CN1225672A - Detergent composition - Google Patents

Abstract

Alkoxylated cationic surfactants, and mixtures thereof, are used in detergent compositions comprising a mixture of alkyl sulfate and alkylbenzene sulfonate surfactants.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions comprising selected mixtures of anionic surfactants and selected ethoxylated quaternary ammonium compounds.

Background of the invention

The formulation of laundry detergents and other cleaning compositions presents a significant challenge due to the need for modern compositions capable of removing a wide variety of soils and stains from a variety of materials. Therefore, laundry detergents require appropriate selection and combination of components in order to function effectively. Generally, such detergent compositions contain one or more types of surfactants designed to remove various types of soils and stains. However, the rapid and efficient removal of body soils, greasy/oily soils and some food stains is a problem. Indeed, while some surfactants and surfactant compositions have desirable effects on some types of soils and stains, they actually reduce the effects on other soils. For example, surfactants that remove greasy/oily soils from fabrics are sometimes not ideal for removing particulate soils, such as clay. The literature indicates that a wide selection of surfactants and surfactant compositions are available to detergent manufacturers, and indeed many of these components are specialty chemicals that are not suitable for low unit price products, such as household laundry detergents. This has led to the fact that most of these domestic laundry detergents contain predominantly one or several conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, which may be due to economic considerations and the need to prepare compositions which act reasonably well on various soils and stains and on various fabrics.

Thus, methods of improving laundry detergents have been sought, but for various reasons, it has been a challenge for detergent manufacturers to find improved performance. For example, some non-biodegradable components have not been favored. Preferred phosphate builders are also prohibited by regulations in many countries. The cost of some classes of surfactants impacts their use. As a result, the producers have some more limitations than the selection of effective still available components suggested in the literature. Consumers still desire that such compositions be of high quality and efficient even when the fabrics are laundered in cold or cold water conditions.

The literature does not suggest that various nitrogen-containing surfactants are effective in various cleaning compositions. Such materials are generally formulated for specific uses in the form of amino-, amido-, or quaternary ammonium or imidazolium compounds. For example, various amino and quaternary ammonium surfactants have been proposed for use in shampoo compositions and are said to have cosmetic effects on the hair. Other nitrogen-containing surfactants may be used in some laundry detergents to soften fabrics and have an antistatic effect. However, the usual use of such materials is quite limited and the above mentioned nonionic and anionic surfactants remain the major active ingredient in today's laundry compositions.

It has now been found that certain Alkoxylated Quaternary Ammonium (AQA) compounds can be used in laundry detergents to boost performance. Importantly, it has further been discovered that low concentrations of these AQA compounds provide superior cleaning performance when used in combination with certain conventional alkyl sulfate and alkylbenzene sulfonate surfactants in specific proportions and portions. Thus, the present invention can enhance laundry washing performance without the need to develop new, expensive surfactant classes.

Moreover, the AQA surfactants currently used are very superior to the cationic surfactants known to date to the formulator. For example, the AQA surfactants of the present invention are compatible with the preferred alkyl sulfate and alkylbenzene sulfonate detersive surfactants. Furthermore, the AQA surfactants may be formulated to have a pH of 5 to 12. The AQA surfactants can be prepared as 30% by weight solutions which can be pumped and therefore easily handled in the manufacturing plant. AQA surfactants having a degree of ethoxylation greater than 5 are sometimes in a liquid state and may be provided as 100% neat materials. In addition to their performance properties, the ability of the AQA surfactants of the present invention to be provided as highly concentrated solutions is very economically advantageous in terms of transportation costs. The AQA surfactants are also compatible with various perfume ingredients, unlike other materials known in the art.

In addition to the above advantages, the AQA surfactants of the present invention reduce or eliminate redeposition of fatty acids/oily materials present in aqueous wash liquor back onto fabrics which have previously been soiled with body soils. Accordingly, the AQA surfactants of the present invention have been found to prevent redeposition of polar lipids from aqueous wash solutions back onto fabrics from which body soils have been removed by the laundering operation. In other words, in the wash liquor, the AQA surfactants of the present invention remove such polar lipids and keep them suspended in the aqueous medium, rather than allowing them to redeposit on the cleaned fabrics.

In addition to the qualities described above, the AQA surfactants of the present invention are unexpectedly compatible with polyanionic materials, such as polyacrylates and acrylate/maleate copolymers, which can be used to provide builder and/or dispersant functions to many conventional detersive surfactants.

Other advantages of the AQA surfactants of the present invention include their ability to enhance enzymatic cleaning and fabric care performance in the wash liquor. Without wishing to be bound by theory, it is speculated that the enzyme is partially denatured by conventional anionic surfactants. It is further believed that the AQA surfactants of the present invention act with anionic surfactants to some extent to inhibit their degradation. Another theory suggests that even when enzymes are used to degrade soils and stains, the degraded residue must be removed from the fabric surface. It is surmised that the improved cleaning performance of the AQA and anionic surfactant mixtures alone works well in removing these residues from the fabric surface.

In addition to the foregoing advantages, the AQA surfactants of the present invention provide greatly improved cleaning performance over conventional detergent mixtures in the removal of clay soils from fabrics. Again, without wishing to be bound by theory, it is speculated that conventional cationic surfactants bind to the clay in a "compact" manner and make the clay less easily removed. In contrast, it is believed that the alkoxylated AQA surfactants more open bond with the clay, which makes the clay easier to remove from the fabric surface. For any reason, the AQA surfactant containing compositions of the present invention have improved performance over conventional cationic surfactants, particularly in clay soil removal.

Other advantages have also been found with the AQA surfactants of the present invention. For example, in bleaching compositions containing bleach activators (disclosed herein), some ion pairs or other associated complexes are found to be formed by peracids released by the activator. It is speculated that the ion pair enters the soil more efficiently as a new, more hydrophobic agent, thereby enhancing the bleaching performance associated with the use of bleach activators such as nonanoyloxybenzene sulphonic acid (NOBS). These effects are produced by AQA surfactants at very low concentrations (as low as 3ppm in the wash liquor).

Furthermore, in bleach-free compositions, formulators may choose to employ higher concentrations of AQA to enhance performance benefits. These effects may be associated with the ability of the AQA surfactants of the present invention to modify the solution characteristics of conventional anionic surfactants, such as alkyl sulfates, or alkyl benzene sulfonates, so that more surfactants can exert their cleaning performance. This is the case for formulators who are faced with detergent compositions that are "under-bound" with respect to calcium and/or magnesium water hardness ions. In such a case, it is preferred that sufficient AQA surfactant is employed so that the amount of AQA surfactant in the wash liquor is from about 10ppm to about 50 ppm. This is converted to a composition in an amount of from about 1% to about 5% by weight of the fully formulated detergent composition. (the concentration may vary with the rate of use of the product and the amount of other surfactants present in the wash liquor. for products having concentrations up to about 3500ppm, the concentration of the AQA may be as high as 100 to 150ppm in solution

It has also been found that the AQA surfactants of the present invention containing about 2 Ethylene Oxide (EO) groups perform quite well under low water hardness conditions or when a well-combined detergent composition is employed. However, at high hardness (about 170ppm calcium carbonate and above), it is more preferred to employ AQA surfactants having at least about 5 EO groups. Also, for some soils and stains, such as fecal matter, AQA surfactants containing from 10 to 20 EO groups are preferred. Thus, it has now been discovered that mixtures of AQA surfactants can be mixed and used to provide broad spectrum cleaning performance over a wide range of soils and stains under a wide range of use conditions. Representative, but non-limiting, examples of such AQA surfactant compositions are disclosed in the form of the following examples.

Various other advantages of the AQA surfactants over cationic surfactants known in the art are described in more detail below. As can be seen from the disclosure herein, the AQA surfactants employed in the manner of the present invention successfully solve many of the problems associated with formulating modern high performance detergent compositions. In particular, the AQA surfactants enable the formulation of effective laundry compositions which can be used to remove a variety of soil and stains under a variety of use conditions.

These and other advantages of the present invention will be apparent from the following disclosure.

Background

US5441541,1995, 8, 15, a.mehretab and f.j.lopast, on anionic/cationic surfactant mixtures. UK2040990,1980, 9 months and 3 days, a.p.murphy, r.j.m.smith and m.p.brooks, for ethoxylated cations in laundry detergents.

Summary of the invention

The present invention relates to compositions comprising, or prepared by mixing, a cationic surfactant and a mixture of two anionic surfactants, each of said surfactants having the general formula:

Ⅱ R⁵OSO₃ ^-M⁺,Ⅲ R⁶SO₃ ^-M’⁺and optionally but preferably

IV nonionic surfactant

Wherein R is¹Is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably from 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; r²Is an alkyl group containing 1 to 3 carbon atoms, preferably methyl; r³And R⁴Can be varied independently and are selected from hydrogen (preferred), methyl and ethyl, R⁵Is a linear or branched alkyl or alkenyl moiety containing from about 10 to about 20 carbon atoms, preferably C₁₂To C₁₈Alkyl or as found in secondary alkyl sulfates; r⁶Is C₁₀-C₁₅Alkylbenzenes, preferably C₁₁-C₁₃An alkylbenzene; m⁺And M'⁺Can vary independently and are selected from the group consisting of alkali metals, alkaline earth metals, alkanolammonium and ammonium; x^-Is an anion sufficient to provide charge neutrality, such as chloride, bromide, methylsulfate, sulfate, and the like. A and A' may vary independently and are selected from C₁-C₄Alkoxy, especially ethoxy (e.g. -CH)₂CH₂O), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4, q isFrom 1 to about 30, preferably 1 to about 4, most preferably to about 4; preferably, both p and q are 1. The weight ratio of (I) to (II) + (III) is preferably from about 1: 100 to 1: 7, more preferably from 1: 50 to 1: 10. The weight ratio of (II) to (III) is preferably 4: 1 to 1:4, more preferably 2: 1 to 1: 2. R⁵And R⁶The weight ratio of (A) to (B) is preferably 1: 13 to 1: 5.

Wherein the hydrocarbyl substituent R¹Is C₈～C₁₁In particular C₁₀The AQA compounds of (a) increase the dissolution rate of the laundry particles compared to longer chain materials, especially under cold water conditions. Thus, C₈-C₁₁AQA surfactants are preferred by some formulators. The concentration of the AQA surfactants used in the preparation of finished laundry detergent compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5% by weight.

In a preferred embodiment, the composition comprises: surfactants (I), (II) and (III) wherein the weight ratio of (I) to (II) + (III) is in the range of at least about 1: 10.

In a preferred embodiment, said anionic surfactant (II) is C₁₂-C₁₈Primary or secondary Alkyl Sulfates (AS), and said anionic surfactant (III) is a surfactant containing C₁₁-C₁₃Alkyl benzene sulphonate of branched or linear alkyl chain.

In a highly preferred embodiment, the composition further comprises a nonionic surfactant selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglycosides, and mixtures thereof.

In particular, highly preferred compositions of the invention comprise:

(a) from about 0.25% to about 3% by weight of Coco Methyl EO2 as surfactant (I);

(b) from about 3% to about 40% by weight of a linear or branched primary or secondary AS AS surfactant (II);

(c) from about 6% to about 23% by weight of an alkylbenzene sulfonate (LAS) as surfactant (iii); and

(d) from about 0.5% to about 20% by weight of a nonionic surfactant (IV).

Other embodiments include:

from about 0.45% to about 2% by weight of (a);

(ii) about 6% to about 13% by weight of (b);

(iii) about 8% to about 23% by weight of (c);

(iv) about 1% to about 5% by weight of (d).

The present invention also includes fully formulated detergent compositions comprising an additive component and at least about 3% by weight of the above-described detersive surfactant system comprising a cationic surfactant, a mixture of anionic surfactants, and optionally a nonionic surfactant, all as disclosed above, the additive component being selected from the group consisting of builders, enzymes, soil release polymers, bleaching agents, clay-removal/anti-redeposition agents, polymeric dispersing agents, brighteners, dye transfer prevention agents, suds suppressors, fabric softeners and other additives disclosed herein, and detergent surfactants not included in surfactants (i) - (iv) such as those selected from the group consisting of soaps, oleyl sulfates, alkyl alkoxy carboxylates, sulfated alkyl polyglycosides, α -sulfonated fatty acid esters, betaines, sulfobetaines, amine oxides and mixtures thereof.

The AQA surfactants employed in the manner of this invention also provide an improved method of removing the following soils and stains from fabrics: bloodstains, greasy food stains, particulate stains, body soils (including "darkening" of fabrics caused by accumulation of small but easily visible stains/soils over time), and other soils as described herein. Such stains and soils can be removed from fabrics such as cotton, polyester/cotton blends (P/C) and Double Knit Polyester (DKPE). The method comprises contacting a fabric in need of such soil removal with an effectiveamount of the composition of the present invention in the presence of water, particularly under agitation. Various suitable use concentrations and methods are disclosed below in this specification.

Furthermore, the AQA surfactants of the present invention, particularly the preferred Coco Me EO2 (herein "AQA-1"), have improved fabric cleaning performance in the presence of bleach. This improvement in washing can be seen at concentrations as low as 3 parts per million (ppm) of AQA used in the wash liquor and is believed to be associated with increased perhydrolysis.

In addition, the AQA surfactants of the present invention, particularly AQA-1, improve (even synergistically) the efficacy of amylases and cellulases. The improvement is particularly pronounced in the absence of bleaching agents.

All percentages, ratios and proportions herein are by weight of the components used to prepare the finished composition, unless otherwise specified. All documents cited herein are, in relevant part, incorporated herein by reference.

Detailed description of the invention

In one aspect, the present invention provides a method for enhancing the removal of greasy/oily soils by combining a lipase with an AQA surfactant. Lipid/oil "everyday" soils are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous substances. When soiled laundry is stored prior to washing, some of the triglycerides are converted to fatty acids by the action of bacteria and lipase can be used to convert any residual triglycerides to fatty acids throughout the wash. In general, for formulations which depend on hardness control by means of dispersing aids, such as layered silicates, early in the wash, what appears to be the absence of builder, is characterized by a high absorption of cold water. In the first few minutes, the fatty acids in the soil interact with hard water without builder to form an insoluble lime-lime soap which hinders subsequent removal of the soil and allows soil residues to remain on the washed fabric. In unbuilt formulations, insolubilization of the fat/oil stain presents further problems. In the case of continuous abrasion/washing, the build-up of residue can lead to yellowing and can trap particulate dust. Eventually, the garment begins to darken, and is not perceived as being re-wearable and is often discarded.

It has now been found that detergent compositions comprising AQA surfactants and lipase enzymes provide superior cleaning and bleaching benefits compared to products containing only one technology. These effects are the following: (1) AQA inhibits lime soap formation (does not hinder lipase action on soil); and (2) effectively release fatty acids from the soil (with AQA) to ensure maximum lipase activity (high concentrations of fatty acids in the soil inhibit lipase action).

The present invention also has improved cleaning and fabric care benefits by combining cellulase and AQA surfactants. In older/penetrating cotton or other fibrous fabrics, the layers covering the individual fibers break down to form a dust-trapping gum/amorphous cellulose "gum". In addition, the gum can be used as an ideal substrate for depositing/retaining lipid/oil body soils (such as on collars and pillows) which are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials. It is very difficult to remove these hydrophobic soils from the passing fabric and small residual stains often remain on the fabric after washing. Again, after continued abrasion/washing, these soils build up, leading to yellowing and more clay being trapped.

Unexpectedly, it has now been found that detergent compositions comprising AQA surfactants and cellulase enzymes (e.g., cellulase and/or endoglucanase) provide superior cleaning and bleaching benefits over products containing only a single component. These effects appear to be a result of the AQA surfactants effectively penetrating hydrophobic body soils. This in turn promotes the action of cellulase enzymes, which degrade amorphous cellulose gel surrounding the fibers (which binds the soil to the fabric). As the gel dissolves, the trapped dust is released and returns to a white color. In addition to the cleaning effect, the cellulase/AQA combination system also has a softening effect compared to the cation or enzyme alone, effectively depilling and removing gels from the passing through fabric, improving the soft feel of the fabric.

As noted, complete removal of very hydrophobic "everyday" or "body" soils is difficult, and typically a small amount of soil remains on the fabrics after washing. These residues build up and act like an amorphous gel between the fibers, trapping particulate dust and yellowing the fabric. It has now further been found that detergent compositions comprising a combination of a water soluble AQA surfactant of the present invention and an amylase enzyme provide superior cleaning and bleaching benefits as compared to compositions comprising either alone. These effects are a result of further enhancement of the "gel" remaining around the fibre (AQA is beneficial in improving the action of amylase enzymes on sensitive soil components by dissolving the soil). As the gel dissolves, the white color recovers and releases trapped particulate dust/for other wash actives, a decolorizing effect on the dust can be achieved.

