MXPA98010100A - Deterge composition - Google Patents

Abstract

A detergent composition suitable for use in laundry or dishwashing methods is provided, comprising: a cationic quaternary ammonium surfactant, and a hydrophobic inorganic peroxy acid bleach system capable of providing a hydrophobic organic peroxyacid compound

Description

DETERGENT COMPOSITION TECHNICAL FIELD The present invention relates to detergent compositions containing a cationic surfactant and a hydrophobic organic peroxyacid bleach system, which are suitable for use in laundry and dishwashing methods.

BACKGROUND OF THE INVENTION The satisfactory removal of soils and grease stains, that is, of soils and stains that have a high proportion of triglycerides or fatty acids, is a challenge faced by the formulator of detergent compositions for use in laundry and laundry washing methods. vaj illas. The surfactant components have traditionally been used in detergent products to facilitate the removal of these soils and grease stains. In particular, surfactant systems comprising cationic esters for use in the removal of dirt and grease stains have been described. A particular challenge for the formulator of detergent compositions for use in a laundry method is the satisfactory removal of soils and bleaching stains such as tea, fruit juice and colored vegetable soils from stained fabrics. It is known that stained fabrics tend to have a "lackluster" appearance after frequent washing. Traditionally, bleaches are used in detergents to remove blemishes or stains, and are also responsible for the "lackluster" appearance of the fabric. It is well established that bleaches and peroxygen bleach systems, based on organic peroxyacids, can provide removal of stains and / or dirt from fabrics. Organic peroxyacids are frequently obtained by in situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach activators). To remove stains and grease stains that are hydrophobic in nature, organic hydrophobic peroxyacids can be used in the detergent products. These organic peroxyacids generally comprise long chain alkyl portions (> 7 carbon atoms). It is known that hydrophobic bleaches have the tendency to migrate rapidly to the surface of fabrics under washing conditions. Bleaching agents that can be hydrophobic are described, for example, in EP-A-0170386. It is stated that these bleaches can be used in compositions that incorporate different types of surfactant materials. Anionic, nonionic, zwitterionic and amphoteric surfactants are described. Also disclosed are hydrophobic whitening agents in 095/3226, as useful foam suppressants in detergent compositions containing high levels of surfactant. The quaternary ammonium compounds are known cationic surfactants. For example, GB-A-5 2040990 uses alkoxylated nonionic and cationic surfactants and anionic surfactants in combination to produce laundry detergents. It has now been found that a problem with hydrophobic bleaches is that despite their tendency to migrate towards the surface of the fabric, not necessarily interact completely with the components of the stain or ^ - dirt. It has been found that "lime soaps" (formed by alkaline earth ions with fatty acids, present in the washing solution) deposited on the fabric, can prevent Migration of hydrophobic whiteners on stains and grease stains. With this, its whitening action may decrease. This results in a reduction of the soil cleaning action of the hydrophobic bleach. The applicants have found that this problem can be reduced by using a particular combination of cationic surfactant and bleach, resulting in a surprising improvement in the bleaching efficiency of the organic peroxyacid hydrophobic bleach system. With this, the overall cleaning action of the detergent is improved. 25 It is believed that three mechanisms are responsible for this unexpected benefit. First, the cationic surfactant is capable of reducing the deposit of "lime soap" on the surface of the fabric, thus facilitating the separation of the hydrophobic organic bleaches towards stains and grease stains. Second, the cationic surfactant reduces the surface tension between the fabric and the wash solution. This will facilitate the interaction between stains and grease stains on the fabric and the organic hydrophobic bleaching agent. Third, cationic surfactant and negatively charged hydrophobic organic peroxyacids, formed in the wash, can form a nonpolar associated pair that rapidly separates towards hydrophobic stains and grease stains on the fabric. All documents cited in the present description are incorporated herein by reference in their relevant part.

BRIEF DESCRIPTION OF THE INVENTION A detergent composition according to a first aspect of the present invention comprises: a) a cationic surfactant of the formula I: R1-N-R4 X "R- (I) in which R1 is a hydroxyalkyl group having not more than 6 carbon atoms, each of R ^ and R is independently selected from alkyl or alkenyl of C1 -4, R is Cg_n alkyl or alkenyl, and X ~ is an anion, and b) a hydrophobic organic peroxyacid bleach system capable of providing a hydrophobic organic peroxyacid compound.The preferred cationic surfactants of formula I are those in which R1 is -CH2CH2OH or -CH2CH2C2OH, each of R and R are, independently, C? _, - R is alkyl or alkenyl of C? -ii and X ~ is an anion An essential characteristic of the detergent compositions of the invention is an organic peroxyacid hydrophobic bleach system capable of providing a hydrophobic organic peroxyacid compound.An organic peroxyacid hydrophobic compound is understood herein as an organic peroxyacid whose original carboxylic acid has a critical micellar concentration. ca less than 0.5 moles / liter, and wherein said critical micellar concentration is measured in aqueous solution at 20 ° -50 ° C. Preferably, the organic hydrophobic peroxyacid contains at least 7 carbon atoms, preferably at least 9 carbon atoms, preferably at least 11 carbon atoms. In a preferred aspect, the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, preferably at least 8 carbon atoms, preferably at least 9 carbon atoms. A preferred organic peroxyacid hydrophobic bleach system is capable of providing a peroxyacid compound of the formula: R- • N- -R '-00H or R "-N- -R' -OOH II 0 R 0 R6 or wherein R is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R is H or an alkyl, aryl group or alkaryl containing from 1 to 10 carbon atoms. According to a second aspect of the invention, a detergent composition is provided which comprises: a) less than 5% by weight of a cationic surfactant of the formula: R "(I) in which R is a group h drox alk which has no more than 6 carbon atoms; each of R and R is independently selected from C 1-4 alkyl or alkenyl; R- is Ci2-14 alkyl or alkenyl / Y x is an anion; and b) a hydrophobic organic peroxyacid bleach system capable of providing a peroxy-acid compound of the formula: R5 C N R7 C 00H or R5 N C R7 C 00H wherein R 5 is an alkyl, aryl or aralkyl group 7 containing 1 to 14 carbon atoms, R is an alkylene, arylene or alkarylene group containing 1 to 14 carbon atoms, and R is H or an alkyl group, aryl or alkaryl containing from 1 to 10 carbon atoms. Particularly preferred cationic surfactants are those of formula I in which R is HOCH2CH2- or HOCH2CH2C2-; each of R2 and R3 are, independently, C] __ 4 alkyl, - R is C2-14 alkyl or alkenyl, and x_ is an anion. The preferred detergent compositions of the invention additionally comprise a hard base polymer component. Unless indicated otherwise, the alkyl or alkenyl as used herein may be branched, linear or substituted. The substituents may be for example aromatic groups, heterocyclic groups containing one or more N, S or O atoms, or halogen substituents.

