MXPA02001718A - Method for improving effervescency of a detergent product. - Google Patents

Abstract

A method of using an aluminosilicate ion exchange material for delivering effervescency in a detergent product, a method for forming a laundry detergent product exhibiting a combination of effervescency and building properties, a laundry detergent product, and a method for laundering soiled clothes are disclosed. In one aspect, a method of using an aluminosilicate ion exchange material for delivering effervescency in a detergent product includes the steps of providing an aluminosilicate ion exchange material having pores, drying the aluminosilicate ion exchange material, entrapping a gas into the pores of the aluminosilicate ion exchange material, adding the aluminosilicate ion exchange material having gas entrapped therein to a detergent composition and forming a detergent product exhibiting effervescency when the detergent product is placed in an aqueous medium.

Description

MfcTODO TO IMPROVE THE EFFERVESCENCE OF A DETERGENT PRODUCT FIELD OF THE INVENTION The present invention relates generally to a detergent product, and particularly to a particulate or non-particulate detergent containing an aluminosilicate ion exchange material serving non-particulate detergent. * only as a builder, but also as a means to improve the effervescence of the detergent product when the detergent product is placed in an aqueous medium.

BACKGROUND OF THE INVENTION Non-particulate detergents are an attractive alternative form for granulating or particular forms of detergents from the point of view of simplifying the dosing of such detergents for clothes washers or automatic dishwashers. Non-particulate detergents are usually supplied in the form of sticks, tablets or briquettes and not only prevent spillage of the detergent composition but also eliminate the need for the consumer to estimate the correct dosage of the detergent composition by washing.

There is a desire by consumers to have non-particulate detergent products, such as detergent tablets, which are effervescent when placed in an aqueous washing medium. Typically the effervescence is supplied by the incorporation of an acid and a carbon form, for example citric acid and sodium bicarbonate, in a detergent composition. However, this does not provide effective weight advantages to the detergent composition, such as improved builder properties. In this way there is a desire for a process to not only provide effervescence but also to provide a byproduct that is useful. Particularly, it has been desirable to have a process for improving both the effervescence and the builder properties. The present invention provides both of the aforementioned desirable attributes by providing a particulate or non-particulate detergent product that contains an aluminosilicate ion exchange material that serves not only as a detergency builder but also as a means to improve the effervescence of the detergent product when The product is placed in an aqueous medium. The invention also provides a process to achieve the aforementioned purposes. The process comprises taking an aluminosilicate ion exchange material, such as for example zeolite, and removing the moisture from the zeolite so that its pores are substantially empty. Then, carbon dioxide or some other suitable gas is trapped inside the pores. When Zeolite is thrown into an aqueous washing medium, the carbon dioxide comes out in bubbles, causing effervescence. The invention thus exploits the use of an aluminosilicate ion exchange material, such as zeolite, which is a useful builder and a useful effervescence delivery agent. These and other purposes, attributes and attendant advantages of the present invention will be apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.

SUMMARY OF THE INVENTION The present invention meets the aforementioned needs by describing a method of using an aluminosilicate ion exchange material to provide effervescence in a detergent product, a method for forming a laundry detergent product that exhibits a combination of effervescence and properties improvers, a detergent product for washing clothes, and a method for washing dirty clothes. In one aspect of the present invention, there is provided a method of using an aluminosilicate ion exchange material to provide effervescence in a detergent product comprising the steps of providing an aluminosilicate ion exchange material having pores. The method includes drying the aluminosilicate ion exchange material, trap a gas within the pores of the aluminosilicate ion exchange material, add the aluminosilicate ion exchange material having gas trapped therein to a detergent composition and form a detergent product that exhibits effervescence when the detergent product is placed in a medium aqueous. In another aspect of the present invention, there is provided a method for forming a laundry detergent product that exhibits a combination of effervescence and detergency builder properties, comprising the steps of providing an aluminosilicate ion exchange material having pores, trap a gas within the pores of the aluminosilicate ion exchange material, add the aluminosilicate ion exchange material having trapped gas within a laundry detergent composition, and form a laundry detergent product that exhibits effervescence and detergency-enhancing properties when the detergent product is placed in an aqueous medium. In yet another aspect of the present invention, a laundry detergent product is provided comprising a laundry detergent composition that includes a surfactant and a detergency builder, wherein the builder is adapted to supply a combination of properties for laundry. The detergency builder includes an aluminosilicate ion exchange material of the formula; Mm / n [(AIO2) m (SIO2) and] «xH2O where n is the valence of the cation M, xs the number of water molecules per unit cell, mey is the total number of tetrahedra per unit cell, and y / m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium. The aluminosilicate ion exchange material has pores, and the aluminosilicate ion exchange material has a gas trapped within the pores. The detergent product exhibits effervescence when the detergent product is placed in an aqueous medium. In still another aspect of the present invention, a method for washing laundry is presented. The method comprises the step of submerging - • Soiled clothes in an aqueous medium containing an effective amount of a laundry detergent product manufactured by a method as set forth above.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT In the preferred embodiment of the present invention, there is provided a method of using an ion exchange material to provide effervescence in a detergent product comprising the steps of providing an aluminosilicate ion exchange material having pores.

Aluminosilicate material The structural formula of an aluminosilicate material is based on the crystalline unit cell, the smallest unit of the structure represented by: Mm / n [(Al? 2) m (SIO2) y] »xH2O Where n is the valence of the cation M, x is the number of water molecules per unit cell, me and are the total number of tetrahedra per unit cell, and y / m is 1 to 100. More preferably, y / m is 1 to 5. The cation M can be elements of Group IA and Group HA, such as sodium, potassium, magnesium, and calcium. The preferred aluminosilicate materials are zeolites. The most preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP and mixtures thereof. The aluminosilicate ion exchange materials used in the present invention have both a high capacity and a high rate of calcium ion exchange. Without the purpose of being limited by theory, it is believed that such high rate and calcium ion exchange capacity are a function of several related factors that are derived from the method by which the aluminosilicate ion exchange material is produced. In this regard, the aluminosilicate ion exchange materials that are used in the present invention are preferably produced according to Corkill et al., Patent of the States No. 4,605,509 (Procter &Gamble), the disclosure of which is incorporated herein by reference. Preferably, the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the present aluminosilicate do not exhibit the high exchange rate and capacity as provided by the sodium form. Additionally, the The aluminosilicate ion exchange material is preferably in the excessively dry form to facilitate the production of crunchy detergent agglomerates as described in the present invention. The aluminosilicate ion exchange materials used in the present invention preferably have particle size diameters that optimize their effectiveness as detergent builders. The term "average particle size diameter" as used in the present invention represents the average diameter of the particle size of an aluminosilicate ion exchange material determined as determined by conventional analytical techniques, such as microscopic determination and electron microscopy. sweep (SEM). The preferred particle size diameter of aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. More preferably, the particle size diameter is from about 1 micron to about 8 microns. In a preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na? 2 [(AIO2)? 2 (SiO2)? 2] - xH2O, wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used in the present invention. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. In the preferred embodiment, the exchange material *. * ¡I .i n ii ?? * t &.li-iu, Má &smtAt? *, < * - > > . . ,. ...-. j.8 jaüanBefa »----- ionic aluminosilicate is zeolite and the zeolite acts as a builder. In the preferred embodiment, the aluminosilicate ion exchange material has pores having a pore diameter in the range of about 2 ANGSTROM to about 12 ANGSTROMS.

