MXPA00009189A - Detergent composition containing cylindrically-shaped bleach activator extrudates having enhanced flowability - Google Patents

Abstract

A bleach-containing detergent composition which contains a peroxygen bleaching compound and a bleach activator is disclosed. The bleach activator is in the form of substantially cylindrically-shaped extrudates having a mean extrudate length of from about 500 microns to about 3500 microns and a mean extrudate diameter of from about 450 microns to about 850 microns wherein said extrudate comprises one or more flowability enhancers.

Description

DETERGENT COMPOSITION CONTAINING MATERIALS EXTRUDED FROM SHAPED BLEACH ACTIVATOR CYLINDRICA WITH INCREASED FLOW CAPACITY FIELD OF THE INVENTION The present invention relates to detergent and bleach compositions containing a peroxygen bleach system, said system comprising a peroxygen bleach and a bleach activator comprising extruded material, said extruded material having increased flowability. The extruded material has a substantially cylindrical shape and provides improved stability and performance.

BACKGROUND OF THE INVENTION As is known, the bleaching of textile surfaces is bleaching in which the bleaching mechanism takes place on the surface of the fabric and, therefore, removes stains and / or dirt. Typical bleaching compositions contain peroxygen bleaches capable of producing hydrogen peroxide in aqueous solutions and bleach activators to increase the performance of the bleach. For a long time it has been known that peroxygen bleaches are effective for the removal of stains and / or dirt from fabrics, but that they are also extremely dependent on temperature. Said bleaches are essentially only practical and / or effective in bleaching solutions, ie, a mixture of bleach and water, wherein the temperature of the solution is more than about 60 ° C. At bleaching solution temperatures of about 60 ° C, the peroxygen bleach is only partially effective and, therefore, in order to obtain a desirable level of bleaching performance extremely high levels of peroxygen bleach have to be added to the system. This is not economically practical for large scale commercialization of modern detergent products. Peroxygen bleach loses its effectiveness by decreasing the temperature of the bleaching solution to less than 60 ° C, regardless of the level of peroxygen bleach added to the system. The temperature dependence of peroxygen bleaches is significant since said bleaches are commonly used as a detergent auxiliary in fabric washing processes using an automatic homemade washing machine at wash water temperatures of less than 60 ° C. Said washing temperatures are used due to considerations of fabric care and energy. As a consequence of said washing process, there has been intensive industrial research to develop substances, generally known as bleach activators, that make effective peroxygen bleaches at bleaching solution temperatures of less than 60 ° C.

Numerous substances in the art have been described as effective bleach activators. For example, bleach activators having the general formula have been described in the art.