The present invention also provides detergent compositions having excellent cleaning of greasy/oil-type everyday soils through the use of the AQA surfactants and percarbonate bleach disclosed herein. Percarbonates, which release peroxide bleach in the wash, are fundamental technology content of modern ultra-compact granular detergent formulations. Peroxide bleach is very hydrophilic and, although it is not as effective in removing color from pigments (such as particulate and beverage stains) as the bleaching action produced by peracids (e.g. produced by the action of peroxide and TAED) and also helps to remove color from organic residues associated with body soils. Unexpectedly, it has now been found that compositions containing AQA surfactants and percarbonate bleach have superior cleaning and whitening benefits compared to products containing only one component. These effects are achieved by AQA effectively solubilizing the greasy/oil soils, thereby allowing the hydrophilic peroxygen bleach to act on the coloured parts of the soil (e.g. entrapped pigments) and consequently enhancing the destaining of the soil.

The present invention also provides detergent compositions which are effective in cleaning greasy/oily everyday soils by means of a hydrophobic bleach activator used in combination with the water-soluble AQA surfactants herein. The cleaning and bleaching effectiveness of hydrophobic bleach activators and peracids on everyday soils has been demonstrated. Such materials have limited penetration through complex/grease soils. It has now been found that detergent and bleaching compositions comprising AQA and a hydrophobic bleach activator (including preformed peracids) have superior cleaning and bleaching performance as compared to similar compositions comprising only one component. The effect of the binding system can reasonably be predicted due to: (1) AQA acts on the soil surface, preventing lime soap formation and eliminating the presence of calcium soap, thus promoting the action of hydrophobic bleaching agents; (2) the surface tension at the soil/wash liquor interface is greatly reduced (with AQA). As surface tension decreases, penetration of hydrophobic bleaching agents (which act like anionic surfactants) through soil is promoted; and (3) the potential contact of hydrophobic peracids with AQA forms very hydrophobic ion pairs that readily penetrate deep into greasy soils.

The present invention also provides compositions having excellent grease/oil soil cleaning performance through the use of bleach catalysts employing AQA surfactants. The bleach catalyst (characterized by the presence of at least one transition metal atom) reacts with the peroxide to form a very effective hydrophilic bleach. These bleaches have a strong effect on colored hydrophilic stains and hydrophilic everyday soils (such as socks). The catalyst is generally used in very low concentrations in the cleaning product. As disclosed herein, products containing AQAs and catalysts have superior cleaning and bleaching benefits compared to products containing only one of them, and are particularly effective on everyday soils. These effects are believed to be produced by the effective dissolution of the greasy/oily soils by AQA, which allows the hydrophilic "catalyst" bleach to act on the coloured bodies in the soil, thereby effectively removing the colour of the soil. Furthermore, historically used bleach catalysts have been difficult to use due to damage to the fabric. It has now been found that fabric damage is greatly reduced when AQA cationic surfactants are present using a dimanganese catalyst which is known to cause fabric damage. It is predicted that these cationic surfactants attract to the fabric where they change the surface charge and form ion pairs with the activated catalyst, reducing or preventing damage to the fabric.

In another aspect, the present invention utilizes high concentrations of insoluble inorganic builder (which does not encrust the fabric) which employs a layered silicate and a water soluble AQA surfactant. Phyllosilicates are composed of fine units, some of the faces of which carry a negative charge. It is surmised that the positively charged head group of AQA contacts the negatively charged surface by forming an electrostatic bond, forming a monolayer of surfactant on which a second "hydrophilic" surfactant layer is formed. This causes the particles to fall off the fabric, thereby reducing encrustation that would otherwise produce a harsh "fabric feel".

The present invention also provides for formulating high concentrations of insoluble inorganic or soluble (bi) carbonate adjuncts in compositions containing relatively low amounts of polycarboxylate polymers without the formation of fabric encrustation using the different types of adjuncts and AQA surfactants of the present invention. Historically, high molecular weight polycarboxylate polymers have been used as dispersants in granular laundry detergent compositions. However, these polymers are generally relatively expensive. The polymer is also effective in controlling fabric encrustation by removing minerals (including builder/precipitated carbonate) from the fabric as is effective in soil suspension. The oligomeric formulations known to date have the disadvantage of being prone to fabric encrustation.

It has now been found that high concentrations of inorganic and/or (bi) carbonate builders can be used in combination with low concentrations of polymers and/or lower molecular weight polymers without accelerating fabric encrustation by the use of AQA surfactants in the manner disclosed herein. The problem of fabric encrustation with low polymer systems is believed to be avoided by two AQA mechanisms: (1) layered silicates and zeolites are composed of fine units, some of whose faces are negatively charged. AQA with positively charged head groups can interact with these surfaces to remove minerals from fabrics by forming a hydrophilic charged surfactant bilayer around the inorganic particles; and/or (2) AQA is more substantive to fabrics than anionic/nonionic surfactants. Thus, small amounts of these substances adsorb on the fabric surface where they change the surface charge. Since the degree of carbonate encrustation depends on the negative surface charge, AQA absorption (which changes the cotton surface charge to neutral/positive) reduces the occurrence of encrustation. In addition, AQA can absorb onto the "growing" surface of calcium carbonate crystals, thereby inhibiting crystal growth and reducing encrustation on the fabric.

The present invention also provides detergent compositions which are more effective in cleaning grease/oil "everyday" soils (and occasional soils) through the use of polyethoxylated polyamines (PPP) and the AQA surfactants of the present invention. As noted, lipid/oil "everyday" soils (e.g. on collars, pillow cases) are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter. Complete removal of these very hydrophobic soils is difficult and small residual stains often remain on the washed fabrics. To improve performance in this critical area, various soil dispersant polymers have been developed. The characteristics of these substances include: (1) a reasonably low molecular weight "hydrophobic" polyamine backbone (which is slightly positive, providing affinity for soil and fabrics); and (2) pendant "hydrophilic" polyethoxylate groups that provide steric stability and oil-and-fat suspension. During the washing process, these polymers act at the spot/wash liquid interface.

Surprisingly, it has now been found that a cleaning composition comprising the AQA surfactants of the present invention and an ethoxylated polyamine polymer provides superior cleaning and whitening benefits as compared to compositions containing either component alone. The effect of the mixed system is believed to be the following: (1) AQA acts on the surface of stains, preventing lime soap formation and removing all calcium soap present, thus facilitating improved polymer deposition; (2) AQAs provide deep dissolution into the soil, while polymers act as a "grease-removing layer" to remove the dissolved stain components of AQAs and disperse them in the wash liquor.

The present invention also provides detergent compositions which effectively clean grease/oil everyday soils by means of employing high concentrations of surfactant, optionally including branched surfactants, and an AQA surfactant. In view of the importance of high surface activity for effective removal of greasy/oily body soils, modern "ultra-compact" detergent compositions typically contain high concentrations of surfactants (nonionic and anionic) and are quite effective in cleaning body soils. Unexpectedly, it has now been found that products containing AQA and a high concentration of anionic or mixed anionic/nonionic surfactants (optionally including branched surfactants) have superior cleaning performance as compared to products containing only one of the components. These effects are obtained by the following actions: (1) AQA acts on the soil surface to prevent lime soap formation and to remove any calcium soaps present (which, if formed and left at the soil-wash liquor interface, would greatly retard the action of the surfactant); (2) AQA reduces the surface tension between the wash liquor and the greasy/oily soils, thereby allowing the surfactant to enter the soil more effectively (thereby promoting cleaning); and (3) the potential for ion-pair formation between cationic and anionic surfactants, forming very hydrophobic surfactant "pair" molecules that can penetrate deep into greasy soils.

In addition, the present invention provides detergents, bleaching agents and other compositions which improve the fragrance retained on fabrics after laundering by the use of perfumes and water soluble AQA surfactants. Natural and synthetic fabrics can be characterized by surface charges on their fibers. Cotton is hydrophilic with a net negative surface charge, while polyester is hydrophobic with a neutral surface charge. Fragrances are complex mixtures of hydrophobic organic actives including esters, alcohols, ketones, aldehydes, ethers, and the like. The durability of different perfume actives on fabrics depends on: (1) functional groups (how polar they are); (2) the molecular weight of the active; and (3) charge on the fabric fibers. Most perfume actives contain electron rich oxygen atoms that are attracted to electron deficient molecules/surfaces.

Unexpectedly, it has now been found that a combination of an AQA surfactant and a perfume (characterized by a molecular weight of>150 for>10% of the components) improves the fabric substantivity of perfumes. Without wishing to be bound by theory, the AQA surfactants, as well as increasing the hydrophobicity of the anionic or anionic/nonionic surfactant system, have high fabric substantivity (especially for cotton). The AQA surfactants are absorbed onto the fibers where they convert the surface charge from a neutral/negative charge to a positive charge (or lack of electrons). The modified fabric surface acts like a magnet to the electron rich regions of the perfume active, thereby pulling them onto the fabric and holding them there by electrostatic action. This greatly improves the durability of the fragrance. These effects are particularly pronounced for perfume components containing at least one oxygen atom and having a molecular weight greater than 150. The concentration of such perfume components should be at least about 10% of the total perfume mixture to obtain the maximum effect of the effect.

The alkoxylated quaternary ammonium ("AQA") compounds useful herein enhance the cleaning performance of fabric laundry detergent compositions containing selected amounts of certain anionic surfactants. In this specification, the AQA compounds of the present invention also have the advantage that they are commercially available and compatible with the various detergent components, such as builders, detersive enzymes, etc., used in many modern high quality fully formulated laundry detergents. Moreover, the AQA compounds are satisfactorily stable in the presence of the bleach components typically used in laundry detergent plus bleach compositions. Importantly, the AQA surfactants of the present invention have particularly good results in the removal of body soils and everyday soils such as socks. The combination of the AQA surfactants with specific anionic surfactants can remove such soils from fabrics. Moreover, the specific combination of the AQA surfactants with other conventional anionic surfactants provides excellent cleaning performance on a variety of other soils and stains including food stains, particulate soils and greasy/oily stains. Briefly, the compositions of the present invention have improved performance in removing a broad spectrum of soils and stains, including body soils from the collar and cuffs, lipid soils and enzyme/bleach sensitive stains, such as spinach juice and coffee. The compositions of the present invention also provide excellent cleaning benefits on adjunct sensitive stains such as clay and are therefore particularly effective in phosphorus-free materials.

Unlike other cationic surfactants known in the art, the bis-alkoxylated cationic surfactants of the present invention have sufficient solubility that they can be used in combination with mixed surfactant systems having very low levels of nonionic surfactant and containing, for example, alkyl sulfate surfactants. It is an important consideration for formulators of detergent compositions designed for use in automatic washing machine types in general, particularly in japan, and in north american use conditions. In general, such compositions contain anionic (total LAS/AS) surfactants: the weight ratio of nonionic surfactant is in the range of from about 25: 1 to about 1: 25, preferably from about 20: 1 to about 3: 1. This is in contrast to the common anions: the European-type formulations differ in nonionic ratio in the range of about 10: 1 to 1: 10,preferably about 5: 1 to 1: 5.

The present invention employs an "effective amount" of the AQA surfactants to improve the performance of cleaning compositions containing other adjunct ingredients. An "effective amount" of the AQA surfactants and additives herein is an amount sufficient to improve the performance of the cleaning compositions, directionally or substantially with a 90% confidence level, against at least some of the target soils and stains. Thus, in compositions whose purpose includes certain food stains, formulators can employ sufficient AQA to at least directionally enhance cleaning of such stains. Also, in compositions whose purpose includes clay soil, formulators employ sufficient AQA to at least directionally enhance the cleaning performance of such soils. Importantly, in fully formulated laundry detergents, the AQA surfactants can be used at concentrations that provide directional improvement in cleaning performance over a wide range of soils and stains, as will be shown from the data herein after.

As noted above, the AQA surfactants can be used in the detergent compositions of the present invention in combination with other detersive surfactants in amounts which provide at least a directional improvement in cleaning performance. In the context of fabric laundry compositions, "usage" may vary depending on the type and severity of the soils and stains as well as the temperature of the wash water, the volume of wash water and the type of washing machine.

For example, in a top-loading, upright, U.S. type automatic washing machine using 45 to 83 liters of water in the wash tank, the wash cycle is 10 to 14 minutes, the wash water temperature is 10 ℃ to 50 ℃, and the wash liquor preferably contains 2ppm to 50ppm, preferably 5ppm to 25ppm, of the AQA surfactant. This becomes a product concentration (by weight) of AQA surfactant of from about 0.1% to about 3.2%, preferably from about 0.3% to about 1.5%, for high performance liquid laundry detergents, based on usage rates of from 50 ml to 150 ml per wash load. For concentrated "compact" granular laundry detergents (densities greater than about 650g/l), this becomes an AQA surfactant product concentration (by weight) of from about 0.2% to about 5.0%, preferably from about 0.5% to about 2.5%, based on the use rate per wash load of from about 60 grams to about 95 grams. This will translate to AQA surfactant product concentrations (by weight) of from about 0.1% to about 3.5%, preferably from about 0.3% to about 1.5%, for spray dried granules ("loose"; density less than about 650 grams/liter) according to a use ratio of from about 80 grams to about 100 grams per load.

For example, in a front loading horizontal automatic washing machine employing from about 8 to about 15 liters of water in the wash tank, the wash cycle is from about 10 to about 60 minutes, the wash water temperature is from about 30 ℃ to about 95 ℃, and the AQA surfactant is preferably present in the wash liquor in an amount of from about 13ppm to about 900ppm, preferably from about 16ppm to about 390 ppm. This becomes an AQA surfactant product concentration (by weight) of from about 0.4% to about 2.64, preferably from about 0.55% to about 1.1%, for high performance liquid laundry detergents, based on a usage rate of from about 45 ml to about 270 ml per wash load. For concentrated "compact" granular laundry detergents (densities greater than about 650g/l), this becomes an AQA surfactant product concentration (by weight) of from about 0.5% to about 3.5%, preferably from about 0.7% to about 1.5%, in accordance with a use rate per wash load of from about 40 grams to about 210 grams. This will translate to AQA surfactant product concentrations (by weight) of from about 0.13% to about 1.8%, preferably from about 0.18% to about 0.76%, for spray dried granules ("loose"; density less than about 650 grams/liter) accordingto a use ratio of from about 140 grams to about 400 grams per load.

For example, in a top-loading, upright, Japanese-type automatic washing machine employing from about 26 to about 52 liters of water in the wash tank, the wash cycle is from about 8 to about 15 minutes, the wash water temperature is from about 5℃ to about 25℃, and preferably from about 1.67ppm to about 66.67ppm, preferably from about 3ppm to about 6ppm, of the AQA surfactant is present in the wash liquor. This becomes an AQA surfactant product concentration (by weight) of from about 0.25% to about 10%, preferably from about 1.5% to about 2%, for high performance liquid laundry detergents, based on a usage rate of from about 20 ml to about 30 ml per wash load. For concentrated "compact" granular laundry detergents (densities greater than about 650g/l), this becomes an AQA surfactant product concentration (by weight) of from about 0.25% to about 10%, preferably from about 0.5% to about 1.0%, in accordance with a use rate per wash load of from about 18 grams to about 35 grams. This will translate to AQA surfactant product concentrations (by weight) of from about 0.25% to about 10%, preferably from about 0.5% to about 1%, for spray dried granules ("loose"; density less than about 650 grams/liter) according to a use ratio of from about 30 grams to about 40 grams per load.

Cationic surfactants-the preferred bis-ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the ETHOQUAD trade name. Optionally, such materials may be synthesized using different reaction schemes (where "EO" stands for-CH)₂CH₂O-units) as follows:

scheme 1

Scheme 2

Scheme 3

Scheme 4

One economical reaction mode is as follows.

Scheme 5

The following parameters summarize the selected and preferred reaction conditions of scheme 5. Step 1 of the reaction is preferably carried out in an aqueous medium. The reaction temperature is generally in the range of 140 to 220 ℃. The reaction pressure is 500 to 1000 psig. A basic catalyst, preferably sodium hydroxide, may be used. The molar ratio of the reactants is from 2: 1 to 1: 1 amine to alkyl sulfate. The reaction preferably employs C₈-C₁₃Sodium alkyl sulfate. The ethoxylation and quaternization steps are carried out using conventional conditions and reactants.

