MXPA96004477A - Additives for detergents in liquids structure - Google Patents

Abstract

The present invention relates to structured liquid detergents consisting of porous hydrophobic materials, porous hydrophobic materials having an active detergent compound absorbed therein, said porous material being subsequently coated with hydrophobic material.

Description

ADDITIVES FOR DETERGENTS IN STRUCTURED LIQUIDS FIELD OF THE INVENTION The present invention relates to detergent additives in structured liquid detergent compositions. Most particularly, the present invention relates to liquid detergents are structured consisting of hydrophobic porous materials, porous hydrophobic materials having an active detergent absorbed therein, said hydrophobic material being subsequently coated with hydrophobic material.

BACKGROUND OF THE INVENTION Detergents + is structured liquids have been extensively described in the art, for the purpose of suspending solid particles that are insoluble in the detergent matrix. In detergen is unstructured liquids, the presence of such ingredients generally leads to sedimentation or phase separation and therefore makes those detergents unacceptable from the point of view of the consumer. In response to this need, detergent formulators have designed structured liquid detergents, which have the ability to suspend solids this way. Such structured liquids can be "internally structured", whereby the structure is formed by primary ingredients, and / or these can be structured by secondary additives that can be added to a composition as "external structuring". Both forms of structuring are well known in the art. The external structuring is normally used for the purpose of suspending the solid particles and / or drops of nonionic surfactant. The internal structuring is normally used to suspend particles and / or to endow properties such as the flow properties and / or cloudy appearance preferred by the consumer. Examples of internally structured liquid and externally structured liquid detergent compositions are given in FP-A-14 295. However, it is also recognized that the relative capacity of the structured liquid to be effective in suspended solid particles depends, among other things, from The nature and concentration of the suspended particle. In their storage, said suspended particles have a tendency to settle, resulting in liquid detergents that are less effective, have a poor appearance and which exhibit physical stability characteristics. Examples of said suspended particles are detergency builders and speckle particles. Surprisingly, it has now been discovered that hydrophobic porous articles having an active detergent absorbed therein, said hydrophobic material being coated with hydrophobic material, are very useful for incorporation in structured liquids. In addition, it has been discovered that the hydrophobic material of the present invention can easily be incorporated into the liquid detergent matrix without the need for an emulsifier or excessive mechanical stirring. These hydrophobic particles can serve as a couple protect active detergent compounds by isolating and protecting said compounds from their hostile environment under storage but releasing said compounds during the washing conditions. Examples of such compounds include perfumes, enzymes, blotters and catalysts. L5 Accordingly, this finding makes it possible to formulate stable detergent liquid compositions containing protected active detergent compositions. In addition, he has discovered that porous hydrophobic materials are more efficient in protecting compounds detergent assets when they are incorporated into structured liquids. EP 593 512 describes the use of porous hydrophobic materials suitable for the protection of active detergent compounds.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to structured liquid detergents comprising porous hydrophobic materials, porous hydrophobic materials having an active detergent absorbed therein, said hydrophobic material being subsequently covered with hydrophobic material.

