MXPA00009336A - Liquid laundry detergent compositions comprising hedp and polyamines - Google Patents

Abstract

Liquid laundry detergent compositions comprising HEDP, and water soluble and/or dispersible, modified polyamines having functionalized backbone moieties which provide a stabilizing effect.

Description

COMPOSITIONS DETERGENTS FOR LAUNDRY COMPRISING HYDROXYETAN-1.1-DIFOSPHONATE AND POLYAMINES FIELD OF THE INVENTION The present invention relates to liquid laundry detergent compositions comprising HEDP and modified soluble and / or water dispersible polyamines having functionalized base structure portions.

BACKGROUND OF THE INVENTION Liquid laundry detergent compositions comprising HEDP (hydroxyethane-1,1-diphosphonate) are known and have been described, for example, in FR 2,677,370, EP 517 605, EP 384 515 and EP 37 184. In liquid laundry detergent compositions, HEDP provides enhanced stain removal and whiteness benefits in fabrics. However, there is one aspect in the formulation of HEDP in liquid detergents - particularly concentrates - since poor stability is obtained in the presence of high levels of surfactants and other detergent ingredients. EP 517 605 describes the use of specific HEDP salts to improve the physical stability of the composition. An object of the present invention is to formulate liquid detergent compositions comprising HEDP and surfactants and, optionally, other detergent ingredients, and which are physically stable. In response, it has now been found that the presence of certain polymers could provide the desired stabilizing effect making it possible to formulate stable compositions comprising HEDP.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses liquid laundry detergent compositions comprising a surfactant, an effective amount of HEDP and a stabilizing amount of a soluble and / or water dispersible modified polyamine comprising a polyamine base structure corresponding to the formula: H [H2N-R] n + 1 - [N-R] m- [N-R] n-NH2 having a modified polyamine formula V (n + i) WmYnZ or a polyamine base structure corresponding to the formula: H R [H 2 N-R] n.k + 1- [N-R] m- [N-R] n- [N-R] k-NH 2 having a modified polyamine formula V (n_k +) WmYnY'k Z, wherein k is less than or equal to n, said polyamine base structure, prior to modification, has a molecular weight greater than about 200 daltons, wherein: i) units V are terminal units having the formula: OE- N- R - E- N-. x R "- E- t N- R- I or I or I E E E ii) units W are base structure units that have the formula: O -N- R- -N- R- -N- R- I E iii) Y units are branching units that have the formula: iv) Z units are terminal units that have the formula: wherein the base structure linking units R are selected from the group consisting of C2-C2 alkylene, C4-C2 alkenylene, C3-C-127 hydroxyalkylene C4-C2-dihydroxyalkylene, dialkylarylene C8-C12, - (R10) XR1-, - (R10) XR5 (OR1) X, - (CH2CH (OR2) CH20) z (R1?) And RI- (OCH2CH (OR2) CH2) w-, -C (O ) (R4) rC (O) -, -CH2CH (OR2) CH -, and mixtures of the same; wherein R "- is C2-C6 alkylene, and mixtures thereof; R2 is hydrogen, - (R" O) XB, and mixtures thereof; R3 is C-j-Ci8 alkyl, C7-C2 arylalkyl, aryl substituted with C7-C2alkyl, aryl of CQ-C- | and mixtures thereof; R 4 is C 1 -C 12 alkylene. C4-C2 alkenylene, C8-C2 arylalkylene, Cg-C-arylene arylene and mixtures thereof; R5 is C- | -C-j2 alkylene, C3-C2 | hydroxyalkylene, C4-C2 dihydroxyalkylene, C8-C2 dialkylarylene, -C (O) -, -C (O) NHR6NHC (O ) -, -R1 (0R1) -, -C (0) (R4) rC (0) -, CH2CH (OH) CH2-, CH2CH (OH) CH2O- (RO) and R1OCH2CH (OH) CH2- and mixtures of the same; R6 is C2-C2 alkylene or C2-C2 arylene; the E units are selected from the group consisting of hydrogen, C- | -C alkyl, C3-C alkenyl, c7 arylalkyl c22, C2-C22 hydroxyalkyl, - (CH2) pCO2M, - (CH2) qS03M, -CH (CH2CO2M) CO2M, - (CH2) pPO3M, - (R1?) XB, -C (0) R3, and mixtures thereof, provided that when any unit E of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, C1-C6 alkyl, - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) q (CHS? 3M) CH2SO3M, - (CH2) q- (CHSO2M) CH2SO3M , - (CH2) pPO3M, -PO3M and mixtures thereof; M is hydrogen or a cation soluble in water in sufficient quantity • to satisfy the load balance; X is a water soluble anion; m has the value of 4 to about 400; n has the value from 0 to about 200; p has the value of 1 to 6, 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 1. All percentages, ratios and proportions of this • 10 are by weight, unless otherwise indicated. All temperatures are in degrees centigrade (° C) unless otherwise specified. All the aforementioned documents are incorporated herein in a relevant part.

DETAILED DESCRIPTION OF THE INVENTION • The liquid detergent composition The compositions herein are liquid detergent compositions and thus, typically but not necessarily comprise water, in amounts of 20% to 70% by weight of the total composition, preferably 25% to 60%, very preferably 30% to 40%. Compositions comprising less than 40% water are generally referred to as concentrated compositions, and it is in those compositions that the stability problem of HEDP is particularly acute.

HEDP The compositions herein comprise an effective amount of HEDP (hydroxyethane-1,1-diphosphonate). By "effective amount" is meant herein a sufficient amount to improve the stain removal properties of the detergent composition, and / or to improve the whiteness performance of that composition. Typically said amounts are in the range of 0.01% to 10% by weight of the total composition, preferably 0.7% to 5%, most preferably 0.2% to 2%. The HEDP in its acid form is suitable for use herein, or in the form of any of its salts. An appropriate commercial form of HEDP is Dequest® 2010, from Monsanto.

Polyamine The compositions herein further comprise a stabilizing amount of a modified polyamine soluble or dispersible in water. These polyamines comprise base structures that can be linear or cyclic. The base structures of the polyamines may also comprise polyamine branching units to a greater or lesser degree. In general, the polyamine base structures described herein are modified such that each nitrogen of the polyamine chain is described below in terms of a unit that is substituted, quaternized, oxidized or combinations thereof. For the purposes of the present invention, the term "modification" is defined as the replacement of a hydrogen atom of -NH from the base structure with an E unit (substitution), quaternization of a nitrogen from the base structure (quaternized ), or oxidation of a nitrogen from the base structure to the N-oxide (oxidized). The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a nitrogen of the base structure with an E. The quaternization or oxidation may take place in certain circumstances without substitution , but the substitution preferably is accompanied by oxidation or quaternization of at least one nitrogen of the base structure. The linear or non-cyclic polyamine base structures comprising the polyamines of the present invention have the general formula: H I I [H2N-R] n + 1 - [N-R] m- [N-R] n-NH2 said base structures, prior to the subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by "linker" units R. The base cyclic polyamine structures have the general formula: H [H2N-R] n.k + 1- [N-R] m- [N-R] n- [N-R] k-NH2 said base structures, prior to the subsequent modification, comprise primary, secondary and tertiary 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 "terminal" units V or Z. For example, when a portion of primary amine located at the end of the base structure of the main polyamine or branch chain having the structure H2N-R] is modified according to the present invention, it is then defined 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 later in the present. These unmodified primary amine portions, by virtue of their position in the base structure chain, remain as "terminal" units. Likewise, when a primary amine portion, located at the end of the main polyamine base structure having the structure -NH2 is modified in accordance with the present invention, it is hereinafter defined as a "terminal" Z unit, or simply a unit Z. This unit may remain unmodified subject to the restrictions described in more detail below herein. Similarly, the secondary amine nitrogens comprising the base structure or branching chain, once modified, are defined as "base structure" units W. For example, when a secondary amine portion, the main constituent of the base structures and the branching chains of the present invention, which has the structure H I - [N-R] - is modified in accordance with the present invention, is hereinafter defined as a "base structure" unit W, or simply a unit W. However, for the purposes of the present invention, some or all of the secondary amine portions may be remain unchanged. These unmodified secondary amine portions, by virtue of their position in the base structure chain, remain as "base structure" units.

In another similar form, the tertiary amine nitrogens comprising the base structure or branching chain, once modified, are further defined as "branching" Y units. For example, when a tertiary amine moiety, which is a point of chain branch or base structure of polyamine or other branching chains or rings, which have the structure - [N-R] - is modified according to 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 unmodified . 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 that serve to connect the polyamine nitrogens will be described later. The modified final structure of the polaminas of the present invention can then be represented by the general formula: V (n + 1) WmYnZ for the linear polyamine polymers of soil release in cotton, and by the general formula (n-k + 1) ) mYnY'kZ for cyclic polyamine polymers of cotton dirt release. For the case of the polyamines comprising rings, a unit Y 'of the formula: R _ [N-R] - serves as a branch point for a base structure or a branch ring. For each unit Y 'there exists a unit Y that has the formula: - [N-Rj- which will form the point of connection of the ring to the chain or branch of the main polymer. In the unique case in which the base structure is a complete ring, the polyamine base structure has the formula: H [H2N-R] n- [N-R] m- [N-R] n- therefore does not comprise any terminal unit Z and has the formula Vn-kWmYnY'k wherein k is the number of ring-forming branching units. Preferably, the polyamine base structures of the present invention do not 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 linear modified polyamine completely unbranched according to the present invention has the formula: VWmZ ie n is equal to 0. The higher the value of n (the lower the ratio of man), the greater the degree of branching in the molecule.

