KR20000011102A - Detergent composition - Google Patents

Abstract

PURPOSE: A detergent composition is provided to include a selected mixture of a cationic surfactant and a selected ethoxy fourth grade ammonium compound. CONSTITUTION: Alkoxylated cationic surfactants, and mixtures thereof, are used in detergent compositions comprising a mixture of alkyl sulfate and alkylbenzene sulfonate surfactants. Herein, the composition is manufactured by including or mixing a bis-alcove AQA cationic surfactant of chemical formula I and an anionic surfactant of chemical formula II and III and a mixture of non-ionic surfactant.

Description

Detergent composition

U. S. Patent No. 5,441, 541, issued August 15, 1995 to Mehreteab A. and Loftrest F. J., relates to anionic / cationic surfactant mixtures. British Patent No. 2,040,090, issued September 3, 1980 to Murphy AP, Smith RJM and Brooks MP, discloses ethoxylated cationic substances in laundry detergents. It is about.

Summary of the Invention

The invention comprises a mixture of the following cationic surfactants of formula (I) with members selected from each of the two classes of anionic surfactants of formulas (II) and (III), and optionally, but preferably nonionic surfactants (IV), or Included are compositions prepared by combining these components.

R ⁵ OSO ₃ ^- M ⁺

R ⁶ SO ₃ ^- M ' ⁺

In the above formula,

R ¹ is an alkyl or alkenyl moiety of about 8 to about 18, preferably 10 to about 16, most preferably about 10 to about 14 carbon atoms,

R ² is an alkyl group having 1 to 3 carbon atoms, preferably methyl,

R ³ and R ⁴ may be independently selected from hydrogen (preferably), methyl and ethyl,

R ⁵ is a straight or branched chain alkyl or alkenyl moiety having from about 10 to about 20 carbon atoms, preferably C ₁₂ to C ₁₈ alkyl or as found in secondary alkyl sulfates,

R ⁶ is C ₁₀ -C ₁₆ alkylbenzene, preferably C ₁₁ -C ₁₃ alkylbenzene,

M ⁺ and M ' ⁺ are independently of each other selected from alkali metals, alkaline earth metals, alkanolammonium and ammonium,

X ⁻ is an anion such as chloride, bromide, methylsulfate, sulfate, etc. sufficient to provide electrical neutrality,

A and A ′ are independently of each other selected from C ₁ -C ₄ alkoxy, in particular ethoxy (ie —CH ₂ CH ₂ O—), propoxy, butoxy and mixed ethoxy / propoxy,

p is 1 to about 30, preferably 1 to about 4,

q is 1 to about 30, preferably 1 to about 4, most preferably about 4, and preferably both p and q are 1.

The weight ratio of (I) to (II) + (III) is preferably about 1: 100 to about 1: 7, more preferably 1:50 to 1:10. The weight ratio of (II) :( III) is preferably 4: 1 to 1: 4, more preferably 2: 1 to 1: 2. The weight ratio of R ⁵ to R ⁶ is preferably 1:13 to 1: 5.

AQA compounds with a hydrocarbyl substituent R ¹ of C ₈ -C ₁₁ , in particular C ₁₀ , enhance the rate of decomposition of the laundry granules, especially under cold water conditions, compared to materials with longer chain lengths. Thus, C ₈ -C ₁₁ AQA surfactants may be desirable for some formulation vendors. The level of AQA surfactant used to prepare the processed laundry detergent composition may range from about 0.1 to about 5 weight percent, typically from about 0.45 to about 2.5 weight percent.

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

In a preferred embodiment, the anionic surfactant (II) is a C ₁₂ -C ₁₈ primary or secondary alkyl sulfate (AS) and the anionic surfactant (III) has a C ₁₁ -C ₁₃ branched or straight chain alkyl chain. Alkyl benzene sulfonate.

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

More preferred specific compositions are:

(a) from about 0.25 to about 3 weight percent of coco methyl EO2 as surfactant (I);

(b) about 3 to about 40 weight percent of a linear or branched primary or secondary AS as surfactant (II);

(c) about 6 to about 23 weight percent alkyl benzene sulfonate (LAS) as surfactant (III); And

(d) about 0.5 to about 20 weight percent of the nonionic surfactant (IV).

Other aspects are:

(Iii) (a) about 0.45 to about 2 weight percent;

(Ii) (b) about 6 to about 13 weight percent;

(Iii) about 8 to about 23 weight percent; And

(Iii) (d) about 1 to about 5 weight percent.

The present invention also encompasses a fully formulated detergent composition comprising an auxiliary component and at least about 3% by weight of the aforementioned cleaning surfactant system, wherein the surfactant system comprises a cationic surfactant, an anionic surfactant. Mixtures and any nonionic surfactants (all of which are as described above) and auxiliary components include builders, enzymes, antifouling polymers, bleaches, mud removers / antideposition agents, polymeric dispersants, varnishes, dye transfer inhibitors Cleaning surfactants not covered by surfactants (I) to (IV), as well as soap foam inhibitors, fabric softeners and other auxiliaries described herein, such as soaps, oleyl sulfates, alkyl alkoxy sulfates, alkyl alkoxy carboxyls Latex, sulfated alkyl polyglycosides, alpha-sulfonated fatty acid esters, betaines, sulfobetaines, sub There are oxide and components selected from the group consisting of a member selected from the group consisting of a mixture thereof.

AQA surfactants used in the manner of the present invention also provide an improved method for removing the following dirt and stains from the fabric: blood; Oily phase plant stains; Particulate stains; Body dirt (including "blackishness" of the fabric caused by small but perceptible stain / dirt accumulation over time) and other stains mentioned herein. These stains and dirt are removed from fabrics such as cotton, polyester / cotton blends (P / C) and double-ply knit polyesters (DKPE). This method involves contacting a fabric in need of removing the dirt with an effective amount of the composition of the present application, preferably with shaking, in the presence of water. Various suitable use concentrations and methods are described below.

Moreover, these AQA surfactants, particularly the preferred CocoMeEO2 (described below as "AQA-1"), provide improved fabric cleaning performance in the presence of bleach. This improvement in cleaning was seen at levels as low as 3 ppm AQA in the wash liquor, which is believed to be associated with increased perhydrolysis.

In addition, these AQA surfactants, especially AQA-1, provide improved (albeit synergistic) performance with amylase and cellulase enzymes. This improvement is especially observed in the absence of bleach.

All percentages, ratios, and ratios used herein are based on the weight of ingredients used to prepare the final treated composition, unless stated otherwise. All documents cited herein are hereby incorporated by reference in their entirety.

The present invention relates to detergent compositions comprising a selected mixture of anionic surfactant and selected ethoxylated quaternary ammonium compounds.

Background of the Invention

Formulating laundry detergents and other cleaning compositions presents a significant challenge, as state-of-the-art compositions must remove various dirt and stains from various substrates. Thus, in order for laundry detergents to work effectively, the components typically need to be selected and blended appropriately. Generally, such detergent compositions will contain one or more types of surfactants designed to dismantle and remove dirt and stains. However, it may be uncertain to remove body dirt, oily / oil phase dirt and certain food stains quickly and effectively. Indeed, although some surfactants and surfactant combinations exhibit optimal performance for certain types of dirt and stains, their performance over other dirt may actually be degraded. For example, surfactants that remove oily / oil phase dirt from fabrics can often be a little less optimal for removing particulate dirt such as clay. A close review of the literature indicates that a wide range of surfactants and surfactant combinations are available to detergent manufacturers, but many of these ingredients are suitable for low cost items such as laundry detergents used at home. The reality is that they are not special chemicals. It is still true that most of these household laundry detergents still contain one or more of the usual ethoxylated nonionic and / or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and various wastes and various This is due to the need to formulate a composition that works fairly well with the fabric.

Thus, while research to improve laundry detergents has continued, the challenge for detergent manufacturers seeking to improve performance has been increased by a variety of factors. For example, some non-biodegradable components have been cold treated. Valid phosphate builders are legally prohibited in many countries. Cost issues associated with certain classes of surfactants have affected their use. As a result, the manufacturer used more effective but more restrictive ingredients than those listed in the literature in selecting the right components. Consumers still expect high quality performance in these compositions, even when washing fabrics in cold water.

Literature in the art suggests that various nitrogen-containing surfactants are useful in various cleaning compositions. Such materials, typically in the form of amino-, amido- or quaternary ammonium or imidazolinium compounds, are often designed for special applications. For example, various amino and quaternary ammonium surfactants have been shown to be used in shampoo compositions, which are said to provide cosmetic benefits to the hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide fabric flexibility and antistatic effects. In most cases, however, the use of such materials is somewhat limited and the aforementioned nonionic and anionic surfactants are the major surfactant components in today's laundry compositions.

It has been found by the present invention that certain alkoxylated quaternary ammonium (AQA) compounds can be used in laundry detergents to improve performance. Importantly, it has further been found that these compounds provide excellent cleaning performance when specifically used in combination with conventional alkyl sulfates and alkyl benzene sulfonate surfactants in specific component ratios. Thus, the present invention provides an improvement in laundry cleaning performance without the need for the development of new and costly surfactant types.

Moreover, the AQA surfactants used in this way offer significant advantages in formulation over the cationic surfactants known to date. For example, AQA surfactants as used herein are compatible with the preferred alkyl sulfates and alkyl benzene sulfonate cleaning surfactants. In addition, such AQA surfactants can be formulated over a wide pH range of 5-12. AQA surfactants can be prepared in 30% pumpable solution, making them easy to operate in equipment construction. AQA surfactants having an ethoxylation degree of at least 5 are often in liquid form and can be provided as 100% pure material. In addition to their operational properties, the ability of the AQA surfactants of the present invention to serve as highly concentrated solutions offers significant economic advantages in terms of transportation costs. Such AQA surfactants are also compatible with various perfume ingredients, unlike those known in the art.

In addition to the aforementioned advantages, the AQA surfactants herein are believed to minimize or prevent redeposition of the fatty acid / oil phase material present in the aqueous wash liquor in contact with the backside of the fabric already stained with body dirt. Thus, it has been found by the present invention that the AQA surfactants herein prevent re-deposition of polar lipids from an aqueous laundry bath that is in contact with the back of the fabric from which body dirt is removed through the washing process. In other words, the AQA surfactant in the wash liquor removes these polar lipids and floats in an aqueous medium without re-depositing them onto the washed fabric.

In addition to the aforementioned properties, the AQA surfactants herein surprisingly combine with polyanionic materials, such as polyacrylates and acrylate / maleate copolymers, used to provide builders and / or dispersing functions to many conventional cleaning surfactants. Compatibility.

Other advantages of the AQA surfactants herein include the ability to enhance enzymatic cleaning and fabric protection in wash liquor. While not intending to be bound by theory, it is expected that the enzyme may be partially modified by conventional anionic surfactants. In addition, the AQA surfactants herein are inferred to somehow interact with the anionic surfactants to inhibit such degradation. Another theory suggests that even if enzymes are used to decompose dirt and stains, these decomposed residues must be removed from the fabric surface. It is inferred that the improved cleaning performance specified in the mixture of the AQA and anionic surfactants herein is merely a better task in removing the residues from the fabric surface.

In addition to the aforementioned advantages, the AQA surfactants herein provide a significant cleaning enhancement effect on the removal of mud from fabrics compared to conventional detergent mixtures. In addition, although not wishing to be bound by theory, it can be inferred that conventional cationic surfactants bind the mud in a "close-packed" manner, making it difficult to remove this mud. In contrast, the alkoxylated AQA surfactants bind more loosely with the mud and are more easily removed from the fabric surface. Whatever the reason, the compositions herein containing AQA surfactants provide improved performance over conventional cationic surfactants, particularly in terms of mud removal.

Further advantages were found for the AQA surfactants herein. For example, in a bleaching composition comprising a bleach activator (as described herein), it is believed that some kind of ion pair or binding complex is formed with the peracid released from the activator. It can be inferred that these ion pairs are transported more efficiently into the mud as new hydrophobic agents, thereby enhancing the bleaching performance in connection with the use of bleach activators such as nonanoyloxy benzene sulfonate (NOBS). A completely low level (low as low as 3 ppm in the wash) AQA surfactants cause this result.

Moreover, for compositions that do not contain bleach, formulators may choose to use somewhat higher levels of AQA to confer enhanced performance benefits. These advantages may be associated with the ability of the AQA surfactants to modify their solution characteristics such that a larger number of conventional anionic surfactants, such as alkyl sulfates or alkyl benzene sulfonates, are available to perform their cleaning functions. have. This is partly true in the context where the detergent composition faces the formulator "building" against calcium and / or magnesium water hardness ions. Under these circumstances, it is preferable to use an AQA surfactant sufficient for the concentration of the AQA surfactant in the wash liquid to be about 10 ppm to about 50 ppm. This translates to an available composition range of about 1 to about 5% by weight in a fully formulated detergent composition (this concentration may vary depending on the rate of product use and the amount of other surfactants present in the wash liquor.) For high concentration products of 3500 ppm or less, the AQA level can be as high as 100-150 ppm in solution, which translates only to 3-4% AQA surfactant in the final treated detergent composition).

It was further found that the AQA surfactants containing about two ethylene oxide (EO) groups performed fairly well under low water hardness or even when a well built detergent composition was used. However, under conditions of high hardness (calcium carbonate of about 170 ppm or more), it is more preferable to use an AQA surfactant having about 5 or more EO groups. Moreover, for some dirt and stains, such as feces, AQA surfactants having 10 to 20 EO groups are preferred. Thus, it has been found by the present invention that a combination of AQA surfactants can be used in combination to provide a broad spectrum cleaning performance under a wide range of dirt and stains and a wide range of use conditions. Representative examples of such combinations of AQA surfactants are described in the examples below, but are not limited thereto.

Various additional advantages of these AQA surfactants over cationic surfactants known in the art will be described in more detail below. As can be seen from the present specification, AQA surfactants used in the manner of the present invention have successfully focused on a number of problems associated with the formulation of state of the art high performance detergent compositions. In particular, AQA surfactants formulate effective laundry compositions that can be used to remove a wide range of dirt and stains under a wide range of use conditions.

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

In one aspect, the present invention provides a means for enhancing oil phase / oil phase dirt removal by combining a lipase enzyme with an AQA surfactant. Oily / oil phase “everyday” dirt is a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials. When stored soiled clothing before washing, some triglycerides are converted to fatty acids by bacterial action; At this time, all remaining triglycerides can be converted into fatty acids through thorough washing using lipase enzyme. In general, for formulations that rely on hardness control by diffusion builders (e.g. layered silicates), a fake dismantling situation will be present early in the wash, which tends to take up a lot of cold water. In the first few minutes, fatty acids in the dirt interact with the dissolution hardness to form insoluble calcium lime soap and then prevent subsequent dirt removal, leaving dirt residues on the fabric even after washing. In dissolution formulations, this oil phase / oil phase stain insolubilization will even cause even more problems. The residue builds up during subsequent wear / wash, which causes the yellowish particles to yellow and penetrate into them. Ultimately, clothing becomes blackish, often thought to be unwearable and often discarded.

It has been found by the present invention that detergent compositions containing AQA surfactants and lipase enzymes result in superior cleaning and whitening performance compared to products containing only any of the above components. These advantages include: (1) AQA inhibits lime soap formation (allowing undisturbed lipase to access dirt); (2) It is believed to be the result of effectively releasing fatty acids from dirt (by AQA) to ensure maximum lipase activity (high levels of fatty acids in dirt inhibit lipase action).

The present invention also provides improved cleaning and fabric protection benefits by combining cellulose degrading enzymes with AQA surfactants. In old / old cotton or other cellulosic fabrics, the sheath surrounding the individual fibers breaks down to form gelatinous / amorphous cellulose “glues” that permeate the dirt. In addition, these glues are ideal for the deposition / preservation of body dirt (eg, present on collar and pillowcases) in oily / oil phase mixtures of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials. Acts as a substrate. Therefore, it is very difficult to remove these hydrophobic dirt from old fabrics and low levels of residual stain often remain on the fabric even after washing. In other words, after successive wear / wash, these stains accumulate, causing the dirt to yellow and seep into it.

Surprisingly, detergent compositions containing AQA surfactants and cellulose degrading enzymes (e.g., cellulase and / or endoglucanase) provide superior cleaning and whitening performance compared to products containing only any of these ingredients. It was revealed by the present invention. This advantage is believed to be the result of the effective penetration of hydrophobic body dirt by the AQA surfactant. This, in turn, enhances access to cellulose degrading enzymes that degrade amorphous cellulose glue around the fibers, which binds dirt on the fabric. As the glue breaks down, dirt that has soaked into it is released, giving it whiteness. In addition to the cleaning benefits, the formulated cellulose degradable / AQA system also offers flexibility advantages over cationic surfactants or enzymes alone, and effectively preventing lint from sticking and sticking in old fabrics improves the fabric's texture flexibility.

As will be appreciated, it is difficult to completely remove extremely hydrophobic "daily" or "bodily" dirt and low levels of residual dirt often remain on the fabric even after washing. This residue builds up and acts as an amorphous glue between the fibers, causing particulate soil to enter and the fabric to turn yellow. It was further found by the present invention that detergent compositions containing a combination of the water soluble AQA surfactant and amylase enzyme herein result in superior cleaning and whitening performance compared to compositions containing only one of the above components. It is believed that this is the result of the degradation of the residual "glue" around the fiber to even more improved levels (AQA promotes improved amylase access to sensitive soil components through effective soil solubilization). As the glue dissolves, it regains the whiteness and releases the particulate soil that soaks into it and / or is liable to be subjected to the decolorizing action of other cleaning actives.