O II R-C-L wherein R is an alkyl group and L is a leaving group. Said bleach activators have typically been incorporated in detergent products such as a granule, agglomerate or other type of mixed particle. However, a problem with said bleach activators is to maintain the stability of the activator before being used by the consumer. The granule or agglomerate of bleach activator has a tendency to degrade over time, which is increased by exposure to environmental effects such as heat and humidity. As a consequence of this, the granule, agglomerate or other particulate form of the bleach activator must be relatively large compared to the other detergent ingredients in a typical granular detergent product. This, in turn, causes another problem associated with the segregation of the detergent product since the larger bleach activator particles tend to accumulate in or near the top of the detergent case, while the detergent ingredients with a Relatively smaller particle sizes accumulate in or near the bottom of the box. further, the segregation of particles occurs during the detergent manufacturing process, leading to an increase in the variability between boxes for the different active detergent ingredients. The actual result of such undesirable product segregation is decreased performance because the user pulls the product from the top to the bottom and each scoop has a disproportionate amount of bleach activator or other detergent ingredient, and similarly, the product yield of different Boxes are affected by the variation in the detergent composition. In this way, it would be desirable to have a detergent product that contains a bleach activator that had improved stability before use, and which did not segregate significantly prior to packaging or while stored in the detergent product box. In addition, it would be desirable to have a detergent composition that also has acceptable physical properties, for example, acceptable flow properties for bulk handling of the composition as part of the large-scale manufacture of detergents. Yet another problem with the bleach activators mentioned above relates to the inability to notice the cleaning effects of the bleach / bleach activator systems mentioned above in the fabrics. Currently, most government regulatory agencies require that announced cleaning guarantees for fabric care can only be made if a relatively high level of microbes is consistently removed from the washed fabrics as a result of using a detergent product containing bleach. However, in the past, the granule, agglomerate or other relatively large particle form of the bleach activator has inhibited said announced cleaning guarantees because the product segregation effects of said larger particles prevented the consistent removal of high levels of microbes of the washed fabrics. The supply of bleach / bleach activator during the washing process varied widely enough to meet most government requirements for announced cleaning guarantees. Therefore, it would be desirable to have a detergent product containing bleach that could be used to wipe fabrics. Accordingly, there remains a need in the art for a detergent product containing bleach activator and having improved stability before use. Also, there is a need in the art for a detergent product that contains a bleach activator that does not segregate significantly while stored in the detergent product box and which has acceptable physical properties, especially increased flow capacity that serves to assist in the processing of the detergent compositions. There remains another need in the art for a detergent composition having a more consistent supply of bleach / bleach activator.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to extruded materials comprising bleach activators, said extruded materials have increased flowability. These extruded materials are useful in detergent compositions containing a peroxygen bleaching compound and which require that the bleach activator in the form of an extruded material in substantially cylindrical form have a relatively small particle size selected. The extruded materials of The smaller bleach activator remain unexpectedly stable during extended storage periods and reduce the segregation of the product in the detergent box in which they are contained, since they are more closely resemble the particle size of the other conventional ingredients of the detergent. Detergent. The increase in flow capacity of the extruded materials taken together with the particle size of the extruded materials provides improved cleaning effects to • fabrics washed more consistently. The phrase "cylindrical extruded materials" means an extruded particle having a surface shape generated by a straight line that moves parallel to a fixed straight line and that crosses a fixed flat closed curve. An "effective amount" of a detergent composition containing a bleach activator is any amount capable of measurably improving both the removal of soils and the cleaning of the fabric when it is washed by the consumer. In general, this amount can vary widely. As used herein, the terms "disinfect", "disinfection", "antibacterial", "eliminate germs" and "cleaning" are designed to mean eliminate microbes that are commonly in fabrics that require washing. Examples of various microbes include germs, bacteria, viruses, parasites and fungi / spores. As used herein, the "free water" level means the level in a percentage by weight of water in the detergent composition that is not bound, or in another detergent such as zeolite; is the level of water in excess of any water trapped, absorbed or otherwise bound in the other detergent ingredients. According to one aspect of the present invention, a bleach-containing detergent composition is provided, which comprises an extruded bleach activator material, said extruded material comprising: a) about 60% to about 95% by weight, of a bleach activator that has the formula: OR II R- C- L wherein R is an alkyl group containing about 5 to about 18 carbon atoms, wherein the longer linear alkyl chain extending from, and including the carbonyl carbon, contains about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pKa on the scale of about 6 to about 13; b) about 0.1% to about 40% by weight, of one or more binder materials and c) about 0.5%, preferably about 0.5% to about 10% by weight, of a flow capacity increaser; said extruded bleach activator material is in the form of an extruded material of substantially cylindrical shape having an average extruded material length of about 500 microns to about 3500 microns and an average extruded material diameter of about 450 microns to about 850 microns. Another aspect of the present invention provides a laundry detergent or bleach composition using said extruded material, said composition comprising: a) at least about 0.1% by weight of a peroxygen bleach compound capable of producing hydrogen peroxide in an aqueous solution; b) an extruded material containing bleach activator comprising: i) about 60% to about 95% by weight, of a bleach activator having the formula: or II R-C-L wherein R is an alkyl group containing about 5 to about 18 carbon atoms, wherein the longer linear alkyl chain extending from, and including the carbonyl carbon, contains about 6 to about 10 carbon atoms. carbon and L is a leaving group, the conjugate acid of which has a pKa on the scale of about 6 to about 13; I) about 0.1% to about 40% by weight, f 10 of one or more binder materials and iii) about 0.5%, to about 10% by weight, of a flow capacity increaser; wherein said extruded material . of bleach activator is in the form of an extruded material of substantially cylindrical shape having a length of extruded material? 