MXPA98009204A - Detergent compositions that comprise polyamine polymers with improved capacity of disciple of suicide - Google Patents

Abstract

The present invention relates to encompassing detergent compositions comprising polymeric polycarboxylates and polyamine soil removal agents, the composition having improved soil dispersion properties, especially for polar soils.

Description

DETERGENT COMPOSITIONS THAT INCLUDE PQLIAMINE POLYMERS WITH IMPROVED CAPACITY OF DIRT DISPERSION CAHPQ pg A tNVEN? IQN The present invention relates to laundry detergent compositions that provide improved soil dispersion benefits. The present invention relates to detergent compositions comprising psimeric polycarboxylates and soil-removing paliamine agents.

BACKGROUND OF THE INVENTION Detergent formulators are faced with the task of designing products to remove a wide spectrum of dirt and stains from fabrics. It is particularly convenient to remove polar dirt, such as protein and clay, from the washing surfaces. Polymeric polycarboxylates are used in detergent compositions to disperse and suspend highly charged hydrophilic polar particles such as clay. It is believed, although it is not intended to be limited by theory, that copolymeric pallets and higher molecular weight organic polycarboxylates (molecular weight above 4000) increase the overall detergency-enhancing action when used in combination with other detergency builders r by means of inhibition of crystal growth »peptization and release and antiredeposition of particulate dirt. Well known polymeric polycarboxylate materials are derived from acrylic acid including water-soluble salts of polymerized acrylic acid. { homopolymers) "and acrylate / alato-based copolymers" such as water-soluble salts of copolymers of acrylic acid and maleic acid. It has now been discovered that compositions comprising the combination of copolymer polycarboxylates and / or higher molecular weight homopolymer polyo arboxylates (molecular weight above 4000) with polyamine soil removers can be used to provide improved effective dispersion benefits of dirt (especially on polar dirt) in washing liquors. Accordingly, an object of the present invention is to provide improved soil dispersing compositions using polymeric polycarboxylates and polyamine soil removal agents. These and other objects are achieved in the present as will be seen from the following description.

TECHNICAL BACKGROUND The use of polymeric polycarboxylates in detergent compositions is reported in the United States Patent 4 »144» 226 »Crutchfield et al.» Issued March 13, 1979 and in the United States Patent 3 »08» 067 »Diehl» Issued on March 7, 1967. See also United States Patent 3,723,322, see also European Patent Application No. 66915 published on December 15, 1982, and published EP 1 3, 60, 60. on September 3, 1986. The following describe different polymers or polyamines modified dirt removers? United States Patent 4 »54?» 744 »Connor» Issued October 22, 1985 »United States Patent 4» 597 »898» Vander Meer »Issued July 1, 1986» United States Patent United 4 »877» 896 »Mandolado y otros» issued on October 31, 1989; United States patent 4 »891» 160 »Vander Meer» issued on January 2, 1990; United States Patent 4 »976» S79 > Mandolado y otros »issued on December 11, 1990» United States patent 5 »415» 807 »Gosselink» issued on May 16, 1995 »United States patent 4» 235 »735» Marco and others »issued on November 25, 1980; W0 95/32272 »published on November 30, 1995; United Kingdom Patent 1 »537» 288 »published on December 29, 1978; United Kingdom patent 1 »498» 520 »published on January 18, 1978; German patent DE 28 29 022 »issued on January 10, 1980» Japanese Kokai patent »published on April 27, 1994.

BRIEF-. PESCf PCEPN pg ^ A liqvEHGl-PN The present invention encompasses detergent compositions comprising polyamine soil removers and polymeric polycarboxylates. The present invention is directed to a laundry detergent composition comprising; (1) at least about 0.01% by weight »of a detersive surfactant selected from the group consisting of anionic, ionic, zonic and ampholytic anionic surfactants and mixtures thereof (2) of 0.1 * / . to about 15% of palletic polycarboxylates selected from the group consisting of polymeric homopolymer carboxylates having a molecular weight greater than 4000 and copolymer polycarboxylates and mixtures thereof (3) from about 0.01% to about 5% polyamine dirt reagents comprising a polyamine backbone corresponding to the formula; V i ÍN ^ Rh + i-- -R-trl -R - t H2 having a modified polyamine formula V < «-. +? > w «? n2» or a polyamine skeleton corresponding to the formula; which has a modified polyamine formula 10 V < .-k *? > wmv.v'k 2 'wherein k is less than or equal to n »said polyamine skeleton» before modification has a molecular weight greater than about 200 daltans »where; i) the units V are terminal units that 15 have the formulas ii) units W are skeleton units that have the formula? N-R- or o -R- iii) the Y units are branching units having the formula; iv) the Z units are terminal units that have the formula; wherein the skeletal linker units R are selected from the group consisting of Alkylene of C & - t YES, alkenylene of C "-Cta» hydroxyalkylene of C3-Ct2 »dihydroxyalkylene of C ^ -C? A!» Dialkylarylene of C? -Cta6 »- (R * 0) R1-, - (RlO) s-eR »(0Rt) > < »- (CHaeCH (0Rß) CHß0) > , (R10) vR1 ~ (0CHßCH (0R ??) CH2) "-» -C (0) (R - *) r.C < 0) - »20 CHaCH (0R? E) CHSE-» and mixtures thereof; wherein R * is alkylene of C ^ -C ^ "and mixtures thereof; R8 * is hydrogen »- (R10) > < B "and mixtures thereof; R3 is C1-Cl-alkyl »arylalkyl of C-r-Clae» aryl substituted with alkyl of C -Cla »aryl of C < Faith-C? a! and mixtures thereof; R is C 1 -C 12 -alkylene, alkenylene of C 1 -C 5 -C 2 -alkylene, C 2 -C 1 -alkylene, and mixtures thereof; Rs is alkylene of Cx-C? Ae »hydroxial qui le or of C? ~ C? 'dihydroxyalkylene of C? -C? a` dialkylarylene of '5 C.-C? A »-C < 0) -, -C < 0) NHR * NHC (0) - »-R OR -» - C (0) (R '*) r.C < 0 > - »CHaCH (OH) CHa-» CHaCH (OH) CHaO- < R? A > R1OCHa! CH (OH) CH! B- »and mixtures thereof; R * is alkylene of Cst-Ct. or arylene of C ^ -C ^ units E are selected from the group The compound consists of hydrogen, alkyl, alkyl, and hydroxyalkyl of Ct-C3 at the hydroxyalkyl of Ca "" "^^ - (CH- ^) ,, COa» - (CHjz) < , S03, M "-CH (CH3? C0aeM> C0ßM» - <CHa) "P0., M" - (R10) ¡. < B "-C (0) R3" and mixtures thereof; oxide? B is hydrogen »C1-C4 alkyl» - (CHa.) < , S03M, ~ (CHa?) -, COstM »- (CHa)" (CHS03M) CHg.SO-.M, - (CHa) ^ - (CHSOaeM> CHssS03M, - (CH2) "P03M» -P03M "and mix of the same; M is hydrogen or a cation soluble in water in sufficient quantity to satisfy the load balance; X is a water soluble anion »has the value of 4 to about 400; n has the value from 0 to about 200; p has the value of 1 to 6 »has the value of 0 to 6» r has the value of 0 or i; w has the value of 0 or l; x has the value of 1 to 100; "y" has the value from 0 to 100 »z has the value of 0 or 1» and (4) the remainder are auxiliary ingredients »wherein the ratio of polymeric polycarboxylates to polyethylene dirt reeding agents is about 100; 1 to i; i.

DETAILED DESCRIPTION OF THE INVENTION All percentages "ratios and proportions used herein are by weight" unless otherwise specified. All references in ppm (parts per million) are the quantities in the final detergent composition. All temperatures are in degrees Celsius (° C) "unless otherwise specified. All the references described are incorporated herein by reference.

Detersive Surfactants The detersive surfactants suitable for use in the present invention are the cationic »anionic» nonionic »ampholytic» zwitterionic surfactants and mixtures thereof described hereinafter. The laundry detergent composition may be in any suitable form, eg high density liquids, light liquids or other pourable forms, as well as granules or laundry bars. The polyamine soil removal agents of the present invention can be formulated in any detersive matrix chosen by the formulator. The laundry detergent compositions according to the present invention may additionally comprise at least approximately 0.01%, preferably at least about 0.1%, preferably at least about 1% by weight of the following detersive surfactants. Non-limiting examples of surfactants useful herein "typically at levels of about 0.1% to about 55% by weight" include the alkyl benzenesulfonates ("LAS") of Ctl-C1? and the secondary alkylsulfates ("AS") of branched-chain and randomized Cto-CXCt »the secondary alkyl sulphates of C10-Clß of the formula CH3 (CHa >; x (CHOS03-M *> CH3 and CH3 (CHaE) and (CH0S03-M *) CHssCH3 »where xy (y + 1) are integers of at least about 7» preferably at least about 9 »and M It is a cation of water solubility, especially sodium, unsaturated sulfates such as oleumsulfa or C10-Cl-alkylalkysulfates ("AE ^ S"), especially etatoxyses of 1-7 of 0E> Chloro alkylalkoxycarboxylates. C1 (especially the ethoxycarboxylates of 1-5 of 0E) »the glycerol ethers of Cto-Clß» the alkyl glycosides of C10-C1ß and their corresponding sulphated polyglycosides »and the aliphosphonate fatty acid esters of Clz-Clß If desired, conventional non-ionic amphoteric surfactants such as C?-CE-Cß alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the alkylphenols of C-fc-C, (especially ethoxylates and mixed ethoxy / propoxy) »betaines and sulfabetaines (" sultaines ") of C1SB-C1ß" or C10-Ctβ amine oxides and the like »can also be included in the overall compositions. The fatty acid amides N-alkyloxyhydroxy ion can also be used. Typical examples include N-methylglucamides of C1SE-Clβ. See WO 9, 206, 154. Other surfactants derived from sugar include the N-alkoxyl-hydroxylic acid amides such as N- (3-methoxypropyl) glucamide of Cto-C? A. The N-propyl to N-hexy I lucamides of C? A [-Ct? Can be used for low foaming. Conventional Ci C soaps, -Ca < i. If high foaming is desired »branched-chain soaps of C10-C4 < ,. Mixtures of anionic and nonionic surfactants are especially useful. Other useful surfactants are listed in the standard texts.

Polymer Polycarboxylates Polymeric dispersants of polycarboxylate can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid »maleic acid (or maleic anhydride)» fumaric acid »itaconic acid» aconitic acid »mesaconic acid» citraconic acid and methylenic acid ionic acid. The presence in the polycarboxylates of polymers of the precursor of monomeric segments which do not contain carboxylate radicals such as vinyl ether, styrene, ethylene, etc., is adequate, provided that said segments do not constitute more than about 40% by weight. . Preferred are polyol monopolyols which have molecular weights greater than 4000, such as those described below. Particularly suitable homopolymeric polyols can be derived from acrylic acid. These acrylic acid-based polymers which are useful herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in the acid form preferably ranges from above 4,000 to 10,000,000, preferably from above 4,000 to 7,000, and preferably from above 4,000. 5,000. The water-soluble salts of these acrylic acid polymers can include, for example, the alkali metal salts, ammonium and substituted ammonium. Copolymeric polycarboxylates such as those described below are also preferred. The acrylate / alato-based copolymers can also be used as a preferred component of the polymeric polycarboxylate dispersants. These materials include the water soluble salts of acrylic acid and maleic acid capolymers. The average molecular weight of these copolymers in the acid form preferably ranges from 2,000 to 100, preferably from 5,000 to 75,000, preferably from 7,000 to 65,000. The proportion of acrylate to malate segments in these copolymers generally varies from 30; i to l; l »preferably 10; 1 to 2; l. The water-soluble salts of these acrylic acid / maleic acid cappolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Polymeric polymer dispersants such as described above can be used at levels of 0.1% to 15%, preferably 3.75% to 7.5%, in the final detergent composition.