DETAILED DESCRIPTION OF THE INVENTION Structured liquid detergent composition The compositions according to the present invention are structured liquid detergent compositions which can be structured either internally or externally. Structured liquid detergent compositions are described in EP 414 549, EP 295 021 and EP 346 994. Structured liquid detergent compositions suitable for the present invention include detergent compositions formulated with ammonium surfactants and polyhydroxy fatty acid amide hydrophilic surfactant. as described in EP 572 723. The preferred polyhydric hydroxy fatty acid amide surfactant component for use in the present invention comprises compounds of the formula is ruc ur l: O Rl (I) R2 C - N Z wherein: R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyl et, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C 4 alkyl, most preferably Ci or C 2 alkyl, and still most preferably Ci alkyl (e.g. methyl); and R2 is a C5-C31 hydrocarbyl, preferably alkyl- or C7-C19 alkemlsulfate straight chain, most preferably alkyl- or straight chain C9-C17 quenil sulfato, even more preferably C11-C17 alkylsulfate or alkyl straight chain, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a straight hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably, the side or propox bundle) thereof. Z ref ri emen e will be derived from a reducing sugar in a reductive reaction; most preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As starting materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as well as the individual sugars listed above. It should be understood that these corn syrups could produce a mixture of sugar components for Z. Z will preferably be selected from the group consisting of -CH2 - (CHOH) n -CH2 -OH, -CH (CH20H) - (CH0H) nl-CH20H, -CH2- (CHOH) 2 -CHOR ') -CHOH) -CH-20H, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R' is H or a monosaccharide cyclic or aliphatic. More preferred are glycityls wherein n is, particularly -CH2- (CHOH) A -CH2-OH. In the formula (I), R 1 may be, for example, N-ethyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxy ?the. R2-C0-N < it can be - for example coca ida, esterarnida, oleainida, lauramida, mipsta ida, caprica ida, palmitarnida, seboamida, etc. Can Z be 1-deox? lucit, 2-deoxyribonucleotide, 1-deoxymalinyl, 1-deoxyribonucleotide, 1-deoxy-galactyl, l-deoxyrnanite, 1-deoxyrinoterotide. oi ilo, etc. Other structured positions of preferred liquid detergents suitable for the present invention include detergent compositions externally bonded with clay. Such structured compositions are very suitable for serving as liquid detergent compositions softening through washing. The clay is present in an amount of at least 0.05%, preferably from 1% to 10%, most preferably from 2% to 5% by weight of the detergent composition. The preferred clays are of the smectite type. I smectite clays are widely used as fabric softening ingredients in detergent compositions. Many of these clays have a cation exchange capacity of at least 50 meq / lOOg. Smectite clays can be described as three-layer expandable materials, consisting of alurninosilicates or magnesium silicates. There are two distinct classes of clays of the srnectite type; in the first, aluminum oxide is present in the silicate crystal lattice, and in the second class of smectites, magnesium oxide is present in the silicate lattice. The general formulas of these esrnectites are Al2 (S? 20s) and 3I20s) (0H) 2, for the clay of the aluminum-magnesium oxide type respectively. The scale of the water of hydration can vary with the procedure to which the clay has been subjected. In addition, the substitution of atoms by iron and magnesium can occur in the crystal lattice of the smectites, while metal cations such as Na +, Ca2 +, as well as H + can be copresent in the water of hydration to provide electrical neutrality. It is customary to distinguish between clays based on a predominant cation or exclusively absorbed. For example, a sodium clay is one in which the absromoid cation is predominantly sodium. Such absorbed cations can be involved in equilibrium exchange reactions with the cations present in aqueous solutions. In such equilibrium reactions, an equivalent weight of cation solution replaces a sodium equivalent, for example, and it is customary to measure the cation exchange capacity of the clay in terms of milliequivalents per 100 g of clay (meq / 1.00g. ). The cation exchange capacity of clays can be measured in many ways, including electrodialysis, by exchange with ammonium ion followed by titration, or by a procedure with methylene blue, all as set forth in Grirnshaw, The Chenistry and Physics of Clays, Interscience Publishers, Inc. pp. 264-265 (1971). The cation exchange capacity of a clay mineral refers to those factors such as those of the expandable properties of the clay, the clay loading, which in turn is determined at least in part by the network structure crystalline, and the like. The ion exchange capacity of clays varies widely in the scale of up to 2 rneq / 100 g for kaolinites, up to 150 meq / 100 g, and higher, for certain clays of the rnontrnorillonite variety. Illite clays have an ion exchange capacity somewhere in the lower portion of the range, approx. 26 meq / 100 g. for an average illite clay. It has been determined that the illite and kaolinite clays, with their relatively low ion exchange capacities, are not useful in instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils. However, smectites, such as nontronite, have an ion exchange capacity of approximately 50 meq / 100 g; Saponite, which has an ion exchange capacity greater than 70 rneq / 100 g, has proven to be useful fabric softeners. The smectite clays commonly used for this purpose herein are all commercially available. Such clays include, for example, rnontmorillomta, volconscolite, nontromta, hecto ita, saponite, saucomta and vermiculite. The clays mentioned here are available under trade names such as "fooler clay" (clay found in a relatively thin vein over the main bentonite or rnontrnorillonite veins in the Colmas Negras) and several trade names such as Thixogel # 1 ( also, "Thixo-Dell") and Gelwhit GP of Georgia Kaolin Co. Elizabeth, New Jersey; Volclay BC and Volclay # 325, from American Colloid Co., Skokie, TLlinois; Black Hills Bentonite BH ^ 50, from International? Merals and Chemicals, and Veegurn Pro and Veegurn F, from R.T. Vanderbilt It should be recognized that such minerals of the srnectite group obtained under the above registered and commercial names may comprise mixtures of the various distinct mineral entities Such mineral mixtures of ectites are suitable for use in the present. a are preferred for use in the present.Something suitable are hectopts of natural or synthetic origin, in the form of particles having the general formula Til pMg3-? L? ") S -yMeyO? o (OFfe-zFi H-í »**) (x + y) M" + n where ein is Al, Fe, or B; or y = o; Mn + is a monovalent (n = l) or divalent metal ion (n = 2), selected, for example from Na, K, Mg, Ca, Sr. In the previous formula, the value of (x + y) is the layer loading of hectopta clay. Such hecto ita clays are preferably selected on the basis of their layer loading properties, for example, at least 50% is on the scale of 0.23 to 0.31. More appropriate are the naturally occurring hectic clays that have a layer charge distribution such that at least 65% is on the scale of 0.23 to 0.31. The appropriate hectorite clays in the present composition should preferably be sodium clays, for a better smoothing activity. Sodium clays are either naturally found or are naturally occurring calcium clays that have been treated to be converted into sodium clays. If calcium clays are used in the present compositions, a sodium salt can be added to the compositions in order to convert the calcium clay to sodium clay. Preferably, that salt is sodium carbonate, typically added at levels up to 5% of the total amount of arc 1 lr. Examples of hectorite clays suitable for the present compositions include Bentone EtJ and Mecaloid, from NL Chernicals, N.3. , USA, and hectoritas of Industrial Mineral Ventures. Clay combinations can be used to improve the stability of the structured liquid. An example of such a combination includes clays of montrnorillonite and hectorite (for example, organoclays). Normally, the clays are processed in the liquid detergent composition by means of high pressure homogenization.