Additionally, and desirably, the aluminosilicate ion exchange material has a total porosity of at least 25%. In the preferred embodiment, the method also includes drying the aluminosilicate ion exchange material. This is achieved by heating the aluminosilicate ion exchange material to a temperature of at least 20 degrees C. In the preferred embodiment, the method also includes trapping a gas within the pores of the aluminosilicate ion exchange material. The preferred gas is carbon dioxide. The method also includes placing the aluminosilicate ion exchange material within a container capable of being pressurized and trapping the gas within the pores of the aluminosilicate ion exchange material at a gas pressure of at least 1 atmosphere. In the preferred embodiment, the method also includes adding the aluminosilicate ion exchange material having trapped gas within a detergent composition and forming a detergent product that exhibits effervescence when the detergent product is placed in an aqueous medium. The aluminosilicate ion exchange material having gas trapped therein is added to the detergent composition in an amount on a scale from about 1% to about 25%, by weight of the detergent composition.

The non-particulate detergent product Detergent tablets can be prepared by simply mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry. The detergent tablets that are provided can be manufactured in any size and shape. Previous to compaction, the detergent particles can be surface treated with a flow aid according to the present invention. The detergent tablets that are provided can be manufactured using any compaction process, such as tableting, briquetting, or extrusion, preferably tableting. Suitable equipment includes a normal single-press or rotary press (such as Courtoy®, Korch®, Manesty®, or Bonals®). As used in the present invention, the term "non-particulate detergent product" includes physical forms such as tablets, blocks, sticks and the like.

Coating for non-particulate detergent product In one embodiment, the tablets are coated with a coating for the purpose of providing mechanical strength and shock resistance and dehulling to the tablet core. The tablets are coated with a coating that is substantially insoluble in water so that the tablet does not absorb moisture, or absorbs moisture only at a very slow rate. The coating is strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and transport results in no more than very low levels of breakage or fracture. Additionally, the coating is preferably brittle so that the tablet breaks when subjected to a stronger mechanical shock. Additionally, it is advantageous if the coating material dissolves under alkaline conditions, or is easily emulsified by surfactants. i * This avoids the deposition of undissolved particles or lumps of coating material in laundry load. This can be important when the coating material is totally insoluble (for example less than 1 g / l) in water. As defined in the present invention, "substantially insoluble" means that it has a very low solubility in water. This should be understood to mean that it has a solubility in water at 25 ° C of less than 1 g / l, preferably less than 5 g / l, and more preferably less than 1 g / l. The solubility in water is measured following the test protocol of ASTM E1148-87 entitled "Standard Test Method for Measurements of Aqueous Solubility". Suitable coating materials are fatty acids, adipic acid, and C 8 -C 13 dicarboxylic acids, fatty alcohols, diols, esters and ethers. Preferred fatty acids are those that have a length of A, a carbon chain of C12 to C22 and more preferably of C18 to C22. Preferred dicarboxylic acids are adipic acid (C6), suberic acid (C8), accelaic acid (C9), sebasic acid (C10), undecanoic acid (C11), dodecanoic acid (C12) and tridecanoic acid (C13). Preferred fatty alcohols are those having a carbon chain length of C12 to C22 and more preferably of C14 to C18. Preferred diols are 1,2-octadecanodiol and 1,2-hexadecanediol. Preferred esters are diethylene glycol mono hexadecylether, diethylene glycol mono octadecylether, diethylene glycol mono tetradecylether, phenylether, ethyl naphthyl ether, 2-methoxynaphthalene, beta-naphthyl methyl ether, and mono-octadecyl ether glycerol. Other preferred coating materials include dimethyl-2, -propanol, 2-hexadecanol, 2-octadecanone, 2-hecatecanone, 2,15-hexadecanedione, and 2-hydroxybenzyl alcohol. The coating is a hydrophilic material having a melting temperature preferably of 40 ° C to 180 ° C. In the preferred embodiment, the coating can be applied in many ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material. In a), the coating material is applied at a temperature above its melting temperature, and solidifies on the tablet. In b), the coating is applied as a solution, the solvent is dried to leave a coherent coating. The substantially insoluble material can be applied to the tablet by, for example, spraying or immersion. Normally when the molten material is sprinkled on the tablet, it is It will solidify quickly to form a coherent coating. When the tablets are immersed in the molten material and then removed, the rapid cooling again causes rapid solidification of the coating material. Clearly substantially insoluble materials having a melting temperature below 40 ° C are not sufficiently solid at room temperature and it has been found that these materials having a melting temperature above 180 ° C are not practical to use.

Preferably, the materials are melted on the scale of 60 ° C to 160 ° C, more preferably 70 ° C to 120 ° C. By "melting temperature" it is desired to mean the temperature at which the material when heated slowly in, for example, a capillary tube becomes a transparent liquid. For most purposes, the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the weight of the tablet.

Surfactants Anionic Surfactant Preferred anionic surfactants include Cn-dß alkylbenzenesulfonates (LAS) and C10-C20 primary alkyl, branched-chain and random alkylsulfates, the secondary alkyl sulfates (2.3) of Cι-Ciß of the formula CH3 (CH2)? (CHOSO3"M +) CH3 and CH3 (CH2) and (CHOSO3" M +) CH2CH3 where xy (y +1) are integers of at least about 7, preferably at least about 9, and M is a cation which is solubilized in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkylalkoxy sulphates of C-? or-C18 ("AEXS", especially EO 1-7 ethoxy sulfates), carboxylates of C10-alkoxy alkoxy C18 (especially the EO 1-5 ethoxycarboxylates), the glycerol ethers of C10-C18, the alkyl polyglycosides of C? 0-C18 and their corresponding sulfated polyglycosides, and esters of C12-C18 alpha-sulphonated fatty acids. Generally speaking, anionic surfactants useful in the present invention are described in U.S. Patent No. 4,285,841, to Barrat et al., Issued August 25, 1981, and in U.S. Patent No. 3,919,678, Laughiin et al., Issued December 30, 1975. Useful anionic surfactants include water-soluble salts, particularly the alkali metal, ammonium and alkylammonium salts (eg, monoethanolammonium or triethanolammonium), of reaction products organic sulfurics having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms, and an ester group of sulfonic acid or sulfuric acid. (The alkyl portion of aryl groups is included in the term "alkyl"). Examples of this group of synthetic surfactants are alkyl sulfates, especially those which are obtained by the sulphation of higher alcohols (carbon atoms of Cß-C-tß) such as those produced by the reduction of tallow glycerides or coconut oil.

