MXPA98009205A - Detergent compositions that include polyamine and enzi bonding agents - Google Patents

Abstract

The present invention encompasses detergent compositions comprising lipase enzymes and polyamine sweeping agents, the detergent composition containing lipase has improved properties of removal of body soils and gravel stains.

Description

Cq-IPOSICIONES PETERgENTEg THAT? GUPR N IN SEATS BARREDORES PE PQ Afl NY- AND ENSWAS CAM q pe L INVENTION The present invention relates to detergent compositions that employ polyamine sweeping agents and enzymes to promote cleaning performance, especially the removal of greasy stains and soils from the body. Hard surface and laundry cleaning compositions are provided with improved properties of removing greasy stains and body dirt.

BACKGROUND S ^ TENVENTION Detergent formulators face the task of glimpsing products to remove a wide spectrum of dirt and stains from the surfaces that will be washed. It is particularly desirable to remove dirt from the body as well as greasy dirt such as butter, margarine and bacon from the surfaces to be washed. Detergent compositions containing enzymes "including lipase enzymes are well known. The detergent compositions containing lipase enzymes are effective in hydrolyzing triglycerides in body and fat soils, thereby effectively removing soils from the body. body and grease stains of the surfaces that will be washed. Without wishing to be limited by theory, it is believed that although the enzyme lipase hydrolyzes triglycerides in body oils and greasy dirt, it is deactivated when it comes in contact with chlorine. During the washing process »the effectiveness of the removal property of greasy dirt and the body of the lipase decreases due to the chlorine in the washing liquid» as in the tap water. Chlorine scavengers such as sodium sulfite and perbarate and ammonium sulfate remove or "sweep" chlorine in washing liquids. However »during a typical washing procedure» many sweepers only remove the chlorine from the washing liquid through the initial washing procedure »and a small sweeping benefit is observed during the rinse step» when additional washing liquid is added It contains chlorine. It has now been discovered that compositions comprising polyamine sweeping agents can be used to sweep chlorine in washing liquids. In addition »the polyamines are deposited on the washing surface» thus maintaining the effectiveness of the lipase enzymes to remove greasy stains and dirt from the body through the rinsing stage. Although it is not desired to be limited by theory, polia inae are deposited on the washing surface during the washing stage and remain on the surface during the rinsing stage, thereby sweeping the chlorine. effectively even during the rinsing stage. The detergent compositions comprising said polyamine sweeping agents thus maintain the effectiveness of the lipase enzymes to remove body soils and greasy stains from the surfaces to be washed. Accordingly, an object of the present invention is to provide improved body dirt removal compositions and grease stains containing lipase enzymes and polyamine sweeping agents. These and other objects are secured here »as will be seen from the following descriptions.

TECHNICAL BACKGROUND The following documents describe various polymers or modified polyamines? patent of E.U.A. Na 4 »5T4,744» Connor »issued on October 22, 1965» patent of E.U.A. No. 4 »597» T98 »Vander Meer» issued on July 1, 1986; patent of E.U.A. No. 4 »877» 896 »Maldonado and others» issued on October 31, 1989; patent of E.U.A. No. 4 »891» 160, Vander Meer »issued on January 22, 1990» patent of E.U.A. No. 4 > 976 »879» Maldonado and others »issued on December 11, 1990; patent of E.U.A. Na 5 »415» 807 »Gosßelink» issued on May 16, 1995 »patent of E.U.A. No. 4 »235» 735 »Marco et al., Issued November 25, 1980; W0 95/32272 »published on November 30, 1995» British patent 1 > 537 > 288 »published on December 29, 1978» British patent 1 »98» 520 »published on January 18, 1978» German patent DE 28 29 022 »issued on January 10, 1980; Japanese application JP 06313271 »published on April 27, 1994. Detergent compositions comprising lipase are reported in the following patents? E.U. 3 »950» 277? E.U. 4r011 »169? EP 205 »208i EP 206» 390 »EP 214,716 and EP 258,068 each give detailed descriptions of lipases.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses detergent compositions comprising lipase enzymes and polyamine sweeping agents. The present invention is directed to detergent compositions comprising? A. Detersive surfactant agent B. Lipase enzymes in an amount from about 0.004 to about 6 lipolytic units per milligram of the composition »C. from about 0.01% to about 15% sweeping agents comprising a polyamine base structure corresponding to the formula; H ZHjM-R 1"+ 1- í IN-R 1 n- 1! N-R 3 ^ -H ^ having a modified polyamine formula Vf "+ > W "Yr, 2 or a polyamine base structure that corresponds to the formula? I H R I I! tHaN-R3"_ 1-CN-R3" -CN-R3"-CN-R-ll < -NH !? having a modified polyamine formula V < r, _ "< .1 > W "Y, Y, l < Z »where is less than or equal to n» said polyamine base structure »before modification» has a molecular weight greater than approximately 200 daltons »in dande? i) units V are terminal units that have the formula? ii) units W are base structure units that have the formula? iii) units Y are branching units that have the formula? -N-R- or - iv) S units are terminal units that have the formula? wherein the base structure linker units R are selected from the group consisting of C-C alkylene, C3-C alkenylene and hydroxyalkylene C3-C? at »dialqui lari log of Cß-C? as» - (R10) xR * -, - (R ^ O ^ R ^ COR *) ,, »- < CHaCH < OR »> CHß0 > , (R ^^ R1- (0CHaCH (0R *) CHS8) v, - »-C (0) (R *) rC (0> -, -CHatCH (0Rat) CHse-» and mixtures thereof; where R 1 is C 1 -C 4 alkyl and mixtures thereof R 1 is hydrogen »- (R 5 O 4 B and mixtures thereof R 3 is C 1 -C 6 alkyl C 1 aralkyl. -C? A »aryl substituted with C7-C? -aryl aryl of C-C1SE and mixtures thereof; * is C1-C? Alkylene, C? -Clf alkenylene, arylalkylene Cm-Ctse »CA-C10 arylene and mixtures thereof; Rβ is C 1 -C 8 alkylene hydroxyalkyl C 3 -C 1 SiO 2 dihydroxyalkylene of C 2 -C 5 cyclohexylene C 1 -C Clse-C < 0 > - »-C.0> NHR * > NHC < 0 > -, -R 0R1) -, -CC0) (R -») rC (0 > - »CH ^ CH < OH > CHa- »CHsaCH (OH) CHa60- (R * 0) and RlOCH3? CH < OH > CH5e- and mixtures thereof; R * is alkylene of Ca-Cta or arylene of CA-Ctae; units E are selected from the group consisting of hydrogen, C 1 -C-alkenyl, C 1 -C 4 alkyl, arylalkyl, C 1 -C 6, hydroxyalkyl, e Cjj-C-taj »- < CH2) pC02» - (CHß) ^ S03M »- CHÍCHßCOßfDCOßM, - (CHg.) "PO., M, ~ (R» 0) > < B »-C < 0) R = »» and mixtures thereof; oxide; B is hydrogen, C1-C alkyl < k »- (CH-jJ ^ SOJI» - (CHa) COaeM, - (CH2) ^ (CHS03M) CHaSO:? M »- (CHß)" - (CHSOSIM) CHaíS03M »- (CH.,.) p , P03 »-P03M and mixtures thereof, M is hydrogen or a cation soluble in water in sufficient quantity to satisfy the charge balance, it is a water soluble anion, it has the value of 4 to about 400; value from 0 to approximately 200 »p has the value from 1 to 6» q has the value from 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, "y" has the value of 0 to 100, z has the value of 0 or 1, and D. the rest are auxiliary ingredients.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, it has been found that detergent compositions containing lipase with excellent release performance of greasy and body dirt can be achieved in said composition comprising an effective amount of a polyamine sweeping agent. All percentages "ratios and proportions herein are by weight" unless otherwise indicated. All temperatures are in degrees centigrade unless otherwise specified. All the aforementioned documents are incorporated herein in a relevant part.

Ag is detersive surfactant. Detersive surfactants suitable for use in the present invention are cationic, anionic, anionic, nonionic, ampholytic, zwitterionic, and mixtures thereof described in more detail below. The laundry detergent composition may have any suitable form, for example, high density liquids, light liquids or other volatile forms, in addition to granules or laundry bars. The sizing agents of the present invention can be formulated in a detersive matrix chosen by the formulation. The laundry detergent compositions according to the present invention may further comprise at least about 0.01%, preferably at least about 0.1%, most preferably at least about 1% by weight of the following detersive surfactants. Non-limiting examples of surfactants useful herein typically at levels from about 1% to about 55% by weight "include C1-C alqu alkylbenzene sulphonates? conventional ("LAS") and alkylated C10-Cao primary branched and random chain alkylsulphonates ("AS") "the secondary (2" 3) alkyl sulfates of Clt > -Ct? of the formula CH3 (CHa) > < (CH0S03-M *) CH3 and CH3 (CHa> (CH0S03 ~ M *) CHaCH3 where xy (y + 1) are integers of at least 7 »preferably at least 9» and M is a cation which is solubilized in water »especially sodium» unsaturated sulfates such as oleyl sulfate, the Ci0-C m alkylalkoxysulfates ("AExS", especially EO 1-7 ethoxysulfates) »C10-Cl- alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates)» glycerol esters of Clo- Clß »the alkyl polyglucosides of Clo-Clß and their corresponding sulphated polyglycosides» and alphasulfonated fatty acid esters of Cx to, -CM. if the alkyl ethoxylates of Cta-Clß ("AE" ", which include those called to the narrow-chain uiletoxylated and alkylphenylalkoxylated CA-C? a (especially ethoxylated and mixed ethoxy / propoxy) »betaines Ci.x ~ Ct.et sulfobetaines ("sultaines") "C10-Clß amine oxides and the like" can also be included in the overall compositions.The N-alkyl hydroxylic acid amides can also be used, Typical examples include N- methanol of C a, -Cx m See WO 9, 206, 154. Other surfactants derived from sugar include fatty acid amines of N-alkoxypol ihydraxy such as N (3-methoxypropyl) Ci-Ct glucamide. The N-propyl to N-hexyl glucamides of C st ~ Cxm can be used for low foaming, conventional Cto-Cao soaps can also be used, if high foaming is desired, C10-CX soaps can be used. branched chain mixtures of anionic and nonionic surfactants are spice Other useful conventional surfactant agents are listed in conventional texts.

Ensmis pan Suitable lipase enzymes are those produced by microorganisms of the Pseudomonas group »such as Pseudamonas stutzeri ATCC 19.154 as described in GB 1» 372 »034. Also see lipases in the Japanese patent application 53 »20487» open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. »Nagoya» Japan »under the trade name Lipasa P" Amano »" Or "Amano-P." Other suitable commercial lipases include AmanóCES »l rais ex Chro obacter viscosum» v.gr. Chromobacter viscosum var. li oliticu NRRLB 3673 »by Toyo Jozo Co.» Tagata »Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp »E.U.A. and Disoynth Co. »Holland. The lipase ex Pseudomonas gladiol i. The LIPOLASE enzyme "derived from Humicola lanuginosa and commercially available from Novo (see also EP 341" 947) is a preferred lipase for use herein, and mixtures of the above lipases may also be used. The lipases of the present invention are included in the detergent composition in an amount such that the final composition has a lipolytic enzyme activity of about 0.004 to about 6 preferably about 0.007 to about 3, most preferably about 0.01 to about 1, lipalitic units per milligram (LU / g) ) of the composition The detergent compositions of the present invention comprise from 0.001% to approximately 5% » preferably about 0.01% to about 2% »very preferably about 0.1% to about 1% by weight of lipase. A Lipolase Unit (LU) is that amount of lipase that produces 1 mmol of titratable fatty acid per minute in a pH state. under the following conditions? temperature 30 ° C »pH = 7.0» the substrate is an emulsion of 4.8% by weight of tributylrin (Merck item 1958) »78.5% by weight of demineralized water and 16.7% by weight of emulsifying reagent. The emulsification rectifier was prepared from a mixture of 17.9 g of sodium chloride »0.41 g of potassium dihydragenphosphate (Merck item 4873)» 400 L of mineralized water »540 mL of glycerol (Merck item 4094) and 6.0 g of gum arabic (Sigma No. G-9752).

Agwnti bi rretfgr The scavenging agent of the present invention refers to modified polyamines. These polyamines comprise base structures that can be either linear or cyclic. The polyamine base structures can also comprise polyamine branching chains to a greater or lesser extent. In general, the polyamine base structures described herein are modified in such a way that each nitrogen of the polyamine chain is subsequently described in terms of a unit that is replaced or quaternized combinations thereof.

For the purposes of the present invention, the term "modification" is defined as replacing a hydrogen atom of the base structure -NH with an E (substitution) unit "or by quaternizing a nitrogen of the base structure (quaternized). The terms "modification" and "substitution" are used interchangeably when referring to the procedure of replacing a hydrogen atom attached to a nitrogen of the base structure with an unit E. Quaternization or oxidation may take place in certain circumstances without substitution. but the substitution is preferably accompanied by the oxidation or quaternization of at least one nitrogen of the base structure. The linear or non-cyclic polyamine base structures comprising the sweeping agents of the present invention have the general formula? H I I CHaN-RD "+ l-CN-R] m - [- N-R: ir, -NHa5 said base structures" before the subsequent modification "comprise secondary and tertiary primary amine nitrogens connected by" linker "units R.