POROUS HYDROPHOBIC MATERIAL The porous hydrophobic material suitable for the present invention can be any hydrophobic-porous material. The average pore diameter of the porous hydrophobic material must be larger than the size of the active detergent compound to be absorbed in the porous material. The distributions in volumes and sizes of the pore can be measured by the recognized mercury intrusion porosimetry technique. For example, if the active detergent compound is an enzyme, an average pore diameter of the hydrophobic material of 500 angstroms or more is preferred.

The preferred hydrophobic material that can later be used is silica. The average pore diameter of The silica normally used is 1000 8, while the absorbed enzyme molecules have diameters within the range of 50 to 150 ft. The silica particles can be made hydrophobic by treating them with dialkisilane groups and / or t-butylane groups, either directly on the silica or by means of silicone resin. Silica is also characterized by a high absorption value. Absorption can be expressed as a number of Dibutylphthalate (DBF). Porous silica suitable for the present invention is available under the trade name of Sipernat (R) from Degussa. The porous hydrophobic material is coated with a hydrophobic coating material. The level of the hydrophobic coating material must be such that the appropriate coating of porous hydrophobic material to be filled with all types of additives is ensured. The hydrophobic coating material is preferably a liquid hydrophobic polymer. Said polymer can be an organopolysiloxane oil, for example, a polyalkyl siloxane, especially a polydirnethylsiloxane. Especially preferred is hydrophobic silicone oil, which has been proposed for use as an antiperspirant in liquid detergents. Alternatively, the hydrophobic material may be a high molecular weight hydrocarbon or petroleum gel, wax or more water soluble but water permeable materials such as caproJctones. The hydrophobic coating material provides a protective coating for the active filled porous hydrophobic materials herein. The pore lining of the hydrophobic material isolates the active compound from detergents from environments that cause the degradation of the active compounds. The active compounds are maintained in their stabilized material environment without interacting with other potentially harmful ingredients of the detergent or the environment is protected from the detergent active compound itself. Said hydrophobic materials when they have been incorporated into structured liquids have been shown to be extremely useful in protecting and providing an active detergent in terms of storage stability and stability. Furthermore, the improved stability of said hydrophobic porous materials in structured liquid detergents allows to increase the amount of active detergent to be protected which, in turn, improves the detent performance. In addition, the hydrophobic material of the present invention can be easily incorporated into the liquid detergent matrix without the need for an emulsifier or excessive mechanical action.