Other anionic surfactants in the present invention are the water-soluble salts of ethylene oxide alkylphenol ether sulphates containing from about 1 to about 4 ethylene oxide units, per molecule and from about 8 to about 12 carbon atoms in the alkyl group . Other anionic surfactants useful in the present invention include the water soluble salts of esters of sulfonated fatty acids containing from about 6 to 20 carbon atoms in - the group of fatty acids and of about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkanesulfonic 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 portion; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and β-alkyloxy-alkanat-sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane portion. Other anionic surfactants useful in the present invention are the polyethoxylated alkyl sulfates of the formula: RO (C2H4O) xSO3-M + wherein R is an alkyl chain having from about 10 to about 22 saturated or unsaturated carbon atoms, M is a cation that makes the compound soluble in water, especially a cation of tl¡á ... * t alkali metal, ammonium or substituted ammonium, and x on average is from about 1 to 15. Other preferred alkyl sulfate surfactants are the non-ethoxylated primary and secondary C12-15 alkyl sulfates. Under washing conditions in cold water, ie, less than about 65 ° F (18.3 ° C), it is preferred that it be a mixture of ethoxylated and non-ethoxylated alkyl sulfates. Examples of fatty acids include capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.

Nonionic Surfactant Conventional nonionic and amphoteric surfactants include ethoxylates of C ?2-C ?β (AE) alkyl including the so-called high narrow alkyl ethoxylates and C6-C12 alkylphenol alkoxylates (especially ethoxylates and ethoxy). mixed propoxy). The N-alkyl polyhydroxylamides of Cι-C-iß fatty acids can also be used. Typical examples include C12-C18 N-methylglucamides. See WO 9,206,154. Other surfactants which are derived from sugar include the N-alkoxy-polyhydroxy fatty acid amides such as N-alkoxy-polyhydric oxides of fatty acids such as N- (3-methoxypropyl) glucamide of C-IO-C-IS. If you want a lot of foam, you can use branched chain C10-C16 soaps. Examples of Nonionic surfactants are described in U.S. Patent No. 4,285,841, to Barrat et al., issued August 25, 1981. Examples of surfactants also include ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OC2H4). nOH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms, and alkylphenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and The average value of n is from about 5 to about 15. These surfactants are described in more detail in U.S. Patent No. 4,284,532, to Leikhim et al., issued August 18, 1981. Other surfactants include alcohols ethoxylates having an average degree of ethoxylation of about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are detailed in the recognized texts including polyhydroxyamides of fatty acids, alkyl glucosides, polyalkyl glucosides, betaines and sulfobetaines (sultaines) of C12-C18. Examples include C12-C18 N-methylglucamides: see WO 9,206,154. Other surfactants that are derived from sugar include N-alkoxy-polyhydroxy fatty acid amides such as N- (3-methoxypropyl) -glucamide of C-io-C-iß. The N-propyl- to the C12-C18 N-hexyl glucamides can be used for low foaming.

? ..? I ?? t. ** ssAAÍ? SStáyS?, *. j ^ - * A Cationic surfactants A class of useful cationic surfactants are the monoalkylammonium quaternary surfactants although any cationic surfactants useful in detergent compositions are suitable for use in the present invention. . The cationic surfactants that can be used in the present invention include quaternary ammonium surfactants of the formula: wherein R-i and R2 are individually selected from the group consisting of C? -C4 alkyl > C 1 -C 4 hydroxyalkyl, benzyl, and - (C 2 H 4 O) H H where x have a value from about 2 to about 5; x is an anion; and (1) R3 and R4 each is a Ce-Cu alkyl or (2) R3 is a C6-C-8 alkyl, and R4 is selected from the group consisting of C1-C10 alkyl, C1-6 hydroxyalkyl C10, benzyl, and - (C2H4O) HH where x have a value of 2 to 5. Other useful quaternary ammonium surfactants are the chloride, bromide and methyl sulfate salts. Examples of mono-long chain quaternary alkylammonium surfactants are those wherein R-i, R 2, and R 4 are each methyl and R 3 is a C 1 -C 7 alkyl; or in R3 is C8-C? -alkyl and R-i, R2 and R4 are selected from methyl and hydroxyalkyl portions. Lauryl trimethylammonium chloride, myristyl trimethylammonium chloride, palmityl trimethylammonium chloride, coconut trimethylammonium chloride, coconut trimethylammonium methylsulfate, coconut dimethyl-monohydroxy-ethylammonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate, stearyl dimethyl-monohydroxy-ethylammonium chloride, stearyl methylsulfate dimethyl-monohydroxy-ethylammonium, di-C?-C?-4-dimethylammonium chloride, and mixtures of these are also desirable. ADOGEN 412 ™, a chloride of commercially available lauryl trimethylammonium from Witco, is also desirable. Other desirable surfactants are lauryl trimethylammonium chloride and myristyl trimethylammonium chloride. Another group of suitable cationic surfactants are the quaternary alkanolamide surfactants of the formula: OR R1-C-N- (CH2) n-Y- (CH2) n-X R2 wherein R1 may be C-IO-C-IS alkyl or substituted or unsubstituted phenyl; R 2 may be C 1 -C 4 alkyl, H or (EO) y, wherein y is from about 1 to about 5; And it is O or -N (R) (R4); R3 can be H, C4alkyl or (EO) alkyl and > wherein y is from about 1 to about 5; each n independently is selected from about 1 to about 6, preferably from about 2 to about 4; X is hydroxyl or -N (R5) (R6) (R7), wherein R5, R6, R7 independently it is selected from C 1 -C 4 alkyl, H or (EO) and, wherein and is from about 1 to about 5. i $ ása.áL í Á,, já¿ j. - a *, ka,, ",. , *,? . ,. **. ^. . "Anafes j * Al. I A * amine oxide surfactants The compositions in the present invention also contain amine oxide surfactants of the formula: R1 (EO)? (PO) and (BO) zN (O) ( CH2R ') 2-qH2? (i) In general, it can be seen that structure (I) provides a long chain portion R1 (EO) x (PO) and (BO) z and two short chain portions CH R '. R 'is preferably selected from hydrogen, methyl and -CH2OH. In general, R1 is a primary or branched hydrocarbyl portion which may be saturated or unsaturated, preferably, R1 is a primary alkyl portion. When x + y + z = 0, R1 is a hydrocarbyl portion having a chain length of about 8 to about 18. When x + y + z is different from 0, R1 may be a little longer, having a length of chain on the scale of C12-Q24. The general formula also comprises amine oxides wherein x + y + z = 0, R1 = C8-C-? 8, R1 is H and q is 0-2, preferably 2. These amine oxides are illustrated by C12 alkyldimethylamine oxide. -14, hexadecyldimethylamine oxide, octadecylamine oxide and its hydrates, especially the dihydrates as described in U.S. Patent Nos. 5,075,501 and 5,071,594, which are incorporated herein by reference. The invention also comprises amine oxides wherein x + y + z is from about 1 to about 10. R1 is a primary alkyl group containing 8 to about 24 carbon atoms, preferably from about 12 to about 16 carbon atoms; in these modalities y + z preferably is 0 and x preferably is from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, for example, by reaction of alkyl ethoxy sulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide. Desirable amine oxides in the present invention are solids at room temperature, more preferably have melting temperatures in the range of 30 ° C to 90 ° C. Amine oxides suitable for use in the present invention are manufactured commercially by many suppliers, including Akzo Chemie, Ethyl Corp., and Procter & Gamble. See the McCutcheon compilation and the Kirk-Othmer review article for alternative amine oxide manufacturers. Other commercially available amine oxides which are available are ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 dihydrate from Ethyl Corp. Other embodiments include dodecyldimethylamine oxide dihydrate, hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris oxide (ethyleneoxy) ) -dimethylamine, tetradecyldimethylamine oxide dihydrate, and mixtures thereof. While in certain embodiments R 'is H, there is some freedom in relation to having R' slightly greater than H. Alternative modes include where R 'is CH2OH, such an oxide as hexadecylbis (2-hydroxyethyl) amine, l ** £. *. - * - * - * * * SÍ? UÁ »sedobis (2-hydroxyethyl) amine, stearylbis (2-hydroxyethyl) amine oxide and oleylbis (2-hydroxyethylamine) oxide.