The cyclic polyamine base structures comprising the sweeping agents of the present invention have the general formula? H R I I I CHaeN-R-lr, _ ^ + 1-CN-R-l "-CN-R-lr, -i: N-R3k-NHa said base structures» before modification Subsequent »comprise secondary and tertiary primary amine nitrogens connected by" linker "units R. For the purpose of the present invention, the primary amine nitrogens comprising the base structure or branching chain" once modified "are defined as units "terminals" V or Z. For example "when a primary amine portion located at the end of the main polyamine base structure or branching chain having the structure H ^ NRI-is modified according to the present invention" is defined then as a "terminal" unit V "or simply a unit V. However" for the purposes of the present invention "some or all of the primary amine portions may remain unmodified subject to the restrictions described in more detail hereinbelow. These unmodified primary amine portions »by virtue of their position in the base structure chain remain as" terminal "units. Likewise »when a portion of primary amine» located at the end of the main polyamine base structure having the structure - Hg. is modified in accordance with the present invention "is hereinafter defined as a" terminal "unit Z" or simply a unit Z. This unit may remain unmodified subject to the restrictions described in more detail below at the moment. Similarly, "secondary amine nitrogens comprising the base structure to branching chain" once modified "are defined as units of" base structure "W. For example" when a secondary amine moiety "the principal constituent of the base structures and branching chains of the present invention "having the structure HI -CN-3 is modified in accordance with the present invention" is hereinafter defined as a unit of "base structure" 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. These unmodified secondary amine portions »by virtue of their position in the base structure chain remain as" base structure "units. In another similar manner, "the tertiary amine nitrogens comprising the base structure or branching chain" once modified "are further defined as" branching "units Y. For example" when a tertiary amine moiety "which is a point of chain branch or base structure of polyamine or other branch chains or rings »having the structure IC NR II is modified in accordance with the present invention is hereinafter 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 modified. These unmodified tertiary amine portions "by virtue of their position in the base structure chain" remain as "branching" units. The R units associated with the nitrogens of unit V »W and Y which serve to connect to the polyamine nitrogens will be described below. The modified final structure of the shovels of the present invention can then be represented by the general formula? for linear polyamine polymers »and for the general formula V V and Y 'Z for cyclic paliamine polymers. For the case of polyamines comprising rings »a unit Y 'of the formula? | R I CN-R3 serves as a branch point for a base structure or a branch ring. For each unit Y 'does a unit Y have the formula? I N- D which will form the connection point of the ring to the chain or branch of the main polymer. In the single case where the base structure is a complete ring, does the polyamine base structure have the formula? H I I CHaN-R 1"- Z -R 1 m- ZN-R3" - therefore it does not comprise any terminal unit Z and has the formula where k is the number of ring forming branching units. Preferably, the polyamine base structures of the present invention comprise rings. In the case of non-cyclic polyamines, 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 that is" n equals 0. The greater the value of n (the smaller the ratio of m to n), the greater the degree of branching in the molecule. Typically »the value varies from a minimum value of 4 to 400» however »values greater than» are also preferred especially when the value of the index n is very low or almost 0. Each polyamine nitrogen »either primary» secondary or tertiary "once modified in accordance with the present invention "is further defined as being a member of one of two general classes" simple substituted "quaternized or oxidized. Those unmodified polyamine nitrogen units are classified into units V »W» Y or Z depending on whether they are primary »secondary or tertiary nitrogens. That is to say that the nitrogens of the unmodified primary amine are units V or Z, the nitrogens of the unmodified secondary amine are units W, and the nitrogens of the unmodified tertiary amine are units Y for the purpose of the present invention. The modified primary amine moieties are defined as "terminal" V units that have one of three forms? a) simple substituted units that have the structure? E- --R- I E b) quaternized units that have the structure? E | X- E- * -R- I E where X is a suitable counter ion that provides load balance; and c) oxidized units that have the structure? 0 E-N-R- | AND Modified secondary amine portions are defined as "base structure" units W that have one of three forms? a) simple substitute units that have the structure; -N- - I E b) quaternized units that have the structure? E I - -N * -R- I E where X is a suitable counter ion that provides load balance; and c) oxidized units that have the structure? 0 - -R- I E Modified tertiary amine moieties are defined as "branching" units that have one of three forms? a) unmodified units that have the structure? -N-R- I Ib) quaternized units that have the structure? E I x- - * -R- where X is a suitable counter ion that provides charge balance; and c) oxidized units that have the structure? 0 - -R- I Certain portions of modified primary amine are defined as "terminal" Z units that have one of three forms? a) simple substituted units that have the structure? -N-E I E b) quaternized units that have the structure? E I? - -N * -E | E where X is a suitable counter ion that provides load balance; and c) oxidized units that have the structure? 0 E- -R- I E When any position on a nitrogen is replaced or not modified it is understood that hydrogen will replace E. For example a primary amine unit comprising an E unit in the form of a hydraxyethyl portion is a terminal unit V that has the formula (HÜCH ^ CH ^) HN-. For the purpose of the present invention »there are two types of chain-terminating units» units V and Z. The "terminal" unit Z is derived from a terminal primary amino portion of the -NHa structure. The non-cyclic polyamine based structures according to the present invention "only comprise a unit Z" while the cyclic polyamines may comprise no unit Z. The "terminal" unit Z may be substituted with any of the units E described in more detail after »Except when unit S is modified to form an N-oxide. At home that the 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 "linker" units R of base structure which serve to connect the nitrogen atoms of the base structure. The R units comprise units which for the purpose of the present invention are called "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are alkylene of Cat-C? A »alkylene of C _ ^ - Cta and hydroxyalkylene of C3-C? At in which the hydroxyl portion can take any position on the unit R» except the atoms of carbon directly connected to the nitrogens of the polyamine-dihydroxyalkylene base structure of C ^ -C1SS where the hydroxyl portions can occupy any two of the carbon atoms of the chain of the R unit except those atoms carbon directly connected to the nitrogens of the polyamine base structure; dialkarylene of Cß-Cta which for the purpose of the present invention are arylene portions having two alkyl substituent groups as part of the linker chain. For example, a dialkylarylene unit has the formula? although the unit does not need to be "substituted", but it can also be 1, 2 or 1, 3-substituted with C 1 -C 4 alkylene, preferably ethylene, 2-propylene and mixtures thereof. themselves »very preferably ethylene. The R "axi" units comprise - (Rl0) > < Rβ (0Rt) "-» -CHßCH (OR *) CHa0) "(R * 0) R * - (0CHS6CH (0Rat> CHSE) w-, CHssCH (ORae) CHss-r - (R * 0)! R1 - and mixtures thereof The preferred R units are alkylene of Ca-C? ae »hydroxy alkylene of C3-C? a» dihydroxyalkylene of C ^ -C1SE »dialkylarylene of Cß-Ctss» - (Rl0) "Rl-, - CH ^ CH (OR *) CHa- »- (CHssCH (0H) CHa0), - (R * 0) >, R * (0CHaeCH-» (0H) CHsí) w- »- (R * 0) > < Rβ (0R *) ,, - »most preferred R-units are C &sub1; -C < RTI ID = 0.0 > alkyd < / RTI > C < RTI ID = 0.0 > R10) > tRß (0R *) ^ - »(CHaeCH (OH) CHae0) III (R10> &1 (0CHSECH- (0H > CHsr > w- and mixtures thereof» R units even more preferred are alkylene of Cx-CX Sf. hydroxyalkylene of C3 and ezclae of the same »much more preferred are alkylene of Cß-CA. The most preferred base structures of the present invention comprise at least 50% R units which are ethereal. The Rl units are alkylene from and mixtures thereof, preferably "ethyl" * is hydrogen and - (R * 0)! B "preferably hydrogen. The alkyl is Ct-Clß-alkyl arylalkylene of Ct-C? a? »substituted aryl-CTS-Cs-alkyl» CA-Cxβ-aryl and mixtures thereof preferably Cx-Cx alkyl, t-alkali of C? -Cx st is most preferably Cx-Cx alkyl s, more preferably methyl. The R3 units serve as part of the E units described below. R "* is C1-C-alkylene, alkenylene of C-CX-t-arylalkylene of C-C-aE» arylene of CA-C10 »preferably alkylene of C ^ -C ^ arylalkyl of Cß-C? a »most preferably alkylene of more preferably ethylene or butylene. R &sub1; is < RTI ID = 0.0 > C < / RTI > C ' -C < RTI ID = 0.0 > C < / > -C (0) NHR < / RTI > NHC (0) - »-C (0) (R- *) rC (0) - »R OR *) -» (CHseCH (0H) CH3e0 (R »0)? R * 0CHS? CH (0H) CHS? -t -C (0) ( R *) rC (0) - » (CH 2 CH 2 OH) - R 2 is preferably ethylene-C (0) - »C (0> NHR * NHC (0) -, R * (0R *) -» -CH 2 CH (OH) CHa-, (CHseCH (0H> CHa0 (R * 0> s, R1OCHßCH- (OH) CHas- »most preferably - (CHSECH (0H) CH3E-.

