PT88563B - A process for the preparation of a thin-walled, non-orthophosphate-containing cleaning composition comprising a naphthol of aluminosilicate - Google Patents

Abstract

A no- or low- (less than 0.01%) phosphorus built aqueous liquid (e.g. automatic dishwasher) detergent composition is based on a mixture of aluminosilicate zeolite and a bleach-stable, water-soluble, carboxyl group-containing polymer, such as sodium polyacrylate, to achieve comparable cleaning performance to a phosphate built formulation. The preferred compositions which include inorganic colloid forming clay and aliphatic fatty acid or salt therof, are viscoelastic and physically stable against phase separation. The compositions contain alkali metal silicate and a chlorine bleach.

Description

relatively low pressure to achieve cleaning efficiency comparable to that of a structured phosphate formulation. Compositions that include inorganic colloid-forming clay and aliphatic fatty acid or a salt thereof, are viscoelastic and physically stable with respect to phase separation.

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The present invention relates to aqueous cleaning compositions for cleaning dishes, etc., especially in an automatic dishwasher. More specifically, the invention relates to compositions such as including any phosphate fillers but which provide comparable or superior cleaning performance compared to liquid detergent compositions containing phosphorus for automatic dishwashers.

The present invention relates specifically to thickened liquid detergent compositions for dishwashers, automatic having viscoelastic properties, improved chemical and physical stability, and with an increased cleaning performance (performance) despite the absence of phosphate filling agents and salts. rapidly dispersible in the washing medium to provide an effective cleaning of dishes, glassware, porcelain, etc.

Detergents for commercially available domestic dishwashers provided in the form of powders have several disadvantages, for example, non-uniform composition; expensive (expensive) operations necessary for its production; tendency at high humidity to form a mass when stored, resulting in the formation of agglomerates that are difficult to disperse; formation of dust, a source of particular irritation for users suffering from allergies; and tendency to form pasta in the dishwasher dispensing element. However, the liquid forms of these compositions cannot generally be used in automatic dishwashers due to high foaming levels, unacceptably low viscosity and excessively high alkalinity.

Recent research and development activities have focused on the gel or thixotropic form of these compositions, for example cleaning agents and products for automatic dishwashing polishing machines and products for machines characterized as thixotropic liquids or pastes. The dishwasher products thus provided are mainly inconvenient in that they are insufficiently viscous to remain anchored in the dishwasher dispensing element, and in addition they give rise to residual stains on dishes, glasses, porcelain, etc.

supply of compositions for automatic dishwashers in the form of gel having stability of supply and satisfactory cleaning properties has thus proved to be quite problematic, particularly with regard to compositions for use in domestic dishwashers, for effective use , it is generally recommended that the detergent for automatic dishwashers, hereinafter referred to as ADD, contains (1) sodium tripolyphosphate (NaTPP) to soften or fix minerals in hard water and to emulsify and / or peptize (digest) dirt; (2) sodium silicate to provide the alkalinity required for effective detergency and to provide protection against the gloss and pattern of fine porcelain; (3) sodium carbonate, generally considered optional, to increase alkalinity; (4) a chlorine-releasing agent to aid in the removal of small dirt stains that cause water to become soiled; and (5) antifoam / surfactant to reduce foam, thereby improving the efficiency of the machine and providing the necessary detergency. See, for example, SDA Depth Detergents, Formulations Aspects of Machine Dishwashing, Thomas Oberle (1974) The cleaning agents that approximate the compositions described above are mainly liquids or powders. Combining these ingredients in an effective thickened form for home machines proved difficult. Generally, these compositions omit the hypochlorite bleach, as it has a tendency

-5 to react with other chemically active ingredients, particularly surfactant, thereby degrading the suspending or thickening agent and impairing its effectiveness.

US Patent Na. 4,115,308 presents thixotropic pastes for automatic dishwashers containing a suspending agent, for example CMC, synthetic clays, etc .; inorganic salts including silicates, phosphates and polyphosphates; a small amount of surfactant and a soap foam depressant. A bleach is not indicated. On the other hand, U.S. Patent No. 3,684,722 has a thickened alkali metal hypochlorite cleaning and bleaching composition with mixtures of 0 _θ -0 ₁₈ alkali metal soaps and hydrotropes, such as amine oxide and betain. The patents describe tests in which various classes of organic polymer thickening agents were either unstable or otherwise failed to provide adequate thickening or resulted in loss of available chlorine. Polyacrylates have been found to provide thickening for several weeks at room temperature after which they decompose.

US Patent Ν ^θ 3,985,668 describes abrasive cleaning agents that give a gloss with a more or less gel consistency containing (1) suspending agent, preferably the types of smectite and atapulgite clay; (2) abrasive, for example silica sand or perlite; and (3) fillers comprising powdered polymers of light density, expanded perlite, etc., which have buoyancy and therefore a stabilizing effect on the composition in addition to serving as bulk (bulking) agents, thereby replacing otherwise available water for the undesirable formation of a floating layer due to water leakage and phase destabilization. The above are essential ingredients. Optional ingredients include hypochlorite bleach, stable surfactant and buffer, for example silicates, carbonates and monophosphates. Filling agents, such as NaTPP, can be included as other optional ingredients to provide or supplement the filling function not provided by the buffer, the amount of that filling agent not exceeding 5% of the total composition, according to the patent. The maintenance of the desired (greater than) pH 10 levels is achieved by those with buffer / filler components. It is said that a high pH minimizes the decomposition of the chlorine bleach and the unwanted interaction between the surfactant and the bleaching agent. When present, NaTPP is limited to 5%, as noted. An anti-foaming agent is not shown.