15 average of approximately 500 microns to approximately 3500 microns and an average extruded material diameter of approximately 450 microns • about 850 microns, and as long as said extruded material comprises sufficient bleach activator so that the ratio of bleach activator to peroxygen bleach compound is more than 20 of 1 and c) the rest are vehicles and other auxiliary ingredients. According to another aspect of the invention, a method for using the detergent composition for cleaning fabrics is provided. The method comprises the step of contacting said fabrics with an effective amount of a detergent composition as described herein in an aqueous solution for cleaning the fabrics. Accordingly, an object of the invention is to provide a detergent composition containing bleach activator particles having adequate stability before use and acceptable physical properties. It is also an object of the invention to provide a detergent composition containing a bleach activator that does not segregate significantly while stored in the detergent product box. Another object of the invention is to provide a detergent product that can be used to clean fabrics. These and other objects, features and advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments and the appended claims. All percentages and ratios used herein are expressed as percentages by weight (anhydrous base) unless otherwise indicated. All the cited documents are incorporated herein by way of reference.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY The detergent or bleaching compositions of the present invention comprise a bleaching system having two essential components: a peroxygen bleach which is capable of producing hydrogen peroxide as an aqueous solution, and a bleach activator which increases the formation of hydrogen peroxide by said bleach # peroxygenated The peroxygen bleach can have any suitable form, for example, a coated particle, however, the bleach activator is in the form of an extruded material of substantially cylindrical shape, said extruded material comprises a flow capacity increaser. The bleach activator containing extruded material is formed using one or more flow capacity enhancers that act to ^ P 10 prevent the particles of extruded material from clumping together or becoming "sticky". Typically, one or more binder materials are included in the extruded bleach activator materials including, but not limited to, palmitic acid, a detersive surfactant, polyethylene glycol, and other fatty acids and polyacrylates. 15 Peroxyated Bleach Compound • Peroxygenated bleach systems useful herein are those capable of producing hydrogen peroxide in an aqueous liquid. These compounds are well known in the art and include peroxide Hydrogen and the bleaching compounds of alkali metal peroxides and organic peroxide such as urea peroxide, and inorganic persal bleach compounds such as alkali metal perborates, percarbonates and perfosphates and the like. Mixtures of two or more of these bleaching compounds can also be used if desired. The peroxygen bleaching compounds that are preferred • include sodium perborate, commercially available in mono-, tri- and 5-tetrahydrated form, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarborate and sodium peroxide. Sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are particularly preferred. Percarbonate is especially preferred because it is very stable during storage and still dissolves very quickly • 10 in the bleaching liquid. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, increased surface bleaching performance. The percarbonate that is too preferred may be in coated or uncoated form. The average particle size of the percarbonate uncoated varies from about 400 to about 1200 microns, most preferably from about 400 to about 600 microns. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate and sulfate, silicate, borosilicate or fatty carboxylic acids. The peroxygen bleach compound will comprise at least about 0.1%, preferably about 1% to about 75%, most preferably about 3% to about 40%, more preferably about 3% to about 25%, by weight of the system bleach or detergent composition. The weight ratio of bleach activator to peroxygen bleach compound in the bleaching system typically varies from • approximately 2: 1 to 1: 5. The preferred ratios range from about 1: 1 to about 1: 3. The molar ratio of hydrogen peroxide produced by the peroxygen bleach compound to the bleach activator is more than about 1.0, most preferably more than about 1.5 and more preferably about 2.0 to about 10. Preferably, the bleaching compositions ^^^^ 10 of the present comprise about 0.5 to about 20, most preferably about 1 to about 10% by weight of the peroxygen bleaching compound. The peroxygen bleach compound is preferably selected from the group consisting of sodium perborate monohydrate, Sodium perborate tetrahydrate, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and mixtures thereof. It is preferred that the detergent composition of the invention contains less than about 3%, preferably less than about 2.5% and most preferably less than about 2% by weight of free water. While not wishing to be bound by theory, it is believed that by maintaining this relatively low level of free water in the composition, the propensity of the bleach activator to degrade by hydrolysis before use is decreased. In this way, the stability of the bleach activator is increased and further prolonged as a result of a selected free water level as described herein. • Extruded material comprising bleach activator Flow capacity enhancers The extruded material comprising bleach activator of the present invention has increased flowability and agglomeration or adhesion resistance. This improvement is achieved by the addition of one or • 10 more "powder formers", "anti-agglomeration agents" or "flowability auxiliaries". Non-limiting examples of these flow capacity enhancers include, aluminosilicates, magnesium silicates, fuming silica, pulverized carbonate, talcum, corn starch and the like. It is suitable to use any high surface that is not hydroscopic. For example, sodium sulfate or anhydrous magnesium sulfate can be used finely divided or pulverized. Preferred flow capacity enhancers can be achieved by spraying zeolites, for example zeolite A, zeolite X or zeolite Y, and adding the necessary amount of said zeolite to the mixture before extrusion. The added benefit to the formulator by adding a material such as powdered zeolite is that the material is useful as a builder once the extruded material is solubilized in the wash liquid.