Polyamine Dirt Remover Agents The paliamine dirt remover of the present invention refers to modified paliamines. These polyamines comprise skeletons which can be either linear or cyclic. The polyamine skeletons can also comprise polyamine branching chains to a greater or lesser extent. In general, the polyamine backbones described herein are modified in such a way that each nitrogen in the pol chain. The ina is described below in terms of a unit that is substituted "quaternized" oxidized "or combinations thereof. For the purposes of the present invention, the term "modification" is defined as the replacement of a hydrogen atom of -NH of the skeleton with an E unit (substitution) »quaternization of a skeleton nitrogen (quaternized)» or oxidation of a nitrogen from the skeleton to N-oxide (oxidized). The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a nitrogen of the skeleton with an E unit. Quaternization or oxidation may take place in certain circumstances without substituting it, but the Preferred substitution is accompanied by oxidation or quaternization of at least one nitrogen of the skeleton. The linear or non-cyclic polyamine skeletons comprising the soil removal agents of the present invention have the general formula; V i [H-N-Rh ++ IN-RhriN-R-t H2 said skeletons »before subsequent modification» comprise primary and secondary and tertiary amine nitrogens linked by "linker" units R. Loe cyclic polyamine skeletons comprising the soil removal agents of the present invention have the following general formula; [HN-Rlrtk said backbones prior to the subsequent modification "comprise primary amine nitrogens" secondary and tertiary amine "joined by" linker "units R. For the purpose of the present invention" the primary amine nitrogens comprising the backbone or branching chain "once modified "are defined as units V or Z" terminals ". For example when a primary amine moiety located at the end of the main backbone or polyamine branch chain having the structure; H-, NRI- is modified according to the present invention »is subsequently defined as a" terminal "V unit" or simply a unit V. However "for the purposes of the present invention» some or all of the primary amine portions they may remain modified »subject to the restrictions described later in the preamble. These portions of the primary amine are unmodified »by virtue of their position in the chain of the skeleton they remain as" terminal "units. Likewise »when a portion of primary amine located at the end of the main polyamine skeleton» having the structure; -NH, modified according to the present invention, is subsequently defined as either a "terminal" S unit or simply a unit Z. This unit may remain unmodified »subject to the restrictions described hereinafter. Similarly, the secondary amine nogens comprising the skeleton or branching chain once modified are defined as "skeleton" units W. For example "when a secondary amine moiety" is the principal constituent of the skeletons and strings of rationing of the present invention "having the structure H I • t-N-R-l- it is modified according to the present invention, which is then defined as a "skeleton" unit W or simply a unit W. However, for the purposes of the present invention, some or all of the secondary amine portions may remain unmodified. . Eetae unmodified secondary amine portions by virtue of their position in the skeleton chain »remain as units of the" skeleton ". In a further similar manner, "the tertiary amine nitrogens comprising the backbone or branching chain" once modified "are further referred to as" branching "Y units. For example when "a tertiary amine moiety" which is a chain branching point of the polyamine skeleton or other branching chain or rings »having the structure; -CN-R - I- is modified according to the present invention, after which it is defined as a "branching" unit Y or simply a unit Y. However, for the purposes of the present invention, some or all of the tertiary amine portions may remain unmodified. These portions of tertiary amine not modified by virtue of their position in the skeleton chain "remain as" branching "units. The R units associated with the nitrogens of the units V »W and Y» which serve to connect the polyamine nitrogens »are described hereinafter. The final modified structure of the polyamines of the present invention can therefore be represented by means of the general formula V w Y ~ z for linear polyamine polymers "and for the general formula V or Y Y 7 for cyclic palm polymers. For the case of palia inas comprising rings »a unit Yr of the formula; I R I -CN-R3- serves as a branching point for a skeleton or branching ring. For each unit Y '»there exists a unit Y that has the formula; --CN-R -] - which forms the point of connection of the ring with the main chain of the polymer or the branch. In the only case in which the skeleton is a complete ring, the palia skeleton has the formula; therefore »they do not comprise terminal Z unit and they have the formula; V W Y Y 'in which k is the number of branching units forming the ring. Preferably, the polyamine backbones of the present invention do not comprise rings. In the case of non-cyclic paliamines, the ratio of index n to index m refers to the relative degree of branching. A completely unbranched linear modified polyamine according to the present invention has the formula; VW "Z this is equal to 0. The higher the value of n (the smaller the proportion of a n), the greater the degree of branching in the molecule. Typically, the value varies from a minimum value of 5 to approximately 400. However, larger values of m are also preferred, especially when the value of the index n is very low or close to 0. Each polyamine nitrogen either primary »secondary or tertiary» once modified according to the present invention »is subsequently defined as a member of one of three general classes; replaced »quaternized or oxidized. The unmodified polyamine nitrogen units are classified into units V »W» Y or Z »depending on whether they are primary» secondary or tertiary nitrogens. This is »the modified primary amine nitrogens are V or Z units» the unmodified secondary amine nitrogens are units W and the modified n-tertiary amine nitrogens are Y units »for the purposes of the present invention. The modified primary amine moieties are defined as "terminal" V units and have one of three forms a) simple substituted units having the structure; E- -R- I E b) quaternized units that have the structure? where X is an adequate counter-ion that provides load balance; and c > rusty units that have the structure; Modified secondary amine moieties are defined as "skeleton" W units having one of three forms; a) simple substituted units that have the structure; ?OR -N-R- b) quaternized units that have the structure! in which X is a suitable cantraion that provides load balance; and c) oxidized units having the structure; The modified tertiary amine moieties are defined as Y "branching" units having one of three forms; a) unmodified units that have the structure; -N-R- b > quaternized units that have the structure! where X is an adequate counter-ion that provides a load balance; and c) oxidized units that have the structure? Certain portions of modified primary amine are defined as "terminal" S units that have one of three forms? a) simple substituted units that have the structure; -N-E É b) quaternized units that have the structure; where X is-an adequate counter-ion that provides a load balance? and c) oxidized units that have the structure? When any position on a nitrogen is not replaced or not modified, it is understood that E will be replaced by hydrogen. For example, a primary amine unit comprising an unit E in the form of a hydraxing portion is a V-terminal unit having the formula (HOCHa.CHa) HN-. For the purposes of the present invention »there are two types of chain terminator units» units V and S. The unit "terminal" Z is derived from a terminal primary amine portion of the structure -NHa. The non-cyclic polyamine skeletons according to the present invention "comprise only one unit Z" while the cyclic polyamines may not comprise units Z. The "terminal" Z unit may be substituted with any of the units E described below in I presented" except when unit Z is modified to form an N-oxide. In the case in which the nitrogen of unit Z is oxidized to an N-oxide »the nitrogen must be modified and therefore E can not be a hydrogen. The polyamines of the present invention comprise skeleton "linker" units R which serve to connect the nitrogen atoms of the backbone. The R units comprise unidadeß which for the purpose of the present invention are called "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are Cx-CX alkylene? C3-C6 alkylene and C3-Cla hydroxyalkylene in which the hydroxyl portion can take any position on the R- unit except the carbon atoms directly connected to the nitrogens of the polyamine skeleton; dihydroxial which is the loam of C ^ -C13 where the hydrophilic portions can occupy any two of the carbon atoms of the chain of the unit R except those carbon atoms directly connected to the nitrogens of the paliamine skeleton? dialkarylene of Cß-Ctae which for the purpose of the present invention are arylene portion having alkyl substituent groups as part of the linker chain. For example, a dialkylarylene unit has the formula? although the unit na needs to be 1 »4-sußti tuido» but it can also be 1 »2 or 1» 3-substituted with alkylene of Ca-CtS? »preferably ethylene» 1 »2-propylene and mixtures of the mimes »very preferably ethylene. The R "oxy" units comprise - (R * 0) > R "3 (0R1 > M-, ~ Chach (0rz > CHß0)" (R10) s, R * - (0CHseCH (0R: K) CHa) w- »CH¡2CH (0Rss) Chai, -? (R10)> R1- and mixtures thereof The preferred R units are alkylene of Cst-Cls. Hydroxyalkyl or of C3-C1se »dihydroxyalkylene of C ^ .- C1z» dialkylarylene of Cß-C? A? »- (R ^ O ^ 1-» -CHSECH (0RSC) CHSÍ- »- (CHssCH (0H) CHa0) B- (R10) and R * (0CHa? CH-» (0H ) CHz) w '- (ROI ^ ÍOR1) -, - "R units highly preferred are alkylene CSS-C1' hydroxyalkylene dihidroxialqui log of C * - C e > (R * 0 >? MR * - t ~ (R * 0) > < Rß (OR1"-, (CHseCH (OH) CHaO), (R10) >, R * (OCHaeCH- (OH) CHss) w ~» mixtures thereof »units Even more preferred are C2-Ct2 alkylene "C3 hydroxyalkylene and mixtures of the most preferred are C? -C alkylene The skeletons which are most preferred in the present invention comprise at least 50% R units. The units R 1 are alkylene of C 2 -C ^ and mixtures of the moieties, preferably ethylene, R 2 is hydrogen and - (R 10)> -Bf preferably hydrogen, R 3 is C 1 -C 3 alkyl. arylalkyl of Ct-C? a »alkyl of C ^ -C? and substituted aryl» aryla of CA-C? ae »and mixtures thereof» preferably alkyl of C, .- C? a. »alkyl The most preferably C 1 -C 4 alkyl is more preferably methyl. The R3 units serve as part of the E deecritae units later. R-* alkylene of Cl-C? As »alkenylene of C-C15e» arylalkote or C? -Cxa'arlene of C < fc-Ct < > Preferably C 1 -C 10 alkylene, C 1 -Clalkylene, most preferably C, -C 2 alkylene, more preferably ethylene to butylene. Rβ is alkylene of Cj-C, hydroxy-alkylene of C3-? A »dihydroxyalkylene of C _ ^ - C?: 2» dialkylalkyl of Cß-Cla? »- C (0) -» -C (0) NHR * NHC (0) - »-C (0> (R») rC (0) - »Rl (0R1) -» (CHaíCH (OH) CH3? O (R »0)>, R1OCHaeCH (OH) CHa, - »-CÍO) (R **) ,. C (0) -» (CH 2 CH (OH) CHa- »Rβ is preferably ethylene» -C (0) - »C (0) NHR * NHC (0> -» R OR 1) -, -CHaCH (OH) CHa- »( CHaeCH (OH) CHse0 (R »0) R1OCHstCH- (OH) CHa-» most preferably - (CHS? CH (OH) CHat-. R *> is alkylene of Cβ-C? A or arylene of Clfc-C1SB. units R "oxy" is further defined in términoß of laß unidadeß R * »Ra and Rss. the units R" oxy "preferred comprise laß R1 units" RSS and preferred RSs. Loe agents removedoreß dirt preferred polyamine of the present invention comprise at least 50% of R * units that are ethylene The preferred R1 »R * and Rβ units are combined with the R" oxy "units to produce the preferred R" oxy "units in the following manner: i) substituting the Rs preferred - (CHS8CH3E0) > < RSS (0CHaeCHsß) >, - »ße produces (H ^ CH ^ O" ^ CH ^ CHOHCHa- (OCHjjCHjg) - ii.) replacing R1 and R * preferred (CHseCH ( ORas) CHa0) -t- (R * 0) R * O (CH¡zCH (OR: B) CH! B) w-, - (CHS8CH (0H) CH3S0> - (CHatCHss 0) CHstCHa0 (CHSÍCH (0H) CHa £) w- iii) substituting Rx preferred by -CHaeCH (0Rse) CHa- »produces -CHSBCH (0H) CHa! -. E units are selected from the group consisting of hydrogen "alkyl Cj-C22" alkenyl Cs ~ 'st t arylalkyl - (! CHa) ^ S03M' -CH (CHßC0aM) C0seM '~ (CHa) "P03M" - (R * 0) "B» -C (0) R = »» preferably hydrogen »C2-C22r hydroxy alkylene benzyl» alkylene of Ct-Caa »- (R * 0)" B »-C (0) R = * »- (CH2) p, C0aeM» (CHas) ^ S03M »-CH (CHaCOa) COa» most preferably alkylene of C _.- Caae »~ (R * 0): B» -C (0) R = » , - (CHa) "C0aM" - (CHa) -, S03M »-CH (CHaC0a) CQa» more preferably alkylene of Cj-Caj »- (R10) H! B and -C (0) R3. When no modification or substitution is made on a nitrogen "then the hydrogen atom will remain as the portion representing E. The units E do not comprise hydrogen atoms when the units V» W to S eßtán axidadaß »this is» the nitrogens are N-oxides. For example, does the skeleton chain or branching chains not contain units of the following structure? Aditionally, the units do not include carbonyl groups directly attached to a nitrogen atom when the units V, W or Z are axidated, and the nitrogens are N-oxides. According to the present invention, the portion -C (0) R3 of unit E is not bound to a nitrogen modified in N-oxide »that is» there is no N-oxide of amides having the structure? or combinations of the ismoß. B eß hydrogen »C1-CA alkyl» - (CHa) ^ S03M »- (CHa) ^ C0aM» (CHa) -, - (CHS03M) CHaS03M »(CHa >" (CHS0aM) CHaS03M »- (CHa) | .P03M »-P03M» preferably hydrogen »- (CHa) ,, S03M» - (CHa) "(CHS03M) CHaS03M, (CHa)" - (HS0a) HaS03 »most preferably hydrogen or - (CHa)«, S03M. hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance, eg, a sodium cation also satisfies - (CHa) -, C0aM and - (CHa) "S03M" resulting in portions (CHa) , C0aNa and - (CHa) ^ S03Na.Most of a monovalent cation (sodium »potassium» etc. can be combined to satisfy the required chemical charge balance, however »the load of more than one anionic group can be balanced by means of a divalent cation "or it may be necessary more than one monovalent cation to satisfy the loading requirements of a polyanionic radical, for example" a portion - (CH,. > ,, P03M substituted with atoms Sodium has the formula - (CHa)., P03Na3 Divalent cations such as calcium (Caß *) or magnesium (Mg **) can be substituted by or combined with other suitable monovalent cations soluble in water. The preferred cations are sodium and potassium and sodium is very preferred.