Typically, the value of m varies from a minimum value of 4 to 400, however, values greater than m 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 replaced, 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, the nitrogens of the unmodified primary amine are V or Z units, the nitrogens of the unmodified secondary amine are units W, and the nitrogens of the unmodified tertiary amine are Y units for the purpose of the present invention. Modified primary amine moieties are defined as "terminal" units V having one of three forms: a) simple substituted units having the structure: E- N- R- b) quaternized units that have the structure: where X is a suitable counter ion that provides charge balance; and c) oxidized units having the structure: OR T E- N- R - The modified secondary amine moieties are defined as "base structure" units W having one of three forms: a) simple substituted units having the structure: - N- R - I E b) quaternized units that have the structure: where X is a suitable counter that provides a load balance; and c) oxidized units having the structure: dfc The modified tertiary amine moieties are defined as units of "branching" AND that have one of three forms: a) unmodified units that have the structure: - N-R- b) quaternized units that have the structure: where X is a suitable counter ion that provides charge balance; and c) oxidized units having the structure: Certain portions of modified primary amine are defined as "terminal" Z units that have one of three forms: 20 a) simple substituted units that have the structure: -N- E I E b) quaternized units that have the structure: where X is a suitable counter ion that provides charge balance; and c) oxidized units having the structure: When any position on a nitrogen is substituted or unmodified, it is understood that hydrogen will replace E. For example, a primary amine unit comprising an E unit in the form of a hydroxyethyl portion is a terminal unit V having the formula (HOCH2CH2) HN-. For the purposes of the present invention, there are two types of chain terminator units, units V and Z. The "terminal" unit Z is derived from a terminal primary amino portion of the -NH2 structure. The non-cyclic polyamine based structures according to the present invention only comprise one unit Z, while the cyclic polyamines can comprise no unit Z. The "terminal" unit Z can be substituted with any of the units E described in more detail after , except when unit Z is modified to form an N-oxide. In case 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 C2-C-j2 alkylene, C4-C2 alkylene, and C3-C2 hydroxyalkylene wherein the hydroxyl portion can take any position on the R unit, except the connected carbon atoms directly to the nitrogens of the polyamine base structure; C 4 -C 2 dihydroxyalkylene wherein the hydroxyl portions can occupy any two of the carbon atoms of the chain of the R unit, except those carbon atoms directly connected to the nitrogens of the polyamine base structure; C8-C- | 2 dialkylarylene 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 1, 4-substituted, but it can also be 1, 2 or 1, 3-substituted with alkylene of C -Cj, preferably ethylene, 1, 2-propylene and mixtures thereof, most preferably ethylene . The R "oxy" units comprise - (R 0) xR5 (OR1) x-, CH 2 CH (OR 2) CH 2 O) Z (R 1 O) y R 1 - (OCH 2 CH (OR 2) CH 2) w-, CH 2 CH (OR 2) CH 2 -, - (R'O ^ R1- and mixtures thereof) Preferred R units are C2-C2 alkylene, C3-C2 hydroxyalkylene, C4-C2 dihydroxyalkylene, C8-C diarylarylene. , - (R1O) xR1-, -CH2CH (OR2) CH2-, - (CH2CH (OH) CH2O) z- (R1O) and R1 (OCH2CH-, (OH) CH2) w-, - (R10) xR5 (OR1 ) X-, most preferred R units are C -C- alkylene; , C3-C-2 hydroxyalkylene, C4-Ci2 dihydroxyalkylene, (RO) xR1-, - (R10) xR5 (OR1) x-, (CH2CH (OH) CH2O) z (R1?) and R "(OCH2CH) - (OH) CH2) w- and mixtures thereof, even more preferred R units are C2-C12 alkylene. C3 hydroxyalkylene and mixtures thereof, mmore preferred are C2-Cß alkylene. The most preferred base structures of the present invention comprise at least 50% R units that are ethylene. The units R ^ are C2-Cg alkylene and mixtures thereof, preferably ethylene, R2 is hydrogen and - (R'-O ^ B, preferably hydrogen) R3 is C1-C18 alkyl, C7-C2 arylalkylene , substituted C7-C- aryl alkyl, Cß-C- | 2 aryl, and mixtures thereof, preferably C-] - C-f2 alkyl, C7-C-2 alkylarylene, most preferably alkyl CJC-J2, more preferably methyl R3 units serve as part of the units E described below R4 is C? -C? 2 alkylene, C4-C? 2 alkenylene, C8-C12 arylalkylene. C-Q, preferably C- | -C- alkylene, or C8-C2-arylalkylene, most preferably C2-C8-alkylene, more preferably ethylene or butylene, R5 is CjC2 alkylene, C3-C hydroxyalkylene. 2, C4-C2-dihydroxyalkylene, dialkylarylene of C8-C-2, -C (O) -, - C (O) NHR6NHC (O) -, -C (O) (R4) rC (O) - , R1 (OR1) -, (CH2CH (OH) CH2O (R10) and R1 OCH2CH (OH) CH2-, -C (O) (R4) rC (O) -, (CH2CH (OH) CH -, R5 is preferably ethylene, -C (O) -, C (O) NHR6NHC (O) -, R1 (0R1) -, -CH2CH (OH) CH2-, (CH2CH (OH) CH2O (R1?) And R1OCH2CH- (OH) CH2-, most preferably - (CH2CH (OH) CH 2 -. R b is C 2 -C 2 alkylene or C 6 -C arylene The preferred R "oxy units" are further defined in terms of the units R 1, R 2 and R 5. Preferred R "oxy units" comprise the Preferred R1, R2 and R5 The preferred polyamine soil release agents of the present invention comprise at least 50% Rl units which are ethylene The preferred R ^, R2 and R5 units are combined with the R "oxy" units to produce the preferred R "oxy" units in the following manner i) substituting the most preferred R for (CH2CH2O) xR5 (OCH2CH2) x- (CH2CH2O) xCH2CHOHCH2- (OCH2CH2) x- is produced. ii) substituting preferred R1 and R2 for (CH2CH (OR) CH2O) z- (R1O) and R1O (CH2CH (OR2) CH2) w- occurs - (CH2CH (OH) CH2O) z- (CH2CH2O) and CH2CH2O (CH2CH (OH ) CH2) w-. iii) substituting preferred R for -CH2CH (OR2) CH2- produces -CH CH (OH) CH2-. The E units are selected from the group consisting of hydrogen, C 1 -C 22 alkyl, C 3 -C 22 alkenyl, C 7 -C 2 arylalkyl, C 2 -C 22 hydroxyalkyl, - (CH) pCO 2 M, - (CH 2) q S 3M, CH (CH2CO2M) CO2M, - (CH2) nPO3M, - (R1?) MB, -C (0) R3, preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C? -C22 alkylene, - (R10) mB, -C (0) R3, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, most preferably alkylene from C < | -C22, - (R1O) xB, -C (0) R3, - (CH) pCO2M, - (CH2) qS? 3M, -CH (CH2C? 2M) C? 2M, more preferably alkylene of C- | - C22 > "(R ^ O)? B and -C (0) R3 When no modification or substitution is made on a nitrogen, then the hydrogen atom will remain as the portion representing E.

The units E do not comprise a hydrogen atom when the units V, W or Z are oxidized, that is, the nitrogens are N-oxides. For example, the chain of the base structure or branch chains does not comprise units of the following structure: O O O -N- R H- N- R - N- H I I H H H Additionally, the units E do not comprise carbonyl moieties directly attached to a nitrogen atom when the units V, W and Z are oxidized, that is, the nitrogens are N-oxides. In accordance with the present invention, the portion -C (O) R3 of the unit E is not bound to a nitrogen modified by N-oxide, that is, there are no N-oxide amides having the structure: O O O O | Or II -N- R or R3- C- N- R- N- C- R3 I C = 0 E E R3 or combinations thereof. B is hydrogen, C-j-Cg alkyl, - (CH2) qS? 3M, - (CH2) pCO2M, (CH2) q- (CHSO3M) CH2SO3M, (CH2) q (CHSO2M) CH2SO3M, - (CH2) pPO3M, - PO3M, preferably hydrogen, - (CH2) qS03M, (CH2) q (CHS? 3M) CH2S? 3M, (CH2) q- (CHSO2M) CH2SO3M, very preferably hydrogen or - (CH2) qS? 3M.

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 - (CH2) pCO M and - (CH2) qS03M, resulting in portions (CH2) pCO2Na and - (CH2) qS03Na. More than one monovalent cation (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, the charge 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 - (CH 2) P 3 M substituted with sodium atoms has the formula - (CH 2) P 3 Na 3. The divalent cations such as calcium (Ca2 +) or magnesium (Mg2 +) can be substituted by or combined with other suitable water-soluble monovalent cations. The preferred cations are sodium and potassium, sodium is very preferred. X is a water-soluble anion such as chlorine (Cl "), bromine (Br) and iodine (I-), or X can be any negatively charged radical such as sulfate (SO42.) And methosulfate (CH3SO3.). of formula 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, m has the value of 4 to 400, n has the value of 0 to 200, m + n has the value of at least 5.