In UK Patent Application GB 2,116,199A and GB 2,140,450A, both assigned to Col ^ gate-Palmolive, compositions are indicated liquid ADD compositions (LADD) that have properties that desirably characterize the thixotropic, gel-like structure and that they have several ingredients necessary for effective detergency with an automatic dishwasher. The aqueous detergent composition for automatic dishwashers normally with a gel appearance having thixotropic properties includes the following ingredients, based on weight:

(a) 5 to 35% alkali metal tripolyphosphate;

(b) 2.5 to 20% sodium silicate;

(c) 0 to 9% alkali metal carbonate;

(d) 0.1 to 5% of active water-dispersible organic detergent material, stable in relation to the chlorine bleach;

(e) 0 and 5% stable foam depressant in relation to the chlorine bleach;

(f) chlorine bleaching compound in an amount that provides about 0.2 to 4% of the available chlorine;

(g) thixotropic thickening agents in an amount sufficient to provide the composition with a thixotropy index of about 2.5 to 10;

(h) sodium hydroxide, as needed, to adjust the pH; and (i) water.

LADD compositions thus formulated form little foam; they are quickly soluble in the washing medium and more effective at alkaline pH values. The compositions are usually of gel consistency, i.e. they are made of an opaque geliform material, highly viscous having a Bingham plastic character and thus showing relatively high yield values. Consequently, a defined shear force is required to initiate or increase the flow, such as that which would be obtained within the agitated supply element of an automatic dishwasher connected to the energy. Under these conditions, the composition is fluidized quickly and easily dispersed. When the shear force is interrupted, the fluid composition rapidly reverts to a high viscosity, with the plastic state of Bingham approaching close to its previous consistency.

U.S. Patent No. 2 -. 4,511,487 dated April 16, 1985, describes a low foaming detergent paste for dishwashers. The patented thixotropic cleaning agent has a rotary viscometer with a spindle speed of 5 revolutions per minute.

The composition is based on a mixture of hydrated sodium tripolyphosphate and hydrated sodium metasiliate, finely divided into a compound with chlorine and a thickening agent which is a laminated silicate of the hectorite type. Small amounts of nonionic tensioners and alkali metal carbonates and / or hydroxides can be used.

Recently, an applicant has developed several modifications and improvements in the liquid detergent compositions for GB 2.116.199A and GB 2.140.450A automatic dishwashers. For example, U.S. Ns. 816,835 discloses liquid cleaning compositions without polymer thickening agent without thixotropic clay with a gel aspect that use a mono- or polycarboxylic acid having 8 to 22 carbon atoms to provide physical stability and thixotropic properties.

In the copending application commonly assigned to the N2 Series 903.924, the physical stability of the liquid detergent positions for automatic dishwashers with thixotropin based on clay is improved by adding small amounts, for example about 0.02 to 1% by weight , of a polyvalent metal salt of a long chain fatty acid, such as aluminum stearate.

Most of these liquid and commercial dishwashing detergents presented and commercial and similar compositions depend on phosphate filling agents, such as sodium tripolyphosphate, to increase cleaning performance.

Although phosphate salts as fillers are highly effective for this purpose, their use has a major disadvantage: they are harmful to aquatic life and waterways in general. Indeed, many jurisdictions have already banned or are considering a general ban on detergent cleaning products containing phosphate.

Although there have been many attempts to provide alternative fillers and many such inorganic and organic non-phosphate detergent fillers are very few in practice, they are able in practice to provide cleaning advantages comparable to those of phosphate fillers. Furthermore, the selection of suitable fillers is even more difficult in the environment (in the vicinity) of the present aqueous compositions containing bleaching agent since the alternative filler must be compatible with the chlorine bleaching agent.

In addition to its function as a detergent filler, the inorganic alkali metal phosphate salt filler provides an important function in contributing to the rheological properties of thickened liquid thixotropic liquid detergent compositions such as those described above in GB 2,116.Í99A and GB 2,140,450A. Consequently, the replacement of a phosphate filler with a non-phosphate filler has not proved to be an easy task since so many different factors have to be taken into account in order to fulfill the multifunctional tasks of the phosphate filler.

Accordingly, it is a main object of the invention to provide weightless compositions containing aqueous bleaching agent that avoids the use of phosphate fillers and not containing or containing only environmentally tolerable levels of phosphorus from other sources.

It is another object of the invention to provide thickened liquid ADD compositions with no or little phosphate with improved physical stability and rheological properties.

It is yet another object of the invention to provide thickened liquid ADD compositions with no or low levels of phosphorus without adversely affecting or even improving cleaning performance (action, action), particularly weak stains and film formation.

These and other objects of the invention that will be more readily understood from the following detailed description of the invention and their preferred presentations are realized by means of an aqueous liquid composition for cleaning with little or no phosphorus comprising water, dispersible organic detergent in water, stable with respect to the chlorine bleaching agent, chlorine bleaching agent, alkali metal silicate and detergent filling agent, wherein the tergent filling agent comprises a mixture of stable zeolite aluminum and water-soluble polymer with respect to the bleaching agent containing a carboxyl group, or a salt thereof. More particularly, according to a preferred and specific presentation of the invention, a thickened liquid automatic washing machine detergent composition is provided which has no phosphate filler salts and which contains no or only low levels of phosphorus and which It is efficient for inhibiting the sedimentation of suspended water-insoluble particles, such as zeolite aluminum filler, whitening particles, etc. The composition can include clay or other thickening agents as well as other stabilizing agents and other conventional ADD additives.