X is a water-soluble anion such as chlorine (Cl ~) »bromine (Br ~) and iodine (I ~)» or X can be any negatively charged radical such as sulfate (SO ^. * -.) And methosulfate (CH3S03_ ). Formula indices have the following values; P has the value of 1 to 6 »q has the value of 0 to 6» r has the value of 0 or 1 »w has the value of 0 or 1» x has the value of 1 to 100; and has the value from 0 to 100; z has the value 0 or 1; m has the value of 4 to 400 »n has the value of 0 to 200; + n has the value of at least 5. The preferred polyamine waste polymers of the present invention comprise polyamine skeletons in which less than about 50% of the R groups comprise R "oxy" units preferably less about 20% »preferably less than 5%» very preferably the R units do not comprise R "oxy" units. The most preferred dirt removing agents which do not comprise R "oxy" units comprise polyamine skeletons in which less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1, 2-praphylen and 1, 3-propylene comprise 3 to less carbon atoms and are preferred R "hydrocarbon" units. That is to say that when the R units of the skeleton are alkylene of Ca-C? A »alkylene of Ca-C3 is preferred and more ethylene is preferred. The polyamine soil removal polymers of the present invention comprise homogenous and nonhomogeneous homogenous palladium skeletons in which 100% or less of the -NH units are modified. For the purpose of the present invention, the term "homogeneous polyamine skeleton" is defined as a polyamine skeleton having R units that are the same (ie, all are ethylene). However, this definition of equality does not exclude polyamines comprising other foreign units comprising the polymer backbone which are present due to an artifact of the chosen chemical synthesis method. For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polytetraimimides, therefore a sample of polyethyleneimipate comprising a hydroxyethyl portion resulting from the "initiator" of polymerization comprises a homogeneous polyamine skeleton for the purposes of the present invention. A polyamine skeleton comprising all R units of ethylene in which no branching units Y 'is present is a homogeneous skeleton. A paliamine skeleton comprising all ethylene units R and a homogenous esskeleton regardless of the degree of branching or the number of cyclic branches presente. For the purposes of the present invention, the term "non-homogeneous polymeric skeleton" refers to polyamine skeletons which are a mixture of various lengths of unit R and types of unit R. For example, a non-homogeneous skeleton comprises R units which they are a mixture of ethylene and 1, 2-propylene units. For the purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" units R is not necessary to provide a non-homogeneous skeleton. Proper handling of this "chain lengths of unit R" provides the formulator with the ability to modify the solubility and substantivity in the fabric of the soil removal agents of the present invention. The preferred polyamine soil remover polymers of the present invention comprise homogeneous polyamine backbones which are fully or partially substituted with partially or fully quaternized polyethylene or amines and mixtures thereof. However, not all the nitrogens of the skeletal amine must be modified in the same way, leaving the choice of modification to the specific needs of the formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator. The preferred polyamines comprising the backbone of the compounds of the present invention are generally polyalkylenamines (PAA's) »polyalkyleneimines (PAI's)» preferably polyethylene (PEA's) »pallethylenimines (PEI'e)» or PEA's or PEI's connected for portions that have longer R units than PAA's »PAI's» PEA's or original PEI's. A common polyalkylene lenamine (PAA) is tetrabutylenepentamine. PEAs are obtained by reactions that include ammonia and ethylene dichloride "followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Among the pentamines, that is to say, lae hexaeas, hepta inae, octanes and possibly nonanes, the cogenetically derived mixture does not appear to be separated by distillation and may include other materials such as cyclic amines and particularly piperazine. Cyclic amines can also be present with side chains in which nitrogen atoms appear. See the patent of E.U.A. 2 »792» 372 »Dickinson» issued on May 14, 1957 »which describes the preparation of PEA'ß. Preferred amine polymer backbones comprise R units which are alkylene units of Ca (ethylene) »also known as poliethenimines (PEI's). Preferred PEIs have at least moderate branching ie the ratio of a n eß to less than 4? i »however» PEIs having an a n ratio of 2 * 1 are preferred. The preferred skeletons "before the modification" have the general formula? H I I tHaNCHaCHa3"-CNCHaCHa3" -CNCHaCHa 1"-NHa where m and n are the same defined above. The preferred PEI's "before modification" will have a molecular weight of more than about 200 dal tons. The relative proportion of the primary amine, secondary and tertiary amine units in the polymer backbone, especially in the case of PEIs, will vary depending on the form of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine skeleton chain represents a potential eitium for subsequent replacement or quaternization or oxidation. These polyamines can be prepared, for example, by polymerizing ethylene imine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. The specific methods for preparing eßtoß polyamine skeletons are described in the patent of E.U.A. No. 2 »182» 306 »Ulrich and others» issued on December 5, 1939; the patent of E.U.A. No. 3 »033» 746 »Mayle et al.» Issued on May 8, 1962; the patent of E.U.A. Na 2 »208» 095 »Essel an et al.» Issued on July 16, 1940; the patent of E.U.A. Na 2 »806» 839, Crowther »issued on September 17, 1957; and the patent of E.U.A. No. 2 »553» 696 »Wilson» issued May 21, 1951; all incarparadaß in the present by reference. Example 1 of modified soil removal polymers of the present invention comprising PEI'ß »η i lußtran in laß for ulae I-IV? Formula I represents a soil-removing polymer comprising a PEI skeleton in which all substitutable nitrogens are modified by replacing the hydrogen with a polyoxyalkynoxy unit - (CHaCH3'0) ^ .H "having the formula? Formula I This is an example of a soil remover polymer that is completely modified with a type of portion. Formula II illustrates a soil remover polymer comprising a PEI backbone in which all the subtitueible primary nitrogens are modified by hydrogen replacement with a polyoxyalkyl unit. - (CHaCHa0) tH »the modified ee molecule then by sub sequential oxidation of all the primary nitrogens and secondary oxidizable to N-oxides? said dirt remover polymer has the formula? Formula I I Formula III represents a soil remover polymer comprising a PEI esskeleton in which all the hydrogen atoms in the skeleton are substitued and some amide units in the eßkeleton are quaternized. The substituents are polyoxyalkylene units "- (CHaCHa0) -rH" or methyl groups. The modified PEI dirt remover polymer has the formula Formula III Formula IV represents a soil remover polymer comprising a PEI skeleton wherein the nitrogens of the backbone are modified by substitution (i.e. by "- (CHaCHa0) ^ H" or methyl) "quaternized" or oxidized to N- oxides »or co binacioneß of them. The resulting dirt remover polymer has the formula? Formula IV In the previous examples "not all nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have ethoxylated a portion of the secondary amine nitrogens having at the same time other secondary amine nitrogens oxidized to N-oxides. This applies to primary amine nitrogens, since the formulator can choose to modify all or a portion of the primary amine nitrogens with one or more substrates before oxidation or quaternization. Any possible combination of E groups can be ßubßti tuyenteß on the primary and secondary amine nitrogens "except for the restrictions described above. The polyamine dirt remover agents of the present invention are included in the detergent composition at about 0.01% to about 5% »preferably about 0.3% to about 4%», preferably about 05% to about 2.5%. The ratio of polymeric carboxylates to a palladium-free dirt reagent is approximately 100? 1 to 1 ? 1 »preferably of approximately 50? 1 to 2? 1 »preferably of about 10; 1 to 5; i.

Auxiliary ingredients Dirt release agent Other polyamine soil remover agents known hereinafter as "SRA" can also be used in the detergent compositions present. If used, the SRAs will generally comprise from 0.01% to 10.0%, typically from about 0.1% to 5%, preferably from about 0.2% to 3.0% by weight, of the compositions. Preferred SRA 's typically have hydrophilic segments to hydrophilicize the surface of hydrophobic fibers such as polyester and nylon' and hydrophobic segments to deposit on hydrophobic fibers and remain adhered to them until the end of the washing and rinsing cycles » thus serving as an anchor for the гельгие hydrafl l icoß. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. SRA's may include a variety of species, eg, anionic or even cationic; see the patent of E.U.A. No. 4 »956» 447 »issued on September 11, 1990 to Gosselink and others» as well as the monomeric units not loaded and whose structures may be linear »branched and even star-shaped. They may include blocking portions that are especially effective in controlling molecular weight or altering physical or surfactant properties. The structures and the dietributions of load can be designed for its application to different types of fibers or textile materials and for detergent products or detergent additives varied. Preferred SRA's include these oligomeric terephthalate esters typically "prepared by methods that include at least one transeterification / oligigation" commonly with a metal catalyst such as a titania (IV) alkoxide. Said esters can be manufactured using monomerßßadditionally ßer capaceß incorporated into the ester structure through a »three» four or more positions »without» of course »forming a densely entangled overall structure. Other SRA's include the polyesters of 1 »2-prapylene / palioxieti le or non-ionic blocked ends of the U.S. patent. No. 4,711,730 of December 8, 1987 to Gosselink et al., For example those produced by the transesterification / olomerization of polyethylene glycol methyl ether "DMT" PG and polyethylene glycol ("PEG"). Other examples of SRA'ß include; loe éßtereß oli americas of ends blocked aniónicaß partially and completely of the patent of E.U.A. No. 4 »721» 580 »of January 26, 1988 to Goßselink» such as ethylene glycol oligomer ("EG") »PG» DMT and Na-3 »6-dioxa-8-hydroxyoctansulfonate; the nonionic blocked block polyester oligomeric compounds of the U.S.A. 4 »702» 857 »of October 27, 1987 to Gosßelink» for example produced from DMT »PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT» EG and / or PG »PEG Me-blocked and Na-dimethyl-5-βulfoißophthalata; and the blocked terephthalate esters of the anionic ends especially sulfoaroyl of the U.S. patent. No. 4 »877» 896 of October 31, 1989 to Maldonado Gosselink and others »the latter being a typical SRA'ß useful both in fabric conditioning product and laundry» being an example an ester composition made from the monosodium salt of the "phenylbenzoic acid" PG and DMT "optionally but preferably also comprising added PG" eg "PEG 3400. The SRA's also include? simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate »see U.S. Pat. No. 3 »959» 230 to Hays of May 25, 1976 and the patent of E.U.A. Na 3 »893» 929 a Basadur »of July 8, 1975» cellulose derivatives such as the hydroxy ether cellulose polymers available as METHOCEL from Dow; the hydrocellular alkyls of Cj-C ^ and hydroxyalky Icelulae of C ^ of the patent of E.U.A. No. 4 »000» 093 »of December 28, 1976 to Nicol" et al. "And the ethylcellulosic esters having an average substitution (methyl) gradation per anhydroglucose unit of from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoißß measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and MET0L0SE SM200, which bear the commercial brands of methyl ether Icelulase manufactured by Shin-etsu Kagaku Kagyo KK. Suitable SRA's characterized by hydrophobic segments of polymethyl ether include polyvinyl ether graft copolymers, eg, vinyl ethers of polyvinyl acetate, preferably grafted onto polyalkylene oxide base structures. See European patent application 0 219 048 »published on April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22"available from BASF» Germany. Other SRA'ß ßan polyesters with repeating units having 10-15% by weight of ethyl terephthalate together with 80-90% in weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol of an average molecular weight of 300-5000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having the empirical formula (CAP) a (EG / PG) ß (t) ß (SIP) t »which comprises unidadeß terephthalaila (T)» sulfoisophthaloyl (SIP) »oxyethylene? I and oxy-1 »2-propylene (EG / PG)» and which preferably terminates with blocks of extensions (CAP) »preferably modified ethylene salts» as in an oligomer comprising a ßulfoisophthaloi unit »5 unidadeß tereftaloi lo» oxietilanexi units and axi 1 » 2-propilenexi in a defined ratio of preferably about 0.5? 1 to approximately 10? 1"and two end blocking units derived from 2- (2-hydroxyethoxy) -ethanesulfonate. Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crys- tality reduction stabilizer, for example an anionic surfactant such as dodecyl Ibencesulfonate linear to a selected member of xylene- and toluenesulfonate or mixtures thereof. these »stabilizers or modifiers being introduced into the synthesis vessel» all as taught in the US patent No. 5 »415» 807r Gosselink Pan »I read Lett and Hall» issued on May 16, 1995. Suitable anomers for the above SRA include Na-2 (2-hydroxyethoxy) -ethansulfanata »DMT» Na-dimeti 1-5 -sulfoisophthalate »EG and PG. The additional classes of SRAs include? (I) non-ionic terephthalates using β-diisocyanate coupling agent β to bind the polymeric ester structures »see E.U.A. 4 »201» 824 »Vialland and others and E.U.A. 4 »240» 918 Lagasse and others »and (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's for converting hydroxy end group to trimethylate esters. With the proper selection of the catalyst, trimellitic anhydride forms bonds at the polymer ends by an ester of carbaxyl acid isolated from the trimellitic anhydride instead of opening the anhydride bond. Either non-ionic or anionic SRA's can be used as starting material "as long as they have hydroxyl terminal groups that can be esterified" see E.U.A. Na 4 »525» 524 Tung and otroe. Other classes include (III) non-anionic terephthalate-based SRAs of the urethane-linked variety »see E.U.A. 4 »201» 824 »Violland and back; (IV) pol ivini Icaprolactam and copolymers related to monomers such as vini Ipirrol idana and / a dimeti the ieti I etacri lato »including nonionic and cationic polymers» véaße E.U.A. 4 »579» 681 »Rupper and others» (V) graft polymers »in addition to the SOKALAN types of BASF» manufactured by grafting acrylic manomers to sulphonated polyesters. These SRA'ß have activity of release of dirt and anti-redeposition of ßimilareß soils to the known cellulose ethers? see EP 279 »134 A. 1988 to Rhone Poulenec Chemie. It also attracts claßeß include? (VI) grafts of monomers such as acrylic acid vinyl acetate and vinyl acetate in proteins such as caseins »see EP 457» 205 A to BASF (1991); and (VID POLYESTER-POLYAMIDE SRA's prepared by condenning adipic acid »caprolactam and polyethylene glycol» especially to treat paliamide fabric »véaße Bevan and other» DE 2 »335» 44 to Unilever NV »1974. Other SRA's useful in US patents Nos. 4 »240» 918 »4» 787 »989 and 4» 525 »524.