Normally, the porous hydrophobic material of the present invention will be simply added in the continuous process of the liquid detergent. In the case that the liquid detergent is structured by the clay, then the porous hydrophobic material is preferably added after the process step of high pressure ogenization. Active detergent-active compounds suitable for the present invention include enzymes, bleaches, bleach activators, bleach catalysts, perfumes, photoactivators, dyes, brighteners / fluorescers, through washing sanitizers.fabric softening or conditioning agents, hydrolyzable surfactants, polymers and other active detergent compounds which are water soluble or water dispersible and mixtures thereof. A preferred class of an active detergent compound is a detergency enzyme. Examples of suitable enzymes for the present invention are enzymes that are active in the removal of dirt or stains such as protease, lipase, amylase, carboxylase, cellulase, oxidase, peroxidase or mixtures thereof. The enzyme may be present in the form of an enzymatic solution, for example in a mono-, di- or lower water-iscible polyhydric alcohol with propylene glycol, and optionally containing enzyme stabilizers as is known in the art. Enzyme stabilizers that may be present include lower alcohols, for example glycerol, ono- or lower carboxylic acid and their salts, especially formates and oxidates, borates and calcium salts. The preferred enzymes are cellulases. Said cellulases include bacterial or fungal cellulases. Preferably, they will have an optimum pH of between 5 and 9.5. Appropriate cellulases are described in the U.S. Patent. 4,435,307, Barbesgoard et al., Issued March 5, 1984, incorporated herein by reference, which describes fungal cellulases produced from Hurnicola insolens. Appropriate cellulases are also described in GB-A-2,075,028; GB-A-.095,275 and DE-OS-2,247,832. Examples of said cellulases are cellulases produced by a strain of Hu icola insulens (Hurnicola grísea var. Ther oidea), particularly the strain of Hurnicola DSM 1800, and cellulases produced by a fungus of the bacillus N or a cellulase 212- producing a fungus belonging to the genus of the Qerononoas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricle Solander). Other suitable cellulases are cellulases originating from the Hurnicola Insulens, which have a molecular weight of almost SOKDa, an isoelectric point of 5.5 and containing 415 amino acids. Said cellulase is described in co-pending European Patent Application No. 93200811.3, issued March 19, 1993. Particularly suitable cellulases are cellulases that have color care benefits. Examples of said cellulases are cellulases described in European Patent Application No. 91202879.2, issued November 6, 1991 Carezyme (Novo). If the active compound of detergents is an enzyme, the ratio of the silicone oil to the silica filled with enzyme must be at least 1.5: 1. Suitable active detergent compounds can also be represented by bleaches, binder activators and bleach catalysts. Suitable inorganic bleaches include perborates and percarbonates. Suitable organic bleaches include peroxidation known in the art. Suitable bleach precursors are peracetic acid bleach precursors such as tetr-aacetylethylenediamine, triacetin, and acetyltrirnethyl citrate. Other active detergent compounds suitable for the present invention are fabric softening or conditioning agents, polymers, fluorescers, colorants, photoactivators through washing sanitizers such as phenoxyethanol, and other detergent-active compounds that are soluble or dispersible in detergents. water and that tend to be unstable during storage, and mixtures thereof. In case the detergent active does not spontaneously wet the surfaces of the hydrophobic material, the active detergent compound is mixed with a surfactant agent before being absorbed into the porous material.

The surfactants suitable for the present invention must be compatible with the detergent active compound. The surfactant is to be used for example, in the case where the detergent active is an enzyme, a surfactant used is preferably a non-limeo surfactant. A wide range of surfactants can be used. A class of nonionic surfactants that can be used in the present invention are condensates of ethylene oxide with a hydrophobic portion to provide a surfactant having an average hydrophilic-lipophilic (EHL) balance in the range of 8 to 17, preferably from .5 to 13.5, most preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety can be aliphatic or aromatic in nature and the length of the poxy-oxyethylene group that is fused with any particular hapthobic group can easily be adjusted to produce a water-soluble compound having the desired degree of equilibrium between the elements hidrofi lieos and hydrophobic. Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing from 3 to 8 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols of C14-C15 containing from 3 to 5 moles of ethylene oxide per mole of alcohol and the primary alcohols of C? 2-C? "containing from 3 to 5 moles of ethylene oxide per mole of alcohol. A highly preferred class of nonionic surfactant to be used includes polyhydroxy fatty acid amide surfactants of the formula R2 - C - N - Z, 0 ?? R i, 1 wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxyl, 2-hydroxyl or a mixture thereof, R2 is hydrocarbyl of O5-31, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight chain of Cn-15 alkyl or alkene such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as gLucose, fructose, maltose, lactose, a reductive arm nation reaction. Ammonium or cationic surfactants are less suitable for use. However, if the absorbed detergent active is not affected by these surfactants, these can alternatively be used. The porous hydrophobic material filled with active ingredient may contain additional ingredients, which may be pre-mixed with the surfactant before being absorbed by the porous hydrophobic material.