The polyamines of the present invention comprise base structures in which less than about 50% of the R groups comprise R "oxy" units, preferably less than about %, most preferably less than 5%, more preferably the R units do not comprise R "oxy" units. The most preferred polyamines which do not comprise 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-propylene and 1,3-propylene comprise 3 or fewer carbon atoms and are the preferred "hydrocarbyl" R units. That is, when the R units of the base structure are C 2 -C 2 alkylene, C 2 -C 3 alkylene is preferred and more ethylene is preferred. The cotton polyamines 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 polyamine base structure having R units that are the same (ie, all are ethylene). However, this definition of equality does not exclude polyamines comprising other foreign units comprising the polymer base structure, which are present due to an artifact of the chosen chemical synthesis method. For example, it is known to those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethyleneimines, therefore a polyethyleneimine sample comprising a hydroxyethyl portion resulting from the polymerization "primer" would be considered. It comprises a homogeneous polyamine base structure for the purposes of the present invention. A polyamine base structure comprising all ethylene R units in which no branching units Y is 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 that are a mixture of various lengths of unit R and types of unit R. For example, an inhomogeneous base structure comprises R units that are a mixture of ethylene and 1, 2-propylene units. For purposes of the present invention, a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous base structure. The polyamines of the present invention comprise homogeneous polyamine base structures that are totally or partially substituted by polyethyleneoxy moieties, total or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof. However, not all the 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 ethoxylation 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 polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected in portions having R units. longer than PAA's, PAI's, PEA's or PEI's relatives. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions that include ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Among the pentamines, that is, hexamines, heptamines, octamines and possibly nonamines, the cogently derived mixture does not appear to be separated by distillation and may include other materials such as cyclic amines and particularly piperazines. Cyclic amines with side chains in which nitrogen atoms appear may also be present. See the patent of E.U.A. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's. The base structures of the preferred amine polymer comprise R units which are C2 alkylene units (ethylene), also known as polyethylene imines (PEI's). Preferred PEI's have at least one moderate branching, that is, the ratio of m to n is less than 4: 1, however, PEI's having a ratio of m to n of 2: 1 are more preferred. The basic structures, before the modification, have the general formula: H I I [H2NCH2CH2] n- [NCH2CH2] m- [NCH2CH2] n-NH2 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 amine, primary, secondary and tertiary 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 polyamine base structure chain represents a potential site for subsequent substitution, quaternization or oxidation. These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine base structures are described in the U.S. 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. No. 2,208,095, Esselman et al., Issued July 16, 1940; the patent of E.U.A. No. 2,806,839, Crowther, issued 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 polyamines of the present invention comprising PEI's are illustrated in formulas I-V: Formula I illustrates a preferred polyamine comprising a PEI base structure in which all substitutable nitrogens are modified by hydrogen replacement with a polyoxyalkylenoxy unit, - (CH2CH2O) 7H, having the formula: Formula I Formula II illustrates a polyamine comprising a PEI base structure in which all substitutable nitrogens are modified by replacing hydrogen with a polyoxyalkylenoxy unit, - (CH 2 CH 2 O) 7 H having the formula: Formula II This is an example of a polyamine that is completely modified by a type of portion.

• The formula III illustrates a polyamine comprising a PEI base structure in which all the substitutable primary amine nitrogens are modified by replacing the hydrogen with a polyoxyalkylenoxy unit, - (CH2CH2O) 7H, the molecule is then modified by the subsequent oxidation of all the primary nitrogens and secondary to N-oxides, said sweetening agent polymer has the formula: Formula Formula IV illustrates a polyamine comprising a PEI base structure in which all hydrogen atoms of the base structure are substituted and some amine units of the base structure are quaternized. The substituents are polyoxyalkylenoxy units, - (CH 2 CH 2 O) 7 H or methyl groups. The modified PEI polyamine has the formula: Formula IV Formula V illustrates a polyamine comprising a base structure of PEI in which the nitrogens of the base structure are modified by substitution (ie by - (CH 2 CH 2 O) 7 H or methyl), quaternized, oxidized to N- oxides or combinations thereof. The resulting polyamine has the formula: Formula V In the previous examples, not all the nitrogens of a class of unit comprise the same modification. The present invention allows the formulator to have ethoxylated 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 can choose to modify all or a portion of the nitrogens of the primary amine 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 here. It is too much preferred to use in the present PEI's ethoxylated with a molecular weight of 200 to 3000, preferably 400 to 700, and an average degree of ethoxylation of 4 to 30, preferably 15 to 25. The compositions herein comprise a stabilizing amount of a polyamine, that is, an amount that is sufficient to solve the problem of instability caused by the presence of the HEDP. The amount of polyamine that is required will depend on the amount of HEDP that is present, but will typically be in the range of 0.05% to 20% by weight of the total composition, preferably 0.1% to 10%, more preferably 5 0.2% to 5%. %. In addition, the polyamines of the present have the advantage that they provide benefits of stain removal and whiteness. The compositions herein comprise a surfactant. In addition to the anionic and nonionic detersive surfactants described herein, other surfactants which are Suitable for use in the present invention are cationic, anionic, non-cationic, • ionic, ampholytic, zwitterionic and mixtures thereof, best described hereinafter. Non-limiting examples of surfactants useful herein typically at levels of about 1% to about 55% by weight, include C- alkylbenzene sulfonates; - | -C < | 8 conventional ("LAS"), the secondary alkyl sulfates (2,3) of C-J Q-C S of the formula • CH3 (CH2) x (CHOSO3-M +) CH3 and CH3 (CH2) and (CHOS? 3-M +) CH2CH3 where xy (y +1) are integers of at least about 7, preferably at least about 9, and M is a cation of Solubilization in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkylalkoxycarboxylates of CJ QC S (especially the ethoxycarboxylates EO 1-5), the glycerol ethers of CI QCJ S, the alkyl polyglycosides of C10-C18 and their corresponding sulfated polyglycosides, and aliphatic acid fatty acid esters of C- | 2-C- | 8- If desired, conventional amphoteric and nonionic surfactants such as C12-C 8 alkyl ethoxylates ("AE") including the so-called narrow peak alkyl ethoxylates and the Cg-C- | 2 alkylphenollalkoxylates (especially mixed ethoxylates and ethoxy / propoxy), C? 2-C? betaines and sulfobetaines ("sultaines"), C10-C8 V amine oxides similar, are also can include in the global compositions. The N-alkyl polyhydroxy fatty acid amides of C? Rj-C 8 can also be used.

Typical examples include N-methylglucamides of C 2 -C-J 8 - See WO 9,206,154. Other surfactants derived from sugar include N-alkoxy polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide of C- | rj- C- | 8- N-propyl glucamides through N-hexyl of C- | 2-C-] 8 can be used for low foam formation. You can also use soaps conventional C- | o-C2o- If high foaming is desired, they can be used • C10-C16 soaps with branched chains. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional surfactants are listed in normal texts. Other anionic surfactants useful for purposes Detersives can also be included in the compositions herein. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di and triethanolamine salts) of soap, C9-C20 linear alkyl benzenesulfonates, C8 primary or secondary alkanesulfonates. C22 C8-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glyceryl sulfonates, acyl glyceryl fatty sulfonates, oleylglyceryl fatty sulfonates, alkylphenoletylene oxide ether sulphates, paraffinsulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially monoesters of C-] saturated and unsaturated 2-C-i8) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-C-14 diesters), N-acyl sarcosinates, alkylpolyaccharide sulfates such as alkyl polyglycoside sulphates, branched primary alkyl sulphates and alkyl polyethoxycarboxylates such as those of the formula RO (CH2CH2?) kCH2COO-M + wherein R is a C8-C22 alkyl. k is an integer from 0 to 10, and M is a soluble salt forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Preferred compositions of the present invention preferably comprise at least about 0.01%, preferably at least 0.1%, most preferably about 1% to about 95%, more preferably about 1% to about 80% by weight, of a anionic detersive surfactant. Alkyl sulfate surfactants, whether primary or secondary, are a type of surfactant of importance for use herein.

