/2 times higher than that under low shear conditions.
10, wherein the composition comprises sufficient amounts of sodium hydroxide, sodium carbonate, and sodium silicate such that the pH of the water reaches at least 11.2 when about 10 g of the composition is added to 1 liter of water.