The porous materials according to the present invention can include other active detergent compounds such as polymers, perfumes, brighteners, bleaches, softeners and other conventional additional ingredients, such as pH regulators, electrolytes, etc., as long as they are chemically compatible with the active solution of the surfactant.

INGREDIENTS OF DETERGENTS In another embodiment of the present invention a liquid detergent composition is provided comprising the dye transfer inhibitor composition mixed with the detergent ingredients. A broad scale of surfactants can be used in the detergent composition of the present invention. A typical listing of ammonium, nonionic, anfoLitic and zwittep ornea classes, and species of these surfactants, is given in the U.S. patent. 3,664,961 issued to Norps on May 23, 1972. Preferred ammonium surfactants include the alkylsulfide surfactants which herein are water soluble salts or acids of the ROSO3M formula wherein R is preferably a C? Or C24 hydrocarbon radical. , preferably an alkyl or hydroxyalkyl having an alkyl component of C? or C C? and very preferably an alkyl or hydroxyalkyl of C? 2-C?, and M is H or a cation, eg, a metal cation of alkali (for example; sodium, potassium, lithium), or substituted ammonium or ammonium (for example, methyl, dirnethyl and trirnetium cations) and quaternary ammonium cations such as tetramethyl and dimethylpyridinium cations and quaternary ammonium cations derived from alkanemams such as ethylamine , diethylane, tpetilarnin and mixtures thereof, and the like). Typically, C ?2-Ci6 alkyl chains are preferred for lower wash temperatures (eg, below about 50 ° C) and Ciß-Cis alkyl chains are preferred for higher wash temperatures ( for example, above about 50 ° W). Highly preferred ammonium surfactants include alkoxylated alkylsulfate surfactants which are present in the water soluble salts or salts of the formula RO (A) S03M wherein R is a C10-C24 lower alkyl or hydroxyalkyl group, having an alkyl component of C? or-C24 preferably an alkyl or hydroxyalkyl of C? 2-C2o, most preferably an alkyl or hydroxyalkyl of C? 2-C? s ^ A is an ethoxy or μropoxy unit, rn is greater than 0, usually between 0.5 and about 6, and preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulphates are contemplated herein. Specific examples of substituted ammonium cations include metU-, dimethyl-, trirnethylammonium cations and quaternary ammonium cations such as tetra ethyl ammonium cations and dimethyl piperdinium and those alkylated derivatives such as ethylamine, diethylamine, triethylamine and mixtures thereof, and similar. Exemplary surfactants are C 2 ~ Ci 8 -polyethoxylated alkylsulfate (1.0) (C 2 -C ?βE (1.0) M), C? 2-C? Polyethoxylated C alqu 2-C? Alqu alqu alqu (((((((((((((((((((((2.25) (C? 2 -Ci8E (2.25) M), polyethoxylated C? 2- Ciß alkyl sulfate (3.0) (C? 2 -Ci8F (3.0) M), and C? 2-Ci8 polyethoxylated alkylsulfate (4.0) (C? 2) -C? ßE (.0) M), where M is conveniently selected from sodium and potassium. Other ammonium surfactants which may be used are surface-active agents of ester sulfate to the chylian including linear esters of carboxylic acids of C 2 -C 2 (for example, fatty acids) which are sulphonated with gaseous SO 3 according to "The Journal of the American Oil Ohernists Society ", 52 (1975), pp. 323-329. Suitable starting materials may include natural fatty substances such as those derived from tallow, palm oil, etc. The preferred alkyl ester sulphonate surfactant, especially for laundry applications, comprises alkyl sterol sulfate surfactants of the structural formula or R3-CH-C-OR * in which R3 is a C8-Q20 hydrocarbyl, preferably an alkyl, or combination thereof, R * is a Ci-Cβ hydrocarbyl, preferably an alkyl or combination thereof, and M is a salt-forming cation soluble in water with the alkyl ester sulphonate. Suitable salt forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as rnonoethanolarnin, diethanolamine, and t-ethanolamine. Preferably, R3 is a C? Or C26 alkyl, and * is methyl, ethyl, or isopropyl. Especially preferred are the methyl estersulfonates in which R3 is alkyl of Cι-Ciß-Otr-os surfactants useful for detersive purposes may also be included in the laundry detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and t-bentanolane salts) of soap, C-0 linear alkylbenzene sulphonates, or primary alkane sulphonates of secondary alcohols. Cß-C22, Cs-C24 olefmsulfonates, sulfonated polycarboxylic acids prepared by the sul pration of the pyrolyzed product of alkali earth metal citrates, for example, as described in the specification of British Patent No. 1,082,179, ether sulfates Alkyl polyglycolics of Ce -C2"(containing up to 10 moles of etheylene oxide) alkylglycerol sulphonates, acrylglycerol fatty sulphonates, oleylglycerol fatty sulphates, ethylene oxide ether sulfates of alkylphenol, parafl sulphonates, alkyl phosphates, phthalate-like esters Acyl isethionates, N-acyltaurates, alkylsuccina and sulfosuccmates, rnonoesters of sul-osuccmates (especially rnonoesters of C? 2-C? saturated and more saturated) and dies sulfosuccinates (specifically saturated and unsaturated Cβ-C? 2-diesters), acyl sarcosmates, alkylpolysaccharide sulfates such as alkylpolyglycoside sulfates (the non-sulphonated non-ionic compounds being described below), branched primary alkyl sulfates , and alkylpolyethoxy carboxylates such as those of the formula R0 (CH2CH20) R -CH2C00 ~ M + wherein R is a C2-C2 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation . Resinous acids and hydrogenated resinous acids are also suitable, such as colophonic acids, hydrogenated colophonic acids, and resinous acids and hydrogenated resinous acids present in, or derived from, tallow oil. More examples are described in "Surface Active Ag nts and Detergent" (Vol. T and TI by Schwartz, Perry and Berch). A variety of such IVOS surfactants is also generally described in the F.U.A patent. No. 3,929,678, issued December 30, 1975 to Laughlin, and others, in column 23, line 58 to column 29, line 23 (incorporated herein by reference).