DETAILED DESCRIPTION OF THE INVENTION Cationic surfactant An essential element of the detergent compositions of the invention is a cationic quaternary ammonium surfactant. The cationic surfactant, unless otherwise indicated, may be present in amounts up to 10.0% by weight of the detergent composition. However, preferably the maximum amount of the cationic surfactant in the detergent composition is less than 5%. Preferably, the cationic surfactant will be present in an amount of less than 4% or up to 4.5% by weight of the detergent composition. Generally, there will be in the composition at least 0.05% by weight, or up to at least 0.1%, or at least 0.5% by weight of the cationic surfactant. Preferably, the group -0H in R1 in formula I is separated from the quaternary ammonium nitrogen atom by not more than 3 carbon atoms. Preferred R1 groups are -CH2-CH2OH, -CH2CH2CH2OH, CH2CH2 (CH3) OH and -CH (CH3) CH20H. CH 2 CH 2 OH and -CH 2 CH 2 CH 2 OH are preferred, and - CH 2 CH 2 OH is particularly preferred. Preferably, R2 and R3 are each selected from ethyl and methyl groups, and preferably both R2 and R3 are methyl groups. Preferred R 4 groups have at least 6 or up to at least 7 carbon atoms. R4 can have no more than 9 carbon atoms, or no more than 8 or 7 carbon atoms. Preferred R groups are linear alkyl groups. Linear R4 groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred. In accordance with a preferred aspect of the • Invention, the cationic surfactant of formula I has a group R which is -CH2CH2OH. Preferably, each of the groups R and RJ are methyl groups. In a preferred aspect of the invention, R is a linear alkyl group, preferably a linear alkyl group of 10 Cg-n- It has been found that mixtures of surfactants • cationics of formula I can be particularly effective, for example mixtures of surfactants in which R can be a combination of linear alkyl groups of Cs and C- ± Q i ° linear alkyl groups of Cg and C] _] _. According to one aspect of the invention, a mixture of cationic surfactants of formula I is present in the composition, the mixture comprising an alkyl surfactant of shorter chain formula I and an alkyl surfactant of formula I of more chain long. The longer alkyl chain cationic surfactant is preferably selected from the surfactants of formula I wherein R is an alkyl group having n carbon atoms, wherein n is from 8 to 11; the shorter alkyl chain surfactant is preferably selected from the of the formula I wherein R is an alkyl group having n-2 carbon atoms. Preferably, the detergent compositions of the invention comprise a combination of cationic surfactants of formula I comprising 1% to 65% of an alkyl group R4 of shorter chain length and 35% to 99% by weight of an alkyl of the length of Largest chain. Particularly preferred are mixtures comprising R groups of Cg and C ^ or • X alkyl groups in formula I can be any counter-ion that provides electrical neutrality, but is preferably selected from the group consisting of halide, methylsulfate, sulfate and nitrate, preferably it is selected from methyl sulfate, chloride, bromide or iodide.

Organic Peroxyacid Hydrophobic Bleach System Preferably, the organic peroxyacid hydrophobic bleach system comprises a source of hydrogen peroxide and an organic peroxyacid hydrophobic precursor bleach compound. The production of the organic hydrophobic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred embodiment, the organic peroxyacid hydrophobic bleach system comprises a preformed organic hydrophobic peroxyacid, which is incorporated directly into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and organic hydrophobic peroxyacid precursor, in combination with a preformed organic hydrophobic peroxyacid.

Inorganic Perhydrate Bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal salt, preferably sodium, at a level of 1% to 40% by weight, most preferably 2% to 30% by weight and more preferably 5% to 25% by weight. weight of the compositions. Examples of inorganic salts of perhydrate include perborate, percarbonate, perfosphate, persulfate and persilicate. The inorganic salts of perhydrate are usually the alkali metal salts. The inorganic perhydrate salts can be included as the crystalline solid without additional protection. However, for certain perhydrate salts the preferred embodiments of said granulated compositions utilize a coated form of the material that provides better storage stability to the perhydrate salt in the granulated product. Suitable coatings comprise inorganic salts such as the alkali metal salts of silicate, carbonate or borate, or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is a preferred perhydrate salt and may be in the form of the monohydrate of the nominal formula NaB02H202 or the tetrahydrate NaB? 2H2O2-H2O.

The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates of the present. Sodium percarbonate is an addition compound having the formula corresponding to 2Na2CO3.3H2O2 / and is commercially available as a crystalline solid. Potassium peroximonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. In general, peroxyacid bleach precursors can be represented as: wherein L is a leaving group and X is essentially any functionality, such that after perhydrosysis, the structure of the produced peroxyacid is: For the purposes of the present invention, X will thus contain 6 carbon atoms.

The hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, preferably from 0.1% to 15% by weight, preferably from 0.2% to 10% by weight of the detergent compositions. Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups; These precursors can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within m these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. 15 Outgoing groups The outgoing group, hereinafter referred to as group L, must be sufficiently reactive for the reaction of B perhydrolysis to occur within the optimum time frame (eg, a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: R3 and I I -O-CH = C-CH = CH2 -O- CH = C-CH = CH2 and mixtures thereof, wherein R is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, RJ is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R and R may be substituted essentially with any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium groups. The preferred solubilizing groups are -S? 3 ~ M +, - C02"M +, -S0 ~ M +, -N + (R3) X" and 0 < -N (R3), and most preferably-S? 3-M + and -C02 ~ M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the activator of bleaching and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with more sodium and potassium being preferred, and X being an anion of halide, hydroxide, methylsulfate or acetate.

^ P Substituted alkylperoxy acid precursors with amide The amide substituted alkylperoxy acid precursors of the second aspect of the invention are also preferred in the first aspect of the invention. These include compounds of the following general formulas: R- -N- -R 'R ~ -N- II I r II Ir II II O Rb O Rb O O where R is an aryl or alkaryl group with •? about 1 to about 14 carbon atoms, R is an alkylene, arylene or alkarylene group containing about 1 to 14 carbon atoms, and R6 is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms. carbon, and L can be essentially any outgoing group. Preferably, R contains about 6 to 12 carbon atoms. Preferably, R contains about 4 to 8 carbon atoms. R can be straight or branched chain alkyl, substituted aryl or alkylaryl with branching, substitution or both, and can come from synthetic sources or natural sources including for example tallow fat. Analogous structural variations for R are permissible. R may include alkyl, aryl, wherein said R may also contain halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. Preferably, R is H or methyl. R * y R must not contain more than 18 carbon atoms in total.

Amide-substituted bleach activator compounds of this type are described in EP-A-0170386. Preferred examples of bleach precursors of this type include amide-substituted peroxyacid precursor compounds, selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene sulfonate, and the highly preferred (6-) 20 nonanamidocaproyl) oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386.

Benzoxazine organic peroxyacid precursors For a first aspect of the invention, precursors of the benzoxazine type are also suitable as described for example in EP-A-332,294 and EP-A-482, 807, particularly those having the formula : wherein R is an alkyl, alkaryl, aryl or arylalkyl containing at least 5 carbon atoms.

Alkylcarboxylic acid bleach precursors The alkylcarboxylic acid bleach precursors form percarboxylic acids by perhydrolysis.

Preferred alkylcarboxylic precursor compounds of the imide type include the N, N, N 1 N 1 -alkyl • lendi • tetraacetylated amides, wherein the alkylene group contains at least 7 carbon atoms. Other preferred alkylcarcarboxylic acid precursors include sodium 3,5-trimethylhexanoyl-oxybenzenesulfonate (iso-NOBS) and sodium nonanoyloxybenzenesulfonate (NOBS).

N-Acylated Lactam Precursors Another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class, generally described in GB-A-955735. Preferred materials of this class comprise the caprolactams. Suitable precursors of caprolactam bleach are of the formula: CH- CH- CH. .1 N / CH- CH- Wherein R is an alkyl, aryl, alkoxyaryl group ^ P or alkaryl containing from 6 to 8 carbon atoms. Preferred hydrophobic bleach precursor materials of N-acylcaprolactam are selected from benzoylcaprolactam, Octanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undequenoylcaprolactam, 3,5,5,5-trimethylhexanoylcaprolactam, and mixtures thereof. Nonanoylcaprolactam is preferred. ? \ Suitable valerolactams have the formula: Wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. Preferably, R is selected from phenyl, ethyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof. Mixtures of any of the peroxyacid bleach precursors described above can also be used. The cationic surfactant and the hydrophobic organic peroxyacid precursor are preferably present in the detergent composition at a ratio of 25: 1 to 1: 1, preferably at a ratio of 10: 1 to 1: 1.