R * is alkylene of Ca-C? A or arylene of CA-C? Ae. The preferred R "oxy" units are further defined in terms of the units R1 »R ~ and Rβ. The preferred R "oxy" units comprise the preferred R * "Ra and Rβ. Preferred polyamine soil release agents of the present invention comprise at least 50% of R * units which are ethylene. The preferred Rx »R * and Rß units are combined with the R" oxy "units to produce the preferred R" oxy "units in the following manner. i) substituting the most preferred Rß by - (CHa! CHae0) s_tRβ (0CHaeCHaE) > , - (CHssCHa0>: CHaíCH0HCHa! - (0CHaCHa) -. ii) is produced by substituting preferred R * and R * for (CH5BCH (0R3t) CHß0), ~ (R10) and R * 0 (CH2CH (0R *) CH * ) w- is produced (CHaCHOHOH), - (CH3? CHß0> yCH_eCHss0 (CHaeCH (0H) CHas) w-. iii) by substituting R * preferred by -CH ^ CH (0R.,.) CHj ,, - produces -CH ^ CH (OH) CHa, -. The units are selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 2 -C 2 alkenyl, C 7 -C 2 arylalkyl, C 2 -C 6 hydroxyalkyl, and C 2 -C 4 -CHCH 2 »- (CHa)" S03M "-CH (CHaC0ßM) C0a! Mr - (CHß), P03M, - (R» 0) (B »~ C (0) R =», preferably hydrogen »hydroxyalkylene from Ca- Caa »benzyl» alkylene of C, - ^, - (R * 0> mB »-C (0) Ra» - (CH ^) ^ CO ^, - (CHas), S03M »-CH (CHssC0aM) C0a! M "most preferably alkylene of C ~ C8 '~ (R10) > < B» -C (0) R = »» - (CH ^) ^ CO ^ M, - (CHa) "S03M» -CH (CH ^ CO ^) CO ^ »more preferably alkylene of Ct-Ca» - (R * 0) !? 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 E units do not comprise a hydrogen atom when the units V» W or Z are oxidized »that is» the nitrogens are N-oxides. For example, does the chain of the base structure or branching chains not include units of the following structure? 0 0 0 -N-R or H-N-R or -N-H i! I H H H Additionallymenter the units E do not comprise carbonyl portions directly attached to a nitrogen atom when the units V »W and Z are oxidized» that is »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 by N-oxide, ie, there is no amide of N-oxide having the structure? 0 0 0 -N-R or R = »- -N-R or -N-C-R3 1 I I C = 0 E E R3 or combinations thereof. B is hydrogen »alkyl of C ^ -C ^ - (Pj) ..SO-g» - (CHae) pC03eM »(CHa)" ~ (HS03M) CH ^ SO- ^ »(CH ^)" (CHS0ßM) CH ^ SO-jM »- (CHSE), P03M» -P03M »preferably hydrogen» - (CH-.) «, S03M» - (CH5a) ^ (CHS03M) CHfl! S03M »(CH-j)., - ( CHS0zM) CHaS03 »very > 5 preferably hydrogen or - (CHa) ^ SO-jM. M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the charge balance. For example, a sodium cation also satisfies - (CH ^) pCO ^ M and and - (CHg.) ,, S03Na. More than one 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 more than one monovalent cation may be necessary to satisfy the loading requirements of a polyanionic radical. For example, a portion - (CHae>P03M substituted with sodium atoms has the formula - (CHa!> -.P03Na; 1. Divalent cations such as calcium (Caß * > or magnesium (Mg ** ) can be replaced by or combined with other suitable water-soluble monovalent cations The preferred sodium and potassium cations are most preferred is sodium X is a water-soluble anion such as chlorine (Cl-) bromo (Br ~) and iodine (I ~) »or X can be any negatively charged radicals such as sulfate (SO ^ * -.) and methosulfate (CH3S03_) .The 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 of 0 to 100, z has the value 0 or 1? has the value of a 400 »n has the value of 0 to 200» m + n has the value of at least 5. The sweeping agents of the present invention comprise paliamine base structures in which less than about 50% of the R groups comprise R "oxy" units, preferably less than approximately 20%. »Very preferably less than 5%» more preferably the units R do not comprise units R "oxy". The sweeping agents most preferred and not comprising R "oxy" units comprise polyamine base structures in which less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1, 2-propionate and 1, 3-propylene comprise 3 or fewer carbon atoms and are the preferred "hydrocarbyl" R units. That is to say that when the R units of the base structure are alkylene of C. ^ -? A », C al-C3 alkylene is preferred and more ethylene is preferred. The sweeping agents of the present invention comprise homogenous and non-homogeneous modified polyamine base structures, in which 100% or less of the -NH units are modified. For the purpose of the present invention, the term "homogeneous polyamine base structure" is defined as a paliamine base structure having R units that are lae ee (ie, all ethylene). However, this definition of equality does not exclude polyamines that comprise other unites of strangers that comprise the base structure of the polymer, which are present due to an artifact of the chemical synthesis method. chosen one. For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethylene imines, therefore a polyethylenimine sample comprising a hydroxyethyl portion resulting from the "initiator" of The polymerization comprises a homogeneous polyamine base structure for the purposes of the present invention. A polyamine base structure comprising all the R units of ethylene in which no branching units are present is a homogeneous base structure. A polyamine base structure comprising all R units of ethylene is a homogeneous base structure regardless of the degree of branching or the number of cyclic branches present. For the purposes of the present invention, the term "non-homogeneous polymer base structure" refers to polyamine base structures which are a mixture of various lengths of unit R and types of unit R. For example, a base structure non-homogeneous comprises R units which are a mixture of ethylene and 1'-2-prapylene units. For the purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous base structure. Proper handling of these "chain lengths of unit R" provides the formulator with the ability to modify the solubility and substantivity in the fabric of the sweeping agents of the present invention. The preferred sweeping agent polymers of the present invention comprise homogeneous polyamine baεe structures which are wholly or partially substituted by partially or fully quaternized polyethylene lenoxy or total or partially oxidized nitrogens to N-oxides and mixtures thereof. However, not all nitrogens of the amine of the base structure must be modified in the same way, leaving the choice of modification to the specific needs of the formulator. The degree of determination is also determined by the specific requirements of the formulator. Preferred polyamines comprising the base structure of the compounds of the present invention are generally polyalkylamines (PAA's) »polyalkyleneimines (PAI's)» preferably polyethylenena (PEA's) »polyethylenimines (PEI's)» or PEA's or PEI's connected in portions that have longer R units than PAA's »PAI's» PEA's or PEI's relatives. A common polyamine lenamine (PAA) is tetrabutylenpentamine. Lae PEA'e are obtained by reactions including ammonia and ethyl chloride, followed by fractional distillation. The common PEA's obtained are triethylene tetramine (TETA) and tetraeti lenpentamine (TEPA). Among the pentamines, ie the hexanes, hepta inas, octane, and possibly nona inas, the cogently derived mixture does not appear to be separated by distillation and may include other materials such as cyclic amines and particularly piperazines. They can also be present cyclic amines 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. The base structures of the preferred amine polymer comprise R units which are alkylene units of CJJ (ethylene) »also known as polyethylene imines (PEI's). Preferred PEI's have at least one moderate branching ie that the ratio of a n is less than 4? 1, however, PEIs having an a n ratio of 2-1 are preferred. The basic structures »before the modification» have the general formula? H I I ZH ^ NCH ^ CH ^ 1"- Z CH ^ C ^ .1 m- ZNCHaCH23 ^ -NH. where m and n are the same as those defined above is this paragraph. Preferred PEI's "before modification" will have a molecular weight of more than about 200 daltons. The relative proportions of the secondary and tertiary "primary" amine units in the polymer base structure, especially in the case of PEI's, will vary depending on the form of preparation. Each hydrogen atom attached to each nitrogen atom of the paliamine base structure chain represents a potential site for subsequent replacement or quaternization or oxidation. Estae polyaminae can prepare »for example» pol ethyleneimine 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 these polyamine base structures are described in the US patent. No. 2 »182» 306- Ulrich et al. »Issued December 5, 1939; the patent of E.U.A. No. 3 »033» 746 »Mayle et al.» Issued May 8, 1962; the patent of E.U.A. Na 2 »208» 095 »Esselman 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 incorporated herein by reference. Examples of modified sweeping agent polymers of the present invention comprising PEI's are illustrated in formulas I and IV? The formula I illustrates a sweeping agent polymer comprising a PEI base structure in which all the substitutable nitrogens are modified by replacing the hydrogen with a polyoxyalkylene unit (CHJJCHJJQ) having the formula? Formula I This is an example of a sweeping agent polymer that is completely modified by a type of portion. Formula II illustrates a sweeping agent polymer comprising a PEI base structure in which all of the hydrogen atoms in the base structure are substituted and some amine units in the base structure are quaternized. The substituents are polyoxyalkyneoxy units - (CH 4 CH 2 O) 7 H or methyl group. The modified PEI cotton dirt-removing polymer has the formula? Formula II Formula III illustrates a sweeping agent polymer comprising a PEI base structure in which all of the hydrogen atoms in the base structure are substituted and some amine units in the base structure are quaternized. The substituents are polyoxyalkynoxy units - (CH ^ CH ^ O) ^ .H or methyl groups. The modified PEI scavenging agent polymer has the formula? Formula m Formula IV illustrates a sweetening agent polymer comprising a base structure of PEI in which the nitrogens of the base structure are modified by substitution (ie »by - (CH ^ CHaO> 7H or methyl)» quaternized » oxidized to N-oxides or combinations thereof The polymer of resolving scavenging agent has the formula? Formula IV In the previous examples "not all the nitrogens of a unit class comprise the same modification. The present invention allows the farulator to have etsxilated a portion of the nitrogens of the secondary amine while having the other nitrogens of the secondary amine oxidized to N-oxides. This also applies to the nitrogens of the primary amine, since the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents before oxidation or quaternization. Any possible combination of E groups can be substituted on the nitrogens of the primary or secondary amine "except for the restrictions described hereinabove. Barredoree agents of the present invention are included in the detergent composition from about 0.01% to about 15% »preferably about 0.05% to about 8%; most preferably around .1% to about 3%.

Dirt release agent The polymeric soil release agents known hereinafter "SRA" "can optionally be used in the present detergent compositions. If used, the "SRA'ß will generally comprise from about 0.01% to 10.0%" typically from 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 hydrophilize the surface of the hydrophobic fibers such as polyester and nylon "and the hydrophobic segments to deposit on and remain adhered to the hydrophobic fibers through the completion of the washing and rinsing cycles." thus serving as an anchor for the hydrophilic segments. This may make it possible for the anchors that occur after the treatment with the SRA to be cleansed more easily in subsequent washing procedures. The SRAs can include a variety of species loaded »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 monomeric unloaded unidadee and their structures which may be linear» branched and even star-shaped. They can include end blocking portions that are especially effective in controlling molecular weight or altering surface or physical active properties. Structures and load distributions can be designed for application to different types of fibers or textiles and for detergent products or various detergent additives. The Preferred include oligomeric terephthalate esters typically "prepared by methods including at least one transesterification / olomerization" commonly with a metal catalyst such as a titanium alkoxide * IV). Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through one or two three or four positions without, of course, forming a densely interlocked overall structure. Other SRA'e include the polyesteree of 1'-2-propylens / polyoxyethylene terephthalate of non-ionic blocked ends of the U.S. patent. Na 4 »711» 730 »of December 8, 1987 to Goseelink and others» for example those produced by the transesterification / olomerization of polyethylene glycol methyl ether »DMT» PG and polyethylene glycol ("PEG"). Other examples of »SRA's include? the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4 »721» 580 »from January 26, 1988 to Gosselink» such as ethylene glycol oligomers <; "EG"), PG »DMT and Na-3» 6-dioxa-8- Hydraxyactansulfanate; the non-ionic blocked block polyester alligamic compounds of the U.S.A. 4 »702» 857- of October 27, 1987 to Goseelink »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-eulfoieophthalate; and the blocked terephthalate ester of the anionic ends "especially of sulfoaroyl of the U.S. patent. Na 4 »877» 896 of October 31, 1989 to Maldonado Gosselink and others »the latter being a typical SRA's useful both in laundry fabric conditioning products with one example being an ester composition made from the monosodium salt of the "sulfobenzaic acid" PG and DMT »optionally but preferably also comprising added PG» eg »PEG 3400. SRAs 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. No. 3 »893» 929 to Basadur »of July 8, 1975» cellulose derivatives such as the hydroxy-ether cellulosic polymers available as METHOCEL from Dow; the cellulosic alkyls of Cx-C ^ and hydroxyalky Cells of C? of the patent of E.U.A. No. 4 »000,093» of December 28, 1976 to Nicol "and others" and the methycellulosic esters having an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoiee measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200 »which are the commercial brands of the methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK. Suitable SRAs characterized by hydrophobic polyvinylmethyl ether segments include polyvinyl ether graft copolymers, eg, vinyl ethers of Cx-C, preferably polyvinylacetate, grafted onto polyalkylene oxide base structures. See European patent application 0 219 048 »published on April 22, 1987 by Kud et al. Commercial examples available include SOKALAN SRA's such as SOKALAN HP-22 »available from BASF» Germany. Other SRA's are polyesters with repeating units having 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from polyoxyethylene glycol having 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) β (t) β (SIP) »which comprises terephthaloyl (T)» sulfoisophthaloyl (SIP) »oxyethyleneoxy and oxy-1» units. -prapi log (EG / PG) »and which concludes preferably with end blocks (CAP) »preferably modified isethionates» as in an aligomer comprising a sulfoisophthaloyl unit »5 terephthaloyl units» oxyethyleneoxy units and oxy-2-pyropionate in a defined ratio preferably of about 0.5? 1 to approximately 10? 1 »and two terminal blockers derived from 2- (2-hydroxyethoxy) -etaneul fonate. Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crystallinity reduction stabilizer "for example an anionic surfactant such as linear Ibencesulfonate dodecyl or a selected member of xylene- and toluenesulfanata or mixtures thereof. »These stabilizers or modifiers being introduced into the synthesis container» all as taught in the US patent No. 5 »415» 807 »Gosselink Pan» Lellett and Hall »issued on May 16, 1995. Suitable monomers for the above SRA include Na-2 (2-hydroxyethoxy) -ethanesulfonate» DMT »Na-dimeti 1-5 -epulfoieophthalate »EG and PG. Additional classes of SRAs include? (I) non-ionic terephthalates using di-socianata coupling agents to link the polymeric ester structures »see E.U.A. 4,201 »824» Violland et al. And E.U.A. 4 »240» 918 Lagasse and others »and (II) SRA'e with carboxylate end groups made by adding trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the right selection of the catalyst »the Trimethyl anhydride forms bonds to the polymer terminals through an activated carboxylic acid ester of the trimethyl anhydride instead of opening the anhydride linkage. It can be used already as non-ionic or anionic SRA'e as starting materials "as long as they have hydroxyl end groups that can be esterified" see E.U.A. No. 4 »525» 524 Tung and others. Other classes include (III) non-anionic terephthalate-based SRAs of the urethane-linked variety »see E.U.A. 4 »201» 824 »Violland and others» (IV) pol ivini Icaprolactam and related copolymers with monomers such as vinyl pyrrolidone and / or di ethylammonyl methacrylate »including nonionic and cationic polymers» see E.U.A. 4 »579» 681 »Rupper and others» (V) graft copolymers »in addition to the SOKALAN types of BASF» manufactured by grafting acrylic monomers to polyesteree sulphonates. These SRA's have soil release and antiredeposition activity similar to the known cellulose ethers? see EP 279 »134 A. 1988 to Rhane Poulenec Chemie. Also other classes include? (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate in proteins such as caseins »see EP 457» 205 A to BASF (1991); and (VID SRA's of polyester ester prepared by condensing adipic acid »caprolactam and polyethylene glycol» especially for treating polyamide fabrics »see Bevan and others» DE 2 »335» 044 to Unilever NV »1974. Other SRA's useful in patents of US Nos. 4 »240» 918 »4» 787,989 and 4,525 »524.