Enzymes Enzymes can be included in the formulations in the present invention for a wide variety of purposes for washing fabrics, including, for example, removal of protein-based, carbohydrate-based, or triglyceride-based stains and to restore fabrics. The enzymes to be incorporated include proteases, amylases, lipases, and cellulases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any origin, such as plant, animal, bacterial, fungal and yeast origin. However, their selection is governed by several factors such as pH activity and / or optimal stability, thermostability, stability versus active detergents, detergency builders, and so on. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions in the present invention will typically comprise from about 0.001% to about 5%, preferably from 0.01% to 1% by weight of a commercial enzyme preparation. Protease enzymes are usually present at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of the composition. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, which has a maximum activity throughout the pH range of 8-12, developed and marketed by Novo Industries A / S under the trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 1, 243,782 to Novo. Suitable proteolytic enzymes for removing protein-based stains that are commercially available include those marketed under the trademarks ALCALASE and SAVINASE by Novo Industries A / S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands) . Other proteases include protease A (see European Patent Application 130,756, published January 9, 1985), and Protease b (see European Patent Application Serial No. 87303761.8, filed April 28, 1987 and the application for European Patent 130,756, by Bott, published on January 9, 1985). Amylases include, for example, α-amylases which are described in British Patent Specification No. 1, 296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. The cellulase that can be used in the present invention includes both bacterial and fungal cellulase. Preferably, they will have an optimum pH of between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Barbesgoard et al., Issued March 6, 1984, which describes fungal cellulase produced from Humicola insolens and the Humicola DSM 1800 strain or a fungus that produces cellulase 212 which belongs the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricola Solander). Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME (Novo) is especially useful. Lipase enzymes suitable for use in detergents include those enzymes produced by microorganisms of the group of Pseudomonas, such as Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. See also lipases in Japanese Patent Application 53,20487, open to the public for public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipasa P "Amano ", henceforth referred to as" P-hand ". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Cromobacter viscosum lipases from Biochemical Corp., U.S.A., and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme which is derived from Humicola lanuginosa and commercially available from Novo (see also EP 341, 947) is a preferred lipase for use in the present invention.

A wide variety of enzymatic materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further described in U.S. Patent 4,101, 457, to Place et al., July 18, 1978, and in U.S. Patent 4,507,219, to Hughes, issued March 26, 1985. of enzymes useful in liquid detergent formulations, and their incorporation into such formulations, are described in U.S. Patent 4,261, 868, to Hota et al., April 14, 1981. Enzymes for use in detergents can be stabilized by means of various techniques. Enzyme stabilization techniques are described and exemplified in U.S. Patent 3,600,319 of August 17, 1971, Gedge et al., And European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published on October 29, 1986, by Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570. The enzymes that are employed in the present invention can be stabilized by the presence of water-soluble calcium and / or magnesium ion sources in the finished compositions that provide such enzymes in the enzymes, calcium is generally a little more effective than magnesium ions and preferred in the present invention only if a type of cation is used.) Additional stability can be provided by the presence of other stabilizers than are described in the art, especially borate species. See Severson, United States Patent 4,537,706. Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and even more preferably from about 8 to about 12 millimoles, of calcium ion per liter of finished composition. This may vary a bit, depending on the amount of enzyme present and its response to calcium or magnesium ions. The level of calcium or magnesium ions should be selected so that there is always some minimum level, available for the enzyme, after allowing the formation of complexes with enhancers, fatty acids, etc., in the composition. Any water soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in enzyme suspension and formulation water. In solid detergent compositions the formulation may include a sufficient amount of a source of water soluble calcium to provide such amounts in the laundry solution. Alternatively, the natural hardness of the water may be sufficient.

It should be understood that the above-mentioned levels of calcium and / or magnesium ions are sufficient to provide enzymatic stability. More calcium and / or magnesium ions may be added to the compositions to provide an additional measure of fat removal performance. Accordingly, as a general proposition the compositions in the present invention will typically comprise from about 0.05% to about 2% by weight of a water soluble source of calcium or magnesium ions, or both. Of course, the * amount may vary with the amount and type of enzyme used in the composition. The compositions in the present invention may optionally contain, but preferably, different additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers are used at levels in the compositions of from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4% by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). The acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (eg, ortho-, meta- and sodium pyrophosphate, and sodium pentaborate) are suitable. Suitable boric acids (eg, phenylboronic acid, butanoboronic acid, and p-bromophenylboronic acid) can also be used in place of boric acid.

