MXPA06010694A - Detergent compositions comprising a modified polyaminoamide - Google Patents

Abstract

Detergent compositions containing modified polyaminoamides and a surfactant system for improved soil cleaning and soil dispersing.

Description

DETERGENT COMPOSITIONS COMPRISING A MODIFIED POLYAMINOAMIDE FIELD OF THE INVENTION The present application relates to detergent compositions having suitable properties of dirt removal and dispersion of particulate hydrophobic dirt, especially clay minerals, by the use of modified polyaminoamides.

BACKGROUND OF THE INVENTION It is known that some polymers prevent the redeposition of dirt by means of stabilizing it in the washing liquid. These include carboxymethylcellulose (CMC), humic acid, polyacrylic acid and copolymers of maleic acid and acrylic acid (see Powdered Detergents, Editor: Michael S. Showell, Surfactant Sci. Ser., Vol. 71, Marcel Decker , New York 1998, pages 111-114; Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York 1997, page 303). It is known that polyaminoamides are polymers whose main chain contains amino (NH) and amide (NH-C (O)) functional groups. Modified polyaminoamides containing polyether side chains attached to the amino nitrogen atoms of the main polymer chain and, if present, to the amino nitrogen atoms of the end groups of the polymer are described, for example, in GB 1218394, EP 1025839, EP 1192941 and WO03 / 050219. In general, modified polyaminoamides from the prior industry contain an average of 1 to 6 repeating units in the polyether side chain. To date, polyaminoamides have not been recommended as useful antiredepositive agents nor as suitable to facilitate the removal of dirt. Accordingly, there is a need to have compounds useful as detergent auxiliaries to prevent redeposition of dirt and to facilitate the removal of dirt.

BRIEF DESCRIPTION OF THE INVENTION The present application relates to a detergent composition comprising by weight, approximately between 0.01% and 90% of a surfactant system and approximately between 0.01% and 20% of a modified polyaminoamide comprising Formula (I) (I) wherein n of Formula (I) is an integer from 1 to 500; R3 of the formula (I) is selected from a C2-C8 alkanediyl, preferably 1,2-ethanediyl or 1,3-propanediyl; R4 of Formula (I) is selected from a chemical bond, C2_2 alkanediyl, C2_2_ alkanediyl comprising 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, CrC20 alkanediyl comprising from 1 to 6. heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical and mixtures thereof, wherein Formula (I) comprises secondary amino groups of the main chain of the polymer; the secondary amino groups comprise amino hydrogens; the amino hydrogens are selectively substituted in the modified polyaminoamide so that the modified polyaminoamide comprises partial quaternization of the secondary amino groups by selectively replacing at least one amino hydrogen with at least one alkoxy entity of the Formula (II): - (CH2-CR1R2-O-) pA (II) wherein A of Formula (II) is selected from hydrogen or an acid group; the acid group is selected from -B1-PO (OH) 2, -B -S (O) 2 OH and -B2-COOH; such that B 1 of Formula (II) is a single bond or alkanediyl of C C6; and B2 of Formula (II) is an alkanediyl of C C6; R1 of Formula (II) is independently selected from hydrogen, C C alkyl? , C2-C8 alkenyl, C6-C16 aryl or Cß-Cie-C ar alkyl aryl; R2 of Formula (II) is independently selected from hydrogen or methyl; and p of Formula (II) is an integer comprising an average of at least 10; The remainder of the amino hydrogens of the secondary amino groups is selected from the group comprising electron pairs, hydrogen, C 6 alkyl, C 6 -C 16 aryl C 1 -C alkyl and Alk-OA of the Formula (III ), wherein A of the Formula (III) is hydrogen or an acid group; the acid group is selected from -B1-PO (OH) 2, -B1-S (O) 2OH and -B2-COOH; such that B1 of Formula (III) is selected from a single bond or an alkanediyl of C -? - C6; and B2 of Formula (III) is selected from alkanediyl of C -? - C6 and Alk of the Formula (III) is C2-C6-1, 2-diyl alkane; the secondary amino groups of Formula (I) are also selected to contain at least one alkylation moiety of Formula (IV): -RX (IV) wherein R of Formula (IV) is selected from the group consisting of: C6-C6-alkyl, C6-C16-aryl-CC alkyl and Alk-OA of Formula (III) and - (CH2-CR1R2-O-) pA of Formula (II).