The present invention also provides a detergent composition that effectively cleans up daily oily / oil phase dirt through the use of AQA surfactants and percarbonate bleach as described herein. Percarbonate, which carries peroxide bleach into laundry, is the basis ingredient for state-of-the-art ultra-compact granular laundry detergent formulations. Peroxide bleach is extremely hydrophobic and although this cannot be matched with the bleaching efficacy implemented by peracids (e.g., formed from the interaction of peroxides with TAED), it does not discolor the pigment (e.g., for particulate or beverage use). Effective in filth) and may help to remove color from organic residues associated with bodily filth. Unexpectedly, it has been found by the present invention that a composition containing AQA surfactant and percarbonate results in superior cleaning and whitening performance compared to products containing only one of the above components. This advantage is believed to be achieved by effectively solubilizing the oil phase oil dirt by AQA, thereby allowing the hydrophobic peroxide bleach to access the color bodies in the dirt (eg, pigments that have soaked into), resulting in improved dirt bleaching.

The present invention also provides a detergent composition that effectively cleans the daily dirt of the oil phase / oil phase through the hydrophobic bleach activator used in combination with the water soluble AQA surfactant herein. Routine dirt cleaning and whitening benefits for hydrophobic bleach activators and peracids have already been demonstrated. Such materials can penetrate to a limited extent complex / oily oily soils. It has been found by the present invention that detergents and bleaching compositions containing AQA and hydrophobic bleach activators (including the peracids performed) result in superior cleaning and whitening performance compared to similar compositions containing only any of these ingredients. . Reasonable deductions of the benefits of this formulated system are carried out by the following factors: (1) hydrophobicity by the AQA action on the dirt surface to prevent lime soap formation and to float all the calcium soap present; By encouraging access to bleach; (2) by a fairly low surface tension at the dirt / wash liquid interface, which is performed by AQA. As the surface tension drops, hydrophobic bleach (which acts like an anionic surfactant) encourages dirt penetration; (3) This is done by the fact that the interaction between AQA and hydrophobic peracids is possible to form extremely hydrophobic ion pairs that easily penetrate deep into the oil phase.

The present invention also provides compositions which result in effective cleaning of oil phase / oil phase dirt through the use of bleach catalysts using AQA surfactants. Bleach catalysts (characterized by the presence of one or more transition metal atoms) interact with peroxides to form very strong hydrophilic bleaches. These bleaching agents offer a strong advantage against colored hydrophilic stains and hydrophilic everyday dirt (i.e. dirt on socks). Such catalysts are typically used at extremely low levels in product cleaning. As discussed herein, a product containing AQA and a catalyst has superior cleaning and whitening performance compared to a product containing only one of the components and is particularly effective against everyday dirt. These advantages are believed to be achieved by effectively solubilizing the oil phase oil dirt by AQA, thereby allowing the hydrophobic “catalyst” bleach to access the color bodies in the dirt, resulting in effective dirt bleaching. Moreover, practical use of bleach catalysts has been difficult because of concerns about fabric damage. When using dimanganese catalysts known to cause fabric damage, it has been found by the present invention that the presence of AQA cationic surfactants significantly reduces the frequency of fabric damage. This is probably because such cationic materials can be absorbed on the fabric and used in ion pairs with activated catalysts by changing the surface charge, thereby minimizing or preventing fabric damage.

In another aspect, the present invention enables the use of high levels of insoluble inorganic builders without covering the fabric surface using laminated silicates with water soluble AQA surfactants. Laminated silicates are composed of discrete units, some of which are negatively charged. The positively charged head group of AQA interacts with the negatively charged surface through the formation of an electrostatic bond to form a surfactant monolayer, which can be inferred from the accumulation of a second "hydrophilic surfactant layer." This minimizes the formation of the shell, which can cause particles to emerge from the fabric resulting in a "rough texture to the fabric".

The present invention also provides compositions containing relatively low levels of polycarboxylate polymers without causing the problem of forming a sheath on the surface of the fabric by using different types of builders with AQA surfactants as described herein. It allows for the formulation of high levels of insoluble inorganic or soluble (bi) carbonate builders. In fact, high molecular weight polycarboxylate polymers have been used as dispersants in granular laundry detergents. However, these polymers are generally expensive. The polymer, which is also effective in dirt suspension, also effectively controls skin formation on the surface of the fabric by allowing inorganics (including builders / precipitated carbonates) to rise from the fabric. Low polymer formulations known to date have been found to have the disadvantage of forming a sheath on the surface of the fabric.

High levels of inorganic and / or (bi) carbonate builders are formulated with low levels of polymers and / or low molecular weight polymers without increasing the envelope formation on the surface of the fabric by using AQA surfactants in the manner described herein. It has been found by the present invention that it can be used. The problem of skin formation on the surface of the fabric is believed to be avoided for the low polymer system due to the following two AQA mechanisms: (1) Laminated silicates and zeolites are composed of distinct units and some of them will be negatively charged. . AQA with a positively charged head group interacts with these faces to form a hydrophilic charged surfactant multilayer around the inorganic particles, causing inorganics to emerge from the fabric and / or (2) AQA to anionic / nonionic surfactants. Compared to more woven fabrics. Thus, low levels of these materials are adsorbed onto the fabric surface to change the surface charge. Since the degree of carbonate sheath formation depends on the surface negative charge, less sheath formation can occur due to AQA adsorption (which changes cotton fabric charge to neutral / positive). In addition, AQA can be adsorbed onto the “growing” side of the calcium carbonate catalyst to inhibit crystal growth and minimize shell formation in the fabric.

The present invention also provides a detergent composition that effectively cleans "routine" dirt (and accidental dirt) in an oil phase / oil phase by using a polyethoxylated-polyamine polymer (PPP) with the AQA surfactants herein. As will be appreciated, the "routine" soil (eg, present in the collar and pillowcase) in the oil phase / oil phase is a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous substances. It is difficult to completely remove these very hydrophobic dirt and low levels of residual stains often remain in the fabric even after washing. In order to improve performance in this major field, various dirt dispersible polymers have been developed. Characteristic aspects of these materials include the following: (1) Reasonably low molecular weight "hydrophobic" polyamine backbones (which are slightly cationic in nature as they provide affinity for dirt and fabric); And (2) pendant “hydrophobic” polyethoxylate groups that provide steric stabilization and oil phase suspended solids. During washing these polymers are operated at the stain / wash liquid interface.

Surprisingly, it has been found by the present invention that detergent compositions containing the AQA surfactants and ethoxylated polyamine polymers of the present disclosure have superior cleaning and whitening performance compared to compositions containing only one of the above components. Advantages for such a mixing system include: (1) the ability of AQA to stain surfaces to prevent lime soap formation and to promote improved polymer deposition by bringing up all the calcium soap present; (2) While the polymer acts as a "maintenance removal framework", it provides solubilization of AQA deep into the dirt, which is believed to be the result of removing AQA-solubilized stain components and dispersing them into the wash liquor.

The present invention also provides a detergent composition that effectively cleans up daily dirt in an oil phase / oil phase by using high levels of surfactants (optionally including side chain surfactants) with AQA surfactants. In view of the importance of high surfactants in the effective removal of body phase oils from oily and oily phases, state-of-the-art “ultra-compact” detergent compositions generally contain high levels of surfactants (nonionic and anionic) and are used for body dirt cleaning. It is quite valid. Unexpectedly, products containing AQA and high levels of anionic surfactants or mixed anionic / nonionic surfactants (optionally including side chain surfactants) are superior to products containing only one of these components. It has been found by the present invention to bring performance. This advantage (1) prevents lime soap formation and floats all calcium soap present (if these soaps are formed and released at the dirt-cleaning liquid interface, they will significantly inhibit the access of the surfactant). Act on dirt surfaces; (2) AQA lowers the surface tension between the wash liquor and the oil phase / oil phase dirt, thereby allowing more effective dirt penetration by the surfactant; (3) Implemented by enabling the formation of ion pairs between cationic and anionic surfactants to form extremely hydrophobic surfactant “pairs” that penetrate deep into oily phase dirt.

The present invention also provides detergents, bleaching and other compositions which improve the perfume residue on the fabric after washing by using the perfume with a water soluble AQA surfactant. Natural and synthetic fabrics can be characterized by the surface charge on their fibers. Cotton is hydrophilic with a total negative charge surface, while polyester is hydrophobic with a neutral charge surface. Fragrances comprising esters, alcohols, ketones, aldehydes, ethers and the like are complex mixtures of hydrophobic organic actives. Fabric directness of different perfumes is based on (1) functional groups (depending on how polar they are); (2) the molecular weight of the active material; And (3) the charge on the fabric fibers. Most perfumes contain electron-rich oxygen atoms that will attach to molecules / surfaces that lack electrons.

Unexpectedly, it has been found by the present invention that a combination of AQA surfactant and perfume (characterized by having> 10% of a component having a molecular weight> 150) improves perfume fabric directness. Without wishing to be bound by any theory, it is believed that AQA surfactants not only increase the hydrophobicity of the anionic or anionic / nonionic surfactant systems, but also have a high directivity to the fabric (particularly cotton). AQA surfactants appear to adsorb on the fiber and change its surface charge from neutral / negative to positive (or electron-deficient). The fabric surface thus deformed acts like a magnet for the electron-rich region of the active fragrance, attracting them into the fabric to keep them electrostatically held. This leads to a significant increase in perfume residues. This advantage is most pronounced for perfume components having one or more oxygen atoms and a molecular weight greater than 150. To maximize this effect, the level of fragrance components should be at least about 10% of the total fragrance mixture.

The alkoxylated quaternary ammonium ("AQA") compounds used in accordance with the present invention enhance the cleaning performance of detergent compositions for textile laundry containing selected amounts of certain anionic surfactants. In this context, AQA compounds herein have the advantage that they are commercially available and compatible with various cleaning ingredients (eg builders, cleaning enzymes, etc.) used in many state-of-the-art, fully formulated, high quality laundry detergents. . Moreover, AQA compounds exhibit satisfactory stability in the presence of the bleach component commonly used in laundry detergent + bleach compositions. Importantly, AQA surfactants perform well in terms of removal of everyday and physical dirt, such as sock dirt. AQA surfactants and certain anionic surfactants and combinations remove the dirt from the fabric. Certain combinations of AQA surfactants with other conventional anionic surfactants provide excellent cleaning performance against a variety of soils and stains, including food stains, particulate soils and oily / oil phase soils. Briefly stated, the compositions of the present invention provide improved performance for cleaning a broad spectrum of dirt and stains, including body dirt from color and cuff, oily dirt and enzyme / bleach-sensitive dirt (e.g. spinach and coffee). Provide. The compositions are also particularly useful in the nil-P context as they provide good cleaning for builder sensitive stains such as mud.

Unlike other cationic surfactants known in the art, the bis-alkoxylated cationic surfactants herein have mixed surfactants that contain significantly lower levels of nonionic surfactants, for example, alkyl sulfate surfactants. Sufficient solubility to be used with the system. This is of significant value for formulators who would like to formulate detergent compositions of the type typically designed for use in automatic washing machines, especially those used in Japan as well as in North America. Typically, such compositions will comprise anionic (total LAS / AS) surfactant: nonionic surfactant in a weight ratio ranging from about 25: 1 to about 1:25, preferably from about 20: 1 to about 3: 1. will be. This may be in contrast to European formulations which comprise anionic: nonionic surfactants, typically in a weight ratio of about 10: 1 to 1:10, preferably about 5: 1 to about 1: 5.

The present invention utilizes an "effective amount" of AQA surfactant to improve the performance of cleaning compositions containing other auxiliary ingredients. By “effective amount” of the AQA surfactant and auxiliary components herein is meant an amount sufficient to directionally or significantly improve the performance of the cleaning composition at least 90% confidence against at least some of the dirt and stain that is targeted. Thus, for compositions whose target is a particular food stain, the formulator will use sufficient AQA to at least directionally enhance the cleaning performance for such stain. Likewise, for compositions whose target is mud, the formulator will use sufficient AQA surfactant to at least directionally enhance the cleaning performance for this mud. Importantly, for fully formulated laundry detergents, AQA surfactants may be used at levels that at least directionally improve cleaning performance for a wide range of dirt and stains, as can be seen from the data presented below. Can be.

As will be appreciated, AQA surfactants are used in the detergent compositions of the present invention in combination with other cleaning surfactants at levels effective to at least directionally improve cleaning performance. In the context of fabric laundry compositions, these "use levels" will vary depending on the type and severity of the dirt and stains, as well as the laundry temperature, the laundry capacity and the type of washing machine.

For example, in a US-type automatic washing machine for longitudinal loads having a washing tub capacity of about 45 to 83 liters, the washing cycle is about 10 to about 14 minutes and the laundry temperature is about 10 to about 50 ° C. It is preferred that the concentration of AQA surfactant in the wash liquor is about 2 to about 50 ppm, more preferably about 5 to about 25 ppm. Based on the use ratio of about 50 to about 150 ml per laundry, this means that for laundry detergents for large baths, the concentration in the product of the AQA surfactant is from about 0.1% to about 3.2% by weight, preferably from about 0.3 to about It is interpreted that it is 1.5 weight%. Based on the use ratio of about 60 to about 95 g per laundry, for dense ("compact") granular laundry detergents (densities of at least about 650 g / l), this results in a concentration of about 0.2% by weight of the AQA surfactant in the product. It is interpreted to be from about 0.5% to about 2.5% by weight, preferably from about 0.5% to about 2.5% by weight. Based on the use ratio of about 80 to about 100 g per laundry, for spray dried granular detergents (i.e., "downy"; densities of about 650 g / l or less), the concentration in the product of the AQA surfactant is about It is interpreted to be from 0.1% to about 3.5% by weight, preferably from about 0.3 to about 1.5% by weight.

For example, in a horizontal automatic front-loading washing machine with a washing tub capacity of about 8 to 15 liters, the washing cycle is about 10 to about 60 minutes and the laundry temperature is about 30 to about 95 ° C. It is preferred that the concentration is about 13 to about 900 ppm, more preferably about 16 to about 390 ppm. Based on the use ratio of about 45 to about 270 ml per laundry, this means that for laundry detergents for large baths the concentration in the product of the AQA surfactant is from about 0.4% to about 2.64% by weight, preferably from about 0.55 to about It is interpreted as 1.1 weight%. Based on the use ratio of about 40 to about 210 g per laundry, for a dense ("compact") granular laundry detergent (density of at least about 650 g / l), this results in a concentration of about 0.5 weight in the product of the AQA surfactant. It is interpreted to be from about 3.5% by weight, preferably about 0.7 to about 1.5% by weight. Based on the use ratio of about 140 to about 400 g per laundry, for spray dried granular detergents (i.e., "downy"; densities of about 650 g / l or less), the concentration of the AQA surfactant in the product is about It is interpreted as being 0.13% to about 1.8% by weight, preferably about 0.18% to about 0.76% by weight.

For example, in a vertical automatic Japanese-type washing machine having a washing tub capacity of about 26 to 52 liters, the washing cycle is about 8 to about 15 minutes and the laundry temperature is about 5 to about 25 ° C. It is preferred that the concentration is from about 1.67 to about 66.67 ppm, more preferably from about 3 to about 6 ppm. Based on the use ratio of about 20 to about 30 ml per laundry, this means that for laundry detergents for large baths, the concentration in the product of the AQA surfactant is from about 0.25% to about 10% by weight, preferably from about 1.5 to about It is interpreted that it is 2 weight%. Based on the use ratio of about 18 to about 35 g per laundry, for dense ("compact") granular laundry detergents (densities of at least about 650 g / l), this results in a concentration of about 0.25 weight in the product of the AQA surfactant. % To about 10% by weight, preferably about 0.5 to about 1.0% by weight. Based on the use ratio of about 30 to about 40 g per laundry, for spray dried granular detergents (i.e., "downy"; densities of about 650 g / l or less), the concentration in the product of the AQA surfactant is about It is interpreted as being 0.25 wt% to about 10 wt%, preferably about 0.5 wt% to about 1 wt%.

Cationic Surfactants—Preferred bis-ethoxylated cationic surfactants herein are marketed under the trade name ETHOQUAD from Akzo Nobel Chemicals Company. Alternatively, such materials can be synthesized using a variety of different schemes, where "EO" represents -CH ₂ CH ₂ O-units:

The economic equation is:

The following parameters summarize the optimal and preferred reaction conditions for Scheme 5 herein. Step 1 of the scheme is preferably carried out in an aqueous medium. The reaction temperature is typically 140 to 200 ° C. The reaction pressure is 50 to 1000 psig. Base catalysts, preferably sodium hydroxide, can be used. The molar ratio of reactants is from 2: 1 to 1: 1 amine to alkyl sulfates. This method is preferably carried out using a C ₈ -C ₁₃ alkyl sulfate sodium salt. Ethoxylation reactions and quaternization reactions are carried out using conventional conditions and reactants.

Under some circumstances, step 1 of Scheme 5 produces a product that is sufficiently soluble that a gel can be formed in the aqueous reaction medium. While the desired product can be recovered from such a gel, in some commercial aspects a two-step synthetic scheme 6, described below, may be more preferred. The second step (ethoxylation) is preferably carried out using an acid (eg HCl) and ethylene oxide to provide a quaternary surfactant. As shown below, it can be reacted with chlorohydrin, ie chloroethanol, to give the desired bishydroxyethyl derivative.

For Scheme 6, the following parameters summarize the optimal and preferred reaction conditions for the first step. The first step is preferably carried out in an aqueous medium. The reaction temperature is typically in the range of 100 to 230 ° C. The reaction pressure is 50 to 1000 psig. A base, preferably sodium hydroxide, can be used to react with HSO ₄ generated during the reaction or an acid can be used with an excess of amine. The molar ratio of amine to alkyl sulfates is typically 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 as a separate phase 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 providing AQA surfactants are carried out under standard reaction conditions.