AJ * iklsA * .t, -? t, *. l * A * *, and polymeric dirt release agents Any polymeric soil release agent known to those skilled in the art can be employed in the compositions or processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to render the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments hydrophilic, to deposit on the hydrophobic fibers and remain adhered to them until the termination of the hydrophobic fibers. the washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This may allow stains that occur subsequent to treatment with the soil release agent to be easier to clean in subsequent washing procedures. Examples of soil release agents useful in the present invention include U.S. Patent 4,721,580, issued January 26, 1998, to Gosselink; U.S. Patent 4,000,093, issued December 28, 1976, to Nicol et al .; European Patent Application 0 219 048, published April 22, 1987, by Kud, et al .; U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink; U.S. Patent 4,968,451, issued November 6, 1990, to J.J. Scheibel. Commercially available soil release agents include the SOKALAN type material, for example, SOKALAN HP-22, available from BASF (Germany). See also United States Patent 3,959,230, to Hays, issued May 25, Í¡? * * * AA.Í. ^ *** 1976, and US Pat. No. 3,893,929, to Basadur, issued July 8, 1975. Examples of this polymer include commercially available material ZELCON 5126 (ex DuPont) and MILEASE T (from ICI). Other suitable polymeric soil release agents include the teretalate polyesters of U.S. Patent 4,771,730, issued December 8, 1987, to Gosselink et al., The anionic oligomeric esters blocked at the ends of the United States 4,721, 580, issued January 26, 1988, to Gosselink, and • the oligomeric block polyester compounds of United States Patent 4,702,857, issued October 27, 1987, to Gosselink. Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989, to Maldonado et al. In case of being used, the dirt release agents will generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions in the present invention, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.

Guelantes agents The detergent compositions in the present invention can also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consists of aminocarboxylates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below in the present invention. Without the desire to be limited by theory, it is believed that the advantages of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash solutions by the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglicines, the alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. The aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions, and include ethylene diamine tetrakis (methylene phosphonates) as DEQUES. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions in the present compositions. See United States Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent to be used in the present invention is ethylene diaminedisuccinate ("EDDS"), especially the [S, S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. If used, these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions in the present invention. More preferably, if used, the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.

Clay Soil Removal / Anti-Deposition Agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and antideposition properties. Liquid detergent compositions typically contain from about 0.01% to about 5%. The most preferred soil release and anti-deposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antideposition agents are the cationic compounds described in the European Patent Application 111, 965, to Oh and Gosselink, published on June 27, 1984. Other agents ÍÁU?.? AÍ.A ± *. ^ - i ~ -,. £ & amp; & amp; Removal / anti-deposition of clay soils that can be used include the ethoxylated amine polymers described in European Patent Application 11,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides which are disclosed in U.S. Patent Application 4,548,744, Connor, issued October 22, 1985. Another type of preferred anti-deposition agent includes the carboxymethyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can be advantageously used at levels of from about 0.1% to about 7% by weight, in the compositions in the present invention, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polycarboxylates and polymeric polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymeric dispersing agents increase the overall performance of the detergency builder, when used in combination with other builders, when used in combination with other builders ( including lower molecular weight polycarboxylates) by inhibiting the The growth of crystals, the peptization of the dirt releaser is particles, and anti-redeposition. Polycarboxylate polymeric materials can be prepared by the polymerization or copolymerization of suitable unsaturated monomers, preferably in their acidic form unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, Itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates in the present invention of monomeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that such segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful in the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form preferably ranges from about 2,000 to 10,000., more preferably from about 4,000 to 7,000, and more preferably still from about 4,000 to 5,000. The water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described in, for example Diehl, US Pat. No. 3,308,067, issued March 7, 1967. Acrylic / maleic-based copolymers can also be used as a preferred component of the agent dispersant / antideposition. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic anhydride. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, more preferably still from about 7,000 to 65,000. The ratio of maleate acrylate segments in such copolymers generally ranges from about 30: 1 to about 1: 1, more preferably from about 10: 1 to about 2: 1. Water-soluble salts of such acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 066 915, published on December 15, 1982, as well as EP 193,360, published on September 3, 1986, which it also describes such polymers comprising hydroxypropylacrylate. Still other dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, acrylic / maleic / vinyl alcohol terpolymer 45/45/10.

Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit an operation of dispersing agent as well as act as an agent for elimination / anti-deposition of clay soil. Typical molecular weights vary for these purposes 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. Polyaspartate - and polyglutamate dispersing agents can also be used, especially in connection with zeolite improvers. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Brightener Any optical brightener or other brightening or brightening agents that are known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, in the detergent compositions in the present invention. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene derivatives, pyrazoline, coumarin, carboxylic acid, metincyanines, dibenzothiophene-5,5-dioxide, azoles , 5- and 6- membered heterocyclic ring, and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon, on December 13, 1988. These brighteners include the PHORWHITE series of Verana brighteners. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2- (4-styrylphenyl) -2H-naphtho [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4.4'-bis (styryl) bisphenols; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-amino-coumarin; 1, 2- (bis- (benzimidazol-2-yl) ethylene; 1,3-diphenyl-frazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naph- [1,2-d] ] oxazole, and 2- (stilbene-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent 3,646,015, issued on February 29, 1972, to Hamilton. in the present invention the anionic brighteners.