DETAILED DESCRIPTION OF THE INVENTION The present application relates to detergent compositions comprising modified polyaminoamides. These compositions can be in any conventional form, namely in the form of liquid, powder, granules, agglomerate, paste, tablet, pouches, bar, gel, in the forms of the products supplied in double-compartment packages, dew-detergents or foam, prewetted wipes (i.e. the detergent composition combined with a nonwoven fabric material such as that described in U.S. Patent No. 6,121,165, Mackey et al.), dry wipes (ie, the composition detergent combined with non-woven fabric materials such as those described in U.S. Patent No. 5,980,931, Fowler et al.) activated with water by a consumer and other homogeneous or multi-phase forms of consumer cleaning products. These detergent compositions often also contain surfactants and other detergent auxiliary ingredients described in detail below. In one embodiment, the detergent composition of the present application is a liquid or solid laundry detergent composition. Modified polyaminoamides consist of the modification of at least a part of the amino nitrogens of the main polymer chain and when present, of the terminal amino groups as defined below and optionally, another modification made using an esterification or etherification as defined below. As used herein, "amino hydrogens" refers to the hydrogen atoms attached to the secondary amino groups of the main polymer chain and if present, to the primary amino groups at the raw material terminals of the unmodified polyaminoamide to distinguish them from the hydrogen atoms attached to the amide nitrogens in the main polymer chain. As used herein, the term "C-C2 alkyl" refers to a straight or branched chain saturated hydrocarbon radical having from 1 to 12, preferably from 1 to 6 carbon atoms, for example methyl, ethyl , propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n -hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1 -ethyl-2-methylpropyl, n-heptyl, n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, 2-nonyl (isononyl), n-decyl or n-dodecyl. As used herein, the term "C2-C2 alkenyl" refers to a straight or branched chain monounsaturated hydrocarbon radical having between 2 and 12, preferably between 2 and 6 and more preferably between 2 and 4 carbon atoms and a double bond at any position, for example ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, -methyl-1 -propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and the like. As used herein, the term "C 6 -C 6 aryl" refers to an aromatic hydrocarbon radical having 6 to 16 carbon atoms such as phenyl or naphthyl and may carry 1, 2, 3 or 4 substituents selected from alkyl of C1-C12 and C2-C2 alkenyl, wherein 2 substituents on the adjacent carbon atoms can form a ring, as in tetrahydronaphthyl or indanyl. As used herein, the term "C6-C16 aryl-d-C alkyl" refers to a straight or branched chain saturated hydrocarbon radical having from 1 to 4 carbon atoms and carrying an aryl group of C-6-C16. Examples are benzyl, 1-phenylethyl and 2-phenylethyl. The term "alkanediyl of Cx-Cy" refers to a divalent alkylene whose chain has between x and carbon atoms as indicated by the subscript (for example, alkanediyl of CrC20). Examples of alkanediyl are methylene (CH2), ethane-1, 1-diyl, ethane-1,2-diyl, propane-1, 1-diyl, propane-1,2-diyl, propane-2,2-diyl, butane-1,3-diyl, butane-1,4-diyl, butane-2,2-diyl, butane-2,3-diyl and the like. All number ranges, when expressed in a format "between X and Y" are considered incorporated and included herein as if they were expressly written. It should be understood that all limits provided throughout this specification shall include all lower or upper limits, as the case may be, as if that lower or upper limit were expressly written herein. The intervals provided throughout this specification will include any narrower range that falls within this wider range, as if these narrower intervals were expressly consigned in the present. Modified Polyaminoamide The present application relates to detergent compositions comprising approximately between 0.01% and 20%, preferably approximately between 0.01% and 10% and more preferably between approximately 0.01% and 8% of a modified polyaminoamide, by weight of the composition Detergent. Depending on their degree of alkoxylation, the modified polyaminoamides according to the application have a number average molecular weight (Mn) of from 1,000 to 1,000,000, preferably from 2,000 to 1,000,000 and more preferably from 2,000 to 50,000. In general, polyaminoamides are polymers whose main chain contains both amine (* -NH- *) functional groups and amide functional groups (* -NH-C (O) - *); the asterisks indicate the main polymer chain. The polyaminoamides also contain primary amino groups (-NH2) and / or carboxyl groups (-COOH) at the terminals of the polymer chain. As used herein, the term "amino" encompasses the secondary amine functional groups of the main polymer chain and the primary amine functional groups at the terminals of the polymer chain. In general, polyaminoamides are linear.

The modified polyaminoamide of the detergent composition of the present application encompasses Formula (I) 0) wherein n of Formula (I) is an integer from 1 to 500, preferably from 1 to 100, more preferably from 1 to 20, with an even greater preference between 1 and 10 and most preferably 1, 2 or 3. R3 of Formula (I) is selected from C2-C8 alkanediyl, preferably C2-C8 alkanediyl and more preferably 1,2-ethanediyl or 1,3-propanediyl. R4 of Formula (I) is selected from a chemical bond, C---C20 alkanediyl, C2C-alkanediyl comprising 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino), C-alkanediyl. C20 comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) and further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical and mixtures thereof. The C? -C2o alkanediyl comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) may contain 1 or 2 carbon-carbon double bonds. The C20 alkanediyl comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) can be a total or partial constituent of one or more saturated or unsaturated carbocyclic rings of 5 to 8 members. R4 is preferably C2-C6 alkanediyl. The modified polyaminoamide comprising Formula (I) contains secondary amino groups of the main polymer chain. The secondary amino groups contain amino hydrogens which are selectively substituted to produce the modified polyaminoamide comprising the partial quaternization of the secondary amino groups by selectively substituting at least one amino hydrogen for at least one alkoxy portion of the Formula (II): - (CH2-CR1R2-O-) pA (II) wherein A of Formula (II) is selected from a hydrogen or an acid group, the acid group is selected from -B1-PO (OH) 2, -B1-S (O) 2OH and -B2-COOH which may be in acid or anionic form. Preferably, A is selected from hydrogen, -B1-PO (OH) 2 and -B1-S (O) 2OH. B of Formula (II) is selected from a simple chemical or alkanediyl bond of C-i-Cß. B2 of Formula (II) is selected from an alkanediyl of C? -C6. R1 of Formula (II) is independently selected from hydrogen, C 1 -C 12 alkyl, C 2 -C 8 alkenyl, C 6 -C 16 aryl or C 6 -C 16 aryl C 1 -C 4 alkyl, preferably hydrogen and C 1 -C 4 alkyl. CT (methyl).