Preformed organic peroxyacid The organic peroxyacid bleach system may contain in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic hydrophobic peroxyacid, typically at a level of from 0.05% to 20% by weight, of preference of 1% to 10% by weight of the composition. A preferred class of hydrophobic organic peroxyacid compounds are the substituted amide compounds of the following general formulas: R- C _.- N - - R7 - - C - - 00H or R5 - - - - C R '• - C OOH II 0 A * II 0 i * or II or II wherein R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R is an alkylene, arylene and alkarylene group containing ^^ approximately 1 to 14 carbon atoms and R is H or a group Alkyl, aryl or alkaryl containing from 1 to 10 carbon atoms. Preferably, R contains about 6 to 12 carbon atoms. R preferably contains about 4 to 8 carbon atoms. R can be straight or branched chain alkyl, aryl or substituted alkylaryl which contains branching, substitution or both, and can come either from synthetic sources or from natural sources including ^ p for example tallow grease. Analogous structural variations for R are permissible. R may include alkyl, aryl, wherein said R may also contain halogen, Nitrogen, sulfur and other typical substituent groups or organic compounds. R is preferably H or methyl. R and R must not contain more than 18 carbon atoms in total.

Amide-substituted bleach activating compounds of this type are described in EP-A-0170386. The right examples of this class of agents include (6-octylamino) -6-oxocaproic acid, (6-nonylamino) -6-oxo-caproic acid, (6-decylamino) -6 -oxocaproic acid, and magnesium monoperoxyphthalate hexahydrate , the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanoic acid. These bleaching agents are described in U.S. Pat. No. 4,483,781, 4,634,551, EP 0,133,354, US patent. 4,412,934 and EP 0,170,386. A preferred preformed hydrophobic bleaching compound preformed for the purpose of the invention is nonanoylamidoperoxycarboxylic acid. Other organic peroxyacids suitable for the first aspect of the invention include diperoxyalkanedioic acids having more than 7 carbon atoms, such as diperoxydecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Other suitable organic peroxyacids include diaminoperoxyacids, which are described in WO 95/03275, with the following general formula: 0 0 0 0 15 ?? , ?? 2 3 2 ?? i ?? MOCR- (R-LN) n - C (NR ^) n. - -R - - (R ^ N) m? --C (NR1) m- -RC00M wherein: R is selected from the group consisting of alkylene 20 C] -C- L2 / C5-C12 cycloalkylene, arylene of Cg-C ^ Y? combinations of radicals thereof; R1 and R2 are independently selected from the group consisting of H, and C1-C1g alkyl and Cg-C12 aryl radicals and a radical that can form a C3-C12 ring together with 3RJ and both nitrogens; R ° is selected from the group consisting of C5-C12 cycloalkylene alkylene and C -C1 arylene] _2"n and n 'are each an integer chosen in such a way that the sum thereof is 1; each of them an integer chosen in such a way that the sum thereof is 1, and M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof. Suitable organic peroxyacids include the aminoperoxy acids that are described in WO 95/16673, with the following general structure: X - Ar - CO - NY - R (Z) - CO - OOH wherein X represents hydrogen or a substituent ^ P compatible, Ar is an aryl group, R represents (CH2) n, where n = 2 or 3, and Y and Z each represent independently a A substituent selected from hydrogen or an alkyl or aryl or alkaryl group or a substituted aryl group by a compatible substituent, provided that at least one of Y and Z is not hydrogen if n = 3. The substituent X on the benzene nucleus is preferably a hydrogen or a substituent k or meta, selected from the group comprising halogen, typically chlorine atom, or some other non-released, non-interfering species, such as an alkyl group, conveniently up to C-6, for example a methyl, ethyl or propyl. Alternatively, X may represent a second substituent of amidopercarboxylic acid of formula: CO NY R (Z) CO OOH in which R, Y, Z and n are as defined above.

MOOC-R1CO-NR2-R3-NR4 -CO-R5COOOM • wherein R is selected from the group consisting of C? -C] alkylene, C5-C12 arylene Cg-C2 cycloalkylene, and combinations of the same; The preferred detergent compositions of In accordance with the present invention, they additionally comprise a hard-base organic polymer component. Preferably, the total cationic surfactant and the polymeric component of ^ hard base will be present in the detergent composition at a weight ratio of 10: 1 to 1: 3, preferably 5: 1 to 1: 2.

The hard base polymer component preferably comprises a polymer having a pendant group (ie, a group that is not a polymeric linking group, such that it is not part of the polymer backbone) which is a harder base than a group of benzenesulfonate according to Pearson's classification of hard and soft behavior. Preferably, the polymer component comprises a polymer having a pendant group which is a harder base than a sulphonate group such as CH3CH CH -S03 ~. The polymer component is generally formed of at least 5%, preferably at least 25% by weight, of monomers that give rise to said pendant groups. The polymer component preferably has a molecular weight of 1,500 to 150,000, preferably 2,000 to 100,000, especially 5,000 to 80,000. Molecular weight measurements are obtained by means of GPC using styrene as standard. Particularly preferred pendant groups are carboxylic groups (references herein to acidic groups also include their salts). Homopolymers or copolymers of acrylate and malate are particularly preferred. The hard base polymer can be any organic polymeric material having a hard base group commonly used as dispersants and anti-redeposition and soil suspension agents in detergent compositions. Examples of organic polymeric compounds include homo- or co-polymeric organic acids soluble in water or their salts, wherein the carboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this last type are described in GB-A-1, 596, 756. Examples of these salts are the polyacrylates of MWt 1500-5000 and their copolymers with maleic anhydride; these copolymers have a molecular weight of 2,000 to 100,000, especially 5,000 to 80,000 or up to 10,000 to 50,000. Polyamino compounds are useful herein, including aspartic acid derivatives such as those described in EP. -A-305282, EP-A-305283 and EP-A-351629. Also suitable herein are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having a molecular weight average of 5,000 to 10,000. The hard base polymer component is preferably present as a constituent of any particulate component where it may be beneficial as a binder.

Additional detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and the flfc levels of incorporation of these will depend on the form physics of the composition and the precise nature of the washing operation for which it will be used. The compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, Bleaches, detergency builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, suspending and antiredeposition agents for soils and corrosion inhibitors.

Additional Surfactant The detergent compositions of the invention preferably contain an additional surfactant selected from anionic, nonionic, additional cationic, ampholytic, amphoteric and zwitterionic surfactants, and mixtures thereof. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the U.S. patent. Do not. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are given in "Surface Active Agents and Detergent" (Vols. I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31, 1981. When present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.