In accordance with this particular aspect, the present invention provides a detergent composition for automatic dishwashers normally with a gel aspect having viscoelastic properties which include, on a weight basis:

(a) 5 to 35% of zeolite aluminum silicate;

(b) 25 to 40% sodium silicate;

(c) 0 to 9% alkali metal carbonate;

(d) 0.1 to 5% of active water-dispersible organic detergent material, stable in relation to the bleaching agent

-11to with chlorine;

(e) 0 to 5% of foam-depressant agent stable in relation to the chlorine bleaching agent;

(f) chlorine bleaching compound in an amount that provides about 0.2 to 4% of available chlorine;

(g) 0 to 5% of a long-chain fatty acid or salt thereof;

(h) 0 to 5% clay thickening agent;

(i) 0 to 8% sodium hydroxide; and (j) water for balance.

Also related to this specific aspect, the invention provides a method for cleaning dishes in an automatic dishwasher with an aqueous bath containing an effective liquid composition (LADD) quantity for automatic dishwashers. In accordance with this aspect of the invention, the LADD composition can be rapidly poured into the dispensing cup element of the automatic dishwasher and will be sufficiently viscous to remain safely inside the dispensing element until shear forces are applied, such as such as spraying water from the dishwasher, at which point the yield value of the composition will be exceeded and the composition will flow.

The invention will now be described in greater detail with a view to its specific presentations.

Taking into account the concerns about the environment that opposes the problem of the elutrification of lakes, rivers and other water courses attributed to the phosphorus deposition from detergents and other products in water courses, a great concern.

removing phosphates from detergent products.

However, attempts to replace the phosphate filler from liquid thixotropic compositions for automatic dishwashers of the type used by the signatory to this application and which typically include 0 to 3% clay thickening agent - usually smectite type who suffers swelling by water; 10 to 25% alkali metal silicate; 0 to 0.5% fatty acid stabilizer; small amounts of bleaching agents, detergent stable against the bleaching agent, antifoam agent stable against the bleaching agent, sodium carbonate, caustic soda, etc., and about 20 to 25% metal phosphate salt alkaline with detergent filling agent, resulted in loss of thixotropic properties and usually worsening cleaning performance (action). Although the exact mechanisms of disruption of rheological properties causing loss of thixotropin have not been fully elucidated, it appears that there is at least some interaction between the suspended phosphate filler particles and the other ingredients in the formulation, especially the clay and thickening agent the fatty acid or fatty acid salt stabilizer and this interaction contributes to the increase in the tension produced and the plastic viscosity of the composition.

The present invention is based on the surprising discovery that rheological properties and physical stability, i.e. resistance to phase separation, sedimentation, etc., similar to those existing in the previous aqueous liquid ADD compositions consisting of phosphates, can be achieved including in the composition zeolite aluminosilicate as an inorganic water-insoluble detergent filler mixed with a water-soluble polymer containing carboxyl group, stable with respect to the bleaching agent as a multifunctional rheological agent

-13e detergent filling agent and increasing the level of alkali metal silicate to more than 25% by weight. At the same time, improvements in performance (action) can be achieved in relation to stains and film formation (ie less stains and reduced film formation).

Although the compositions of the present invention do not have toxotropic properties, they have viscoelastic properties and have a yield point (the maximum stress in a shear stress curve versus shear rate) high enough that these compositions do not flow in the form exerted by the its own weight, this is gravitational forces. Thus, the compositions of the invention can easily be poured into an automatic dishwasher supply element and will not flow until a sufficiently high shear stress is applied, such as the force of the water jet hitting inside the dispensing element. during the dispersion cycle.

Of course, it is understood that when physical stability is not necessary for long periods of several weeks or months and when it is not necessary to provide a highly thickened solution, the high levels of silieate, the clay thickening agent and / or fatty acid or stabilizer of fatty acid can be omitted from the formulation without adversely affecting the cleaning performance (action) provided by the zeolite aluminum filler and by the polymer stable in relation to the water-soluble bleaching agent (or its salt).

The fillers which are useful here are water-insoluble aluminum aluminosicates, both crystalline and amorphous. Various crystalline zeolites are described in British Patent No. 1,504,168, U.S. Patent No. 4,409,136 and Canadian Patent Nos. 1,072,835 and 1,087,477, all of which are incorporated herein by reference for ί

-14these descriptions. An example of amorphous zeolites useful here can be found in Belgian Patent 835,351 and this patent is also incorporated herein by reference. Zeolites generally have the formula ^(M 2 ⁰⁾ x- ^(A1 2 ⁰ 3 ⁾ y ^{Si0 2 ^{) z- WH} 2 ° where X is 1, y varies between 0.8 and 1.2 and is preferably 1 , z varies between 1.5 and 3.5 or more and preferably between 2 and 3 and w varies between 0 and 9, preferably between 2.5 and 6 and M is an alkyl metal, preferably sodium or potassium, especially of preferably sodium. A typical zeolite is type A or has a similar structure, with type 4A being particularly preferred. Preferred aluminosicates have ion exchange capacities of about 200 ml equivalent per gram or more, for example 400 meq / g.

zeolite aluminosilicate filler may be present in the formulations in the same amounts that have been found useful for alkali metal phosphate fillers, generally varying between about 5 and 35 weight percent, preferably between about 20 and 30 percent by weight.

Water-soluble polymers stable with respect to the carboxyl group-containing bleaching agent useful herein include, for example, acrylic acid homopolymers and copolymers and their salts. These materials are generally commercially available and can be described as follows.

The polyacrylic acid polymers and their salts that can be used comprise water-soluble low molecular weight polymers having the formula

Rl _? 2 λ cc -Jr ₃ with J _n

wherein R ₁ , R ₂ and Rg may be the same or different and may be hydrogen, C 1 -C 4 lower alkyl, or combinations thereof; n is a number ranging between 5 and 250, preferably between 10 and 150, and most preferably between 20 and 100; and M represents hydrogen, or an alkali metal, such as sodium or potassium.

preferred substituent for M is sodium.