Scheme 7 may optionally be carried out using ethylene oxide under standard ethoxylation conditions without using a catalyst to achieve monoethoxylation.

The following shows these additional schemes where "EO" represents -CH ₂ CH ₂ O-unit. In this scheme, either inorganic or organic bases or excess amine reactants are used to neutralize the HSO ₄ generated.

The following are some examples of such schemes for the convenience of the formulator, but are not limited thereto.

Synthetic A

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

To the glass autoclave liner is added 19.96 g (0.06921 mole) of sodium dodecyl sulfate, 14.55 g (0.1384 mole) of diethanolamine, 7.6 g (0.095 mole) of 50% by weight sodium hydroxide solution and 72 g of distilled H ₂ O. This glass liner is sealed into a vibrating autoclave of 500 ml stainless steel and heated to 160-180 ° C. for 3-4 hours under 300-400 psig nitrogen. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured with 80 ml of chloroform and 250 ml separatory funnel. Shake this funnel well for several minutes and allow the mixture to separate. The lower chloroform layer is drained and this chloroform is evaporated to yield the product.

Synthetic B

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

One mole of sodium dodecyl sulfate is reacted with one mole of ethanolamine in the presence of a base in the manner described in Synthesis A. The resulting 2-hydroxyethyldodecylamine is recovered and reacted with 1-chloroethanol to prepare the title compound.

Synthetic C

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

To the glass autoclave liner are added 19.96 g (0.06921 mole) of sodium dodecyl sulfate, 21.37 g (0.3460 mole) of ethanolamine, 7.6 g (0.095 mole) of 50% by weight sodium hydroxide solution and 72 g of distilled H ₂ O. This glass liner is sealed into a vibrating autoclave of 500 ml stainless steel and heated to 160-180 ° C. for 3-4 hours under 300-400 psig nitrogen. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured with 80 ml of chloroform and 250 ml separatory funnel. Shake this funnel well for several minutes and allow the mixture to separate. The lower chloroform layer is drained and this chloroform is evaporated to yield the product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of a base catalyst at 120 to 130 ° C. to produce the desired final product.

The bis-substituted amines prepared in the above synthesis can be further ethoxylated in a standard manner. Quaternization reactions with alkyl halides to form AQA surfactants are common.

In accordance with the foregoing description, the following presents non-limiting and specific examples of AQA surfactants used herein. It should be appreciated that the alkoxylation degree referred to herein for the AQA surfactant is reported as an average value after performing conventional practice for conventional ethoxylated nonionic surfactants. This is because ethoxylation reactions typically produce mixtures of materials with different degrees of ethoxylation. It is common to report total EO values, such as "EO2.5", "EO3.5", etc., rather than as natural numbers.

designation R ¹ R ² ApR ³ A'qR ⁴ AQA-1 (also called Coco methyl EO2) C ₁₂ -C ₁₄ CH ₃ EO EO AQA-2 C ₁₂ -C ₁₆ CH ₃ (EO) ₂ EO AQA-3 (Coco Methyl EO4) C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₂ AQA-4 C ₁₂ CH ₃ EO EO AQA-5 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₃ AQA-6 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₃ AQA-7 C ₈ -C ₁₈ CH ₃ (EO) ₃ (EO) ₂ AQA-8 C ₁₂ -C ₁₄ CH ₃ (EO) ₄ (EO) ₄ AQA-9 C ₁₂ -C ₁₄ C ₂ H ₅ (EO) ₃ (EO) ₃ AQA-10 C ₁₂ -C ₁₈ C ₃ H ₇ (EO) ₃ (EO) ₄ AQA-11 C ₁₂ -C ₁₈ CH ₃ (Propoxy) (EO) ₃ AQA-12 C ₁₀ -C ₁₈ C ₂ H ₅ (Isopropoxy) ₂ (EO) ₃ AQA-13 C ₁₀ -C ₁₈ CH ₃ (EO / PO) ₂ (EO) ₃ AQA-14 C ₈ -C ₁₈ CH ₃ (EO) ₁₅ ^* (EO) ₁₅ ^* AQA-15 C ₁₀ CH ₃ EO EO AQA-16 C ₈ -C ₁₂ CH ₃ EO EO AQA-17 C ₉ -C ₁₁ CH ₃ EO 3.5 average AQA-18 C ₁₂ CH ₃ EO 3.5 average AQA-19 C ₈ -C ₁₄ CH ₃ (EO) ₁₀ (EO) ₁₀ AQA-20 C ₁₀ C ₂ H ₅ (EO) ₂ (EO) ₃ AQA-21 C ₁₂ -C ₁₄ C ₂ H ₅ (EO) ₅ (EO) ₃ AQA-22 C ₁₂ -C ₁₈ C ₃ H ₇ Bu (EO) ₂ * Ethoxy optionally end-capped with methyl or ethyl.

Considerably preferred bis-AQA compounds for use herein are

Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is all anions convenient to provide charge balance, preferably Is chloride. Referring to the general AQA structure mentioned above, in a preferred compound, since R ¹ is derived from coconut (C ₁₂ -C ₁₄ alkyl) fractional fatty acid, R ² is methyl and ApR ³ and A'qR ⁴ are each monoethoxy, Compounds of this preferred type are referred to as "CocoMeEO2" or "AQA-1" in the above list herein.

Other preferred AQA compounds herein include

Wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl, preferably C ₁₀ -C ₁₄ alkyl, p is independently 1 to about 3, q is 1 to about 3, and R ² is C ₁ -C ₃ alkyl, preferably methyl, and X is an anion, in particular chloride.

Other compounds of the foregoing types include ethoxy (CH ₂ CH ₂ O) units (EO) having butoxy (Bu), isopropoxy [CH (CH ₃ ) CH ₂ O] and [CH ₂ CH (CH ₃ O). ] Compounds substituted with units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units.

Anionic Surfactants-The alkyl benzene sulfate ("LAS") and primary (preferably "AS") or secondary alkyl sulfate components of the compositions according to the invention are well known and widely used commercially available surfactants. As mentioned above, one of the important advantages of the present invention is the discovery that when using AQA surfactants in the manner described herein, these AQA surfactants inspire the performance of other conventional materials. Such LAS surfactants typically have alkyl chain lengths in the range of C ₁₀ -C ₁₆ and the average alkyl chain length of commercially available LAS is in the range of 11 to 13, typically approximately 11.5. AS surfactants typically have alkyl chain lengths in the C ₁₀ -C ₂₀ range and many AS commercial products range from 12 to 18. All such commercially available LAS and AS materials can be used in the present invention. Unsaturated sulfates, such as oleyl sulfate, can also be used. Formula _{CH 3 (CH 2) x (} CHOSO 3 - M +) CH 3 and _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 ( where, x and (y + 1) is about 7 or more It is also possible to use secondary (2,3) alkyl sulfates and branched CC alkyl sulfates of integers and M is a water-solubilizing cation, in particular sodium. Mixtures of primary, secondary and side chains can be used.

Nonionic Surfactants-Non-limiting examples of nonionic surfactants useful herein typically at levels of about 1 to about 55 weight percent include alkoxylated alcohols (AE's) and alkyl phenol polyhydroxy fatty acid amides (PFAA's), alkyl poly Glycosides (APG's), C ₁₀ -C ₁₈ glycerol ethers and the like.

More specifically, condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as nonionic surfactants in the present invention. The alkyl chains of these aliphatic alcohols may be linear or branched primary or secondary and generally contain about 8 to 22 carbon atoms. About 1 to about 10 moles, preferably 2 to 7 moles, most preferably 2 to 5 moles per alcohol and alcohol having an alkyl group of about 8 to about 20, more preferably about 10 to about 18 carbon atoms Condensation products with ethylene oxide are preferred. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (condensation products of C ₁₁ -C ₁₅ straight chain alcohols with 9 moles of ethylene oxide) and tergitol 24-L -6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide, with a narrow molecular weight distribution), both of which are sold by Union Carbide Corporation; Neodol ^TM 45-9 (condensation product of C ₁₄ -C ₁₅ straight chain alcohol with 9 moles of ethylene oxide), marketed by Shell Chemical Campy, Neodol 23-3 (C ₁₂ -C ₁₃ straight chain) Condensation products of alcohol with 3 moles of ethylene oxide), neodol 45-7 (C ₁₄ -C ₁₅ straight chain condensation products of alcohol with 7 moles of ethylene oxide) and neodol 45-5 (C ₁₄ -C ₁₅ straight chain) Condensation products of alcohols with 5 moles of ethylene oxide); Kyro ^™ EOB (condensation products of C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide) sold by The Procter & Gamble Co .; And Genapol (Genapol LA 030 or 050 (condensation products of C ₁₂ -C ₁₄ alcohols with 3 or 5 moles of ethylene oxide) sold by Hoechst.) The preferred range of HLB in these AE nonionic surfactants is 8 to 11 and the most preferred range is 8 to 10. Condensates of propylene oxide and butylene oxide may be used.

Another class of preferred nonionic surfactants for use herein are Polyhydroxy fatty acid amide surfactant, wherein R ¹ is H, or C _1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, R ² is C _5-31 hydrocarbyl Z is a polyhydroxyhydrocarbyl, or an alkoxylated derivative thereof, wherein the at least three hydroxyls have a straight chain hydrocarbyl chain directly linked to the chain. Preferably, R ¹ is methyl and R ² is straight chain C _11-15 alkyl or C _15-17 alkyl or alkenyl chain such as coconut alkyl or a mixture thereof and Z is glucose in a reductive amination reaction, Derived from reducing sugars such as fructose, maltose and lactose. Typical examples are C ₁₂ -C ₁₈ and C ₁₂ -C ₁₄ N-methylglucamide (see US Pat. Nos. 5,194,639 and 5,298,636). N-alkoxy polyhydroxy fatty acid amides may also be used (see US Pat. No. 5,489,393).

Also useful as nonionic surfactants in the present invention are hydrophobic groups containing from about 6 to about 30, preferably from about 10 to about 16 carbon atoms, and from about 1.3 to about 10, preferably from about 1.3 to 3 Polysaccharides, most preferably containing about 1.3 to about 2.7 saccharide units, for example, US Pat. No. 4,565,647 (Lienado, issued Jan. 21, 1986) having a polyglycoside hydrophilic group. Alkylpolysaccharides as described in Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl residues can replace glucosyl residues (optionally with the hydrophobic groups 2-, 3 -, Attached at the 4-, etc. position to provide glucose or galactose in contrast to glucoside or galactose). For example, saccharide interbonds can be made between the additional saccharide units and the 2-, 3-, 4- and / or 6-positions on the preceding saccharide units.

Preferred alkylpolysaccharides have the formula R ² O (C _n H _2n O) _t (glycosyl) _x , wherein R ² is a group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof Wherein the alkyl group contains about 10 to about 18, preferably about 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is 0 to about 10, preferably Is 0, x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7. Such glycosyl is preferably derived from glucose. To prepare these compounds, alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form glucoside (attached at the 1-position). Additional glucosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and / or 6-position, preferably mainly 2-position.

Polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols are suitable for use as nonionic surfactants in the surfactant systems of the present invention, with polyethylene oxide condensates being preferred. These compounds include condensation products of alkyl phenols with alkylene oxides having alkyl groups in straight or branched chain form having from about 6 to about 14 carbon atoms, preferably about 8 to 14 carbon atoms. In a preferred embodiment, ethylene oxide is present in an amount of about 2 to about 25 moles, more preferably about 3 to about 15 moles per mole of alkyl phenol. Nonionic surfactants of this type which are commercially available include Igepal ^™ CO-630 (available from GAF Corporation); And Triton ^™ X-45, X-114, X-100 and X-102 (all sold by Rohn & Haas Company). These surfactants are commonly referred to as alkylphenol alkoxylates (eg alkyl phenol ethoxylates).

Condensation products of hydrophobic bases with ethylene oxide formed by the condensation reaction of propylene oxide with propylene glycol are also suitable for use as additional nonionic surfactants in the present invention. Hydrophobic fractions of these compounds will preferably have a molecular weight of about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to these hydrophobic fractions tends to increase the water solubility of the entire molecule, and the liquid properties of these products have a polyoxyethylene content of 50% of the total weight of the condensation product, which is less than about 40 moles of ethylene oxide. Corresponds to An example of this type of compound is the particular commercial Pluronic ^™ surfactant (available from BASF).

Also suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention are the products resulting from the reaction of propylene oxide with ethylenediamine and the condensation products of ethylene oxide. The hydrophobic moieties of these products consist of the reaction product of ethylenediamine with excess propylene oxide and generally have a molecular weight of about 2500 to about 3000. These hydrophobic moieties are condensed with ethylene oxide to such an extent that the condensation product contains about 40 to about 80 weight percent polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. An example of a nonionic surfactant of this type is the specific commercially available Tetronic ^™ compound (commercially available from BASF).

Additional Surfactants—Non-limiting examples of additional surfactants useful herein with alkyl sulphate and LAS mixtures, typically at concentrations of about 1 to about 55% by weight, include conventional C ₁₀ -C ₁₈ alkyl alkoxy sulfates (" AE _x S ″; in particular EO 1-7), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO 1-5) and C ₁₀ -C ₁₈ alpha-sulfonated fatty acid esters. C ₁₂ -C ₁₈ betaines and sulfobetaines (“sultaines”), C ₁₀ -C ₁₈ amine oxides and the like may also be used. C ₁₀ -C ₂₀ Conventional soaps can be used. If you want to get a lot of soap bubbles, you can use branched C ₁₀ -C ₁₆ soap. Other commonly useful surfactants are listed in the standard booklet.

The following are examples of, but are not limited to, various accessory ingredients that can be used in the compositions of the present invention. Although combinations of AQAs and anionic surfactants with these auxiliary component ingredients can be provided as final products in the form of liquids, gels, bars, etc. using conventional techniques, the granules herein can be used to achieve optimal performance. Some special processing techniques are required for the manufacture of laundry detergents. Thus, the preparation of laundry granules will be described separately in the granule preparation section (described below) for the convenience of the manufacturer.

Builders-Detergent builders, although optional, are included, for example, in the compositions of the present invention to assist in controlling the minerals, especially Ca and / or Mg hardness, or to remove particulate dirt from the surface of the laundry. It is preferable to be. Builders can be operated by a variety of mechanisms, including by forming soluble or insoluble complexes with the hardness ions by ion exchange and by providing a surface more favorable for precipitation of the hardness ions than the surface of the laundry to be cleaned. Builder levels can vary considerably depending on the end use and the physical form of the composition. Built detergents typically comprise at least about 1% builders. Liquid formulations typically comprise about 5 to about 50%, more typically 5 to 35% builders. Granular formulations typically comprise about 10 to about 80 weight percent, more typically 15 to 50 weight percent builder, based on the weight of the detergent composition. Higher or lower level builders are not excluded. For example, certain detergent additives or high surfactant formulations may not be built.

Suitable builders include phosphates and polyphosphates, especially sodium salts; Silicates, including water-soluble and hydrated solid types, silicates having a chain structure, layer structure or three-dimensional structure, as well as amorphous-solid or unstructured liquid types; Carbonate minerals other than carbonate, bicarbonate, sesquicarbonate, and sodium carbonate and sesquicarbonate; Aluminosilicates; Oligomeric or water soluble low molecular weight polymers including aliphatic and aromatic types as well as organic mono-, di-, tri- and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium or alkanolammonium salts Carboxylates; And pitsan. These may be supplemented with, for example, borates for pH buffering purposes, or sulfates, in particular sodium sulfate, and other fillers or carriers that may be important for engineering the stable surfactant and / or builder containing detergent compositions.

Builder mixtures, often referred to as “builder systems,” can be used, which typically include two or more conventional builders, sometimes supplemented with chelating agents, pH buffers, or fillers, which supplemental materials generally refer to components herein. It may be considered separately when describing the quantity of. In terms of the relative amount of surfactant and builder in the detergents according to the present invention, preferred builder systems are formulated with a weight ratio of surfactant to builder typically between about 60: 1 and about 1:80. Certain preferred laundry detergents have a weight ratio in the range of 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.0 to 3.0: 1.0.

Legally acceptable builders for P-containing detergents include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates and phosphonates such as tripolyphosphate, pyrophosphate, glassy polymeric meta-phosphate, etc. no.

Suitable silicate builders include alkali metal silicates, in particular solid hydrated 2-non-silicates for the purpose of automatic dish washing (BRITESIL, eg, marketed by PQ Corp. under the trade name BRITESIL H2O). Liquid and solid silicates having a SiO ₂ : Na ₂ O ratio in the 3.2: 1 range; And laminated silicates, such as those described in US Pat. No. 4,664,839 (May 12, 1987; HP Rieck). NaSKS-6, often abbreviated "SKS-6", is a crystalline laminated aluminum-free δ-Na ₂ SiO ₅ polymorphic silicate marketed by Hoechst and is particularly preferred for granular laundry compositions. For the preparation thereof see German DE-A-3,417,649 and DE-A-3,742,043. Other laminated silicates, for example the formula NaMSi _x O _{2x + 1 y y 2} O, where M is sodium or hydrogen and x is a number from 1.9 to 4, preferably 2 and y is from 0 to 20, preferably Silicate is a number of 0) may be used herein. Laminated silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 as α, β and γ laminated silicates are formed. Other silicates, such as magnesium silicate, which may act as crispening, stabilizers for bleaching and soap bubble control systems in granules may also be useful.

Also suitable for use herein are the following formulas _x M ₂ O. _y SiO ₂ .zM'O in the form of anhydrides as taught in US Pat. No. 5,427,711 (June 27, 1995; Sakaguchi et al.). Wherein M is Na and / or K, M 'is Ca and / or Mg, y / x is from 0.5 to 2.0 and z / x is from 0.005 to 1.0) and the synthesized crystalline ion exchange material having a chain structure. Or a hydrate thereof.