In some cases, scheme 5, step 1, results in a product with sufficient solubility in an aqueous reaction medium that may form a gel. Although the desired product can be recovered from the gel, an alternative two-step synthesis scheme 6 below is more desirable in some industrial situations. The second step (ethoxylation) is preferably carried out using ethylene oxide and an acid to provide a quaternary ammonium surfactant, such as HCl. Chlorohydrins such as chloroethanol may also be reacted to form the desired dihydroxyethyl derivative, as described below.

For scheme 6, the following parameters summarize optional and preferred reaction conditions for the first step. The first step is preferably carried out in an aqueous medium. The reaction temperature is generally in the range of 100 to 230 ℃. The reaction pressure is 50-1000 psig. A base, preferably sodium hydroxide, may be used to react with HSO produced during the reaction₄Alternatively, an excess of amine may be used to react with the acid. The molar ratio of amine to alkyl sulfate is generally from 10: 1 to 1: 1.5, preferably from 5: 1 to 1: 1.1, more preferably from 2: 1 to 1: 1. In the product recovery step, the desired substituted amine is simply separated in heterogeneous form from the aqueous reaction medium in which it is insoluble. The second step of the process is carried out under conventional reaction conditions. Further ethoxylation and quaternization reactions to prepare the bis-AQA surfactants were carried out under standard reaction conditions.

Scheme 7 optionally utilizes ethylene oxide under standard ethoxylation conditions, but does not utilize a catalyst to achieve an ethoxylation reaction.

These additional reaction schemes are illustrated below, where "EO" represents-CH₂CH₂An O-unit. In this reaction, the HSO formed is neutralized with an inorganic or organic base or an excess of the amine reactant₄。

Scheme 6

Scheme 7

The reactions described above are further illustrated below and are only convenient for the formulator to use, but not to useIs a limitation thereof.

Synthesis A

Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To a glass autoclave liner were added 19.96 grams of sodium dodecyl sulfate (0.06921 moles), 14.55 grams of diethanolamine (0.1384 moles), 7.6 grams of 50 wt% sodium hydroxide solution (0.095 moles), and 72 grams of distilled water. The glass gasket is sealed in a 500 ml stainless steel rocking autoclave and heated to 160-180 ℃ for 3-4 hours under nitrogen at 300-400 psig. The reaction mixture was cooled to room temperature and the liquid contents of the glass pad were poured into a 250 ml separatory funnel with 80 ml chloroform. The funnel was shaken well for a few minutes, and then the mixture was separated. The lower chloroform layer was withdrawn and the chloroform was evaporated to give the product.

Synthesis of B

Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

1 mol of sodium dodecyl sulfate was reacted with 1 mol of ethanolamine in the presence of a base in the manner described in the synthesis of A. The resulting 2-hydroxyethyldodecylamine was recovered and reacted with 1-chloroethanol to prepare the title compound.

Synthesis C

Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To a glass autoclave liner were added 19.96 grams of sodium lauryl sulfate (0.06921 moles), 21.37 grams of ethanolamine (0.3460 moles), 7.6 grams of 50 weight percent sodium hydroxide solution (0.095 moles), and 72 grams of distilled water. The glass liner is sealed in a 500 ml stainless steel rocking autoclave and heated to 160-180 ℃ for 3-4 hours under nitrogen at 300-400 psig. The reaction mixture was cooled to room temperature and the liquid contents of the glass liner were poured into a 250 ml separatory funnel along with 80 ml chloroform. The funnel was shaken well for a few minutes, and then the mixture wasseparated. The lower chloroform layer was withdrawn and the chloroform was evaporated to give the product. And then the product reacts with 1 molar equivalent of ethylene oxide in the presence of an alkaline catalyst at 120-130 ℃ to generate the required final product.

The disubstituted amines prepared in the above synthesis may be further ethoxylated in a conventional manner. The present invention is directed to the formation of AQA surfactants using alkyl halides for quaternization.

In view of the foregoing, the following is a non-limiting detailed description of the AQA surfactants employed in the present invention. The degree of alkoxylation described herein for AQA surfactants is believed to be described in the average general embodiment for conventional ethoxylated nonionic surfactants. This is because ethoxylation generally produces a mixture of ethoxylated products of varying degrees. Due to the fact thatHere, the total EO value is generally recited, but not all values, such as "EO 2.5", "EO 3.5". Name R¹R²ApR³A’qR⁴AQA-1 C₁₂-C₁₄CH₃EO (also referred to as Coco Methyl EO2) AQA-2C₁₂-C₁₆CH₃(EO)₂EOAQA-3 C₁₂-C₁₄CH₃(EO)₂(EO)₂(Coco Methyl EO4)AQA-4 C₁₂CH₃EO EOAQA-5 C₁₂-C₁₄CH₃(EO)₂(EO)₃AQA-6 C₁₂-C₁₄CH₃(EO)₂(EO)₃AQA-7 C₈-C₁₈CH₃(EO)₃(EO)₂AQA-8 C₁₂-C₁₄CH₃(EO)₄(EO)₄AQA-9 C₁₂-C₁₄C₂H₅(EO)₃(EO)₃AQA-10 C₁₂-C₁₈C₃H₇(EO)₃(EO)₄AQA-11 C₁₂-C₁₈CH₃(propoxy) (EO)₃AQA 12 C₁₀-C₁₈C₂H₅(Isopropoxy)₂(EO)₃AQA-13 C₁₀-C₁₈CH₃(EO/PO)₂(EO)₃AQA-14 C₈-C₁₈CH₃(EO)15^*(EO)15^*AQA-15 C₁₀CH₃EO EOAQA-16 C₈-C₁₂CH₃EO EOAQA-17 C₉-C₁₁CH₃Average EO_3.5AQA-18 C₁₂CH₃Average EO_3.5AQA-19 C₈-C₁₄CH₃(EO)₁₀(EO)₁₀AQA-20 C₁₀C₂H₅(EO)₂(EO)₃AQA-21 C₁₂-C₁₄C₂H₅(EO)₅(EO)₃AQA-22 C₁₂-C₁₈C₃H₇Butoxy (EO)₂

Ethoxy, optionally terminated with methyl or ethyl.

Highly preferred bis-AQA compounds for use herein have the general formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl and mixtures thereof, preferably C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof, and X is any suitable anion that provides charge balance, preferably chloride. With reference to the general formula of AQA above, since in preferred compounds R¹Is prepared from coconut (C)₁₂-C₁₄Alkyl) moiety, R²Is methyl, ApR³And A' qR⁴Each is a monoethoxy group, and this preferred class of compounds is referred to herein as "coconut methyl EO 2" or "bis-AQA-1" as listed above.

Other AQA surfactants useful herein include compounds having the general formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl, p is 1 to 3, q is 1 to 3, R²Is C₁-C₃Alkyl, preferably methyl, and X is an anion, particularly chloride and bromide.

Other compounds of the above type include those in which the ethoxy group (CH)₂CH₂O) units (EO) are propoxylated [ CH (CH) by butoxy (Bu)₃)CH₂O]And [ CH₂CH(CH₃)O]Units (i-Pr) or n-propyl units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Anionic surfactants-the alkylbenzene sulfonate ("LAS") and primary (preferably "AS") or secondary alkyl sulfate components of the present compositions are known and widely used in the industry. As noted above, an important advantage of the present invention is the discovery of AQA surfactants which, when used in the manner disclosed herein, enhance the performance of these other conventional materials. The alkyl chain length of LAS surfactants is generally at C₁₀-C₁₆And the average alkyl chain length of commercially used LAS is in the range of 11 to 13, typically around 11.5. The chain length of the AS surfactant is generally C₁₀-C₂₀And AS for many industrial feedstocks is in the range of 12-18. All such industrial LAS and AS feedstocks are useful in the present invention. Unsaturated sulfates, such as oleyl sulfate, may also be employed. Branched chains C may also be used₁₀-C₂₀Alkyl sulfurAcid salts and secondary (2,3) alkyl sulfates of the general formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃Wherein x and (y +1) are integers of at least about 7 and M is a water-soluble cation, particularly sodium. Mixtures of primary, secondary and branched chains may also be employed. Nonionic surfactant

Non-limiting examples of nonionic surfactants that can be used in the present invention, typically at concentrations of 1% to 55% by weight, include alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C₁₀-C₁₈Glycerol ethers, and the like.

More specifically, condensation products (AE) of primary and secondary fatty alcohols with about 1 to 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the present invention. The alkyl chain of the aliphatic alcohol may be a straight or branched primary or secondary alcohol, typically containing from 8 to 22 carbon atoms. Preferably the condensation products of alcohols bearing an alkyl group containing from 8 to 22, more preferably from 10 to 18 carbon atoms, with from 1 to 10, preferably from 2 to 7, more preferably from 2 to 5, moles of ethylene oxide per mole of alcohol. Examples of such industrially useful nonionic surfactants include: tergitol^TM15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide) and Tergitol^TM24-L-6NMW(C₁₂-C₁₄Condensation products of primary alcohols with 6 moles of ethylene oxide, with narrow low molecular weight distribution), all provided by Union carbide corporation; neodol commercially available from Shell Chemical Company^TM45-9(C₁₄-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Neodol^TM23-3(C₁₂-C₁₃Condensation products of linear alcohols with 3 moles of ethylene oxide), Neodol^TM45-7(C₁₄-C₁₅Condensation products of linear alcohols with 7 moles of ethylene oxide) and Neodol^TM45-5(C₁₄-C₁₅Condensation products of linear alcohols with 5 moles of ethylene oxide); kyro, marketed by the Procter&Gamble Company^TMEOB(C₁₃-C₁₅Condensation products of alcohols with 9 moles of ethylene oxide); and Genapol LA 030 or 050 (C) commercially available from Hoechst₁₂-C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide). The preferred range of HLB in these AE nonionic surfactants is 8 to 11, more preferably 8 to 10. Condensation products with propylene oxide and butylene oxide may also be employed.

Another preferred class of nonionic surfactants useful herein are polyhydroxy fatty acid amide surfactants having the formula:wherein R is¹Is hydrogen or C_1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R²Is C_5-31A hydrocarbon group,z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain or an alkoxylated derivative thereof. Preferably is R¹Is methyl, R²Is straight chain C_11-15Alkyl or C_15-17Alkyl or alkenyl chains, such as coconut alkyl or mixtures thereof, and Z is produced from a reducing sugar, such as glucose, fructose, maltose, lactose, in a reductive amination reaction.Typical examples include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamide. See US5194639 and 5298636. N-alkoxy polyhydroxy fatty acid amides may also be employed; see US 5489393.

Also useful as nonionic surfactants in the present invention are the alkyl polysaccharides disclosed in US4565647, llendado, 1986, 1/21, which carry hydrophobic groups containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and polysaccharides, such as polyglycosides, containing hydrophilic groups containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be employed, such as glucose, galactose, and the galactitol moiety may be replaced by a glucosyl moiety (optionally with a hydrophobic group attached at the 2-,3-, 4-, etc. position, thus producing a glucose or galactose as opposed to a glucoside or galactoside). The internal sugar linkage may be, for example, between a position of another sugar unit and the 2-,3-, 4-, and/or 6-position of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula:

R²O(C_nH_2nO)_t(glucosyl)_xWherein R is²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glucosyl group is preferably produced from glucose. To prepare these compounds, an alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a glucose source to form the glucoside (attachment at the 1-position). Then a further glucosyl unit may be attached in their 1-positionThe preceding glucosyl units are in the 2-,3-, 4-and/or 6-position, preferably predominantly in the 2-position.

Condensates of alkyl phenols of polyethylene oxide, polypropylene oxide and polybutylene oxide are also suitable for use as the nonionic surfactant of the surfactants of the present invention, with polyethylene oxide condensates being preferred. These compounds include condensates of alkyl phenols having a linear or branched chain structure with an alkyl group containing from 6 to 14, preferably from 8 to 14, carbon atoms with alkylene oxides. In a preferred embodiment, the ethylene oxide is present in an amount equal to 2 to 25 moles, more preferably 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Such commercially useful nonionic surfactants include GAFIgepal commercially available from Corport^TMCO-630; triton, marketed by Rohm&Haas Company^TMX-45, X-114, X-100 and X-102. These surfactants are typically referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol are suitable for use as the co-nonionic surfactant of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and is insoluble in water. The addition of a polyoxyethylene moiety to the hydrophobic moiety increases the overall water solubility of the molecule and the liquid nature of the product is maintained at the point where the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of such compounds include some of the commercially available Pluronic available from BASF^TMA surfactant.

Nonionic surfactants also suitable for use in the nonionic surfactant systems of the present invention are the condensation products of ethylene oxide with the product formed by the reaction of ethylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of 2500 to 3000. The hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains 40 to 80% by weight polyoxyethylene and has a molecular weight of 5000 to 11000. Examples of such nonionic surfactants include the commercially available Tetronic surfactants marketed by BASF^TM。

Co-surfactants-non-limiting examples of useful co-surfactants of the present invention containing a mixture of alkyl sulfate and LAS at a concentration generally of about 1% to 55% by weight include: c₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS', in particular EO1-7), C₁₀-C₁₈Alkylalkoxycarboxylates (especially EO1-5) and C₁₀-C₁₈α -sulfonated fatty acid esters C may also be used₁₂-C₁₈Betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈Amine oxides, and the like. May also adopt C₁₀-C₂₀Conventional soaps. If high foam is desired, a branched chain C may be used₁₀-C₁₆Soap. Other commonly used effective surfactants are listed in standard articles.

Various other additive components that may be used in the compositions of the present invention are described below, but are not limited thereto. Although the combination of AQA and anionic surfactant with such additive composition components can be provided as a finished product in the form of a liquid, gel, bar, etc. using conventional techniques, the manufacture of the granular laundry detergents of the present invention requires some specialised processing techniques to achieve the desired performance. Therefore, the production of the detergent granuleswill be described separately below in the granule production section (below) to provide convenience to the formulator.

Adjunct-detergent adjuncts may optionally but preferably be included in the compositions of the invention, for example to assist in controlling the hardening of minerals, especially Ca and/or Mg, in the wash water or to assist in the removal of particulate soils from surfaces. The adjuvant may function by a variety of mechanisms including the formation of soluble or insoluble complexes with the hardening ions by ion exchange and by providing a surface that favors precipitation of the hardening ions over the surface of the object to be cleaned. The level of adjuvant may vary over a wide range depending on the end use of the composition and its desired physical form. Built detergents generally contain at least 1% of an auxiliary. Liquid formulations typically contain from 5% to 50%, more typically from 5% to 35% of the adjuvant. Granular formulations typically contain from 10% to 80%, more usually from 15% to 50% by weight of the detergent composition. Lower or higher levels of auxiliaries are not excluded. For example, some detergent additives or high surfactant builders may be unformulated.

The auxiliaries suitable for use in the present invention are selected from phosphates and polyphosphates, especially sodium salts; silicates, including water soluble and hydrated solids, and including those having chain-, layer-, or three-dimensional structures as well as amorphous solids or unstructured liquids; carbonate, bicarbonate, sesquicarbonate and carbonate minerals other than sodium carbonate or sesquicarbonate; an aluminosilicate; organic mono-, di-, tri-and tetracarboxylic acid salts, especially water-soluble non-surfactant carboxylates, in the form of the acid, sodium, potassium or alkanolammonium salts, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including fats and aromatics; and phytic acid. They may be complementary to borates, for example to buffer pH, or to sulfates, especially sodium sulfate and any other fillers or carriers, which are important in making stable surfactant and/or builder-containing detergent compositions.

Auxiliary mixtures, sometimes called "auxiliary systems", can also be used and generally contain two or more conventional auxiliaries, optionally assisted by chelating agents, pH buffers or fillers, the latter substances being described individually in connection with the amounts of substances according to the invention. In terms of the relative amounts of surfactant and adjuvant of the present invention, the preferred adjuvant system is generally formulated in a weight ratio of surfactant to adjuvant of from 60: 1 to 1: 80. This ratio for some preferred laundry detergents is in the range of 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.0 to 3.0: 1.0.

Phosphorus-containing detergent builders are generally preferred where permitted by law, but are not limited to the alkali metal, ammonium and alkanolammonium salts of polyphosphoric acids, representative being the tripolyphosphonates, pyrophosphates and glassy polymeric metaphosphates and phosphates.