Preferably, the flow capacity enhancer has a particle size of less than 10 microns (10 μ), preferably 1-10 μ. and most preferably 3-5 μ. The flow capacity enhancer is present in the extruded material comprising bleach activator at a level of at least about 0.5%, preferably about 0.5% to about 10%, most preferably about 2% to about 3% in weight, of the extruded material. The preferred flow rate enhancers are selected from the group consisting of aluminosilicates, silicas, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, sodium carbonate, talc, corn starch and mixtures thereof.

Bleach activators The bleach activator for the bleach systems useful herein preferably has the following structure: OR II R-C- L wherein R is an alkyl group containing about 5 to about 18 carbon atoms, wherein the longer linear alkyl chain extending from, and including the carbonyl carbon, contains about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pKa on the scale of about 6 to about 13, preferably about 6 to about 11, more preferably about 8 to about 11. L can be essentially any suitable leaving group .

A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack in the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid. Generally, for a group to be a suitable leaving group it must exert an electron-attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion. The L group must be reactive enough for the reaction to occur within the optimal time frame (eg, a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize. These characteristics are generally followed by the pKa of the conjugate acid of the leaving group, although exceptions to this rule are known. The bleach activators that are preferred are those of the general formulas: R5 O O O R5 O, i ?? «?? ?? i "?? R1- N-C-R2-C-L or R1-C-N-R2-C-L wherein R1 is an alkyl group containing about 6 to about 12 carbon atoms, R 2 is an alkylene containing 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl or alkaryl containing about 1 to about 10 carbon atoms, and L is selected from the group consisting of in: Y R3 I I - 0-CH = -C-CH = CH2, - O-C = CHR4, and wherein R6 is an alkylene, arylene or alkarylene group containing about 1 to about 14 carbon atoms, R3 is an alkyl chain containing about 1 to about 8 carbon atoms, R4 is H or ^^ R3, and Y is H or a solubilizing group. And it is preferably selected from the group consisting of -SO3-M +, -COO-M +, -S04-M +, (-N + R'3) X- and 0 < -N (R'3), wherein R 'is an alkyl chain containing about 1 to about 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the activator of bleach. Preferably, M is an alkali metal cation, • 10 ammonium or substituted ammonium, with more sodium and potassium being preferred, and X is an anion selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions. More preferably, Y is -SO3-M + and -COO-M +. It should be noted that bleach activators with a leaving group that does not contain a solubilization group should be well dispersed in the bleaching solution to help its dissolution. It preferred: wherein R3 is as defined above and Y is -SO3-M + or -COO-M +, wherein 20 M is as defined above. Particularly preferred bleach activators are those in which R1 is a linear alkyl chain containing about 6 to about 12 carbon atoms, R2 is a linear alkylene chain containing about 2 to about 6 carbon atoms, R5 is H, and L is selected from the group consisting of: where R3 is as defined above, Y is -SO3-M + or -COO-M + and M is • 10 as defined above. A bleach activator that is preferred is: • wherein R is H, alkyl, aryl or alkaryl. This is described in the patent of E.U.A. 4,966,723, Hodge et al., Incorporated herein by reference. The preferred bleach activators are: wherein R1 is H or an alkyl group containing about 1 to about 6 carbon atoms and R2 is an alkyl group containing about 1 to about 6 carbon atoms and L is as defined above. Preferred bleach activators are those of the above general formula, wherein L is as defined in the general formula, and R1 is H or an alkyl group containing about 1 to about 4 carbon atoms. Still more preferred are the bleach activators of the above general formula, wherein L is as defined in the general formula and R1 is an H. Preferred bleach activators are those of the above general formula, wherein R is a linear alkyl chain containing about 5 to about 12 and preferably about 6 to about 8 carbon atoms, and L is selected from the group consisting of: - N-C-R, - O-C-R, -0- < (T) R2 'I Y R2 R2 I - 0-CH = C- CH- Chfe, - 0-C = CHR3 wherein R, R2, R3 and Y are as defined above. Particularly preferred bleach activators are those of the above general formula, wherein R is an alkyl group containing about 5 to about 12 carbon atoms, wherein the longest linear portion of the alkyl chain extending from, and which includes the carbonyl carbon, is from about 6 to about 10 carbon atoms, and L is selected from the group consisting of: here R2 is an alkyl chain containing about 1 to about 8 carbon atoms, and Y is -SO3M + or -COO-M +, wherein M is an alkali metal, ammonium or substituted ammonium cation. Particularly preferred bleach activators are those of the above general formula, wherein R is a linear alkyl chain containing about 5 to about 12 and preferably about 6 to about 8 carbon atoms, and L is selected from the group which consists of: where R2 is as defined above and Y is -SO3M + or -COO-M +, where M is as defined above. The most preferred bleach activators have the formula: wherein R is a linear alkyl chain containing from about 5 to about 12, and preferably from about 6 to about 8 carbon atoms and M is sodium or potassium. Preferably, the bleach activator of the present invention is sodium nonanoyloxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate (BOBS). It is particularly preferred to use in the compositions bleaching agents of the present invention the following bleach activators which are particularly safe to use with machines having natural rubber parts. It is believed that this is the result of not producing oily diacyl peroxide (DAP) species by means of the perhydrolysis reaction of these amido acid-derived bleach activators, but rather of forming DAP's insoluble crystalline solids. It is believed that these solids do not form a coating film and thus • Natural rubber parts are not exposed to DAPs for extended periods of time. These bleach activators that are preferred are members selected from the group consisting of: a) a bleach activator of the general formula: or mixtures thereof, wherein R 1 is an alkyl, aryl or alkaryl group containing about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene or alkarylene group containing about 1 to about 14 carbon atoms, R 5 is H or an alkyl, aryl or alkaryl group containing about 1 to about 10 carbon atoms, and L is a leaving group; b) benzoxazine type bleach activators of the general formula: wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, t and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COORß (where RT is H or an alkyl group) and carbonyl functions; c) activators of N-acyl caprolactam bleach of the formula: wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms; and d) mixtures of a), b) and c). Preferred bleach activators a) are those in which R1 is an alkyl group containing about 6 to about 12 carbon atoms, R2 contains about 1 to about 8 carbon atoms and R5 is H or methyl. Particularly preferred bleach activators are those of the above general formulas wherein R 1 is an alkyl group containing about 7 to about 10 carbon atoms and R 2 contains about 4 to about 5 carbon atoms. Bleach activators type b) which are preferred are those in which R2, R3 > R4 and R5 are H and R- * is a phenyl group. The acyl portions of said N-acyl caprolactam bleach activators type c) which are preferred have the formula R6-CO-, wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, preferably 6 to 12 carbon atoms. In highly preferred embodiments, R6 is a member selected from the group consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof. same.

Amido-Derby Bleach Activators The bleach activators of type a) used in the present invention are the amide-substituted compounds of the general formulas: • 10 O-OROR-1-C-N-R2-C-L, R .1- N- C ?? - R2- C ?? - LII R5 R5 or mixtures thereof, wherein R1, R2 and R5 are as defined above, and L may be essentially any suitable leaving group. The preferred bleach activators are those of the above general formula wherein R1, R2 and R5 is as defined for the peroxyacid and • L is selected from the group consisting of: R3 and I I - 0-CH = C-CH = CH2, - 0-CH = C-CH = CH2 R3 OR Y - 0 - C i = CHR4 and - N_S ?? _ C i H_R4 I II R3 O and mixtures thereof, wherein R1 is an alkyl, aryl or alkaryl group containing about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from 1 to about 8 carbon atoms, R4 is H or R3, and Y is selected from H or a solubilization group. The solubilization groups that are preferred are -SO3"M +, -CO2" M +, -SO4"M +, -N + (R3) ^" and O < N (R3) 3 and most preferably -SO3"M + and -CO2" M +, wherein R3 is an alkyl chain containing about 1 to about 4 carbon atoms, M is hydrogen or a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, hydrogen, ammonium or substituted ammonium cation, more sodium and potassium being preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain solubilization groups should be well dispersed in the bleaching solution to assist in their dissolution. The bleach activators that are preferred are those of the above general formula, wherein L is selected from the group consisting of: where R3 is as defined above and Y is -SO3"M + or -C? 2_M + where M is as defined above.Another important class of bleach activators, including those type b) and type c), provides organic percents as described herein by ring opening as a consequence of the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion.For example, this ring opening reaction in activators type c) includes the attack on the carbonyl of caprolactam ring by hydrogen peroxide or its anion Since the attack of an acyl caprolactam by hydrogen peroxide or its anion occurs preferentially in the exocyclic carbonyl, obtaining a significant fraction of ring opening may require a catalyst. of ring-opening bleach activators can be found in type b) activators, such as those described in US Patent 4,966,723, Hodge et al, gone on October 30, 1990.

Benzoxazine type bleach activators Said activating compounds described by Hodge include benzoxazine type activators having the formula: including the substituted benzoxazines type wherein Ri is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2, R 3, R 4 and R 5, can be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino functions , alkylamino, COORß (wherein R6 is H or an alkyl group) and carbonyl.