Suitable carbonate builders include alkaline earth metals and alkali metal carbonates as described in German Publication No. 2,321,001 published November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals, such as For example, a convenient complex salt of sodium carbonate and calcium carbonate, such as having a 2Na ₂ CO ₃ .CaCO ₃ composition when it is trona or anhydrous, and even calcium carbonate, especially calciite, including calsite, aragonite and batterite Larger surface areas in comparison can be useful, for example, for use as a seed or in synthetic detergent bars.

Aluminosilicate builders are particularly useful for granular detergents, but can also be incorporated into liquids, pastes or gels. Suitable for this purpose are those of the formula [M _z (AlO ₂ ) _z (SiO ₂ ) _v ] · _x H ₂ O, wherein z and v are integers greater than 6 and the molar ratio of z to v is 1.0 to 5.0 and x is 15 to It is an integer of 264). Aluminosilicates may be naturally or synthetically derived, crystalline or amorphous. Aluminosilicate preparation methods are described in US Pat. No. 3,985,669 (Krummel, et al., October 12, 1976). Preferred synthetic crystalline aluminosilicate ion exchange materials are zeolite A, zeolite P (B), zeolite X, and so-called zeolite MAPDLEK, depending on how different it is from zeolite P. Natural types can be used, including clinoptilolite. Zeolide A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _.x H ₂ O, where x is from 20 to 30, in particular 27. Dehydrated zeolites (x is 0 to 10) may also be used. Preferably, the particle size of the aluminosilicate is 0.1 to 10 microns in diameter.

Suitable builders for organic detergents include polycarboxylate compounds including water-soluble non-surfactant dicarboxylates and tricarboxylates. More typically, builder polycarboxylates have a plurality of carboxylate groups, preferably three or more carboxylate groups. Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. In the salt form, alkali metal or alkanolammonium salts such as sodium, potassium and lithium are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydiisuccinate (US Pat. No. 3,128,287 to Berg, April 7, 1964.) and US Pat. No. 3,635,830 to Lambert et al. (1972. 1. 18.)]; The “TMS / TDS” builder of US Pat. No. 4,663,071 to May 5, 1987 to Bush et al .; And other ether carboxylates, including cyclic and cycloaliphatic compounds, as described, for example, in US Pat. Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other suitable builders include ether hydroxypolycarboxylates, ie copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid; Carboxymethyloxysuccinic acid; Various alkali metal, ammonium and substituted ammonium salts of polyacetic acid such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; And melic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy-methyloxysuccinic acid and soluble salts thereof.

Citrate, for example citric acid and its soluble salts, are carboxylate builders that are important, for example, in bulk bath detergents, because the material is available and renewable from renewable resources. Citrate may also be used in granular compositions, in particular in combination with zeolites and / or laminated silicates. Oxydisuccinates are particularly useful in such compositions and combinations.

Alkali metal phosphates, such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, can be used where permitted and especially in bar formulations used for hand washing. Ethane-1-hydroxy-1,1-diphosphonates and other known phosphonates such as those of US Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137 Phonate builders may be used and may have the desired scale protection properties.

Certain cleaning surfactants or short chain homologues thereof also act as builders. When considering modest formulations, these materials are evaluated as cleaning surfactants if they have surfactant performance. Preferred types for builder functional groups are exemplified by 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds described in US Pat. No. 4,566,984 (January 28, 1986) to Bush. Succinic acid builders include C ₅ -C ₂₀ alkyl and alkenyl succinic acid and salts thereof. Succinate builders include lauryl succinate, myristyl succinate, palmity succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate, and the like. Lauryl-succinate is described in European Patent Publication No. 86200690.5 / 0,200,263, published November 5, 1986. Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may be incorporated into the compositions as surfactant / builder materials or in combination with the aforementioned builders, in particular citrate and / or succinate builders, to provide additional builder activity. Can be. Other suitable polycarboxylates are described in US Pat. No. 4,144,226 (Crutchfield, et al .; Mar. 13, 1979), and US Pat. No. 3,308,067 (Diehl, Mar. 7, 1967) and US Pat. No. 3,723,322 (Diehl). ).

Other types of inorganic builder materials that can be used are the formula (M _x ) _i Ca _y (CO ₃ ) _z , where x and i are integers from 1 to 15, y is integers from 1 to 10 and z is from 2 to 25 And M _i is a cation, at least one of which is water soluble) and the formula Σ _i = _1-15 (valence of x _i × M _i ) + 2y = Meets 2z. These builders are referred to herein as "inorganic builders". Anions other than carbonates or water for hydration can be added, assuming that the overall charge is balanced or neutral. The charge or valence effect of these anions should be added to the right side of the equation. Preferably, there is a water soluble cation 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 are quite preferred. Non-limiting examples of anions other than carbonates are those selected from the group consisting of chlorides, sulfates, fluorides, oxygen, hydroxides, silicon dioxides, chromates, nitrates, borates and mixtures thereof. Preferred builders of this type in the simplest form are Na ₂ Ca (CO ₃ ) ₂ , K ₂ Ca (CO ₃ ) ₂ , Na ₂ Ca ₂ (CO ₃ ) ₃ , NaKCa (CO ₃ ) ₂ , NaKCa ₂ (CO ₃ ) ₃ , K ₂ Ca ₂ (CO ₃ ) ₃ , and combinations thereof. Particularly preferred materials for the builders described herein are Na ₂ Ca (CO ₃ ) ₂ in any crystalline modified form. Suitable builders of the type defined above are exemplified in natural or synthetic form of any of the following substances or combinations thereof: Agfanite, Andersonite, Ashcroftin Y, Bayerite, Borcarite, Bourban Kite, Bootslite, Khancriteite, Caboserite, Calettonith, Davine, Donite Y, Pilditite, Ferrisurite, Frangineite, Gaudeproit, Greyrusite, Zirvasite, Gregorite, Zourabsky, Campauzite Y, Ketnerite, Canneshite, Lepersonite Gd, Ioite, McKellbayite Y, Microsomite, Emroseate, Natropyridite, Nyrerate, lemonite Ce, sacrophanite, shroking zeolite, sorbite, sulite, tonicite, tuscanite, tyrolite, bischrebit and gemcolite. Preferred material forms include nyrates, pyridylites and sorbite.

Enzymes-Enzymes can be included in the detergent composition for a variety of purposes, including preventing the escape of dyes in fabric laundering and removing protein-based, carbohydrate-based or triglyceride-based stains from the substrate for fabric restoration. have. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures of any suitable origin, for example mixtures of vegetable, animal, bacterial, fungal and yeast origin. Preferred choices are influenced by factors such as pH activity and / or stability optimality, thermal stability, and stability to active ingredients, builders and the like. In this regard, bacterial or fungal enzymes such as bacterial amylases and proteases and fungal cellulase are preferred.

"Cleaning enzyme" as used herein means any enzyme that has cleaning, stain removal or other beneficial effects in laundry, hard surface cleaning or human protective detergent compositions. Preferred washing enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for washing include, but are not limited to, proteases, cellulases, lipases and peroxidases. Considerably preferred for automatic dishwashing are amylases and / or proteases, which include both types currently on the market and improved types that are more suitable for bleaching due to successful improvements but which remain bleaching deactivation susceptibility.

Enzymes are typically incorporated into a detergent or detergent additive composition at a level sufficient to provide a "cleaning-effective amount". The term " cleaning-effective amount " refers to any amount that can produce cleaning, stain removal, dirt removal, whiteness, deodorization or vivid enhancement effects on substrates such as fabrics and cutlery. In substantial terms for formulations currently on the market, typical amounts are up to about 5 mg, more typically 0.01 to 3 mg of active enzyme per gram of detergent composition. In other words, the composition will typically comprise from 0.001 to 5% by weight, preferably 0.01 to 1% by weight of a commercial enzyme preparation. Protease enzymes are typically present in such enzyme preparations at a level sufficient to provide 0.005 to 0.1 ornson active units (AU) per gram of the composition. In the case of certain detergents, such as automatic dishwashing detergents, in order to improve spotting / filming or other final results by minimizing the total amount of non-catalytically active substance, increasing the active enzyme content of the commercially available formulations is necessary. It may be desirable. Highly active levels may also be desirable in highly concentrated detergent formulations.

Suitable examples of proteases are B. a. B. subtilis and b. Subtilisin obtained from certain strains of B. licheniformis. One suitable protease is from Bacillus strains exhibiting maximal activity over a range of pH 8-12, developed by Danish Novo Industries A / S (described below as "Novo") and marketed as ESPERASE ^™ . Obtained. The preparation of such and similar enzymes is described in GB 1,243,784 (Novo). Other suitable proteases include ALCALASE ^™ and SAVINASE ^™ (Novo) and MAXATASE ^™ (International Bio-Synthetics, Inc., The Netherlands); And protease A as described in EP 130,756 A (1/9/1985) and protease B as described in EP 303,761 A (4/28/1987) and EP 130,756 A (1/1985). There is. There is also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A (Novo). Enzymatic detergents comprising proteases, one or more other enzymes and reversible protease inhibitors are described in WO 9203529 (Novo). Other preferred proteases are those of WO 9510591 A (Procter & Gamble). If desired, proteases with reduced adsorptivity and increased hydrolysis are available as described in WO 9507791 (Procter & Gamble). Recombinant trypsin-like proteases for detergents suitable herein are described in WO 9425583 (Novo).

More particularly, a particularly preferred protease, referred to as "protease D", is a US patent application filed by Back et al. Under the name "Protease-containing Cleaning Composition", preferably at position +76 in the carbonyl hydrolase. No. 08 / 322,676 and "bleaching composition comprising protease enzyme" under the name of the invention. Of Bacillus amyloliquefaciens subtilisin as described in the parent application of U.S. Patent Application No. 08 / 322,677, filed Oct. 13, 1994, filed by Gosch et al. +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197 depending on the numbering Different amino acids, with one or more amino acid residue positions equivalent to those selected from the group consisting of: +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 Is a carbonyl hydrolase variant with an amino acid sequence not found in nature derived from precursor carbonyl hydrolases by replacing with a plurality of amino acid residues.

Examples of amylases that are particularly suitable herein for use in, but not limited to, automatic dish washing include, for example, α-amylases described in GB 1,296,839 (Novo); RAPIDASE ^™ (International Bio-Synthesis, Inc.) and TERMAMYL ^™ (Novo) and FUNGMYL from Novo are particularly useful. It is known to engineer enzymes for enhanced stability, eg oxidative stability. J. Biological Chem., Vol. 260, no. 11, June 1985, pp. 6518-6521. In certain preferred embodiments of the present invention it is possible to use amylases with enhanced stability in detergents such as the automatic dishwashing type, in particular the enhanced oxidative stability as measured relative to the reference point of TERMAMYL ^™ sold in 1993. Preferred amylases herein are, for example, oxidative stability against hydrogen peroxide / tetraacetylethylenediamine in a buffer solution at pH 9-10; Thermal stability at washing temperatures such as, for example, about 60 ° C .; Or share stability of the "stable-enhanced" amylase, characterized in that at least one of the alkaline stability at a pH of about 8 to about 11, measured against the identified reference point amylase, is improved to a measurable level. have. Stability can also be measured using any of the technical tests described in the art (see, eg, the document described in WO 9402597). Stability enhanced amylases can be obtained from Novo or Genencor International. One class of highly preferred amylases herein is site-directed mutations from one or more of the Bacillus amylases, particularly from Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are immediate precursors. Have commonalities derived using. Oxidative stability enhanced amylases are particularly preferred to the reference amylases mentioned above for bleaching, more preferably for oxygen bleaching (separate from chlorine bleaching) the detergent compositions herein. Examples of such preferred amylases include (a) a ratio known as TERMAMYL ^™ . A mutant in which the methionine residue located at position 197 of rickeniformis alpha-amylase is substituted with alanine or threonine, preferably threonine, or similar parent amylase such as B. a. Amyloliquefaciens, B. Subtilis or b. Amylases according to WO 9402497 (Novo; February 3, 1994), previously inserted, as further illustrated by the homologous positional variation of B. stearothermophilus; In a paper entitled "Oxidally Resistant Alpha-Amylase" by Genenkor International (which was submitted by C. Mitchinson at the 207th American Chemical Society National Meeting, March 13-17, 1994) There is stability-enhanced amylase as described. In this document, bleaching agents in automatic dishwashing detergents inactivate alpha-amylase, but enhanced oxidative stability amylase is not. It is mentioned that it was made by Genenkor from Rikeniformis NCIB8061. Methionine (Met) has been identified as the most susceptible residue. Met is substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438 to produce specific mutants, of which the most important are the M197L and M197T variants, the variants with the most stable expression of the M197T variant to be. Stability is measured in CASCADE ^™ and SUNLIGHT ^™ ; (c) Particularly preferred amylases herein are amylase variants with additional modifications at the immediate parent as described in WO 9510603 A, which are commercially available as DURAMYL from Novo. Other oxidative stability enhanced amylases which are particularly preferred are those described in WO 9418314 (Genencor International) and WO 9402597 (Novo). For example, other oxidative stability-enhanced amylases can be used, such as those induced by site-directed mutations from known chimeric, hybrid or simple mutant parent forms of amylase available. Other preferred enzyme modifications can be used (WO 9509909 (Novo)).

Other amylase enzymes are those described in PCT / DK 96/00056, which is currently pending by WO 95/26397 and Novo Nordisk. Certain amylase enzymes for use in the detergent compositions of the present invention include at least 25% greater than the intrinsic activity of TERMAMYL in the pH range of 25-55 ° C. and 8-10, as measured by Phadebas α-amylase activity assay. There is an α-amylase characterized by a high intrinsic activity (such Padades α-amylase activity assays are described in WO 95/26397, page 9-10). Also included are examples of α-amylases having at least 80% homology with the amino acid sequences shown in the sequences listed in the above references. These enzymes are preferably incorporated into the laundry detergent composition at a level of 0.00018 to 0.060 weight percent pure enzyme, more preferably 0.00024 to 0.048 weight percent pure enzyme, based on the weight of the total composition.

Compositions useful herein are bacterial and fungal types, preferably having a pH optimum of 5 to 9.5. US Pat. No. 4,435,307 (Barbesgoard et al., Mar. 6, 1984) discloses suitable fungi from Humicola insolens or Humicola strain DSM1800 or Cellulase 212-producing fungi belonging to the genus Aeromonas. Sex cellulase and cellulase isolated from the liver pancreas of marine molluscs, Dolabella Auricula Solander, are described. Suitable cellulase are also described in GB-A-2,075,028; GB-A-2,095,275; And DE-OS-2,247,832. CAREZYME ^™ and CELLUZYME ^™ (Novo) are particularly useful [see WO 9117243 (Novo)].

Lipase enzymes suitable for detergent use are those produced by microorganisms of the Pseudomonas group, such as Pseudomonas sturzyri ATCC 19,154, as described in GB 1,372,034. See also the lipases of Japanese Patent Laid-Open No. 53,20478, published February 24, 1978. Such lipases are marketed by Amano Pharmaceutical Co., Ltd. (Nagoya, J. Memu) under the trade names Lipase P “Amano” or “Amino-P”. Other suitable commercial lipases include Chromobacter Biskosum, for example Amano-CES (Toyo Jozo Co., Tagata, Japan), which is a lipase from Chromobacter Biskosium mutant Ripolinicum NRRLB 3673; Chromobacter biskosium lipase (US Biochemical Corp., USA and Disoynth Co., The Netherlands); And lipases from Pseudomonas gladiolus. LIPOLASE ^™ enzymes derived from Humicola ranuginosa and commercially available from Novo (see EP 341,947) are preferred lipases for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 (Novo) (see also WO 9205249 and RD 94359044).

Despite the considerable number of publications on lipase enzymes, only lipases derived from Fumi-cola ranuginosa and produced in Aspergillus Orizae as a host have been used extensively as additives to textile laundry products. To optimize the stain removal performance of repolarase, it is available under the trade name Repolarase ^™ from Novo Nordisk as mentioned above. Novo Nordisk made a number of variants. As described in WO 92/05249, the D96L variant of the original Fumi-Cola ranuginosa lipase improves lard stain removal efficacy by factor 4.4 over wild-type lipase (enzyme in an amount ranging from 0.075 to 2.5 mg of protein per liter). Compared). Investigation specification 35944 published by Novo Nordisk on March 10, 1994, added the lipase variant (D96L) in an amount corresponding to 0.001 to 100 mg (5 to 500,000 LU / liter) lipase variant per liter of wash liquor. It can be described. The present invention relates to fabrics using low levels of D96L variants in detergent compositions containing AQA surfactants in the manner described herein, especially when D96L is used at levels ranging from about 50LU to about 8500LU per liter of wash solution. It provides an improved whiteness maintenance advantage.

Cutinase enzymes suitable for use herein are described in WO 8809367 A (Genencor).

In order to “bleach the solution” or to prevent the transfer of dyes or pigments removed from the substrate during washing to other substrates present in the laundry solution, the peroxidase enzyme is provided with an oxygen source such as percarbonate, perborate hydrogen peroxide. It can be used in combination with. Known peroxidases include haloperoxidases such as horseradish peroxidase, ligninase, and chloro- or bromo-peroxidase. Peroxidase containing detergent compositions are described in WO 89099813 A (October 19, 1989 Novo) and WO 8909813 A (Novo).