Suitable silicate builders include alkali metal silicates, especially those of SiO₂∶Na₂The ratio of O is 1.6: 1 to 3Between 2: 1 liquids and solids, including solid hydrated 2-fold silicates, especially for automatic dishwashing purposes, by PQ Corp under the trade name BRITESSIL^_Commercially available, e.g. BRITESSIL H₂O; and layered silicates, such as those described in US4664839, h.p. rieck, 5.12.1987. NaSKS-6, sometimes abbreviated as "SKS-6" isCrystalline layered aluminum-free delta-Na provided by Hoechst₂SiO₅The silicates in their form and are particularly preferred for use in granular laundry detergent compositions. See DE-A-3417649 and DE-A-3742043 in Germany for the preparation thereof. Other layered silicates of the formula NaMSi_xO_2X-1.yH₂The layered silicates provided by Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, such as α, β and γ layered silicates other silicates are also effective, such as magnesium silicate, which act as crisping agents in granular formulations, as stabilizing agents for bleaching agents and as a component of foam inhibition systems.

Also suitable for use in the present invention are synthetic crystalline ion exchange materials or hydrates thereof, which have a chain structure and whose composition is represented by the general formula: xM₂O.ySiO₂zM 'O, wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as described in US5427711, Sakaguchi et al, 1995, month 6 and day 27.

Suitable carbonate builders include alkaline earth and alkali metal carbonates, such as disclosed in German patent application 2321001, 1973, 11/15/although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonates, such as sodium bicarbonate or any conventional double salt of sodium carbonate and calcium carbonate, such as those having a composition of 2Na when anhydrous₂CO₃.CaCO₃And even calcium carbonate, including calcite, aragonite and vaterite, especially having a high surface area relative to dense calcite, for example as a seed or for use in synthetic detergent bars, may be employed.

Aluminosilicate builders are particularly effective in granular detergents and can be added in liquid, paste or gel form. Suitable for the purposes of the present invention have the following general formula: [ M]A_z(AlO₂)_z(SiO₂)_v].xH₂O, wherein z and v are integers of at least 6, the molar ratio of z to vis in the range of 1.0 to 0.5, and x is an integer from about 15 to about 264. The aluminosilicate may be crystalline or amorphous, natural aluminosilicate or synthetic. A process for the preparation of aluminosilicates is disclosed in US3985669, K rummel et al, 1976, month 10 and day 12. Preferred synthetic crystalline aluminosilicate ion exchange materials may employ zeolite a, zeolite P (b), zeolite X and differ to some extent from zeolite P, the so-called zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite a has the general formula: na (Na)₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O, wherein x is a number from about 20 to about 30, especially about 27. Dehydrated zeolite (x =0 to 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1 to 10 μm in diameter.

Suitable organic detergent builders include polycarboxylate compounds, including water-soluble non-surfactant di-and tri-carboxylates. More typical coagent polycarboxylates are compounds containing a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate aids can generally be formulated in an acidic, partially neutral, neutral or overbased form. When in salt form, alkali metal salts, such as sodium, potassium and lithium or alkoxide salts are preferred. Polycarboxylate adjuvants include ether polycarboxylates such as oxybutyrate, see US3128287, berg.,1964, 7.4 and US3635830, Lamberti et al, 1972, 1-18.2; US4663071 Bush et al, 5.5.1987 for "TMS/TDS" adjuvant; and other ether polycarboxylates further comprising cyclic and alicyclic compounds, as disclosed for example in US3923679, 3835163, 4158635, 4120874 and 4102903.

Other useful detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, carboxymethyloxysuccinic acid, polyacetic acids such as the various alkali metal, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3, 5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its sodium salt, are particularly important polycarboxylate builders, for example for high-performance liquid detergent formulations, as they are available because of the renewable raw materials and their biodegradability. Citrate salts may also be used in the particulate composition, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly effective in these compositions and combinations.

Alkali metal phosphates such as sodium tripolyphosphate, pyrophosphate and sodium orthophosphate can be used if permitted, and particularly when formulating sticks for hand washing operations. Phosphonate builders may also be employed and may have antifouling properties, for example ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates, for example US3159581, 3213030, 3422021, 3400148 and 3422137.

Some detersive surfactants or their short chain homologs also have an adjunct role. When they function as surfactants, these materials together act as detersive surfactants for what is commonly referred to as a purpose. Preferred types of adjuvant action are illustrated by 3, 3-dicarboxy-4-oxa-1, 6-adipates and related compounds, which are disclosed in US4566984, Bush, 28.1.1986. The succinic acid auxiliary agent comprises C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. The succinate adjuvant also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinateSuccinates and thelike. Lauryl succinate is described in EP86200690.5/0200263,1986 at 11/5 days. Fatty acids, such as C12-C18 monocarboxylic acids, may also be added to the composition, alone or in combination with the above adjuvants, as surfactants/adjuvants, especially citrate and/or succinate adjuvants, to provide adjuvantsAnd (4) auxiliary agent activity. Other suitable polycarboxylates are disclosed in US4144226, Crutchfield et al, 3.13.1979 and US3308067, Diehl, 3.7.1967. See US3723322 to Diehl.

Other types of inorganic adjuvants that may be employed have the general formula: (M)_x)_iCa_y(CO₃)_zWherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_iIs cationic, at least one is water soluble, and satisfies the equation ∑_i=1-15(x_iMultiplying by M_iThe valence of) +2y =2z renders the formula neutral or "balanced" charge. These auxiliaries are referred to herein as "inorganic auxiliaries". Hydration water or anions other than carbonate may be added as long as the overall charge is balanced or neutral. The charge or valence of these anions can be added to the right side of the above equation. Preferably, a water-soluble cation is present selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred. Non-limiting ions of non-carbonate anions are selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate and mixtures thereof. Preferred such adjuvants in their simplest form are selected from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And combinations thereof. Particularly preferred materials for the auxiliaries of the invention are any Na crystal-modified Na₂Ca(CO₃)₂. Suitable adjuvants of the above type are further described and include any one or a combination of the following in natural or synthetic form: acalcite, uraninite, offretite, bayerite, colemanite, strontianite, canasite, cancrinite, cerite, canasite, kalsilite, strontianiteY, kalanchite, Ferrisurite, forskolite, cancrinite, cancerate, monetite, Girvasite, ilmenite, canasite, Kamphaugite, Kettnerite, Khannesite, Lepersonneite Gd, eucryptite, barite Y, micro kalinite, Mroseite, nysferrite, Nintenite, Remonite, savealite, Arkunitanite, Caulonite, Naringite, Sukekalite, Alkulite, Alcalite, Naringite, Sukekalite, Cuplodite, Caulgite, and Zemkorite preferred minerals include, barite Y, micro kalinite, Mroseite, Nicancrite, kallaite, and hydrocalcite.

Enzyme

Enzymes may be included in the detergent compositions of the present invention for a variety of uses, including removal of protein-based, carbohydrate-based or triglyceride-based stains from substrates to prevent dye transfer during laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures of any suitable starting material, for example of vegetable, animal, bacterial, fungal and yeast origin. The preferred choice is influenced by factors such as pH activity and/or stability, thermal stability and stability to the active detergent, adjuvants and the like. In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.

As used herein, "detersive enzyme" refers to any enzyme that has a cleaning, stain removal or other benefit in a laundry, hard surface cleaning or body care detergent composition. Preferred detergent enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for washing purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, both of the type currently used in the industry and of the modified type, which, despite the increasing improvement of the adaptability of the bleaching agents, still have a sensitivity to bleach deactivation.

The enzyme is typically added to the detergent or detergent additive composition in an amount sufficient to provide a "detergent effective amount". By "wash effective amount" is meant any amount that is capable of producing a cleaning, stain removal, soil release, whitening, deodorizing or vibrant enhancing effect on a substrate, such as a fabric. In fact, for current commercial production, typical amounts are up to about 5 mg by weight, more usually 0.01 to 3 mg, of active enzyme per gram of detergent composition. It is also to be noted that the compositions of the invention generally contain from 0.001% to 5%, preferably from 0.01% to 1% by weight of the industrial enzyme preparation. Proteases are generally present in these industrial formulations in amounts sufficient to have an activity of 0.005 to 0.1 daltons units (AU) per gram of composition. For some detergents, it is desirable to increase the active enzyme content of an industrial formulation to reduce the total amount of non-catalytically active material, thereby improving spotting/filming or other end results. Higher levels of activity are also desirable for high level detergent formulations.

Examples of suitable proteases are subtilisins, which are prepared from specific genera of Bacillus subtilis and Bacillus licheniformis. A suitable protease is prepared from the genus Bacillus, as ESPERASE from Novo Industries A/S (Novo) of Denmark, with a maximum activity pHin the range of 8-12^_Developed and sold. The preparation of this and similar enzymes is described in GB1243784 to Novo. Other suitable enzymes include ALCALASE supplied by Novo^_And SAVINASE^_And MAXATASE supplied by International Bio-Synthesis, Inc. of the Netherlands^_(ii) a And in EP130756A,1985Protease A at 9.1.1987 and protease B disclosed in EP303761A, 28.4.1987 and EP130756A, 9.1.1985. See also WO9318140A in Novo for high pH proteases from Bacillus NCIMB 40338. Enzymatic detergents containing a protease, one or several other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those described in WO9510591 to Procter&Gamble. When desired, proteases which reduce absorption and increase hydrolysis as described in WO9507791 to Procter&Gamble may be used. Recombinant trypsin-like proteases for use in the detergents of the invention are described in WO9425583 to Novo.

More specifically, a particularly preferred Protease, namely "Protease D", is a variant of a carbonyl hydrolase having an amino acid sequence not found in nature, which is prepared from a carbonyl hydrolase precursor by substituting a plurality of amino acid residues with different amino acids at positions equivalent to position +76 in said carbonyl hydrolase, preferably in combination with one or more amino acid residues equivalent to a sequence selected from the group consisting of +99, +101, +103, + 104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, + 63218, +222, +260, +265 and/or +274 in the sequence of Bacillus amyloliquefaciens subtilisin, as described in US08/322676 and C.Ghoschinges et al, entitled "Protease-Containing cleavage reactions", of A.Baeck et al, both were published at 10/13 of 1941.

Amylases suitable for use in the present invention, particularly but not exclusively forautomatic dishwashing purposes, include, for example, the α -amylase described in GB1296839 to Novo, RAPIDASE from International Bio-Synthesis, Inc^_TERMAMYL OF NOVO^_FUNGAMYL of Novo^_Is particularly effective. Techniques for using enzymes to improve stability, e.g., oxidative stability, are known. See, e.g., J.biological chem., volume 260, volume 11, 6.1985, pages 6518-6521. Some preferred embodiments of the compositions of the present invention may employ amylases of improved stability in detergents, particularly an improvement over TERMAMYL, which was industrially employed in 1993^_Reference point of (2) oxidation stability. These preferred amylases of the invention have the characteristics of an "improved stability" amylase characterized by a major improvement in at least one or more of the following: oxidation stability, such as in a buffered solution of hydrogen peroxide/tetraacetylethylenediamine at a pH of 9-10; thermal stability, e.g., at typical washing temperatures, e.g., about 60 ℃; or alkaline stability, e.g., at a pH of about 8 to about 11, as determined with the above-mentioned ginsengAnd (5) enzyme comparison of test spots. Stability can be tested using any of the techniques disclosed in the artSee, for example, reference WO 9402597. enzymes of enhanced stability are available from Novo or Genencor International A very preferred class of enzymes of the invention have in common the use of in situ mutagens for preparation from one or more bacterial amylases, particularly Bacillus α -amylase, regardless of whether one, two or more amylase strains are transient precursors^_(ii) a stability-enhancing amylase, as described in the paper entitled "oxidative stability Resistant α -Amylases" published by C.Mitchinson in the 207th American chemical Society National Meeting of 3, 13-17, 1994, wherein it is noted that bleaching agents inactivate α -Amylases in automatic dishwashing detergents, but the oxidation stability-enhancingamylase was produced by Genencor from Bacillus licheniformis NCIB8061 methionine (Met) can be considered to be the most likely residue to be modified^_And SUNLIGHT^_Is determined in (a); (c) particularly preferred amylases include amylase variants having further improvements in transient matrix, as described in WO9510603A and sold by Novo under DURAMYL^_Provided is a method. Other particularly preferred oxidative stability-enhancing amylases include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other amylase that improves oxidative stability may be used, for example from known chimeras, hybrids or simple mutants of the amylases that may be usedVariant precursors were prepared by direct mutagenesis. Modifications of other preferred enzymes may be made. See WO9509909 to Novo.

Other amylases include those described in WO95/26397 and in PCT/DK96/00056, commonly owned by Novo Nordisk specific amylases useful in the detergent compositions of the invention include α -amylases characterized by a specific activity at least higher than Termamyl in the temperature range of 25 to 55 ℃ and pH range of 8 to 10^_25% of the total content is expressed by Phadebas^_α -determination of amylase activity (Phadebas of this type)^_α -determination of the activity of Amylase is described in WO95/26397Pages 9-10.) the present invention also includes α -amylases of which at least 80% of the homologues have the amino acid sequences shown in the reference table of SEQ ID the enzymes are preferably incorporated into a laundry detergent composition at a level of from 0.00018% to 0.060% by weight, more preferably from 0.00024% to 0.048% pure enzyme based on the total weight of the composition.

Cellulases usable in the present invention include those of bacteria and fungi, and preferably have a pH of between 5 and 9.5. US4435307 by Barbesgoard et al, 3/6/1984, discloses fungal cellulases or cellulases 212 prepared from Humicola insolens or pythium DSM 1800-prepared from fungi belonging to the genus aeromonas, and the cellulase Dolabella Auricula Solander extracted from the liver pancreas of ship maggots. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832. CAREZYME^_(Novo) and CELLU ZYME^_(Novo) is particularly effective. See WO9117243 to Novo.

Suitable lipases for use in washing applications include those prepared from microorganisms of the genus Pseudomonas, e.g., Pseudomonas stutzeri ATCC19.154, as disclosed in GB 1372034. Lipase can also be found in Japanese patent application No. 5320487 published on 24/2 of 1978. Such lipases are supplied by Amano Pharmaceutical co. Other suitable industrial lipases include Amano-CES, lipases produced by Chromobacter viscosum, such as Chromobacter viscosum NRRLB3673 supplied by Toyo Jozo Co.Tagata, Japan; U.S. Bi by the United statesChromobacter viscosum lipases from Ocomical Corp. and Di soynth Co. of the Netherlands, and lipases prepared from Pseudomonas gladioli. Lipolase derived from Humicola lanuginosa and industrially produced by Novo^_Enzymes, see EP341947, are preferred lipases herein. Peroxidase-stabilized lipase and amylase variants are described in WO9414951A to Novo. See WO9205249 and RD 94359044.

Despite the extensive disclosure of lipases, only lipases produced from Humicola lanuginosa and in Aspergillus oryzae as substrates have now found widespread use as additives for fabric washing products. It is produced by Novo Nordisk under the above-mentioned trade name Lipolase^TMProvided is a method. To optimize the soil removal performance of Lipolase, Novo Nordisk produced a number of variants. The D96L variant of the native Humicola lanuginosa lipase, as described in WO92/05249, enhances the soil removal effect by a factor of 4.4 over the wild-type lipase (enzyme containing 0.075 to 2.5 mg protein per liter relative to the amount). "open research" 3/10/35944,1994 Novo Nordisk discloses that lipase variants (D96L) may correspond to0.001-100 mg (5-500000 LU/l) lipase variant per liter of wash liquor. The present invention provides that the use of low concentrations of the D96L variant in detergent compositions containing bis-AQA surfactants in the manner disclosed herein facilitates improved fabric bleaching maintenance, particularly with D96L at 50LU to 8500LU per liter wash solution.

The Cutinase enzyme suitable for use in the present invention is described in WO8809367A to Genencor.

Peroxidases can be combined with oxygen sources, such as percarbonates, perborates, hydroxides, etc., to "solution bleach" or to prevent dye transfer or pigment transfer from a substrate to other substrates present in the wash solution during the wash process. Known peroxides include horseradish peroxidase, ligninase, haloperoxidases, such as chloro-or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO89099813A, which was entitled to by Novo at 10/19 in 1989, and WO8909813A by Novo.

The range of enzymatic materials and methods for their incorporation into synthetic detergent compositions are described in WO9307263A and WO9307260A by Genencor International, WO8908694A by Novo, and US3553139 by McCarty et al, entitled 1/5 of 1971. Enzymes are also disclosed in US4101457 by Place et al, entitled 7/18 in 1978, and US4507219 by Hughes, entitled 26/3 in 1985. Enzymes useful in liquid detergent formulations and methods of incorporating them into such formulations are disclosed in US4261868 entitled by Hora et al at 4/14 1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and are typically described in US3600319, entitled by Gedge et al, 8/17 in 1971, and EP199405 and EP200586, entitled by Venegas, 10/29 in 1986. Enzyme stabilization systems are also described, for example, in US 3519570. An effective subtilisin AC13 for the production of proteases, xylanases and cellulases is described in WO9401532A to Novo.