When included, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of said surfactants. ammonia One class of nonionic surfactants that can be used in the present invention are condensates of ethylene oxide with a hydrophobic portion to provide a surfactant having an average lipophilic hydrophilic-LC) (EHL) balance in the range of 8 to 17, preferably from 9.5 to 13.5, most preferably from 12 to 14. The hydrophobic (lipophilic) portion may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any hydrophobic group in In particular, it can be easily adjusted to produce a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements. In the case that the liquid detergent is structured with clay, the EHL value should preferably be less than 10. [0111] Especially preferred non-halogen surfactants of this type are the C9-C15 primary alcohol ethoxylates containing from 3 to 12 nozzles of ethylene oxide by alcohol rnol, particularly the primary alcohols of C? - C15 containing from 5 to 8 moles of ethylene oxide per mol of alcohol. Another class of nonionic surfactants comprises glycol alkyl compounds of the general formula RO (C "H2n0) tZx wherein Z is a glucose-derived portion; R is a saturated hydrophobic alkyl group containing from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds include less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglycosides. Compounds of this type and their use in detergents are described in EP-B 0 070 077, 0 075 996 and 0 094 118. Very suitable as non-halogen surfactants are the polyhydroxy fatty acid amide surfactants of the formula R2 where R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxyl, and 2-hydroxyl? proyl or a mixture thereof, R2 is hydrocarbyl of O5-31, and Z is a hydroxycarbonyl polyhydric having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight chain of alkyl or alkenyl of Cn-is + al as the coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose , in a reductive reaction.