Cffnp-iffi M. frlir-qy-gidorif - Aqgntet frlar-qygf.ti9rsf and ftc ygdflrtg de blan WQg The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing an agent and one or more bleach activators. When present, bleaching agents are typically at levels of from about 0.05% to about 30%, most preferably about 5% to about 20%, of the detergent composition, especially for fabric washing. If present "the amount of bleach activators is typically from about 0.1% to about 60%" very typically from about 0.5% to about 40% of the bleaching composition containing the bleaching agent plus the bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in the cleaning of textiles, cleaning of hard surfaces or other cleaning purposes now known or known later. These include oxygen bleaches as well as other bleaching agents. Perborate whiteners »eg, sodium perborate (e.g., mono and tetrahydrate) can be used herein. Another category of bleaching agent that can be used without restriction comprises percarboxic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy phthalate hexahydrate »the magnesium salt of metachloroper-benzoic acid» 4-noni lamino-4-oxoperoxybutyl acid and hyperoxydedecanedioic 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» Burns »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-oxoperoxycaproic acid as described in US Pat. 4 »634» 551 issued on January 6, 1987 to Burns et al. Peroxygen bleaching agents can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches. sodium pyrophosphate peroxyhydrate »urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g. »OXONE» commercially manufactured by DuPont) can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles being larger than approximately 1 micron. 250 microns. Optionally »the percarbonate can be coated with agents silicate surfactants »borate or water soluble. The percarbonate is available from varioe its commercial inistroe such as FMC »Solvay and Tokai Denka. Mixtures of bleaching agents can also be used. The peroxygen bleaching agents »perborates» perca bonatos »etc.» are preferably combined with bleach activators »which lead to the in situ production in the aqueous solution (ie» during the washing process) of the peroxyacid corresponding to the activator bleaching. Various non-limiting 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"Activators of nonanoyloxy-benzenesulonate (NOBS) and tetraaceti let i lamina (TAED) are typical and mixtures thereof may also be used. See also E.U.A. 4 »634» 551 for other blanqueadoree and typical activators useful herein. Preferred amide-derived bleach activators are those of the formulas? R * N (Rβ) C) 0) R * C (0) L or R * C (0) N (Rß) R * C (0) L where R 1 is a group at uyl containing from about 6 to about 12 carbon atoms »* is an alkylene containing from 1 to about 6 carbon atoms» Rβ is H or alkyl »aryl or alkaryl containing about l about 10 carbon atoms and L is any group appropriate reeidual. A 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 residual group is feni Isul fonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl > oxybenzenesulfonate »(6-nonanamidocaproi) oxybenzenesulfonate and mixtures thereof as described in US Pat. No. 4,634,551 which is incorporated to the present for reference Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. in U.S. Patent 4,966,723 issued October 30, 1990, which is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type Yet another class of preferred bleach activators includes the acyl-lactam activators, especially the caprolactams and acvavalerolactams of the formulas. wherein R * is H or an alkyl or aryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam »octanoi Icaprolactam» 3 »5» 5-trimethyl-hexanoi Icapralactam »nonanoi Icaprolactam» decanoi Icaprolactam »undecenoi Icaprolactam» benzai l lerolactam »octanoi lvalerolactam» decanoi Ivalerolacta to »undecenoi lvalerolactam» nonanai lvalerolactam »3» 5r5 -trimeti Ihexanoi Ivalerolactam and mixtures thereof. See also the U.S. Patent. 4, 545, 784 issued to Sanderson on October 8, 1985, incorporated herein by reference, which describes the accaprolactams "including benzoylcaprolactam" adsorbed on sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. A type of bleaching agent that is not oxygen of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. See U.S. Pat. 4 »033» 718 issued July 5, 1977 to Holcombe et al. If they are used, the detergent compositions should typically contain from about 0.025% to about 1.25% by weight of said bleaches, especially sulfonated zinc phthalocyanine. If desired, the bleach compounds can be catalyzed by means of a manganese compound. Dichso compueetoe are well known in the art and include »for example» the manganese-based catalysts described in the US patent. No. 5 »246» 621 »patent of E.U.A. No. 5 »244» 594 »patent of E.U.A. No. 5 »114» 606 and you are. from pat. European pub. Nos. 549 »271A1» 549 »272A1» 544 »440A2 and 544» 490A1. Preferred examples of these catalysts include Mnxvat (u-0) 3 (1 »4» 7-tri ethyl-1 »4» 7-triazacyclononane) a- (PF?)? »Mn 'xxa (u-0 >; (u-0Ac> a (1 »4» 7-trimeti 11 »4» 7-triazacy clononane > ß- (ClO) a »MnIV (u-0) < fa (1» 4 »7-triazaci clononane ) ^ - (ClO?) A »MnIIIMn? U-0) 1 (u-OAc> se (l» 4,7-trimethyl-l »4,7-triazaci clononane) a- (C10 ^) 3» Mnxv (1 »4» 7-trimethyl 11 »4» 7-triazacyclononane) - (0CH3) 3 (PFA) and mixtures thereof Other metal-based catalysts include those described in the US patent 4,430,243 and US Patent 5, 114, 611. The use of manganese with several complex ligands to improve bleaching is also reported in the following United States patents? 4,728 »455; 5» 284 »944? 5,246» 612; 5 »256» 779; 5 »280» 117? 5,274 »147; 5» 153 »161 and 5,227» 084. As practical, and not by way of limitation, the compositions and methods herein can be adjusted to provide in the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquid "and will preferably provide about 0.1 ppm to about 700 ppm", most preferably about 1 ppm to about 500 ppm of the catalyst species in the washing liquid . A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein "including other active ingredients" vehicles »hydr tropes» processing aids »dyes or pigments» solvents for liquid formulations »solid fillers for bar compositions " etc. If high foaming is desired, foaming agents such as Cx-C13 alkanolaides can be incorporated into the compositions typically at levels of 1% -10%. The monoethanol and diethanolamides of C1C, -C1 < # illustrate a typical class of such foam boosters. The use of such foam boosters with adjunct high foaming surfactants such as the amine oxides betaines and sultaines mentioned above is also advantageous. If desired, soluble magnesium salts such as MgCla »MgSO, and the like can be added at typically 0.1% -2% levels to provide additional foam and to improve the fat removal performance. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a hydrophobic substrate. porous »after coating said suvstrato with a hydrophobic revetment. 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 »Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C13_tß (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with stirring in silicone oil (various viscosities of silicone 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. By this means »ingredients such as. enzymes »landerers» bleach activators »bleach catalysts» photoactives »dyes» fluorescers »fabric conditioners and hydrolyzable teneoactive agents mentioned above can be" protected "for use in detergents" including liquid laundry detergent compositions. The liquid detergent compositions may contain water and other solvents such as vehicles. The Low molecular weight primary and secondary alcohols illustrated by methanol »ethanol» pra prate and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (eg, 1, 3-propanediol, ethylene glycol) can also be used. glycerin and 1 »2-propanediol). The compositions may contain from 5% to 90% »typically from 10% to 50% of said vehicles. The detergent compositions herein will preferably be formulated in such a manner that during use in aqueous cleaning operations the washing water has a pH of between about 8.5 to 11, preferably between about 9 and 11, most preferably a pH of 9 to 10. Techniques for controlling pH at recommended usage levels include the pH regulators "alkalis» acids »etc. and are well known to those skilled in the art.

Ot ay nzymes Other enzymes other than lipase may also be included in the present detergent compositions for a variety of purposes "including the removal of protein-based and carbohydrate-based stains from surfaces such as fabrics or dishes" for the prevention of transfer of dyes »for example in laundry» and for fabric restoration. Suitable enzymes include proteases »ami lasas» cellulases »peroxidases and mixtures thereof of any suitable origin» such as vegetable »animal» bacterial »fungal and yeast. Preferred selections are influenced by factors such as optimal levels of pH activity and / or stability »thermostability» stability versus active detergents »detergency builders» etc. In this respect »bacterial or fungal enzymes are preferred» such as a ilasae and bacterial proteases and fungal celluloses. The term "detersive enzyme" as used herein means any enzyme that has a beneficial cleaning effect "stain removal or any other beneficial effect in a laundry detergent composition" of hard surface cleaning or personal care. Preferred detersive enzymes are hydrolasaß such as proteases and amylases. Lae enzymes that are preferred for laundry purposes include but are not limited to "proteaeae" cellulases and peroxidases. Amines and / or proteases for automatic dishwashing are highly preferred, "including both commercially available types and improved types" which, although they are becoming more compatible due to successive improvements, still have a degree of susceptibility to deactivation. of the bleach. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount".

The term "effective cleaning amount" refers to any amount capable of producing a cleaning-removing effect "stain removal" removal of dirtiness "whiteness" deodorizing or freshness on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations "typical amounts are up to about 5 mg by weight" more typically about 0.01 mg to about 3 mg "of active enzyme per gram of composition. In other words, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of non-catalytically active materials and thereby improve splashes / films or other re-growth. final. Higher active levels may also be desirable in formulations of highly concentrated detergents. Suitable examples of proteases are the euthylieins that are obtained from particular strains of B. subtilis v B.1 and chenforms. Other suitable proteases are obtained from a Bacillus strain »having a maximum activity on the entire pH scale of 8 to 12» developed and sold as ESPERASE '* by Novo Industries A / S of Denmark "hereafter" Novo ". The preparation of this enzyme and analogous enzymes is described in GB 1 »243» 784 »by Novo. Other suitable proteases include ALCALASE * and SA INASE * from Novo and MAXATASE * from International Bio-Synthetics »Inc.» The Netherlands; as well as Protease A as described in EP 130 »756 A» January 9, 1985 and Protease B as described in EP 87303761 A, April 28, 1987 and EP 130 »756 A» January 9, 1985. See also a high pH protease from Bacillus SP. NCIMB 40338 described in W0 9318140 A to Novo. Enzymatic detergents comprising protease »one or more other enzymes and a reversible protease inhibitor are described in W0 9203529 A to Novo. Other proteases that are preferred include those of W0 9510591 A to Procter S Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in W0 9507791 to Procter & amp;; Gamble. A recombinant trypsin-like protease for detergents suitable in the present is as described in W0 9425583 to Novo. In more detail "a particularly preferred protease" called "protease D" is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature "which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residue in a poem in said carbonyl hydrolase equivalent to the position +76 »preferably also in combination with one or more amino acid residue positions 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 numeration of Bacillus amyloliguefacienß subti lysine as described in the patent applications of A. Baeck and others» entitled "Protease-Containing Cleaning Compositions" which has a number of series of E.U. No 08 / 322,676, and C. Ghosh and others »" Bleaching Compositions Comprising Protease Enzymes "» that has the serial number of E.U. No. 08 / 322,677, both filed October 13, 1994. Amylases suitable herein, especially for, but not limited to, automatic dishwashing purposes, include, for example, amylases described in GB 1,296,839 to Novo; RAPIDASE *, International Bio-Synthetics, Inc. and TERMAMYL *, Novo. FUNGAMYL from Novo is especially useful. Genetic manipulation of enzymes is known for improved stability, e.g., oxidative stability. See, for example »J. Biological Chem, Vol. 260, No. 11, June 1985, PP 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as those used for automatic dishwashing, especially improved oxidative stability as the measure against a reference point of TERMAMYL "'1 in commercial use in 1993. These preferred amylases share the characteristics of" improved stability "amylases characterized, at a minimum, by a measurable improvement in one or more of" oxidant stability "v. gr. »to hydrogen peroxide / tetraacet i leti len-diamine in pH-regulated solution at pH 9-10, thermal stability, eg at common wash temperatures such as about 60 ° C, or alkaline stability, e.g. "at a pH of about 6 to about 11, measured against the amylase of the reference point identified above, The stability can be measured using any of the technical tests described in the art. See, for example, the references described in FIG. WO 9402597. The improved stability amides can be obtained from Novo or Genencor International A class of amylases highly preferred herein has the common property of being derived using directed mutagenesis a site of one or more of Bacillus amylases, especially Bacillus amylases, regardless of whether one or two strains of amylases are the immediate precursors. It is preferred to use the oxidative amylases of improved stability vs. the aforementioned reference amylase "especially in bleaching compositions, most preferably oxygenated bleaching, other than chlorine bleaching" of the present invention. Said preferred amylases include a) an amylase according to WO 9402597 »Novo» Feb. 3 »1994 previously incorporated» as illustrated A mutant in which replaces "using alanine or threonine" preferably threonine "the methionine residue located at position 197 of alpha-a -lase of B.1 ichemiformiß, known as TERMAMYL *" or the variation of position homologous to a similar progenitor amylase, such as B. amyloli uefaciens, B. subtilis, or B. stearothermophi lus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylaes" presented at the 207 American Chemical Society National Meeting »March 13-17, 1944, by C. Mitchinsop. There it is mentioned that the bleaches in detergents for automatic dishwashing inactivate alpha-amylases "but that oxidant amylases of improved stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was replaced, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants »particularly important being the variants MI97L and MI97T, with the variant M197T being the most stable expressed variant. The stability was measured in CASCADE * and SUNLIGHT "; < c > Particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and available from the Assignee Novo, such as DURAMYL *. Another oxidative amylase of improved stability that is preferred includes that described in W0 9418314 to Genencor International and W0 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example that derived by the site-directed mutagenesis of known hybrid or simple chimeric mutant progenitor forms of available amylases. Other modifications of enzyme that are preferred are also accessible. See WO 9509909 to Novo. The amylase enzyme should be at a concentration of about 0.0018% to about 0.06% pure enzyme by weight of the total composition, preferably about 0.00024% to about 0.048% pure enzyme by weight of the total composition. Cellulases that can be used herein include both bacterial and fungal cellulases, preferably at an optimum pH between 5 and 9.5. The U.S. 4,435,307, Barbesgoard et al. »March 6, 1984» describes suitable fungal cellulases of the strain DSM 1800 of Humicola insolens or Humicola »or a cellulase-producing fungus 212 belonging to the genus Aeromonas» and the cellulase extracted from the hepatopancreas of a marine mollusk Dolabella Auricle Solander. Suitable cellulases are also described in GB-A-2,075,028, * GB-A-2 »095,275 and DE-0 S-2,247,832. CAREZYME * (Novo) is especially useful. See also W0 9117243 to Novo. Suitable cutinase enzymes to be used here are described in W0 8809367 A to Genencor. Peroxidase enzymes are used in combination with oxygen sources, eg, percarbonate, perborate, peroxide hydrogen »etc.» for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the washing solution. Known peroxidase enzymes include horseradish peroxidase »ligninase and halogenoperoxidase such as chloropero idase and bromopero idase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are disclosed in WO 9307263 A and W0 9307260 A to Genecor International, W0 8908594 A to Novo and US patent. 3,553,139 »January 5, 1971 to McCarty and others. Aditionally, enzymes are described in the U.S. patent. 4,101,457, Place et al., July 18, 1978 and in the patent of E.U.A. 4,507,219, Hughes, March 26, 1985. The enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in US Pat. 4,261 »868, Hora et al., Issued April 14, 1981. Enzymes for detergents can be stabilized by various techniques. Lae enzyme stabilization techniques are described and illustrated in the patent of E.U.A. 3,600,319, August 7, 1971 to Gedge et al., And EP 199,405 and EP 200,586, October 29, 1986, Venegas. The enzyme stabilization sevenmae are also described, for example, in E.U. 3,519,570. A Bacillus sp. Useful AC13 that gives proteases, Xylanases and cellulaeae is described in WO 9401532 A to Novo. g twr d *, eet-3bi? flc ps gpsipi The compositions (including, but not limited to liquid compositions) containing pre-active enzymes may comprise from about 0.001% to about 10%, preferably about 0.005% to about 8% , most preferably about 0.01% to approximately 6% by weight of an enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is compatible with the detersive enzyme, said system can be inherently provided by another active β formulation, or can be added separately, eg, by the formulator or by a manufacturer of enzymes ready for detergents. Said enzyme stabilization systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof and are designed to satisfy different stabilization problems depending on the type and form Physical detergent composition. A stabilization approach is the use of water soluble sources of calcium and / or magnesium ions in the finished compositions, which provide said ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred here if only one cation is used. The detergent compositions typical »especially liquid» will comprise about 1% to about 30%, preferably about 2 to about 20 »very preferably about 8 to about 12 millimole of calcium ion per liter of finished detergent composition» although variation depending on the factors that include the multiplicity »type and level of incorporated enzymes. Preference is given to using water-soluble calcium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, very generally, Calcium or magnesium salts corresponding to the exemplified calcium salts can be used. Further increased levels of calcium and / or magnesium may of course be useful, for example to promote the fat cutting action of certain types of surfactant. Another approach to stabilization is through the use of borate species. See Severson »E.U. 4,537,706. Borate stabilizers, when used, may be at 10% or greater of the composition, although more typically, about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable. the use of liquid detergents. Substituted boric acids such as phenylboronic acid, butanboronic acid, p-bromophene Iboronic acid or the like » they can be used in place of boric acid and reduced levels of total boron can be possible in the detergent compositions by the use of said substituted boron derivatives. The stabilization systems of certain cleaning compositions may further comprise from 0 to about 10%, preferably about 0.01% to about 6% by weight »of chlorine bleach sweepers» added to prevent the chlorine bleaching species present in many Water sources attack and inactivate enzymes, especially under alkaline conditions. Although the chlorine levels in the water may be small, typically in the range 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, for example during dishwashing or fabrics, can be relatively large; consequently, the stability of the enzyme to chlorine during use ee somete veeee problematic. Since percarbonate or perborate, which have the ability to react with chlorine bleach, may be present in some of the present compositions in amounts independent of the stabilization system, "the use of additional stabilizers against chlorine can, very generally." not be essential, although improved results can be obtained from its use. Suitable chlorine scavenging anions are widely known and are readily available, and, if used, may be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Similarly, antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof monoethanolamine (MEA) and mixtures thereof can be used. Equally »can be incorporated in the inhibition of enzyme-specific peptides so that different enzymes have maximum compatibility. If desired, other conventional sweeteners 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 can be used »Formate, lactate, malate, tartrate, salicylate, etc. and mixtures of the miemos. In general, since the chlorine sweeping function can be carried out per ingredient listed separately under better recognized functions (eg, hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound that performs that function to the desired degree is absent in an embodiment of the invention that contains enzymes; even in that case »the sweeper is added only for optimal results. Furthermore, the formulator will exercise a normal chemical ability by avoiding the use of any scavenger or enzyme stabilizer that is primarily incompatible "as formulated" with others.