The range of enzymatic materials and methods for incorporating them into synthetic detergent compositions are also described in WO 9307263 A and WO 930777260 (Genencor Internationa), WO 8908694 A (Novo) and US Pat. No. 3,553,139 (January 5, 1971, McCarty et al) It is described in Enzymes are further described in US Pat. No. 4,101,457 (Place et al, July 18, 1978) and US Pat. No. 4,507,219 (Hughes, March 26, 1985). Enzyme materials useful in liquid detergent compositions and mixing them into such formulations are described in US Pat. No. 4,261,868 (Hora et al, April 14, 1981). Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are illustrated in US Pat. Nos. 3,600,319 (August 17, 1971, Gedge et al), EP 199,405 and EP 200,586 (October 29, 1986, Venegas). Enzyme stabilizing enzymes are also described, for example, in US Pat. No. 3,519,570. Bacillus sp. AC13 useful for providing proteases, xylanases and cellulases is described in WO 9401532 A (Novo).

Enzyme Stabilization System—An enzyme containing composition herein may optionally comprise about 0.001 to about 10 weight percent, preferably about 0.005 to about 8 weight percent, most preferably about 0.01 to about 6 weight percent enzyme stabilization system. Such enzyme stabilization system can be any stabilization system that is compatible with the cleaning enzyme. Such a system may be inherently provided by other formulation actives or may be added separately by the formulator or the enzyme manufacturer for detergent injection. Such stabilizing enzymes may include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

One stabilization approach is the use of an aqueous source of such ions in the processed composition, which provides calcium and / or magnesium ions to the enzyme. Calcium ions are generally more effective than magnesium ions and calcium ions are more preferred when only one type of cation is used. Typical detergent compositions, particularly liquid compositions, will include from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ions per liter of processed detergent composition, It may vary depending on factors including the multiplicity, type and level of enzyme. Preferably, water-soluble calcium or magnesium salts are used, including calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, more generally calcium sulfate corresponding to the calcium salts exemplified as such. Or magnesium salts may be used. Further increased levels of calcium and / or magnesium may be useful, for example, to enhance the fatal cleavage of certain types of surfactants.

Another stabilization approach is to use a borate type (see US Pat. No. 4,537,706 (Serverson)). If a borate stabilizer is used it may be at or below 10% of the composition, but more typically at or below about 3% by weight of boric acid or other borate compounds (eg borax or orthoborate) is used for liquid detergents. Suitable. Substituted boric acid, such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid, etc. can be used in place of boric acid and through the use of boron derivatives such that reduced levels of total boron in the detergent composition are thus substituted. It may be possible.

Stabilizing enzymes in certain cleaning compositions, such as compositions for automatic dishwashing, have a chlorine bleach scavenger 0 to about 10 added to prevent chlorine bleach, which is present in many tap waters, especially under alkaline conditions, from attacking and inactivating the enzyme. Weight percent, preferably from about 0.01 to about 6 weight percent. Although chlorine levels in water can typically be as low as about 0.5 to about 1.75 ppm, chlorine is used because the available chlorine in the total volume of water that comes into contact with enzymes, for example, during dish washing or fabric washing can be relatively large. Enzyme stability in cases can often cause problems. The use of additional stabilizers for chlorine is most generally not necessary, since perborate or percarbonate that is reactive with chlorine bleach may be present in certain compositions of the invention in amounts contemplated separately from the stabilization system. Using these, improved results can be obtained. Suitable chlorine scavenger anions are broadly known and readily available and may be salts containing ammonium cations with sulfites, bisulfites, thiosulfites, thiosulfates, iodides and the like. Antioxidants such as carbamate and ascorbate; Organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof; Monoethanolamine (MEA), and mixtures thereof can also be used. Likewise, special enzyme inhibitor systems can be inserted so that different enzymes have maximum compatibility. If desired, bisulfates, nitrates, chlorides, sources of hydrogen peroxide (eg sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate), and phosphates, condensed phosphates, acetates, benzoates, citrate, fort Other conventional scavengers can be used, such as mate, lactate, maleate, tartrate, salicylate, and mixtures thereof. In general, since chlorine scavenger function can be performed by components (e.g., hydrogen peroxide sources) listed separately in the list of better recognized functions, compounds which perform this function to the desired extent are enzyme-containing embodiments of the present invention. If not present, it is not necessary to add a separate chlorine scavenger, where the scavenger is added only for optimal results. Moreover, formulators will utilize the chemist's conventional techniques in avoiding the use of any enzyme scavenger or stabilizer that is mostly incompatible when formulated with other reactive ingredients. With regard to the use of ammonium salts, these salts may simply be mixed with the detergent composition, but this is likely to absorb water during storage and release the ammonium. Thus, when such materials are present, it is desirable to protect the particles as described in US Pat. No. 4,652,392 (Baginski et al).

Polymeric Antifouling Agents-Known polymeric antifouling agents (described below as "SRA" or "SRA's") can optionally be used in the detergent compositions of the present invention. When used, SRA's will generally be included in amounts of 0.01 to 10.0%, typically 0.1 to 5%, preferably 0.2 to 3.0% by weight based on the weight of the composition.

Preferred SRA's typically have hydrophobic fibers (e.g., polyester and nylon) and hydrophilic segments for hydrophilizing the surface of the hydrophobic segments, depositing them on the hydrophobic fibers and attaching them until the wash and clean cycle is complete. It remains as it acts as an anchor for the hydrophilic segment. As a result, stains generated following treatment with the SRA can be more easily cleaned in later laundering processes.

SRA's may include various charged, for example anionic or even cationic (see US Pat. No. 4,956,447) and uncharged monomeric units and structures (which may be straight, branched or even star shaped). Can be. These may include capping moieties that are particularly effective for controlling molecular weight or modifying physical or surface active properties. The structure and charge distribution can be tailored to the application for different fiber or textile types and to the needs for various detergents or detergent addition products.

Preferred SRA's are oligomeric terephthalate esters prepared by processes that typically involve one or more ester transfer reactions / oligomerizations using metal catalysts such as titanium (IV) alkoxides. Such esters can be made using additional monomers that can be inserted into the ester structure through one, two, three, four or more positions without the process of forming a densely crosslinked whole structure.

Suitable SRA's include the following: oligomeric ester backbones of terephthaloyl and oxyalkyleneoxy repeat units and substantially straight chain ester oligomers consisting of allyl-derived sulfonated terminal residues covalently attached to these backbones. Sulfonated products, such as those described in US Pat. No. 4,968,451 (June 6, 1990; JJ Scheibel and EP Gosselink); Such ester oligomers include (a) ethoxylating allyl alcohol, (b) the product of step (a) in a two-step ester transfer reaction / oligomerization process, with dimethyl terephthalate ("DMT") and 1,2-propylene Reacting with glycol (“PG”) and (c) reacting the product of step (b) with sodium metabisulfite in water; Nonionic end capped 1,2-propylene / polyoxyethylene terephthalate polyesters of US Pat. No. 4,711,730 (Dec. 8, 1987; Gosselink et al), such as poly (ethyleneglycol) methyl ester, DMT Prepared by ester transfer reaction / oligomerization of PG and poly (ethyleneglycol) (“PEG”); Partially-and fully anionic end capped oligomeric esters of U.S. Patent No. 4,721,189 (January 26, 1988; Gosselink), for example ethylene glycol ("EG"), PG, DMT and Na-3, Oligomers from 6-dioxa-8-hydroxyoctanesulfonate; For example, nonionic capped block polyester oligomeric compounds of US Pat. No. 4,702,857 (Gosselink), generated from DMT, Me-capped PEG and EG and / or PG, or DMT Combinations of EG and / or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; And anionic, especially sulfoaroyl end capped terephthalate esters of US Pat. No. 4,877,896 (October 31, 1989; Maldonado, Gosselink et al). For example, an ester composition made of m-sulfobenzoic acid monosodium salt, PG and DMT and optionally (but preferably) added PEG, eg PEG 3400, can be used to wash and fabricate the latter compound. It is typical of SRA's useful for both conditioning products.

SRA's also include simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate (see US Pat. No. 3,959,230 (Hays, May 26, 1976) and US Pat. No. 3,893,929). (Basadur, July 7, 1975)]; Cellulosic derivatives such as hydroxyether cellulosic polymers commercially available as METHOCEL (Dow); And C ₁ -C ₄ alkylcelluloses and C ₄ hydroxyalkyl celluloses (see US Pat. No. 4,000,093 (Dec. 28, 1976; Nicol, et al)). Suitable SRA's characterized by poly (vinyl ester) hydrophobic segments include poly (vinyl esters) grafted onto polyalkylene oxide backbones, for example C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate) Graft copolymers are described in European Patent Publication No. 0 219 048 (Kud et al), published April 22, 1987). Examples of commercially available products are SOKALAN SRA's, for example SOKALAN HP-22 (BASF, Germany). Other SRA's are polyesters with repeating units containing from 10 to 15 weight percent ethylene terephthalate 90 to 80 weight percent polyoxyethylene terephthalate, derived from polyoxyethylene glycols having an average molecular weight of 300 to 5,000. Commercially available products include ZELCON 5126 (Dupont) and MILEASET (ICI).

Another preferred SRA comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG) units; One sulfoisophthaloyl unit, five terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably from about 0.5: 1 to about 10: 1 and sodium 2 As in oligomers comprising two end caps derived from-(2-hydroxyethoxy) ethanesulfonate, the formula preferably terminates with an end-cap (CAP), preferably a modified isothionate ( CAP) ₂ (EG / PG) ₅ (T) ₅ (SIP) ₁ oligomer. Such SRAs are preferably selected from crystallinity-reducing stabilizers, such as linear nitrile dodecylbenzenesulfonate or xylene-, cumene- and toluene-sulfonate or mixtures thereof, based on the weight of the oligomer. It further comprises 0.5 to 20% by weight of anionic surfactant such as one circle, and these stabilizers or modifiers are all taught in US Pat. No. 5,415,807 (Gosselink, Pan, Kellett and Hall; May 16, 1995). As introduced into the synthesis port. Suitable monomers for the SRA include Na-2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl 5-sulfoisophthalate, EG and PG.

Another group of preferred SRA's is (1) (a) dihydroxysulfonates, polyhydroxysulfonates, trifunctional or higher trifunctional units, and combinations thereof, which form side chain oligomer backbones by forming ester linkages. One or more units selected from the group consisting of: (b) one or more units that are terephthaloyl residues; And (c) at least one unsulfonated unit that is a 1,2-oxyalkyleneoxy moiety; (2) nonionic capping units, anionic capping units such as alkoxylation, preferably ethoxylated isethionates, alkoxylated propanesulfonates, alkoxylated dipropanesulfonates, alkoxylated phenolsulfonates, sulfoaroses Oligomeric esters comprising at least one capping unit selected from one derivative and mixtures thereof. Preferred esters are esters of the formula {(CAP) _x (EG / PG) _{y '} (DEG) _{y "} (PEG) _y"' (T) _z (SIP) _{z '} (SEG) _q (B) _m } CAP, EG / PG, PEG, T and SIP are as defined above and (DEG) represents di (oxyethylene) oxy unit; (SEG) represents units derived from sulfoethyl ethers of glycerine and related residue units, (B) represents trifunctional or higher than trifunctional side chain units that form side chain oligomer backbones by forming ester bonds, and x is about 1 To about 12, y 'is about 0.5 to about 25, y "is 0 to about 12, y'" is 0 to about 10, and the sum of y '+ y "+ y'" is about 0.5 to 25; z is from about 1.5 to about 25, z 'is from 0 to about 12, z + z' sum is from about 1.5 to about 25, q is from about 0.05 to about 12, m is from about 0.01 to about 10, x , y ', y ", y'", z, z ', q and m represent the average moles of the corresponding unit per mole of said ester and the molecular weight of said ester ranges from about 500 to about 5,000.

Preferred SEG and CAP monomers for such esters include Na-2- (2,3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2- {2- (2-hydroxyethoxy). Methoxy} ethanesulfonate ("SE3") and its homologues and mixtures, and the product of ethoxylated and sulfonated allyl alcohol. Preferred SRAs in this class include sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or sodium 2- [2- {2- (2- using a suitable Ti (IV) catalyst. Ester transfer and oligomerization of hydroxyethoxy) ethoxy} ethoxy] ethanesulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG and PG (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13 ( wherein, CAP is _{^{(Na + O 3 S [CH}} 2 CH 2 O] 3.5) - and B is a unit from glycerin EG / PG ratio is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis).

Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures (see US Pat. No. 4,201,824 to Violland et al. And US Pat. 4,240,918 to Lagasse et al; (II) SRA's having carboxylate terminal groups prepared by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. When a suitable catalyst is selected, trimellitic anhydride forms a bond to the end of the polymer through the ester of the separated carboxylic acid of trimellitic anhydride rather than exposing the trimellitic anhydride bond. Nonionic or anionic SRA's can be used as starting materials as long as they have hydroxyl end groups that can be esterified (US Pat. No. 4,525,524 (Tung et al)); (III) anionic terephthalate-based SRA's of urethane linked analogs (US Pat. No. 4,201,824 to Violland et al); (IV) poly (vinyl caprolactam), including both nonionic and cationic polymers, and related copolymers having monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate [see US Patent No. 4,579,681 to Ruppert et al; (G) Graft copolymers other than SOKALAN type (BASF) prepared by grafting acrylic monomers onto sulfonated polyesters; These SRA's have antifouling activity and anti-sedimentation activity similar to known cellulose esters (EP 279,134 A, 1988, Rhone-Poulinc Chemie); (VI) a substance in which vinyl monomers such as acrylic acid and vinyl acetate are grafted onto proteins such as casein (EP 457,205 A (BASF, 1991)); (Iii) Polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam and polyethylene glycol, in particular for treating polyamide fabrics (DE 2,335,044 (Bevan et al; Unilever N.V., 1974)). Other useful SRA's are described in US Pat. Nos. 4,240,918, 4,787,989, 4,525,524, and 4,877,896.

Bleach Compositions-Bleach and Bleach Activators-The detergent compositions of the present invention may optionally contain a bleach composition containing a bleach or bleach and one or more bleach activators. If present, the bleach will in particular be at a level of about 1 to about 30%, more typically about 5 to about 20%, based on the total amount of the detergent composition for fabric laundry. If present, the bleach activator will typically be at a level of about 0.1 to about 60%, more typically about 0.5 to about 40%, based on the total amount of the bleach composition comprising the bleach + bleach activator.

As used herein, the bleach may be any bleach useful in detergent compositions for textile cleaning, hard surface cleaning, or other cleaning uses known or known. These include oxygen bleach and other bleaches. Perborate bleaches such as sodium perborate (eg mono- or tetra-hydrate) can be used herein.

Another category of bleaches that can be used without limitation includes percarboxylic acid bleaches and salts thereof. Suitable examples of this class of preparations are magnesium monoperoxyphthalate hexahydrate, which is a magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxopoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are described in US Pat. No. 4,483,781 (Hartman, Nov. 20, 1984), US Pat. No. 740,446 (Bums et al, June 3, 1985), and European Patent Publication No. 0,133,354 (Banks et al. 2 February 1985) and US Patent 4,412,394 (Chung et al; 1 November 1983). Highly preferred bleaches are also 6-nonylamino-6-oxperoxycaproic acid as described in US Pat. No. 4,634,551 (January 6, 1987; Bums et al).

Peroxy bleach can also be used. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (such as OXONE manufactured by DuPont) can also be used.

Preferred percarbonate bleaches include anhydrous particles having an average particle size in the range of about 500 to about 1,000 microns, wherein up to about 10 weight percent of such particles are less than about 200 microns and up to about 10 weight percent of such particles are about 1,250 microns. Greater than Optionally, such percarbonates can be coated with silicates, borates or water soluble surfactants. Percarbonates are available from various manufacturers, such as FMC, Solvay and Tokai Denka.

Mixtures of bleaches can also be used.

Peroxy bleach, perborate, percarbonate and the like are preferably combined with a bleach activator which causes in situ production in an aqueous solution of the peroxy acid corresponding to the bleach activator (ie during the washing process). Various non-limiting examples of activators are described in US Pat. No. 4,915,854 (April 10, 1990; Mao et al) and US Pat. No. 4,412,934. Nonanoyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and mixtures thereof may be used. See US Pat. No. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido induced bleach activators

R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N ( ⁵ R) R ² C (O) L, wherein R ¹ is from about 6 to about 12 carbon atoms Is an alkyl group, R ² is alkylene having 1 to about 6 carbon atoms, R ⁵ is H, or alkyl, aryl or alkaryl having about 1 to about 10 carbon atoms, and L is any suitable leaving group. Leaving groups are all groups that are substituted from the bleach activator as a result of nucleophilic attack on the bleach activator by the perhydrolysis action. Preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formula are (6-octane amido-caproyl) oxybenzenesulfonate, (6-nonanami), as described in US Pat. No. 4,634,551, which is incorporated herein by reference. Do-caproyl) oxybenzenesulfonate, (6-decaneamido-caproyl) oxybenzenesulfonate, and mixtures thereof.

Another class of bleach activators includes benzoxazine type activators described in US Pat. No. 4,966,723 (Hodge et al; October 30, 1990), incorporated herein by reference. Highly preferred activators of the benzoxazine type are:

Another class of preferred bleach activators include acyl lactam activators, in particular Acyl caprolactam and acyl valerolactam of wherein R ⁶ is H, or an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to about 12 carbon atoms. Highly preferred lactam activators 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 [ Reference: US Pat. No. 4,545,784 (October 8, 1985; Sanderson), incorporated herein by reference, which describes acyl caprolactam, including benzoyl caprolactam adsorbed into sodium perborate.

Bleaches other than oxygen bleaches are known in the art and may be used herein. One type of non-oxygen bleach that is of particular interest is photoactivated bleach such as sulfonated zinc and / or aluminum phthalocyanine (US Pat. No. 4,033,718 (July 5, 1977; Holcombe et al)). If used, the detergent composition will contain from about 0.025 to about 1.25 weight percent of such bleach, particularly sulfonate zinc phthalocyanine.