R2 of Formula (II) is independently selected from hydrogen or methyl, preferably hydrogen. The index p of Formula (II) is an integer comprising a number with a minimum average value of 10. Preferably, the minimum average value of p in Formula (II) is 15 and more preferably, 21. Therefore, Generally, the maximum average value of p is 200, preferably 150, and more preferably, 100. Most preferably, the average value of p varies between 15 and 70, especially between 21 and 50. The rest of the hydrogens of the The amino of the secondary amino groups is selected from the group comprising electron pairs, hydrogen, C 1 -C 6 alkyl, C 6 -C 16 aryl CrC alkyl and Alk-OA of the formula (III): Alk-O-A (lll) A of Formula (III) is selected from hydrogen or an acid group, the acid group is selected from -B1-PO (OH) 2, -B1-S (O) 2OH and -B2-COOH which may be in acid form or anionic Preferably, A is selected from hydrogen, -B1-PO (OH) 2 and -B1-S (0) 2OH. B1 of Formula (II) is selected from a simple or C6-C-alkanediyl chemical bond. B2 of Formula (II) is selected from an alkanediyl of C? -C6. Alk of the Formula (V) is selected from a C2-C6 alkane-1,2-diyl.

The secondary amino groups of Formula (I) are also selected such that they contain at least one alkylation moiety of Formula (IV): -RX (IV) R of Formula (IV) is selected from the group consisting of C 1 -C 6 alkyl, C 6 -C 6 aryl C 4 alkyl, and Alk-OA of Formula (III) and - (CH 2 -CR 1 R 2 - 0-) pA of the Formula (II). X of Formula (IV) is a leaving group which can be replaced with nitrogen and epoxides having from 2 to 6 carbon atoms, generally alkylene oxides of C2-C6. Suitable leaving groups X of Formula (IV) are halogen, especially chlorine, bromine or iodine, sulfate (i.e., -O-SO 3 H or -O-SO 3"), alkylsulfonate such as methanesulfonate, arisulfonate such as tolylsulfonate and alkyl sulfate as methosulfate ( ie, -0-SO2-OCH3.) Preferred alkylation moieties are the alkyl halides of CrC6, bis- (C6-alkyl) sulphates and benzyl halides, examples of these alkylating agents being ethyl chloride, Ethyl bromide, methyl chloride, methyl bromide, benzyl chloride, dimethyl sulfate and diethisulfate The preferred C2-C6 alkylene oxides are ethylene oxide and propylene oxide The modified polyaminoamide can also be selected so as to contain a portion of esterification or etherification of some hydroxyl group present in Formulas (II), (III), (IX), (X), (XI) and (Xll) described below.The appropriate esterification portions can be selected from the acid sulfuric, ac gone phosphoric and the derivatives of these ester formers. Suitable etherification moieties are selected from Formula (V) L-B3-AS wherein A 'of Formula (V) is selected from -COOH, -SO3H and -PO (OH) 2, B3 of the Formula (V ) is selected from C6 alkanediyl; and L of the Formula (V) is a leaving group which can be replaced with nucleophiles. The modified polyaminoamide of the detergent composition of the present application also contains aliphatic, aromatic or cycloaliphatic diamines as shown in Formula (VI): (SAW) wherein R3, R4 and the index n of Formula (VI) are the same as defined in Formula (I). R7 of the Formula (VI) is a divalent organic radical carrying between 1 and 20 carbon atoms, C20 alkanediyl, C20 alkanediyl comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino), alkanediyl of CrC20 comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) which further comprise one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical and mixtures thereof. The C 2 O alkanediyl comprising 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) may contain 1 or 2 carbon-carbon double bonds. The alkanediyl of CrC20 comprising between 1 and 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen (imino) can be a total or partial constituent of one or more carbocyclic rings of 5 to 8 saturated or unsaturated members. When R 7 of the formula (VI) is selected as the divalent aromatic radical, 1, 2, 1,3 or 1,4-phenylene is preferred. The divalent aromatic radical can also carry 1, 2 or 3 substituents selected from C 1 -C 4 alkyl, C 4 alkoxy, C 3 -C 7 cycloalkyl, halogen, hydroxyl and the like. Preferably, R7 of Formula (VI) is an alkanediyl of Cr-C4 or a C4-C20 alkanediyl interrupted by 1, 2, 3 or 4 non-adjacent oxygen atoms. One embodiment of the modified polyaminoamides of the application encompasses Formula (VII): (VII) The index n and R3 of the Formula (VII) are the same as those described in Formula (I). R4 of the Formula (VII) is a chemical bond, alkanediyl of C C20, alkanediyl of C1-2 or interrupted by oxygen, sulfur and / or an imino group which may contain 1 or 2 carbon-carbon double bonds, in whole or in part , one or more carbocyclic rings of 5 to 8 saturated or unsaturated members where the alkanediyl can carry one or more hydroxyl groups. R4 is preferably C2-C6 alkanediyl. R5 of Formula (VII) is selected from hydrogen, dC-β alkyl, C6-C16 aryl-C4 alkyl, and Alk-OA of Formula (III) and - (CH2-CR1R2-O-) pA the Formula (II). R6 of the Formula (VII) is present at least once as - (CH2-CR1R2-O-) pA of the Formula (II) and any remaining R6 of the Formula (VII) is selected from an electron pair (i.e. non-quaternized), hydrogen, CrC6 alkyl, CrC4 aryl, Alk-OA of the formula (III) and - (CH2-CR1R2-O-) pA of the formula (III). One embodiment of the modified polyaminoamides of the application encompasses Formula (Vlll): (Vlll) wherein R3, R4 and the index n of the Formula (Vlll) are the same as defined in Formula (I). R7 of the Formula (Vlll) is the same as defined in Formula (VI). R5 and R6 of the Formula (Vlll) are the same as those defined in Formula (VII).