Preferred R ^, R ₂ and Rg groups are hydrogen, methyl, ethyl and propyl. The preferred acrylic monomer is one in which R ^ and Rg are hydrogen, for example acrylic acid, or when R ^ and Rg are hydrogen and Rg is methyl, for example methacrylic acid monomer.

degree of polymerization, i.e. the value of n, is generally determined by the limit compatible with the solubility of the polymer or copolymer in water. The terminal or end groups of the polymer or copolymer are not of critical importance and can be H, OH, CHg or a low molecular weight hydrocarbon.

Typically polyacrylic acid copolymers can include copolymers of, for example, acrylic acid or methacrylic acid and a polycarboxylic acid anhydride or acid, such as succinic anhydride, i

maleic, maleic anhydride, citric acid, etc. Copolymers of acrylic or methacrylic acid with maleic anhydride are preferred.

The monomer of acrylic acid or methacrylic acid comprises 40-60 weight percent, for example about 50 weight percent of the copolymer with a polycarboxylic acid or anhydrous.

Polyacrylic acid polymer can have a molecular weight (average weight) of 500 or 1,000 to 25,000, preferably 1,500 to 15,000 and especially preferably 2,000 to 10,000. Copolymers can have high molecular weights, for example, up to about 100,000.

Specific examples of polyacrylic acid polymers that can be used include the Acrysol LMW acrylic acid polymers from Rohm and Haas, such as Acrisol LMW-45NX, a neutralized sodium salt that has a molecular weight of about 4,500 and Aerysol LMW -20NX, a neutralized sodium salt, which has a molecular weight of about 2,000.

A specific example of a polyacrylic acid copolymer that can be used is Sokalan CP5 (from BASF) which has a molecular weight of about 70,000 and which is the reaction product of more or less the same moles of methacrylic acid and anhydride maleic which has been completely neutralized to form its sodium salt.

The above-mentioned polymers and copolymers can be produced by processes known in the art. See, e.g., U.S. Patent ^Nos. 4,203,858.

It has been found that polymers stable with respect to the bleaching agent containing water-soluble carboxyl group provide three primary functions in the liquid detergent compositions for automatic washing machines of this invention; rheological control; calcium isolation; and dispersion of dirt.

As a rheological control agent, the polymer additive apparently works as a thickening agent and together with the high levels of alkali metal silicate, clay (when present) and fatty acid or salt (when present), communicates viscoelasticity to the composition and a viscosity plastic varying between 200 and 10,000 centipioses, preferably 2,000 and 8,000 centipoises, that is 5,000 centipoises. The desired variations in viscoelasticity and plastic viscosity are best achieved when the polecular weight is not more than 10,000, especially between 2,000 and 10,000, that is, between about 4,000 and 5,000.

As a calcium insulating agent it is important that the polymer has an especially good water solubility. Here again, better results are achieved when the polymer has a molecular weight of 10,000 or less, especially between 2,000 and 10,000.

In a manner similar to that of an agent that disperses dirt contributing to the desired improvement of anti-stain and anti-film formation properties, the molecular weights of the polymer additive preferably range from 2,000 to 10,000.

The amount of polymeric additive or polyacrylic acid copolymer required to achieve the desired increase in physical stability and cleaning performance (action) will depend on factors such as the nature of the fatty acid or salt (when present), the nature and quantity of the clay thickening agent (when present), active detergent compound, bleaching agent,

-18as well as the planned storage and shipping (distribution) conditions.

Generally, however, the amounts of acrylic acid polymer or copolymer additive that can be used vary between about 0.5 and 10% by weight, preferably between about 0.80 and 8.0% by weight, especially of preferably between about 2 and 6 weight percent.

detergent active material useful here must be stable in the presence of chlorine bleaching agent, especially hypochlorite bleaching agent, and those of the surfactant type dispersible in water sulfoxide or betaine, phosphine oxide, amine oxide, organic anionics are preferred, most preferred are the anionics mentioned first. They are used in amounts ranging from about 0.1 to 5%, preferably between about 0.3 and 2.0%. The particularly preferred surfactants referred to herein are mono- and / or di- (C _Q -C ₁₄ ) mono and / or di- (C _Q -C ₁₄ ) alkaline metal alkyl commercially available, for example as DOWFAX (registered trade name) 3B-2 and DOWFAX 2A-1. In general, paraffin sulfonates tend to unduly increase viscosity causing shear strength problems. In addition, the surfactant must be compatible with the other ingredients of the composition. Other suitable surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates and primary sec-alkyl sulfates. Examples include C ₁₀ -Cq alkyl sodium sulfates, such as sodium dodecyl sulfate and sodium sebaceous alcohols; C ₁₀ -C ₁₈ sodium alkanesulfonates, such as sodium hexadecyl-1-sulfonate and sodium C 1 -C ₁₈ alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonates. The corresponding potassium salts can be used.

-19As with other suitable surfactants or detergents, amine oxide surfactants

-j typically have the structure R ₉ R NO, where R represents a lower alkyl group, for example, methyl, and R represents a long chain alkyl group of 8 to 22 carbon atoms, for example, a lauryl, myristyl group , palmityl or cetyl. Instead of an amine oxide, a corresponding phosphine oxide surfactant R ₉ R ¹ PO or sulfoxide RR ¹ SO can be used. Betaine surfactants typically have the structure R2R N - RCOO-, where each R represents a lower alkylene group having between 1 and 5 carbon atoms. Specific examples of these surfactants are Lauryl dimethylamine oxide, myristyldimethylamine oxide, the corresponding phosphite oxides and sulfoxides, and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexadecyl dimethylammonium hexanoate, etc. As for biodegradability, the alkyl groups in these surfactants must be linear, and these compounds are preferred.