The alkyl sulphates have the general formula ROSO3M wherein R is preferably C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of C? Rj-C2o, most preferably alkyl or hydrocarbyl of C- | 2-C- | 8 . and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium) or ammonium or dusinstituted ammonium (e.g., methyl-, dimethyl- and trimethylammonium cations) and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. Typically, the C12-C6 alkyl chains are preferred for washing temperatures for lower wash temperatures (e.g., less than about 50 ° C) and alkyl chains of C- | 6_- | 8 are preferred for higher wash temperatures (e.g., greater than about 50%). Alkoxylated alkylsulphate surfactants are another category of useful anionic surfactants These surfactants are water soluble salts or acids typically of the formula RO (A) mS? 3M wherein R is an alkyl or hydroxyalkyl group of C-] rj -C24 not replaced having an alkyl component of CI Q-C24, preferably an alkyl or hydroxyalkyl of C? 2-C2rj, most preferably alkyl or hydroxyalkyl of C-? 2-C8 > is an ethoxy or propoxy unit, m is greater than zero, typically about 0.5 and about 6, most preferably about 0.5 and about 3, and m is H or a cation which may be, for example, a metal cation (v. gr., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulphates are contemplated herein. Specific examples of the substituted ammonium cations include methyl-dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines, e.g., mono-stanolamine, diethanolamine and triethanolamine, and mixtures thereof. Exemplary surfactants are alkyl polyethoxylated C-2_18 sulfate (1.0), C-2-alkyl] -8-polyethoxylated sulfate (2.25) alkyl, C- | 2-Ci8 polyethoxylated sulfate (3.0), and C- | 2-Ci8 alkyl polyethoxylated sulfate (4.0) where M is conveniently selected from sodium and potassium. Preferred compositions of the present invention also preferably comprise at least 0.01%, preferably at least 0.1%, most preferably from about 1% to about 95%, more preferably from about 1% to about 80% by weight, of a non-ionic detersive surfactant. Preferred nonionic surfactants such as C? 2-C? Alkylethoxylates ("AE") including the so-called narrow-peak alkyletoxylated and Cfen-C 2 alkylphenyl α-alkoxylates (especially ethoxylated and mixed ethoxy / propoxy), condensed alkylene oxide block of alkylphenols from Cg to C? 2, alkylene oxide condensates of Cs-C22 alkanols and ethylene oxide / propylene oxide block copolymers (Pluronic ™ -BASF Corp.), as well as Semi-polar nonionics (e.g., amine oxides and phosphine oxides) can be used in the present compositions. An extensive description of these types of surfactants is found in the U.S. patent. 3,929,678, Laughiin et al., Issued December 30, 1975 and incorporated herein by reference. The alkylpolysaccharides such as those described in the patent of E.U.A. 4,565,647, Filling (incorporated herein by reference) are also nonionic surfactants that are preferred in the compositions of the invention. The most preferred nonionic surfactants are polyhydroxy fatty acid amides having the formula: O R8, II I R7-C-N-Q wherein R7 is C5-C31 alkyl, preferably straight chain C7-C- | g alkyl or alkenyl, most preferably Cg-C-17 alkyl or alkenyl of straight chain, more preferably alkyl or alkenyl of C-1 -C-15 chain straight, or mixtures thereof; Rβ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, preferably methyl or ethyl, very preferably methyl. Q is a polyhydroxyalkyl portion having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; the preferred alkoxy is ethoxy or propoxy and mixtures thereof. The preferred Q is derived from a reducing sugar in a reductive amination reaction. Most preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. Crude high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup, as well as the individual sugars listed above, can be used as raw materials. These corn syrups can produce a mixture of sugar components for Q. It should be understood that in no way is it desired to exclude other suitable raw materials. Q is most preferably selected from the group consisting of CH2 (CHOH) nCH2OH, -CH (CH2OH) (CHOH) n- CH2OH, -CH2 (CHOH) 2- (CHOR ') (CHOH) CH2OH, and alkoxylated derivatives thereof, wherein n is an integer of 3 to 5, inclusive, and R 'is hydrogen or a cyclic or aliphatic monosaccharides. The most preferred substituents for the Q portion are the glycityls wherein n is 4, particularly -CH 2 (CHOH) 4CH 2 OH.

R ^ CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Rβ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl. Q can be 1-deoxyglucityl, 2-d-phexyl-ethyl, 1-deoxy-thomethyl, 1 - . 1-deoxylactityl, 1-deoxygalactitiy, 1-deoxyanityl, 1-deoxy-thiotriotityl, etc.

A particularly desirable surfactant of this type for use in the compositions herein is alkyl-N-methylglucomide, a compound of the above formula wherein R7 is alkyl (preferably C11-C13), R8 is methyl and Q is 1-deoxyglucityl. Other surfactants derived from sugar include the N-alkoxy polyhydroxy fatty acid amides, such as N- (3-methoxypropyl) glucamide from CJ O-CIS- The N-propyl to N-hexylglucamides from Cl2"Ci8. They can be used for low foaming. can the conventional C- | o-C2 soaps be used? - If high foaming is desired, the branched chain C- | 0-C1 g soaps can be used.

Optional ingredients The compositions herein may further comprise a variety of optional ingredients. A wide variety of other useful ingredients in detergent compositions can be included in the compositions herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for stick compositions, etc. . If high foaming is desired, foam boosters such as the Cl? "Ci6 alkanolamides" may be incorporated into the compositions typically at levels of 1% -10%. C10-C14 monoethanol and diethanolamides illustrate a class Typical of such foam boosters The use of such foam boosters with high foaming adjunctive surfactants such as the amine oxides, betaines and sultaines mentioned above is also advantageous.If desired, soluble magnesium salts such as MgCl2, MgS4 and the like, 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 substrate porous hydrophobic, then coating said suvstrato with a hydrophobic coating., 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 D10, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C13..15 (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation 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 the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, colorants, fluorescers, fabric conditioners and hydrolyzable surfactants 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, propanol and isopropanol f 10 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 (e.g., 1,3-propanediol, ethylene glycol, glycerin) can also be used. and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions of the present preferably f will be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. The 20 laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Enzymes Enzymes may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as fabrics, for the prevention of dye transfer, for example. in laundry, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, 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 levels • Optimum activity of pH and / or stability, thermostability, stability versus active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. The term "detersive enzyme", as used herein, means any enzyme that has a beneficial cleaning effect, removal of • stains or any other beneficial effect in a laundry detergent composition, hard surface cleaning or personal care. Preferred detersive enzymes are hydrolases such as proteases and amylases. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases and peroxidases. 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, stain removal, dirt removal, whiteness, deodorizing or freshness enhancing effect 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. Stated otherwise, 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 results. final. Higher active levels in highly concentrated detergent formulations may also be desirable. Amylases suitable herein include, for example, -amylases described in GB 1, 296, 839 to Novo.; RAPIDASER, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by 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 oxidation stability as the measure against a reference point of ® TERMAMYL in commercial use in 1993. These preferred amylases of the present share the characteristics of being "improved stability" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidant stability, e.g., to hydrogen peroxide / tetraacetylethylene diamine in pH regulated solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60 ° C; or alkaline stability, e.g., at a pH of about 8 to about 11, measured against the amylase of the reference point identified above. Stability can be measured using any of the technical tests described in the art. See, for example, the references described in WO 9402597. The improved stability amylases can be obtained from Novo or Genencor International. A class of highly preferred amylases herein has the common property of being derived using the site-directed mutagenesis of one or more of the Bacillus amylases, especially the Bacillus amylases, regardless of whether one, two or multiple 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 the 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 incorporated above, as further illustrated by a mutant in which it is substituted, using alanine or threonine, preferably threonine, the residue of methionine located at position 197 of the alpha-amylase of B.lichemiformis, known as TERMAMYL, or the variation of the homologous position of a similar progenitor amylase, such as B. amyloliquefaciens, B. subtilis or B. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. There it is mentioned that the bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that oxidative 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 substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 carrying 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) the 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, as DURAMYL. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidizing amylase can be used • improved stability, for example that derived by site-directed mutagenesis of chimeric, hybrid or simple known mutant progenitor forms of available amylases. Other modifications of enzyme that are preferred are also accessible. See WO 9509909 to Novo. Cellulases that can be used herein include F 10 both bacterial and fungal cellulases, preferably with 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 DSM 1800 strain 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-OS-2,247,832. CAREZYME® (Novo) is especially useful. See also WO 9117243 to Novo. The lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomona stutzeri ATCC 19,154, as described in British Patent 1, 372,034. See also lipases in Japanese Patent Application 53,20487, open for public inspection on February 24, 1987.