Foam suppressors Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. Foam suppressors may be of particular importance in so-called "high concentration cleaning processes" as described in Í ^? ^, = ^^ j ^ I & i patents of the United States 4,489,455 and 4,489,574, and in European-style front-loading washing machines. A wide variety of materials can be used as foam suppressants, and foam agents are well known to those skilled in the art. See, for example, Kirk Othmer, Encvclopedia of Chemical Technology, Third Edition, volume 7, pages 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressant of particular interest comprises the monocarboxylic acid and the soluble salts thereof. See United States Patent 2,954,347, issued September 27, 1960, to Wayne St. John. The monocarboxylic fatty acids and salts thereof which are used as suds suppressors typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as the sodium, potassium, and lithium salts, and the ammonium and alkanolammonium salts. The detergent compositions in the present invention may also contain non-surfactant foam suppressing agents. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (for example, fatty acid triglycerides), fatty acid esters of monovalent alcohols, ketones (for example, C-? 8-C4o aliphatic stearone, etc.) Other foam inhibiting agents include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminoclortriazines which are formed as cyanuric chloride products with two or three moles of primary or secondary amine containing 1 to 24. carbon atoms, propylene oxide, and monostearyl phosphates such as alcohol phosphate ester and phosphates and dicalkali metal phosphate esters (eg, K, Na, and Li) monostearyl hydrocarbons such as paraffin and haloparaffin can be use in liquid form.The liquid hydrocarbons will be liquid at ambient temperature and atmospheric pressure, and will have a critical flow temperature in the scale of approximately -40 ° C and about 50 ° C, and a minimum boiling temperature of less than about 110 ° C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably having a melting temperature of less than about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressants for detergent compositions. Hydrocarbon foam suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981, to Gandolfo et al. Thus, the hydrocarbons include aliphatic, alicyclic, aromatic, and saturated or unsaturated heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in the present invention in this discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant foam suppressants comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and polyorganosiloxane combinations of silica particles wherein the polyorganosiloxane is chemically absorbed or fused to the silica. Silicone foam suppressing agents are well known in the art and are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981, to Gandolfo et al., And the application for a European patent. do not. 89307851.9, published February 7, 1990, by Starch, M.S. Other silicone suds suppressors are described in U.S. Patent 3,455,839, which relates to compositions and processes for removing foam from aqueous solutions by 15 means of incorporating therein small amounts of polydimethylsiloxane fluids. Silica and silanated silica mixtures are described, for example, in the German patent application DOS 2,124,526. In the preferred silicone foam suppressor used in In the present invention, the solvent for a continuous phase is made from certain polyethylene glycols or copolymers of polyethylene polypropylene glycols or mixtures thereof (preferred), or polypropylene glycol. The main silicone foam suppressor is branched / crosslinked and preferably non-linear. g ^ | «wC jM ^ Í» ¡j | For any of the detergent compositions to be used in automatic laundry washing machines, the foam should not be formed in the amount that overflows from the washing machine. The foam suppressors, when used, are preferably present in a "foam suppressant amount". By "foam suppressant amount" is meant the composition formulator can select the amount of this foam controlling agent that will sufficiently control the foam to result in a low foaming laundry detergent for use in automatic washing machines. of clothes. The compositions in the present invention will generally comprise from 0% to about 5%, of foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts within, will typically be present in amounts up to about 5% by weight, of the detergent composition. Silicone foam suppressors are typically used in amounts of up to about 2.0% by weight, of the detergent composition, although higher amounts may be used. This upper limit is of a practical nature, due mainly to considerations of keeping costs minimized and the effectiveness of lower quantities to effectively control the foam. Preferably from about 0.01% to about 1%, more preferably from about 0.25% to about 0.5% is used. As used in the present invention, these weight percent values include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can be used. Monostearyl phosphate foam suppressants are generally used in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. Alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Dye transfer inhibiting agents The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the washing process. Usually, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. Preferred polyamide N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. If used, these agents will typically comprise from about 0.01% to about 10%, by weight of the composition, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2%. More specifically, the preferred polyamine N-oxide polymers for use in the present invention contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group or the N-O group is attached is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: wherein R-i, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and nitrogen the N-O group can be fixed to be part of any of the groups before Ífj.? U,?,?.?. Átííít¡ ... mentioned. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably a pKa < 7, more preferably a pKa < 6. Any polymer backbones can be used provided that the amine oxide polymer that is formed is water soluble and has suitable transfer inhibiting properties are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures of these. These polymers include random or block copolymers where one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by means of an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably from 1,000 to 500,000; more preferably still from 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions in the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50,000 and an amine to N-oxide ratio of amine. approximately 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (which are mentioned as a class as "PVPVI") are also preferred for use in the present invention. Preferably, the PVPVI has an average molecular weight scale of 5,000 to 1,000,000, more preferably 5,000 to 200,000, and more preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, et al., Chemical Analvsis, Vol. 113, "Modern Methods of Polymer Characterization", the disclosure of which is incorporated in the present invention as reference). PVPVI copolymers typically have a molar ratio of N-vinylmidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, more preferably from 0.6: 1 to 0.4: 1. These copolymers can be linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVPs are known to those with experience in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, which are incorporated herein by reference. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 10,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP based on ppm delivered to the wash solutions is from about 2: 1 to about 50: 1 and more preferably from about 3: 1 to about 10: 1.

Optical brighteners The detergent compositions in the present invention may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide an inhibitory action of dye transfer. If used, the compositions in the present invention will preferably comprise from about 0.01% to 1%, by weight of such optical brighteners.

Bleaching compounds - bleaching agents and whitening activators The detergent compositions in the present invention may optionally contain bleaching agents or bleaching compositions containing a bleaching people and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric washing. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching composition comprising the bleaching agent plus the bleach activator. The bleaching agents that are used in the present invention can be any of the bleaching agents useful for detergent compositions in fabric cleaning, hard surface cleaning or other cleaning purposes that are known or will be known. These include bleaches. Perborate whiteners, for example, sodium perborate (e.g., mono- or tetrahydrate) can be used in the present invention. Another category of bleaching agent can be used without restriction comprising percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include hexahydrate of magnesium monoperoxyphthalate, the magnesium salt of metachloroperbenzoic acid, 4-nonyllamino-4-oxyperoxybutyric acid and diperoxydecandioic acid. Such bleaching agents are described in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, to Burns et al., Issued June 3, 1985, European patent application 0,133,354, Banks et al., published February 20, 1985, and United States patent 4,412,934, Chungt et al., issued November 1, 1983. Very preferred bleaching agents also include acid 6- Nonylamino-6-oxoperoxycaproic, as described in U.S. Patent 4,634,551, issued January 9, 1987, to Burns et al. Peroxygen bleaching agents can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and the equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach can also be used (for example, OXONE, manufactured commercially by DuPont). Mixtures of bleaching agents can also be used. Peroxygen bleaches, perborates, percarbonates, etc. they are preferably combined with bleach activators, which lead to in situ production in aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are described in U.S. Patent 4,915,854, issued April 10, 1990, to Mao et al., And U.S. Patent 4,412,934. Activators of nonanoyloxybenzene sulfonate (NOBS), 3,5,5 sulfonate, -tri-methylhexanoyloxy-benzene (ISONOBS) and tetraacetylethylenediamine (TAED) are typical, and mixtures of these can also be used. See also U.S. Patent 4,634,551, for other typical bleaches and activators useful in the present invention. Very preferred amido derivative bleach activators are those of the formulas: R1N (R5) C (O) R2C (O) L or R1C (O) N (R5) R2C (O) L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable residual group. A residual group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack in the bleach activator by the perhydrolysis anion. A preferred residual group is phenyl sulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamidocaproyl) -oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxy-benzenesulfonate, and mixtures thereof as described in the US Pat. United States 4,634,551, which is incorporated herein by reference. Another class of bleach activators comprises the benzoxazine activators described by Hodge et al, in U.S. Patent 4,966,723, issued October 30, 1990, which is incorporated herein by reference. Still another class of preferred bleach activators include acyl lactam activators, especially acyl caprolactams and acyl valero lactams. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl calerolactam, octanoyl valerolactam, decanoyl valerolactam, valerolactam of undecenoyl, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which is incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactams, adsorbed to sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used in the present invention. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulphonated phthalocyanines of zinc and / or aluminum. See U.S. Patent 4,033,718, issued July 5, 1977, to Holcombe et al. If used, the detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonated zinc phthalocyanine. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts which are described in the US Pat.