Previous type surfactants, all well known in the art, are described, for example, in U.S. Pat. 3,985,668 and 4,271,030.

Although any chlorine bleaching compound can be used in the compositions of this invention, such as dichloro isocyanurate, dieloro-dimethylhydantoin, or chlorinated TSP, alkali metal hypochlorite, for example potassium, lithium, magnesium and especially sodium, is especially preferred. The composition must contain sufficient chlorine bleaching compound to provide about 0.2 to 0.4% by weight of available chlorine, as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid. A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite contains or provides approximately the same percentage of available chlorine. Especially preferred is about 0.8 to 1.6% by weight ζ

ί

of available chlorine. For example, sodium hypochlorite solution (NaOCl) with between about 11 and about 13% available chlorine in amounts of about 3 to 20%, preferably about 7 to 12%, can be used to advantage.

sodium or potassium silicate, which provides alkalinity and protection of hard surfaces, such as the gloss and pattern of fine porcelain, is normally used in an amount ranging from about 2.5 to 20 or 25 weight percent. At levels greater than about 10 weight percent the silicate also provides increased anti-stain action.

However, for a preferred viscoelasticity of the physically stable liquid aqueous dishwashing detergent compositions of this invention it is essential to incorporate excess amounts of the alkali metal silicate over the amounts normally used, especially more than 25 weight percent, for example , between about 28% and 40%, especially between about 30 and 38%, by weight of the composition.

sodium silicate is generally added in the form of an aqueous solution, preferably having a NaGiSií ratio of about 1: 2.2 to 1: 2.8, for example, 1: 2.4. Most of the other components of the composition, especially NaOH, sodium hypochlorite and foaming depressant can also be added in the form of an aqueous dispersion or solution.

The inhibition of foaming is important to increase the efficiency of the dishwasher and to minimize the destabilizing effects that can occur due to the presence of excess foam inside the machine during use. The foam can be sufficiently reduced by means of appropriate selection of the type and / or quantity

-21 of the detergent active material, the main foam producing component. The degree of foaming also depends to some extent on the hardness of the washing water in the machine so that an appropriate adjustment of the proportions of NaTPP that have a water softening effect can help to provide the desired degree of foaming inhibition. However, it is generally preferred to include a depressant or foaming inhibitor stable over the chlorine bleaching agent. Particularly effective in this respect, where a certain content of phosphorus can be tolerated, are the esters of alkyl phosphonic acid with the formula

II

HO-P-R

OR and especially the phosphate esters of alkyl acid with the formula

HO-P-OR.

OR

In the aforementioned formulas, one or both of the R groups in each type of ester can independently represent a ^ ΐ2 ~ ^ 2ο alkyl group. The ethoxylated derivatives of each type of ester for example, the condensation products of one mole of ester with 1 to 10 moles, preferably 2 to 6 moles, more preferably 3 or 4 moles of ethylene oxide can also be used. Some examples of the above are commercially available, such as Hooker's SAP products and Knapsack's LPKn-158. Mixtures of the two types may be used, or

-22 of any other types stable with chlorine bleaching agents, or mixtures of mono- and di-esters of the same type. Especially preferred is a mixture of mono- and di-C C-C. ^ Alkyl acid phosphate esters such as 1,2 / 1 monostearyl / distearyl acid phosphates and their colors [densified with 3 to 4 mole of ethylene oxide. When used, proportions of 0.01 to 0.5 weight percent, preferably 0.02 to 0.4 weight percent, especially about 0.1 to 0.2 weight percent, of the forming depressant of foam in the composition are typical, the weight ratio between the active detergent component and the foam depressant agent generally vary between about 20: 1 and 4: 1 and preferably between about 10: 1 and 5: 1. With these low levels of anti-foaming agent, the total phosphor content in the composition will generally and preferably be no more than 0.01 weight percent, based on the total composition.

When it is desired to completely exclude phosphorus, any of the silicone anti-foaming agents compatible with the bleaching agent can be used.

In the preferred thickened LADD compositions of this invention, thickening is provided by inorganic clays, which are swollen by the formation of smectite and / or atapulgite colloid types. These materials can generally be used in amounts of about 0.1 to 10, preferably 1 to 5, percent by weight, to impart the desired properties. However, in the presence of fatty acid stabilizers or fatty acid metal salt, smaller amounts of inorganic colloid-forming clays of the smectite and / or atapulgite types can be used. For example, amounts of clay ranging between about 0.1 and 3%, preferably 0.1 and 2.5%, especially 0.1 to 2%, are generally sufficient to achieve the desired viscoelastic properties when used in combination with the stabilization

-23zador fatty acid (or salt of fatty acid), and other ingredients.

Smectite clays include montmorillonite (bentonite), hectorite, atapulgite, smectite, saponite, etc. Montmorillonite clays are preferred and are available under cormecial names, such as Thixogel (registered trade name) Ns. 1 and Gelwhite (registered trade name) GP, H, etc., by Georgia Kaolin Company; and ECCAGUM (registered trade name) GP, H., by Luthern Clay Products.

Atapulgite clays include materials that are commercially available under the trade name Attagel (registered trade name), i.e. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of the smectite and atapulgite types with weight ratios ranging from 4: 1 to 1: 5 are also useful here. Thickening or suspending agents of the types mentioned above are well known in the art.

The physical stability, i.e. resistance to phase separation, sedimentation, etc., of these liquid aqueous ADD compositions can be significantly improved by adding to the composition a small but effective amount of a long chain fatty acid or a metal salt thereof. Indeed, under the preferred alkaline pH conditions of the LADD compositions, i.e., pH 10.5 to 13.5, the fatty acids will be converted into the corresponding alkali metal salts.