This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the registered trademark Lipasa P "Amano" or "Amano-P". Other commercial lipases include Amano-CES, ex Chromobacter viscosum lipases, e.g. Chromobacter viscosum var. lipolyctum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and in addition the Chromobacter viscosum lipases from U.S. Boichemical Corp., E.U.A. Y Disoynth Co., The Netherlands, and the lipases of ex Pseudomonas gladioli. The ® LIPOLASE enzyme derived from Humicola lanuginosa and which is commercially available from Novo (see also EPO 341, 947) is a preferred lipase for use herein. Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A a Novo See also WO 9205529 and RD 94359044. Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B.subtilis and B.licheniformis. Other suitable proteases are obtained from a Bacillus strain, having a maximum activity on the whole pH scale of 8 to 12, developed and sold as ® WAIT for Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, by Novo. Other suitable proteases include ALCALASE and SAVINASE® by Novo and MAXATASE® by 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 protease. pH of Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other proteases that are preferred include those of WO 9510591 A to Procter & Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is as described in WO 9425583 to Novo. The liquid laundry detergent compositions that are preferred according to the present invention further comprise at least 0.001% by weight of a protease enzyme. However, an effective amount of protease enzyme is sufficient for use in the liquid laundry detergent compositions described herein. The term "an effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, dirt removal, whiteness, deodorizing or freshness enhancing effect on substrates such as fabrics. 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. Stated otherwise, 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. Preferred liquid laundry detergent compositions of the present invention comprise a protease enzyme, called "protease D", which is a variant of carbonyl hydrolase 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 residues at a position in said carbonyl hydrolase equivalent to the +76 position, 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 the subtilisin of Bacillus amyloliquefaciens as the described in WO 95/10615 published April 20, 1995 by Genencor International. Useful proteases are also described in the publications of PCT: WO 95/30010, published November 9, 1995 by The Procter & Gamble Company; WO 95/30011, published November 9, 1995 by The Procter & Gamble Company; and WO 95/29979, published November 9, 1995 by The Procter & Gamble Company. Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European patent application Serial No. 87 303,761.8, filed on April 28, 1987 (particularly pages 17, 24 and 98), which is called in the present "Protease B", and in the European patent application 199,404, Venegas, published on October 29, 1986, which refers to a bacterial serine proteolytic enzyme that is called "Protease A" in the present , < f 10 protease A as described in EP 130,756, January 9, 1985 and protease B as described in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. Peroxidase enzymes can be used in combination with sources of oxygen, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc., for "bleaching in solution" or to avoid transfer of dyes or pigments removed from substrates during washing operations, towards other substrates in the washing solution. F peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and halogenoperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 A to Novo, and E.U. 3,553,139, January 5, 1971 to McCarty and others. Enzymes are also described in E.U.A. 4,101, 457, Place and others, July 18, 1978 and in E.U. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in E.U. 4,261, 868, Hora et al., April 14, 1981. The enzymes that will be used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in E.U. 3,600,319, August 17, 1991, Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U. 3,519,570. A Bacillus sp. AC13 useful and which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme stabilization system Enzyme-containing compositions, including but not limited to liquid compositions, herein can comprise from about 0.001% to about 10%, preferably about 0. 005% to about 8%, most preferably about 0.01% to about 6% by weight of an enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation actives, or it 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 physical form of the 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 herein if only one type of cation is being used. The typical detergent compositions, especially liquid, will comprise about 1 to about 30, preferably about 2 to about 20, most preferably about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. 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 sulfate or the 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 stabilization approach is through the use of borate f species. See Severson, E.U. 4,537,706. Borate stabilizers, When used, they may be at levels of up to 10% or more of the composition, although more typically levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for the use of detergents liquids. Substituted boric acids such as phenylboronic acid, butanboronic acid, p-bromophenylboronic acid or the like may be used in place of boric acid and reduced levels of total boron may 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 scavengers, added to prevent the chlorine bleach species present in many water sources from attacking and inactivating the enzymes, especially under alkaline conditions. Although chlorine levels in water can be small, typically on the scale of approximately 0.5 ppm to approximately 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during the washing of dishes or fabrics, can be relatively large; consequently, the stability of the enzyme to chlorine during use is sometimes 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 may, very generally, not be essential, although improved results can be obtained from its use. Suitable chlorine scavenging anions are widely known and readily available, and, if used, may be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Likewise, 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. Similarly, -They can incorporate special enzyme inhibition systems so that the different enzymes have maximum compatibility. If desired, other conventional sweepers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate can be used. , formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof. In general, since the chlorine sweeping function can be carried out by separately listed ingredients 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. Moreover, the formulator will exercise a normal chemical ability by avoiding the use of any enzyme scavenger or stabilizer that is primarily incompatible, as formulated, with other reactive ingredients, if used. In connection with the use of ammonium salts, said salts can be simply mixed with the detergent composition, but are prone to adsorb water and / or release ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in E.U. 4,652,392, Baginski et al.

Detergency Enhancers The detergency builders may optionally be included in the compositions herein to help control 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. However, it is not intended to exclude lower or higher levels of detergency builder. Inorganic or phosphate-containing builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by crystalline polymeric tripolyphosphates, pyrophosphates, and meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate detergent builders are required in some places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" builders (as compared to phosphates) such as citrate, or in the so-called "poor detergency" situation that can occur with zeolite or layered silicate builders. Examples of silicate builders are alkali metal silicates, particularly those having an SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1 and crystalline layered silicates, such as the layered sodium silicates described in US patent No. 4,664,839.

Examples of carbonate builders are the alkaline earth metal and alkaline carbonates as described in German Patent Application No. 2,321,001 published November 15, 1973. f The aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most of the heavy duty granular detergent compositions currently marketed, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders of f 10 include those having the empirical formula: Mz (zAIO2) and] xH2O where z and y are integers of at least 6, the molar ratio of zay is in the range of 1.0 to about 0.5, and x is an integer from about 15 to about 264. 15 Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived aluminosilicates. A method for producing aluminosilicate ion exchange materials is described in the US Patent 3,985,669, Krummel et al. Issued October 12, 1976. The 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 crystalline aluminosilicate ion exchange material has the formula: Na-j 2 [(AI02) 12 (S02) 12. * H20 where x is from about 20 to about 30, especially around 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but they can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders comprises ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. 3,128,287, issued April 7, 1964, and Lamberti et al., US patent. 3,635,830, issued January 18, 1972. See also "TMS / TDS" detergency builders 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 U.S. Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal salts, ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof . Citrate builders, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and its biodegradability. The citrates can also be used in granular compositions, especially in combination with aeolith and / or layered silicate builders. Oxydisuccinates are also especially useful in said compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanodiates and the related compounds described in the U.S. patent. 4,566,984, Bush, issued January 28, 1986. Acid detergency builders Useful succinic include the C5-C2o alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristiisuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and • 10 similar. Lauryl succinates 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. Patents. Nos. 4,144,226, Crutchfield et al., Issued March 13, 1979 and the US patent. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, E.U. 3,723,322. Fatty acids, for example, Ci2 ~ C8 monocarboxylic acids > they may also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in decreased foaming, which should be taken into account by the formulator.

In situations where phosphorus-based builders can be used, and especially in the bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate, can be used. and sodium orthophosphate. Phosphonate builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, US 3, 159,581, 3,213,030, 3,422,021, 3,400, 148 and 3,422, 137 patents). ).

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending to be limited by theory, it is believed that the benefit of these materials is in part due to their exceptional ability to remove iron and manganese solutions from the washing solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediamonotetraproprionates, triethylenetetra-aminohexacetates, diethylenetriaminepentaacetates and ethanololdiglicines, substituted alkali metal, ammonium and ammonium salts thereof and mixtures thereof. 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 ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A biodegradable chelator that is preferred to be used herein is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in the U.S.A. 4,704,233, November 3, 1987 to Hartman and Perkins. The compositions herein may also contain water-soluble salts of methylglycine diacetic acid (MGDA) (or acid form) as a useful builder or co-builder with, for example, insoluble builders such as zeolites, layered silicates and the like.

If used, these chelating agents should generally comprise from about 0.1% to about 15% 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.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of ethoxylated amines soluble in water; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are more fully described in the U.S.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal / anti-redeposition agents are the cationic compounds described in European patent application 111, 965, Oh and Gosselink, published on June 27, 1984. Other clay soil removers / anti-redeposition agents that may be used include the ethoxylated amine polymers described in European patent application 111, 984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S.A. 4,548,744, Connor, issued on 22 • October 1985. Other clay removers and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose (CMC) materials. These materials are well known in the art. 10 • Polymeric dispersion agents Polymeric dispersion agents can be advantageously used at levels of 0.1% to 7%, by weight, in the compositions herein, especially in the presence of detergency builders. zeolite and / or stratified silicate. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the overall detergency builder, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by inhibition of crystal growth, peptization of particulate and antiredeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates • include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid. The presence of the polymeric polycarboxylates in the present or polymer segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that • 1 0 such segments do not constitute more than about 40% by weight. Particularly suitable polymeric 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 The acid form perferrably ranges 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. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. The 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 on March 7, 1967.

Acrylic / maleic acid-based copolymers can also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from 5,000 to 75,000 and most preferably from 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 from 10: 1 to 2: 1. The water soluble salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European patent application No. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, the terpolymer 45/45/10 maleic / acrylic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes vary from 500 to 100,000, preferably from 1,000 to 50,000 and most preferably from 1,500 to 10,000. The dispersing agents of polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of polyaspartate preferably have a molecular weight (avg.) Of 10,000.

Brightener Any optical brighteners or other 10 brightening or bleaching agents known in the art at levels typically ranging from 0.01% to 1.2% by weight, in the detergent compositions herein, can be incorporated. Commercial optical brighteners that may be useful in the present invention can be classified into subgroups that include, but are not necessarily limited to, stilbene, pyrazoline, coumarin derivatives, carboxylic acid, methinocyanins, 5,5-dibenzotifen dioxide, azoles, 5- and 6-membered ring heterocycles, and various other agents. Examples f of said brighteners are described in "The Production and Application of Fluorescent Brightening Agents ", M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the patent of E.U.A. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the Verana PHORWHITE series of brighteners.

Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2,3-triazol-2-yl) -stilbenes; 4,4'-bis (steryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthyl- [1,2-s] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton.