Bleaching Compounds -Blackening Agents and Bleach Activating Agents The detergent compositions herein may optionally contain bleaching agents or whitening compositions containing a bleaching agent and one or more bleach activators. When they are present, the bleaching agents will be at levels from about 0.05% to about 30%, preferably from about 1% to about 30%, preferably from about 5% to about 20% of the detergent composition, especially for fabric washing. . If present »the amount of bleach activators will typically be from about 0.1% to about 60%» more typically from about 0.5% to about 40% of the bleaching composition comprising bleaching agent plus bleach activator.

The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in the cleaning of textile materials, cleaning of hard surfaces or other cleaning purposes now known or known later. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, eg, sodium perborate (e.g., mono- and tetrahydrates) may be used herein. Another category of bleaching agent which can be used ßin-restriction comprises the percarboxylic acid bleaching agents and the saltse of the mole. Suitable examples of this class of agents include magnesium monaperoxy phthalate hexahydrate, the magnesium salt of ethachloroper-benzoic acid, 4-noni-lamin-4-oxoperoxybutyric acid and diperaxyddecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4 »483» 781 »Hartman» issued on November 20, 1984 »the Patent Application of E.U.A. 740 »446» Burne »and others» registered on June 3, 1985 »European Patent Application 0» 133 »354 Banks and others» published on February 20, 1985 »the Patent of E.U.A. 4 »412» 934 Chung et al. »Issued November 1, 1983. Highly preferred bleaching agents also include 6-noni lamino-6-axoperaxicapraica acid as described in US Pat. 4 »634» 551 issued on January 6, 1987 to Burne et al.

They can also use pero agente bleached agent peroxygen. Suitable peroxygen bleach compounds include sodium carbonate, peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate but ihydrate, urea but ihydrate and sodium peroxide. Persulfate bleach (e.g. »OXONE» commercially manufactured by DuPont) can also be used. A preferred bicarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, not more than about 10% in weight of said particles being larger than approximately 1%. 250 microns. Optionally, the percarbonate can be coated with silicate surfactants borate or water-soluble. Percarbonate is available from various commercial sources such as FMC »Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents »perborates» percarbonates »etc.» are preferably combined with bleach activators »which leads to the in-situ production in the aqueous solution (ie» during washing) of the peroxyacid corresponding to the bleach activator . Various examples of activators are described in the U.S. Patent. 4 »9151» 854 issued on April 10, 1990 to Mao et al. And in the U.S. Patent. 4 »412» 934. Typical nonanoyloxy-benzene sulfonate (NOBS) activators and tetraaceti leti lamina (TAED) and mixtures of loeßamßßß also can be used. See also E.U.A. 4 »34» 551 for other typical bleaches and activators useful herein. The most preferred amide derivative bleach activators are those of the formulas? R1N (Rß) C (0) R * C (0) L or R1C (0) N (Rß) RseC (0) L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms. R a is an alkylene containing from 1 to about 6 carbon atoms. R b e H or alkyl aryl or alkaryl containing about 1 to about 10 carbon atoms and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a result of a nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylisulfonate. Preferred examples of bleach activators of the above-mentioned formula include (6-octanamido-caproyl) -o-benzeneulphone or (6-nonanamidocaproyl) oxybenzene-fonate and mixture thereof as described in the US Pat. 4 »634» 551 »which is incorporated herein by reference.

Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In U.S. Pat. 4 »966» 723 issued on October 30, 1990 »what? it is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type is? Yet another class of preferred bleach activators includes the activators of acyl-lactam, especially acylcaprolactams and acvalavalent of the formulas. wherein R * is H to an alkyl or aryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam »octanai Icaprolactam» 3 »5» 5-trimethyl-hexanoi Icapralacta to »nonanoi Icapralactam» decanoi Icaprolactam »undequenoi Icaprolactam» benzoi lvalerolactam »octanoi Ivalerolacta to» decanoylvalerolacta to »undequenoyl-valerolac ama» nonanoi Ivalerolactam »3 »5» 5-trimethyhexanoyl-valerolac ama and mixtures thereof. See also U.S. Patent 4,454,784 issued to Sanderßon on October 8, 1985 incorporated herein by reference "describing the acylcaprolactams" including benzai Icaprolactam "adsorbed to sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of bleaching agent that is not oxygen of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See the Patent of E.U.A. 4 »033» 718 issued July 5, 1977 to Holcombe et al. If used, the detergent compositions typically should contain from about 0.025% to about 1.25% by weight of said bleaches, especially zinc phthalocyanine sulfonate. If you wish »the bleaching compounds can be catalyzed by a compound of manganese. Said compounds san well known in the art and include, for example, the manganese-based catalysts described in the U.S. Pat. 5 »246» 621 »Patent of E.U.A. 5 »244» 594; Patent of E.U.A. 5 »194,416; Patent of E.U.A. 5,114,606; and Publications of European Patent Applications Nos. 549 »271Al» 549 »272A1» 544 »440A2» and 544 »490A1. Preferred examples of these catalysts include Mnx a (u-0) 3 (1 »4» 7-tri eti 1-1 »4» 7-triazacyclononane) a (PF < fc) a »Mn * * xa (u-0 ) t (u-0Ac) a (1 »4» 7-trimethyl-l »4» 7-triazacyclononane) a (CI0 ^) a »Mnxs ^ (u-0) < fc (l »4» 7-triazacyclononane) ^ (CI0 ^) ^ Mn * x xMn, v "- (u-0) x (u-OAc) a- (1» 4 »7-tri et i ll» 4 7-tiazaciclononano) ae (Cl0 ^) 3r Mnxv (l »4» 7-trimethyl-l »4» 7-triazacyclononane) - (0CH3) 3 (PFA) »and mixtures of loe miemoe. Other metal-based bleach catalysts include those described in the U.S. Patent. 4 »430» 243 and Patent of E.U.A. 5,114 »611. The use of manganese with varioe complex ligands to improve bleaching is also recorded in the follg US Patents; 4 »728» 455? 5 »284.944; 5 »246.612; 5 »256» 779; 5 »280.117; 5 »274,147? 5 »153.16l; and 5,227,084. As a practical matter » and not by way of limitation »the bleaching solutions of this invention may consist of at least one part per ten million of the active bleach catalyst species in the washing liquid and will preferably provide from about 0.1 ppm to about 700 ppm »very preferably about the approximately 500 ppm of the catalyst species in the washing liquid. A wide variety of other useful ingredients in detergent cleaning compositions ee may include in the compositions herein "including other active ingredients" hydrotrope vehicles »auxiliary for treatment» dyes or pigments »solvent for liquid formulations» solid fillers for bar compositions » etc. If high foam formation is desired, it will increase the foam content such as Clo-Ct alcohols.; fc »can be incorporated into the compositions» typically at levels of from about 1% to about 10%. The C10-Ct monoethanol- and diethanolamides illustrate a typical clause of said increased β of eepu a. The use of said increased foam ester with high foaming auxiliary surfactants such as the abovementioned amine oxides, betaines and sultaines is also advantageous. If desired, soluble magnesium salts can be added, or MgCla, MgSO, and silage typically at levels from about 0.1% to about 2% to provide additional foaming and to increase fat removal performance. Various detersive ingredients employed in the present compositions can be stabilized internally by absorbing said ingredient on a hydrophobic porous hydrate, then by coating said substrate with a hydrophobic coating. Preferably the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use "the detersive ingredient is released from the substrate in the aqueous wash liquor" where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO »Degusea) is mixed with a proteolytic enzyme solution containing 3% -5% of nonionic non-ionic alcohol ethoxylated C-.3-1 »(7 OE). Typically, the enzyme / surfactant solution is 2.5 times the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicon oil can be used in the range of 500-12'500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. Thus, the ingredients such as the enzymes, bleaches, bleach activators, bleach catalysts, photoactive stabilizers, dyes, fluorescers, fabric conditioners and hydrolysable surfactants can be "protected" to be used in detergents, including detergent compositions. liquid for laundry. Compositions and detergents can contain water and other solvents as vehicles. Suitable primary and secondary low molecular weight alcohols are illustrated by methanol, ethanol, propanal and isopropanol. Monohydric alcohols are preferred for surfactant surfactant sol vent but can also be used as the polyols containing from 2 to 6 carbon atoms and from 2 to about 6 hydroxyl groups (eg 1 to 3). -propanediol »ethylene glycol» glycerin and 1 »2-propanediol). The compositions may contain from 5% to 90% »typically from 10% to 50% of said vehicles.

The detergent compositions of the present invention will preferably be formulated such that during use in aqueous cleaning operations the wash water has a pH between approximately 6.5 and approximately 11, preferably between approximately 7.5 and 10.5. The formulations of automatic dishwashing products preferably have a pH between about 6.8 and about 9.0. Laundry laundry products typically have a pH of 9 to 11. Techniques for controlling pH at recommended usage levels include the use of buffers »alkalis» acid »etc.» and are well known to those skilled in the art. .

Enzymes Enzymes may be included in the present detergent compositions for a variety of purposes "including the removal of protein-based stains" based on carbohydrates aa baεe of surface triglycerides such as materialeß textileß or "tableware" for the prevention of transfer of migratory dye »for example in the washing of clothes and for the restoration of the fabric. Suitable enzymes include protease »amylases» lipases »cellulase» peroxidases and mixtures of the same from any suitable origin »eg of vegetable» animal »bacterial» fungal and yeast origin. The preferred selections are influenced by factors such as pH-activity and / or stability-optimal thermostability and stability to active detergents and similar detergency builders. Concerning this »bacterial or fungal enzymes are preferred» such as amylasae and bacterial proteaeae and fungal cellulases. "Detersive Enzyme" as used herein means any enzyme that has a cleaning effect, "stain remover or otherwise beneficial in a laundry detergent composition" for cleaning hard surfaces or for personal care. Preferred detersive enzymes are "hydrolases" such as proteases and amylases Preferred enzymes for laundry purposes include but are not limited to "proteases" cellulases "and peroxidase." Amylases are highly preferred for automatic dishwashing. and / or the proteases, including both commercially available common types and improved types which, although increasingly compatible with the bleach by successive improvements, have a residual degree of susceptibility to deactivation of bleach. detergent additive compositions at levels sufficient to provide an "effective amount of cleaning." The term "effective cleaning amount" refers to any amount capable of producing a better cleaning effect »stain remover» whitening remover », deodorant or refreshing on substrates »such as fabrics» crockery and if ilareß. In practical terms for the common commercial preparations "typical amounts are up to about 5 mg by weight" more typically 0.01 mg to 3 mg "of the active enzyme per gram of the detergent composition. Expressed differently, the fields of the present invention will typically comprise 0.01% to 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at sufficient levels to provide 0.005 to 0.1 Anson units (AU) of activity per gram of the composition. For certain detergents, for example in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve staining behavior. movies or other final results. They can also be convenient to level higher activates in highly concentrated detergent formulations. Some suitable examples of protease with the subtilisins that are obtained from particular JEL strains. subtilis and B. licheniformis. A suitable protease is obtained from a strain of Bailus which has a maximum activity on the whole pH scale of? -12, developed and sold as ESPERASE "* by Novo Industries A / S of Denmark" hereinafter referred to as "Nova." The preparation of this enzyme and enzi aß analogues are described in GB 1 »243» 784 »by Novo. Suitable proteases include LACALASE "and SAVINASE" from Novo and MAXATASE * from International Bio-Synthetics »Inc.» Netherlands »as well as protease A as described in EP 130» 75 A »of January 9, 1985» and protease B as describes in EP 303 »761 A» of April 28, 1987 »and EP 130» 7546 A »of January 9, 1985. See also a high pH protease of Basillus SP NCIMB 40338 described in WO 9318140 A of Novo. Enzymatic detergents comprising protease "one or more additional enzymes" and a reversible protease inhibitor are described in Novo W0 9203529. Other preferred proteases include those of W0 9510591 A of Procter S Gamble. which has decreased adsorption and increased hydrolysis »is available camo se d write in W0 9507791 of Procter &; Gamble. A recombinant protease similar to trypsin for detergents "suitable herein" is described in W0 9425583 by Novo. More particularly, "an especially preferred pratease" referred to as "Protease D" is a variant of carbonyl hydrolase having a second amino acid content not found in nature "which is derived from a precursor carbonyl hydrolase eubeti having a different amino acid by a multitude of amino acid residues at a position in said carbanil hydralase equivalent to the passage +76 »preferably also in combination with one or more amino acid residue compositions equivalent to those selected from the group consisting of +99» +101 »+103» +104 »+107» +123 »+27» +105 »+109» +126 »+128» +135 »+156» +166 »+195» +197 »+204» +206 »+ 210 »+216» +217, +218, +222 »+260» +265 and / or +274 »according to the Bacillus amyloliguefacienß subtilisin numbering as described in the patent specifications of A. Baeck et al. atroe »entitled" Proteaße-Cantaining Cleaning Comparisons "that have the number of being ie from E.U.A. 08/322 »676» and C. Ghoßh and other »» "Bleaching Ca pasitians Camprising Protease Enzymes" which has the serial number of E.U.A. 08/322 »677» both filed on October 13, 1994. Amylases suitable herein for, but not limited to, automatic dishwashing purposes include, for example, -amylases described in GB 1,296,839 to Novo; RAPIDASE »International Bio-Synhetics, Inc. and TERMAMIY * Novo. FUNGAMYLm by Novo is especially useful. The engineering of enzymes for improved stability "for example oxidative stability" is known. See »for example J. Biological Che., Vol. 260, No 11, June 1985» pp 6518-6521. Certain preferred embodiments of the present compositions can make amylases having improved stability in detergents as measured against a reference point of TERMAMYL * in commercial use in 1993. These amylases preferred from the present share the characteristic of being amylases. of improved stability "» characterized »minimum camo» by a measurable improvement in one to more than; oxidative stability »for example to hydrogen peroxide / tetracet i lendiamine in buffered solution at pH 9-10» thermal stability »for example at common washing temperatures» such as about 60 ° C; or alkaline solubility "for example at a pH of about 8 to about 11" measured with respect to the above-identified reference point amylase. The stability can be mediated using any of the technical tests ß described in the art. Véaße »for example» lae reference deßcritae in WO 9402597. It is possible to obtain the improved stability alylase from Novo or Genencor International. A class of highly preferred amylases herein have the common trait of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially Bacillus amylases, regardless of whether a Multiple amylase strains are the immediate precursors. The use of oxidizing amides of improved stability with respect to the above-identified reference amylase is preferred, especially in bleaching compositions, most preferably oxygen bleaching, to the chlorine bleach detergent compositions herein. Preferred talee amilsae include (a) an amylase according to WO 9402597 »Novo» of February 3, 1994, incorporated hereinbefore »as illustrated in more detail by a mutant in which substitution is made, using alanine or treanine» preferably the threonine of the methionine residue located at position 197 of the "-amylase of B. I i cheni formiß" known as TERMAMYLR "or the homologous position variation of a similar original amylase" such as B. a yloliguefaciens "B. ßubti 1 is or B. eteari thermophilus; (b) the improved stability amylases described by Genencord International in a paper entitled "Oxidatively Resistant alpha-Am laseß" presented at the 207 National Meeting of the American Chemical Society "from March 13 to 17, 1994 by C. Mitchison. There it was observed that laß blanqueadareß and detergents for automatic dishwashing inactivate lae al fa-alasias, but Genencor has obtained improved oxidative stability amylasse from NCIB8061 of B. licheniformis. Methionine (Met) was identified as the most likely reeiduo to be modified. Methionine was replaced »one at a time» in positions 8 »15» 197 »256, 304, 366 and 438 leading to specific mutants, M197L and M197T being particularly important with the variant M197T, the variant being expressed in a more stable form. Stability was measured in CASCADE ** and SUNLIGHT *; (c) Particularly preferred amylases of the present invention include amylase variants having further modification in the immediate parent molecule as described in WO 9510603 A and available from the proxy »Novo» as DURAMYL1"1. Others to ilasae are particularly preferred. of improved oxidative stability include those described in W0 9418314 by Genencor International and W0 9402597 par Nava.Any other amylase of improved oxidative stability can be used, for example, those derived by site-directed mutagenesis from original chimeric mutant forms. hybrid or dielecule-containing amylae Other modifications of preferable ßon-accessible enzyme See Novo WO 9509909 A The cellulases usable in the present invention include fungal and bacterial-derived types preferably having an optimum pH between 5 and 9.5. of the United States 4,435,307 of Barbeßgoard and other, of the 6th of March zo of 1984, describes cellulasaß suitable for fungi of the species Humicola insolens or strain DSM1800 Humicola, or a fungus producer of cellulase 212 belonging to the genus Aeromonaß, and cellulase extracted from the hepatopancreas of a marine mollusc »Dalabella auricle Solander Celulasaß adecuaß, also described in GB-A-2,075,028; GB-A-2,095,275 and DE-0S-2,247,832. CAREZYMER (Novo) is especially useful. See also WO 9117243, by Novo. Suitable lipase enzymes include the β produced by microorganisms of the group Pseudomonas β such as Pseudomonas stutzeri ATCC 19,154 as described in GB 1,372,034. See also lipases in Japanese Patent Application 53, 20487, filed on February 24, 1978. Eßta lipase is available from Amano Pharmaceuti to Co. Ltd. »Nagoya» Japan »under the trade name Lipaßa P" Amano »" or "Amano-P". Other 1 i suitable commercial raisins include Amano-CES »Chromobacter viscssum lipases, for example» NRRLB 3673 from Chromobacter viscosum var. Toyo Jozo Co.'s lipolvticu »Tagata» Japan; Chromobacter viscoßum lipases from U.S.