A preferred benzoxazine activator is: When the activators are used, the optimum surface bleaching performance is obtained with washing solutions in which the pH of said solution is between about 8.5 and 10.5, preferably between 9.5 and 10.5 to facilitate the perhydrolysis reaction. Said pH can be obtained with substances commonly known as pH regulating agents, which are optional components of the bleaching systems herein.

N-acyl caprolactam bleach activators The N-acyl caprolactam type c) bleach activators employed in the present invention have the formula: wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms. The caprolactam activators in which the R6 portion contains at least about 6, preferably from 6 to about 12 carbon atoms, provide hydrophobic bleaching which produces nucleophilic cleansing and body fouling as mentioned above. The caprolactam activators in which R6 comprises from 1 to about 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage spots. Hydrophobic and hydrophilic caprolactam mixtures can be used herein for mixed dirt removal benefits, typically at weight ratios of 1: 5 to 5: 1, preferably 1: 1. The highly preferred N-acyl caprolactams are selected from the group consisting of benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam and mixtures thereof. Methods for making N-acyl caprolactams are well known in the art. Contrary to the teachings of the patent of E.U.A. No. 4,545,784, the bleach activator is preferably not absorbed onto the peroxygen bleach compound. Doing this in the presence of other organic detersive ingredients could cause safety problems. Bleach activators type a), b) or c) will comprise at least about 0.1%, preferably about 0.1 to about 50%, most preferably about 1% to about 30%, more preferably about 3% to about 25% , by weight of the bleaching system or detergent composition.

The bleach activators derived from amido and caprolactam which are preferred herein may also be used in combination with safe hydrophobic activators for enzymes and rubber-based activators such as TAED, typically at weight ratios of activators derived from amido or caprolactam: TAED in the scale from 1: 5 to 5: 1, preferably around 1: 1.

Binder The extruded bleach activator-containing materials of the present invention comprise about 0.1% to about 40% by weight of one or more binders. Preferably, the binders include, but are not limited to, palmitic acid, detersive surfactants, polyethylene glycol, and fatty acids. In a highly preferred embodiment of the invention, the substantially cylindrically extruded material comprises, by weight of the extruded material, about 60% to about 95% of a bleach activator, about 0.1% to about 10% of palmitic acid, about 0.1% to about 10% of a detersive surfactant, about 0.1% to about 10% polyethylene glycol and about 0.1% to about 10% fatty acid. Without attempting to be limited by theory, it is believed that by selecting a particle size as described herein, the binding materials in the extruded materials gravitate or migrate towards the surface of the individual extruded material particles, thereby inhibiting excessive exposure. from the bleach activator to environmental conditions such as heat and humidity before use. As a consequence, the bleach activator in substantially cylindrically extruded materials does not degrade and remain stable, while at the same time carrying a particle size that closely approximates the size of the other detergent ingredients in the detergent composition. As mentioned, the added unanimity of particle size makes the detergent composition less susceptible to the segregation of the product in the detergent case before use. As is known, product segregation occurs during the handling, transportation and storage of the detergent composition before use; the vibration, agitation or other movements of the detergent product box cause the composition to segregate into particle size. The detergent composition of the present invention reduces this problem by means of a choice of choice of particle size and shape. In this regard, the substantially cylindrically extruded materials have an average extruded material length of about 500 microns to about 3500 microns, preferably about 700 microns to about 3000 microns and most preferably about 900 microns to about 2500 microns. Preferably, the average extruded material diameter is from about 450 microns to about 850 microns, preferably about 500 microns to about 800 microns, and most preferably about 550 microns to about 750 microns. The average extruded material diameter can be measured in a variety of ways, one of which is to measure a representative sample of the extruded materials using a microscope and determine the average by calculation. The average diameter can be determined similarly or by extrapolation of the hole diameter of the extrusion die. The relatively smaller particle size and cylindrical shape selected from the extruded bleach activator materials result in a more consistent supply of activator in the aqueous wash solution. Stated another way, the variation around the target level of bleach activator that will be supplied to the wash solution is unexpectedly reduced as a result of the use of the aforementioned substantially cylindrically extruded materials. Incidentally, this allows the detergent composition to supply the bleach activator at a more consistent level to achieve cleaning effects on the washed fabrics. Most government agencies require a very small variation around the bleach activator or other target levels of the cleaning agent to make the announced cleaning warranties legally public. In this way, the invention also provides a suitable and convenient method for cleaning fabrics that may be suitable for being advertised to the public. Preferably, the number of microbes present on said fabrics is reduced by at least about 50%, most preferably by at least about 90%, and more preferably by at least about 99.9%. This cleaning method is used in a ^^ interchangeable with disinfection, antibacterial, germ removal and germ removal methods that cause odor in accordance with the invention. In addition, the specific bleach activator and the peroxygen bleach composition in the detergent composition are preferably present at specific molar ratios of hydrogen peroxide to bleach activator. Said compositions provide extremely effective and efficient fabric surface bleaching which in this way removes stains and / or dirt from the fabrics. Said compositions are particularly effective for removing percutaneous dirt from fabrics. The soiled dirt is dirt that accumulates on the fabrics after numerous cycles of use and washing and, in this way, originate a white cloth that has a grayish tint. These soils tend to be a mixture of particulate and greasy materials. The removal of this type of dirt is sometimes referred to as "percussion fabric cleaning". The detergent compositions containing bleach of this invention provide such bleaching over a wide range of bleaching solution temperatures. Said bleaching is obtained in bleaching solutions in which the temperature of the solution is at least about 5 ° C. Without the bleach activator, said peroxygen bleach would not be effective and / or tical at temperatures of less than about 60 ° C. Much lower levels of activators are required • bleach in the invention, on a molar basis, to achieve the same level of surface bleaching performance as that obtained with similar bleach activators containing only about 2 to about 5 carbon atoms in the linear alkyl chain longer that extends from, and that includes the carbonyl carbon. Without being limited by theory, it is believed that this efficiency is achieved due to the fact that The bleach activators of the invention exhibit surfactant activity. This can be explained as follows. Generally the bleaching mechanism, and the surface bleaching mechanism in particular, are not completely understood. However, it is generally believed that the bleach activator undergoes the nucleophilic attack of a perhydroxide anion, which is generated from the hydrogen peroxide generated by the peroxygen bleach to form a percarboxylic acid. This reaction is commonly known as perhidróllsis. The percarboxylic acid then forms a dimer reactive with its anion which, in turn, generates an oxygen in singlet that is believed to be the active bleaching component. It is theorized that oxygen in singlet should be generated at or near the surface of the fabric to provide surface bleaching. Otherwise, singlet oxygen will provide bleaching, but not on the surface of the fabric. Said bleaching is known as bleaching in solution, that is, the bleaching of soils in the bleaching solution. To ensure that singlet oxygen is generated more efficiently on the surface of the fabric, it is essential that the longer linear alkyl chain extending from, and including the carbon of the percarboxylic acid carbonyl have from about 6 to about 10 atoms of carbon. Said percarboxylic acids are surfactants and, therefore, tend to be concentrated on the surface of the fabric. Percarboxylic acids containing fewer carbon atoms in said alkyl chain have similar oxide reduction potentials, but do not have the ability to concentrate on the surface of the fabric. Therefore, the bleach activators of the invention are extremely efficient because much lower levels, on a molar basis, of such bleach activators are required to obtain the same level of surface bleaching performance as with similar bleach activators than contain less carbon atoms in said alkyl chain; which are not part of the invention. An optimum surface bleaching performance is obtained with bleaching solutions in which the pH of said solution is between about 8.5 and 10.5, preferably between 9 and 10. It is preferred that said pH be more than 9, not only to optimize the bleaching performance of surfaces, but also to prevent the bleaching solution from having an undesirable odor. It has been observed that once the pH of the bleaching solution falls to less than 9, the bleaching solution has an undesirable odor. Said pH can be obtained with substances commonly known as pH regulating agents, which are optional components of the bleaching compositions herein.