Suitable cationic detersive surfactants for use in laundry detergent compositions of the present invention are those having a group of long chain hydrocarbyls. Examples of such cationic surfactants include ammonium surfactants such as alkyldi etiiamomo halogémdos, and those surfactants having the formula: [R2 (0R3) y] [R * (0R3) y] 2RSN »X- Where R2 is an alkyl or alkyl pentyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 1 is selected from the group consisting of -CH 2 CH 2 -, -ChbCl-HOHs) -, -CH 2 CH (Cl-fc OH) -, -CH2CH2CH2- and mixtures thereof; each R * is selected from a group consisting of Ci-C¿ alkyl, Ci-C4 hydroxyalkyl with the benzyl ring structures formed by joining the two groups R *, -0H2CH0H-CH0HC0R6CH0HCH 0H wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when and is not 0; R5 is the same as R * or is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values y is from 0 to approximately 15; and X is any other anion. The preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition, which have the formula: R? R2R3R4N + X- (i) wherein Ri is C 1 -C alkyl, each R 2, R 3. and R * is independently a CI-CÜ alkyl, hydroxyalkylbenzyl of CI-CA, and (C2H_vO) HH, where x has a value of 1 to 5, and X is an anion. No more than one of R2, Rg_ or R * must be benzyl. The length of the preferred alkyl chain for Ri is C ?2-Ci5 ^particularly when the alkyl group is a mixture of chain lengths derived from coconut fat or palm seed or is synthetic derived by olefin accumulation or synthesis of alcohols 0X0. The preferred groups for R2 R3_ and R * are methyl and hydroxy ethyl groups and the anion X can be selected from halide, ethosulfate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds of the formula (1) for use herein are coconut or tprnetium ammonium chloride or bromide; coconut or coconut methyl dihydroxyethylium chloride or bromide; Decidnet chloride 1 larin o; decildirneti chloride or bromide Ihydroxie ílarnome; dimethyl lhydroxyl chloride or bromide of C? 2-0? s; dimethylhydroxyethylamide or coconut chloride or bromide; I put Lusul fato of rnipstiltrime til ammonium; chloride or bromide of laurylidene or benzylaryl; chloride or bromide of 1-aldldimethyl (ethenoxy L-ammonium; fullers' esters (compounds of formula (1) where Ri is 1) of which -CH2 -0-C-C? 2-? "and R2 R _R4 are methyl) or II dialikyl lirnidazole ace (compound of formula (i).] Other cationic surfactants useful herein are also described in US Patent 4,228,044, Carnbre, issued October 14, 1980. When included there, laundry detergent compositions of The present invention typically comprises from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants The compositions according to the present invention can subsequently comprise a detergency builder system. Any conventional detergency improvement system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, ethylene diamine tetraacetate materials, metal ion sequestrants such as amy oppyphosphonates, particularly phosphonic acid. of etilendiarna ntet rarnet i lono and pentamethyl acid enfosfónico of diet ilentpami no. Although less preferred for obvious environmental reasons, phosphate detergent builders may also be used herein. Polycarboxylate builder builders suitable for use herein include citric bottom, preferably in the form of a water soluble salt, succimic acid esters of the formula R-CH (C00H) CH2 (C00H) wherein R is alkyl or alkene of C10-20 preferably of C12-16, or where R can be substituted with hydroxyl, sulphoxyl or sulfone substitutes. Specific examples include lauryl succinate, myristyl succinate, palylsuccinate, 2-dodecemlsucc ato, 2-tetradecen-lucuccinate. Succ ato detergency builders are preferably used in the form of their water soluble salts, including sodium, potassium, ammonium salts and alkanolamome salts. Suitable polycarboxylates are oxodisuccinates and mixtures of tartrate and monosuccimic tartrate disuccimic acid, or are described in US Pat. No. 4,663,071. Specifically for the liquid embodiment herein, fatty acid detergent builders suitable for use herein are saturated 010-18 fatty acids or unsaturated fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred detergency system for liquid compositions is a dodecemlysuccinic acid-based system. The regenerative salts are usually included in amounts of 1% to 50% by weight of the composition preferably from 5% to 30% and very commonly from 5% to 25% by weight. Other components used in detergent compositions, such as enzymes and stabilizers or activators thereof, soil suspending agents, soil release polymers, other optical brighteners, abrasives, bactericides, stain inhibitors, coloring agents, agents with foam rollers, corrosion inhibitors and perfumes. Especially preferred are combinations with enzyme technologies that also provide a kind of color care benefit. Examples are - cellulases for maintenance / rejuvenation of color. Other examples are the polymers described in EP 92870017.8 issued on January 31, 1992 and erythromatic oxidation scavengers described in EP 92870018.6 issued on January 31, 1992. Also particularly suitable are amine base catalyst stabilizers described in EP 92870019.4 issued on January 31, 1992. I particularly preferred the liquid compositions according to the present invention are in "concentrated form"; in such a case, the liquid detergent compositions according to the present invention will contain a smaller amount of water, compared to conventional liquid detergents. The water level is less than 50%, preferably less than 40%, most preferably less than 30% water by weight of the detergent compositions. These concentrated products provide advantages to the consumer, who has a product that can be used in lower quantities and for products, which has lower shipping costs. The detergent compositions according to the present invention include compositions that can be used to clean substrates, such as fabrics, fibers, hard surfaces, skin etc.; for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions. The following examples are for exemplifying compositions of the present inventions, but are not necessarily made with the intent to limit the scope of the invention.