Reagent ingredient »yes use. In relation to the use of ammonium salts, said salts can be simply mixed with the detergent composition, but they are prone to adsorb water and / or release ammonia during storage. Accordingly, said materials "if present, are desirably protected in a particle such as that described in E.U. 4,652 »392» Baginski and others.

The detergency builder may optionally be included in the compositions herein to help control the mineral hardness. Inorganic as well as inorganic builders can be used. Builders are typically used in fabric washing compositions to aid in the removal of particulate soils. The level of builder can vary greatly depending on the final use of the composition and the desired physical form. When present, the compositions commonly comprise at least 1% builder. Liquid formulations typically comprise from 5% to about 50% »very typically from about 5% to about 30% by weight» of the builder. The granulated formulations typically comprise from about 10% to about 80%, most typically from about 15% to about 50% by weight, of the detergent improver. Without However, it is not intended to exclude inferior or superior levels of detergency builder. Inorganic or phosphate-containing detergent enhancers include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by half of crystalline polyphosphate, pyrophosphate, and polymeric meta-phosphates), phosphonates, acid phytic, silicates, carbonates (including bicarbonates and seekycarbonates), sulfates and aluminosilicates. However, the improved detergency which is not phosphatous is required in some places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" (as opposed to phosphateß) talee co or citrate "detergency enhancer" or in the so-called "poor detergency" condition which can occur with zeolite or layered silicate builders. Examples of improved silicate detergency are the alkali metal silicates, particularly those having an SiO2? Na20 ratio in the range of 1.6? 1 to 3.2? 1 and crystalline layered silicates, such as the layered sodium silicates described in the U.S.A. No. 4,664,839 »issued on May 12, 1987 to H.P. Rieck NaSKS-6 is the trademark of a crystalline stratified ßl ithine marketed by Hoescht (commonly abbreviated here as "SKS-6"). Unlike the Zealite builder enhancers, Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphology of stratified silicate ta-NaßSiaOß. It can be prepared by methods such as those described in DE-A-3, 17,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicate for use herein, but other layered silicates such as those having the general formula Na Si ^ O ^^ j -yH ^ O wherein 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. Other different stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As mentioned above »the (NaSKS-6 form) is most preferred for use herein. Other layered silicates, for example magnesium silicate, which can serve as a crispening agent in granular formulations, can also be useful as a stabilizing agent for oxygen bleaches and as a component of foam control systems. Examples of carbonate builders are the alkali earth and alkali metal carbonates such as loc deßcritaß in the German patent application No. 2 »231» 001 »published on November 15, 1973. The aluminosilicate builder enhancer is useful in the present invention. The aluminosilicate builders of great importance in the compositions heavy duty granular detergents currently sold most »and can also be an important detergent builder ingredient in liquid detergent formulations. The aluminosynthetic detergent enhancers include those that have the empirical formula? M, C (, Al0as) y3.xHa0 where zey eon integers from the menae 6, the molar ratio of zay eßtá in the scale from 1.0 to 0.5, and x ee an integer from 15 to 264. The ion exchange materials of alu inosilicate useful commercially available dietary. These aluminos can be crystalline or amorphous in structure and can be naturally occurring or synthetically derived aluminosi 1 icatoe. A method for producing aluminosilicate ion exchange materials is described in US Patent 3,985,669 »Kru mel and others issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline aluminosilicate has the formula? Nata [- (AlOa.) 12 (SiOß) ta3xHSB0 where x is from about 20 to about 30, specifically about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) also ee They can be in the preeent. Preferably, the aluminosilicate has a particle size of approximately 0.1-10 microns in diameter. The detergent compositions of organic detergents suitable for the purposes of the present invention include but are not restricted to a wide variety of polycarboxylate compounds. As used in the preamble, "polycarboxylates" refers to compounds having a plurality of carboxylate groups β, preferably at least 3 carboxylates. Polycarboxylagen builders can generally be added to the pharmacological composition, but can also be added in the form of a neutralized salt. When used in the salt form, the alkali metals such as sodium, potassium and lithium, or preferred alkanolammonium salts. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders include polycarboxylates of ether, including oxydisuccinate, as described in Berg, U.S. 3 »128» 287 »issued April 7, 1964, and Lamberti et al., Patent of E.U.A. 3,635,830, issued January 18, 1972. See also detergency builders of "TMS / TDS" of the U.S. patent. 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in the US Pat. 3.923.679; 3,835,163, * 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the eterhydroxypol icarboxylates »maleic anhydride copolymers with ethylene or vinyl methyl ether» 1 »3» 5-trihydroxybenzene-2,4,6-trieulphonic acid, and carboxymethyloxy-β-succinic acid, various alkali metal salts »Ammonium and substituted ammonium of polyacetic acids such as eti-lendiaminotetraacetic acid and trichloroacetic acid as well as polycarboxylic acids such as ethylic acid» succinic acid, oxydisuccinic acid »pali-aleic acid, benzene-acid, 3,5 -tricarboxy lico, carboxymethyloxysuccinic acid and soluble saltse thereof. Citrate builders, e.g., citric acid and saline eolublee thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The citrates can also be used in granulated compositions, especially in combination with aeolith detergent builder and / or crosslinked agent. The axidisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of The present invention is 3,3-dicarboxy-4-axa-1, 6-hexanediates and the related compounds described in the U.S. Pat. No. 4,566,984, Bush, issued January 28, 1986. The detergent enhancers of ucucinic acid útilee include the alkyl and alkenyl succinic acids of C ^ -C ^ ^, and leave them. A particularly preferred compound of this type is β-dodecenic acid leuccinic. Exampleß-specific succinate builders include? lauryl succinate, myristi Ißuccinate, palmiti leuccinate, 2-dodeceni Isuccinate (preferred), 2-pentadecenyl succinate, and the like. Lauri Isuccinatoe are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263"published on November 5, 1986. Other suitable polycarboxylates are described in the U.S. patent. 4,144,226 »Crutchfield et al., Issued March 13, 1979 and in the U.S. patent. 3,308,067, Diehl "issued March 7, 1967. See also Diehl, patent of E.U.A. 3,723,322. The fatty acids, e.g., monocarboxylic acids of Cx st-C r 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. Said fatty acids will generally result in a decrease in foaming. what would be considered by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the bar formulations used for hand-washing operations, various alkaline metal phosphides can be used as the well-known sodium tripolyphosphate, pyrophosphate sodium and sodium orthophosphate. Builders can also use detergents such as ethane-1-hydroxy-1,1-di-foefonate and other known phosphonates (see, for example, US Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137). wU B qug itidQr The detergent compositions of the pre-tenant may also optionally contain one or more chelating agents of iron and / or manganese. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphates, aromatic chelating agents polyfunctionally substituted and mixed therewith, all as defined below. Without pretending to be liquearse by theory, "he believes that the benefit of this materiae is due in part to its exceptional ability to remove iron and manganese from the lavage by the formation of chelate eolublee. The aminocarboxylates useful as optional chelating agents include ethylendia inotetracetatos »N- hydro ieti leti 1endiaminotriacetatos »ni trilotriacetatos» eti lendiamonotetraproprionates »trieti lentetraaminohexacetatos» diethylenetriaminepentaacetates and etanoldiglicinae, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof. Also suitable for use as a chelator is ethylglycine diacetic acid (MGDA). The aminophosphates are also useful 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 ethylendia inotetrakis (methylene phosphates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Poly-functionally substituted aromatic chelating agents are also useful in the compositions of the present invention. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Cannar et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-dieulfobenzene. A preferred biodegradable chelatadar for use herein is ethylene diamine disuccinate ("EDDS"), especially the isomer CS "S" 3 as described in US Pat. 4,704 »223 issued on November 3, 1987 to Hartman and Perk ins.

If they are used »eßtoß 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.

Aqtmgir pq? qrgg /? n -rfdfpffffi ^ p dt dirt g go? i U » The compositions of the present invention may also conveniently contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred soil remover and anti-redeposition agent is ethoxylated tetraet i lenpentamine. The exemplary ethoxylated amines are described more fully in the U.S.A. 4 »597» 898 »VanderMeer» issued on July 1, 1986. Another group of clay removal / anti-redeposition agents with the catonic compounds described in the European patent application 111,965 »Oh and Gosselink» published on 27 June 1984. Other agents remodoreß / ant i-redeposition of clay material that can be Use include the ethoxylated amine polymer 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 US patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions of the present invention. Another type of preferred anti-redeposition agent includes the carboxy-ethylcellulose (CMC) materials. These materials are well known in the art.

The polymer dispersion 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 zeolite builders and builders. / or stratified silicate. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. Although not intended to be limited by theory, it is believed that polymer dispersion agents increase the performance of the overall detergency mole, when used in combination with other detergency builders (including weight polycarboxylates). lower molecular weight) by inhibition of growth of crietals, peptization of release of dirt into particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomersß, preferably in their acid form. Monomeric unsaturated acids which can polymerize to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, esaconic acid, citraconic acid, methylenic acid. The presence of polymeric polycarbons in the present or non-carboxylic radicals, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% in weight. Particularly suitable palmeric polycarboxylates can be derived from acrylic acid. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of said acrylic acid polymerics may include, for example, the alkali metal, ammonium and substituted ammonium. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl »U.S. Pat. 3,308,067, issued March 7, 1967. Acryl / aleic acid bae copolymers can also be used as a preferred component of the dewatering / anti-redeposition agent. Talee materials include the water-soluble salts of mere copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid pharmacy preferably ranges from about 2,000 to 100,000, more preferably about 5,000 to 75,000 and most preferably about 7,000 to 65,000. The ratio of the acrylate segments to those of maleate in said copolymers generally ranges from about 30? 1 to about 1? 1 »most preferably about 10? 1 to 2-1. The water-soluble salts of said acrylic acid / maleic acid copolymers can include, for example, the alkali metal salts, ammonium and substituted ammonium. Soluble acrylate / aleate copolymers of this type are known materials which are described in European patent application No. 66915 »published on December 15, 1982» as well as in EP 193,360, published on September 3, 1986 » which also describes palímeraß comprising hydraxipropy lacri lato. Other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers.