Anionic Surfactant The detergent compositions according to the present invention preferably comprise an additional anionic surfactant. Essentially any surfactant useful for detersive purposes may be comprised in the detergent composition. These may include salts (including, for example, sodium, potassium, ammonium salts). and substituted ammonium such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include isethionates such as acyl isethionates, N-acyltaurates, fatty acid amides of methyl tauride, alkyl succinates and WW sulfosuccinates, monoesters of sulfosuccinate (especially monoesters of saturated and unsaturated C ^ -Cis) diesters of sulfosuccinate (especially Cg-C ^ saturated diesters) unsaturated), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in the oil. 4fc tallow or derivatives thereof. Sulfate Anionic Surfactant The anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, Alkyl ethoxysulfates, fatty oleylglycerol sulfates, ethylene oxide ether sulfates of alkylphenol, acyl glucamin sulfates of C5-C17-N- (C1-C4 alkyl) and -N- (hydroxyalkyl of C? -C2), and alkylpolysaccharide sulfates as alkylpolyglucoside sulfates (described herein) ^^ non-sulfated non-ionic compounds). The alkylsulfate surfactants are preferably selected from the linear and branched primary alkyl alkylsulfos, most preferably the branched chain C 11 -C 15 alkyl sulfates and the straight chain C 1 -C 4 alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of C 1 -C 8 alkyl sulfates are either ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. Most preferably, the alkyl ethoxy sulfate surfactant is an alkyl sulfate of C] _] _- C 8 most preferably of C] _3_-C? _5, which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5 moles of ethylene oxide per molecule. A particularly preferred aspect of the invention employs mixtures of the alkyl sulfate surfactants and preferred alkyl ethoxylates. Such mixtures have been described in PCT application No. WO) 3/18124.

Sulfonate anionic surfactant The appropriate sulfonate anionic surfactants for use herein include salts of linear alkylbenzene sulphonates of c5_c20 'alkyl ether sulfonates, primary or secondary Cg-C22 alkan sulfonates, sulfonated polycarboxylic acid olefinsulfonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof .

Anionic carboxylate surfactant Anionic carboxylate surfactants include alkylethyloxycarboxylates, surfactants alkylpolyethoxy polycarboxylate and soaps ("alkylcarboxyls"), especially certain secondary soaps ^ like those described here. Suitable alkyleoxycarboxylates include those with the formula RO (CH2CH20) xCH2C00"M + wherein R is a The alkyl group from Cg to C ^ g, x varies from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material in which x is 0 is less than 20% and M is a cation Suitable alkylpolyethoxy polycarboxylate jß surfactants include those having the formula RO- (CHR) _- CHR 2-0) -R 3 wherein R is an alkyl group from Cg to C ^ g, x is from 1 to 25, R] and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, Or substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants containing a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are the water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-ethyl propyl-l-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors.

Alkaline metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R) CH2C00M, wherein R is a straight or branched C5-C1 alkyl or alkenyl group, R is an alkyl group of C1-C4 and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts.

Non-ionic alkoxylated surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. Non-ionic ethoxylated and propoxylated surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, ethoxylated / propoxylated nonionic fatty alcohols, ethoxylated / propoxylated non-ionic condensates with propylene glycol and the non-ionic ethoxylated condensation products with adducts of propylene oxide / ethylenediamine.

Nonionic surfactant of alkoxylated alcohol The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Non-ionic surfactant of polyhydroxy fatty acid amide The polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2C0NR1Z, wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl , ethoxy, propoxy, or a mixture thereof, preferably 1-C alkyl, most preferably C 1 or C 2 alkyl, more preferably C 1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C5-C5 alkyl or alkenyl, most preferably straight chain C9-C17 alkyl or alkenyl, more preferably C2-C6 alkyl or alkenyl of chain straight or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably be derived from a reducing sugar in a reductive amination reaction; most preferably Z is a glycityl.

Non-ionic fatty acid amide surfactant Suitable fatty acid amide surfactants r 7 g include those having the formula: R ° CON (R ') 2 wherein R is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R is selected from the group consisting of hydrogen, C-C4 alkyl, hydroxyalkyl of C] _-04, and - (C2H?) XH, wherein x is on the scale of 1 to 3.

Non-ionic surfactant of alkylpolysaccharide Suitable alkylpolysaccharides which are used herein are described in the U.S. patent. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing from 1.3 to 10. saccharide units. Preferred alkyl polyglycosides have the formula R ^ O (CnH2nO) t (glycosyl) x wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glyoosyl is preferably derived from glucose.

Amphoteric Surfactant Amphoteric surfactants suitable for use in the present invention include the amine oxide surfactants and the alkylamphocarboxylic acids. Suitable amine oxides include those Compounds having the formula R3 (OR4) xN ° (R5) 2, wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, containing from 8 to 26 carbon atoms; R is an alkylene group m- \) or hydroxyalkylene containing from 2 to -3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R is an alkyl or hydroxyalkyl group containing 1 to 3 carbon atoms, or a group of polyethylene oxide containing 1 to 3 ethylene oxide groups. Preference is given to the alkyl dimethylamine oxide of C ^ g-Cis and the oxide of Acylamidodimethylamine of C? O ~ Ci8- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, New Jersey E.U.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are examples of zwitterionic surfactants that can be used herein. Suitable betaines are those compounds having the formula: R (R1) 2N + R2COO- wherein R is a hydrocarbyl group of Cg-C ^ g, each R is typically C] _-C3 alkyl, and R2 is a group hydrocarbyl of C] _- C5. The preferred betaines are the betaines of dimethyl ammonium hexanoate of c12 ~ c18 and the acylamidopropane (or ethane) dimethyl (or diethyl) betaines of C? O ~ ci8- The complex betaine surfactants are also suitable for use herein.

Cationic Surfactants Additional cationic surfactants may also be used in the detergent compositions herein. Suitable cationic surfactants include ethoxylated quaternary ammonium surfactants as described in GB-A-20409990, or ester surfactants. Suitable ester cationic surfactants, including • choline ester surfactants, have been described for example 5 in the US patents. Nos. 422,8042, 4239660 and 4260529.

Alkalinity In the detergent compositions of the present invention preferably a system of alkalinity to achieve optimum performance of the cationic ester surfactant. The alkalinity system comprises components capable of providing alkalinity species in the solution. By species of alkalinity we try to say in the present: carbonate, bicarbonate, hydroxide, the different anions of silicate, percarbonate, perborates, perfosphates, persulfate and persilicate. Said alkalinity species can be formed, for example, when the alkali salts selected from carbonate, bicarbonate, hydroxide or alkali metal or alkali metal silicate salts. terreo, including crystalline layered silicate and mixtures thereof are dissolved in water. Examples of carbonates are the alkali earth and alkali metal carbonates, including carbonate and sodium sesquicarbonate and any mixture thereof with Ultra-fine calcium carbonate, such as those described in German Patent Application No. 2,321,001, published November 15, 1973. Suitable silicates include water-soluble sodium silicates with a SiO: Na20 ratio of 1.0. to 2.8, with the relationships of 1.6 to 2.0 being preferred, and the ratio of 2.0 being more preferred. The silicates may be in the form of the anhydrous salt or the hydrated salt. Sodium silicate with a ratio of Si02: Na2? 2.0 is the most preferred silicate. Preferred crystalline layered silicates for use herein have the general formula: NaMSix02x +? and H20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are described in EP-A-0164514, and the methods for their preparation are described in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has the value of 2, 3 or 4, and is preferably 2. The most preferred material is Ü-Na Si20-5, available from Hoechst AG as NaSKS-6.