Preferred long-chain fatty acids are the highest aliphatic fatty acids having about 8 to about 22 carbon atoms, more preferably about 10 to 20 carbon atoms, and most preferably about 12 to 18 carbon atoms, includes sivé of the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical can be saturated or unsaturated and can be

saturated or unsaturated and can be linear or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids, such as those derived from natural sources, such as sebaceous fatty acid, coconut fatty acid, soy fatty acid, etc., or derivatives from synthetic sources available from industrial production processes can be used.

Thus, examples of fatty acids include, for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, sebaceous fatty acid, coconut fatty acid, soy fatty acid, mixtures of these acids, etc. Stearic acid and mixed fatty acids are preferred.

Metal salts of fatty acids can also be used and any of the monovalent and polyvalent metals can be used. Monovalent metals include, for example, alkali metals, especially sodium and potassium. Sodium salts (soaps) are especially preferred.

The preferred polyvalent metals are the polyvalent metals of Groups IIA, IIB and IIIB of the Periodic Table of the Elements, such as magnesium, calcium, aluminum and zinc, although other polyvalent metals including those of Groups IIIA, IVA, VA, IB, IVB, VB , VIB, VIIB, and VIII of the Periodic Table of Elements can also be used. Specific examples of these other polyvalent metals include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. In general, metals can be present in the divalent or polyvalent state. Preferably, the polyvalent metal salts are used at their highest oxidation stages. Naturally, for LADD compositions, as well as for any other applications where the composition of the invention will or may come into contact with articles used for manufacture, storage

or service of food products or that in any other way come into contact with or are consumed by people or animals, the metal salt should be selected taking into account the toxicity of the metal. For this purpose, calcium and magnesium salts are especially highly preferred as generally safe food additives.

Many of these metal salts are commercially available. For example, aluminum salts are available in triidide form, for example aluminum stearate such as aluminum tristearate,

Al (C ^ HggCOOJg. Monoacid salts, for example aluminum monostearate and diacid salts, for example aluminum distearate, and mixtures of two or three of the mono-, di- and tri-acid salts can be used for those metals, for example example A1, with valences of +3, and mixtures of the mono- and diacid salts can be used for these metals, for example Zn, with valences of +2. +3 brave metals, and tetraacids with +4 metals and pentaacids with +5 brave metals, are used in predominant quantities.

Metal salts, as mentioned above, are generally available commercially but can be easily produced, for example, by saponification of a fatty acid, for example animal fat, stearic acid, etc. or the corresponding fatty acid ester, followed by treatment with a hydroxide or polyvalent metal oxide, for example, in the case of aluminum salt, with alum, alumina, etc., or by reaction of a metal salt soluble with a soluble fatty acid salt.

calcium stearate, i.e. calcium distearate, magnesium stearate, i.e. magnesium distearate, aluminum stearate, i.e. aluminum tristearate and zinc stearate, i.e. zinc distearate,

I

are the preferred polyvalent fatty acid salt stabilizers.

Mixed fatty acids, such as naturally occurring acids, for example coconut acid, as well as mixed fatty acids resulting from commercial production processes are also advantageously used as cheap but effective sources of long chain fatty acid.

In addition, dimers or trimers of these acids can also be used.

The amount of fatty acid or fatty acid salt stabilizers to achieve the desired improvement in physical stability will depend on factors such as the nature of the fatty acid (or its salt), the nature and quantity of the clay thickening agent, the detergent active compound, inorganic salts, other LADD ingredients, as well as expected storage and shipping conditions (distribution)

Generally, however, amounts of polyvalent metal fatty acid salt stabilizing agents varying between about 0.02 and 1%, preferably between about 0.06 and 0.8%, especially preferably between about 0, 08 and 0.4%, provide long-term stability and the absence of a separation phase after resting or during transport at both low and high temperatures as is desired for a commercially acceptable product.

Although a connection with any particular theory such as the mode of action of the fatty acid stabilizers (metal salt) is not desired, it is hypothesized that these stabilizers, which in alkaline conditions, are anionic salts, interact with the surface of the particles of the cationic clay used as a thickening agent whereby the fatty acid halves help to keep the clay particles in suspension. In addition, depending on the amounts, proportions and types of physical stabilizers and clay thickening agents, the addition of fatty acid (or its salt) not only increases physical stability but also provides a simultaneous increase in apparent viscosity. Relationships between fatty acid (salt) and the clay thickening agent varying between about 0.08-0.4 weight percent of the clay thickening agent are usually sufficient to provide these simultaneous benefits and, therefore, the use of these ingredients in these relationships is more preferred.

Generally, the effectiveness of LADD is directly related to (a) available levels of chlorine; (b) alkalinity; (c) solubility in the washing medium; and (d) inhibition of foaming. It is preferred here that the pH of the LADD composition has at least a value of 9.5, more preferably between about 10.5 and 13.5 and most preferably at least about 11.5. With relatively lower pH values, the LADD product is often too viscous, that is, it has a solid appearance, thus not being rapidly fluidized under the shear force levels created inside the supplier element under normal conditions of operation of the machine. Essentially, the composition loses much, if not all, of its viscoelastic characteristic. Thus, the addition of NaOH is often necessary to increase the pH above the aforementioned averages, and to increase the flow properties. The presence of carbonate is also often necessary here, as it acts as a buffer that helps to maintain the desired pH level. However, an excess of carbonate should be avoided, as it can lead to the formation of needle-shaped carbonate crystals, thereby impairing the stability, thixotropy and / or detergency of the LADD product, and also impairing the product distribution to

-28✓Τ '.7 from, for example, bottles with a compression tube. Caustic soda (NaOH) has yet another function, that of neutralizing the foam depressant agent when phosphoric acid or phosphonic acid. of the present. About 0.5 to 3 weight percent NaOH and about 2 to 9 weight percent sodium carbonate in the LADD composition are typical values, although it should be noted that sufficient alkalinity can be provided by the alkali metal silicate .