Said materials are also described in EP 193,360, including, for example, the terpolymer 45/45/10 of maleic / acrylic / vinyl alcohol. Another polymeric material that may be included is polyethylene glycol (PEG). PEG can exhibit performance of dispersing agent and can act as an anti-redeposition agent for clay soiling. Typical molecular weight scales for these purposes range from about 500 to about 100,000, preferably about 1,000 to about 50,000 and most preferably about 1,500 to about 10,000. The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. The dispersing agents such as those of polyaspartate preferably have a molecular weight (avg.) Of about 10,000.

A ndmgr Any optical brighteners or other brightening or bleaching agents known in the art can be incorporated at levels typically from about 0.05% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups, including, but not necessarily limited to, stilbene derivatives, pyrazoline »cu arina» carbaxyl acid, methinocyanins, 5,5-dibenzotifen dioxide, azoles, 5- and 6-membered ring heterocycles »and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agent," M.? Ahradnik, published by John Wiley & Sonß, New York (1982). Specific examples of optical brighteners that are useful in the preement compositions are those identified in the U.S. patent. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the April series lantadoreß PHORWHITE of Verona. Other open rims described in this reference include? Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, dipanibles from Hilton-Davis, located in Italy; 2- (4-styryl-phenyl) -2H-naphthol Cl, 2-dJ triazole; 4,4'-biß- (1, 2 »3-triazol-2-yl) -etissi Ibienes; 4,4 ' -biß (styryl) bispheni, and the β-aminocoumarin β Example of βßpecific β of ethoin april lantadoreß include 4-methyl-7-diethyl-aminocoumarin; 1'-2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenol; Ipyrazines, 2,5-bis (bepzoxazol-2-yl) thiophene, 2-styryl-naphthyl-Cl, 2-s3axazal, and 2- (eeti-lben-4-yl) -2H-naphtho-Z, 2-d ] triazole Also see US Patent No. 3,646,015 issued to Hamilton on February 29, 1972. Anionic brighteners are preferred here.

Compounds for reducing or suppressing the formation of foams can be incorporated into the compositions of the present invention. The suppression of foams may be of particular importance in the "high concentration cleaning processes" as described in E.U. 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 Othmer Encyclopedia of Chemical Technology» 3a. Edition »Volume 7» pages. 430-447 (John Wiley 8 Sonß »Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble saltse to them. See the patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic acid acids and ions thereof used as the eupressor of foams typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal taels such as sodium, potassium and lithium, and salts of ammonium and alkanolammonium. The detergent compositions herein may also contain ßupresors of foams that are not a β-surfactant. Eßtoß include, for example? hydrocarbons high molecular weight such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of C 1 -C ^ 0 (e.g., stearone), etc. . Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkyl elamines or di- to tetra-alkyldia in-loglotriazines formed as products of cyanuric chloride with doe or tree moleß of a primary amine or secondary ester containing from 1 to 24 atom. of carbon. propylene oxide and monostearyl phosphates such as monoearyl alcohol phosphate ester and alkali metal diphosphates (e.g., K, Na and Li) monoetearyl licosis and ether phosphate. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure, and will have a pour point on the scale of about -40 ° C to about 50 ° C, and a minimum boiling point not less than about 110 ° C (atmospheric pressure ). Also known is the use of hydrocarbon ceroeoe, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. The hydrocarbon foam suppressors are described, for example, in U.S. Patent No. 4,665,779 issued May 5, 1981 to Gando !. fo and others. Hydrocarbons »therefore» include saturated or unsaturated hydrocarbons aliphatic, alicyclic, aromatic and heterocyclic having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of foam suppressors, is intended to include admixture of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors that are not surfactants comprise silicone foam suppressors. This category includes the use of poiorganoei loxane oils such as poly idimeti lei loxane, dispersions or emulsions of polyorganosi laxane or resinß oils, and combinations of polyorganosiloxane with silica particles wherein the polyorganosi loxane is chemoabsorbed or fused onto the silica. The β-silicon foam suppressors are well known in the art and are described, for example, in the U.S. patent. 4,265 »779» issued on May 5, 1981 to Gandolfo and other and in the application of European patent No. 89307851, published on February 7, 1990 by Starch, M.S. Other suppressors of silicone foams are described in the patent of US Pat. No. 3,455,839 which refers to compositions and processes for the desorption of aqueous solutions incorporating thereto small amounts of poly idimeti Isi loxane fluids. Silicone and silanated silica mixtures are described, for example, in the German patent application DOS 2 »124» 526. The eliminators of silicone foams and the controlling agents of foams in compoßicioneß detergentß granulates are described in US Pat. No. 3,933,672 Bartolotta et al. and in US Patent No. 4,652,392, Baginski et al., issued March 24, 1987. An illustrative silicone-based foam suppressant for use in the present is a foam suppressant amount of a foam controlling agent consisting essentially of? (i) polydimethylsi loxane fluid having a viscosity of from about 20 c.sup.-1 to about 1,500 c.sup.-25 ° C; (ii) around 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of unidadeß of (CH 3) 3 Si04 / .a of SiO 2 units in a unit ratio of (CH 3) 3 Si01 /, to SiOa unit of about 0.6? 1 to approximately 1.2? l; and (iii) about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred emulsifier foam suppressor used herein, the solvent for a continuous phase is made of polystyrene or polyethylene-polypropylene glycol copolymers or mixtures of the (preferred) or palpated polypropylene glycol. The primary ßilicón foam suppressor is branched / interlaced and non-linear. To illustrate this point further, typical liquid controlled laundry detergent compositions optionally controlled will comprise about 0.001 to about 1, preferably about 0.01 to about 0.7, most preferably about 0.05 to about 0.5 weight percent of said silicone foam suppressor, comprising (1) a non-aqueous emulsion of a primary foam antifoaming agent which is a mixture of (a) a polyorganosiloxane »(b) a resinous siloxane or a silicone resin producing silicon compound» (c) a finely divided filler material and (d) a catalyst to promote the reaction of mixing components (a) ) »(B) and (c) to form silanolates; (2) at least one nonionic surfactant of silicon; and (3) polyethylene glycol or a polyethylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granulated compositions »gels» etc. See also patents of E.U.A. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288 »431» Huber et al., Issued on February 22, 1994 and patents of E.U.A. 4,639,489 and 4,749,740 »Aizawa and others in column 1» row 46 to column 4, row 35. The silicone foam suppressant of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a lower average molecular weight of about 1,000, preferably between about 100 and 800. The copolymers of The pallet and the polymer / polypropylene of the present have a solubility in water at room temperature of about 2% by weight, preferably about 5% by weight. The preferred solvent of the precursor is polyethylene glycol having an average molecular weight of less than about 1,000, most preferably between about 100 and 800, most preferably still 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, most preferably between 1? 3 and 1? 6"of polyethylene, is preferred. polyethylene-polypropylene glycol copolymer. The ßupreeoreß of preferred silicate foams and ußadoß in the present do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably, they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam euphorpressants useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with oils of silicon and silicone described in the USA 4 »798» 679 »4» 075 » 118 and EP 150 »872. The secondary alcohols include alkyl alcohols of CA-C1? that have a string of C ^ -C ^. A preferred alcohol is 2-butyloctanol »which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols they are available under the trade name ISALCHEM 123 from Enichem. The mixed foam ßupresors typically comprise mixtures of alcohol + silicone at a ratio of 1? 5 to 5? 1. For any detergent compositions to be used in automatic wng machines »the foams should not be formed to the extent that they overflow from the wng machine. The foam suppressors "when used" are preferably present in an amount of foam suppression. By "foam suppression amount" it is understood that the formulator of the composition can select an amount of this foaming controlling agent that will sufficiently control the foams to result in a low foaming laundry detergent for use in automatic wng machines. The compositions herein will generally comprise from 0% to about 5% foam suppressant. When they are used as foam suppressors »the onocarbaxyl ácidos fatty acids and salts of the miemoms» will typically be present in approximately 5% by weight of the detergent composition. Preferably, about 0.5% to approximately 3% fat suppressant of onocarboxylate fat is used. The silicone foam suppressors are typically used in amounts of up to about 2.0% by weight of the detergent composition, although higher amounts can be used. This limit Superior is practical in 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% ßupreßor of ßilicon foam, most preferably from about 0.25% to about 0.5%. As used herein, these values in percent by weight include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can be used. The monostearyl phosphate foam suppressants are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. The hydrocarbon foam ßupresors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam ßupresors are typically used at 0.2% -3% by weight of the finished compositions. 8mv * n w to% I \ ~ M Various fabric softeners that soften during wng can be optionally used, especially the impalpable smectite clays of the U.S. patent. 4,062,647, Stor and Nirsch, issued December 13, 1977, as well as other softening clays known in the art, typically at levels of about 0.5% to about % by weight in the fields herein to provide softening benefits concurrently with fabric cleaning. Smoothing can be used on a clay bath in combination with amine and cationic softeners as described, for example, in the US patent. 4,375,416, Crisp et al., March 1, 1983 and in the patent of E.U.A. 4,291,071, Harris et al., Issued September 22, 1981.

Dye transfer inhibiting agents The compositions according to the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, paliamine N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, manganese phthalocyanine, peroxidases 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%. Very specifically, the polyamine N-oxide polymers preferred for use in the present contain units having the following structural formula? R-A ^ -P; where P is a polymerizable unit to which a N-O group can be attached or the N-O group can form part of the unit polymerizable or the N-O group can be attached to both units; A is one of the following structures? -NC (O) -, -C (0) 0-, -S-, -0-, -N =; x is 0 or i, and R is aliphatic, aliphatic, ethoxy-side, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. The preferred polyamine N-oxides are β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-β-phenylenediamine, and pyrrole, pyrrole, imidazole, pyrrole, piperidine and derivatives thereof. The N-O group can be represented by the following general structure? 0 0 wherein Rt, Rβ, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x "y and z are 0 or 11 and the nitrogen of the N-O group can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10"preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has heat transfer inhibiting properties. Examples of suitable polymeric structure are polyvinyl, polyalkylene, polyesters, polyethers, polyamide, poly-idaß, polyacrylates and mixtures of the same. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymers typically have 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 capylation or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. This preferred class of materials can be termed "PVNO". The most preferred paliamine N-oxide useful in the detergent compositions herein is poly-4-vinyl pyridine N-oxide having an average molecular weight of about 50,000 and an amine to N-oxide ratio of amine of approximately 1? 4. Polymer copolymers of N-vini 1 porrol idona and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by the scattering of light such as dee dee dee cribe cribe cribe cribe en en en en en en en en en en en en Vol Modern Modern Modern Modern Modern Modern Modern. Modern Methads of Polymer Characterization ", the descriptions of which are incorporated herein by reference.) PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1? 1 to 0.2? 1, preferably from 0.8? 1 to 0.3? 1, most preferably from 0.6-1 to 0.4 1. These copolymers can be either linear or branched.The campsßicianes of the present invention can 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 about 5,000 to about 50,000.The PVP's are known to those skilled in the detergent field art, 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 about 500 to about 100.0. 00, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to P ^ P on a basis of ppm assorted in wash solutions is from about 2? 1 to about 50? 1, and most preferably from about 3? 1 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 transfer inhibitory action of Colorant. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of said optical brighteners. What are the optical latent hydrophilic april in the present invention are those that have the structural formula? wherein Rx is selected from anilino, N-2-bis-hydroxyethi and NH-2-hydroquinone; Ra is selected from N-2-bis-hydroxyethi, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M eß a salt-forming cation such as sodium or potassium. When in the previous formula Rx is anilino, Ra is N-2-bie-hidraxieti lo and M is a cation such as ßadio, the brightener is acid 4,4 ', bisC (4-ani lino-6- (N- 2-bis-hydroxy-yl) -s-triazi-2-yl) amino-3-2'-2'-ethe phonylbenzene and disodium salt. This particular brightener species is commercially marketed under the trade name Tinapal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener in the present compositions.