Enzyme stabilizing system

The liquid compositions of the present invention containing enzymes, but not limited thereto, may contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detergent enzyme. Such systems are inherently provided by the active substance of other formulations or are provided separately by the formulator or by the manufacturer of the finished detergent enzyme. Such stabilizing systems may, for example, contain calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof, and are designed for different stability issues depending on the type and physical state of the detergent composition.

One method of stabilization is to employ water-soluble sources of calcium and/or magnesium ions in the final composition so that the enzyme contains such ions. Calcium ions are generally more effective than magnesium ions and are preferred in the present invention, if only one, calcium ions may be used. Typical detergent compositions, especially liquid, contain from about 1 to about 30, preferably from about 2 to 20, more preferably from about 8 to 12 millimoles of calcium ion per liter of finished detergent composition, and will vary depending upon factors including variety, type and concentration of enzyme added. Water-soluble calcium and magnesium salts are preferably employed, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate; calcium sulfate or magnesium salts corresponding to typical calcium salts may generally be employed. Further increasing the calcium and/or magnesium concentration is of course effective, for example to promote the degreasing action of certain types of surfactants.

Another method of stabilization is the use of borates. See Severson, US 4537706. When borate stabilizers are used, the concentration may be as high as 10% or more of the composition, while generally concentrations of boric acid or other borate compounds, such as borax or orthoborate, of up to about 3% by weight may be suitable for liquid detergent use. Substituted boronic acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid and the like may be used in place of the boronic acid, and the total amount of boron in the detergent composition may be reduced by employing such substituted boron derivatives.

Some cleaning composition stabilizing systems, such as automatic dishwashing compositions, may further contain from 0 to about 10%, preferably from about 0.01% to about 6%, by weight, of a chlorine bleach scavenger to prevent chlorine bleach materials present in many water sources from acting on and deactivating the enzyme, especially under alkaline conditions. When the concentration of chlorine in water is small, typically in the range of about 0.5ppm to about 1.75ppm, the available chlorine in the total volume of total water that contacts the enzyme, such as in a fabric washing process, can be substantial; thus, the stability of the enzyme to the chlorine used sometimes presents problems. Since perborate or percarbonate, which are capable of reacting with chlorine bleach, may be present in certain instant compositions in amounts separate from the stabilizing system, the use of other anti-chlorine stabilizers may be less important, although improved results may be obtained with them. Suitable chlorine scavenger anions are known and readily available and, if used, may be salts containing an ammonium cation with sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. Antioxidants such as carbamates, ascorbic acid, and the like, organic amines such as Ethylene Diamine Tetraacetic Acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof may also be used. Likewise, special enzyme inhibition systems may be added to maximize the compatibility of the various enzymes. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate, and sodium percarbonate, as well as phosphates, concentrated phosphates, acetates, benzoates, citrates, formates, laurates, malates, tartrates, salicylates, and the like, and mixtures thereof may also be employed if desired. In general, since the action of the chlorine scavenger can be performed by separately listed components (e.g., hydrogen peroxide feedstock) that are considered to perform better, there is no need to add a separate chlorine scavenger unless compounds having this desired degree of action are not included in the enzyme-containing embodiments of the present invention; even more, the scavenger is added only for optimal results. Moreover, the formulator will avoid using any enzyme scavengers or stabilizers, if used, which are not very compatible with the other reaction components at the time of formulation, according to the chemist's general experience. As with ammonium salts, such salts can simply be mixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. Thus, such materials, if present, need to be protected in particles, as described in US4652392 to Baginski et al.

Polymeric soil release agents

Known polymeric soil release agents, referred to herein as "SRA" or "SRA's", may optionally be used in the compositions of the present invention. If employed, the SRA's are generally from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition.

Preferred SRA's generally contain hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain attached thereto by performing washing and rinsing operations, thus serving to anchor the hydrophilic segments. This allows stains generated after treatment with SRA to be easily removed in the following washing step.

SRA's may comprise various charged, such as anionic or even cationic (see US4956447), as well as uncharged monomeric units, and their structure may be linear, branched or even star-like. They may include end-capping moieties which are particularly effective in controlling molecular weight or adjusting physical properties or surface activity. The structure and charge distribution can be tailored for use with different fiber or fabric types and for use in various detergent or detergent additive products.

Preferred SRA's comprise oligomeric terephthalates, generally prepared by a process comprising at least one transesterification/oligomerization reaction, typically using a metal catalyst, such as a titanium alkoxide (iv). Such esters may be prepared using other monomers that can be incorporated into the ester structure through one, two, three, four or more positions, without forming, of course, a densely crosslinked overall structure.

Suitable SRA's include: sulfonated products of oligomers of substantially linear esters containing an oligoester backbone of terephthaloyl and oxyalkylene repeat units and allyl-derived sulfonated end moieties covalently bonded to the backbone, as described, for example, in US4968451 entitled j.j.scheibel and e.p.gosselink, 6.1990, 11.s. Such ester oligomers can be prepared by: (a) ethoxylated allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") in a two-step transesterification/oligomerization step; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the non-ionically end-capped 1, 2-propylene/polyoxyethylene terephthalate polyesters of Gosselink et al, US4711730, entitled 12/8/1987, prepared, for example, by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) ("PEG"). Other examples of SRA's include: partially and fully anionic-capped oligoesters such as those prepared from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctyl sulfonate, obtained by Gosselink et al in US4721580, entitled 26/1/1988; non-ionic end-capped block polyester oligomeric compounds, such as prepared from DMT, methyl (methyl) -capped PEG and EG and/or PG, or combinations of DMT, EG and/or PG, methyl-capped PEG and Na-dimethyl-5-sulfoisophthalate, of Gosselink et al, entitled, 27.10.1987; and anionic, particularly sulfoaroyl, capped terephthalates of US4877896, entitled, by Maldonado, Gosselink et al, 31/10/1989, which are typical of SRA's used in laundry and fabric conditioning products, one example being an ester composition prepared from monosodium m-sulfobenzoate, PG and DMT, optionally but preferably further containing added PEG, such as PFG 3400.

SRA's also include: simple block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see Hays, US3959230 on 25/5/1976 and Basadur, US3893929 on 8/7/1975; cellulose derivatives, for example hydroxy ether cellulose polymers such as METHOCEL supplied by Dow; c₁-C₄Alkyl celluloses and C₄Hydroxyalkyl cellulose, see Nicol et al, US4000093 at 12.28.1976. Suitable SRA's characterized by a poly (vinyl ester) hydrophobic segment include graft copolymers of poly(vinyl esters), such as C₁-C₆Vinyl esters, preferably poly (vinyl acetate), are grafted onto a polyalkylene oxide backbone. See EP0219048, published by Kud et al at 22.4.1987. Examples of commercially available include SOKALAN SRA's, such as SOKALAN HP-22, supplied by BASF in Germany. Other SRA's are polyesters containing 10 to 15 weight percent ethylene terephthalate and 90 to 80 weight percent polyethylene terephthalate repeat units derived from polyethylene oxide glycol having an average molecular weight of 300 to 5000. Industrial examples include ZELCON5126 supplied by Dupont and millase supplied by ICI.

Another preferred SRA is an oligomer having the formula: (CAP)₂(EG/PG)₅(T)₅(SIP)₁It contains p-benzoyl (T), sulfo-m-benzoyl (SIP), oxygenEthylene oxide and oxy-1, 2-propylene (EG/PG) units, and which are preferably capped with a capping group (CAP), preferably a modified isethionate, as in the case of a compound containing a sulfoisophthaloyl groupUnits, 5 terephthalyl units, defined proportions of oxyethylene and oxy-1, 2-propyleneoxy units, preferably in a ratio of 0.5: 1 to about 10: 1, and two capping units derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate. Said SRA preferably further contains from 0.5% to 20% by weight of an oligomeric crystallization-reducing stabilizer, such as an anionic surfactant, e.g. linear sodium dodecylbenzenesulfonate or a substance selected from the group consisting of xylene-, cumene-and toluene-sulfonates or mixtures thereof, which stabilizers or modifiers may be added to the synthesis vessel, all of which are described in US5415807 to which Gosselink, Pan, Kellett and Hall were entitled 5/16 of 1995. Suitable monomers for use in the above-described SRA include sodium 2- (2-hydroxyethoxy) -ethane sulfonate, DMT, sodium dimethyl isophthalate-5-sulfonate, EG, and PG.

Yet another preferred class of SRA's are oligomeric esters, which include: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonate, polyhydroxysulfonate, an at least trifunctional unit whereby ester linkages result in a branched oligomer backbone, and combinations thereof; (b) at least one unit of a terephthaloyl moiety and (c) at least one unsulfonated unit that is a1, 2-oxyalkylene moiety; and (2) one or more end-capping units selected from the group consisting of nonionic end-capping units, anionic end-capping units, such as alkoxylated, preferably ethoxylated isethionates, alkoxylated propane sulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred esters are of the formula:

{ (CAP) x (EG/PG) y ' (DEG) y ' (PEG) y- (T) z (SIP) z ' (SEG) q (B) m } where CAP, EG/PG, PEG, T and SIP are as described above, (DEG) represents di (oxyethylene) oxy units, (SEG) represents units derived from sulfonated ethyl ether of glycerol and related partial units, (B) represents branched units which are at least trifunctional with which ester groups are formed to produce a branched oligomeric backbone, x is from about 1 to about 12, y ' is from about 0.5 to about 25, y ' is from 0 to about 12, y ' is from 0 to about 10, the sum y ' + y ' is from about 0.5 to about 25, z is from about 1.5 to about 25, and z ' is from 0 to about 12; z + z' together is from 1.5 to about 25 and q is from about 0.05 to 12; m is from about 0.01 to about 10, and x, y ', y ", y '", z ', q, and m represent the average number of moles of the corresponding units per mole of said ester, said ester having a molecular weight of from about 500 to about 5000.

Preferred SEG and CAP monomers for use in the above esters include Na-2- (2-, 3-dihydroxypropane)Oxy) ethanesulfonate ("SEG"), Na-2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3") and its homologs, and mixtures thereof and productsof ethoxylated and sulfonated allyl alcohols. Preferred SRA esters in this class include those which are transesterified and oligomerized with a suitable Ti (IV) catalyst sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethane sulfonate and/or 2- [2- {2(2 hydroxyethoxy) ethoxy } -ethoxy]ethane sulfonate]Sodium ethane sulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethane sulfonate, EG, and PG, and can be expressed as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is (Na + O)₃S[CH₂CH₂O]3.5) -and B are units derived from glycerol, and the molar ratio of EG/PG, as determined by conventional gas chromatography after hydrolysis is complete, is about 1.7: 1.

Other types of SRA's include: nonionic terephthalates with a diisocyanate coupling agent for linking the polymeric ester structures are described in U.S. Pat. No. 4,4201824 to Violland et al and U.S. Pat. No. 4,4240918 to Lagasse et al; and (II) SRA's having carboxylate end groups prepared by converting terminal hydroxyl groups to trimellitate esters by adding trimellitic anhydride to known SRA's. With proper selection of the catalyst, the trimellitic anhydride bonds to the polymer ends through the ester of the carboxylic acid alone of trimellitic anhydride rather than by opening the anhydride linkage. Nonionic or anionic SRA's may be used as starting materials, provided they have hydroxyl groups which can be esterified. See Tung et al, US 4525524. Other types include: (III) anionic terephthalate-based SRA's in the form of urethane linkages, see U.S. Pat. No. 4,4201824 to Violland et al; (iv) poly (vinyl caprolactam) and related copolymers made from monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including nonionic and cationic polymers, see US4579681 to Ruppert et al; (V) graft copolymers, in addition to the SOKALAN types provided by BASF, are prepared by grafting acrylic monomers onto sulfonated polyesters. These SRA's should have soil release and anti-redeposition activitysimilar to known cellulose ethers: see EP279134A by Rhone-Poulenc Chemie in 1988. Still other types include: (VI) grafting of vinyl monomers, such as acrylic acid and vinyl acetate, onto proteins, such as casein, see EP457205A to BASF (1991); and (VII) polyester-polyamide SRA's prepared by condensation of adipic acid, caprolactam and polyethylene glycol, are particularly useful for treating polyamide fabrics, see Bevan et al, Unilever N.V. DE2335044 in 1974. Other effective SRA's are described in US4240918, 4787989, 4525524 and 4877896.

Bleaching compounds-bleaching agents and bleach activators-the detergent compositions of the present invention may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When included, the bleaching agent will be present in an amount of from about 1% to about 30%, more preferably from about 5% to 20% of the detergent composition, especially for fabric laundering. If included, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleach composition containing the bleach plus bleach activator.

The bleaching agent employed in the present invention may be any of those presently known or to be known for use in detergent compositions for fabric cleaning. They include oxygen bleaches, as well as other bleaching agents. Perborate bleaches such as sodium perborate (e.g., mono-or tetrahydrate) may be used.

Other classes of non-limiting bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, magnesium meta-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. These bleaches are disclosed in US4483781, entitled by Hartman at 20/11 1984, US740446, entitled by Burns et al at 3/6 1985,EP0133354, issued by Bank et al at 20/2 1985, and US4412934, entitled by Chung et al at 1/11 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxyhexanoic acid, as described in US4634551 by Burns et al, entitled 1/6 in 1987.

Peroxygen bleaches may also be employed. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent amounts of "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE commercially produced by DuPont) may also be used.

Preferred percarbonate bleach compositions contain dry particles having an average particle size in the range of from about 500 microns to about 1000 microns, no more than about 10% by weight of said particles being less than about 200 microns, and no more than about 10% by weight of said particles being greater than about 1250 microns. Optionally, the percarbonate may be coated with silicate, borate or water soluble surfactants. Percarbonate can be derived from a variety of industrial feedstocks, for example FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be employed.

Peroxygen bleaches, perborates, percarbonates, and the like are preferably used in combination with bleach activators, which may be prepared in situ (e.g., during a wash) in an aqueous solution of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of active agents are disclosed in US4915854 and US4412934, which Mao et al have acquired rights in 4/10 1990. Typically nonanoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TAED) actives, and mixtures thereof may also be employed. See US4634551 for other types of bleaching and active agents.

Highly preferred amide derived bleach activators are of the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C(O)L

Wherein R is¹Is an alkyl radical having from about 6 to 12 carbon atoms, R²Is an alkylene radical having from about 1 to 6 carbon atoms, R⁵Is hydrogen or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms and L is any leaving group which may be used. The leaving group being a result of the nucleophilic action of the perhydrolyzed anion on the bleach activatorAny group displaced from the bleach activator. Preferably the leaving group is benzenesulfonate.

Preferred examples of bleach activators having the above general formula include (6-octanoylamide-hexanoyl) oxybenzene-sulfonate, (6-nonanoylhexanoyl) oxybenzene-sulfonate, (6-decanoyl-hexanoyl) oxybenzene-sulfonate and mixtures thereof, which are described in US4634551, which is incorporated herein by reference.

Other classes of bleach activators include benzoxazines disclosed in US4966723 issued by Hodge et al on 1990, 30.10.4, which is incorporated herein by reference. Highly preferred benzoxazine-based active agents are:

yet another preferred class of bleach activators includes acyl lactam activators, particularly acyl caprolactams and acyl valerolactams of the general formula:

wherein R is⁶Is hydrogen or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam actives include benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also SandersonUS 454545784, which is entitled to 1985 at 10/8, and which is incorporated herein by reference, discloses acyl caprolactams, including benzoyl caprolactam, absorbed in sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and may be used in the present invention. One particularly advantageous class of non-oxygen bleaching agents includes photosensitizing bleaching agents such as sulfonated zinc and/or aluminum phthalocyanine. See US4033718 entitled to holcomb et al, 5/7 1977. If employed, detergent compositions typically contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially zinc phthalocyanine sulfonates.

If desired, the bleaching compound may be catalyzed by a manganese compound. Such compounds are known in the art and include, for example, manganese-based catalysts, which are disclosed in US5246621, US5244594, US5194416, US5114606 and EP549271a1, 549272a1, 544440a2 and 544490a 1; preferred examples of these catalysts include Mn^Ⅳ ₂(u-O)₃(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂、Mn^Ⅲ ₂(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(ClO₄)₂、Mn^Ⅳ ₄(u-O)₆(1,4, 7-triazacyclononane)₄(ClO₄)₄、Mn^ⅢMn^Ⅳ ₄(u-O)₁(u-OAc)₂- (1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^Ⅳ(1,4, 7-trimethyl-1, 4, 7-triazacyclononane) - (OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include those disclosed in US4430243 and US 5114611. The use of manganese with various complex ligands to promote bleaching is also disclosed in US4728455, 5284944, 5246612, 5256779, 5280117, 5274147, 5153161 and 5227084 below.