PROOF PROCEDURE The stability of the structured liquid detergent compositions containing porous hydrophobic material according to the present invention was measured under storage at room temperature. More in particular, the structured liquid detergent compositions of. Table I were supplemented with cellulase (Carezyme) as indicated below: * The cellulase solution contains 4.98% polyhydroxyl lamide, 95% solution of cell starting material lasa and 0.1% polyethylene glycol. - ** Aerosil 5% based on the total weight of the silica filled with cellulase. * • * • * The weight ratio of silicone to silicone oil filled with cellulase was 1.8. The following liquid detergent compositions were made: II III IV V fll quilbencensuLalphalonate 18 - - 10 - C? 2 - C? Alkyl sulfate 12 12.4 - 18 - 10 Allylsulfate and C? 2 - Ci5 3. - 5 N-rnethylglucamide of Cl2-Ci4 4 4 6 6 Chlorides of dimethylhydroxy and coconut iodide 2 2 2 _ 2 Fatty acid of C? 2-C6 17 16.5 10 10 1 Citric acid anhydrous 1.5 1.5 5 - L.5 Smectite clay 3.5 3.4 3.5 - -0 r-ga noa rc 111 a de c-tor-it a 0.5 0.4 0.5 - -NaOH 6.5 4.7 5 - - Propanediol 8.5 9.0 9 9 9 Ethanol 1.5 1.0 l 1 1 FNA base (34g / l) 0.7 0.72 0.7 0.7 0.7 rerrnamyl (300KNU / g) 0.3 0.25 0.2 0.2 0.2 \ ipolase - 0.2 0.2 0.2 0.2 polyethylene oxide - - 0.2 - - Boric acid 1.2 1.2 2 2 2 Yes. tin 0.03 0.03 0.03 0.03 0.03 Silicon 0.25 0.2 0.25 0.25 0.05 Dispersant 0.05 0.05 0.05 0.05 0.05 Water 20 40 30 60 50 P1: _? ? \ 4- i r-lüHcao rnar \ r \ r a i pnr - TABLE I Structured liquid detergent compositions according to the present invention (I, II, III, IV and V) are stable, even after prolonged periods of storage.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A liquid detergent composition containing a hydrophobic porous material, the hydrophobic porous material having an active ingredient absorbed, said porous material being coated with a hydrophobic material, further characterized in that said liquid detergent composition is a structured liquid detergent composition.

2. A liquid detergent composition according to claim 1 further characterized in that said active detergent compound is selected from enzymes, bleaches, bleach activators, bleach catalysts, perfumes, photoactivators, dyes, rinsers, and fluoroscers. Washing heaters, softening agents or fabric conditioners, hydrolysable surfactants, polymers and other active detergent compounds which are water soluble or water dispersible and mixtures of the same.

3. A liquid detergent composition according to claim 1, further characterized in that said liquid detergent composition is externally structured.

4. A liquid detergent composition according to claim 3, being structured by clay.

5. A liquid detergent composition according to claim 1, further characterized in that said liquid detergent composition is internally structured.

6. A liquid detergent composition according to claim 5, being structured by a polyhydroxyanide surfactant.

7. A liquid detergent composition according to claim 1, further characterized in that said porous hydrophobic is silica and said hydrophobic coating material is silicone oil.

8. The use of the liquid detergent composition according to claim 1, for cleaning fabrics, fibers, hard surfaces and skin.