When in the above formula R1 is anilino, R2 is N-2-hydroxyethylN-2-methylamino and M is a cation such as iodo, the brightener is the disodium salt of 4,4'-bist acid (4-ani). l ino-6- (N-2-hydroxyethyl-1-N-methylamino) -s-triazin-2-yl) amino-2,2'-styrene-behenyl sulphonic acid. This particular brightener species is commercially marketed under the trade name Tinopal 5BM-GX by 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-ani-lino-6-morphino-s-triazin) -2 ~ il) amino32 »2'-est ibenedieulfonic. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The specific optical blinding species selected for use in the present invention provides specifically effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVP I) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of these detergent composition components when used alone. Without being limited to the theory »it is believed that said brighteners work in this way because they have high affinity for fabrics in the washing solution and therefore they are deposited 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 "exhaustion coefficient". The depletion coefficient is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. The brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional optical brightener of compound may optionally be present in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye traneferring inhibiting effect. Said conventional and well known ußo for detergent formulations. The modified polyamipads of the present invention useful as sweeping agents are suitably prepared by the following methods. flUBQWiiMaJUbiBii L Prtp? Rac * ó? g PE IflQP E-ir Ethoxylation is carried out in a 2-gallon agitated stainless steel autoclave equipped for measurement and temperature control »pressure measurement» purged under vacuum 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 (ARC) is installed to supply 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 changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) is added to the autoclave (Nippon Shokubai, Epomin SP-018 having an average listed molecular weight of 1800 »corresponding to functions of 0.417 mole of polymer and 17.4 mole of nitrogen). The autoclave is then sealed and purged of air (applying a vacuum at 711 mm Hg followed by pressurization with nitrogen at 17.57 kg / cm *, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while vacuum is applied. After about one hour, the autoclave is charged with nitrogen to approximately 17.57 kg / cm * while the autoclave is cooled to approximately 105 ° C. Deßpuéß ße adds ethylene oxide to the autoclave in increment during the time while the monitor carefully monitor the temperature, temperature and flow rate of ethylene oxide. of 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 charged 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 unreacted ethylene oxide. Afterwards, the vacuum is continuously applied 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 the PEI nitrogen). The methoxide solution is sucked into the autoclave under vacuum and then the programming point of the autoclave temperature controller is increased to 130 ° C. A bipolarizer 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 stabilizes in about one hour indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum during additional 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 vented 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 ethylene oxide in the autoclave, maintaining at the same time the temperature between 100 and 110 ° C and limiting any increase in temperature due to the exotherm of the reaction. After 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 increases to 110 ° C and the mixture is increased. Shake for an additional hour. The reaction mixture is then collected in a nitrogen-purged container and transferred to a 22-liter, three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst was neutralized by adding 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing about 2.831 dm3 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 EMPLO I? C ffl rn & sicPP g PE WQ E- »To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethylenimine having a molecular weight of 1800, which is further modified by ethoxylation to a degree of about 7%. ethyleneoxy residues by nitrogen (PEI 1800, Et) (207.3 g, 0.590 moles of nitrogen, prepared as in Example I) and acetonitrile (120 g>.) Dimethyl sulfate (28.3 g, 0.224 mole) is added in one portion to the solution in rapid stirring, which is covered and stirred at room temperature overnight.The acetonitrile is removed by rotary evaporation at about 60 ° C, followed by further purification of the solvent using a Kugelrohr apparatus at approximately 80 ° C. give 220 g of the desired partially quaternized material as a dark brown viscous liquid.The NMR-l3C spectrum (Dß0> 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 about 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 ni trogens.

EEMPLO II Formation of amine oxide of PEI 100 E- To a 500 L Erlen eyer flask equipped with a magnetic stirring bar is added polyethylenimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI -1800, Et> (209 g, 0.595 moles of nitrogen »prepared as in example I), and hydrogen peroxide (120 g of a 30% solution in water, 1.06 mole). after an initial exotherm, the solution is stirred at room temperature overnight The NMR-H (D ^ O) spectrum obtained in a sample of the reaction mixture indicates complete conversion Lae resonances assigned to adjacent methylene protons Nitrogen oxides were displaced from their original position at ~ 2.5 ppm to ~3.5 ppm.The reaction solution is added with about 5 g of 0.5% Pd ßabout alumina pellets and the solution is allowed to stand at room temperature for approx. 3 days The solution is tested and found to be negative for peroxide by indicator paper. The material obtained is suitably stored as an active solution at 51.1% in water.

Formation of amine oxide of PEI 1800 E-quaternized To a 500 L 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 residues per nitrogen (PES 1800 Et) and then further modified by quaternization to about 38% with dimethyl sulfate (130 g, 0.20 moles of oxidizable nitrogen, prepared as in example II), hydrogen peroxide (48 g of a solution 30% by weight 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 (D? 0) spectrum obtained in a sample taken from the reaction mixture indicates the complete conversion of the ß-resonances 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 quaternized nitrogens and 62% of the nitrogens oxidized to amine oxide and stored adequately with an active solution at 44.9% in water.

EXAMPLE IV Prgpara? IPP < z \ e ^ \ Z E- »The ethoxylation is conducted in a 2-gallon agitated stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for the introduction of ethylene oxide as a liquid. A cylinder of 7.5 kg net of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by means of a pump to the autoclave placing the cylinder on a scale in order to monitor the changes in the weight of the cylinder. A 750 g portion of polyethylenimine (PEI) (having a listed average molecular weight of 1200, equivalent to 0.625 moles of polymer and 17.4 moles of nitrogen) is added to the autoclave. The autoclave is then sealed and purged of air (applying vacuum to minus 711 mm Hg followed by pressurization with nitrogen at 17.57 kg / cm *, then ventilating at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while 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 05 ° C. Then ethylene oxide is added to the autoclave in increments during the time while mani cough the pressure carefully » 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 exam. The temperature is maintained between 100 and 110 ° C while the total pressure is allowed to gradually increase during the course of the reucián. After a total of 750 grams of ethylene oxide have been charged into the autoclave (almost equivalent to one mole of ethylene oxide per PED nitrogen function), the temperature ß increases to 110 ° C and the autoclave ß stops stirring At this point, apply vacuum to remove any residual unreacted ethylene oxide, then apply vacuum 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 PEI nitrogen funcianeß.) The methanol solution is sucked into the autoclave under vacuum and then the temperature controller programming point of the The autoclave is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator.The power of the agitator is monitored along with the temperature and pressure. is the power and temperature of the agitator gradually increase when the methanol is removed from the autoclave »and the viscosity of the The mixture increases and stabilizes in an hour approximately 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 loaded with nitrogen at 17.57 kg / cm * and then ventilated to room temperature. The autoclave is charged at 14.06 kg / cm * with nitrogen. Ethylene oxide is again added to the autoclave in increment as mentioned above by carefully monitoring the pressure, temperature and flow rate 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 achieving the addition of 4,500 g of ethylene oxide (resulting in a total of 7 mole 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 eß deßpußß reaction mixture collected in nitrogen-purged containers is optionally transferred to a 22-liter three-neck 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 followed by stirring about 2.831 dm3 of inert gae (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while stirring and stirring. heat the mixture to 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 before the discharge of the product. Another preferred example 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.

EXAMPLE V C at rp-i -;? C * or? - < ? r7% d PEÍ XZ99 ET To a 500 L Erlenmeyer flask equipped with a magnetic stirring bar, add polyethyleneimine, PM 1200 ethoxylated to a degree of 7 (248.4 g, 0.707 moles of nitrogen »prepared as in example 5) and acetonitrile (Baker »200 mL). Di-ethyl sulfate (Aldrich »8.48 g» 0.067 mol) is added in one fell swoop to the solution in rapid stirring, which is then capped and stirred at room temperature overnight. The acetonitrile ß is evaporated on the rotary evaporator at "60 ° C, followed by a Kugelrohr (Aldrich) apparatus at ~80 ° C to give ~ 220 g of the dyed material as a dark brown viscous liquid.A t3C NMR spectrum (DaQ) > shows the absence of a peak at "58 ppm corresponding dimethyl sulfate. An NMR-H spectrum (Da0> shows partial displacement of the pike at 2.5 ppm (methylenes bound to non-quaternized nitrogens) at ~ 3.0 ppm.

Laundry compositions EXAMPLES VI-IX Composition of high density granular detergents (more than 600 g / 1) comprising the following ingredients are prepared.

EXAMPLES VI-IX (CONTINUED) EXAMPLES VI-IX < ONTINUATION * 1. Enzyme LIPOLASE "by Novo Industri A / S» Denmark 2. Polyamine sweeping agent according to example I 3. Dirt releasing polymer according to the U.S. patent. No. 4,968,451 »Scheibel et al., Issued on November 6, 1990 4.- The 100% balance may include, for example, minor components such as optical brightener, perfume, suds suppressor, dirt matrix, protease, cellulase, chelating agents, dye transfer inhibiting agents, additional water and fillers, including CaCO3, talc, silicates, etc. The following test method is used to verify the performance in the removal of grease stains and dirt from the body, from the detergent composition comprising lipase enzymes and sweeping agents.

EXAMPLE X A suitable laundry rod is prepared for hand washing soiled fabrics by normal extrusion processes, and comprising the following? Component "/ in Weight Cise 30 Phosphate linear alkylbenzene sulphonate (as sodium tripolyphosphate) 7 Sodium carbonate 25 Sodium pyrophosphate 7 Coetanoate Monaetanolami 2 Zeolite A (0.1-10 microns) 5 Carbaximeti Icelulosa 0.5 Polyacrylate (p.m. 1400) 0.2 Paliamine sweeping agent (Example I) 1.0 Lipase1 (100 LU / mg) 0.1 Brightener, perfume 0.2 CaSO ^ 1 MgSQ 1 Moisture 4 Other minor components »including filler2 Balance to 100% 1. Enzyme LIPOLASE "by Novo Induetri A / S, Denmark 2. It can be selected from suitable materials such as CaCO3, talc, clay, silicate and the like US Pat. No. 3,178,370, Okenfuss, issued on April 13, 1965 describes laundry detergent bars and procedures to manufacture them. The Philippine patent 13,778 »Anderson» issued on 23 September 1980 »describes einthetic laundry detergent bars. The method for manufacturing laundry detergent for laundry by various extrusion methods is well known in the art.

EXAMPLES XI AND XII Are suitable laundry rods prepared for handwashing of soiled fabrics by normal extrusion methods? And which comprise the following? % in weigh 1. Dirt releasing polymer in accordance with the U.S. patent. 4 »968» 451 »Scheibel et al.» Issued on November 6, 1990 2. LIPOLASE * Enzyme from Novo Industri A / S, Denmark 3. It is possible to choose from suitable materials such as calcium carbonate, talc, clay, silicates and Similar EXAMPLES EHI-XIV The following describes liquid detergent compositions according to the present invention? % in weigh EXAMPLES XIII-I (CONTINUED) 1. Minor components - includes optical brightener 2. Dirt release polymer according to the US patent. A.4,968,451, Scheibel et al 3. Enzyme LIPOLASE * by Novo Industri A / S, Denmark 4. Polyamine sweeping agent PEÍ 1200 E20 prepared according to example IV Coppogicippts p ri i laya or dg Ya.iiUag Another aspect of the present invention relates to dishwashing compositions, in particular compositions for manual and automatic dishwashing, especially composicianeß for manual dishwashing. The liquid dishwashing compositions according to the present invention preferably comprise at least about 0.1%, most preferably about 0.5% to about 30%, more preferably about 1% to about 15% of the dispersing agent and from about 1% to about 99.9% of a detersive surfactant. The liquid dishwashing compositions according to the present invention may comprise any of the ingredients listed hereinabove. In addition, the dishwashing compositions may comprise other ingredients such as bactericides, chelators, foam enhancers, opacifiers and calcium and magnesium ions.

EXAMPLE XV The following liquid compositions of the present invention are prepared by mixing the listed ingredients in the given amounts. Composition (% in kind) Ingredientente A B C D E F Water 28.0 34.0 30.0 41.0 41.0 36.0 Ethanol 13.0 8.0 8.0 8.0 8.0 8.0 Acid dodecy lbencenesulfonic linear 9.0 9.0 9.0 9.0 9.0 9.0 Sodium Cacaylsulphate iO 1.0 Candensation product of one mol of o-alcohol of C ».3-C? And 7 moles of ethylene oxide 7.0 7.0 Condensation product of one mole of oxoalcohal of Ct3 ~ Ctß and 5 molees of oxide of ethylene 7.0 7.0 7.0 7.0 Chloride of (2-hydroxyethyl D-dimethylammonium from Ctae-Cx ^ 0.5 0.5 0.5 0.5 Dadeceni acid Isuccinic 12.5 10.0 Dodecenic acid l Tetradeceni l-succinic 10.0 TMS / TDS * 12.5 Tripol i sodium phosphate 15.0? Eolite 15.0 Citric acid 1.0 3.0 2.8 2.8 3.0 2.8 Oleic acid 3.0 Diethylenetriandiphenylmethylenephosphonic acid 0.7 0.7 Hexamethylenediaminetetramethylphosphosphonic acid co - - - - 0 .6 - - - 0.7 Sweeping agent (Example I) 0.5 1 .5 2.0 0.5 1 .0 1 .0 Lipaßa2 lOOLU / g 0.3 0.3 0.5 0.5 0. 3 0.3 Proteaβa 8KNPU / g 0 .5 _ - ___ ___ - - ___ Protease 16 KNPU / g 0.3 0.3 0.3 0.3 0.3 Amylase 0.2 0.2 Sodium formate 1.0 1.5 1.0 Sodium acetate 2.5 2.5 Magnesium acetate tetrahydrate 1.7 1.7 0.1 Magnesium chloride hexahydrate 1.7 0.1 0.7 Sodium hydroxide 5.0 5.0 5.0 5.0 5.0 5.0 Perfume and componentß menoreß 100% Balance 1. Mixture (80? 20 > of tartrate monoeuccinate and tartrate disuccinate 2. Enzyme LIPOLASE * by Novo Industri A / S, Denmark EXAMPLE XVI A composition for automatic dishwashing is as follows. Ingredient% by weight Trisodium Citrate 15 Sodium Carbonate 20 Silicate * 9 Agent »Nonionic Teratoactive2 3 Sodium Polyacrylate (MW 4000) 3 5 Lipase Enzyme * (100 LU / mg) 0.5 Termamyl Enzyme (60T) 1.1 Enzyme Savinaße (12T) 3.0 Sweeping agent (Example I) 1.0 Minor components 100% balance 1. BRITESIL, PQ Corporation 2. Low polyurethane oxide / polypropylene oxide foam former 3. ACCUS0L, Rohm and Haas 4. LIPOLASE * Enzyme from Novo Industri A / S »Denmark In the above composition» the surfactant can be replaced by an equivalent amount of any low foaming nonionic surfactant. Examples include straight ethoxylated straight-chain alcohols foam or non-foaming such as the Plurafac * RA series sold by Eurane Co., Lutensol * LF, sold by BASF Co., Triton * DF, sold by Rohm & Haas Co., and Synperonic * LF, sold by ICI Co. Compositions for automatic dishwashing can be granulated, tablet, bar or rinse aid. The methods for making granules, tablets, bars or rinsing aids are known in the art. See, for example, the patents of E.U.A. Nae series 08 / 106,022, 08 / 147,222, 08 / 147,224, 08 / 147,219, 08 / 052,860 »07/867» 941.