The amount of water contained in these compositions must, of course, be neither so high as to produce undue low viscosity and fluidity, nor so low as to produce undue high viscosity and low fluidity, in both cases the viscoelastic properties being reduced or destroyed. That amount is readily determined by routine experimentation in any particular case, generally ranging from about 25 to 75 weight percent, preferably from about 55 to 65 weight percent in total, from all sources. The water should also preferably be deionized or softened (made less hard).

Other conventional ingredients can be included in these compositions in small amounts generally less than about 3 weight percent, such as perfume, hydrotropic agents, such as sodium benzene toluene xylene and cumene sulfonates, preservatives, dyes and pigments, etc., being all of them, of course, stable in relation to the chlorine bleaching compound and in relation to high alkalinity (properties of all components). Especially preferred for staining are chlorinated phthalocyanines and aluminum silicate polysulfides which provide pleasant green and blue tones, respectively. Ti0 ₂ can be used to whiten or neutralize accessory shades. Abrasives or polishing agents should be avoided in LADD compositions

as they can damage the surface of fine glassware, etc.

According to a preferred method for the production of these compositions, all inorganic salts, for example carbonates (when used), silicates and zeolite, must first be dissolved or dispersed in the aqueous medium. The thickening components including the polymer containing carboxyl group and clay (when present) are added last. The foam depressant (when used) is provided preliminarily in the form of an aqueous dispersion, as is the case with the thickening agent. The foam depressant dispersion, caustic soda (when used) and inorganic salts are first mixed at elevated temperatures in aqueous solution (deionized water) and then cooled, using complete stirring. 0 whitening agent, surfactant, fatty acid (or its metal salt stabilizer), and polymer thickener dispersion at room temperature are then added to the cooled (25-35 ² C). With the exception of the chlorine bleaching compound, the total concentration of (e.g. silicate salt and sodium carbonate) is generally about 20 to 50 weight percent, preferably 25 to 40 weight percent in the composition.

Another highly preferred method for mixing the ingredients of the LADD formulations involves first forming a mixture of water, foam suppressant, detergent, polymer containing carboxyl group, fatty acid or clay salt. These ingredients are mixed together until high shear conditions are reached, preferably starting at room temperature, to form a uniform dispersion. In this pre-mixed portion, the remaining ingredients are introduced under mixing conditions with low shear. For example, the required amount of the pre-mix is introduced into a low-shear mixer and then the remaining ingredients are added, with mixing, either sequentially or simultaneously.

Preferably, the ingredients are added sequentially, although it is not necessary to complete the addition of all of an ingredient before beginning to add the next ingredient. In addition, one or more of the ingredients can be divided into portions and added at different times. Good results were obtained by adding the remaining ingredients in the following sequence: sodium hydroxide, alkali metal carbonate, sodium silicate, zeolite aluminosilicate, bleaching agent (preferably sodium hypochlorite) and sodium hydroxide.

The liquid ADD compositions of this invention are used quickly in a known manner for washing dishes, other kitchen utensils, etc., in the automatic dishwasher, and providing with an appropriate detergent dispenser, in an aqueous washing bath containing a effective amount of the composition.

Although the invention has been particularly described in connection with its application to detergents for automatic dishwashers, it will be readily understood by any person skilled in the art that with or without the benefits of viscoelasticity and physical stability that are obtained by the additional amounts of metal silicate alkali and the interaction of clay and fatty acid, the cleaning advantages provided by the combination of stable detergent over the bleaching agent, bleaching agent, and zeolite and polymer filler containing water-soluble carboxyl group, stable in relation to to the bleaching agent make the compositions of this invention useful as a general type of composition for cleaning dishes, glassware, cutlery, pots, pans, etc.

The cleaning performance (action), in terms of removing a wide range of food stains, from the composition of the invention is comparable to or slightly superior to that of detergents with polyphosphate fillers.

L-r '', sy.

^ "PssThis is an alkali, eg sodium tripolyphosphate. For example in cleaning tests against various food residues, some of which are cooked, including egg, peanut butter, tea, coffee, milk, chocolate milk, tomato juice, rice, rice / cheese mixture, white sauce, oatmeal and spinach, the LADD composition of the invention achieved a cleaning slightly higher or equal cleaning for 14 to 16 food stains on various substrates (glasses, cups, cutlery, plates, pots) and only slightly lower for the stains of chocolate milk and rice cooked in pots.

Furthermore, as will be indicated in the following example, the compositions of this invention are generally superior to the compositions with phosphate filler in terms of staining and film formation.

The invention can be practiced in several ways and a number of specific presentations have been described in order to illustrate the invention as a reference to the accompanying example.

All amounts and proportions referred to herein are by weight of the compositions and unless otherwise stated.

EXAMPLE

The following two compositions are prepared in order to compare the properties of the composition of the invention with a similar composition with phosphate filler.