Indeed, and not by way of limitation, the compositions and methods of the present invention can be adapted to have at least one part per million concentration of active bleach catalyst species in the aqueous wash liquor, and preferably from about 0.1ppm to about 700ppm, more preferably from about 1ppm to about 500ppm, of catalytic species in the laundry liquor.

Cobalt bleach catalysts for use in the present invention are known and described, for example, in "Base Hydrolysis of Transition-Metal Complexes", adv. Inorg. Bioinorg. mech. (1983),2, p1-94, M.L. Tobe. The most preferred cobalt catalyst of the present invention is cobalt pentamine acetate having the general formula: [ Co (NH)₃)₅OAc]T_yWherein "OAc" represents an acetate moiety, "T_y"is an anion, in particular Copentamine acetate chloride, [ Co (NH)₃)₅OAc]Cl₂(ii) a And [ Co (N)]H₃)₅OAc](OAc)₂；[Co(NH₃)₅OAc](PF₆)₂；[Co(NH₃)₅OAc](SO₄)；[Co(NH₃)₅OAc](BF₄)₂(ii) a And [ Co (NH)₃)₅OAc](NO₃)₂(herein "PAC").

These cobalt catalysts are readily prepared by known methods, for example as described in the article by Tobe and in U.S. Pat. No. 4,4810410, Diakun et al, 3.7.3.1989, J.chem.Ed. (1989),66(12), 1043-45; the Synthesis and Classification of organic Compounds, W.L. Jolly (Prentice-Hall; 1970) pp 461-3; chem.,18,1497-1502 (1979); chem.,21,2881-2885 (1982); chem, 18,2023-2025 (1979); synthesis,173- "176 (1960); and Journal of physical Chemistry,56,22-25 (1952).

In practice, and not by way of limitation, the compositions and methods of the present invention can be adjusted to have at least one-part-per-billion concentrations of active bleach catalyst species in the aqueous wash liquor, and preferably from about 0.01ppm to about 25ppm, more preferably from about 0.05ppm to about 10ppm, and most preferably from 0.1ppm to 5ppm, of bleach catalyst in the laundry liquor. To achieve this concentration in the wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions of the present invention contain from 0.0005% to 0.2%, more preferably from 0.004% to 0.08% of the wash composition of a bleach catalyst, especially a manganese or cobalt catalyst.

Clay removal/antiredeposition agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay-removing and anti-redeposition properties. Granular detergent compositions containing these compounds generally contain from about 0.01% to about 10.0% by weight of a water-soluble ethoxylated amine; liquid detergent compositions typically contain from about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Representative ethoxylated amines are described in US4597898, which VanderMeer entitled 11/7 in 1986. Another preferred class of clay-removal-antiredeposition agents are cationic compounds, which are disclosed in EP111965 published by Oh and Gosselink at 27.6.1984. Other clay-removal/anti-redeposition agents that may be used include ethoxylated amine polymers disclosed in EP111984, published on day 27 of 1984, to Gosseink; amphoteric polymers disclosed in EP112592, published on 7/4/1984, to Gosseink; and amine oxide disclosed in US4548744 by Connor on 22.10.1985. Other clay-removing and/or anti-redeposition agents known in the art may also be used in the compositions of the present invention. See US4891160, VanderMeer,1990, 1/2 and WO95/32272,1995, 11/30. Anotherpreferred class of antiredeposition agents includes carboxymethyl cellulose (CMC) materials. Such materials are known in the art.

Polymeric dispersants-polymeric dispersants are advantageously used in amounts of from 0.1% to about 7% by weight of the composition of the present invention, particularly in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, without wishing to be bound by theory, that the polymeric dispersants, when used in combination with other builders (including low molecular weight polycarboxylates), enhance overall detergent builder performance by inhibiting crystal growth, dispersing particulate soil and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. It is suitable that there be polymeric polycarboxylate or monomer segments that do not contain carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., as long as such segments do not exceed about 40 weight percent.

Particularly suitable polymeric polycarboxylates can be prepared from acrylic acid. Such acrylic-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such acid form polymers is preferably 2000 to 10000, more preferably 4000 to 7000, most preferably 4000 to 5000. Water-soluble salts of such acrylic polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known substances. Such polyacrylates have been disclosed for use in detergent compositions, for example in US3308067, which Diehl was entitled to 3,7, 1967.

Acrylic acid/maleic acid based copolymers may also be used as preferred components of the dispersing/anti-redeposition agent. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid form copolymers is 2000 to 100000, more preferably about 5000 to 75000, most preferably about 7000 to 65000. The ratio of acrylate to maleate segments in the polymer is generally from 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Aqueous salts of such acrylic acid/maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such water-soluble acrylate/maleate copolymers are known and are described in EP66915, 12/15 th 1982 and EP193360, 9/23 th 1986, which also describe polymers containing hydroxypropyl acrylate. Other useful dispersants include maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP193360 and include maleic/acrylic/vinyl alcohol terpolymers such as 45/45/10.

Another polymer that may be included is polyethylene glycol (PEG). PEG has a dispersing effect and can be used as a clay-removal anti-redeposition agent. For this reason they generally have a molecular weight in the range from about 500 to about 100000, preferably from about 1000 to about 50000, more preferably from about 1500 to 10000.

Polyaspartic and polyglutamic acid dispersants may also be employed, particularly with zeolite builders. The dispersant, for example polyaspartic acid, preferably has a molecular weight (average) of about 10000.

Brighteners-any fluorescent whitening agent known in the art or other brighteners can be added to the detergent compositionsof the present invention in amounts generally from 0.01% to about 1.2% by weight. Commercially available optical brighteners useful in the present invention may be classified into subclasses which include, but are not limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methines, dibenzothiophene-5, 5-dioxides, pyrroles, 5-and 6-membered heterocycles and other mixed agents. Examples of such whitening Agents are disclosed in "The production and Application of Fluorescent whitening Agents" by M.Zahradnik, published by John Wiley&Sons, New York (1982).

Specific examples of optical brighteners which can be used in the compositions of the present invention are illustrated in US4790856, entitled by Wixon at 12.13.1988. These include the PHORWHITE series of whitening agents supplied by Verona. Other whitening agents disclosed in this document include: tinopal UNPA, Tinopal CBS and Tinopal 5 BM; supplied by Ciba-Geigy; artic White CC and Artic White CWD; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d]triazole; 4, 4' -bis- (1,2, 3-triazol-2-yl) -stilbene; 4, 4' -bis (styryl) biphenyl; and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1, 2-bis (benzooxazol-2-yl) ethylene; 1, 3-diphenyl-pyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho- [1,2-d]oxazole; and 2- (stilben-4-yl) -2H-naphthalen- [1,2-d]triazole. See US3646015, Hamilton entitled to it on month 2, 29, 1972.

Dye transfer inhibiting agents-the compositions of the present invention may also contain one or more substances capable of inhibiting the transfer of dyes from one fabric to another during the laundering process. In general, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If employed, these agents are generally present in an amount of fromabout 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention contain units having the general structural formula: R-A_x-P; wherein P is a polymerizable unit, which may be linked to an N-O group or the N-O group may form part of a polymerizable unitAre connected to the two units; a has one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the N-O group may be attached or which is part of such groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine and derivatives thereof.

The N-O group can be represented by the following structural formula:

wherein R is₁、R₂、R₃Is an aliphatic, aromatic, heterocyclic or alicyclic group or combination thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group may be attached to or form part of any of the above groups. The amine oxide units of the polyamine N-oxide have a pKa of<10, preferably a pKa of<7, and most preferably a pKa of<6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are vinyl polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random polymers or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymer typically hasan amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can vary depending on the appropriate copolymerization or depending on the appropriate degree of N-oxidation. The polyoxyamines can be prepared in almost any degree of polymerization. Generally, the average molecular weight is from 500 to 1000000; more preferably 1000 to 500000; most preferably 5000 to 100000. Such preferred substances may be denoted by "PVNO".

The most preferred polyamine N-oxide in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of about 50000 and an amine to amine N-oxide ratio of about 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI") are also preferred for use herein. Preferably the average molecular weight of the PVPVI is from 5000 to 1000000, more preferably from 5000 to 200000, most preferably from 10000 to 20000. (average molecular weight ranges are described by Barth et al in "model Methods of Polymer Characterization", volume 113 of Chemical anlysis, the disclosure of which is incorporated herein by reference.) PVPVPVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. These copolymers may be linear or branched.

The compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5000 to 400000, preferably from about 5000 to about 200000, and most preferably from about 5000 to about 50000. PVP's are known to those skilled in the detergent art; see, for example, EP-A-262897 and EP-A-256696, which are incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100000, preferably from about 1000 to about 10000. Preferably, the ratio of PEG to PVP in ppm in the wash solution is from about 2: 1 to about 50: 1, more preferably from 3: 1 to about 10: 1.

The detergent compositions of the present invention may also optionally contain from about 0.005% to 5% by weight of some type of hydrophilic optical brightener which also has the effect of inhibiting dye transfer. If such a brightener is employed, the compositions of the present invention will preferably contain from about 0.01% to 1% by weight of such fluorescent whitening agent.

Hydrophilic fluorescent whitening agents useful in the present invention have the following general structural formula:

wherein R is₁Selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium.

When in the above formula, R₁Is anilino, R₂Is N-2-bis-hydroxyethyl and M is a cation, such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino]-2, 2' -stilbene disulphonic acids and the disodium salts thereof. This particular class of whitening agent is sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is useful in the detergent compositions of the present inventionPreferred hydrophilic fluorescent whitening agents for use in the compositions.

When in the above formula, R₁Is anilino, R₂Is N-2-hydroxyethyl-N-2-methylamino, M is a cation, such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino]-2, 2' -stilbene disulphonic acid disodium salt. Such special whitening agents are sold under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R¹Is anilino, R²Is morpholino and M is a cation, such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6-morpholino-s-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acid, sodium salt thereof. Such special whitening agents are sold under the trade name Tinopal AMS-GX by Ciba-Geigy corporation.

The particular fluorescent whitening agents used in the present invention have a particularly effective dye transfer inhibiting effect when used in combination with the selected polymeric dye transfer inhibiting agents described above. The use of such selected polymers (e.g., PVNO and/or PVPVI) in combination with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides a more pronounced dye transfer inhibition effect in aqueous wash solutions than when either of the two detergent composition components is used alone. Without being limited by theory, it is believed that such brighteners work because of their strong affinity for fabrics in the wash solution and therefore deposit relatively quickly on fabrics. The extent to which the brightener deposits on the fabric in the wash solution can be determined by the so-called parameter "exhaustion coefficient". The exhaustion coefficient is generally the ratio of (a) the brightener deposited on the fabric to (b) the original concentration of brightener in the wash liquor. Brighteners with a relatively high dissipation factor are most suitable for the dye transfer inhibiting agents of the present invention.

It is, of course, contemplated that other conventional optical brightener-type compounds may optionally be used in the compositions of the present invention to produce a "whitening" effect on conventional fabrics, rather than a truedye transfer inhibition effect. Such uses are conventional and known for detergent formulations.

Chelating agents-the detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all of which are described hereinafter. Without wishing to be bound by theory, it is believed that the effect of these materials is due in part to their unexpected ability to remove iron and manganese ions from the wash solution by forming soluble chelates.

Aminocarboxylates useful as selective chelating agents include ethylenediamine tetraacetate, N-hydroxyethylethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetramine hexaacetate, diethylenetriamine pentaacetate and ethanoldiglycine, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in the detergent composition, and include ethylenediamine tetrakis (methylenephosphonates) such as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, which Connor et al gained right on 21/5/1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

The preferred biodegradable chelating agents for use in the present invention are ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomers, as described in US4704233, issued by Hartman and Perkins on 3.11.1987.

The compositions of the invention may also contain a water-soluble salt of Methyl Glycerol Diacetic Acid (MGDA) (or in acid form) as a chelating agent or co-agent with, for example, an insoluble adjuvant such as zeolites, layered silicates.

If used, these chelants typically comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, the chelating agent, if used, is about 0.1% to about 3.0% by weight of the composition.

Suds suppressors-compounds for reducing or suppressing foam formation may be added to the compositions of the present invention. Suds suppressors are particularly important in the so-called "high intensity cleaning process" as described in US4489455 and 4489574 and in front-loading euro-type washing machines.

Various materials and suds suppressors which can be used as suds suppressors are known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, third edition, volume 7, pages 430-447 (John Wiley&Sohs., Inc., 1979). One particularly effective class of suds suppressors comprises monocarboxylic fatty acids and soluble salts thereof. See US2954347, waynest.john entitled to 27/9/1960. Monocarboxylic fatty acids and salts thereof useful as suds suppressors contain a hydrocarbyl chain of from 10 to about 24, preferably from 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium salts, and alkanolammonium salts.

The detergent compositions of the present invention may also contain a non-surfactant suds suppressor. They include, for example: high molecular weight hydrocarbons, e.g. paraffins, fatty acid esters (e.g. fatty acid triglycerides), fatty acid estersof monohydric alcohols, fatty acids C₁₈-C₄₀Ketones (e.g., stearyl ketone), and the like. Other suds suppressors include NAlkylated aminotriazines, such as the di-to tetra-alkyldiamine chlorotriazines which are the products of tri-to hexa-alkylmelamines or cyanuric chloride with two or three moles of a primary or secondary amine having from 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates, for example monostearyl alcohol phosphate and monostearyl dibasic alkali metal (e.g. K, Na and Li) phosphates and phosphates. Hydrocarbons, such as paraffins and halogenated paraffins, may be employed in their liquid form. Liquid hydrocarbonsIs liquid at room temperature and atmospheric pressure, has a pour point of from about-40 ℃ to about 50 ℃, and a minimum boiling point of not less than about 110 ℃ (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ℃. Hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US4265779 entitled 5.5.1981 by Gandolfo et al. Hydrocarbons include aliphatic, alicyclic, aromatic, and heterocyclic saturated and/or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. In discussing the suds suppressor as "paraffin", it is intended to mean a mixture of true paraffin and cyclic hydrocarbon.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. This class includes the use of polyorganosiloxane oils, such as polydimethylsiloxanes, polyorganosiloxane oils or resinous dispersing or emulsifying agents, in combination with silica particles, where the polyorganosiloxane is chemisorbed or dissolved on the silica. Silicone suds suppressors are known in the art and are disclosed, for example, in US4265779, entitled 5/5 1981 by Gandolfo et al, and in EP89307851.9, entitled 2/7 1990 by m.s.

Other silicone suds suppressors are disclosed in US3455839 which relates to compositions and methods for preparing aqueous defoaming solutions by adding small amounts of polydimethylsiloxane fluids thereto.

Mixtures of siloxanes and silanized silicas are described, for example, in German patent DOS 2124526. Silicone defoamers and suds suppressors disclosed in granular detergent compositions are disclosed in US3933672 to Bartolotta et al and US4652392 to Baginski et al, 24.3.1987.

A typical silicone based suds suppressor for use herein is a suds suppressing amount of a suds suppressor consisting essentially of:

a polydimethylsiloxane fluid having a viscosity of from 20cs. to about 1500cs. at 25 ℃;

(ii) about 5 to about 50 parts by weight of a compound of formula (CH) per 100 parts by weight of (i)₃)₃SiO_1/2Unit and SiO₂Unit is represented by (CH)₃)₃SiO_1/2Unit and SiO₂The ratio of units is from 0.6: 1 to about 1.2: 11;

(iii) from about 1 to about 20 parts of solid silica gel per 100 parts by weight of (i).

In the preferred silicone suds suppressors employed herein, the solvent for the continuous phase is comprised of polyethylene glycol or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably not linear.

To further illustrate, conventional liquid laundry detergent compositions containing suds suppressors optionally contain from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5% by weight of an aqueous silicone suds suppressor comprising (1) a non-aqueous emulsifier which is a basic antifoam agent which is a mixture of (a) polyorganosiloxane, (b) resinous silicone or silicone compound prepared from silicone resin, (c) well-dispersed filler, and (d) a catalyst which promotes the reaction of mixture components (a) (b) and (c) to form silanol salts (silaolates); (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature greater than about 2% by weight; and no polypropylene glycol. Similar amounts can be used for particulate compositions, gels, and the like. See column 1, line 46 through column 4, line 35 in US4978471 entitled to Starch on month 12, 18, 1990 and 4983316 entitled to Starch on month 1, 8, 1991, Huber et al 5288431 entitled to month 2, 22, 1994, and US4639489 and 4749740 of Aizawa et al.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol and polyethylene/polypropylene glycol copolymers each having an average molecular weight of less than about 1000, preferably between 100 and 800. The solubility of the polyethylene glycol and polyethylene/polypropylene glycol copolymers of the present invention is greater than about 2% by weight, preferably greater than about 5% by weight, at room temperature.