United 5,246,621; U.S. Patent 5,244,594; U.S. Patent 5,194,416; U.S. Patent 5,114,606; and European Patent Application Publication Nos. 549,271 A1, 549,272A1, 544,440A2, and 544,490A1. As a practical matter, and not by way of limitation, the compositions and processes in the present invention can be adjusted to provide about at least one part per ten million of the active species of bleach catalyst in the aqueous wash solution, and preferably will provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the wash solution.

Antistatic Agents The present compositions may also comprise antistatic agents as illustrated in U.S. Patent 4,861, 502. Preferred examples of antistatic agents include ionic alkylamine-anionic surfactant pairs, such as cumene distearylamine sulphonate ion pairs. If present, antistatic agents are present in an amount of from about 0.5% to about 20%, preferably from about 1% to about 10%, more preferably from about 1% to about 5%, by weight of the detergent composition. t JHÉfclu «fc« .. - a? ** t * ,.

Abbreviations used in the Examples In detergent compositions, the identification of Abbreviated components has the following meanings: Sodium linear alkyl benzene sulfonate C-11-13 TAS Sodium alkyl sulphate sodium CxyAS Sodium alkyl sulfate of C-? X - C-? And C46SAS Sodium alkyl sulphate secondary (2,3) CxyEzS Sodium alkyl sulphate of linear C? X-C-? And branched condensed with z moles of ethylene oxide CxyEz Primary alcohol of C? X-C-? And predominantly linear condensed with an average of z moles of ethylene oxide. QAS R2 N + (CH3) 2 (C2H4? 4H) with R2 = C12-C14 QAS 1 R2 N + (CH3) 2 (C2H4? 4H) with R2 = C8-Ci? APA Amidopropyldimethylamine of C8-C? Or Sodium linear alkyl carboxylate soap derived from an 80/20 blend of tallow and coconut fatty acids STS Sodium toluene sulfonate CFAA Alkyl N-methylglucamide from C16-C? 8 coconut TFAA Alkyl N- C? 2-C? 8 Methylglucamide TPKFA Blocked Whole C12-C-14 Blocked Fatty Acids STPP Sodium Tripolyphosphate Anhydride TSPP Tetrasodium Pyrophosphate Zeolite A Hydrated sodium aluminosilicate of the formula Na? 2 (AIO2Si? 2) i2 '27H2O having a Main particle size on the scale from 0.1 to 10 micrometers (weight expressed on anhydrous basis) NaSKS-6 Layered crystalline silicate of the formula d-Na2Si2O5 Citric acid Anhydrous citrate acid Borate sodium borate Carbonate Sodium carbonate anhydride with a size of particle between 200μm and 900μm Bicarbonate Sodium bicarbonate anhydride with a particle size distribution between 400 μm and 1200 μm l -A-AAA Silicate Amorphous sodium silicate (ratio Si02: Na2O = 2.0: 1) Sulfate Sodium sulphate anhydride Sulfate Mg Magnesium sulphate anhydride Citrate trisodium citrate activity dihydrate 86.4% with a particle size distribution between 425 μm and 850 μm MA / AA Copolymer of 1: 4 maleic / acrylic acid with average molecular weight of about 70,000 MA / AA (1) Copolymer of 4: 6 maleic / acrylic acid with average molecular weight of about 10,000 AA Polyacrylate polymer sodium with average molecular weight of 4,500 CMC Sodium Carboxymethylcellulose Cellulose ether Cellulose methylether with a degree of polymerization of 650 available from Shin Etsu Q Chemicals Protease Proteolytic enzyme having 3.3% by weight of active enzyme, marketed under the trademark Savinase by Novo Industries A / S Protease I Proteolytic enzyme having 4% on that of active enzyme, as described in WO 95/10591, trade alized by Genencor Int. Inc. Alcalase Proteolytic enzyme that has 5, 3% by weight of active enzyme, marketed by NOVO 5 Industries A / S Cellulase Cellulite enzyme having 0.23% by weight of active enzyme, marketed by Novo Industries A / S under the trademark Carezyme Amylase Amylolytic Enzyme having 1. , 6% by weight of active enzyme, marketed under the trademark Termamyl 120T by Novo Industries A / S Lipase Lipolytic enzyme having 2.0% by weight of 0 active enzyme, marketed under the trademark Lipolase by NOVO Industries A / S Lipase (1) Lipolytic enzyme having 2.0% by weight of active enzyme, marketed under the trademark Lipolase by Ultra by NOVO Industries A / S ílj.? J *?.? í? *? tt. Ha? "* - Endolase Enzyme of endogluconease having 1.5% by weight of active enzyme, marketed by NOVO Industries A / S PB4 Sodium perborate tetrahydrate of the nominal formula NaBO2 3H2O H2H2 PB1 Sodium perborate anhydride bleach of the nominal formula NaB02 H2H2 Percarbonate Sodium percarbonate of the nominal formula 2Na2CO3 3H2O2 NOBS Sulfonate of nonanoyloxybenzene in the form of the sodium salt. NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate TEAD Tetraacetylethylenediamine DTPA Diethylenetriaminepentaacetic acid DTPMP Diethylenetriaminepenta) methylenephosphonate), marketed by Monsanto under the trademark Dequest 2060 EDDS Ethylenediamine-N, N'-disuccinic acid Brighloate Ftalocyanine Zinc sulfonated encapsulated photoactivated (1 ) in dextrin-soluble polymer Ftalocyanine Brightener in Photoactivated Sulfonated Aluminum (2) encapsulated in Dextrin-soluble polymer Brightener 1 4,4 '. bis (2-sulfistyryl) biphenyl disodium Brightener 2 4,4 '. bis (4-anilino-6-morpholino-1, 3,5-triazine-2-yl (amino) -stilbene-2,2'-disulfonate disodium HEDP 1,1-Hydroxyethane-diphosphonic acid PEGx Polyethylene glycol, with a molecular weight x (typically 4000) PEO Polyethylene oxide, with a molecular weight of 50,000 TEPAE Ethoxylated tetraethylene pentaamine PVI Polyvinylimidazole, with an average molecular weight of 20,000 PVP Polyvinylpyrrolidone polymer, with an average molecular weight of 60,000 PVNO Polymer N-oxide polyvinylpyridine, with an average molecular weight of 50,000 PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole with an average molecular weight of 20,000 itt? * Í.?. ít..Ai?. * ÍA? Í? & S * U. ÜI ^ Í ^. . i¡AAJUi QEA b¡s (C2H5?) (C2H4?) n) (CH3) -N + -C6H12-N + - (CH3) bis (C2H5?) - (C2H4?) n 'where n = from 20 to 30 SRP 1 Anionically blocked poly esters SRP 2 Poly (1, 2-propylene terephthalate) di-ethoxylated PEI short block polymer Polyethylenimine with an average molecular weight of 1800 and an average degree of ethoxylation of 7 ethyleneoxy residues per nitrogen. Foam Polydimethylsiloxane Silicone Foam Controller with siloxane-oxyalkylene copolymer as the dispersing agent with a ratio of the aforesaid foam controller to the dispersing agent with a ratio of the aforementioned foam controller to the aforementioned dispersing agent of 10: 1 to 100: 1. Mixing agent of monostyrene latex based on water opacity, marketed by BASF Aktiengesellschaft under the trademark Lytron 621 Wax Paraffin Wax In the following examples all the levels are mentioned as weight percentage of the composition: EXAMPLE 1 In this example 400 grams of activated X zeolite is placed in a high pressure container. The container was evacuated. The vessel was then charged with CO2 at a pressure of 10 barg. This pressure was maintained for 10 minutes. The pressure was then released and the zeolite loaded with C02 removed and stored in a glass jar. After the addition of 10 grams of the CO2-laden zeolite to a bottle of water there is a rapid release of CO2 to produce bubbles, and the evolution of significant localized heat.