Water Soluble Builder Compound The detergent compositions of the present invention preferably contain a water soluble builder compound, typically present at a level of 1% to 80% by weight, preferably from 10% to 70% by weight, more preferably from 20% to 60% by weight of the composition. Water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts, in which the polycarboxylic acid comprises at least two carboxylic radicals separated from one another by no more of two carbon atoms, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxyl group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in British Patent No. 1,389,732 and the aminosuccinates described in Dutch application 7205873 and oxypolycarboxylate materials such as 2-oxa-l, 1,3-propane tricarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829, 1, 1, 2, 2-etanttracarboxylates, 1, 1, 3, 3-propanetracarboxylates and the 1,1,2,3-propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and the US patent. No. 3,936,448 and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. The original acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, v.gr. , mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. Borate builders, as well as builders that contain borate-forming materials that can produce borate under detergent storage or washing conditions, are water soluble builders that are useful herein. Suitable examples of phosphate builders are alkali metal tripolyphosphates, pyrophosphate ^^ of sodium, potassium and ammonium, sodium and potassium pyrophosphate and ammonium, sodium and potassium orthophosphate, and sodium polymetaphosphate, in which the degree of polymerization varies from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% in weight, most preferably from 20% to 60% by weight of the composition. Examples of detergents largely soluble in water include sodium aluminosilicates. Suitable aluminosilicate zeolites have the unit cell formula Naz [(Al02) z (Si0) y] -xH 0, where z and y are integers of at least 6; the molar ratio of zay is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, most preferably from 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing 10% 28%, most preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites may be materials that occur naturally, but are preferably derived in synthetic form. Synthetic crystalline aluminosilicate ion exchange materials are available under • the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na12 [(A102) 12 (Si02)? 2] "xH20 where x is from 20 to 30, especially 27. The Zeolite X has the formula: Na8g [(A102) 86 (si02) 106 ^ '276H2 ° - ^ P Bleaching catalyst The compositions optionally contain a bleach catalyst containing a transition metal. A suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity , such as zinc or aluminum cations and a scavenger having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra- (methylene phosphonic) acid and the water soluble salts thereof. Said catalysts are described in the U.S. patent. No. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes described in the U.S. patent. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Examples ^^ preferred of these catalysts include Mn 2 (u ~ °) 3 X '4' 7_ 5 trimethyl-1,4, 7-triazacyclononane) 2 ~ (PFd) 2 'MnIu2 (u-0)] _ (u- OAc ) 2 (1,4, 7-trimethyl-1,4-, 7-triazacyclononane) - (CIO4) 2, MnIV4 (u-0) (1,4, 7-triazacyclononane) 4- (C104) 2, MnIIIMnIV (u - 0) 1 (u-OAc) 2 (1,, 7-trimethyl-1,4-, 7-triazacyclononane) 2- (CIO 4) 3 and mixtures thereof. Others are described in the publication of European Patent Application No. 549,272. Other ligands suitable for use herein include 1, 5, 9-trimethyl-1, 5, 9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-l, 4,7-triazacyclononane and mixtures thereof. For examples of suitable bleach catalysts see the patent of E.U.A. No. 4,246,612 and in the patent of E.U.A. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches manganese (IV) complexes (A mononuclear, such as Mn (1,4,4-trimethyl-1,4,4,7-triazacyclononane) (OCH 3) 3. (PFg) Another type of bleach catalyst as described in US Pat. 5,114,606 is a water soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three C-OH groups consecutive. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-toothed ligands, including N4M11111 (u-0) 2MnIVN4) + Y [Bipy2MnI ?: r (u-0) 2MnIVbipy2] - (C104) 3. Suitable and additional bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), applications • 5 of European patent -Nos. No. 384,503 and 306,089 (metalloporphyrin catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4,711,748 and European patent application Publication No. 224,952 (manganese catalyst absorbed on aluminosilicate), E.U.A. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 ^ P (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and non-catalytic metal cations) and E.U.A. 4,728,455 (manganese gluconate catalysts).

Heavy metal ion sequestrant The detergent compositions of the invention preferably contain a heavy metal ion sequestrant as an optional component. By heavy metal ion sequestrant, it is tried here to say components that act to kidnap (chelate) heavy metal ions. These components may also have calcium and magnesium chelating ability, but preferably show selectivity to bind heavy metal ions such as iron, manganese and copper. to-. Heavy metal ion sequestrants are present generally at a level of 0.005% to 20%, preferably from 0.1% to 10%, most preferably 0.25% at 7. 5% and more preferably 0.5% to 5% by weight of the compositions. The suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), ethane-1-hydroxy alkali metal bisphosphonates and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylenephosphonate), ethylenediaminetri- (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate. Another heavy metal ion sequestrant suitable for use herein includes nitrilotriacetic acid and polyaminocarboxylic acids such as acid Ethylenediaminetetraacetic acid, ethylenetriaminpentaacetic acid, ethylenediamine disuccinic acid, ethylene diamine diglutaric acid, 2-hydroxypropylenediamindisuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, metal salts Alkaline earth, ammonium or substituted ammonium thereof, or mixtures thereof.

Other heavy metal ion sequestrants suitable for use herein are the iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryliminodiacetic acid, described in EP-A-317,542 and EP-A-5 399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid-N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-10 diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also • adequate. EP-A-476,257 describes suitable amino-based sequestrants, EP-A-510,331 describes sequestrants Suitable derivatives of collagen, keratin or casein. EP-A-528,859 discloses a suitable alkyl iminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutan-1,2,4-tricarboxylic acid. The acid ^ P glycinamide-N-N'-disuccinic (GADS), ethylene diamine N-20 N 'diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in the compositions detergents is one or more additional enzymes. Additional preferred enzyme materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases and incorporated in conventional manner in the detergent compositions. Suitable enzymes are also described in the patents of E.U.A. Nos. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A / S (Denmark), those sold under the trade name Maxatase, Maxacal and Maxapem by Gist-Brocades, m ^ r% those sold by Genecor International and those sold under the trade name Opticlean and Optimase by Solvay Enzimes. The protease enzyme can be incorporated into compositions according to the invention at a level of 0.001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, alpha-amylases obtained from a special strain of B. licheniformis. described in greater detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the trade name Termamyl and BAN by Novo Industries A / S. The amylase enzyme can be incorporated into composition according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition.

The lipolytic enzyme may be present at levels of active lipolytic enzyme from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions. The lipase can be of fungal or bacterial origin, being obtained, for example, from a lipase-producing strain of the Humicola species, the Thermomyces species or the Pseudomonas species, including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. The lipase that comes from mutants Chemically or genetically modified strains of these strains are also useful in the present. A preferred lipase is derived from ^ P Pseudomonas pseudoalcaligenes, which is described in the European patent granted EP-B-0218272. Another preferred lipase herein is obtained cloning the gene of Humicola lanuginosa and expressing the gene in Aspergillus oryza as host, as described in the European patent application EP-A-0258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, ^ Denmark under the trade name Lipolase. The lipase is also disclosed in the US patent. No. 4,810,414, Huge-Jensen et al., Issued March 7, 1989.

Organic polymeric compound Organic polymeric compounds are components Additional preferred ones of the detergent compositions according to the invention are preferably present as components of any particulate components, where they can act such as to bind the particulate component together. By "organic polymeric compound" is meant essentially any polymeric organic compound that is not an oligoester or polyamine soil release polymer, and which are commonly used as dispersants and anti-redeposition agents and suspension of soils in detergent compositions , including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein. The organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include organic homo- or copolymeric water-soluble polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of the latter type are described in GB-A-1, 596, 756. Polyamino compounds are useful herein, including those derived from aspartic acid such as those described in EP-A-305282, EP-A-305283 and EP-A-351629. Also suitable herein are terpolymers containing selected monomeric units of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of 5,000 to 10,000. ? Other organic polymeric compounds suitable for incorporated in the detergent compositions herein include essentially any charged and uncharged cellulose derivative such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Additional and useful organic polymeric compounds with the polyethylene glycols, particularly those with a molecular weight of 1000-10000, very particularly 2000 to 8000 and ^ P more preferably around 4000.