Preferred solvents of the present invention are polyethylene glycol, and polyethylene/polypropylene glycol, preferably PPG200/PEG300 copolymers, having an average molecular weight of less than about 1000, more preferably between 100 and 800, and most preferably between 200 and 400. Preferably, the weight ratio of polyethylene glycol to polyethylene glycol/polypropylene glycol copolymer is between about 1: 1 and 1: 10, more preferably between 1: 3 and 1: 6.

Preferred silicone suds suppressors for use herein are free of polypropylene glycol, and particularly have a molecular weight of 4000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors of the present invention comprise secondary alcohols (e.g. 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US4798679, 4075118 and EP 150872. Such secondary alcohols include those containing C₁-C₁₆C of the chain₆-C₁₆An alkyl alcohol. The preferred alcohol is 2-butyloctanol, which is supplied by Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trade name ISALCHEM 123. Mixed suds suppressors typically comprise a mixture of alcohol + silicone in a weight ratio of from 1: 5 to 5: 1.

For any detergent composition to be used in an automatic washing machine, suds should not form to the extent that they spill out of the washing machine. When a suds suppressor is used, it is preferably present in a suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition selects an amount of the suds suppressor sufficient to control suds, resulting in a low sudsing laundry detergent for use in an automatic washing machine.

The compositions of the present invention typically contain from 0% to about 10% of suds suppressors. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof are generally present at levels up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of the fatty-monocarboxylic acid salt suds suppressor is employed. Silicone suds suppressors are generally used in amounts up to 2.0% by weight of the detergent composition, although higher amounts may be used. The upper limit is practically feasible due to the effectiveness of the lower amount, which is primarily a compromise between cost reduction and effective foam control. Preferably, from about 0.01% to about 1%, more preferably from about 0.25% to about 0.5% of silicone suds suppressors are employed. As used herein, these weight percent values include all silicas used in combination with polyorganosiloxanes, as well as all additive materials that may be employed. Monostearyl phosphate suds suppressors are generally used in amounts of about 0.1% to 2% by weight of the composition. Hydrocarbon suds suppressors are generally used in amounts of from about 0.01% to about 5.0%, although higher amounts may be used. Alcohol suds suppressors are generally 0.2% to 3% by weight of the finished composition.

Alkoxylated polycarboxylates-alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein to provide an auxiliary degreasing effect. Such materials are described in WO91/08281 and PCT90/01815p4, et al, which are incorporated herein by reference. Chemically, these materials contain polyacrylates with an ethoxy side chain per 7-8 acrylic acid units. The side chain has the general formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chains are ester chains attached to the polyacrylate "backbone" side chains to provide a "honeycomb" polymer-like structure. The molecular weight may vary, but is generally from about 2000 to 50000. Such alkoxylated polycarboxylates may comprise from about 0.05% to 10% by weight of the compositions of the present invention.

Fabric softener-various fabric softeners throughout the wash process, particularly Storm and Nirschl, US4062647, which was issued on 12/13 of 1977, and other softener clays known in the art, can optionally be used in amounts of 0.5% to about 10% by weight of the composition of the present invention to provide fabric softener action while washing fabrics. The clay softeners may be used in combination with amine and cationic softeners, as disclosed, for example,in US4375416 by Crisp et al, 3/1, 1983, and in US4291071 by Harris et al, entitled, 22/9, 1981.

Fragrance-the fragrance component used in the compositions and methods of the present invention comprises a variety of different natural and synthetic chemical components including, but not limited to, aldehydes, ketones, esters. Also included are various natural extracts and essences comprising a complex mixture of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam, sandalwood oil, pine oil, cedar. The finished fragrance may contain a large number of complex mixtures of such components. Finished perfumes typically contain from about 0.01% to 2% by weight of the detergent compositions of the present invention, and individual perfume components may contain from about 0.0001% to 90% of the finished perfume composition.

Non-limiting examples of perfume components useful in the present invention include 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, ionone methyl, ionone gamma-methyl, methylcedrenone, methyl dihydrojasmonate, methyl 1,6,10 trimethyl-2, 5, 9-cyclododecatrien-1-yl ketone, 7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin, 4-acetyl-6-tert-butyl-1, 1-dimethylindane, p-hydroxyphenylbutanone, benzophenone, methyl β -naphthyl ketone, 6-acetyl-1, 1,2,3,3, 5-hexamethylindane, 5-acetyl-3 isopropyl-1, 1,2, 6-tetramethylindane, 1-dodecylpropionaldehyde, 4- (4-hydroxy-4-methylphenyl) -3-hexahydro-1, 1,2, 6-tetramethylvalerolactone, 3, 5-cyclohexylcinnamaldehyde, 2, 7-cyclohexylcyclohexanecarbonyl-1, 3, 8-2, 6-trimethylcinnamic aldehyde, 3, 2-cyclohexylindole-2, 7-6-2, 7-hexahydro-1, 7-1, 6-hexadecyl-1, 6-1, 1,2, 6-dimethylvaleryl-dihydroinden-2, 7, 6-1, 7-and 5-tert-butylcinnamaldehyde, 4- (4-hydroxy-cyclohexyl) and the condensation products of a, 2, 7-cyclohexyl-2, 7-cyclohexyl-1, 7-cyclohexyl-2, 2, 7-cyclohexyl-1, 2, 8-cyclohexyl-1, 8-cyclohexyl-1, 2, 8-cyclohexyl-1, 7-cyclohexyl-1, 8-cyclohexyl-1, 8-1, 7-1, 2-cyclohexyl-1, 8-cyclohexyl-1, 2-1, 8-methyl-1, 7-methyl-1, 8-cyclohexyl-1, 7-cyclohexyl-2-cyclohexyl-1, 2-cyclohexyl-1, 8-cyclohexyl-1, 2-cyclohexyl-1, 8-cyclohexyl-1, 2-2.

These perfumes include, but are not limited to, hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, phenyl salicylate, 7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β -naphthylmethyl ether, methyl- β -naphthyl ketone, 2-methyl-2- (p-isopropylphenyl) -propionaldehyde, 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopent-gamma-2-benzopyran, dodecahydro-3 a,6,6,9 a-tetramethylnaphthalene [2,1b]furan, anisaldehyde, coumarol, cedrol, vanillin, pentacyclopentadienol acetate, tricyclopentadienyl decene propionate, and tricyclodecenyl decene.

Other fragrances include essential oils, resinoids, and resins from a variety of sources including, but not limited to, the following: peru balsam, Boswellia resin, storax, Cistus resin, semen Myristicae, oleum Cinnamomi, benzoin resin, coriander oil, and Lavender. Other fragrance chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1, 1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethyl terephthalate may be used in the finished fragrance composition.

Other ingredients-many other ingredients useful in detergent compositions may be included in the composition, including other active ingredients, carriers, hydrotropes, processing aids, pigments or dyes, solvents for liquid formulations, solid fillers for stick compositions, and the like. If high foam is desired, a foam booster, such as C, may be added to the composition₁₀-C₁₆Alkanolamides, generally from 1% to 10%. C₁₀-C₁₄Monoethanol and glycol amides illustrate the general class of such foam boosters. It is also advantageous to employ such foam boosters containing high foam additive surfactants such as amine oxides, betaines and the sulfobetaines described above. If desired, soluble magnesium and/or calcium salts, e.g. MgCl₂、MgSO₄、CaCl₂、CaSO₄Etc. may be added at a concentration of 0.1% to 2% to provide more foam and promote degreasing.

Various detersive ingredients used in the compositions of the present invention optionally may be further stabilized by absorbing said ingredients into a porous hydrophobic matrix, followed by coating said matrix with a hydrophobic coating. Preferably the detergent component is mixed with the surfactant before being absorbed into the porous matrix. In use, the detergent composition is released from the matrix into the aqueous wash liquor where it serves its desired cleaning function.

To illustrate the technique in more detail, porous hydrophobic silica (trademark SIPERNATD10, DeGussa) was mixed with a mixture containing 3% -5% C₁₃-C₁₅A hydrolyzed protease solution of ethoxylated alcohol (EO7) nonionic surfactant was mixed. Generally, the enzyme/surfactant solution is 2.5 times the weight of the silica. The resulting powder was dispersed in a silicone oil with stirring (various silicone oils with viscosities of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent base. By this means, components, e.g. the above-mentioned enzymes, bleaches, bleach activators, bleach catalysts, photosensitizers, pigments, optical brighteners, textilesThe conditioning agents and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions contain water and other solvents as carriers. Low molecular weight primary and secondary alcohols, typically methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for enhancing the solubility of the surfactant, however, polyhydric alcohols, such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., 1, 3-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) may also be employed. The composition may contain from 5% to 90%, typically from 10% to 50% of such a carrier.

The detergent compositions herein are preferably formulated to provide a wash water pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5, during use in an aqueous washing operation. The liquid dishwashing formulation preferably has a pH of about 6.8 to 9.0. The laundry product generally has a pH of 9-11. Techniques for controlling the pH within the recommended use range include the use of buffer solutions, bases, acids, and the like, as known to those skilled in the art.

In the following examples, the abbreviations used for the components of the compositions have the following meanings: alkylbenzenesulfonic acid anionic surfactants having an average LAS chain length of C11.5, preferably

Sodium salt AS primary alkyl sulfate with average chain length of C14-15

Agent, preferably a C12-15 ethoxylated alcohol (nonionic) with an average degree of ethoxylation of NI, sodium salt, EO9

Surfactant) SKS-6 layered silicate, sodium salt zeolite 1-10 micron zeolite APEG4000 polyethylene glycol from Hoechst copolymer acrylic acid/maleic acid copolymer; PB-1 sodium perborate monohydrate protease, a 4000NOBS nonanoyloxybenzene sulfonate bleach activator, the proteolytic detergent enzyme; detergent enzyme SRA-1 detergent comprising BIOSAM 3.0 Amylase amylolysis, methylcellulose, molecular weight of about 13000, degree of substitution

1.8-1.9 SRA-2 US5415807 detergentWhitening agent X Tinopal^_CBS-X, stilbene biphenyl disulfonates, Ciba

Geigy brightener Y Tinopal^_UNPA-GX, Cynauric chloride/diaminostilbenes,

Ciba-Geigy suds suppressor silica/siloxane suds suppressor

Preparation of granules

The addition of the bis-alkoxylated cations of the present invention to a blender for mixing, followed by conventional spray drying, helps to remove all remaining primarily malodorous short chain amine contaminants. If the formulator wishes to prepare mixable particles containing alkoxylated cations for use in, for example, high density particle formulations, it is preferred that the particle composition is not highly basic. A process for preparing high density (greater than 650g/l) granules is described in US 5366652. Such particles can be formulated to have an effective use pH of 9 or below 9 to avoid the odor of the contaminating amine. This can be done by adding small amounts of acid starting materials, such as boric acid, citric acid, etc. or suitable pH buffer solutions to the granules. An optional way is to mask the problems associated with amine malodour by using the perfume component.

The following examples illustrate the invention but are not intended to limit its scope in any way. All parts, percentages and ratios used in the present invention are expressed as weight percentages unless otherwise indicated.

Granular detergents are described below in examples I and II.

Example I

(ii) Ppm surfactant as a component

LAS 21.47 143.20

AS 6.5543.69

NI 3.30 22.01

CocoMeEO2 × 0.473.13 adjuvant-basic

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 17.84118.99

Silicate (2.0R) 11.4076.04 bleaching agent

NOBS 4.05 27.01

PB-13.9226.15 enzyme

Protease 0.855.67

Amylase 1.208.00 other Components

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X0.211.40

Whitening agent Y0.100.67

Hydrophobic silica 0.302.00

Suds suppressor 0.171.13

Sodium sulfate 5.1434.28

Fragrance 0.251.67

Total amount of trace components and water 3.2821.88 100667.00

Dosage-20 g/30L

The AQA-1(CocoMeEO2) surfactant of the examples may be replaced by an equivalent amount of any of the surfactants AQA-2 to AQA-22 or other AQA surfactants of the invention.

Example II component wt% ppm surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 × 0.473.13 adjuvant-basic

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 19.04127.00

Silicate (2.0R) 11.4076.04 bleaching agent

NOBS 4.05 27.01

PB-13.9226.15 enzyme

Other Components of protease 0.855.67

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X0.211.40

Whitening agent Y0.100.67

Hydrophobic silica 0.302.00

Suds suppressor 0.171.13

Sodium sulfate 5.1434.28

Fragrance 0.251.67

Total amount of trace components and water 3.2821.88 100667.00

The bis-AQA-1 (CocoMeEO2) surfactant of this example may be replaced by an equivalent amount of any of the surfactants bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants of the invention.

The following describes the test procedures and test results for various soils and stains using the compositions of the present invention. The data show that there is an overall cleaning effect on a wide variety of soils and stains on different fabrics.

Performance test procedure

Preparation of samples

The preparation of the sample essentially comprises the following steps:

1. preparation of Pre-blended LAS + AS

2. Preparation of premix LAS + AS + cation

3. Preparation of raw material nonionic (AE) surfactant

4. Preparation of the adjuvant solution

5. Preparation of the granules

Surfactant (b): surfactant weight active washes

Gram% concentration ppmLAS 78.8544.50143.20 AS 34.5531.0043.70 cation 01.9040.003.10 AE 19.44100.0022.00

(actual weight and percentage of activity different)

Sequence of product preparation for performance testing:

step I:

the individual surfactants were weighed and mixed in the following order:

1. 78.85 grams of LAS were weighed.

2. 34.55 grams of AS were weighed into the same beaker.

3. 498.10 ml of distilled water were added to the mixture of LAS and AS.

4. Pre-mix LAS and AS until completely dissolved while heating at 40 ℃ for about 30 minutes until completely dissolved.

Step II:

1. 01.90 grams of cationic surfactant were weighed into the same beaker containing the LAS + AD premix solution.

2. The total volume of the solution is now 500 ml.

This mixture of 500 ml of surfactant was used for exactly five washes, and 100 ml of the stock solution was used for one wash. This 100 ml solution when added to 49 liters of tap water produced the corresponding wash concentration of the individual surfactants.

Step III:

1. each weighed 19.44 grams AE.

2. To AE 900 ml of distilled water was added.

3. This 900 ml solution was used for exactly 18 washes.

4.50 ml of this solution can be used for one wash.

Step IV:

silicate salt: 148.32 g per 900 ml of distilled water, 50 ml of this solution are used per wash.

Copolymer (b): 92.88 g per 900 ml of distilled water, 50 ml of this solution was used for each wash.

And (3) particle: each particle component was weighed separately in the same beaker.

Sequence of addition to the washing machine:

the components were added with stirring in the following order:

1. silicate (2.0R)

2. Copolymers (as described above)

3. Granules

At this point, the agitation was stopped (to avoid foaming during the addition of the surfactant)

LAS + AS + cationic solution

AE solution

Stirring for 15 seconds

Hardness: no additional hardness was added in addition to the hardness of tap water.

Loading: a load of 2.4 kg of the following composition is generally used

Cotton shirt (1)

Old T shirt (pendists) (3)

Big T shirt (11)

DKPE T shirt (1)

P/C pants (2)

Cotton shorts (1)

DKPE is a double-knit polyester

DMO is dirty engine oil

Test results I below show the performance of the compositions of the invention using a mixture of CoCoMeEO2 plus LAS + AS, and test results II show the performance of CoCoCoMeEO 10 plus LAS + AS compared to CoCoMeEO 2/LAS. In this test, performance was measured on various types of soils, i.e., body soils, adjuvant sensitive soils, bleach sensitive soils, surfactant sensitive soils and socks^*. By "bis" is meant that "EO 10" refers to two poly-EO chains that average 10EO over the entire molecule, typically with each chain being (but not limited to) about 5.