Biochemical Corp. »E.U.A. and Disoynth Co. »Holland. The lipase from Pseudomonaß gladioli. The LIPOLASE enzyme derived from Humicala lanuginoßa and dißpanible from Novo iNDUSTRI a / e, dSNAMARCA; see also EP 341 »947» is a preferred lipase for use in the present invention. Mixtures of the above lipases can also be run. Suitable cutinase enzymes for use in the present invention are described in WO 8809367 A of Genencar. You can use enzymes but idases in combination with oxygen sources »for example» percarbonate »perborate» hydrogen peroxide »etc.» for "solution bleaching" or prevention of transfer of dyes or pigment removed from the substrates during washing to another ß Substrates present in the washing solution. Known peroxidases include horseradish peroxidase »ligninase and haloperoxidase, such as clear- to bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A of October 19, 1989 by Novo and WO 8909813 A by Novo. A range of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in W0 9307263 A, and W0 9307260 A by Genencor International »W0 8908694 A by Novo» and US Pat. 3,553 »139» of January 5, 1971 by McCarty and others. Other enzymes are described in the U.S. patent. 4 »101» 457 »Place and others» of July 18, 1978 »and in the patent of E.U.A. 4,507 »219» by Hughes »of March 26, 1985.

Utilee enzyme materials for formulations and liquid detergents "and their incorporation into such formulations" are described in US 4, 261, 868, Hora et al., April 14, 1981. The enzymes used in detergents can be stabilized. through various techniques. Enzyme stabilization techniques are described and exemplified in the US patent. 3 »600» 319 »of August 17, 1971, of Gedge et al., EP 199,405 and EP 200,586» of October 29, 1986, of Venegas. Enzyme stabilization systems are also described, for example, in the U.S. patent. 3,519,570. A useful bacillus »the AC13 species» that produces proteases, xylanases and cellulases »is described in W0 9401532 A» de Novo.

Enzyme Stabilizer System - The enzyme stabilizer systems of the present invention which contain enzymes and which include but are not limited by »liquid compositions» may comprise from about 0. 001% to about 10%, preferably around 0. 005% to approximately 8%, more preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizer system can be any stabilizer system that is compatible with the detersive enzyme. Said system can be inherently provided by other active agents of the formulation, or separate pair can be added "for example" by the formulator or by a manufacturer of enzymes ready for detergent. Such stabilizing systems may comprise, for example, "calcium ion", boric acid, propylene glycol, short chain carboxylic acid, boronic acids, and mixtures of the same and various gases to handle different problems of stabilization depending on the type and physical form of the detergent composition. A stabilization approach is the use of water-soluble sources of calcium ions and / or magnesium in the finished compositions that supply said ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred in the present invention if only one type of cation is used. Typical, especially liquid, detergent compositions will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although certain variations depending on factors that include the multiplicity "type and levels of incorporated enzymes. Hydrosoluble calcium or magnesium salts are preferably used "including, for example, calcium chloride» calcium hydroxide »calcium formate» calcium malate »calcium maleate» calcium hydroxide and calcium acetate; Generally, magnesium salts or calcium sulphate corresponding to the calcium levels exemplified can be used. In fact, increased levels of calcium and / or magnesium may be useful, for example to promote the short-fat action of certain types of tenectant. Another approach to stabilization is the use of borate species. See Severeon »US patent, 4» 537, 706. Borate stabilizers »when used» may be at levels of up to 10% or more of the composition »although more typically» levels of up to about 3% by weight of boric acid or other compounds of borate such as borax or orthoborate ßon suitable for use in liquid detergents. Substituted boric acids such as phenylboronic acid »butanebaronic acid» p-bromopyric acid and similar »can be used instead of boric acid» and reduced total boron in detergent compositions can be made possible by the use of such boron derivatives replaced. The stabilizer elements of certain cleaning compositions, eg, automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of bleach scrubbers. chlorine »added to prevent the chlorine bleach species preferentially in their water inietroe from attacking and inactivating the enzymes» especially under alkaline conditions. Even though chlorine levels in water can be small »typically on the scale of about 0.5 ppm to about 1.75 ppm» the available chlorine in the total volume of water that comes in contact with the enzyme »eg during the washing of fabrics or tableware »may be relatively large; consequently, the stabilization of the enzyme to chlorine is sometimes problematic. Since perborate or percarbonate, which have the ability to react with chlorine bleach, may be present in some of the present compositions in amounts determined separately by the stabilizer system, the use of stabilizer added to chlorine may be »More generally» not essential »although improved results of its use can be obtained. Suitable chlorine scavenging anions are widely known and readily available and can be salts containing ammonium cations with sulfite, bisulfite, thiosulphite, thiosulfate, iodide, etc. In the same way, antioxidants such as carbamate, aßcorbate, etc., can be used as organic amines such as acidic lei-diamine tetraacetic acid (EDTA) or alkali metal salts of the same monoethanolamine (MEA), and mixtures thereof. In the same way, special enzyme inhibition systems can be incorporated, so that different enzymes have maximum compatibility. If you can use other conventional sweepers such as bisulfate, nitrate »chloride» hydrogen peroxide sources such as sodium perborate tetrahydrate »sodium perborate monohydrate and sodium percarbonate» as well as phosphate »condensed phosphate» acetate »benzoate» citrate »formate» lactate »malate» tartrate »salicylate» etc. »and mixtures thereof. In general »since the chlorine sweeping function can be carried out by separately included ingredients under better recognized functions» (eg »hydrogen peroxide sources)» there is no absolute requirement to add a chlorine scavenger separately »unless that a compound that performs that function to the desired degree "is absent from an embodiment of the invention that contains an enzyme; even so »the sweeper is added only for optimal results. In addition »the formulator will exercise the normal dexterity of a chemical to avoid the use of any enzyme scavenger or stabilizer that is primarily incompatible» as formulated »with other ingredients and reagents» if used. In relation to the use of ammonium salts, said salts may simply be mixed with the detergent composition, but are subject to absorbing water and / or releasing ammonia during storage. Accordingly, said materials, if present, are conveniently protected in a particle such as that described in the US patent. 4 »62» 392 »de Baginski and otroe.

Detergency Metering - Detergency builders can be included in the present compositions to help control the hardness of minerals. Inorganic and organic builders can be used. Builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, very typically from about 5% to about 30% »by weight builder. Granulated formulations typically comprise from about 10% to about 80%, very typically from about 15% to about 50% by weight of the builder. However, "lower or higher detergency builder levels are not excluded. Inorganic or P-containing detergents include, but are not limited to, alkali metal salts, ammonium and alkanolamelium, of polyphosphates (lysed by tripol ifosfatoe, pyrophosphatic, and metameric polypheric, metamorphatae), phosphonates, phytic acid, eilactones, carbonates. - (including bicarbonates and sesquicarbonates), sulfates and alu l icates. However, improved builder detergents are required in certain locations. Importantly, the compositions of the present work surprisingly well even in the presence of so-called "weak" builders (as compared to phosphates) such as citrates "or in the so-called" lower detergency breeding "situation that It can occur with the detergent aradsres of zeolite or layered silicate. Examples of alkaline metal silicates ions silicate builders, particularly those that have a SiOa? NaaO ratio in the 1.6 scale? 1 to 3.2? 1 and layered silicates »such as the sodium silicates stratified as described in US Pat. No. 4,664,839 issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Haechst (commonly abbreviated as "SKS-6"). Unlike the zeolite builders, the NaSKS-6 eIicast detergent builder does not contain aluminum. NaSKS-6 has the morphological form of stratified silicate delta-NaaSiOß. It can be prepared by methods such as those described in German Application DE-A-3,417,649 and DE-A-3,742,43. SKS-6 is a highly preferred layered silicate for use herein but can be used in the present other layered silicate, such as those having the general formula and Ha0 where M is sodium or hydrogen "x is a number from 1.9 to 4" preferably 2, and "y" is a number from 0 to 20, preferably 0. Some Other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-ll as the alpha-beta and gamma forms. As indicated above, the shape of the ta- a ^ iO ,,, (NaSKS-6) is the most preferred for ußarße in the preeent. Other lichens can also use such as magnesium silicate, for example, which can serve as a tightening agent in granulated formulations as a stabilizing agent for oxygen bleaches and as a component of foam control systems. Examples of carbonate builders are alkaline and alkaline alkali metal carbonates as described in the application of German Patent No. 2 »321» 001 published on November 15, 1973. The useful san aluminosilicate builders in the present invention. AdjuSilicata alumina detergent builders are of great importance in most of the currently commercially available heavy-duty granular detergent compositions and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilica detergent builders include those that have the empirical formula? M "(zAl0a.) Y3xHa0 where z and "y" are integers of at least 6"the molar ratio of z a and is on the scale of about 1.0 to about 0.5" and x is an integer of about 15 to about 264.