If desired, the bleaching compound can be catalyzed using a manganese compound. Such compounds are known in the art and examples thereof include US Pat. Nos. 5,246,621, 5,244,594, 5,194,416, 5,114,606 and EP 549,271A1, 549,272A1, 544,440A2 and 5 Manganese-based catalysts described in 544,490A1; Preferred examples of these catalysts are Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u- OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal-based bleach catalysts are those described in US Pat. Nos. 4,430,243 and 5,114,611. The use of ligands with various complex ligands to enhance bleaching activity is described in US Pat. Nos. 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161, and 5,227,084. Reported.

As a practical but non-limiting example, the compositions and methods can be adjusted to provide in order of at least 1 ppm of the active bleach catalyst material in the aqueous wash liquor, preferably from about 0.1 to about 700 ppm of catalyst material in the wash liquor, more preferably about Will provide from 1 to about 500 ppm.

Cobalt bleach catalysts useful herein are known and are described, for example, in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Meth., (1983), 2, pages 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaamine acetate salts of the formula [Co (NH ₃ ) ₅ OAc] T _y , where "OAc" represents an acetate moiety and "T _y " represents an anion), in particular of formula [ Cobalt pentaamine acetate chloride of Co (NH ₃ ) ₅ OAc] Cl ₂ ; As well as [Co (NH ₃ ) ₅ OAc] (OAc) ₂ , [Co (NH ₃ ) ₅ OAc] (PF ₆ ) ₂ , [Co (NH ₃ ) ₅ OAc] (SO ₄ ), [Co (NH ₃ ) ₅ OAc] (BF ₄ ) ₂ , and [Co (NH ₃ ) ₅ OAc] (NO ₃ ) ₂ (“PAC” herein).

These cobalt catalysts are known processes, for example, in the Tobe literature and in the literature cited therein. US Pat. No. 4,810,410 to Diakun et al. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

As a practical but non-limiting example, the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide at least 1 ppm of the active bleach catalyst material in the aqueous wash medium, preferably from about 0.01 to about bleach catalyst material in such wash liquid. About 25 ppm, more preferably about 0.05 to about 10 ppm, most preferably about 0.1 to about 5 ppm. In order to achieve this level in the wash liquor of the automatic washing process, the typical automatic dishwashing compositions herein are based on the weight of such cleaning compositions, from about 0.0005 to about 0.2% by weight of bleach catalysts, especially manganese or cobalt catalysts, more preferably. Preferably from about 0.004 to about 0.08 weight percent.

Mud Removal / Redeposition Inhibitors—The compositions of the present invention may optionally contain water-soluble ethoxylated amines having mud removal and anti-deposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01 to about 10.0 weight percent of water soluble ethoxylate amines and liquid compositions typically contain from about 0.01 to about 5 weight percent.

Most preferred mud removal and redeposition inhibitors are ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in US Pat. No. 4,597,898 (VanderMeer, July 1, 1986). Another group of preferred mud removal and re-deposition inhibitors is the cationic compounds described in European Patent Publication No. 111,965 (Oh and Gosselink) published June 27, 1984. Other mud removal / resemination inhibitors that may be used include ethoxylated amine polymers described in European Patent Publication No. 111,984 (Gosselink) published June 27, 1984; Zwitterionic polymers described in European Patent Publication No. 112,592 (Gosselink) published July 4, 1984; And amine oxides described in US Pat. No. 4,548,744 (Connor; October 22, 1985). Other mud removal and / or re-deposition inhibitors known in the art may also be used in the compositions herein. See, for example, US Pat. No. 4,891,160 (VanderMeer, Jan. 2, 1990) and WO 95/32272 (Nov. 1995). 30.)]. Another type of preferred antideposition agent is a carboxy methyl cellulose (CMC) material. These materials are well known in the art.

Polymeric Dispersants—The polymeric dispersants may be advantageously used at levels of about 0.1 to about 7 weight percent in the compositions herein, particularly in the presence of zeolites and / or laminated silicate builders. Examples of suitable dispersants include polymeric polycarboxylates and polyethylene glycols, although other agents known in the art may also be used. While not wishing to be bound by theory, polymeric dispersants, when used in combination with other builders (including low molecular weight polycarboxylates), improve overall detergent builder performance due to crystal growth inhibition, particulate dirt release, and anti-deposition properties. It is believed to enhance.

Polymeric polycarboxylate materials may be prepared by polymerizing or copolymerizing preferably unsaturated monomers in 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, aconic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments that do not contain carboxylate radicals in the polymeric polycarboxylates herein, such as vinylmethyl ether, styrene, ethylene, etc., is suitable to ensure that these segments do not constitute at least about 40% by weight. Do.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers useful herein are water soluble salts of polymerized acrylic acid. The average molecular weight of the polymer in this acid form is preferably in the range of about 2,000 to 10,000, more preferably about 4,000 to 7,000, most preferably about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers are, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of this type of polyacrylate in detergent compositions is described, for example, in US Pat. No. 3,308,067 (Diehl; March 7, 1967).

Acrylic acid / maleic acid copolymers may also be used as preferred components of the dispersion / redeposition inhibitor. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid form copolymers is preferably in the range of about 2,000 to 10,000, more preferably about 5,000 to 7,500, most preferably about 7,000 to 65,000. The ratio of acrylate to maleate segments in the copolymer will generally range from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers are, for example, alkali metals, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are disclosed in European Patent Publication No. 66915 published December 15, 1982 and European Patent Publication No. 193,360 published September 3, 1986 (also referred to as Hyde). Polymers comprising oxypropylacrylate are described). Other useful dispersants include maleic acid / acrylic acid / vinyl alcohol trimer. Such materials, including 45/45/10 trimers of acrylic acid / maleic acid / vinyl alcohol, are also described in EP 193,360.

Another polymeric material that may be mentioned is polyethylene glycol (PEG). PEG not only exhibits dispersant performance but can also act as a mud removal-redeposition inhibitor. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartates and polyglutamate can also be used, in particular with zeolite builders. Dispersants such as polar aspartate have an average molecular weight of about 10,000.

Brighteners-Any optical brightener or other brightening or whitening agent known in the art may be inserted into the detergent compositions herein typically at a level of about 0.01 to about 1.2 weight percent. Commercially available optical brighteners that may be useful in the present invention include stilbene, pyrazoline, coumarin, carboxylic acid, methacyanine, dibenzothiophene-5,5-dioxide, azole, 5- and 6-membered ring heterocycles, and Subgroups, including but not limited to derivatives of other micelle preparations. Examples of such brightening agents are described in "The Production and Application of Fluorescent Brightening Agents", M. Zabradnik, Published by John Wiley & Sons, New Yo (1982).

Specific examples of optical brighteners useful in the present invention are identified in US Pat. No. 4,790,856 (Wixon, Dec. 13, 1988). These varnishes include the PHORWHITE family of varnishes (Verona). Other brighteners described in this document include Tinopal UNPA, Tinopal CBS and Tinopal 5BM (available from Ciba-Geigy); Artic White CC and Artic White CWD, ie 2- (4-styryl-phenyl) -2H-naphtho [1.2-d] triazole; 4,4'-bis- (1,2,3-triazol-2-yl) -stilbene; 4,4'-bis (styryl) bisphenyl; And amino-coumarin. Specific examples of these brighteners include 4-methyl-7-diethyl amino coumarin; 1,2-bis (benzimidazol-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-naphtho [1,2-d] triazole (US Pat. No. 3,646,015 (February 29, 1972; Hamilton).

Dye Transfer Inhibitors—Compositions of the present invention may also include one or more materials effective to inhibit the dye from transferring from one fabric to another during the cleaning process. Generally, such dye transfer inhibitors include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures thereof. have. When used, these formulations typically comprise in an amount of about 0.01 to about 10 weight percent, preferably about 0.01 to about 5 weight percent, more preferably about 0.05 to about 2 weight percent, based on the weight of the composition. do.

More specifically, preferred polyamine N-oxide polymers for use herein include units of the formula RA _x -P, wherein P may form part of the unit to which the NO group may be attached or to which the NO group may be polymerized. Or a NO group is a polymerizable unit to which both units can be attached, A is one of -NC (O)-, -C (O) O-, -S-, -O-, -N =; Is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or acyclic group, or any combination thereof in which the nitrogen of the NO group may be attached or the NO group is part of these groups) . Preferred polyamine N-oxides are compounds wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

NO group is a chemical formula Wherein R ₁ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or acyclic groups or combinations thereof, x, y and z are 0 or 1 and the nitrogen of the NO group is It may be attached to or form part of the mentioned group. The amine oxide units of the polyamine N-oxides have pKa <10, preferably pKa <7, most preferably pKa <6.

Any polymer backbone may be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibitory properties. Examples of suitable polymeric backbones are polyvinyl, polyalkylene, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one monomer type is amine N-oxide and the other monomer type is N-oxide. Amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in such polyamine oxide polymers may vary by appropriate degree of copolymerization or appropriate N-oxidation. Such polyamine oxides can be obtained with almost any polymerization. Typically, the average molecular weight is in the range of 500 to 1,000,000, more preferably 1,000 to 500,000, most preferably 5,000 to 100,000. This preferred class of materials may be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent composition of the present invention is poly (4-vinylpyridine-N-oxide) with an average molecular weight of about 50,000 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, PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, more preferably 5,000 to 200,000, most preferably 10,000 to 20,000. Average molecular weights are described in Barth, et al., Chemical Analysis, Vol. 113, "Modern Methods of Polymer Characterization"; The specification of which is incorporated herein by reference], as measured by light scattering. PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone between 1: 1 and 0.2: 1, more preferably between 0.8: 1 and 0.3: 1 and most preferably between 0.6: 1 and 0.4: 1. These copolymers may be straight or branched.

The compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000. PVP is known to those skilled in the detergent field (see EP-A 262,897 and EP-A 256,696, incorporated herein by reference). Compositions containing PVP may also contain polyethylene glycol (“PEG”) having an average molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000. Preferably, the ratio (in ppm) of PEG to PVP delivered in the wash solution is about 2: 1 to about 50: 1, more preferably about 3: 1 to about 10: 1.

Detergent compositions of the present invention may also optionally contain about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners that provide dye transfer inhibitory activity. When used, the compositions of the present invention will preferably comprise about 0.01 to 1% by weight of such optical brighteners.

Hydrophilic optical brighteners useful in the present invention

Having a brightener, wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, and R ₂ is N-2-bis-hydroxyethyl, N-2-hydroxy Hydroxyethyl-N-methylamino, morpholino, chloro and amino, and M is a salt forming cation such as sodium or potassium.

In the formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anilino-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid and disodium salt. This particular brightener is sold under the trade name Tinopal-UNPA-GX (Ciba-Geigy Corporation). Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent composition of the present invention.

In the formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anilino -6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenesulfonic acid and disodium salt. This particular brightener is commercially available under the trade name Tinopal-5BM-GX (Ciba-Geigy Corporation).

In the formula, when R ₁ is anilino, R ₂ is morpholino, and M is a cation such as sodium, the brightening agent is 4,4'-bis [(4-anilino-6-morpholino-s-triazine -2-yl) amino] -2,2'-stilbenesulfonic acid, sodium salt. This particular brightener is commercially available under the trade name Tibapal-AMS-GX (Ciba-Geigy Corporation).

Certain optical brighteners selected for use in the present invention provide particularly effective dye journaler inhibitory performance when used in combination with a polymeric dye transfer inhibitor selected as described above. Combinations of these selected polymeric materials (e.g. PVNO and / or PVPVI) with selected optical brighteners (e.g. Tinopal-UNPA-GX, Tinopal-5BM-GX and / or Tinopal-AMS-GX) can be combined with these two in aqueous wash solution. When used alone, the detergent composition provides significantly better dye transfer inhibition. Without being limited to a particular theory, the polish is operated in this manner, which is deposited relatively quickly on these fabrics because of the high affinity for the fabric in the wash solution. The degree to which the brightener is deposited on the fabric in the cleaning solution can be defined by a parameter called "consumption factor". The consumption factor is generally the ratio of a) gloss material deposited on the fabric to b) the initial gloss concentration in the wash liquor. Brighteners with relatively high consumption coefficients are best suited to inhibit dye transfer in the context of the present invention.

Of course, one of ordinary skill in the art will recognize that other conventional optical brightener types of compounds may optionally be used in the present compositions to provide conventional fabric “gloss” benefits rather than true dye transfer inhibitory effects.

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, multifunctionally substituted aromatic chelating agents and mixtures thereof, all of which are described below herein. Without being limited to a particular theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the wash solution by forming soluble chelates.

Amino carboxylates useful as any chelating agent include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate And ethanol diglycine, alkali metals, ammonium and substituted ammonium salts and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of phosphorus total content is acceptable in detergent compositions, examples of which are ethylenediaminetetrakis (methylenephosphonates) as DEQUEST There is this. Preference is given to those amino phosphonates which do not contain alkyl or alkenyl groups of at least about 6 carbon atoms.

Multifunctionally substituted aromatic chelating agents are also useful in the compositions herein. US Pat. No. 3,812,044 (May 21, 1974; Connor et al). Preferred compounds of this acid type are 1,2-dihydrate. Dihydroxydisulfobenzenes such as oxy-3,5-disulfobenzene.

Preferred biodegradable chelators for use herein are ethylenediamine disuccinates (“EDDS”), in particular the [S, S] isomers as described in US Pat. No. 4,704,233 (Nov. 3, Hartman and Perkins). .

The compositions herein may also contain a water soluble methyl glycine diacetic acid (MGDA) salt (or acid form) as a chelator or co-builder useful with, for example, insoluble builders such as zeolites, laminated silicates, and the like.

When used, these chelating agents will generally contain from about 0.1 to about 15 weight percent of the detergent composition herein by weight. More preferably, such chelating agents, when used, will contain from about 0.1 to about 3.0 weight percent of the composition by weight.

Soap Bubble Inhibitors—Compounds for reducing or inhibiting soap bubble formation can be incorporated into the compositions of the present invention. Soap foam inhibitors may be particularly important in the so-called "highly concentrated cleaning processes" and front-loaded European washing machines as described in US Pat. Nos. 4,489,455 and 4,489,574.

A wide range of materials can be used as soap depressants and soap depressants are well known to those skilled in the art. See Kirt Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of soap foam inhibitors of particular interest encompasses monocarboxylic acid fatty acids and mixtures thereof (see, eg, US Pat. No. 2,954,347, Sep. 27, 1960; Wayne St. John). Monocarboxylic fatty acids and salts thereof used as soap foam inhibitors typically have a hydrocarbyl chain of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.

The detergent composition of the present invention may also contain a soap foam inhibitor that is a non-surfactant. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C ₁₈ -C ₂₀ ketones (e.g. stearones) and the like. have. Other soap foam inhibitors include di- to tetra-alkyldiamine chlorotriles formed as products of N-alkylated amino triazines, such as cyanuric chloride and 2 or 3 moles of primary or secondary amines having 1 to 24 carbon atoms. Monostearyl phosphates such as azine or tri-tetra-alkylmelamine, propylene oxide, and monostearyl alcohol phosphate esters and monostearyl di-alkali metals such as K, Na and Li phosphate and phosphate esters. Hydrocarbons such as paraffin and haloparaffin may be used in liquid form. The liquid hydrocarbon will be liquid at room temperature and atmospheric pressure and will have a pour point of about −40 ° C. to about 50 ° C. and a maximum boiling point (atmospheric pressure) of at least about 110 ° C. It is known to use waxy hydrocarbons which preferably have a melting point of about 100 ° C. or less. Such hydrocarbons constitute a preferred category of soap foam inhibitors for detergent compositions. Hydrocarbon soap foam inhibitors are described, for example, in US Pat. No. 4,265,779 (May 5, 1981; Gandolfo et al.). Thus, such hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of soap foam inhibitor herein is considered to include a mixture of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant soap foam inhibitors include silicone soap foam inhibitors. These categories include polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica particles, wherein the polyorganosiloxanes are chemically adsorbed or fused onto silica. Includes the use of. Silicone soap foam inhibitors are well known in the art and are described, for example, in US Pat. No. 4,265,779 (May 5, 1981; Gandolfo et al.) And EP 89307851.9 (Feb. 7, 1990). ; Starch, MS).

Other silicone soap foam inhibitors are described in US Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids.

Mixtures of silicon and silanized silica are described, for example, in DOS 2,124,526. Silicone antifoams and soap foam inhibitors in granular detergent compositions are described in US Pat. No. 3,933,672 (Bartolotta et al) and US Pat. No. 4,652,392 (Baginski et al; March 24, 1987).

Examples of silicone-based soap bubble inhibitors for use herein are essentially:

(Iii) a polydimethylsiloxane fluid having a viscosity at 25 ° C. of about 20 to about 1,500 cs;

(Ⅱ) (ⅰ) per 100 parts by weight of (CH _{3) 3} SiO _1/2 units to SiO ₂ units in ratio of about 0.6: 1 to about 1.2: 1, (CH _{3) 3} SiO _1/2 units and SiO ₂ About 5 to about 50 parts of a silonic acid resin composed of units; And

(Iv) (v) A soap foam inhibitor with a soap foam inhibiting amount consisting of about 1 to about 20 parts of a solid silica gel per 100 parts by weight.

In preferred silicone soap foam inhibitors herein, the continuous solvent consists of a specific polyethylene glycol or polyethylene-polypropylene glycol copolymer or mixture thereof (preferably), or polypropylene glycol. The primary silicone soap foam inhibitor is branched / crosslinked and preferably not straight chain.