Test results I

CocoMeEO2 cation premixed with LAS and AS (anionic system AS a whole) fouling test I test II average used collar-0.02-0.27-0.15 collar liner 0.77S 0.73S 0.75 Cuffs-0.170.330.08 jet black-0.10.17S 0.04 body fouling (average) 0.120.240.18 clay C/D1.03S 0.7S 0.87 clay DKPE 0.7S-0.020.34 adjuvant sensitive fouling (average) 0.870.340.61 cuff 0.330.560.45 coffee 0.210.42S 0.32 bleach sensitive fouling (average) 0.270.490.38 broth 0.84S 1.08S 0.96 bone oil 1.14S 1.11S 1.13 animal oil 0.10.160.13 DMO 0.44-0.340.05 surfactant sensitive fouling (average) 0.630.50.57 average (including sock) 0.390.380.39 sock (before) 0.320.35A 0.34 sock (after) 0.080.64A 0.36 sock (before) -0.240.280.02 incremental fouling

Test results I

CocoMeEO2 cation only with LAS premix soil test I test II average used collar 0.27-0.73-0.23 collar liner-0.040.150.06 Cuffs-0.35-0.25-0.30 micro black 0.130.51S 0.32 body soil (average) 0.00-0.08-0.04 clay C/D0.590.79S 0.69 clay DKPE 0.040.660.35 adjunct sensitive soil (average) 0.320.730.53 cuff 0.070.580.33 coffee 0.240.240.24 bleach sensitive soil (average) 0.160.410.29 broth-0.1-0.08-0.09 bone oil 0.10.540.32 animal oil-0.53-0.02-0.28 DMO-0.220.05-0.09 surfactant sensitive soil (average) -0.190.12-0.04 average (including sock) 0.040.190.12 sock (before) 0.33-0.070.13 sock (after) 0.7S-0.050.33 sock (before) 0.360.020.19 sock (after) 0.360.020.19

Test results II

CocoMeEO10 cation with LAS and AS Pre-mix soil test I test II average collar used 0.48-0.020.23 collar pad 0.020.060.04 Cuffs 0.330.250.29 jet black-0.280.11-0.09 body soil (average) 0.140.100.12 soil C/D0.75S 0.440.60 soil DKPE 0.27-0.47-0.10 adjuvant sensitive soil (average) 0.51-0.020.25 cuff 0.000.330.17 coffee 0.380.82S 0.60 bleach sensitive soil (average) 0.190.580.39 broth 0.050.96S 0.51 bone oil 0.420.91S 0.67 animal oil 0.23-0.070.08 DMO 0.31-0.130.09 surfactant sensitive soil (average) 0.250.420.34 average (including sock) 0.20.260.23 sock (before) 0.140.230.19 sock (after) -0.190.48S 0.15 sock (increment) -0.320.25-0.04

Test results II

CocoMeE10 cation with LAS premix soil only used Collar 0.17 Collar liner-0.52 Cuffs 0.19 jet Black-0.17 body soil (average) -0.08 Clay C/D-0.34 Clay DKPE 0.09 aid sensitive soil (average) -0.13 Cuff 0.06 coffee 0.08 Bleach sensitive soil (average) 0.07 Broth-0.20 bone oil-0.38 animal oil-0.33 DMO-0.33 surfactant sensitive soil (average) -0.31 average (including sock) -0.11 sock (before) 0.42S sock (after) 0.64S sock (increment) 0.22S sock (after)

Example III

Compositions of examples I and II were prepared by removing the bleaching System (NOBS/PB)₁) To modify. The concentration of AQA was adjusted to 1.5% (0.5-5%) of the composition. Ensuring a very satisfactory cleaning effect on various soils and stains even in the absence of bleaching agents.

Examples I, II and III may also be provided in tablet form by standard tableting and compression techniques.

Example IV

Detergent bars are prepared from surfactant mixtures using conventional extrusion techniques and contain:

(weight) range of component (% by weight)

A B AQA-1* 2.0 0.6 0.15-3.0 C₁₂-C₁₈Sulfate 15.7513.505-25

LAS 6.75 5.5 3-25 Na₂CO₃15.00 3.00 1-20 DTPP¹0.700.700.2-1.0 Bora-10.00-20 Sokolan CP-5²0.401.000-2.5 TSPP 5.00- - -0-10 STPP 5.0015.000-25 zeolite 1.251.250-15 sodium laurate- - -9.000-15SRA-10.300.300-1.0 protease- - -0.120-0.6 amylase 0.12- - -0-0.6 lipase- - -0.100-0.6 cellulase- - -0.150-0.3

Balancing³

¹Diethylene triamine penta (sodium phosphonate)

²Sokolan CP-5 is a maleic acid-acrylic acid copolymer

³The balance includes water (about 2% to 8%, including hydrated water), sodium sulfate, calcium carbonate, and other minor components.

The AQA-1(CocoMeEO2) surfactant of this example may be replaced by equivalent amounts of the surfactants AQA-2 to AQA-22 or other AQA surfactants of the invention.

Example V

Mixtures of AQA surfactants that can be substituted for the AQA surfactants listed in any of the preceding examples are illustrated below. As disclosed above, the use of such mixtures can result in certain properties and/or provide cleaning compositions that can be used under a variety of use conditions. Preferably the AQA surfactants differ in total EO units in the mixture by at least 1.5, preferably from 2.5 to 20. The ratio (by weight) for the mixture is generally in the rangeof 10: 1 to 1: 10. Non-limiting examples of such mixtures are as follows.

Proportion of the Components (by weight)

AQA-1+AQA-5 1∶1

AQA-1+AQA-10 1∶1

AQA-1+AQA-15 1∶2

AQA-1+AQA-5+AQA-20 1∶1∶1

AQA-2+AQA-5 3∶1

AQA-5+AQA-15 1.5∶1

AQA-1+AQA-20 1∶3

Mixtures of the bis-AQA surfactants of the present invention containing a corresponding cationic surfactant containing only a single ethoxylated chain may also be used. Thus, the present invention may also employ mixtures of, for example, di-ethoxylated cationic surfactants of the general formula R¹N⁺CH₃[EO]_x[EO]_yX^-And R¹N⁺(CH₃)₂[EO]_zX^-Wherein R is¹And X is as defined above, and wherein one cation has an (X + y) or z in the range of 1 to 5, preferably 1 to 2, and the other has an (X + y) or z in the range of 3 to 100, preferably 10 to 20, most preferably 14 to 16. Such compositions advantageously provide improved cleaning performance (particularly in fabric laundering) over a wider range of water hardness conditions than the cationic surfactants used alone in the present invention. It has been found that shorter EO cations (e.g. EO2) improve the detergency of anionic surfactants in soft water, whereas higher EO cations (e.g. EO15) act to improve the hardness tolerance of anionic surfactants, thereby improving the detergency of anionic surfactants in hard water. General knowledge in the washing art suggests that the adjunct can optimise the performance "window" of the anionic surfactant. However, it has not previously been possible toenlarge the window to include substantially all water hardness conditions.

Example VI

Having described various non-limiting examples of the compositions of the present invention and their use, the invention is further described below, particularly with respect to fabric laundry detergents. The granular, use, stick, tablet or gel-like compositions of the present invention may comprise a detersive non-AQA surfactant and optionally a detersive non-AQA surfactant in the concentrations and ranges disclosed herein aboveOptional adjuvants, said composition further comprising an effective amount of one or more of the following components in combination: the components AQA: the weight ratio of the components of the percarbonate bleaching agent is 1: 100-1: 1, preferably 1: 20-1: 5 branched alkyl sulfate is 1: 100-1: 2, preferably 1: 10-1: 3 bleaching activator^*2: 1 to 1: 10, preferably 1: 1 to 1: 5, peracid bleaching agent^**1: 10-2: 1, preferably 1: 5-1: 1, of a photosensitive bleaching agent 1: 100-1: 2, preferably 1: 5-1: 1, of a layered silicate assistant 1: 300-1: 1, preferably 1: 100-1: 5, of an SRA 1: 20-1: 2, preferably 1: 10-1: 1, of an enzyme^***1: 10-10: 1, preferably 1: 3-3: 1EDDS 1: 20-10: 1, preferably 1: 3-3: 1MGDA 1: 20-10: 1, preferably 1: 3-3: 1PFAA 1: 50-1: 2, preferably 1: 25-1: 3APG 1: 50-1: 2, preferably 1: 25-1: 3Ca⁺⁺1: 10-10: 1, preferably 1: 5-5: 1Mg⁺⁺1: 10-10: 1, preferably 1: 5-5: 1Co catalyst 1: 10-10: 1, preferably 2: 1-1: 1Mn catalyst 1: 10-10: 1, preferably 2: 1-1: 1DTI reagent 1: 20-20: 1, preferably 1: 10-10: 1 zeolite P (MAP) 1: 300-1: 1, preferably 1: 100-1: 5 inorganic auxiliary agent 1: 300-1: 1, preferably 1: 100-1: 5 combined dispersing agent^****1: 10 to 10: 1, preferably 1: 5 to 1: 1, alkoxylated polycarboxylate 4: 1 to 1: 10, preferably 1: 5 to 1: 1, clay-removing/anti-redeposition agent 4: 1 to 1: 20, preferablySelecting 1: 5-1: 1 clay softener 3: 1-1: 10, preferably 2: 1-1: 1

^*Including for example, a mixture of NOBS + TAED.

^**Including mixtures.

^***Based on the proportion of industrially produced enzyme. It can be based on the active enzyme of the industrial enzyme preparationThe concentration is changed.

^****Polyacrylate or acrylic acid/maleic acid copolymers are preferred.

Laundry detergent compositions prepared using a composition of one or more of the above components may optionally be formulated with non-phosphate or phosphate builders or mixtures thereof, typically at concentrations of from 5% to about 70% by weight of the finished composition.

Example VII

Mixtures of conventional non-AQA surfactants useful in combination with the AQA surfactants described in any of the preceding examples are set forth below, but are not limited thereto. The proportion of non-AQA surfactant in the mixture is expressed as parts by weight of the surfactant mixture.

Mixtures A to C

Component ratio

AS*/LAS 1∶1

AS/LAS 10: 1 (preferably 4: 1)

AS/LAS 1: 10 (preferably 1: 4)

In the above description, the substantially linear primary AS surfactant may be replaced by equivalent amounts of secondary AS, branched AS, oleyl sulfate and/or mixtures thereof, including mixtures with the linear, primary AS described above. The "tallow" chain length AS is particularly effective in hot water conditions where temperatures are AS high AS boiling point. "coconut" AS is preferred for cooler wash temperatures.

The alkyl sulfate/anionic surfactant mixture described above is modified by the addition of a nonionic non-AQA surfactant in an anionic (total) to nonionic weight ratio of from about 25: 1 to about 1: 5. The nonionic surfactant may comprise any conventional type of ethoxylated alcohol or alkyl phenol, alkyl polysaccharide or polyhydroxy fatty acid amide (less preferred), or mixtures thereof, such as those disclosed herein.

Highly preferred compositions of the foregoing non-AQA surfactants comprise from about 3% to about 60% by weight of the total finished laundry detergent composition. The finished composition preferably contains from about 0.25% to about 3.5% by weight of the AQA surfactant.

Example VIII

This example provides the perfume formulations (a-C) incorporated into any of the AQA containing detergent composition examples described above, but is not intended to be limiting thereof. The various ingredients and concentrations are listed below.

(wt.%) fragrance component A B C hexyl cinnamic aldehyde 10.0-5.02-methyl-3- (p-tert-butylphenyl) -propionaldehyde 5.05.0-7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-5.010.010.01, benzyl 1,6, 7-tetramethylnaphthalene salicylate 5.0- -7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin 10.05.010.0 p- (tert-butyl) cyclohexyl acetate 5.05.0-methyl dihydrojasmone ester-5.0-naphthol methyl ether-0.5-methyl β -naphthalenone-0.5-2-methyl-2 (p-isopropylphenyl) -propionaldehyde 2.0-1, 3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-9.5-hexamethyl-cyclopentyl-gamma-2-benzopyran-dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [2,1B]cumyl decalin-3- (p-tert-butyl) propanal-benzyl alcohol 673, 5,6,7,8, 9.5-hexamethyl-cyclopenta-gamma-2-benzopyran-dodecahydro-3 a-3, 6,9 a-2-methyl-2-benzyl alcohol acetate- -2-ethyl-2-ethyl-3, 3-5, 3-methyl-2-benzyl alcohol-5, 3-2-ethyl-2-ethyl-2-5-methyl-benzyl alcohol-3-5, 3-5-2-ethyl-2-ethyl-2-5-ethyl-2-ethyl-5-2-ethyl-2-5-

The foregoing perfume compositions are either admixed or sprayed (typically up to about 2% by weight of the total detergent composition) onto any of the detergent compositions disclosed herein containing AQA surfactants. This ensures improved deposition and/or retention of the perfume or individual components thereof on the surface being washed.

Claims (25)

1. A composition comprising or prepared by admixing a bis-alkoxylated AQA cationic surfactant and a mixture of two anionic surfactants, said cationic surfactant having the formula:

and said anionic surfactant has the following general formula

Ⅱ R⁵OSO₃ ^-M⁺

Ⅲ R⁶SO₃ ^-M’⁺

And optionally

IV nonionic surfactant, wherein R¹Is an alkyl or alkenyl moiety containing from 8 to 18 carbon atoms; r²Is an alkyl group containing 1 to 3 carbon atoms; r³And R⁴Can be varied independently and are selected from hydrogen, methyl and ethyl, R⁵Is a linear or branched alkyl or alkenyl moiety containing from 10 to 20 carbon atoms; r⁶Is C₁₀-C₁₆An alkylbenzene; m⁺And M'⁺Can vary independently and are selected from the group consisting of alkali metals, alkaline earth metals, alkanolammonium and ammonium; x^-Is an anion; a and A' may vary independently and are each selected from C₁-C₄An alkoxy group; p is from 1 to 30 and q is from 1 to 30; wherein the weight ratio of (I) to (II) + (III) is 1: 100 to 1: 7; the weight ratio of (II) to (III) is 4: 1-1: 4; r⁵And R⁶The weight ratio of (A) to (B) is 1: 13-1: 5.

2. A composition according to claim 1 comprising from 0.1% to 5% by weight of said AQA cationic surfactant (i).

3. The composition of claim 2 wherein R is in said AQA cationic surfactant (I)¹Is C₁₀-C₁₈Alkyl radical, R²Is methyl, and p and q are each 1 to 4 ethoxy.

4. The composition of claim 3 wherein said anionic surfactant (II) is C₁₂-C₁₈Primary or secondary, linear or branched alkyl sulfates and wherein said anionic surfactant (III) is C₁₁-C₁₃An alkylbenzene sulfonate.

5. The composition of claim 1 wherein said nonionic surfactant iv is selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polysaccharides, and mixtures thereof.

6. The composition of claim 1, comprising:

(a)0.25 to 3% by weight of Coco methyl 1E 02 as surfactant (I);

(b) 3% to 40% by weight of a linear or branched primary or secondary alkyl sulfate as surfactant (II);

(c) 6% to 23% by weight of an alkylbenzene sulfonate as surfactant (III); and

(d)0.5 to 20% by weight of a nonionic surfactant (IV).

7. The composition of claim 6, comprising:

0.45% to 2% by weight of (a);

(ii) 6% to 13% by weight of (b);

(iii) 8% to 23% by weight of (c);

(iv) 1 to 5% by weight of (d).

8. A detergent composition according to claim 1 additionally comprising conventional additive components or mixtures thereof.

9. The composition of claim 8 wherein the additive component is an adjuvant.

10. The composition of claim 8 wherein the additive component is an enzyme.

11. The composition of claim 8 wherein the additive component is a soil release polymer.

12. The composition of claim 8 wherein the additive component is a bleach, a bleach activator, or mixtures thereof.

13. The composition of claim 8, wherein a component of the additive is a clay-removing/anti-redeposition agent.

14. The composition of claim 8 wherein the additive component is a polymeric dispersing agent.

15. The composition of claim 8 wherein the additive component is a whitening agent.

16. The composition of claim 8 wherein the additive component is a dye transfer inhibitor.

17. The composition of claim 8 wherein the additive component is a suds suppressor.

18. The composition of claim 8 wherein the additive component is a detersive surfactant selected from the group consisting of soaps, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, sulfated alkyl polysaccharides, α -sulfonated fatty acid esters, betaines, sulfobetaines, amine oxides, and mixtures thereof.

19. The composition of claim 8 wherein the additive component is a fabric softener.

20. The composition of claim 8 which is substantially free of bleach.

21. The composition of claim 8 wherein the additive component is a perfume.

22. The composition of claim 8 wherein the additive component is a chelating agent.

23. The composition of claim 8 wherein the additive component is a manganese, iron or cobalt catalyst.

24. A composition according to claim 1 comprising a mixture of AQA surfactants.

25. A composition according to claim 1 comprising a mixture of a bis-alkoxylated AQA surfactant and a mono-alkoxylated cationic surfactant.