Useful ioneß aluminoeil icate exchange materials are commercially available. Eßtoß aluminosilicates may be of crystalline or amorphous structure and may be aluminosilicates of natural origin or synthetically der. A method for producing aluminosilicate ion exchange materials is described in the U.S. Patent. 3 »985» 669, Krummel et al. Issued October 12, 1976. Synthetic crystalline aluminosilicate ions exchange materials preferred herein are available under the designations Zeolite A »Zeolite P (B), Zeolite MAP and Zealite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula? Na? AC (Al0a) xa (Si0a)? A-IxHa0 wherein x is from about 20 to about 30% specific: about 27. The material known is camo? eolite A. Lae zeolites dehydrated (x = 0-10) can also be used in the present. Preferably, the aluminosilicate has a particle size of about 0.1-10 ml in diameter. Citric acid detergency enhancers, eg, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. The citrate can also be used in granular compositions, especially in combination with zeolite builders and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are 3'-3-dicarboxy-4-oxa-1'-6-hexanediates and the related compounds described in US Pat. 4,566"984» Bush »filed on January 28, 1986. Useful succinic acid builders include alkyl and alkane Cs-Cao isuccinic acids and salts thereof. A particularly preferred compound of this type is dodeceni Iuccinic acid. Specific examples of β-succinate builder include:? lauryl succinate »miristi leuccinate» palmi ti leuccinate, 2-dodeceni Isuccinate (preferred), 2-pentadecenylsuccinate, and similaree. The leuccinates are the preferred detergency builders of this group, and are described in European Patent Application 86200690.5 / 0,200,263, published on November 5, 1986. The fatty acids »eg» monocarboxylic acids of cta ~ c? ß 'can also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders "to provide additional builder activity. Such use of fatty acids will generally result in decreased foaming "which would be considered by the formulator. In situations where phosphorus-based detergency builders can be used "and especially in bar formulations used for hand-washing operations" various alkali metal phosphates such as the well-known epoxide tripolyphosphates can be used "sodium pyrophosphate and sodium orthophosphate. Phosphonate builders such as ethan-1-hydroxy-1-dipheophonate and other known foefonatoe can also be used (see for example »US Patent 3» 159 »581? 3» 213 »030? 3,422» 021 »'3» 400 »148 and 3» 422.137).

Guiding agents - The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of incarboxylamino-aminsphosphates, substituted aromatic chelating agents and substituted mixtures thereof, all as defined below. Without intending to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the washing solutions through the formation of soluble chelates.

Possible aminocarbaxylase agents as chelating agents include eti lendia inotetraacetatos »N-hydroxyethylethylenediaminetriacetatae» or trilstriacetates »eti lendia inotetrapropionates» triethylenetetraaminohexaacetates »clieti lentriaminopenta ethylfasphonic acid and salts of ethanoldigl icines» alkali metal »ammonium and substituted ammonium of lae mie.mae and mix of them. The aminophosphates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions and include eti lendiaminotetraquiß (methy lenphaphafanatoß) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. The aromatic lacting agents that are optionally substituted are also useful in the compositions of the preeent. See the patent of E.U.A. 3 »812, 044 issued May 21, 1974 to Cannar et al. The preferred compounds are of this type in the acid form dihydro-dihydro-sulfobenzene, such as 1-2-dihydro-i-3'-disulfabenzene. A preferred biodegradable chelator for use herein is eti lendiaminadisuccinate ("EDDS") "especially the CS» S »3 isomer is camo described in the US Patent. 4 »704» 223 issued on November 3, 1987 to Hartman and Per ins.

If used, these chelating agents should generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably "if used" the chelating agents should comprise from about 0.1% to about 3.0% by weight of said compositions.

Reagents / anti-redeposition of clay dirt. The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The granulated compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the ethoxylated amines salubleß in water; Liquid compositions typically contain from about 0.01% to about 5%. The preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Illustrative ethoxylated amines are further described in the U.S. Patent. 4 »597,898» VanderMeer »issued on July 1, 1986. Another group of preferred clay soil removal / anti-redeposition agents are the cationic compounds described in European Patent Application 111» 965 »Oh and Gasselink» published on June 27, 1984. Other clay soil removal / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592 »Gosselink» published on July 4, 1984; and the amine oxides described in the U.S. Patent. 4 »548» 744 »Connor» requested on October 22, 1985. Other clay soil removal and / or anti-redeposition agents known in the art can be used in the ca-locations herein. Another type of preferred anti-redeposition agent includes the carbaxy eti Icelulase (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents can be advantageously used at levels of from about 0.1% to about 7% »by weight» in the compositions herein especially in the presence of layered silicate builders and / or zeolite. Suitable plastic dispersing agents include polyethylene glycols (PEG). The PEG can exhibit the action of dispersing agent? »And also act as a remover and anti-deposition agent of clay dirt. Typical molecular weight scales for this purpose vary from about 500 to about 100,000, preferably from about 1,000 to about 50,000, most preferably from about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutate can also be used, especially together with the zeolite detergency builders. The disperfecting agents and the polyapartate preferrably have a molecular weight (avg.) of approximately 10,000.

April Lighter Any optical brighteners or other brightening agents or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2% by weight »in the detergent compositions herein. The commercial optical brighteners which may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene derivatives »pyrazaline» coumarin »carboxylic acid» etinocyanin »5» 5-dioxide di-benzothiaphene » azoleß, 5- and 6-membered ring heterocycles, and various other agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agent ", M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S. Patent. 4 »790» 865 issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE '"series of brighteners from Verona." Other ripplers included in this reference include: Tinopal® UNPA »Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy, Artic White * CC and Artic White CWD »available from Hil ton-Davis» with ßede in Italy? Loe 2- (4-eßtiri 1-feni l) -2H-naphthoCl, 2-d-] t iazolee; 4,4'-bis (1, 2,3-triazal-2-i-1) -etilbenes, 4,4'-bie (styrene l> bisphenyls, and the inocoumarins, specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 2-bis (-benzy-idazal-2-yl) eti -le? -3,3-diphenyl-1-pyrazolines; 2,5-biß (benzoxazol-2-yl) thiophene; 2-eetyryl-naphthoCl, 2-dDoxazole; - (Esthene-4-i 1) -2H-naphtha-C 1, 2-d-ltriazole See also US Patent 3,646,015, issued to Hamilton on February 29, 1972. Anionic brighteners are preferred here.

Foam suppressors In the compositions of the present invention, compounds may be incorporated to reduce or suppress the formation of foams. Said suppression of foams may be of particular importance in the so-called "high concentration cleaning process", as described in the U.S. patent. 4,489,455 and 4,489,574, and in front-loading European style washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See »for example» Kirk Oth er Encyclopedia of Chemical Technology »3rd Edition» Volume 7 »pages 430-447 (John Wiley &Sons» Inc. »1979). A category of spurious suppressors of particular interest comprises monocarboxylic acid fatty acid and ßaleß ßalubleß of the miemos. See Patent of E.U.A. 2,954,347 »issued on September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used 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 sodium, potassium and lithium salts as well as ammonium and alkanolammonium salts. The detergent ions of the present may also contain supreeoree of non-surfactant foams. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid ester (for example, fatty acid triglycerides), fatty acid ester of monovalent alcohols, aliphatic ketones of beta-C, 0 (for example, stearone). ), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylamine or di- to tetra-alkyldiaminoclortriazines formed as a product of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates, such as monostearyl alcohol ester phosphate and monosodium alkali metal phosphate and monoesteric esters (e.g., K, Na, and Li). Hydrocarbons such as paraffin and haloparaffin can be used in liquid form. The liquid hydrocarbons shall be liquid at room temperature and at atmospheric pressure and shall have a pour point in the range of approximately -40 ° C and approximately 50 ° C, and a minimum boiling point not less than approximately 110 ° C (atmospheric pressure). . The use of waxy hydrocarbons is also known, preferably having a melting point less than about 100 ° C. Hydrocarbons constitute a preferred category of eßpumaß suppressants for co-detergent detergents. The hydrocarbon foam suppressors are described, for example, in the U.S. Patent. No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic and heterocyclic, unsaturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this description of "foam suppressor" is intended to include mixtures of true paraffin and cyclic hydrocarbons. Another preferred category of non-surfactant foam suppressors comprises silicone foam suppressors. This category includes the use of iorganasi laxane oils, such as poly idimeti Isi loxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosi loxane with particles of silica in which the polyorganosi loxane is absorbed or blended. about silica Silicone foam suppressors are well known in the art and for example are described in the U.S. Patent. 4 »265» 779 »issued on May 5, 1981 to Gandolfa et al. And European Patent Application No. 89307851.9, published on February 7, 1990, by Starch M. S. Other supreme sellers of ee foam of eilicon are described in US Pat. 3 »455» 839 »which relates to compositions and methods for removing foam from aqueous solutions by incorporating in them small amounts of poly idimeti Isi loxane fluids. Silicone and silica mixtures if labeled "for example" in German Patent Application DOS 2 »124» 526 are described. Descriptions of silicone foams and foam controlling agents in granular detergent compositions are described in U.S. Pat. 3,933,672, Bartolotta et al. "And in the U.S. Patent. 4 »652» 92 »Ba ins i et al.» Issued March 24, 1987. An illustrative foamed silicone bauble suppressor for use in the foregoing is a foaming suppressant amount of a foam controlling agent that essentially depletes; (i) poly idimetißi loxane fluid having a viscosity from about 20 cs to about 1 500 cs at 25 ° C. (ii) from about 5 to about 50 parts per 100 parts per cent of (i) of siloxane resin composed of (CH3) 3SiOt units, a of SiOa units in a ratio of units of (CH3) 3 SiO1 to units of SiOa of around 0.6? 1 to approximately 1.2? 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) a solid silica gel.

In the preferred silicone foam suppressor used herein, the solvent for a continuous phase is formed from certain palletics to polypropylene copolymers or mixtures thereof (preferred) or pal ipropilengl icol. The suppression of primary silicone foams is branched / interlaced and preferably non-linear. To further illustrate this point, typical liquid laundry detergent compositions with optionally controlled foams will comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, highly preferred from about 0.05 to about 0.5 percent by weight. of said silicone foam suppressant »comprising (1) an aqueous emulsion of a primary anti-foaming agent which is a mixture of (a) a polyganasi loxane» (b) a resinous siloxane or a silicone compound which produces silicone resin »(c) a finely divided filler material» and (d) a catalyst to promote the reaction of the components of the mixture (a), (b) and (c), to form silanolate; (2) at least one non-ionic ionic agent; and (3) polyethylene glycol or copolymer of polyethylene polypropylene which has a solubility in water at room temperature of more than about 2% by weight; and ein pal iprapilengl icol. Similar quantities can be used in granular compositions, gels, etc. See also Patents of E.U.A. 4,978 »471» Starch »issued on 18 December 1990» and 4 »983,316» Starch »issued on 8 January 1991» 5 »288» 431 »Huber and others» issued on 22 February 1994 »and Patents of USA 4 »639» 489 and 4 »749» 740 »Aizawa and atros in column 1» line 46 to column 4, line 35. The silicone foam suppressant of the present preferably comprises polyethylene glycol and a copolymer of polyethylene glycol / pol The polyethylene glycol having an average molecular weight of less than about 1,000 »preferably between about 100 and 800. The polyethylene glycol and the polyethylene / polypropylene copolymers of the present have a solubility in water at room temperature. of about 2% by weight »preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000 »more preferably between about 100 and 800» most preferred between 200 and 400 »and a copolymer of polyethylene glycol / polypropylene glycol» preferably PPG 200 / PEG 300. A weight ratio of between about 1? 1 and 1? 10"preferably between 1? 3 and 1? 6" of palletri lengl icol is preferred? capol number of polieti leno-pal ipropi lenglicol. The supresarers of preferred silicone foams used herein do not contain polymers of particularly high molecular weight of 4,000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLUR0NICR LlOl. Other excipients of the present invention include secondary alcohols (eg, 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones described in US Pat. 4,798 »679, 4,075» 118 and EP 150 »872. The secondary alcohols include the alkyl alcohols of CA-Ct4- having a C1-C1A chain. A preferred alcohol is 2-butyl octane which is available from Candea under the brand name ISOFOL '* 12. Mixtures of secondary alcohols are available under the brand name ISALCHEMR 123 from Enichem. Ixtoe foam suppressors typically comprise a mixture of alcohol + silicone at a weight ratio of 1? 5 to 5? 1. For any detergent composition to be used in automatic washing machines »no foam should be formed to the extent that it runs off the washing machine. The foam suppressors when used are preferably present in a "foam suppressant amount". By "foam suppressant amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that sufficiently controls the foam to produce a low foaming laundry detergent for use in automatic washing machines. The compositions herein will generally comprise from 0% to about 5% of foam suppressors. When they are used as supressors of foams »monocarboxylic fatty acids» and ealee de loe, typically will be present in amounts of up to about 5% by weight of the detergent composition. Preferably, about 0.5% to about 3% of monocarboxylate fat suppressant is used. Silicone foam suppressors are typically used in amounts up to approximately 2.0% by weight of the detergent composition, although larger amounts may be used. This euperior limit is of a practical nature, mainly due to the interest of keeping costs down to a minimum and the effectiveness of lower quantities to effectively control foaming. Preferably from about 0.01% to about 1% silicone foam suppressant is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percent values include any silica that may be used in combination with polior anosi laxane as well as any auxiliary material that may be used. The monosteary foam phosphate suppressors are generally used in amounts ranging from about 0.1% to about 2% by weight of the composition. The hydrocarbon foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although they can be used at higher levels. The eßpu aß alcohol suppressors typically use 0.2% -3% by weight of the finished compositions.