In Formulas (II), (VI), (X) and (XI), at least 30 mol% and more preferably at least 50 mol% of the repeating units CH2-CR1R2-O of Formula (II), R and R2 of Formula (II) are preferably hydrogen.

In another preferred embodiment, Formula (II) contains at least 90 mol% repeating units of the formula CH2-CH2-0, ie R1 and R2 of Formula (II) are hydrogen.

In another preferred embodiment, Formula (II) contains between 10 and 70 mol%, preferably between 10 and 50 mol% of repeating units of the formula CH2-CH (CH3) -O and between 30 and 90 mol%, in Specially between 50 and 90 mol% of repeating units CH2-CH2-O. In this embodiment, the different repeating units can be distributed randomly or preferably in the form of blocks.

In the modified polyaminoamides of the present application, by at least a part of the amino groups, ie the amino groups in the The main polymer chain is selected to be quaternized functional groups as shown in Formula (a): RI - -N- (a) R "R5 of Formula (a) is the same as defined in Formula (VII) .R6 of Formula (a) is the same as defined in Formula (VII) .If they are present, the primary (terminal) amino groups of the modified polyaminoamide according to the application can also be selected so that they are quaternized as shown in Formulas (b1) and (b2): R5 of the formulas (b1) and (b2) is the same as that defined in the formula (VII). R6 of the formulas (b1) and (b2) is the same as that defined in the formula (VII). In the modified polyaminoamide of the application, at least a portion of the amino nitrogen atoms of the polymer are replaced with quaternized functional groups of Formulas (a), (b1) and (b2) as described above. Preferably, at least 50 mol% and more preferably at least 70 mol% of the amino groups of the polymer is quaternized. The amount of quatemized portions in Formulas (a), (b1) and (b2) of the modified polyaminoamides of the application is preferably from 0.1 mol / kg to 3.0 mol / kg and more preferably between 0.2 mol / kg and 2 mol / kg. The amount of quatemized portions can be calculated from the difference in the number of amine in the non-quaternized product and in the quaternized polyaminoamide. The number of the amine can be determined according to the method described in the standard methods DGF - section H - surfactants, method H-III 20a (98) "Potentiometric titration of the total basic nitrogen I surfactants" (DGF Einheitsmethoden - Abteilung H - Tenside, Methode H-lll 20a (98) "Potentiometrische Titration des Gesamtbasenstickstoffs von Tensiden"). In the modified polyaminoamides of the application in which A of Formulas (II) and (III) is an acidic group it may be in the neutralized (anionic) or in the acid (ie neutral) form. The net charge of the modified polyaminoamide will depend, therefore, of the relative molar amounts of the acid groups with respect to the quaternized portions (ie, when both the alkoxy portion and the alkylation portion are in the same nitrogen of the main chain; R5 and R6 of the formulas (Vil) and (a), (b1) and (b2) are present in the same main chain in sufficient quantities to give rise to quaternization), the number of charges per acid group and the degree of neutralization of the acid groups. Suitable counterions to compensate for the net charge of the modified polyaminoamide when it is positive are selected from the mineral acids. Preferred mineral acids include sulfate, hydrogen sulfate, monoalkylsulfate, phosphate, hydrogen phosphate, chloride and the like. Suitable counterions to compensate for the net charge of the modified polyaminoamide when it is negative is selected from the alkali metal ions such as sodium ions, ammonium such as NH 4 +, ammonium ions derived from ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine and the like. In a first embodiment of the application, R of Formula (IV) is selected from a C6 alkyl or benzyl, preferably methyl, ethyl or benzyl. In another embodiment of the application, R of Formula (IV) is [Alk-O-A] of Formula (III) as defined above, preferably ethane-1,2-diyl and propane-1,2-diyl. In a preferred embodiment of the application, at t 25 mol% and especially at t 50 mol% of Formula (II) and if present, of Formula (III) carry an acidic / anionic group A, i.e. A is not hydrogen. The acid group in particular is selected from B1-PO (OH) 2 and B1-S (O) 2 OH wherein B1 of Formulas (II) and (III) is the same as defined above and in particular, a single bond. In another embodiment of the application, the acid group is B2-COOH of Formulas (II) and (III) and in particular, CH2-COOH. In a preferred embodiment, the detergent composition contains a modified polyaminoamide of the Formula (IX); (IX) wherein x of Formula (IX) is from 10 to 200, preferably approximately from 15 to 150 and most preferably approximately from 21 to 100. Most preferably, the average value of x of the Formula ( IX) varies between 15 and 70, especially between 21 and 50. In Formula (IX), EO