* Foam Suppressants Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression of foam can be of particular importance in the so-called "high-level cleaning procedures" and in European-style front-loading 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, in the Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressors of particular interest comprises monocarboxylic fatty acids and soluble salts thereof. See the Patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, used as suds suppressors typically f have hydrocarbyl chains of 10 to about 24 atoms, preferably from 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. The detergent compositions may also contain foam suppressants that are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (v. gr., stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or chlorotriazines of di to tetra-alkylamines formed as cyanuric chloride products with 2 or 3 moles of primary or secondary amine containing from 1 to 24 carbon atoms. carbon, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal monostearyl diphosphates (e.g., Na, K, Li) and phosphate esters, the latter being used only at very low levels. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point on the scale of around minus 40 ° C and about 50 ° C, and a minimum boiling point not less than about 110 ° C (atmospheric pressure ). The use of waxy hydrocarbons is also known, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressors for detergent compositions. The hydrocarbon foam suppressors are described, for example, in the U.S. Patent. 4,265,779, issued May 5, 1981 to Gandolfo et al. In this manner, the hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin", as used in this description of foam suppressors, is intended to include mixtures 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 polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles in which the polyorganosiloxane is chemoabsorbed or fused to the silica. Silicone foam suppressors are well known in the art and, for example, are described in the U.S. Patent. 4,265,779, issued May 5, 1981 to Gandolfo et al., And European Patent Application No. 89397851.9, published on February 7, 1990, by Starch, M.S.

Other silicone foam suppressors are described in the U.S. Patent. No. 3,455,839, which relates to compositions and methods for removing foams from aqueous solutions by incorporating in them small amounts of polydimethylsiloxane fluids. Mixtures of silicone and siiated silica are described, for example, in German Patent Application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are described in the U.S. Pat. 3,933,672, Bartolotta et al., And in U.S. Pat. No. 4,652,392, Baginski et al., Issued March 24, 1987. An illustrative silicone-based foam suppressant to be used herein is a foam suppressor amount of foam controlling agent consisting essentially of: (i) polydimethylsiloxane fluid which It has a viscosity of about 20 cs to about 1,500 cs at 25 ° C. (I) from about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of units (CH 3) 3 S 2 O 2/2 SiO 2 units in a proportion of units of (CH 3) 3 SiO-j / 2 to units of S02 of about 0.6: 1 to about 1.2: 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel. In the preferred silicone-based foam suppressors used herein, the solvent for a continuous phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone-based foam suppressor is branched / crosslinked and preferably non-linear. To further illustrate this point, typical liquid laundry detergent compositions with controlled foams optionally consist of 0.001 to 1, preferably 0.01 to 0.7, more preferred 0.05 to 0.5% by weight of said silicone-based foam suppressors, which consist of (1) a non-aqueous emulsion of a primary anti-foaming agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone compound that produces silicone resin, (c) a finely divided filler material and (d) a catalyst for promoting the reaction of the mixture of components (a), (b) and (c), to form silanolates; (2) at least one nonionic surfactant based on silicone; and (3) polyethylene glycol or a polyethylene glycol propylene glycol copolymer having a solubility in water at room temperature of more than about 2% by weight; and without propylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994 and U.S. Patents. 4,639,489 and 4,749,740, Aizawa and others in column 1, line 46 to column 4, line 35.

The silicone-based foam suppressors herein preferably consist of polyethylene glycol and a polyethylene glycol / propylene glycol copolymer, all having an average molecular weight of less than 1,000, preferably between 100 and 800. Polyethylene glycol and The polyethylene / propylene copolymers herein have a solubility in water at room temperature of about more than 2% by weight, preferably more than 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1,000, preferably about 100 to 800, more preferred between 200 and 400, and a polyethylene glycol / propylene glycol copolymer, preferably PPG 200 / PEG 300. A weight ratio of approximately between 1: 3 1: 6 polyethylene glycol: polyethylene-propylene glycol copolymer is preferred. The preferred silicone-based foam suppressors used herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. These also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other foam suppressors useful herein include secondary alcohols (e.g., 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones described in US Pat. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include the C alco-C -β alkyl alcohols having a C?-C6 chain. A preferred alcohol is 2-butyloctanol, which can be obtained in Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the tradenames ISALCHEM 123 from Enichem. Mixed foam suppressors typically consist of alcohol + silicone in a weight ratio of 1: 5 to 5: 1. For any detergent composition for use in automatic washing machines, the foam should not be formed to the extent that it flows excessively out of the washing machine. The foam suppressors, when used, are preferably present in a "foam suppressant amount". By "foam suppressant amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foams which will result in a laundry detergent with low foaming to be used in automatic washing machines. The compositions herein will generally comprise from 0% to about 5% foam suppressant. When used as suds suppressors, the monocaboxylic fatty acids and salts thereof will typically be present in amounts of up to 5% by weight of the detergent composition. Preferably, 0.5% to 3% of fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts of up to 2% by weight, of the detergent composition although larger amounts may be used. This upper limit is of a practical nature, mainly due to the concern to keep costs to a minimum and the effectiveness of smaller quantities to effectively control the foam. Preferably from 0.01% to 1% of silicone foam suppressant is used, more preferably from 0.25% to about 0.5%. As used in the present, • these weight percentage values include any silica that could be used in combination with polyorganosiloxane, as well as any auxiliary material that could be used. Monostearyl phosphate foam suppressors are generally used in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon foam suppressors are typically used in amounts ranging from 0.01% to 5%, although higher levels may be used. Alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Fabric softeners Various fabric softeners can be used as an option. soften during washing, especially the impalpable smectite clays of the U.S. patent. 4,062,647, Storm and Nirschi, issued December 13, 1977, as well as other softening clays known in the art, typically at levels from about 0.5% to about 10% by weight in the compositions herein invention to provide softening benefits concurrently with fabric cleaning. Clay-based softeners may be used in combination with amine and cationic softeners as described, for example, in the U.S. 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 of 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 polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents typically constitute 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 preferred polyamine N-oxide polymers for use in the present invention contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group may be attached or the N-O group may be part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: wherein R-], R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or be part of any of the groups mentioned above. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, most preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. 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 copolymerization 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; most preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. This class f. Preferred materials may be referred to as "PVNO". The most preferred polyamine N-oxide useful in the detergent compositions of the present invention is the poly (4-vinylpyridine N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to N-amine oxide of about 1: 4. 15 The polymer copolymers of N-vinylporrolidone and N-vinylimidazole (referred to as a class known as "PVPVI") are also W preferred for use in the present invention. 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 range is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods 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. f The compositions 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. PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated in the present invention for reference. The compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the The ratio of PEG to PVP in a base in ppm delivered in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The granular compositions of the present invention may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions of the present invention will preferably comprise from about 0.01% to 1% by weight of said optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R-] is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4,, bis [(4-anilino-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is sold commercially under the name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of the acid 4,4'-b¡s [(4 -anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-ii) amino] -2,2'-stilbenedisulfonic acid. This particular brightener species is sold commercially under the name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula Ri is anilino, R2 is morphino and M is a cation such as sodium, the brightener is the sodium salt of 4,4'-bis [(4-anilino-6-morphino-s-triazin- 2-yl) amino] 2,2'-stilbenesulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The specific optical brightener species selected for use in the present invention provides especially 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 PVPVI) with said selected optical brighteners (for example, Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provide significantly better dye transfer inhibition in aqueous wash solutions than any of these two components of granulated composition when used alone. Without being limited to theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "depletion coefficient". The coefficient of depletion is in general the ratio of a) the polishing material deposited on the cloth to b) the initial concentration of polish in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that the other types of conventional optical brightening compounds can optionally be used in the compositions of the present invention to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations.

PREPARATION OF POLYAMINES EXAMPLE 1 Ethoxylation of poly (ethyleneimine) with average molecular weight of 1800 To a 250 milliliter three-necked ball flask equipped with a Claisen head, thermometer connected to a temperature controller (Therm-O-Watch, l2R), bubble tube and magnetic stir bar, poly (ethyleneamine) is added. of molecular weight 1800 (Polysciences, 50 g, 0.028 moles). Ethylene oxide gas (Liquid Carbonics) is added through the bubbling tube under argon at about 140 ° C with very rapid stirring, until a weight gain of 52 g (corresponding to 1.2 ethoxy units) is obtained. A 50 g portion of this yellow gel-like material is stored. To the rest of the material, potassium hydroxide pellets are added (Baker, 0.30 g, 0.0053 mol). After the potassium hydroxide is dissolved, ethylene oxide is added as described above until a weight gain of 60 g (corresponding to a total of 4.2 ethoxy units) is obtained. A portion of 53 g of this viscous brown liquid is stored. Ethylene oxide is added to the remaining material as described above to obtain a weight gain of 35.9 g (corresponding to a total of 7.1 ethoxy units) to achieve 94.9 g of dark brown liquid. The potassium hydroxide in the last two samples is neutralized by adding theoretical amounts of methanesulfonic acid.

EXAMPLE 2 Quaternization of PEÍ 1800 E7 To a 500 ml Erienmeyer flask equipped with a magnetic stir bar is added poly (ethyleneimine) having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800, E7) ( 207.3 g, 0.590 mol nitrogen, prepared as in example 1) and acetonitrile (120g). Dimethyl sulfate (28.3 g, 0.224 moles) is added in a single dose to the rapidly stirring solution, which is then capped and stirred at room temperature overnight. The acetonitrile is removed by rotary evaporation at about 60 ° C, followed by further removal of the solvent using a Kugeirohr apparatus at about 80 ° C to produce 220 g of the desired partially quaternized material as a viscous dark brown liquid. A spectrum of 3 C-NMR (D 2 O) obtained from a sample of the reaction product indicates the absence of a carbon resonance at -58 ppm corresponding to dimethyl sulfate. The 1 H-NMR spectrum (D 2 O) shows a partial displacement of the resonance at approximately 2.5 ppm for non-quaternized non-quaternized methylenes has shifted to approximately 3 ppm. This is consistent with the desired quaternization of approximately 38% of the nitrogens.