Fabric softeners Various fabric softeners which soften during washing can be used optionally, especially the impalpable smectite clays of US Pat. 4 »062» 647 »Stor and Nirschl» issued December 13, 1977 »as well as other softening clays known in the art» typically at levels of from about 0.5% to about 10% by weight in the compositions herein to provide softening benefits »concurrently with fabric cleaning. Clay-based softeners can be used in combination with amine and cationic softeners, as described, for example, in US Pat. 4 »375» 416 »to Crisp et al.» Of March 1, 1983 and the Patent of E.U.A. 4 »291» 071 to Harris and others »issued on September 22, 1981.

Dye transfer inhibitor agents The compositions of the present invention may also include one or more effective materials for inhibiting the transfer of dyes from one fabric to another during the cleaning process. In general, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, N-vinyllpyrralidone and N-vinylimidazole phthalocyanine manganese phthalocyanine polymers, and peroxides and mixtures thereof. If used, these agents typically comprise from about 0.01%, to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and most preferably from about 0.05% to about 2%. More specifically, the preferred β-polyamine N-oxide polymers for ußarße in the present contain units having the following structural formula? R-A - ^ - P; where P is a palimerizable unit to which a group N-0 »or the group N-O can be part of the polymerizable unit» or the group N-O can be attached to both units »A eß one of the following structures? -NC (0) - »-C (0> 0 ~» -S- »- 0-» -N = »x is 0 or 1, and R is aliphatic» aliphatic acidic »aromatic» heterocyclic to alicyclic or any combination thereof »to which the group nitrogen N-O can be joined »or the N-O group is part of these groups. Preferred paliamine N-oxides are those wherein R is a heterocyclic group such as pyridine »pyrrole» imidazole »pyrrolidine» piperidine and derivatives thereof. The N-O group can be represented by the following general structures? wherein Rx rRa »R3 are aliphatic» aromatic »heterocyclic or alicyclic groups or combinations of the members; x »y and z are 0 or 1; and the nitrogen of the group N- > 0 can join or be part of any of the groups mentioned above. The amine oxide unit of the polyamine N-oxides has a pKa < 10"preferably pKa < 7 »most preferably pKa < 6. Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has heat transfer inhibiting properties. Examples of suitable palmeric skeletons are polysaccharides, palyalkylene, polyesters, polyether-polyamide, polyamides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an N-oxide or an amine and the other monomer type is an N-oxide. The amine N-oxide polymers typically have an amine to amine N-oxide ratio of 10? 1 to 1? 1 »000» 000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-o-tion. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000? very preferred from 1 000 to 500 00; even more preferred 5'000 to 100'000. This preferred class of materialeß can be referred to as "PVN0". The most preferred polyamine N-oxide useful in the detergent compositions herein is pal i (4-vinylpyridine N-oxide >; having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1? 4. The copolymers of N-vinylpyrrolidone and N-vinylimidazole (known in a class as "PVPVI") are also preferred for use in the present. Preferably, the PVPVI has an average molecular weight in the range from 5,000 to 1,000,000, most preferably from 5,000 to 200,000 and most preferably even from 10,000 to 20,000. (The average molecular weight scale is determined by means of light scattering "as described in Barth" and others »Chemical Analvsiß» Vol. 113. "Modern Methods of Polymer Characterization" "whose descriptions are incorporated herein by reference). The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1? 1 to 0.2? 1 »most preferably 0.8 1 to 0.3? 1, most preferably 0.6? 1 to 0.4? 1. These copal numbers may be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000"preferably from about 5,000 to about 200,000" and most preferably still from around 5,000 to about 50,000. Are the PVP known to those skilled in the detergent field? see »for example» EP-A-262 »897 and EP-A-256» 696, incorporated herein by reference. The compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000"preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis in wash solutions is from about 2? 1 to about 50; 1"and most preferably from about 3; l to about 10? 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. The compositions of the preemer will preferably comprise from about 0.01% to 1% by weight of said optical brighteners if they are used. The hydrophilic optical brighteners useful in the present invention are those having the structural formula? where R ,. it is selected from anilino »N-2-bie-hydroxyethyl and NH-2- idera; Ra ß selects from N-2-biß-hydroxyethyl the »N-2-hydroxyethyl-N-methyl-amino-morphino-chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the previous formula, Rx is aniline »Ra. eß N-2-bis-hydroxyethyl and M eß a cation such as sodium »the brightener is acid 4» 4 '»bislT (4-ani l ino-6- (N-2-bis-hydra-methyl) -s- triazin-2-yl) amine 1- »2'-ester and Ibendi-sulphonic acid and disodium salt. This particular kind of brightener is marketed under the trade name Tinopal-UNPA-GX? by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R 1 is anilino, R 2 is N 2 -hydroxy-1N-2-methylamino and M ee a cation such as eiodium, the brightener is the disodium salt of 4 4 4 -bisC (4-anion). l ino-6- (N-2-hydroxyethiN-methylamino) -e-triazin-2-yl) amino3-2 »2'-stilbenedisulfonic acid. This particular brightener species is marketed under the Tinopal SBM-GX '* brand of Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4'4'-bisC (4-anilino-6-morphino-b-triazine). 2-il > amino_l2 »2'-est &Ibendisulfonic This particular brightener species is commercially sold under the Tinopal brand AMS-GX * from Ciba-Geigy Corporation The specific optical brightener species selected for use in the present invention» provide benefits of dye transfer inhibiting action especially effective when used in combination with the selected "selected infrared dye transfer inhibitor agents" described above.The combination of said polymeric materials is selected (e.g. »PVNO and / or I). ) with such selected optical brighteners (eg »Tinspal UNPA-GX» Tinopal 5BM-GX and / or Tinapal AMS-GX) provides significantly better dye transfer inhibition in aqueous washing solutions »than any of those two components of detergent composition when using ßolss. Without being limited by theory, cree believes that such brighteners work in this way because they have high affinity for fabrics in the washing solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "depletion coefficient". The coefficient of depletion is generally camo the ratio of a) the polishing material deposited on the fabric to b) the initial rinse aid concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. It will then be appreciated that other types of conventional optical brightener compounds may optionally be used in the compositions herein to provide conventional "glossy" benefits to fabrics rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations. The modified polyamines of the present invention are used as polyaminic soil release agents, and are conveniently prepared by the following methods.

EXAMPLE I Preparation of PEÍ lßOO Et The ethoxylation is carried out in a stirred stainless steel autoclave of 7.56 liters equipped for measurement and temperature control, pressure measurement, vacuum and inert gassing, sampling and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide is installed (ARO to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to monitor the changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) (Nippon Shokubai »Epo in SP-018 having an average listed molecular weight of 1800" equivalents to about 0.417 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then blown and purged of air (applying vacuum to minus 711 mm Hg followed by application of pressure with nitrogen at 17.57 kg / cm *, then ventilating at atomic pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. Deepuée of about one hour, the autoclave is charged with nitrogen at approximately 17.57 kg / cm 5 * while the autoclave is cooled to approximately 105 ° C. Ethylene oxide is then added to the autoclave in increments over time while carefully monitoring the pressure and temperature of the ethylene oxide flow in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature caused by any reaction exotherm. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After it has loaded a total of 750 grams of ethylene oxide into the autoclave (almost equivalent to one mole of ethylene oxide per function of PEI nitrogen), the temperature is increased to 110 ° C and the autoclave is left to stir for an additional hour. At this point, vacuum is applied to remove any residual ethylene oxide that did not react. Then vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C »by introducing 376 g of a 25% sodium methoxide solution in methanol (1.74 moles) to achieve a catalyst load of 10% based on the functions of PEI nitrogen). The methoxide solution is sucked into the autoclave under vacuum and after the programming point of the autoclave temperature controller is increased to 130 ° C. A disparate is used to monitor the energized energy for the agitator. The power of the agitator is monitored together with the temperature and pressure. The power and temperature values of the agitator increase gradually as the methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about one hour indicating that most of the methanol has been removed. The mixture was heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17.57 kg / cm * and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cma with nitrogen. Ethylene oxide is again added to the autoclave in increments as mentioned above by carefully monitoring the temperature and flow velocity of ethylene oxide in the autoclave while maintaining the temperature between 100 and 110 ° C and limiting any increase in temperature due to the exotherm of the reaction. After attaining the addition of 4,500 g of ethylene oxide (resulting in a total of 7 malee of ethylene oxide pair mole of nitrogen function of PEI) for several hours, the temperature increases to 110 ° C and the mixture Shake for an additional hour. The reaction mixture is collected in nitrogen-purged containers and finally transferred to a 22-liter three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then passed through about 2 831 dm 3 of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and heating the mixture to 130 ° C.

E ^ Pj.Q - (A Quaternization of PEÍ 1800 Et To a 500 ml Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residue per nitrogen (PEI). 1800 »E-) (207.3 g» 0.590 moles of nitrogen »prepared as in Example I) and acetonitrile (120 g). Dimethyl sulfate (28.3 g »0.224 mol) is added in one portion to the solution in rapid stirring which is then capped and stirred at room temperature overnight. The acetonitrile is removed by rotary evaporation to approximately 60 ° C followed by further purification of the solvent using a Kugelrohr apparatus at about 80 ° C to give 220 g of the desired partially quaternized material as a viscous brownish liquid. The 13 C-NMR (Da0) spectrum obtained on a sample of the reaction product indicates the absence of a carbon resonance at -58 ppm corresponding to dimethyl sulfate. The NMR spectrum * H (Da0) shows that a partial displacement of the resonance at approximately 2.5 ppm for methylenes adjacent to non-quaternized nitrogen has shifted to approximately 3.0 ppm. This is consistent with the desired quaternization of approximately 38% of the nitrogens.

Egypt p Formation of aniña oxide of PEÍ 1800 Z- To a 500 ml Erlenmeyer flask equipped with a magnetic stirring bar is added polyethylenimine having a molecular weight of 1800 and ethoxy lated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800 »£ -) (209 g» 0.595 moles of nitrogen »prepared as in Example D» and hydrogen peroxide (120 g of a 30% by weight solution in water »1.06 mole) The flask is capped and after an initial exotherm the solution is stirred at room temperature During the night, the NMR-xH spectrum (Da0) obtained in a sample of the reaction mixture indicates complete conversion.The resonances assigned to the methylene protonee adjacent to non-oxidized nitrogen were displaced from their original position to "2.5 ppm At ~ 3.5 ppm, approximately 5 g of 0.5% Pd are added to the reaction solution on alumina pellets and the solution is allowed to stand at room temperature for approximately 3 days. that is negative for peroxide by means of indicator paper. The material obtained is suitably stored as an active solution at 51.1% in water.

EJ p ^ q Hl Amine oxide formation of PEI 1800 E? quaternized To a 500 ml Erlenmeyer flask equipped with a magnetic stirring bar there is added pallethylenimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E. ,) and then further modified by quaternization to approximately 38% with dimethyl sulfate (130 g, 0.20 mole of oxidizable nitrogen, prepared as in example II), hydrogen peroxide (48 g of a 30% by weight solution in water »0.423 moles) and water (~ 50 g). The flask is capped and after an initial exotherm the solution is stirred at room temperature overnight. The NMR-H (Da0) spectrum obtained in a sample taken from the reaction mixture indicates the complete conversion of the β-refferences attributed to the methylene peaks previously observed in the 2.5-3.0 ppm scale to a material having methylenes with a chemical shift of approximately 3.7 ppm. To the reaction solution is added about 5 g of 0.5% Pd on alumina pellets and the solution is allowed to stand at room temperature for about 3 days. The solution is tested and found to be negative for peroxide by indicator paper. The desired material is obtained with -38% of the nitrogen quaternized and 62% of the oxidized nitrogens to amine oxide and is suitably stored as an active solution at 44.9% in water.