represents ethoxy portions. In another preferred embodiment, the detergent composition contains a modified polyaminoamide wherein the ratio of dicarboxylic acid: polyalkylenepolyamines ranges from 4: 5 to 35:36; the polyalkylene polyamine is quaternized as described in Formulas (a), (b1) and (b2) included above. The process The unmodified polyaminoamide used as a raw material in the process of preparing the modified polyaminoamide for the detergent composition of the present application is generally a condensate of a dicarboxylic acid with a polyalkylene polyamine and optionally with an aliphatic diamine , aromatic or cycloaliphatic. Suitable dicarboxylic acids and derivatives of these amide-forming agents used to prepare the unmodified polyaminoamides are represented by Formula (X): HOOC-R4-COOH (X) R4 of the Formula (X) is the same as that described in Formula (I). Preferably, R4 of Formula (X) is C2-C6 alkanediyl. Preferred dicarboxylic acids are those having between 2 and 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, tartaric acid, maleic acid, itaconic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, acid phthalic and terephthalic acid. Also suitable are dibasic amino acids such as iminodiacetic acid, aspartic acid and glutamic acid. Preferred acids are adipic acid, glutaric acid, aspartic acid and iminodiacetic acid. The dicarboxylic acids can be mixed together. In a particularly preferred embodiment of the application, the dicarboxylic acid is adipic acid. The amide-forming derivatives of dicarboxylic acids suitable for the present invention are anhydrides, esters, amides or acid halides, especially chlorides. Some examples of these derivatives are maleic anhydride, succinic anhydride, phthalic anhydride and itaconic anhydride; adipic dichloride; preferably esters with C? -C2 alcohols, such as dimethyl adipate, diethyl adipate, dimethyl tartrate and dimethyl iminodiacetate; amides, such as adipic acid diamides, adipic acid monoamides and glutaric acid diamide. Preferably, free carboxylic acids or carboxylic anhydrides are used. As used herein, "polyalkylene polyamines" refers to compounds that consist of a saturated hydrocarbon chain with terminal amino functional groups interrupted by one or more secondary amino groups (imino group). Suitable polyalkylene polyamines can be described by Formula (XI): H2N-R3- (NH-R3) n-NH2 (XI) The index n and R3 of Formula (XI) are the same as those described in Formula (I). Suitable polyalkylene polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diaminopropylethylenediamine (N, N'-bis (3-aminopropyl) -1,2-diaminoethane), ethylenepropylenetriamine, 3- (2-aminoethyl) aminopropylamine, dipropylenetriamine, bis (hexamethylene). triamine and polyethyleneimines with molar masses of 300 to 20,000, especially 300 to 5000. Poly-C2-C3-alkyleneamines with 3 to 10 nitrogen atoms are preferred. Among these, diethylenetriamine, 3- (2-aminoethyl) aminopropylamine, dipropylenetriamine and diaminopropylethylenediamine are especially preferred. The polyalkylene polyamines can be mixed together. Suitable aliphatic, aromatic or cycloaliphatic diamines can be described by Formula (XII): NH2-R7-NH2 (XII) R7 of the Formula (Xll) is the same as that described in Formula (VII). When R7 of the Formula (Xll) is selected as the divalent aromatic radical, 1, 2, 1, 3 or 1, 4-phenylene is preferred. The divalent aromatic radical can also carry 1, 2 or 3 substituents selected from C 4 alkyl, C 4 alkoxy, C 3 -C 7 cycloalkyl, halogen, hydroxyl and the like. Preferably, R7 of (Xll) is an alkanediyl of C-i-Ce or a C4-C20 alkanediyl interrupted by 1, 2, 3 or 4 non-adjacent oxygen atoms. Examples of suitable diamines include ethylenediamine, 1,3-propylene diamine, 1,6-hexanediamine, 1,4-diaminocyclohexane, bis- (4-aminocyclohexyl) methane, bis (aminopropyl) methylamine, 4,4'-diaminodiphenylmethane, 1, 4-bis- (3-aminopropyl) -piperazine, 3-oxapentane-1,5-diamine, 3-oxahexane-1,6-diamine, 4,7-dioxadecane-1, 10-diamine 4,8-dioxaundecane-1 , 11-diamine, 4,9-dioxadodecane-1, 12-diamine and 4,7,10-trioxatridecane-1, 13-diamine. The molar ratio of the dicarboxylic acid to the total amount of the polyalkylene polyamine combined with the optional diamine [ie, the molar ratio dicarboxylic acid: (polyalkylene polyamine and optional diamine)] is generally from 2: 1 to 1: 2, preferably from 1 : 1 and 1: 2, more preferably between 1: 1.05 and 1: 1.7 and most preferably between 1: 1.1 and 1: 1.5. In general, the proportion of the diamine does not exceed 50 mol%, preferably 30 mol% of the total molar amount of (polyalkylene polyamine and optional diamine). If convenient, the diamine forms between 1 and 50 mol%, preferably between 5 and 30 mol% of the total molar amount of (polyalkylene polyamine and optional diamine). In a preferred embodiment, the diamine forms up to 5 mol% of the total molar amount of (polyalkylene polyamine and optional diamine).