Auxiliary detergent ingredients Preferably, the auxiliary detergent ingredients selected from the group consisting of enzymes, soil release agents, dispersing agents, optical brighteners, suds suppressors, fabric softeners, enzyme stabilizers, perfumes, colorants, fillers, inhibitors, the transfer of dyes and mixtures thereof are included in the compositions of the invention. The following are representative examples of the detergent surfactants useful in the present detergent composition. When present, the detersive surfactants comprise at least about 0.01% by weight, preferably about 0.1% to about 60%, most preferably about 0.1% to about 30% by weight, of a detersive surfactant selected from the group it consists of anionic, cationic, nonionic, zwitterionic and ampholytic surfactants, and mixtures thereof. The water-soluble salts of higher fatty acids, ie, "soaps", are anionic surfactants useful in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, preferably about 12 to about 18 carbon atoms. Soaps can be manufactured • by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, that is, sodium or potassium tallow and coconut soap. Additional anionic surfactants that are suitable for use herein include the water soluble salts, Preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight chain alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or ester group of sulfuric acid. The term "alkyl" includes the alkyl portion of acyl groups. Examples of this group of synthetic surfactants are sodium and potassium alkyl sulphates, especially those obtained • sulfating the higher alcohols (Cß-is carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkylbenzenesulfonates in which the alkyl group contains about 9 to about 15 carbon atoms, straight chain, for example, those of the type described in the patents of E.U.A. 2,220,099 and 2,477,383. Straight-chain linear alkylbenzene sulphonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as LAS of Cn-13, are especially valuable. Other anionic surfactants suitable for use in • the present are sodium alkyl glyceryl ether sulphonates, especially the 5 ethers of higher alcohols derived from tallow and coconut oil; sulphates and sulfonates of fatty acid monoglyceride of coconut oil; sodium or potassium salts of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkylethylene oxide ether sulfates - ^^ _ ^ '10 containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains about 10 to about 20 carbon atoms. In addition, suitable anionic surfactants include the water soluble salts of esters of alpha-sulfonated fatty acids which contain about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group; you go out - water-soluble 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffinsulfonates containing about 12 to 20 carbon atoms; and beta-alkoxy alkane sulfonates containing about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane portion. The preferred anionic surfactants that are preferred for the detergent composition are linear C 1 io-iß alkylbenzene sulphonate and C 10-18 alkyl sulfate-If desired, a low moisture content alkylsulfate paste (less than about 25% water). ) may be the only ingredient in the surfactant paste. Most preferred are C10-18 alkyl sulphates, linear and branched, and either primary, secondary or tertiary. A preferred embodiment of the present invention is that in which the surfactant paste comprises about 20% to about 40% of a mixture of linear sodium alkylbenzene sulphonate of C-? -13 and sodium alkyl sulfate of C1-6 in a weight ratio of approximately 2: 1 to 1: 2. Water-soluble nonionic surfactants also are useful in the present invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups f (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group that is condensed with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkylphenols, for example, the condensation products of alkylphenols having an alkyl group containing about 6 to 15 carbon atoms, either in a straight chain configuration or branched, with from about 3 to 12 moles of ethylene oxide per mole of alkylphenol. Includes the water-dispersible and water-soluble condensation products of aliphatic alcohols containing 8 to 22 carbon atoms, either in straight or branched chain configuration, with 3 to 12 moles of ethylene oxide per mole of alcohol . A further group of nonionic surfactants suitable for use herein are semi-polar nonionic surfactants including water-soluble amine oxides containing an alkyl portion of about 10 to 18 carbon atoms and two portions selected from the group of alkyl and hydroxyalkyl portions - from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of about 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to 3 carbon atoms.