To further illustrate this point, typical soap lather suppressed liquid laundry detergent compositions include (1) (a) polyorganosiloxanes, (b) dendritic siloxanes or silicone resin producing silicone compounds, and (c) finely divided filler materials. And (d) a non-aqueous emulsion of primary antifoam agent which is a mixture of catalysts to enhance the reaction of the mixtures of components (a), (b) and (c) to form silanolates; (2) one or more nonionic silicone surfactants; And (3) copolymers of polyethylene glycol or polyethylene-polypropylene glycol having a solubility in water of at least about 2% by weight at room temperature; And about 0.001 to about 1 weight percent, preferably about 0.01 to about 0.7, and most preferably about 0.05 to about 0.5 weight percent of a silicone soap foam inhibitor comprising no polypropylene glycol. Similar amounts can be used for granular compositions and the like. See, for example, US Pat. Nos. 4,978,471 (Starch; Dec. 19, 1990) and 4,983,316 (Starch; Jan. 8, 1991), 5,288,431 (Huber et al. February 22, 1994) and US Pat. Nos. 4,639,489 and 4,749,740 (Aizawa et al, column 1, column 46 to line 4, line 35).

The silicone soap foam inhibitor herein preferably comprises a copolymer of polyethylene glycol and polyethylene glycol / polypropylene glycol, all of which have an average molecular weight of less than about 1,000, preferably from about 100 to 800. Polyethylene glycol and polyethylene / polypropylene copolymers have a solubility in water at room temperature of at least about 2% by weight, preferably at least about 5% by weight.

Preferred solvents herein are copolymers of polyethylene glycol having an average molecular weight of less than about 1,000, more preferably from about 100 to 800, most preferably from 200 to 400, and polyethylene glycol / polypropylene glycol, preferably PPG 200 / PEG 200. The weight ratio of the copolymer of polyethylene glycol: polyethylene-polypropylene glycol is preferably about 1: 1 to 1:10, most preferably 1: 3 to 1: 6.

Preferred silicone soap foam inhibitors used herein do not contain polypropylene glycols having a molecular weight of 4,000 in particular. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide such as PLURONIC L101.

Other soap foam inhibitors useful herein include secondary alcohols (such as 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as silicones described in US Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. It includes. Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having C ₁ -C ₁₆ chains. Preferred alcohols are 2-butyl octanol, which is commercially available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are sold under the trade name ISALCHEM 123 (Enichem). Mixed soap foam inhibitors typically comprise a mixture of alcohol + silicone in a weight ratio of 1: 5 to 5: 1.

For all detergent compositions used in automatic washing machines, soap bubbles should not be formed to overflow the washing machine. If a soap bubble inhibitor is used it is preferably present in the "soap bubble suppression amount". The term " soap bubble inhibiting amount " means that the formulator of the composition can sufficiently control the soap bubbles to select an amount of soap foam inhibitor that produces a low- soap foam laundry detergent for use in an automatic washing machine.

The composition of the present invention will generally comprise from 0 to about 10% soap foam inhibitor. When used as a soap foam inhibitor, monocarboxylic fatty acids and salts thereof will typically be present in amounts of up to about 5% by weight of the detergent composition. Preferably, about 0.5 to about 3% of a fatty monocarboxylate soap bubble inhibitor is used. Silicone soap foam inhibitors are typically used in amounts of up to about 2.0% by weight, based on the weight of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, primarily to minimize costs and maintain efficiency for effectively controlling soap bubbles in lower amounts. Preferably from about 0.01 to about 1%, more preferably from about 0.25 to about 0.5% of silicone soap foam inhibitor is used. As used herein, these weight percent values include any silica that can be used in combination with polyorganosilonic acid, as well as all auxiliary materials available. Monostearyl phosphate soap foam inhibitors are generally used in amounts ranging from about 0.1 to about 2 weight percent based on the weight of the composition. Hydrocarbon soap foam inhibitors are typically used in amounts ranging from about 0.01% to about 5.0% by weight, although higher amounts may be used. Alcohol soap foam inhibitors are typically used in amounts of 0.2 to 3 weight percent based on the weight of the final composition.

Alkoxylated Polycarboxylates—Alkoxylated polycarboxylates such as those made from polyacrylates are useful herein to provide additional oil removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 (p.4 et seq.), Incorporated herein by reference. Chemically, these materials include polyacrylates with one ethoxy side chain per every 7 to 8 acrylate units. Such side chains represent the formula-(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are ester bonded to the polyacrylate "backbone" to provide a "comb" type polymer type structure. The molecular weight varies but typically ranges from about 2000 to about 50,000. Such alkoxylated polycarboxylates may be included from about 0.05 to about 10 weight percent based on the weight of the composition.

Fabric Softeners-Various laundry passing fabric softeners, particularly the fine smectite clays of US Pat. No. 4,062,647 (Storm and Nirschl; December 13, 1977), as well as other softener clays known in the art, typically range from about 0.5 to about 0.5 to this composition. It may optionally be used at a level of about 10% by weight to provide fabric softener benefits while simultaneously cleaning the fabric. Clay softeners are used in combination with amines and cationic softeners as described in US Pat. No. 4,375,416 (Crisp et al; Mar. 1, 1983. 3. 1983) and US Pat. No. 4,291,071 (Harris et al., Sep. 22, 1981.) Can be used.

Fragrances-Fragrances and flavoring ingredients useful in the compositions and processes of the present invention include a wide variety of natural and synthetic chemical ingredients, including but not limited to aldehydes, ketones, esters, and the like. There are also various natural extracts and essences which may include complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, mud, patchouli oil, valsham essence, sandalwood oil, pine oil, cedar and the like. . Processed perfume is the largest complex mixture of these ingredients. Processed perfume is typically included in about 0.01% to about 2% by weight of the detergent composition herein, and individual perfume ingredients may be included in about 0.0001% to about 90% of the processed perfume composition.

Some perfume formulations are described below in Example VII. Non-limiting examples of perfume components useful herein are as follows: 7-acetyl-1,2,3,4,5,6,7,8-octahydroxy-1,1,6,7-tetramethyl naphthalene ; Ionone methyl; Ionone gamma methyl; Methyl cedrylone; Methyl dihydrozasmonate; Methyl 1,6,10-trimethyl-2,5,9-cyclododecanetrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; Para-hydroxy-phenyl-butanone; Benzophenones; Methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal-4- (4-hydroxy-4-methylphenyl) -3-cyclohexane-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; Isohexenyl cyclohexyl carboxaldehyde; Formyl tricyclodecane; Condensation products of hydroxycitronella and methyl anthranilate, condensation products of hydrocitronelia and indole, and condensation products of phenyl acetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; Ethyl vanillin; Heliotropin; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde; Coumarin; Decalaton gamma; Cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; Beta-naphthol methyl ether; Ambroxane; Dodecahydro-3a, 6,6,9-tetramethylnaphthol [2,1b] furan; Cedrol, 5 (2,2,3-trimethylcyclopent-3-enyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; Cariophyllene alcohol; Tricyclodecenyl propionate; Tricyclodecenyl acetate; Benzyl salicylate; Cedryl acetate; And para- (tert-butyl) cyclohexyl acetate.

Particularly preferred perfume materials are those that provide the greatest aroma improvement to the processed product crude fish containing cellulase. These flavors include, but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tertiary butylphenyl) -propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; Benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; Para-tertiary butyl cyclohexyl acetate; Methyl dihydro jasmonate; Beta-naphthol methyl ether; Methyl beta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran; Dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2.1b] furan; Anisealdehyde; Coumarin; Cedrol; vanillin; Cyclopentadecanolide; Tricyclodecenyl acetate; And tricyclodecenyl propionate.

Other fragrance materials include, but are not limited to, essence oils, resinoids, and Peruvian valsham, olibanum resinoids, spirax, rabdanium resins, nutmeg, cassia oil, benzoin resins, corianders, and lavandines. There is resin from the source. Other perfume chemicals include phenyl ethyl alcohol, terpinol, linalol, linalyl acetate, geraniol, nerol, 2- (1,1-dimethylethyl) -cyclohexanol acetate, benzyl acetate and eugenol. Carriers such as diethyl phthalate can be used in the processed perfume composition.

Other Ingredients-A wide variety of other ingredients useful in detergent compositions can be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, and the like. If high soap bubbles are desired, soap foam promoters such as C ₁₀ -C ₁₆ alkanolamides may typically be incorporated into the composition at levels of 1 to 10%. C ₁₀ -C ₁₄ monoethanol and diethanol amides are typical classes of such soap bubble promoters. It is also advantageous to use such soap foam promoters with high soap foam co-surfactants such as the amine oxides, betaines and sultaines mentioned above. If desired, water-soluble magnesium and / or calcium salts, such as MgCl ₂ , MgSO ₄ , CaCl ₂ , CaSO ₄ , may typically be added at levels of 0.1 to 2% to provide additional soap bubbles and enhance fat removal performance. .

The various cleaning components used in the compositions of the present invention may optionally be further stabilized by adsorbing the components onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Preferably the cleaning component is mixed with a surfactant prior to adsorption on the porous substrate. In use, the cleaning components are released from the substrate into the aqueous cleaning liquid to perform their desired cleaning function.

To illustrate this technique in more detail, porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3-5% C _13-15 ethoxylated alcohol (EO 7) nonionic surfactant. . Typically, such enzyme / surfactant solutions are 2.5 times the silica weight. The resulting powder is then dispersed in the silicone oil (various silicone oil viscosities in the range of 500 to 12,500 may be used) with stirring. The resulting silicone oil dispersion is emulsified or added to the final detergent matrix. This means that the aforementioned ingredients such as enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, phosphors, fabric conditioners and hydrolyzable surfactants may be "protected" for use in detergents including liquid laundry detergent compositions. That means you can.

The liquid detergent composition may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Although monohydric alcohols are preferred for dissolving the surfactant, polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (eg, 1,3-propanediol, ethylene glycol, glycerin and 1 , 2-propanediol) may be used. Such compositions may contain 5 to 90%, typically 10 to 50%, of the carrier.

Detergent compositions herein will preferably be formulated such that the pH of the wash water is from about 6.5 to about 11, preferably from about 7.5 to 10.5, during use in an aqueous cleaning operation. The product dish for liquid dish washing preferably has a pH of about 6.8 to about 9.0. Laundry products are typically at pH 9-11. Techniques for adjusting the pH to the recommended level include the use of buffers, alkalis, acids and the like, which are well known to those skilled in the art.

In the following examples, abbreviations for the various components used in the composition have the following meanings:

LAS: C11.5 alkyl benzene sulfonate anionic surfactant of average chain length, preferably sodium salt

AS: C14-15 primary alkyl sulfate anionic surfactant, preferably sodium salt, of average chain length

NI: C12-15 ethoxylated alcohol (nonionic surfactant) with average EO9 ethoxylation degree

SKS-6: Laminated Silicate (Hoechst)

Copolymer: Copolymer of acrylic acid / maleic acid and sodium salt

Zeolite: 1-10 micron zeolite A

PEG 4000: Polyethylene glycol with an average molecular weight of 4000

NOBS: nonanoyloxybenzene sulfonate bleach activator

PB-1: Sodium Perborate Monohydrate

Protease: proteolytic cleaning enzymes as described above, including BIOSAM 3.0

Amylase: Amylose Degradable Cleansing Enzyme

SRA-1: antifouling agent; Methyl cellulose; Molecular weight about 13,000, substitution degree 1.8-1.9

SRA-2: antifouling agent according to US Pat. No. 5,415,807

Polish X: Tinopal ^R CBS-X; Disodium 4,4'-bis- (2-sulphostyryl) biphenyl; Ciba-geigy

Polish Y: Tinopal ^R UNPA-6X; 4,4'-bis-{{4-anilino-6- [bis (2-hydroxy-ethyl) amino] -s-triazin-2-yl} -amino} -2,2'-stilbendi Sulfonates;

Ciba-geigy

Soap Bubble Control: Silica / Silicone Soap Bubble Inhibitor

Granule manufacturers

When the bis alkoxylated cationic material of the present invention is added to a mixer and then conventionally spray dried, this aids in the removal of all potentially odorous remaining short chain amine contaminants. In such cases, the formulator would like to produce blendable particles containing alkoxylated cationic materials for use in, for example, high density granular detergents, which particle composition is preferably not highly alkaline. Methods of making high density (650 g / l or more) granules are described in US Pat. No. 5,366,652. Such particles can be formulated to be effective for use at pH 9 or below to avoid odors of impurity amines. This can be accomplished by adding a small amount of acidity source, such as boric acid, citric acid, or the like or a suitable pH buffer to the particles. In another embodiment, the expected problems with amine malodors can be masked by the use of perfume components as described herein.

The following examples illustrate the invention but do not limit the scope thereof. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise noted.

Examples I and II illustrate the granular detergent composition of the present invention.

Example I

Component Weight% ppm

Surfactants

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13

Builder-Alkaline

SKS-6 3.29 21.94

Copolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Carbonate, Na 17.84 118.99

Silicate (2.0R) 11.40 76.04

bleach

NOBS 4.05 27.01

PB-1 3.92 26.15

enzyme

Protease 0.85 5.67

Amylase 1.20 8.00

Etc

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Polish X 0.21 1.40

Polish Y 0.10 0.67

Hydrophobic Silica 0.30 2.00

Soap Bubble Control 0.17 1.13

Sulfate, Na 5.14 34.28

Spices 0.25 1.67

Trace Substances and Moisture 3.28 21.88

Total 100 667.00

Usage-20g / 30L

^* The AQA-1 (CocoMeEO2) surfactants of this example may be replaced with equivalent amounts of any of the surfactants AQA-2 to AQA-22 or other AQA surfactants described herein.

Example II

Component Weight% ppm

Surfactants

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13

Builder-Alkaline

SKS-6 3.29 21.94

Copolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Carbonate, Na 19.04 127.00

Silicate (2.0R) 11.40 76.04

bleach

NOBS 4.05 27.01

PB-1 3.92 26.15

enzyme

Protease 0.85 5.67

Etc

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Polish X 0.21 1.40

Polish Y 0.10 0.67

Hydrophobic Silica 0.30 2.00

Soap Bubble Control 0.17 1.13

Sulfate, Na 5.14 34.28

Spices 0.25 1.67

Trace Substances and Moisture 3.28 21.88

Total 100 667.00

^* The AQA-1 (CocoMeEO2) surfactants of this example may be replaced with equivalent amounts of any of the surfactants AQA-2 to AQA-22 or other AQA surfactants described herein.

The following shows experimental procedures and test results for various soils and stains using the composition within the scope of the present invention. As can be seen from these data, overall cleaning improvements have been made for a wide range of dirt and contamination on various fabrics.

Performance test process

Sample manufacture:

Sample preparation basically includes the following steps:

1. Manufacturing steps of premixed LAS + AS

2. Preparation of Premixed LAS + AS + Cationic Materials

3. Preparation of Stock Nonionic (AE) Surfactants

4. Preparation Steps of the Builder Solution

5. Manufacturing Step of Granules

Surfactants:

Surfactant Weight ^* , g Active% Wash Concentration, ppm

LAS 78.85 44.50 143.20

AS 34.55 31.00 43.70

Cationic 01.90 40.00 3.10

AE 19.44 100.00 22.00

* (Actual weight will be different from% active)

Product manufacturing sequence for performance testing:

Phase Ⅰ

Individual surfactants are weighed and mixed in the following order:

1. Weigh 78.85 g of LAS.

2. Weigh 34.55 g of AS in the same beaker.

3. Add 498.10 ml of distilled water to the mixture of LAS & AS.

4. Premix the LAS and AS while heating at 40 ° C. for about 30 minutes until complete dissolution.

Step II:

1. Weigh 01.90 g of cationic to the same beaker containing LAS + AS premixed solution.

2. At this time, the total volume of the solution is 500 ml.

This 500 ml mixture of surfactant is good for 5 washes and 100 ml of the stock solution is used for every wash. The 100 ml solution was added to 49 liters of tap water to provide the corresponding wash concentrations for the individual surfactants.

Phase III:

1. Weigh 19.44 g AE separately.

2. Add 900 ml of distilled water to AE.

3. This 900 ml solution is good for 18 washes.

4. 50 ml of the solution is used for each wash.

Step IV:

Silicate: 148.32 g per 900 ml of distilled water: 50 ml of this solution is used for every wash.

Copolymer: 92.99 g per 900 ml of distilled water; 500 ml of this solution is used for each wash.

Granules: Each granule component is weighed separately in the same beaker.

Order to add to washing machine:

While stirring, the ingredients are added in the following order:

1.Silicate (2.0R)

2. Copolymers (as mentioned previously)

3. Granule

Stop stirring here (to avoid soap bubbles during surfactant addition)

4. LAS + AS + Cationic Solution

5. AE solution

Stir for 15 seconds

Hardness: No additional hardness is added above the tap water hardness

Loads: 2.4 kg of loads of the following composition are typically used

Cotton Dress Shirts (1)

Old T-shirt (from panelist) (3)

Large T Shirts (11)

DKPE T-Shirt (1)

P / C Shorts (2)

Cotton Shorts (1)

DKPE is a double-ply knit polyester.

DMO is dirty car oil.

Test results I described below show the performance of the compositions according to the invention with CoCoMeEO2 + LAS / AS mixtures and test results II show the performance with CoCoMeEO10 ^* + LAS / AS compared to CoCoMeEO2 / LAS. In this test, performance is measured for various types of dirt: body dirt, builder sensitive dirt, bleach sensitive dirt, surfactant sensitive dirt and stock. ^* According to the term "bis" herein, "EO10" refers to two poly-EO chains (typically but not limited to five per each chain) having an average of 10 EO units in the molecule.