Foam suppression system 15 The detergent compositions of the invention, when formulated for use in machine wash compositions, preferably comprise a foam suppression system present at a level of from 0.01% to 15%, preferably from ^ B 0.05% to 10% and most preferably from 0.1% to 5% by weight of the composition. The foam suppression systems suitable for use herein may comprise essentially any known antifoam compound, including, for example, silicone antifoam compounds and 2-25 alkylalcanol antifoaming compounds. By "antifoaming compound" is meant any compound or mixtures of compounds which act to depress the foaming produced by a solution of a detergent composition, particularly in the presence of the stirring of that solution. Particularly preferred defoaming compounds for use herein are the silicone anti-foaming compounds defined herein as any defoaming compound that includes a silicone component. These silicone antifoam compounds also contain typically a silica component. The term "silicone", as used herein and in general in the industry, Wr encompasses a variety of relatively high molecular weight polymers containing siloxane units and a hydrocarbyl group of various types. The anti-foam compounds of Silicones which are preferred are siloxanes, particularly polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoaming compounds include the monocarboxylic fatty acids and the soluble salts of the same. These materials are described in the patent of E.U.A. No. 2,954,347, issued September 27, 1960 to Wayne St. John The monocarboxylic fatty acids and the salts thereof for use as suds suppressors typically have hydrocarbyl chains of 10 to 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. Other suitable defoaming compounds include, for example, high molecular weight fatty esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (e.g., stearone), N-alkylated amino triazines such as tri- or hexa-alkylmelamines or di- to tetra-alkyldiaminclortriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing 1 to 24 10 carbon atoms, propylene oxide, bis stearic acid amide and the di-alkali metal mono-stearyl phosphates ^ P (e.g., sodium, potassium, lithium) and phosphate esters . A preferred foam suppressor system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination: (i) polydimethylsiloxane, at a level of 50% at BP 99% , preferably 75% to 95% by weight of silicone antifoam compound 20; and (ii) silica, at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound; wherein said silica / silicone antifoam compound is incorporated at a level of 5% to 50%, preferably 10% to 40% by weight; (b) a dispersing compound, most preferably comprising a silicone glycol copolymer with a polyoxyalkylene content of 72-78% and a ratio of ethylene oxide to propylene oxide of from 1: 0.9 to 1: 1.1, at a level of 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred glycol silicone hardener copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising an alcohol of ethoxylated Cg with an ethoxylation degree of 5 to 50, preferably 8 to 15, at a level of 5% to 80%, preferably 10 % to 70% by weight; A highly preferred particulate foam suppression system is disclosed in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point on the scale of 50 ° C to 85 ° C, wherein The organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate foam suppressor systems in which the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms or a mixture thereof , with a melting point of 45 ° C to 80 ° C.

Clay Softening System The detergent compositions may contain a clay softening system comprising a compound? clay mineral and optionally a flocculating agent of clay. The clay mineral compound is preferably a smectite clay compound. Smectite clays are described in the U.S. Patents. Nos. 3,862,058, 3, 94 $, 790, 3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 10 and EP-A-313,146 in the name of the Procter & Gamble Company describes suitable organic polymeric clay flocculants ^ P.

Polymeric Dye Transfer Inhibitory Agents The detergent compositions herein may additionally comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof. a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: where P is a polymerizable unit, and O O O II II II A is NC, CO, C, -O-, -S-, -N-; x is o or 1; R are aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following general structures: O wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and / oyo / yz is or 1 and wherein the nitrogen of the NO group can be fixed or where the nitrogen of the group NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric backbone or to a combination of both. Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit comprise the polyamine N-oxides in which R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. A class of polyamine N-oxides comprises the group of 5-polyamine N-oxides in which the nitrogen of the group NO is part of the group R. The preferred N-oxides of polyamine are those in which R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides to which the N-O group is attached to the unit B polymerizable. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic group, Alicyclic heterocyclic in which the nitrogen of the functional group is NOT part of said group R. Examples of these classes are the polyamine oxides in which R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives f) thereof . The polyamine N-oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the water solubility and the desired dye suspension power. Typically, the average molecular weight is within of the scale from 500 to 1,000,000. b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The copolymers of N-vinylimidazole and N-vinylpyrrolidone suitable in the present invention have an average molecular weight scale of 5,000 to 50,000. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") BP that has an average molecular weight from 2,500 to 400,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product names PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K-90 ( average molecular weight of 360,000). PVP K-15 is ^ also available from ISP Corporation. Other Suitable polyvinyl pyrrolidones that are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. d) Polyvinyloxazolidone The detergent compositions herein can also use polyvinyloxazolidones as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of 2,500 to 400,000. e) Polyvinylimidazole The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of 2,500 to 400,000.

Optical brightener The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: wherein R ^ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and ^ amino; and M is a salt forming cation such as sodium or potassium When in the above formula R] _ is anilino, R 2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4 '-bis [(4-anilino-6- (N- 2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2 '-stilbenedisulfonic acid and the disodium salt. This particular brightener species is marketed under the trade name Tinopal UNPA-GX by Cibam Geigy Corporation. The Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula R] _ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [( 4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] - ^ P 2, 2 '-stilbenedisulfonic acid. This kind of brightener In particular, it is traded commercially under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R] _ is anilino, R is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4 '-bis [(4-anilino-6-morphino-s- Triazin-2-yl) amino] 2,2 '-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Cationic fabric softening agents ?? They can also be incorporated into the compositions of In accordance with the invention, cationic fabric softening agents are used. Suitable cationic fabric softening agents include water insoluble tertiary amines or dilarga chain amide materials such as those described in GB-Al 514 276 and EP-B-0 011 340. Cationic fabric softening agents are typically incorporated at total levels of 0.5% to 15% by weight, ^ P normally from 1% to 5% by weight.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colors and filler salts, with a preferred filler salt being sodium sulfate.

The pH of the compositions The present compositions preferably have a pH measured as a 1% solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, more preferably from 9.5 to 11.0. Form of the compositions The compositions according to the invention can have a variety of physical forms including the granulated forms, in tablets, in bars and liquids. The compositions are particularly so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a delivery device placed in the tub of the washing machine with the load of laundry. In general, the granular detergent compositions according to the present invention can be made by a variety of methods, including dry blending, spray drying, agglomeration and granulation. The average particle size of the components of the granular compositions according to the invention should preferably be such that no more than 5% of the particles are more than 1.7 mm in diameter and no more than 5% of the particles are less than 0.15. mm in diameter. The term "average particle size" as defined herein is calculated by screening a sample of the composition in a number of fractions (typically 5 fractions) in a series of Tyler sieves. The fractions of weight thus obtained are plotted against the opening size of the sieves. The average particle size is considered the size of the opening through which 50% by weight of the sample would pass. The overall density of the detergent compositions according to the present invention is typically an overall density of at least 600 g / liter, most preferably from 650 g / liter to 1200 g / liter. The density á? global is measured by means of a simple 5-cup funnel device consisting of a conical funnel rigidly molded on a base and provided with a butterfly valve at its lower end to allow the contents of the funnel to be emptied into an aligned cylindrical cup axially arranged below the funnel. The funnel is 130 mm high and 10 has internal diameters of 130 mm and 40 mm in its respective upper and lower extremities. It is mounted in such a way that • the lower extremity is 140 mm above the upper surface of the base. The cup has a total height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Your volume nominal is 500 ml. To carry out a measurement, the funnel is filled with manually poured dust, the butterfly valve is opened and the powder is allowed to overfill the cup. The full cup is ^ P removal from the frame and excess dust is removed from the cup passing a straight edge implement, v.gr. , a knife, through its upper edge. The full cup is then weighed and the value obtained for the weight of the powder is doubled to provide a global density in g / liter. Measurements are made in duplicate as required. 25 Agglomerated Surfactant Particles The cationic ester surfactant herein, preferably with additional surfactants, is preferably present in the granulated compositions of the present invention.