Preferred nonionic surfactants have the formula R1 (OC2H) nOH, wherein R1 is a C10-C16 alkyl group or a C8-C12 alkylphenyl group, and n is from 3 to about 80. Products are particularly preferred. of condensation of C12-C15 alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, for example, C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol. Suitable and additional nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-1-deoxyglucitylcocoamide of N-methyl and N-1-deoxyglucityl-amide of N-methyl. The procedures for making polyhydroxy fatty acid amides are known and can be found in Wilson, patent of E.U.A. No. 2,965,576 and Schwartz, US patent. No. 2,703,798 whose descriptions are incorporated herein by reference. Ampholytic surfactants include aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic portion can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent it contains an anionic group of solubilization in water. Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms. Cationic surfactants may also be included in the present invention. Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methylsulfate and hydroxide. Tertiary amines may have characteristics similar to those of cationic surfactants at pH values in wash solution of less than about 8.5. A more complete description of these and other cationic surfactants useful herein can be found in the U.S.A. 4,228,044, issued October 14, 1980 and incorporated herein by reference. Cationic surfactants are commonly used in detergent compositions to provide fabric softening and / or antistatic benefits. Antistatic agents that provide some smoothing benefit and which are preferred herein are the quaternary ammonium salts described in the U.S.A. 3,936,537, Baskerville, Jr. et al., Issued February 3, 1976 and whose description is incorporated herein by reference.

In addition to a detersive surfactant, at least one suitable auxiliary detergent ingredient such as a builder is preferably included in the detergent composition. For example, the detergency builder may be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates, and mixtures thereof. Other suitable auxiliary detergency builders are described hereinafter. Preferred builders include aluminosilicate ion and sodium carbonate ion exchange materials. The aluminosilicate ion exchange materials useful herein as a builder preferably have both a high ion exchange capacity and a high exchange rate. Without attempting to be bound by theory, it is believed that said high rate and exchange capacity of calcium atoms are a function of several interrelated factors that are derived from the method by which the aluminosilicate ion exchange material is produced. In that regard, the aluminosilicate ion exchange materials useful herein are preferably produced according to Corkill et al, U.S. No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate ion exchange material is in the "sodium" form, since the potassium and hydrogen forms of the present aluminosilicate do not exhibit a rate and exchange capacity as high as that provided by the sodium form. In addition, the aluminosilicate ion exchange material is preferably in # Extremely dry shape to facilitate the production of agglomerates crisp detergents as described herein. The aluminosilicate ion exchange materials used herein preferably have particle size diameters that optimize their effectiveness as builders. The term "particle size diameter" as used herein represents the average particle size f 10 diameter of certain aluminosilicate ion exchange material determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope.

(SEM). The diameter of particle size that is preferred for the aluminosilicate is from about 0.1 microns to about 10 microns, most preferably around 0.5 microns to about 9 microns. More preferably, the particle size diameter is from about 1 to about 8 microns. Preferably, the aluminosilicate ion exchange material has the formula: Naz [(AI02) z (S1? 2) and] xH2O where z and (y) are integers of at least 6, the molar ratio of zay is from about 1 to about 5 and x is from about 10 to about 264. Most preferably, the aluminosilicate has the formula: Na12 [(AI02) i2 (Si? 2) i2] xH2O • wherein x is from about 20 to about 30, 5 preferably about 27. These preferred aluminosilicates are commercially available, for example, with the designations zeolite A, zeolite B and zeolite X. Alternatively, the natural or synthetic aluminosilicate ion exchange materials suitable for use herein may be made as is described in Krummel et al, US patent Do not • 10 3,985,669, the disclosure of which is incorporated herein by reference. The aluminosilicates used herein are further characterized by their ion exchange capacity, which is at least about 200 mg hardness equivalent of CaCO3 / gram, calculated on an anhydrous basis, and which is preferably on a scale of about 300 to 352 mg hardness equivalents of CaCO3 / gram. In addition, the present aluminosilicate ion exchange materials are further characterized by their calcium ion exchange rate which is about 34.2 mg / l Ca ++ / 2.78 liters / minute / -gmo / 2.78 liters, and most preferably on a scale of about 34.2 mg / l of Ca ++ / 2.78 liters / minute / -gmo / 2.78 liters to about 102.7 mg / l of Ca ++ / 2.78 liter / minute / -gram / 2.78 liters.

In order that the present invention may be more easily understood, reference is made to the following examples, which are designed to be illustrative only and not to limit the scope.

EXAMPLE 1 The following ingredients are added to a Littleford FM mixer: 81% sodium nonanoyloxybenzenesulfonate ("NOBS"); 6% palmitic acid, 3% linear sodium alkylbenzenesulfonate surfactant; 10 6% polyethylene glycol (MW = 4000); 2% C9 fatty acid and 3% pulverized aluminosilicate (Z zeollta) (3-5 microns). The mixture is stirred and fed to a laboratory extruder (Fuji Padel Co. Ltd., Dome Granulator, DG-L1) and extruded through dies having diameters of 350 microns, 500 microns, 700 microns and 890 microns, respectively. Each of the Four extruded materials of substantially cylindrical shape of different diameter are configured to an average length of 2000 microns. The following examples illustrate the use of the bleach activator with increased flowability comprising extruded materials of the present invention.