Test result Ⅰ

Premixing CoCoMeEO2 Cationic Materials with LAS & AS (Total Anionic Systems)

Soil Test I Test II Average

Color Used -0.02 -0.27 -0.15

Insert collar 0.77S 0.73S 0.75

Cufflinks -0.17 0.33 0.08

Darkness -0.1 0.17S 0.04

Physical dirt (average) 0.12 0.24 0.18

Clay C / D 1.03S 0.7S 0.87

Clay DKPE 0.7S -0.02 0.34

Builder Sensitivity (Average) 0.87 0.34 0.61

Spinach 0.33 0.56 0.45

Coffee 0.21 0.42S 0.32

Bleach Sensitive Dirt (Average) 0.27 0.49 0.38

Meat sauce 0.84S 1.08S 0.96

Curry 1.14S 1.11 1.13

Bacon oil 0.1 0.16 0.13

DMO 0.44 -0.34 0.05

Surfactant sensitive dirt

0.63 0.5 0.57

Average (including stock) 0.39 0.38 0.39

Stock (Previous) 0.32 0.35A 0.34

Stock (after) 0.08 0.64A 0.36

Stock (Delta) -0.24 0.28 0.02

Test result Ⅰ

Premixing CocoMeEO2 Cationic Materials with LAS Alone

Soil Test I Test II Average

Color Used 0.27 -0.73 -0.23

Insert collar -0.04 0.15 0.06

Cufflinks -0.35 -0.25 -0.30

Darkness 0.13 0.51S 0.32

Body Soil (Average) 0.00 -0.08 -0.04

Clay C / D 0.59 0.79S 0.69

Clay DKPE 0.04 0.66 0.35

Builder Sensitivity (Average) 0.32 0.73 0.53

Spinach 0.07 0.58 0.33

Coffee 0.24 0.24 0.24

Bleach Sensitive Dirt (Average) 0.16 0.41 0.29

Meat Sauce -0.1 -0.08 -0.09

Curry 0.1 0.54 0.32

Bacon oil -0.53 -0.02 -0.28

DMO -0.22 0.05 -0.09

Surfactant sensitive dirt

(Average) -0.19 0.12 -0.04

Average (including stock) 0.04 0.19 0.12

Stock (Previous) 0.33 -0.07 0.13

Stock (After) 0.7S -0.05 0.33

Stock (Delta) 0.36 0.02 0.19

Test result Ⅱ

Premix of CoCoMeEO10 Cationic Material with LAS + AS

Soil Test I Test II Average

Color Used 0.48 -0.02 0.23

Insert collar 0.02 0.06 0.04

Cufflinks 0.33 0.25 0.29

Darkness -0.28 0.11 -0.09

Physical dirt (average) 0.14 0.10 0.12

Clay C / D 0.75S 0.44 0.60

Clay DKPE 0.27 -0.47 -0.10

Builder Sensitivity (average) 0.51 -0.02 0.25

Spinach 0.00 0.33 0.17

Coffee 0.38 0.82S 0.60

Bleach Sensitive Dirt (Average)

Meat source 0.05 0.96S 0.51

Curry 0.42 0.91S 0.67

Bacon oil 0.23 -0.07 0.08

DMO 0.31 -0.13 0.09

Surfactant sensitive dirt

0.25 0.42 0.34

Average (including stock) 0.2 0.26 0.23

Stock (Previous) 0.14 0.23 0.19

Stock (after) -0.19 0.48S 0.15

Stock (Delta) -0.32 0.25 -0.04

Test result Ⅱ

Premixing CocoMeEO10 Cationic Materials with LAS Alone

soil

Used collar 0.17

Insert collar -0.52

Cufflinks 0.19

Darkness -0.17

Somatic Obstruction (Average) -0.08

Clay C / D -0.34

Clay DKPE 0.09

Builder Sensitivity (average) -0.13

Spinach 0.06

Coffee 0.08

Bleach Sensitive Dirt (Average) 0.07

Meat Sauce -0.20

Curry -0.38

Bacon oil -0.33

DMO -0.33

Surfactant sensitive dirt

(Average) -0.31

Average (includes stock) -0.11

Stock (Previous) 0.42S

Stock (after) 0.64S

Stock (Delta) 0.22

Example III

This is modified by removing the bleaching system (NOBS / PB ₁ ) from the compositions of Examples I and II. The AQA level is adjusted to about 1.5% (range 0.5-5%) of the composition. A fairly satisfactory cleaning performance against various dirts and stains is obtained even in the absence of bleach.

The compositions of Examples I, II and III can also be provided in the form of tablets using standard tableting and densification devices.

Example IV

Conventional extrusion techniques are used to prepare bar detergents having a surfactant mixture and comprising the following ingredients:

Component weight percent range (weight percent)

A B

AQA-1 ^* 2.0 0.6 0.15-3.0

C ₁₂ -C ₁₈ Sulfate 15.75 13.50 5-25

LAS 6.75 5.5 3-25

Na ₂ CO ₃ 15.00 3.00 1-20

DTPP ¹ 0.70 0.70 0.2-1.0

Bentonite Clay --- 10.0 0-20

Sokolan CP-5 ² 0.40 1.00 0-2.5

TSPP 5.00 --- 0-10

STPP 5.00 15.00 0-25

Zeolite 1.25 1.25 0-15

Sodium Laurate --- 9.00 0-15

SRA-1 0.30 0.30 0-1.0

Protease Enzyme --- 0.12 0-0.6

Amylase Enzyme 0.12 --- 0-0.6

Lipase Enzyme --- 0.10 0-0.6

Cellulase Enzyme --- 0.15 0-0.3

--balance--

¹ sodium diethylenetriamine penta (phosphate)

² Skolan CP-5 is a maleic acid-acrylic acid copolymer.

³ Balance comprises water (about 2-8% including hydrate), sodium sulfate, calcium carbonate and other trace components.

^* The AQA-1 (CocoMeEO2) surfactants of this example may be replaced with equivalent amounts of any of the surfactants AQA-2 to AQA-22 or other AQA surfactants described herein.

Example Ⅴ

The following illustrates a mixture of AQA surfactants that may be substituted for the AQA surfactants listed in any one of the previous examples. As described above, such mixtures may be used to provide specific cleaning performance benefits and / or to provide useful cleaning compositions under a wide range of use conditions. Preferably, the AQA surfactants in such mixtures differ by at least about 1.5, preferably about 2.5 to 20, in total EO units. The ratio range (weight) for this mixture is typically from 10: 1 to 1:10. Non-limiting examples of such mixtures are as follows:

Component ratio (weight)

AQA-1 + AQA-5 1: 1

AQA-1 + AQA-10 1: 1

AQA-1 + AQA-1 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 herein with the corresponding cationic surfactants containing only one ethoxylated chain can also be used. Thus, for example, the formula _{^{R 1 N + CH 3 [EO}} ] x [EO] y X - and _{^{R 1 N + (CH 3)}} 2 [EO] z X - ( wherein, R ¹ and X are described above And one cationic material has (x + y) or z in the range of 1 to 5, preferably 1 to 2 and the other cationic material is 3 to 100, preferably 10 to 20, most preferably 14 Mixtures of bis-ethoxylated cationic surfactants ranging from (x + y) or z in the range from 16 to 16 can be used herein. Such compositions advantageously provide improved cleaning performance (especially in fabric laundering conditions) over a wider range of water hardness than the cationic surfactants used herein separately. The shorter the EO cationic material (eg, EO2), the better the cleaning performance of the anionic surfactant in soft water, while the longer the EO cationic material (ie, EO15), the hardness of the anionic surfactant By working to improve resistance, the cleaning performance of anionic surfactants in hard water is improved. Common wisdom in the field of detergents suggests that builders can optimize the performance "window" of anionic surfactants. However, up to now it has not been possible to extend the window to cover essentially all the conditions of water hardness.

Example VI

While various non-limiting examples of the compositions herein and their use have been described, the following further illustrates the invention encompassed herein, particularly in terms of detergents for fabric laundry. The granular, liquid, bar, tablet, or gel compositions of the present disclosure may comprise cleansable non-AQA surfactants and any builder at the levels and ranges described above, and such compositions may also comprise one or more combinations of the following ingredients: Effective amounts include:

Component weight ratio AQA: Component

Percarbonate bleach 1: 100-1: 1, preferably 1: 20-1: 5

Branched alkyl sulfates 1: 100-1: 2, preferably 1: 10-1: 3

Bleach activator ^* 2: 1-1: 10, preferably 1: 1-1: 5

Peracid bleach ^** 1: 10-2: 1, preferably 1: 5-1: 1

Photobleach 1: 100-1: 2, preferably 1: 5-1: 1

Laminated Silicate Builder 1: 300-1: 1, preferably 1: 100-1: 5

SRA 1: 20-1: 2, preferably 1: 10-1: 1

Enzyme ^*** 1: 10-10: 1, preferably 1: 3-3: 1

EDDS 1: 20-10: 1, preferably 1: 3-3: 1

MGDA 1: 20-10: 1, preferably 1: 3-3: 1

PFAA 1: 50-1: 2, preferably 1: 25-1: 3

APG 1: 50-1: 2, preferably 1: 25-1: 3

Ca ⁺⁺ 1: 10-10: 1, preferably 1: 5-5: 1

Mg ⁺⁺ 1: 10-10: 1, preferably 1: 5-5: 1

Co catalyst 1: 10-10: 1, preferably 2: 1-1: 1

Mn catalyst 1: 10-10: 1, preferably 2: 1-1: 1

DTI Formulations 1: 20-20: 1, preferably 1: 10-10: 1

Zeolite P (MAP) 1: 300-1: 1, preferably 1: 100-1: 5

Weapon Builder 1: 300-1: 1, preferably 1: 100-1: 5

Polymeric dispersant ^**** 1: 10-10: 1, preferably 1: 5-1: 1

Alkoxylated polycarboxylate 4: 1-1: 10, preferably 1: 5-1: 1

Mud removal / re-deposition inhibitor 4: 1-1: 20, preferably 1: 1-1: 10

Clay softener 3: 1-1: 10, preferably 2: 1-1: 1

* Includes mixtures such as NOBS + TAED.

** Contains mixtures.

*** Based on commercial enzyme preparations. This may vary depending on the level of active enzyme of the enzymatic product on the market.

**** Preferably polyacrylate or acrylic acid / maleic acid copolymer

Laundry detergent compositions prepared using one or more of these ingredient combinations may optionally be built into any non-phosphate or phosphate builder or mixtures thereof, typically at levels of 5 to about 70% by weight of the final composition.

Example Ⅶ

The following illustrates, but is not limited to, a mixture of conventional non-AQA surfactants that can be used in combination with the AQA surfactants in any of the previous examples. The ratio of non-AQA surfactants in the mixture is referred to as parts by weight of the surfactant mixture.

Mixture A-C

Ingredient ratio

AS ^* / LAS 1: 1

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

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

In the above, substantially straight primary AS surfactants may be replaced with mixtures thereof including equivalent amounts of secondary AS, branched AS, oleyl sulfate, and / or mixtures of the linear AS described above with primary AS. . AS of "tallow" chain length is particularly useful under hot water conditions prior to boiling. "Coconut" AS is preferred for colder washing temperatures.

A mixture of the aforementioned alkyl sulphate / anionic surfactants is incorporated, wherein a non-AQA surfactant is used with a weight ratio of anionic surfactant (total) to nonionic surfactant in the range of about 25: 1 to about 1: 5. By deforming. Nonionic surfactants may include any of the conventional classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid amides (less preferred), or mixtures thereof as mentioned above.

Highly preferred combinations of the foregoing non-AQA surfactants will comprise from about 3 to about 60 weight percent based on the total weight of the processed laundry detergent composition. The final composition will preferably comprise from about 0.25 to about 3.5 weight percent of AQA surfactant.

Example Ⅷ

This example provides a perfume formulation (A-C) that can be incorporated into any composition in the AQA-containing detergent composition of the previous example. Various ingredients and levels are presented as follows:

weight%

Perfume Ingredient A B C

Hexyl Cinnamic Aldehyde 10.0-5.0

2-methyl-3- (para-tert-butylphenyl) -propionaldehyde 5.0 5.0-

7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-

Tetramethyl naphthalene 5.0 10.0 10.0

Benzyl Salicylate 5.0--

7-acetyl-1,1,3,4,4,6-hexamethyltetraline 10.0 5.0 10.0

Para- (tert-butyl) cyclohexyl acetate 5.0 5.0-

Methyl Dihydro Jasmonate-5.0-

Beta-naphthol methyl ether-0.5-

Methyl beta-naphthyl ketone-0.5-

2-Methyl-2- (para-iso-propylphenyl) -propionaldehyde-2.0-

1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-

Cyclopenta-gamma-2-benzopyran-9.5-

Dodecahydro-3a, 6,6,9a-tetramethylnaphtho-

[2,1b] furan--0.1

Anisealdehyde--0.5

Coumarin--5.0

Cedrol--0.5

Vanillin--5.0

Cyclopentadecanolide 3.0-10.0

Tricyclodecenyl acetate--2.0

Rabdanium Resin--2.0

Tricyclodecenyl propionate--2.0

Phenyl Ethyl Alcohol 20.0 10.0 27.9

Terpineol 10.0 5.0-

Linalol 10.0 10.0 5.0

Linalyl Acetate 5.0-5.0

Geraniol 5.0--

Nerol-5.0-

2- (1,1-dimethylethyl) -cyclohexanol acetate 5.0--

Orange Oil (Cold Pressed)-5.0-

Benzyl acetate 2.0 2.0-

Orange Terpene-10.0-

Eugenol-1.0-

Diethylphthalate-9.5-

Lemon Oil (Cold Pressed)--10.0

Total 100.0 100.0 100.0

The foregoing perfume composition is mixed or sprayed up (typically up to about 2% by weight based on the total weight of the detergent composition) with any of the compositions in the AQA surfactant-containing cleaning composition described herein. In this way, improved deposition and / or preservation of the perfume or individual components on the surface to be cleaned is obtained.

Claims (25)

A composition prepared by combining or combining a bis-alkoxylated AQA cationic surfactant of Formula I with two classes of anionic surfactants of Formulas II and III and optionally a nonionic surfactant (IV). Formula I Formula II R ⁵ OSO ₃ ^- M ⁺ Formula III R ⁶ SO ₃ ^- M ' ⁺ In the above formula, R ¹ is an alkyl or alkenyl residue having 8 to 18 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, R ³ and R ⁴ may be independently selected from hydrogen, methyl and ethyl, R ⁵ is a straight or branched chain alkyl or alkenyl moiety having 10 to 20 carbon atoms, R ⁶ is C ₁₀ -C ₁₆ alkylbenzene, M ⁺ and M ' ⁺ are independently of each other selected from alkali metals, alkaline earth metals, alkanol ammonium and ammonium, X ^- is an anion, A and A 'are independently of each other C ₁ -C ₄ alkoxy, p is from 1 to about 30, q is 1 to about 30, The weight ratio of component (I) to (II) + (III) is from 1: 100 to 1: 7 and the weight ratio of component (II) :( III) is from 4: 1 to 1: 4 and the weight ratio of R ⁵ to R ⁶ is 1:13 to 1: 5. The composition of claim 1 comprising from 0.1 to 5% by weight of AQA cationic surfactant (I). The composition of claim 2 wherein in the AQA cationic surfactant (I) R ¹ is C ₁₀ -C ₁₈ alkyl, R ² is methyl and p and q are each 1 to 4 ethoxy. 4. The composition of claim 3 wherein the anionic surfactant (II) is C ₁₂ -C ₁₈ primary or secondary straight or branched chain alkyl sulfate and the anionic surfactant (III) is C ₁₁ -C ₁₃ alkyl benzene sulfonate. The composition of claim 1 wherein the nonionic surfactant (IV) is a member selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides and mixtures thereof. The method of claim 1, (a) 0.25 to 3 weight percent of Coco methyl EO2 as surfactant (I); (b) 3 to 40 weight percent of a linear or branched primary or secondary alkyl sulfate as surfactant (II); (c) 6 to 23 weight percent alkyl benzene sulfonate as surfactant (III); And (d) 0.5 to 20% by weight of a nonionic surfactant (IV). The method of claim 6, (Iii) 0.45 to 2 weight percent; (Ii) (b) 6 to 13 weight percent; (Iii) 8-23 weight percent (c); And (Iii) 1 to 5 weight percent of (d). The detergent composition of claim 1 further comprising conventional auxiliary components and mixtures thereof. The composition of claim 8, wherein the auxiliary component is a builder. The composition of claim 8 wherein the accessory ingredient is an enzyme. The composition of claim 8 wherein the auxiliary component is an antifouling polymer. The composition of claim 8 wherein the accessory ingredient is a bleach, bleach activator or mixtures thereof. The composition of claim 8 wherein the auxiliary component is a mud removal / redeposition inhibitor. The composition of claim 8 wherein the auxiliary component is a polymeric dispersant. The composition of claim 8 wherein the auxiliary component is a brightener. The composition of claim 8, wherein the auxiliary component is a dye transfer inhibitor. The composition of claim 8, wherein the auxiliary component is a soap bubble inhibitor. 9. A group according to claim 8, wherein the auxiliary component is a group consisting of soap, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, sulfated alkyl polyglycosides, alpha-sulfonated fatty acid esters, betaines, sulfobetaines, amine oxides and mixtures thereof. Wherein the composition is a cleaning surfactant that is one member selected. The composition of claim 8 wherein the auxiliary component is a fabric softener. The composition of claim 8 which is substantially free of bleach. The composition of claim 8 wherein the auxiliary component is a perfume. The composition of claim 8 wherein the auxiliary component is a chelating agent. The composition of claim 8 wherein the auxiliary component is a manganese, iron or cobalt catalyst. The composition of claim 1 comprising a mixture of AQA surfactants. The composition of claim 1 comprising a mixture of bis-alkoxylated AQA surfactants and mono-alkoxylated cationic surfactants.