EXAMPLE 3 Formation of the amine oxide of PEI 1800 E7 A polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 moles) is added to a 500 ml Erlenmeyer flask equipped with a magnetic stir bar. of nitrogen, prepared as in example 1), and hydrogen peroxide (120 g of a solution in water at 30% by weight, 1.06 mol). The flask is capped and after an initial exotherm the solution is stirred at room temperature overnight. The 1 H-NMR spectrum (D 2 O) obtained on a sample of the reaction mixture indicates complete conversion. The resonances assignable to the methylene protons adjacent to the non-oxidized nitrogens have been displaced from the original position of -2.5 ppm to -3.5 ppm. Approximately 5 g of 0.5% Pd are added to the reaction solution on alumina pellets, and the solution is • let stand at room temperature for about 3 days. The solution is tested and found negative for peroxide by indicator paper. The material as obtained is stored appropriately as an active solution to! 51.1% in water.

EXAMPLE 4 • 1 0 Formation of amine oxide of PEI 1800 E quaternized To a 500 ml Erlenmeyer flask equipped with a magnetic stir bar is added polyethyleneimine which is further modified by ethoxylation to a degree of about 7. ethyleneoxy residues per nitrogen (PEI 1800, E7), and then further modified by quaternization to about 38% with dimethyl sulfate (130 g, -0.20 moles of oxidizable nitrogen, prepared as in example 2), hydrogen peroxide (48 g of a solution in water at 30% by weight, 0.423 moles), and water (-50 g). The flask is capped and after a Initial exotherm The solution is stirred at room temperature overnight. The 1H-NMR (D2O) spectrum obtained on a sample taken from the reaction mixture indicates complete conversion of the resonances attributed to the methylene peaks previously observed in the range of 2.5-3.0 ppm to a material having methylenes with a displacement chemical 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 negative for peroxide by indicator paper. The desired material is obtained with -38% of the quaternized nitrogens and 62% of the oxidized nitrogens up to the amine oxide and is suitably stored as an active solution at 44.9% in water.

EXAMPLE 5 Preparation of PEI 1200 E? The ethoxylation is carried out in a stirred stainless steel autoclave of 7.56 liters, equipped for measurement and temperature control, pressure measurement, vacuum and purge with inert gas, sampling and for introduction of ethylene oxide as liquid. A cylinder of around 9.06 kg net of ethylene oxide (ARC) is connected to supply ethylene oxide as a liquid, by means of a pump to the autoclave, placing the cylinder on a balance so that the change in weight can be monitored of the cylinder. A 750 g portion of polyethylenimine (PEI) (having an average molecular weight, listed, of 1200, which is equal to about 0.625 moles of polymer and 17.4 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (applying vacuum to less than 711 mm Hg, followed by pressurization with nitrogen at 17.57 kg / cm2 absolute, and then opening at atmospheric pressure). It is heated to 130 ° C • contents of the autoclave, while vacuum is applied. After about one hour the autoclave is charged with nitrogen to approximately 17.57 kg / cm2 absolute, while the autoclave is cooled to around 105 ° C. Ethylene oxide is then added to the autoclave, in increments over time, while at the same time monitoring the pressure of the autoclave, the • 1st temperature and the flow rate of ethylene oxide. The ethylene oxide pump is switched off and cooling is applied to limit any temperature rise that is the result of any reaction exotherm. The temperature is maintained between 100 and 110 ° C, while the total pressure is allowed to increase gradually during the course of the reaction.

After a total of 750 g of ethylene oxide has been charged to the autoclave (approximately equivalent to one mole of ethylene oxide per nitrogen function of PEI), the temperature is increased to 110 ° C and the autoclave is left stirring for a period of time. more time At this point vacuum is applied to remove any unreacted residual ethylene oxide. Afterwards, vacuum is continuously applied while the autoclave is cooled to around 50 ° C, while introducing 376 g of a 25% solution of sodium methoxide in methanol (1.74 moles, to obtain a 10% catalyst load, based on the nitrogen functions of PEI). The methoxide solution is sucked into the autoclave, under vacuum, and then the fixed point of the autoclave temperature controller is increased to 130 ° C. A device is used to monitor the power consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power of the agitator and the temperature values increase gradually as the methanol is removed from the autoclave and the viscosity of the mixture increases, and stabilizes in about an hour, which indicates that most of the methanol has been removed. The mixture is further heated and stirred under vacuum for another 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C, while it is being loaded with nitrogen at 17.57 kg / cm2, and then opened to ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is added again to the autoclave, in increments, as before, while carefully monitoring the pressure of the autoclave, the temperature and the flow velocity of the ethylene oxide, while maintaining the temperature between 100 and 110 ° C. and limiting any increase in temperature due to the exotherm of the reaction. After the addition of 4500 g of ethylene oxide (which results in a total of 7 moles of ethylene oxide per mole of nitrogen function of PEI) is attained for several hours, the temperature is increased to 110 ° C and the Stir the mixture for another hour. The reaction mixture is then collected in nitrogen-purged vessels and optionally transferred to a 22-liter three-necked round bottom flask equipped with heating and stirring.

The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by passing approximately 2.83 m 3 of inert gas (argon or nitrogen) through a porous glass for gas dispersion and through the reaction mixture, while stirring and heating the mixture to 130 ° C. . The final product of the reaction is cooled slightly and collected in glass vessels purged with nitrogen. In other preparations, neutralization and deodorization is achieved in the reactor, before discharging the product. Other preferred examples, such as PEI 1200 E15 and PEI 1200 E20 can be prepared by the above method, adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.

EXAMPLE 6 Quaternization at 9.7% of PEI 1200 E7 To a 500 ml Erlenmeyer flask, equipped with magnetic stirring bar, is added poly (ethyleneimine), of molecular weight 1200, ethoxylated to a degree of 7 (248.4 g, 0.707 mol of nitrogen, prepared as in example 5) and acetonitrile (Baker, 200 ml). Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) is added at once, to the rapidly stirred solution, which is then plugged and stirred at room temperature overnight. The acetonitrile is evaporated on the rotary evaporator at ~60 ° C, followed by a Kugeirohr (Aldrich) apparatus at ~80 ° C to produce -220 g of the desired material, as a viscous dark brown liquid. A spectrum of 13 C-NMR (D 2 O) shows the absence of a peak at -58 ppm, which corresponds to dimethyl sulfate. A spectrum of 1 H-NMR (D 2 O) shows the partial displacement of the peak at 2.5 ppm (methylenes bound to non-quaternized nitrogens) to -3.0 ppm.

EXAMPLE 7 Preparation of PEI 600 Egn The ethoxylation is carried out in a stirred stainless steel autoclave of 7.56 liters, equipped for measurement and temperature control, pressure measurement, vacuum and purge with inert gas, sampling and for introduction of ethylene oxide as liquid. A cylinder of around 9.06 kg net of ethylene oxide (ARC) is connected to supply ethylene oxide as a liquid, by means of a pump to the autoclave, placing the cylinder on a balance so that the change in weight can be monitored of the cylinder. A 250 g portion of polyethylenimine (PEI) (Nippon Shokubai, having an average molecular weight, in the list, of 600, which is equal to about 0.417 moles of polymer and 6.25 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (applying vacuum to less than 711 mm Hg, followed by pressurization with nitrogen at 17.57 kg / cm2 absolute, and then opening 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 / cm2 absolute, while the autoclave is cooled to around 105 ° C. Ethylene oxide is then added to the autoclave, in increments over time, while at the same time the autoclave pressure, the temperature and the flow rate of ethylene oxide are carefully monitored. The ethylene oxide pump is switched off and cooling is applied to limit any temperature rise that is the result of any reaction exotherm. The temperature is maintained between 100 and 110 ° C, while the total pressure is allowed to increase gradually during the course of the reaction. After a total of 275 g of ethylene oxide has been charged to the autoclave (approximately equivalent to one mole of ethylene oxide per nitrogen function of PEI), the temperature is increased to 110 ° C and the autoclave is left stirring for one hour plus. At this point vacuum is applied to remove any unreacted residual ethylene oxide. Then, vacuum is applied continuously while the autoclave is cooled to around 50 ° C, while introducing 135 g of a 25% solution of sodium methoxide in methanol (0.625 mol, to obtain a 10% catalyst load, with based on PEI nitrogen functions). The methoxide solution is sucked into the autoclave, under vacuum, and then the fixed point of the autoclave temperature controller is increased to 130 ° C.