• Form of agglomerated particles of surfactant, which may be in the form of flakes, pellets, discs, noodles, tapes, but preferably have the form of granules. The most preferred way to process the particles is by agglomerating powders (eg, aluminosilicate, carbonate) with pastes highly active surfactants and controlling the particle size of the resulting agglomerates within limits ^ P specific. Said process includes mixing an effective amount of powder with a highly active surfactant paste in one or more agglomerators such as an agglomerator. container, a Z-shaped pallet mixer or most preferably an in-line mixer such as those manufactured by Schugi (The Netherlands) BV, 29 Chroomstraat 8211 AS, Leyland, The Netherlands, and Gebruder Lodige Maschinebau GmbH, D- ^ 4790 Paderborn 1, ElsenerstraSe 7-9, Postfach 2050, Germany.

Most preferably a high shear mixer is used, such as a Lodige CB (tradename). A highly active surfactant paste comprising from 50 wt% to 95 wt%, preferably 70 wt% to 85 wt% of agent is typically used. surfactant. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to prevent degradation of the anionic surfactants used. A pulp operating temperature of 50 ° C to 80 ° C is typical.

Laundry Washing Method The laundry washing methods of the present invention typically comprise treating laundry with an aqueous wash solution in a washing machine having dissolved or supplied laundry therein an effective amount of a washing detergent composition in a washing machine according to the invention. By a The effective amount of the detergent composition is intended to be 40 g to 300 g of product dissolved or dispersed in a washing solution of a volume of 5 to 65 liters, which are typical doses of product and volumes of wash solution commonly used in conventional laundry washing methods. In a preferred use aspect, a ^ P supply device in the washing method. He The delivery device is loaded with the detergent product and used to introduce the product directly into the drum of the washing machine before starting the washing cycle. Its volume capacity must be such that it is capable of containing sufficient detergent product that would normally be used in the washing method. Once the washing machine has been loaded with clothes, the delivery device containing the detergent product is placed inside the drum. At the beginning of the washing cycle of the washing machine, water is introduced into the drum and it rotates periodically. The design of the delivery device should be such as to allow the dry detergent product to be contained but then allow this product to be released during the wash cycle in response to its agitation when the drum is turned and also as a result of its contact with the washing liquid. In order to allow the release of the detergent product 10 during X.-- \ z, the device may possess a number of openings through which the product can pass. In alternative form, the device can be made of a material that is permeable to liquid but impermeable to the solid product, which will allow the product to be released. dissolved. Preferably, the detergent product will be released rapidly at the start of the wash cycle, thereby providing transient localized concentrations of the product in the washing machine drum at this stage of the wash cycle. ^ P Preferred delivery devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during the wash cycle. Especially preferred delivery devices for use with the composition of the invention have been described in the following patents: GB-B-25 2,157,717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland, published in Manufacturing Chemist, November 19889, p. 41-46, also discloses especially preferred supply devices for use with granulated laundry products, which are of a type commonly known as "granulette". Another preferred delivery device for use with the compositions of this invention is described in PCT patent application No. W094 / 11562. Essentially preferred delivery devices are described in patent application publications European Nos. 0343069 and 0343070. This application describes a device comprising a flexible liner in the form of a ^ bag extending from a support ring defining a hole, the orifice being adapted to admit sufficient product into the bag for a wash cycle in a process washing. A portion of the washing medium flows through the orifice into the bag, dissolves the product and the solution then passes down through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent product leakage wetted and undissolved, this arrangement typically comprises radial walls extending from a protuberance in a spoke wheel configuration or similar structure, in which the walls have a helical shape. Alternatively, the delivery device may be a flexible container, such as a bag or bag. The bag may be made of a fibrous structure coated with a waterproof protective material to retain the contents, such as that described in published European patent application No. 0018678. Alternatively, it may be formed of a polymeric material. water-insoluble synthetic provided with an edge or seal seal designed to break in the aqueous medium as described in published European patent applications Nos. 0011500, 0011501, 0011502 and 0011968. A convenient form of water cracking comprises a water soluble adhesive disposed along and sealing an edge of a sack formed of a polymeric film ^ P waterproof, such as polyethylene and polypropylene.

Packaging of the compositions 15 The commercially sold executions of the washing compositions can be packed in any suitable container including those made of paper, cardboard, plastic materials and any laminates ^ P suitable. A preferred packaging mode is described in European application No. 94921505.7.

/ Abbreviations used in the examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS: Linear sodium alkylbenzenesulfonate of C] _2 TAS: Sodium alkyl sulfate C45AS: C14-C15 linear sodium alkyl sulfate CxyEzS: Ct_x-Ciy branched sodium alkyl sulfate condensed with z moles of ethylene oxide C45E7: A predominantly linear C 4 -C 5 primary alcohol condensed with an average of 7 moles of ethylene oxide C 25 E 3: A primary alcohol of C] _ 2-C 15 branched condensed with an average of 3 moles of ethylene oxide C 25 E 5: A primary alcohol of branched C? _2 ~ i5 condensed with an average of 5 moles of ethylene oxide CEQ I: R1COOCH2.N + (CH3) 3 with R = Cp-C13 CEQ II: R1COOCH2CH2CH2N + (CH3) 3 with R = C11-C13 CEQ III R1COOCH2CH2N + (CH3) 2 (CH2CH2OH) with R = C1X-C13 CEQ IV: R1COOCH2CH2N + R2R3 (CH3) with R = C13_-C13 and R2 and R3 = C2-C3 QASI: R2.N + (CH3) 2 (C2H40H) with R2 = C12-C14 QASII: R2.N + (CH3) 2 (C2H40H) with R2 = C8 QASIIII R2.N + (CH3) 2 (C2H40H) with R2 = 50% Cg; 50% Cll QASIV: R2.N + (CH3) 2 (C2H40H) with R2 = 70% C10; 30% c8 Jabó: Linear sodium alkylcarboxylate derived from a mixture of 80/20 tallow and coconut oils TFAA: Cyl-Cis alkyl N-methylglucamide TPKFA: C 2-C 4 whole cut fatty acids STPP: Tripolyphosphate sodium anhydrous Zeolite A: Hydrated sodium aluminosilicate of the formula Na12 (A102Si02) 2. 27H20, which has a primary particle size in the range of 0.1 to 10 microns. NaSKS-6: Crystalline layered silicate of the formula Ü-Na2Si205 Citric acid: Anhydrous citric acid Carbonate: Anhydrous sodium carbonate with an average particle size of 200μm and 900μm Bicarbonate: Anhydrous sodium bicarbonate with a particle size distribution of between 400μm and 1200μm Silicate: Amorphous sodium silicate (ratio Si0: Na20 = 2.0) Sodium sulphate: Anhydrous sodium sulfate Citrate: Trisodium citrate dihydrate of 86.4% activity with a particle size distribution of between 425 / xm and 850μm MA / AA: Copolymer of 1: 4 maleic acid / acrylic acid with an average molecular weight of about 70,000 CMC: Carboxymethylcellulose sodium Protease; Proteolytic enzyme of activity 4KNPU / g sold under the trade name Savinase by Novo Industries A / S Alkalies: Prussolytic enzyme of activity 3AU / g sold by Novo Industries A / S Cellulase: Cellulite enzyme of activity lOOOCEVU / g sold by Novo Industries A / S under the trade name Carezyme Amylase: Activity amylolytic enzyme 60KNU / g sold by Novo Industries A / S under the trade name Termamyl 60T Lipase: Lipolytic enzyme of activity lOOkLU / g sold by Novo Industries A / S under the trade name Lipolase Endolasa : Endoglucose Enzyme Activity 3000CEVU / g sold by Novo Industries A / S PB4 Anhydrous sodium perborate tetrahydrate of nominal formula NaB02.3H2O.H202 PBl Anhydrous sodium perborate bleach monohydrate of nominal formula NaB02.H202 Percarbonate: Sodium percarbonate of nominal formula 2Na2C03.3H202 NOBS: Nonanoyloxybenzenesulfonate in the form of sodium salt NAC-OBS: (Nonanamidocaproil) oxybenzenesulfonate in the form of the sodium salt NACA: 6-Nonylamino-6-oxo-capronic acid TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminpenta (methylenephosphonate), marketed by Monsanto under the trade name Dequest 2060. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer 1: 4, 4'-bis (2-sulphotrisyl) biphenyl disodium brightener 2: 4 brightener , 4'-bis (4-anilino-6-morpholino-l. 3,5-triazin-2-yl) amino) stilben-2: 2'-disulfonate disulfonate HEDP: 1, 1-hydroxyethanophosphonic acid PVNO: N-oxide of polyvinylpyridine PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole SRP 1: End esters blocked with sulfobenzoyl with base structure of oxyethyleneoxy and terephthaloyl SRP 2: Short block polymer of poly (1) , 2-propylene terephthalate) diethoxylated Silicon Defoamer: Polydimethylsiloxane foam controller with a siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1.