Component Series Ns.1 I invent Series N ^s . 2 Invention Deionized water 16.44 30.44 Stearic acid 0.10 0.10 Smectite clay (Van Gel ES) 1.50 1.50 Sodium silicate (47.5% Na ₂ 0: Si0 _{2 solution} ratio 1: 2.4) 35.00 25.00 Sodium tripolyphosphate (substantially anhydrous, ie about 3% moisture) 12.00 Sodium tripolyphosphate hexahydrate 12.00 Zeolite aluminum silicate 24.00 Sodium carbonate, anhydrous 6.00 6.00 Sodium hypochlorite (1% available chlorine) 9.00 9.00 Surfactant (Dowfax 3B-2, 45% aqueous solution of mono- and di-decyl disulfo- Na born) 0.80 0.80 Anti-foam agent (Knapsack LPKn 158, mixture of mono- and di-stearyl esters (C-jg-C-jg) alkyl of phosphoric acid, molar ratio of about 1: 1.3 0.16 0.16 Caustic soda solution (50% NaOH) 3.00 3.00 Sodium polyacrylate (MW = 4,500) (45% solution) 4.00 100.00 100.00

Each of the Series 1 and 2 formulations are tested to compare cleaning performance (action) (formation of stains and films on glass objects) using a Kenmore dishwasher with 100 grams of glass objects using tap water temperature at 130 ^s F and 120 ppm hardness. The test procedure is described in ASTM D3566-79, except that only four cleaning cycles are used. The formation of films and stains is evaluated according to the following scales:

Film Evaluation Scale

1. Better, no apparent film

2. Light film, becoming apparent

3. Apparent film, increasing

4. Continued increase in significant film

5. Excessive film

6. High film, excessive production

7. Continued increase in excessive film

Stain Assessment Scale

A. Better - no stains

B. Very few apparent stains

C. Clear

D. Significant coverage of approximately 50%. The results are shown below:

-Ζ4 Grade of Performance (Action) Stains_ Films

Cycle Series 1 Series 2 Series 1 Series 2

1 A, B B 1.2 1.2 2 A; B B 1.2 1.2 3 A, B-B B-C 1.2 1.2 4 B B-C 2 2

Results similar to those described above will be obtained if the polyacrylate is replaced with a methacrylic acid / maleic anhydride copolymer, for example

Claims (19)

CLAIMS: 1 ^â . - Process for the preparation of a structured aqueous liquid cleaning composition with little or no phosphorus content, characterized in that water, water-dispersible organic detergent, stable in the presence of chlorine-based bleach, alkali metal silicate, is included in the said composition, chlorine bleach and detergent builder, wherein said detergent builder comprises a mixture of an aluminosilicate zeolite and a stable polymer in the presence of the water-soluble bleach containing carboxyl groups. 2 ^â . Process according to claim 1, characterized in that the polymer stable in the presence of the bleach is a polymer of polyacrylic acid or polyacrylate and has a molecular weight ranging from about 1,000 to about 25,000. 3 ³ . Process according to claim 2, characterized in that the polymer stable in the presence of the bleach has a molecular weight ranging from about 2,000 to about 10,000. 4 ³ . Process according to claim 1, characterized in that the detergent builder comprises between about 5 and about 35% by weight of the aluminosilicate zeolite and between about 0.5 and 10% by weight of stable polymer in the presence of bleach . 5 ^â . - Process according to claim 1, characterized in that it also includes in the reference X? -36 of the composition an inorganic colloid-forming clay-based thickening agent. 6 ^â . Process according to claim 5, characterized in that an aliphatic carboxylic acid C _g to C ₂₂ or a salt thereof is also included in said composition. 7 ^ã . Process according to Claim 1, characterized in that a stable foaming depressant in the presence of the bleach is also included in the composition. 8 ^â . - Process according to claim 7, characterized in that the depressor foaming compreender'um acid ester alkyl phosphate or an alkyl phosphonic acid ester containing one to two ^ 12 ^ 20 groups ^{Qu a} mixture thereof. 9 ^â . Process according to claim 1, characterized in that a composition without phosphorus is obtained. 10 ^â . Process according to claim 9, characterized in that a silicone based foam depressant is also included in the composition. 11 ^â . - Process for the preparation of a thickened aqueous liquid detergent composition for automatic dishwashers containing no more than -37bx about 0.01% by weight of phosphorus, characterized in that said composition includes, approximately, by weight, (a) 5 to 35% of aluminosiicate zeolite; (b) more than 25% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5% of active organic detergent material, dispersible in water, stable in the presence of the bleach; (e) 0 to 5% of stable foaming depressant in the presence of bleach; (f) chlorine bleach compound in an amount that provides about 0.2 to 4% of available chlorine; (g) 0 to 3% of a thickening agent based on clay forming inorganic collodions; (h) 0 to 0.5% of an aliphatic fatty acid having 8 to 22 carbon atoms, their dimers or trimers, or their metal salts; (i) 0 to 8% sodium hydroxide; (j) 0.5 to 10% of a polymer containing carboxyl groups, soluble in water, stable in the presence of the bleach; and (k) water; said composition having a pH of at least 9.5. 12 ^â . Process according to claim 11, characterized in that the polymer stable in the presence of the bleach is a polymer of polyacrylic acid or polyacrylate and has a molecular weight ranging from about 1,000 to about 25,000. 13â. Process according to claim 12, characterized in that the polymer stable in the presence of the bleach has a molecular weight varying between -38 about 2,000 and about 10,000. 14 ⁵ . Process according to claim 11, characterized in that said composition includes 0.03 to 0.5% of said aliphatic fatty acid or its salt (h) and 0.1 to 3% of said thickening agent at clay base (g). 15 ^â . Process according to claim 14, characterized in that the fatty acid is stearic acid or a salt thereof and the clay is a smectite clay or an atpulgite clay. 16 ^â . Process according to claim 11, characterized in that the chlorine-based bleach compound (f) is sodium hypochlorite. 17®. Process according to claim 11, characterized in that at least about 0.1 weight percent of the foaming depressant (e) is included in said composition. 18 ^â . - Process according to claim 17, wherein the depressing agent is foamed mation be a phosphate alkyl ester or an alkyl ester of phosphonic acid containing one or two ^C 12 ^C 2O ^alk l ^{uil0 'or a} mixture. 19 ^â . Process according to claim 11, characterized in that a composition is obtained