EXAMPLE 2 The following laundry detergent compositions A to F are prepared and 10% by weight of material prepared as in Example 1 is added to each of the formulations. By adding water to each of the resulting formulations, bubbles according to the invention were observed. .r.a & sac MMiiiiaÉ j í Accordingly, in thus describing 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 to be limited to what is is described in the specification.

Claims (16)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for using an aluminosilicate ion exchange material to provide effervescence in a detergent product, which is characterized by the steps of: providing an ion exchange material of aluminosilicate having pores; drying said aluminosilicate ion exchange material; entrapping a gas within said pores of said aluminosilicate ion exchange material; adding said aluminosilicate ion exchange material having trapped gas within a detergent composition; and forming a detergent product that exhibits effervescence when said detergent product is placed in an aqueous medium.

2. The method according to claim 1, further characterized in that the aluminosilicate ion exchange material has a formula, Mm / n [(Al? 2) m (SIO2) and] * xH2O, where n is the valence of the cation M, x is the number of water molecules per unit cell, me and are the total number of tetrahedra per unit cell, and y / m is 1 to 100, and where M is selected from the group consisting of sodium, potassium, magnesium , and calcium.

3. The method according to claim 1, further characterized in that said aluminosilicate ion exchange material is zeolite. * it «...., ta í¿a» «Bt,».

4. - The method according to any of claims 1-3, further characterized in that said aforementioned aluminosilicate ion exchange material acts as a detergent builder in the detergent product. 5.- The method according to any one of claims 1-4, further characterized in that said aluminosilicate ion exchange material has pores having a pore diameter on a scale of about 2 ANGSTROM to about 12 ANGSTROM. 6. The method according to any of claims 1-5, further characterized in that said aluminosilicate ion exchange material has a total porosity of at least 25%. 7. The method according to any of claims 1-6, further characterized in that said gas is carbon dioxide. 8. The method according to any of claims 1-7, further characterized in that it includes heating said aluminosilicate ion exchange material at a temperature of * 20 minus 20 degrees C trapping said gas within said said pores »Aluminosilicate ion exchange material. 9. The method according to any of claims 1-8, further characterized in that it includes placing said It is a material of ionic exchange of aluminosilicate within a container that can be pressurized and trapped said gas within said pores of said aluminosilicate ion exchange material at a gas pressure. of at least 1 atmosphere. 10. The method according to any of claims 1-9, further characterized in that said aluminosilicate ion exchange material having gas trapped therein is added to said detergent composition in an amount in the range of 1% to 25%. in tr * weight of said detergent composition. 1Q 11. The method according to any of claims 1-19, further characterized in that said detergent composition is free of citric acid and bicarbonates. 12. A laundry detergent product, characterized by: a laundry detergent composition that includes a surfactant and a detergency builder; wherein said builder is adapted to provide a combination of builder properties and effervescence properties to the aforementioned laundry detergent composition; said detergency builder includes an ion exchange material of * 20 aluminosilicate of the formula, Mm / n [(Al? 2) m (Sl? 2) and] »xH2 ?, where n is the valence of the cation M, x is the number of water molecules per unit cell, mey are the total number of tetrahedra per unit cell, and y / m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium, said aluminosilicate ion exchange material has pores, and aluminosilicate ion exchange material has a gas trapped within said pores; and said detergent product exhibits effervescence when said detergent product is placed in an aqueous medium. 13.- The laundry detergent product in compliance - with any of claims 1-12, further characterized in that it includes zeolite having carbon dioxide gas trapped therein, said ~ * zeolite is present in said detergent composition for laundry in 1§ an amount on a scale of 1% to 25% by weight. 14. The laundry detergent product according to any of claims 1-13, further characterized in that said detergent laundry product is in the form of particles. 15.- The laundry detergent product in compliance 15 with any of claims 1-14, further characterized in that said laundry detergent product is not in the form of particles. 16. The laundry detergent product according to any of claims 1-15, further characterized in that it accompanies auxiliary detergent ingredients that are selected from the group that * 20 consists of enzymes, soil release agents, dispersing agents, optical brighteners, suds suppressors, fabric softeners, enzyme stabilizers, perfumes, colorants, fillers, dye transfer inhibitors, and mixtures thereof. ÍÚ ..? Í? <