For this reason, the unmodified polyaminoamides used for elaborate the modified polyaminoamides for the detergent compositions of the present application have a numerical average molecular weight (Mn) of 150 to 50,000, preferably between 250 and 10,000. The unmodified polyaminoamides can be characterized by 1H-, 13C- and 15N-NMR spectroscopy and also by mass spectrometry (MS). MALDl MS can be used to determine the distribution of molecular weights and the type of repeating units. To determine the types of terminal groups can be used NMR Since the structure of the unmodified polyaminoamides is linear, the number average molecular weight can be determined from the ratio of the integrals of the NMR signals. Modification of the unmodified polyaminoamide The modified polyaminoamide for use in the detergent composition of this application can be prepared by the general process consisting of: i) reacting the unmodified polyaminoamide with at least 10 moles per mole of amino hydrogen in the unmodified polyaminoamide of one or more epoxides of the Formula (Xlll) (X? DR ^ wherein R1 and R2 are the same as defined for Formula (II): ii) reacting the modified polyaminoamide of step i) with at least one alkylation moiety [-RX] of the Formula (IV) ) wherein R and X are as defined above in Formula (IV), thereby obtaining a cationically modified polyaminoamide; and iii) optionally, esterifying / etherifying the hydroxyl groups in the cationically modified polyaminoamide obtained in step i) with: (a) sulfuric acid or phosphoric acid or with an ester-forming derivative thereof; or (b) the etherification of the hydroxyl groups in the cationically modified polyaminoamide obtained in step ii) with a compound of the Formula (XIV) L-B3-AS wherein A 'of the Formula (XIV) is selected from -COOH , - S03H and -PO (OH) 2, B3 of the Formula (XIV) is selected from alkanediyl of CrC6; and L of the Formula (XIV) is a leaving group which can be replaced with nucleophiles. Step i) of the process of the application can be carried out analogously to known methods for the alkoxylation of amines. Preferably, the raw material of the unmodified polyaminoamide is reacted in a first step with an epoxide of Formula (Xlll) without a catalyst. A polyaminoamide in which most or all of the amino hydrogens are replaced with a radical CH2-CR1R2-OH, wherein R1 and R2 of Formula (II) are as described above and p of Formula (II) is the same a 1. To obtain modified polyamidoamines with the p-value of Formula (II) greater than 1 greater amounts of epoxide of Formula (Xlll) are used, preferably in the presence of a base as a catalyst. Examples of suitable bases are the alkali metal and alkaline earth metal hydroxides, alkali metal alkoxides, sodium hydride, calcium hydride and alkali metal carbonates. The preferred bases are the alkali metal hydroxides and the alkali metal alkoxides. The amount of base used generally varies between 0.05 and 10% by weight, preferably between 0.5 and 2% by weight, based on the total amount of raw material. The alkoxylated polyaminoamides obtained in step i) are then reacted with an alkylation moiety (step ii). As used herein, the term "alkoxylation moiety" refers to [-RX] of Formula (IV), wherein R and X are identical to those defined above in Formula (IV). See Houben-Weyl, Methoden der organischen Chemie, 4th ed., Vol. XI / 2, p. 608-613. The amount of the alkylation portion determines the amount of quaternization of the amino groups in the main polymer chain, ie the number of quatemized portions shown in Formulas (a), (b1) and (b2). The amount of the alkylation portion usually varies between 0.1 mol and 2 mol, especially between 0.5 mol and 1.5 mol and more preferably between 0.7 mol and 1.2 mol per mol of amino groups in the modified polyaminoamide obtained in step i ). The amount of epoxides used as the alkylating agent usually varies between 0.1 mol and 2 mol, preferably between 0.5 mol and 2 mol and more preferably between 0.7 mol and 1.5 mol per mol of amino groups in the modified polyaminoamide obtained in step i). The modified cationic polyaminoamides thus obtained carry hydroxyl groups as terminal groups of the Formula (II) and if present, in the form of Alk-OH groups of the Formula (III), when A of the Formula (III) is selected as hydrogen. These hydroxyl groups can be esterified in step iii), thus obtaining esterified polyaminoamides wherein A of Formulas (II) and (III) is selected from -PO (OH) 2 and -S (O) 2OH. See W.H. de Groot: "Sulfonation Technology n Detergent Industry" (Sulfonation Technology in the detergent industry), Kluwer Academic Publishers, Dordrecht 1991 (Sulfur trioxide acid); WO 02/12179 (dialkylsulfate); the "Encyclopedia of Industrial Chemistry" of Ullmann, Sixth Edition, the electronic version year 2000 of "SURFACTANTS - Anionic Surfactants" (Kurt Kosswig) -6.3. sulfates and 6.4 phosphates; "THIN-FILM REACTORS - Thin Film Reactors for Industrial Sulfonation" (Thin film reagents - Thin film reagents for use in industrial sulfonation) (Bernhard Gutsche, Christoph Breucker, Günter Panthel); "CHLOROSULFURIC ACID - Chemical Properties" (Chlorosulphuric Acid - Chemical Properties) (Joachim Maas, Fritz Baunack); Stache (Hrsg.), "Anionic Surfactants - Organic Chemistry", S. 647-696, New York: Dekker 1995. These hydroxyl groups can also be etherified with L-B3-A 'compounds of the Formula (XIV) as previously defined. The incorporation of L-B3-A 'of the Formula (XIV) into the terminals of the polyether side chains, especially of a carboxylic acid functional group -B-COOH of the Formulas (II) and (III), can carried out by means of the etherification of the terminal hydroxyl groups with halocarboxylic acids Hal-B2-COOH. { Hal = halogen, especially chlorine or bromine, B2 of Formulas (II) and (III) as defined above, in particular with α-halocarboxylic acids, such as chloroacetic acid. The etherification can be carried out analogously to known methods for producing carboxymethylcellulose (Houben-Weyl E20, p.2072-2076 and Ullman, 5th ed., A5, p.477-478). Surfactants The surfactants useful in the present application may encompass a surfactant or surfactant system comprising those selected from nonionic, anionic, cationic, ampholytic, zwitterionic, non-ionic semi-polar, other auxiliaries such as alkyl alcohols or mixtures thereof. The approximate amount of the surfactant system composed of one or more surfactants contained in the detergent composition of the present application varies between 0.01% and 90%, preferably between 0.01% and 80%, more preferably between 0.05% and 60% and most preferably between 0.05% and 30% by weight of the detergent composition.