A device is used to monitor the power consumed by the agitator. The power of the agitator is monitored together with the temperature and pressure. The power of the agitator and the temperature values increase gradually as the methanol is removed from the autoclave and the viscosity of the mixture increases, and it stabilizes in about one hour, which indicates that most of the methanol has been removed. The mixture is further heated and stirred under vacuum for another 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C, while it is being loaded with nitrogen at 17.57 kg / cm2, and then opened to ambient pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. Ethylene oxide is added again to the autoclave, in increments, as before, while carefully monitoring the pressure of the autoclave, the temperature and the flow velocity of the ethylene oxide, while maintaining the temperature between 100 and 110 ° C. and limiting any increase in temperature due to the exotherm of the reaction. After the addition of 5225 g of ethylene oxide (which results in a total of 20 moles of ethylene oxide per mole of nitrogen function of PEI) is attained for several hours, the temperature is increased to 110 ° C and the Stir the mixture for another hour. The reaction mixture is then collected in nitrogen-purged vessels and optionally transferred to a 22-liter three-necked round bottom flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 60 g of methanesulfonic acid (0.625 moles). The reaction mixture is then deodorized by passing approximately 2.83 rri3 of inert gas (argon or nitrogen) through a porous glass for gas dispersion and through the reaction mixture, while stirring and heating the mixture to 130 ° C. . The final product of the reaction is cooled slightly and collected in glass vessels purged with nitrogen. In other preparations, neutralization and deodorization is achieved in the reactor, before discharging the product. The following discloses high density liquid detergent compositions in accordance with the present invention: TABLE I 1. Ethoxylated alcohols Eg as sold by The Shell Oil Co. 2. Ethoxylated tetraethylenepentamine (PEI 189 E-is-E-iß) in accordance with document E.U.A. 4,597,898, Vander Meer issued on July 1, 1986. 3. BPN variant 'stable to the bleach (protease A-BSV) such as that described in EP 130,756 A, January 9, 1985. 4. Variant of region 6 of the subtilisin 309 loop. 5. Proteolytic enzymes as they are. sold by Novo. 6. Polyamine according to example 7 (PEI 600 E20). 7. Polyamine according to example 5 (PEI 1200 E20). 8. The rest at 100% may include, for example, minor ingredients such as optical brightener, perfume, suds suppressor, dirt dispersant, chelating agents, transfer inhibitors, • dye, additional water and filling materials including CaC? 3, talc, silicates, etc.

TABLE II% by weight • 10 fifteen 1. Ethoxylated alcohols Eg as sold by The Shell Oil Co. 2. Variant of BPN 'stable to bleach (protease A-BSV) such as that described in EP 130,756 A, January 9, 1985. 3. Variant of region 6 of the subtilisin 309 loop. 4. Proteolytic enzymes as sold by Novo. 5. Polyamine according to example 7 (PEI 600 E20). 6. Polyamine according to example 5 (PEI 1200 E20). 7. The rest at 100% may include, for example, minor ingredients such as optical brightener, perfume, suds suppressor, dirt dispersant, chelating agents, dye transfer inhibiting agents, additional water and fillers including CaCOß, talc , silicates, etc.

TABLE III 1. Ethoxylated alcohols E9 as sold by The Shell Oil Co. 2. Protease B variant of BPN 'in which Tyr 217 is replaced with Leu. 3. A variant of subtilisin 309 having a modified amino acid sequence of the wild-type amino acid sequence of subtilisin 309 in which the substitutions occur in one or more of positions 194, 195, 196, 199 or 200. 4. Polyamine according to example 4. 5. Polyamine according to example 7. 6. The rest at 100% may include, for example, minor ingredients such as optical brightener, perfume, suds suppressor, dirt dispersant, chelating agents, dye transfer inhibiting agents, additional water and fillers including CaCO3, talc, silicates, etc.

TABLE IV 1. Ethoxylated alcohols E9 as sold by The Shell Oil Co. 2. Protease B variant of BPN 'in which Tyr 217 is replaced with Leu. 3. A variant of subtilisin 309 having a modified amino acid sequence of the wild-type amino acid sequence of subtilisin 309 in which the substitutions occur in one or more of positions 194, 195, 196, 199 or 200. 4. Polyamine according to example 4. 5. Polyamine according to example 7. 6. The rest at 100% may include, for example, minor ingredients such as optical brightener, perfume, suds suppressor, dirt dispersant, chelating agents, dye transfer inhibiting agents, additional water and fillers including CaCO3, talc, silicates , etc.

TABLE V 1. C12-C13 E9 alkyl ethoxylate as sold by The Shell Oil Co.

Ilisina of Bacillus amyloliquefaciens as described in document / 10615 published on April 20, 1995 by Genencor International. nest of Humicola lanuginosa and commercially available from Novo. rite in WO 9510603 A and available from Novo. mine according to example 7.

TABLE VI mine of example 7. mine of example 1.

TABLE VII 1. Polyamine of example 7.. Polyamine of example 1. 3. Polyamine of example 5.

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - A liquid detergent laundry composition comprising a surfactant, an effective amount of HEDP and a stabilizing amount of water soluble or dispersible modified polyamine comprising a polyamine base structure corresponding to the formula: H I I [H2N-R] n + 1 - [N-R] m- [N-R] n-NH2 having a modified polyamine formula V (n + -nWrr- | YnZ or a polyamine base structure corresponding to the formula: H R [H2N-R] n.k + 1- [N-R] m- [N-R] n- [N-R] k-NH2 having a modified polyamine formula V (n_k + i) WmYnY'k Z, wherein k is less than or equal to n, said polyamine base structure, prior to modification, has a molecular weight greater than about 200 daltons, where: i) units V are terminal units that have the formula: OR E- N- R- E- N fr- R- 'E- N- R - I E ii) units W are base structure units that have the formula: iii) Y units 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 C2-C-j alkylene, C4-C-j2 alkenylene, hydroxy alkylene of C3-C-1;?, C4-C? 2 dihydroxyalkylene, dialkylarylene C 8 -C 12, - (R 1?) X R 1 -, - (R 1 O) X R 5 (OR 1) X, - (CH 2 CH (OR 2) CH 2 O) z (R 1?) And R 1 - (OCH 2 CH (OR 2) CH 2) w-, -C (O) (R4) rC (O) -, -CH2CH (OR2) CH2-, and mixtures of the same; wherein R 1 is C 2 -C 6 alkylene, and mixtures thereof; R2 is hydrogen, - (RlO ^ B, and mixtures thereof, it is C-C-J8 alkyl, C7-C2 arylalkyl, aryl substituted with C7-C12 alkyl, Cg-C aryl, And mixtures thereof, R 4 is C 2 -C 2 alkylene, C 4 -C 12 alkenylene, C 1 -C 4 arylalkylene, Cg-C-jf 1 arylene and mixtures thereof; • is alkylene of C? -C- | 2 > C3-C12 hydroxyalkylene. C4-5 C2 dihydroxyalkylene, C8-C2 dialkylarylene, -C (O) -, -C (O) NHR6NHC (O) -, -R1 (OR1) -, - C (O) (R4) rC (O) -, CH2CH (OH) CH2-, CH2CH (OH) CH2O- (R1?) And R1OCH2CH (OH) CH2- and mixtures thereof; R 6 is C 2 -C 2 alkylene or Cg-C 2 arylene; the E units are selected from the group consisting of hydrogen, C1-C22 alkyl. C3-C22 alkenyl. A C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) pCO2M, - (CH2) qS? 3M, - CH (CH2CO M) CO2M, - (CH2) pPO3M, - (RO) xB, -C ( O) R3, and mixtures thereof; provided that when any unit E of a nitrogen is a hydrogen, said nitrogen is also not an N-oxide; B is hydrogen, C 1 -C 4 alkyl, - (CH 2) qSO 3 M, - (CH 2) pCO 2 M, - (CH 2) q (CHSO 3 M) CH 2 SO 3 M, - (CH 2) q- (CHS 2 M) CH 2 SO 3 M, - (CH 2) pPO 3 M, -PO3M and mixtures thereof; M is hydrogen or a cation soluble in water in an amount sufficient to satisfy the balance of the charge; X is a water soluble anion; m has the value of 4 to about 400; n has the value from 0 to about 200; p has the value of 1 to 6, q has the value of 0 to 6; r has the value of 0 or 1; 20 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.

2. - A composition according to claim 1, further characterized in that said detersive surfactant comprises an anionic surfactant selected from the group consisting of alkylalkoxysulfate, alkylsulfate and mixtures thereof.

3. A composition according to claim 1 or 2, further characterized in that R is C 2 -C 2 alkylene, C 3 -C 12 hydroxyalkylene. C4-C12 dihydroxyalkylene, dialkylarylene of C8-C-2, - (R10) XR1-, - (R1O) XR5 (OR1) X, - (CH2CH (OH) CH2O) 2 (R1?) and R1- (OCH2CH (OH) CH2) w-, -CH2CH (OR2) CH2-, and mixtures thereof.

4. A composition according to claim 3, further characterized in that R is C2-C alkylene.

5. A composition according to claim 4, further characterized in that R is alkylene dylene of C2.

6. A composition according to any of the preceding claims, further characterized because E is (R- | O) xB.

7. A composition according to claim 6, further characterized in that Rj is alkylene of C and Q TS hydrogen- 8.

A composition according to claim 7, further characterized in that x has the value of 5 to 30.

A composition according to claim 7, further characterized in that said PEI, before modification, has a molecular weight of 200 to 3000.

10. - A composition according to any of the preceding claims, which comprises from 0.1% to 5% of HEDP.

11. A composition according to claim 10, which comprises from 0.2% to 2% of HEDP.

12. A composition according to any of the preceding claims, which comprises from 0.1% to 10% of said polyamine.

13. A composition according to claim 12, which comprises from 0.2% to 5% of said polyamine.

14. A composition according to any of the preceding claims, which comprises water in amounts of less than 40%.