In the following examples all levels are cited as% by weight of the composition: EXAMPLE 1 The following laundry detergent compositions A to F according to the invention were prepared: EXAMPLE 1 (CONTINUED) EXAMPLE 2 The following granular laundry detergent compositions G 1 with an overall density of 750 g / liter according to the invention were prepared: EXAMPLE 2 (CONTINUED) EXAMPLE 3 The following detergent formulations were prepared according to the present invention, wherein J is a phosphorus-containing detergent composition, K is a detergent composition containing zeolite and L is a compact detergent composition: EXAMPLE 3 (CONTINUED) EXAMPLE 4 The following detergent formulations according to the invention were prepared: EXAMPLE 4 (CONTINUED 8 EXAMPLE 5 The following formulations were prepared á? detergents according to the present invention: EXAMPLE 5 (CONTINUED) EXAMPLE 6 The following are high density detergent formulations containing bleach according to the present invention: EXAMPLE 6 (CONTINUED) EXAMPLE 7 The following high density detergent formulations were prepared according to the present invention: • • EXAMPLE 7 (CONTINUED) EXAMPLE 8 The following liquid detergent formulations were prepared according to the present invention: EXAMPLE 8 (CONTINUED)

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: (a) a cationic surfactant of the formula: + R1-N-R4 X "R- (I) in which R is a hydroxyalkyl group having not more than 6 carbon atoms, each of R and R is independently selected from alkyl or alkenyl of C? _4, - R is alkyl or alkenyl of Cg_n, and X ~ is a counterion, and b) a hydrophobic organic peroxyacid bleach system capable of providing a hydrophobic organic peroxyacid compound

2. - A detergent composition according to claim 1, characterized in that the cationic surfactant of formula I is selected from those in which R1 is -CH2CH2OH or -CH2CH2CH2OH, each of R2 and R3 are independently, C4 alkyl, R is alkyl or alkenyl of Cg_n and X "is an anion.

3. - A detergent composition according to claim 1 or claim 2, characterized in that the hydrophobic bleach system is capable of providing a peroxyacid compound of the formula: R- -N- -R -OOH R- -N- -C0OH, 6 II II OR Rc OO (II) (III) wherein R is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms , R is an alkylene, aplene or alkarylene group containing 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms.

4. A detergent composition according to any of the preceding claims, characterized in that the cationic surfactant is present in an amount of less than 5% by weight of the total detergent composition.

5. A detergent composition comprising: (a) less than 5% by weight of a cationic surfactant of the formula: wherein R is a hydroxyalkyl group having not more than 6 carbon atoms; each of R and R is independently selected from C 1 -4 alkyl or alkenyl, - R is C 12-14 alkyl or alkenyl, and X ~ is an anion; and (b) a hydrophobic organic peroxyacid bleach system, capable of providing a peroxyacid compound of the formula: R 5 CN R 7 C OOH or R 5 NC R 7 C OOH (II) (III) wherein R is an alkyl, aryl or aralkyl group containing from 1 to 14 carbon atoms, R is an alkylene, aplene or alkarylene group which contains from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms 6.- A detergent composition according to claim 5, characterized in that the cationic surfactant of formula I is selected from those in which R.sub.1 is -CH.sub.2 CH.sub.2 OH or CH.sub.2 CH.sub.2 CH.sub.2 OH, each of R.sub.2 and R.sub.3 are independently C.sub.4 alkyl.The detergent composition according to any of the preceding claims, characterized in that the organic peroxyacid hydrophobic bleach comprises a source of hydrogen peroxide and a hydrophobic organic peroxyacid precursor 8. - A detergent composition according to claim 7, characterized in that said hydrophobic precursor Organic peroxyacid ion is a precursor compound of alkylperoxy acid substituted with amide, selected from the group consisting of: R 5 C N R 7 C L and R 5 N C R 7 C L II II II O Rc OR R6 O O where L can be any outgoing group, R is a group , 7 aplo or alkaplo with 1 to 14 carbon atoms, R is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, and R is H or an alkyl, aryl or alkaryl group that C. g 5 contains from 1 to 10 carbon atoms, so that R and R do not contain more than 18 carbon atoms in total. 9. - A detergent composition according to claim 7 or claim 8, characterized in that the cationic surfactant and the organic peroxyacid hydrophobic precursor are present in the composition in a ratio of 25: 1 to 1: 1. 10. A detergent composition according to any of the preceding claims, characterized in that the cationic surfactant is present in an amount of 0.05% to 4.5% by weight of the detergent composition. 11. A detergent composition according to claim 10, characterized in that the cationic surfactant is present in an amount of not more than 4.0% by weight. 12. A detergent composition according to any of the preceding claims, characterized in that R1 is CH2CH2OH and each of R2 and R3 are methyl. 13. - A detergent composition according to any of the preceding claims, characterized in that R is a straight chain alkyl group. 14. - A detergent composition according to any of the preceding claims, further characterized in that it comprises a polymeric component of hard base, the proportion of cationic surfactant to polymer component ^ k hard base in the composition is 10: 1 to 1: 3. 15. A detergent composition according to claim 12, characterized in that the amount of hard base polymer component is less than 1.7% by weight of the detergent composition. 1

6. - A detergent composition according to claim 12 or claim 13, characterized in that the hard base polymer component has pendant carboxylic functionality and a molecular weight of 20,000 to 150,000. 1

7. - A method of washing clothes in a domestic washing machine in which, a dispensing device that 15 contains an effective amount of a solid detergent composition according to any of claims 1 to 16, is introduced into the drum of the washing machine before starting the washing, wherein said dispensing device allows the progressive release of said 20 detergent composition towards the wash liquor during washing.