Anionic Surfactants: Some non-limiting examples of anionic surfactants useful herein include alkylbenzene sulfonates (LAS) of C-n-C-i; primary alkylsulfates (AS) of branched chain C10-C20 and randomized; secondary alkyl sulfates (2,3) of C? 0-C18; C-io-C-is alkyl alkoxy sulfates (AEXS), wherein preferably x is from 1 to 30; C18 alkyl alkoxy carboxylates which preferably comprise from 1 to 5 ethoxy units; branched half chain alkyl sulfates, such as those described in U.S. Pat. num. 6,020,303 and 6,060,443; branched chain half alkyl alkoxy sulfates, such as those described in U.S. Pat. num. 6,008,181 and 6,020,303; modified alkylbenzene sulfonates (MLAS), as described in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00 / 23549 and WO 00/23548; methyl ester sulfonate (MES); and alpha olefin sulfonate (AOS). Nonionic Surfactants Non-limiting examples of anionic surfactants useful herein include: C 2 -C 8 alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell; C 6 -C 2 alkylphenol alkoxylates, wherein the alkoxylate units are a mixture of ethylene oxide and propylene oxide units; C-? 2-C18 alcohol and C6-C12 alkylphenol condensates with block polymers of ethylene oxide / propylene oxide, such as Pluronic® from BASF; branched half chain alcohols of C14-C22, BA, as described in U.S. Pat. no. 6,150,322; branched half-chain alkyl alkoxylates of C-? -C22, BAEX, where x is from 1 to 30, as described in U.S. Pat. num. 6,153,577, 6,020,303 and 6,093,856; as described in U.S. Pat. no. 4,565,647 (Filling), issued January 26, 1986; specifically the alkyl polyglycosides, as described in U.S. Pat. num. 4,483,780 and 4,483,779; polyhydroxy fatty acid amides, such as described in U.S. Pat. no. 5,332,528 and in WO 92/06162, WO 93/19146, WO 93/19038 and WO 94/09099; and ether poly (oxyalkylate) alcohol surfactants, such as described in U.S. Pat. no. 6,482,994 and in WO 01/42408. Attachments and Detergent Methods for Use A detergent aid is usually a material necessary to transform a detergent composition containing only the minimum essential ingredients into a detergent composition useful for laundry or for personal, commercial or industrial cleaning. In certain embodiments, the detergent adjuncts are easily recognizable by experts in the technical field since they are completely characteristic of detergent products, especially detergent products for direct use by a consumer in a domestic environment. The precise nature of these additional components, and the levels of incorporation of these will depend on the physical form of the detergent composition and on the nature of the cleaning operation in which they will be used.