E, j tPtP Preparation of PEÍ 1200 Et The process is carried out in a stirred stainless steel autoclave of 7.56 liters, equipped for measurement and temperature control, pressure measurement, vacuum purging and with inert gas »sampling» and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide is installed (ARO for ßu inißtrar ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale to be able to monitor the change in the cylinder bone. 750 g portion of polyethylenimine (PEI) (having a lysed average molecular weight of 1200 »equivalents to 0.625 moles of polymer and 17.4 moles of nitrogen functions) The autoclave is deßpuéß ßellada and purged of air (applying vacuum to enaß 711 mm of Hg followed by application of pressure with nitrogen at 17.57 kg / cm², then ventilating at atmospheric pressure.) The contents of the autoclave are heated to 130 ° C while a vacuum is applied, after approximately one hour »the autoclave is charged with nitrogen at approximately 17.57 kg / cm * while the autoclave is cooled to approximately 105 ° C. After ethylene oxide is added to the autoclave in increments over time or while carefully monitoring the pressure »temperature and flow velocity of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and cooling is applied to limit any increase in temperature that results from any reaction exotherms. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 750 grams of ethylene oxide has been loaded into the autoclave (almost equivalent to a bad ethylene oxide by PEI nitrogen function), the temperature is increased to 110 ° C and the autoclave is allowed to shake for an additional hour. At this point »vacuum is applied to remove any residual ethylene oxide that did not react. Then vacuum is applied continuously while the autoclave is cooled to approximately 50 ° C by introducing 376 g of a 25% sodium methoxide solution in methanol (1.74 moles) to achieve a catalyst load of 10% based on the functions of PEI nitrogen). The methoxide solution is sucked into the autoclave under vacuum and after the programming point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power and temperature values of the agitator increase gradually as the methanol is removed from the autoclave, and the viscosity of the mixture increases and it stabilizes in about one hour indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17.57 kg / cm * and then ventilated at ambient pressure. The autoclave is charged at 14.06 kg / cm * with nitrogen. Ethylene oxide is again added to the autoclave in increments as mentioned above, carefully monitoring the pressure »temperature and flow velocity of the autoclave ethylene oxide» while maintaining the temperature between 100 and 110 ° C and limiting any increase in temperature due to the exotherm of the reaction. After attaining the addition of 4,500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) for several hours, the temperature is increased to 110 ° C and the mixture Shake for an additional hour. The reaction mixture is then collected in nitrogen purged containers and optionally transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing approximately 2, 831 dm3 of inert gas (argon or nitrogen) through a gaß dispersion frit and through the reaction mixture is stirred and heated at 130 ° C. The final reaction product is cooled slightly and collected in glass containers purged with nitrogen. In other preparations, neutralization and deodorization are achieved in the rector before unloading the product. Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction. aa-B-UiMiu ----- J Cuatamization at 9.7% of PEI 1200 E- To a 500 ml Erlen eyer flask equipped with a magnetic stirring bar is added polyethyleneimine »PM 1200 etholated to a degree of 7 (248.4 g» 0.707 moles of nitrogenor prepared as in example 5) and acetanitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich »8.48 g» 0.067 mol) is added in a single stroke to the rapid stirring which is covered and stirred at room temperature overnight. The acetonitrile is evaporated on the rotary evaporator at ~60 ° C, followed by a Kugelrohr (Aldrich) apparatus at ~80 ° C to give "220 g of the desired material as a dark brown viscous liquid.A 13C NMR spectrum ( Da0) shows the absence of a peak at ~ 58 ppm corresponding dimethyl sulfate.A NMR spectrum * H (Da0> shows the partial displacement of the peak at 2.5 ppm (methylenes bound to non-quaternized nitrogens) at ~ 3.0 ppm .

EHPLQS V -? X High density granular detergent compositions (more than 600 g / l) comprising the following ingredients are prepared.

EXAMPLES VI-IX (CONTINUED) 1. The proportion of acrylate to maleate segments in the copolymer is 7? . 2. The proportion of eeg entae of acrylate to maleate in the copolymer is 6? . 3. Polyamine soil removal agent according to example I. 4. The rest for 100% may include, for example, minor components, tacky or optical brightener, perfume, foam, and so on, soil dispersant, protease, cellulase, etc. chelating agents »agent inhibitors of dye traneference» additional water and fillers »including CaC03, talc, silicates, etc.

EXAMPLE X A suitable laundry bar is prepared for hand washing soiled fabrics by normal extrusion processes, and comprising the following? Component% by weight C 1 to 30 linear phosphate (as sodium tripolyphosphate) 7 Sodium carbonate 25 Sodium pyrophosphate 7 Coconut monoethanolamine 2? Eolite A (0.1-10 microns) 5 Carboxymethylcellulose 0.5 Polyamine dirt remover ( Example 1) 0.5 Copolymer Polycarboxylate (MW 65,000) * 0.2 Rinse aid »perfume 0.2 CaSO. * 1 SO ^ 1 Moisture 4 Other minor components »including filler5 the rest for 100% 1. The ratio of sec entoß acrylate to maleate in the copolymer eß of 7? 3. 2. It can be selected from convenient materials such as CaCO3 »talc, clay» silicate and the like The patent of E.U.A. 3 »178» 370 »Okenfuse» issued on April 13, 1965 deßcribe bar detergent for laundry and procedure for manufacturing. The Philippine patent 13 »778» Andereon, issued on September 23, 1980 »describes synthetic laundry detergent bars. The methods for making laundry detergent bars by various extrusion methods are well known in the art.

EXAMPLES XI AND EU Are suitable laundry rods prepared for hand-washing euciae fabrics by normal extrusion processes and comprising the following? % in weigh 1. The proportion of acrylate to maleate segments in the copolymer is 6? 4. 2. Can be selected from suitable materials such as calcium carbonate »talc» clay »silicates and simi laree.

Claims (10)

NOVELTY OF THE INVENTION REVIVITIONS

1. - A laundry detergent composition comprising? A. at least about 0.01% by weight »of a detergent active agent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactants and mixtures of the same? B. from 0.1% to about 15% of poly-carboxylic acids selected from the group consisting of monocarboxylic polycarboxylates having a molecular weight greater than 4000 and copolymeric polycarboxylates and mixtures of the mers. C. from about 0.01% to about 5% paliamine soil removal agents comprising a polyamine skeleton corresponding to the formula? having a modified polyamine formula V < "^. x > WmY "Z" or a polyamine skeleton corresponding to the formula? having a modified polyamine formula V < n_k, t > W «Y» - "k Z" where k is less than or equal to "said polyamine skeleton" before the modification has a molecular weight greater than about 200 daltons "where i) the units V eon terminal units who have the formula? ii) W units are skeleton units that have the formula? iii) units Y are branching units that have the formula? iv) Z units are terminal units that have the formula? in dande the skeletal linker units R are selected from the group consisting of alkylene of Ca-C? a »alkenylene of C_» C? a »hydroxyalkylene of C3-C? a» dihydroxyalkylene of C ^ -C? a, dialkylarylene of Cβ-Cα, - (R ^O ^R1-, - (R10)> RB (0R *) x, - (CHaCH (OR *) CHaO), (R * 0) > R1 ~ (OCHaCH (OR *) CHa) w-, -C (0) (R '") r -.C (0> ~, -CHaCH (OR *) CHa-» and mixtures thereof; R1 is alkylene of Ca-CA "and mixtures thereof" R * eβ hydrogen "- (R * 0)> tB" and mixtures thereof; R3 * is Cx-Cl-alkyl »arylalkyl of C7-Ct2» aryl substituted with alkyl of Ct-Cta »aryl of CA-C ?, and mixtures thereof, R is alkylene of Ct-Cta» alkenylene of C _-Cta »arylalkyl of Cß-C? a» arylene of CA ~ C10 and mixtures thereof; RB is alkylene of Cj-C? A »hydroxy alkylene of C3-C? A» dihydroxyalkylene of C ^ -C? »Dialkylarylene of Cu-C x, -C (0) -, - C (0) NHR * NHC (0) - »-R OR1) -» -C (0) (R *) rC (0) - »CHaCH (0H) CHa-» CHaCH (0H) CHa0- (Rt0) >, R * -0CHa CH (0H) CHae ~ "and mixtures thereof; R * is alkylene of Ca-C? A or arylene of C? LC xi units E ß ß selects from the group consisting of hydrogen »alkyl of C ,, - Caa» C3-Caa alkenyl »arylalkyl of Ct-Caa» hydroxyalkyl Ca-Caßr - (CHa)., C0aM, - (CHa) "S03M, -CH (CHaC0aM> C0aM, - (CHa)., P03M, - (R * 0) !? B, -C (0) Rat , and mix of them, oxide, B is hydrogen, C, - ^, - (CHa) ^ S03M, - (CHa) "C0aM, - (CHa)" (CHS03M) CHaS03M, - (CHa) " - < CHS0a) CHaS03M, - (CHa) -, P03M, -P03M, and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the balance of the charge; X is a water soluble anion; m has the value of 4 to about 400 »n has the value of 0 to about 200; p has the value of 1 to 6 »q has the value of 0 to 6; r has the value of 0 or 1; w has the value of 0 or i; x has the value of 1 to 100; "y" has the value of 0 to 100; z has the value of 0 or 1 »and D. the rest are auxiliary ingredients» where the ratio of polymeric polycarboxylates to polyamine soil removal agents is approximately 100? 1 to 1? 1.

2. A composition according to claim 1, characterized in that the homopolymer polycarboxylate has a molecular weight of more than 4000 to 10,000 and the polycarboxylate copolymer has a molecular weight of about 2000 to 100,000.

3. A composition according to claim 2, characterized in that the capolymeric polycarboxylate is an acrylate / malate based layer polymer having a molecular weight of about 5,000 to 75,000 and a proportion of acrylate to malate 30? 1 to 1? 1.

4. A composition according to claim 3 »characterized in that R is alkylene of C- ^ C ^; R1 is at least 50% ethylene »R * is hydrogen; the units E ε selects from the group that you con dest of hydrogen alquilo Cx-C r r ~ alkyl (R10) B B »-C (0) R = * and mixtures thereof; B is hydrogen »- (CH-.)«, SQ3 »and mixtures thereof; and q has the value from 0 to 3.

5. A composition according to claim 4 »characterized in that R1 is ethylene; the units E are (R10)? B; and B is hydrogen.

6. A composition according to claim 5 »characterized in that it comprises about 0.3% to about 4% of polyamine soil removal agents.

7. A laundry detergent composition of comprises? A. at least about 0.1% by weight »of a detective surfactant ß selected from the group which can be anionic, nonionic, zwitterionic and ampholytic surfactants and mixtures thereof; B. from about 3.75% to about 7.5% polymeric polycarboxylates having a molecular weight greater than approximately 4000 to 7000 ° and palcarboxy copal bottles having a molecular weight of approximately 2000 to 100000 and mixtures of the same »C. from about 0.3% to about 4% of paliamine soil removal agents comprising a paliamine skeleton corresponding to the formula; having a modified polyamine formula V < "+1 > W "Y? Z" or a polyamine skeleton corresponding to the formula? having a modified polyamine formula Vtr, _k + 1 > WmYr? Y'k Z »where k is less than or equal to n» said polyamine skeleton »before modification has a molecular weight greater than approximately 200 daltons» where; i) the 10 V units are terminal units that have the formula; 15 ii) Are the W units the skeleton units that have the formula? A. or iii) Y units are branching units that have the formula? iv) Unidadee S are terminal units that have the formula? wherein the β-linkers of the skeleton linkers are selected from the group consisting of C?-C ¡-C al-alkenylene alkylene of C C-C ?a, C 3 -C 7 hydroxyalkylene, di-hydroxyalkylene of C ~ Cta, dialkylarylene Cß-C? A, - '^ R * -, - < R * 0 > "R" < OR *), .. »- (CHaCH (OR *) CHaO), (RlO) and R1- (OCHaCH (OR *) CHa) w-, -C (0) (R *») rC ( 0) - »-CHaCH (OR *) CHa-» and mixtures thereof, wherein R1 is alkylene of Ca-CA »and mixtures thereof» R * eß hydrogen »- (R1Q)) <B» and mixtures thereof: R 3 is C 1 -C 6 alkyl arylalkyl of C 1 -CJJ 2, aryl is substituted with C 1 -C 6 alkyl, C 1 -C 6 aryl and mixtures thereof; Cj-C ^ a »alkenylene of C ^ -C? A» arylalkyl of Cß-C? A »arylene of CA-Cto and mixtures thereof; R? Is alkylene of Ct-C st r hydroxyalkylene of C3-Cta» dihydroxyalkyl log of C "-Cta» dialkylarylene of Cß-C? a »-C (0) -» -C (0) NHR * NHC (0) - »-R * (0R * > -» -C (0 ) (R ") rC (0 > -» CHaCH (0H) CHa- »CHaCH (0H) CHa0- (R * 0) and Rl0CHaCH (0H) CHa-» and mixtures thereof, R * is alkylene of Ca- C arylene of CA-C? A »laß unidadeß E ε elect from the group consisting of hydrogen» C 1 -Ca alkyl, C 3 -Ca alkenyl, C 2 -Ca arylalkyl hydroxyalkyl Caa, - (CHa) pC0aM, - (CHS?) ^ S03M, -CH (CHaC0a) C0a »- (CHa) pP03M, - (R ^ OJ ^ B» -C (0) R3 »and mixtures thereof; oxide; B is hydrogen »C, .- ^, - (CH2) alkyl," S03M "- (CHa> pC0a» - (CHa) "(CHS03M) CHaS03M, - (CHa)" - (CHSOaM) CHaS03M »- ( CHa) "P03M, -P03M, and mixtures thereof: M is hydrogen or a water-soluble cation in an amount sufficient to satisfy the charge balance, X is a water-soluble anion, m has a value of 4 to about 400; n has the value of 0 to approximately 200; p has the value of ia 6 »q has the value of 0 to 6, r has the value of 0 or 1, w has the value of 0 to 1» x has the value from 1 to 100, "y" has the value of 0 to 100, z ti? »ne the value of 0 ol, and D. the rest are auxiliary ingredients» where the proportion of polymeric polycarboxylates to agents removes dirt from polyamine is from about 100? 1 to 1?

8. A composition according to claim 7 »characterized in that the copolymeric copolymer is an acrylate / malate based copolymer having a molecular weight of approx. 5,000 to 75,000, and a ratio of acrylate to malate segment of about 10? 1 to 2? 1.

9. A composition according to claim 8 »characterized in that the ratio of polymeric polycarboxylates to paliamine soil removal agents is about 50? 1 to 2? 1.

10. A method for providing improved dispersion of dirt from a washing surface. The method comprises contacting the washing surface with the composition according to claim 1. -L-3-B-ú --- L --_ s --- Sflt-t? - L ---- ^^ The present invention encompasses detergent compositions comprising polymeric polycarboxylates and polyamine soil removal agents. "The composition has improved soil dispersion properties" especially for polar soils. P98 / 1264F EA / e11 # apm * xma * l p