Claims (10)

NOVEPAP PE THE INVENTION REIVINPICACIQNES

1. - A detergent composition for laundry comprising? A. Detersive Contaminant Agent. B. Lipase Enzymes in an Amount of Approximately 0.004 to Approximately 6 Units L ipolitics per Milligram of the Composition »C. From about 0.01% to about 15% of sweeping agents comprising a structure of polyamine bar that corresponds to the formula? H II CHaN-R3, + l-N-R3 (-CN-3r, -NHa having a modified polyamine formula V <"x, Y" Z or a polyamine bae structure corresponding to the formula ? I H R I I I CHaN-R3"" ^ 1-CN ~ R, -CN-R r -, --- N-R3, < -NHa you have a modified polyamine formula t "_ < .1 > WmYr, Y'l < Z »in dande k is less than or equal to n, said polyamine base structure, before modification, has a molecular weight greater than about 200 daltons» where? i) Are the V units are terminal units that have the formula? ii) W units are units of base structure that have the formula? iii) units Y are branching units that have the formula? iv) Z units are terminal units that have the formula? wherein the basic structure linker units R are selected from the group consisting of alkylene of Ca-C? at »- (R * 0)! KR3 (OR * >) < , - (CHaCH (0R *) CHss0) > - (R * 0) s, R * - (0CHaCH (0R *) CHas) "-, -CHaCH (OR *> CHa- and mixtures thereof, as long as when R comprises an alkylene of C1-Cta , R also comprises at least one unit - (R * 0> > cR3 (0R * > ,,, (CHaCH (0R *> CHa0> "(R * 0) and R * - (0CHaCH (0R *) CHa) w- or -CHaCH (0R *) CHa-; R * is alkylene of C ^ -C r and mixtures thereof; R * eß hydrogen, - (R * 0) > < B, and mixtures thereof; R3 is Ct-C? A alkylene, C3-C? A hydroxyalkylene, CA-C? A dihydroxyalkylene, C? -Ctat dialkylarylene, -C (0> -, -C (0) NHR? NHC (0 > ~, C (0> (R "*), C (0> -, CHaCH (OH) CHaO (R * 0) and R * 0-CHaCH (OH) CHSE- and mixtures of loe ißmoß; R * is alkyl of C4-C? a »alkenylene of C-C? ae, arylalkylene of C? -C? a, arylene of C? -C?, and mixtures thereof; R? e? alkylene of Ca-C? a or arylene of CA-C? A; the units E are selected from the group that connects from - (CHa) "C0aM, - (CHa) ^ S03M, -CH (CHaC0aM> C0aM, - (CHa)" P03M, - (R * 0 ) &bt, and mix thereof, B is hydrogen, - (CHa) «, S03M» - (CHa) pC0aM, - (CHa) "(CHS03M) CHaS03M, - (CHa)" - (CHSOaM) CHaSa3M- , - (CHse) P03M, -PO ^ and mixtures thereof, M is hydrogen or a cation soluble in water in sufficient quantity to satisfy the balance of the charge, X is a water-soluble anion, has the value of 4 to approximately 400, n has the value of 0 to approximately 200, p has the value of 1 to 6, q has the value lor from 0 to 6, r has the value of 0 or 1; w has the value of 0 or l; 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 réßto are au iliary ingredients.

2. A composition according to claim 1 »further characterized in that the enzyme lipase is derived from Humicola lanuginosa, which has an enzyme activity of about 1 to about 50 LU / mg of the composition.

3. - A composition according to claim 1 which comprises at least about 0.01% of a detergent tenective agent selected from the group consisting of anionic, cationic, nonionic, zwitterionic and ampholytic, and mixtures thereof.

4. A composition according to claim 3, further characterized in that R ee alkylene of Ca-C4; R * eß at least 50% ethylene; R * eβ hydrogen; The units E ß are selected from the group consisting of hydrogen, C4-Caa alkyl, - (R * 0) eB, -C (0) R3 and mixtures thereof; B is hydrogen, - (CHa)., S03M and mixtures thereof; and q has the value from 0 to 3.

5. A composition according to claim 4, further characterized in that R * is ethylene; the E units are - (R * 0) ¡? B; and B eß hydrogen.

6. A composition according to claim 5, which comprises approximately 0.05% to about 8% sweeping agents.

7. A laundry detergent composition comprising? A. at least about 0.1% by weight of a detersive surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic and ampholytic agents, and mixtures thereof; B. lipase enzymes in an amount of about 0.007 to about 3 lipolytic units per milligram (LU / mg) of the composition; C. from about 0.05% to about 8% sweeping agents comprising a polyamine base structure corresponding to the formula? H I | HaN-R3"+ 1- ZN-R3" - ZN- ^ -NH "having a modified polyamine formula V < "«. , U "" ~ ° a polyamine base structure that corresponds to the formula? I H R I I I ßN-R3"_k-1-CN-R r-CN-R3? -CN-R k-NHa having a modified polyamine formula V < r (_k4.1> W, Yr_, Y'l <Z, where k is less than or equal to n, said polyamine base structure »before modification, has a molecular weight greater than about 200 daltons, where? i) units V are terminal units that have the formula? E-N-R- or E- jNE ±? R "- or E-? N-R- ii) units W are baee structure units that have the formula? iii) Y units are branching units that have the formula? iv) the Z units are unidadeß ter inaleß that have the formula; wherein the basic structure linking units R are selected from the group consisting of alkylene of Ca-C? a »alkenylene of? -C? a?» C3-C? a? dihydroxyalkylene hydroxyalkylene of C? C? a, dialkylarylene of Cß-Cta, - (R * 0) = t * -, - (R * 0) > «R» (0R *) > ,, - (CHaCH (0R * > CHa0) M (R * 0) >, R * - (0CHaCH (0R *) CHa) w-, -C (0) (R *) rC (0) -, CHACH (OR *) CHa-, and mixtures thereof, wherein R * is alkylene of Ca-C ^, and mixtures thereof, R * eβ hydrogen, - (R * 0)? < B, and mixtures of the mißmoß, R 3 e β Cl-Clß alkyl, C -C arylalkyl, aryl substituted with C 7 -C 15 alkyl, aryl CA-Cta and mixtures thereof, ñ * is alkylene of Cx-Ct s? C 1 -C a alkenylene, arylalkylene of Cm-C x are C 1 -C 2 arylene, and mixtures thereof, R 3 is C 1 -C 4 Alkylene, C 3 -C 5 hydroxyalkylene, C 4 -hydroxyalkylene Cta, dialkyl ylene of C? -Clse, -C (0> -, -C (0) NHR * NHC (0> -, -R * (0R *) -, -C (0) (R *) rC (0 > -, CHaCH (OH > CHa-, llß CHaCH (OH) CHaO- (R * 0> s, R * OCHaíCH (OH) CHa- and mixtures of the same; R * eß alkylene of Ca-CtaB or arylene of C ^ -C ^ i units E are selected from the group consisting of hydrogen, Ct-CM alkylaryl of C3-Caa, arylalkyl of C? -C ?? hydroxyalkyl of Ca-Caae, - (CHa> pCOaM, - (CHa) ^ S03M, CH (CHaCOaM) COaM, - (CHa) pP03M, - (R * 0)! KB, -C (0) R3, and mixtures thereof; oxide; B is hydrogen, Ct-CA alkyl, - (CHa)., S03M, - (CHa> "COaM, - (CHa) (CHS03M) CHaS03M, - (CHj,.) ^ - (CHS0a) CHaS03M, - ( CHa), .P03M, -P03M and mixtures thereof, M is hydrogen or a cation soluble in water in a sufficient amount to satisfy the charge balance, X is a water soluble anion, m has a value of 4 to imadamente 400; n has the value of 0 to approximately 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 1; x has the value of 1 to 100, "y" has the value of 0 to 100, z has the value of 0 or l and D. The rest are auxiliary ingredients

8. A composition according to claim 7, further characterized because the lipase enzyme is derived from Humicola lanuginosa, which has an enzyme activity of from about 0.01 to about 1 LU / mg of the composition

9. A composition according to claim 8 which comprises from about 0.1% to Approximately 3% of sweeping agents. 10.- A detergent composition for laundry that understand? A. at least about 0.1% by weight of a detersive surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic and ampholytic surfactants, and mixtures thereof; B. lipase enzymes in an amount of about 0.007 to about 3 lipolytic units per milligram (LU / mg) of the composition? C. from about 0.05% to about 8% sweeping agents comprising a polyamine base structure corresponding to the formula? H I I CHaN-R3"+ 1-CN-R3" --- N-R3"-NHa having a modified polyamine formula V < "+ X" ^ Y ^ Z or a paliamine baß structure that corresponds to the formula? H R I I I CHaN-R3rv _ ", 1-CN-R3" --- N-R3r -, - CN-R3l < -NHa it has a modified paliamine formula Vtr, _k4.1 > W "Y? Y'k Z, where k is less than or equal to n, said polyamine base structure, before modification, has a molecular weight greater than about 200 daltons, in dande? i) the units V ßon unidadeß terminaleß that have the formula? ii) W units are base structure units that Do they have the formula? iii) units Y are unidadee of branching that have the formula? iv) Z units are terminal units that have the formula? -N-E or H- * FEE o0 --J¿MHE wherein the basic structure linking units R are selected from the group consisting of alkylene of Ca-C? a, alkenylene of C? -Cta, hydroxy alkylene of C3-Cta »dihydro? alkylene of C? -C? a, dialkylarylene of Cß-C? a¡, - (R'O ^ R * -, - (R * 0) > < R,! '(OR *) > «, - (CHaCH (0R *) CHa0)" (R * 0) >, R * - (0CHaCH (0R *) CHa> w-, -C (0) (R ^) PC (0> -, -CHaCH (0R *) CHa-, and mixtures of the same, wherein R * is alkylene of Ca-CA and mixtures of the miemos; R * is hydrogen, - (R * 0) > < B &mixture of the same; R3 is Cx-Cx alkyl arylalkyl of Ct-C? A, aryl is substituted with alkyl of Ct.-Cla, aryl of CA-C? A and mixtures thereof; R is alkylene of Z x-CXllt < alkenylene of C ^ -C? a?, arylalkin of C? -C? a, arylene of C) b-C10 and mixtures thereof; Rβ is C 1 -C 6 alkylene, hydroxyalkylene of r, β-Cxxt dihydroxyalkylene of C ^-C ?a, dialkylarylene of Cβ-Cta, -C (0) -, -C (0) NHR * NHC (0) -, -R * (OR * > -, -C (0) (R '*) rC (0) -, CHaCH (OH) CHa-, CHaCH (0H) CHa0- (R * 0) R * 0CHaCH ( 0H > CHa- and mixtures thereof; R * eß alkylene Ca-C? Ao arylene of C ^ -C, ^, laß unidadeß E? Select from the group that you congest of hydrogen, alkyl of c? "~ Caa, alkenyl of C3-Caa, arylalkyl of Ct-Caa, hydroxyalkyl of £> -> ** - (CHa), .C0a, - (CHa) ,, S03, CH (CHaC0aM) C0aM, - (CHa) ^ POaM, - (R * 0) > < B, -C (0) R3 &bgr; and mixtures of the rings, B, is hydrogen, Cj-C ^ alkyl, - (CHa) "S03M, - ( CHa) "C0aM, - (CHa) (CHS03M) CHaS03M, - (CHa)" - (CHSOaM) CHaS03M, - (CHa) P03M, -P03M and mixtures thereof, M is hydrogen or a soluble cation ep water ep amount enough to satisfy the charge balance, X is a water soluble anion, m has a value of 4 to about 400n, and has a value of 0 to about 20. 0; p has the value of 1 to 6, which has the value of 0 to 6; r has the value of 0 or lí has the value of 0 or 1; x has the value of 1 to 100; "y" has the value of 0 to 100; z has the value of 0 or 1; D. an amylase enzyme in an amount of about 0.00018% to about 0.06% pure amylase enzyme by weight of the total composition; and E. the rest are auxiliary ingredients.