TABLE I % by weight s 2 3 4 5 linear of 11.0 11.0 11.0 1 1.0 C-I4- 10.4 10.4 10.4 10.4 C14-15 2.2 2.2 2.2 2.2 Polyacrylate (MW = 4500) 3.0 3.0 3.0 3.0 Polyethylene glycol (MW = 4000) 1.2 1.2 1.2 1.2 Sodium sulphate 10.5 10.5 10.5 10.5 Aluminosilicate 26.6 26.6 26.6 26.6 Sodium carbonate 21.0 21.0 21.0 21.0 Protease enzyme 0.4 0.4 0.4 0.4 Sodium perborate .2.6 2.6 2.6 2.6 monohydrate Enzyme lipase 0.2 0.2 0.2 0.2 • 10 Cellulase enzyme 0.1 0.1 0.1 0.1 Extruded materials of NOBS 6.0 - - - (diameter of 500 microns) Extruded materials of NOBS - 6.0 - - (diameter of 700 microns) Extruded materials of NOBS - - - 6.0 (diameter of 350 microns) Extruded materials of NOBS - - 6.0 - (diameter of 890 micras) Free water 15 2.0 2.0 2.0 2.0 Other minor ingredients 8 Z8 8 23. (bound water, perfume, etc) 100.0 100.0 100.0 100.0 1. C12-C13 alkyl ethoxylate (EO = 6.5) commercially available from Shell Oil Company.

Having thus described the invention in detail, it will be obvious to those skilled in the art that various changes can be made without departing from the scope of the invention, and that the invention should not be considered limited to what has been detailed in the description.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - An extruded bleach activator material having increased flow properties, which comprises: a) from 60% to 95% by weight, of a bleach activator having the formula: OR II R-C- in a donate R is an alkyl group containing from 5 to 18 carbon atoms, wherein the longest linear alkyl chain extending from, and including the carbonyl carbon, contains from 6 to 10 carbon atoms and L is a outgoing group, the conjugate acid of which has a pKa on the scale of 6 to 13; b) from 0.1% to 40% by weight, from one or more binder materials and c) from 0.5% by weight, from a flow capacity increaser; said extruded material has a substantially cylindrical shape and has an average extruded material length of 500 microns to 3500 microns and an average extruded material diameter of 450 microns to 850 microns.

2. A composition according to claim 1, further characterized in that said average extruded material length is 700 microns to 3000 microns and an average extruded material diameter is 500 microns to 800 microns.

3. - A composition according to claim 1, further characterized in that said average extruded material length is from 900 microns to 2,500 microns and an average extruded material diameter is from 550 microns to 750 microns.

4. - A composition according to claim 1, further characterized in that R is a linear alkyl chain containing

5 to 9 and L is selected from the group consisting of: R2 R2 I -CH = C-CH-CH2, - O-C = CHR3 wherein R2 is a linear alkyl chain containing from 2 to 6 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms and Y is -S03'M + or -C? 2'M +, wherein M it is an alkali metal, ammonium or substituted ammonium cation. 5. A composition according to claim 1, • further characterized in that said bleach activator has the formula: wherein R is a linear alkyl chain containing from 5 to 9, and M is sodium or potassium.

6. A composition according to claim 1, further characterized in that said bleach activator is sodium nonanoyloxybenzenesulfonate, sodium benzoyloxybenzenesulfonate and mixtures thereof.

7. A composition according to claim 1, 15 further characterized in that said extruded material is coated with 0.5% to 10% by weight of a flow enhancer selected from the group consisting of aluminosilicates, silicas, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, sodium carbonate, talc , corn starch and mixtures thereof.

8. A detergent or bleaching composition comprising: a) at least 0.1% by weight of a peroxygen bleach compound capable of producing hydrogen peroxide in an aqueous solution; b) an extruded material containing bleach activator comprising: i) from 60% to 95% by weight, of a bleach activator having the formula: || R-C- L 5 wherein R is an alkyl group containing from 5 to 18 carbon atoms, wherein the longer linear alkyl chain extending from, and including the carbonyl carbon, contains from 6 to 10 carbon atoms and L is a salient group, the conjugate acid of which has a pKa on the scale from 6 to 10 13; ii) from 0.1% to 40% by weight, from one or more binder materials and iii) from 0.5% to 10% by weight, from a flow capacity increaser; wherein said extruded bleach activator material is in the form of a substantially cylindrically extruded material having an average extruded material length of 500 microns to 3500 microns and an average extruded material diameter of 450 microns to 850 microns, and provided that said extruded material comprises sufficient bleach activator as f so that the ratio of bleach activator to peroxygen bleach compound is more than 1 and c) the remainder are vehicles and other auxiliary ingredients, said auxiliary detergent ingredients are selected from group 20 which consists of enzymes, dirt release agents, dispersing agents, optical brighteners, suds suppressors, fabric softeners, enzyme stabilizers, perfumes, colorants, fillers, dye transfer inhibitors and mixtures thereof.

9. - A composition according to claim 1, further characterized in that said extruded material comprises a binder material selected from the group consisting of palmitic acid, a detersive surfactant, polyethylene glycol, Cg fatty acid, polyacrylate and mixtures thereof.

10. A composition according to claim 13, which further comprises 0.01% to 60% by weight of a detersive surfactant selected from the group consisting of anionic, cationic, nonionic, ampholytic, zwitterionic surfactants and mixtures. thereof.