In the case that the adjunct detergent ingredients are used with some bleach they should have a good stability with it. Certain embodiments of the detergent compositions of the present invention should be free of boron and / or free of phosphates as required by law. The levels of detergent adjuncts are from about 0.00001% to 99.9% by weight of the detergent compositions. The levels of use of the total detergent compositions can vary widely, which depends on the intended application, varying, for example, from a few ppm in the solution to the so-called "direct application" of the simple detergent composition to the surface that is will clean Very commonly, the detergent compositions of the present invention, such as laundry detergents, additives for laundry detergents, hard surface cleaners, laundry bars based on soap or synthetics, fabric softeners, liquids and solids for the treatment of fabrics and articles for treatment of all kinds that will require various attachments, although certain products simply formulated, such as Whitening additives may only require, for example, an oxygenated bleaching agent and a surfactant, as described in the present invention. A complete list of cleaning and laundry auxiliary methods and materials that are considered suitable can be found in WO 99/05242.

Auxiliary Materials Common auxiliaries include additives, enzymes, enzyme stabilizing agents, bleaches, bleach activators, catalytic materials and similar polymers to the exclusion of any material already defined herein as part of the essential component of the compositions of the invention. Other adjuncts, suitable for the present invention, may include foam potentizers, suds suppressors (antifoaming agents) and the like, various active ingredients or specialized materials, such as, for example, dispersing polymers (eg, provided by BASF Corp. or Rohm). &Haas) different from those described above, colored specks, anti-corrosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, antioxidants, perfume precursors, perfumes, solubilizing agents, carriers, process aids, pigments and for liquid formulations, solvents, chelating agents, dye transfer inhibiting agents, dispersants, brighteners, suds suppressors, dyes, structure-elasticizing agents, fabric softeners, anti-abrasion agents, hydrotropes, process aids and other agents for the care of fabrics. Suitable examples of these auxiliaries and concentrations of use are indicated in U.S. Pat. num. 5,576,282, 6,306,812 B1 and 6,326,348 B1. Additive Preferably, the detergent compositions of the present application contain one or more additives or detergent additive systems. The typical concentration of the detergent additive in the compositions varies from at least about 1%, preferably about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably about 30% in weight. The additives include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth metal and alkali metal carbonates, aluminosilicate additives, polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethioxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid and also polycarboxylates such as melific acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Enzymes The concentration of pure enzymes in detergents generally varies between 0.0001% and 2%, preferably between 0.001% and 0.2% and more preferably between 0.005% and 0.1% by weight of the composition. The detergent compositions may contain one or more of the following enzymes: proteases, amylases, cellulases, lipases, cutinases, esterases, carbohydrases for example mannanase, pectate lyase, cyclomaltodextringlucanotransferase and xyloglucanase. Bleaching enzymes with potentiators include, for example, peroxidases, laccases, oxygenases, (for example catechol 1,2 dioxygenase, lipoxygenase (WO 95/26393), haloperoxidases (non-heme), It is a common practice to modify the wild-type enzymes by of protein / genetic engineering techniques to optimize their performance in detergent compositions Enzyme Stabilizers Enzymes can be stabilized using any known stabilizing system, such as calcium or magnesium compounds, boron compounds and substituted boric acids, borate aromatic esters, peptides and derivatives of peptides, polyols, low molecular weight carboxylates, relatively hydrophobic organic compounds [eg, some esters, dialkyl glycol ethers, alcohols or alcohol alkoxylates], alkyl ether carboxylate in addition to a source of calcium ion, hypochlorite benzoamidine, carboxylic acids and lower aliphatic alcohols Carboxylic acids and acids, N, N-bis (carboxymethyl) serine salts; copolymer of (meth) acrylic acid-ester of (meth) acrylic acid and PEG; composed of lignin, oligomer of polyamide, glycolic acid or its salts; polyhexamethylene biguanide or N, N-bis-3-amino-propyl-dodecylamine or salt; and mixtures of these. The degradation of secondary enzymes by means of the proteolytic enzyme in a liquid matrix can be avoided by using reversible protease inhibitors [for example, of the peptide or protein type, in particular the modified inhibitor of subtilisin of the family VI and plasminoestrepine; leupeptin, peptide trifluoromethyl ketones, peptide aldehydes.

Bleach Suitable bleaching agents for use in the detergent composition of the present application may be selected from the group consisting of catalytic metal complexes, activated sources of peroxide compound, bleach activators, bleach boosters, photobleaching agents, free radical initiators and hypohalide bleach. U.S. Patent Nos. num. 5,576,282 and 5,597,936. Suitable MRLs of transition metals are prepared rapidly by known procedures such as those described for example in WO 00/332601 and in U.S. Pat. no. 6,225,464. Suitable activated peroxide compound sources include, but are not limited to, preformed peracids, a source of hydrogen peroxide combined with a bleach activator or a mixture thereof. Suitable preformed peracids include, but are not limited to, compounds selected from the group comprising salts and percarboxylic acids, salts and percarbon acids, salts and perimidic acids, salts and peroxymonosulfuric acids and mixtures thereof. Suitable sources of hydrogen peroxide include, but are not limited to, compounds selected from the group comprising perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof. Suitable types and concentrations of activated sources of peroxide compound are included in U.S. Pat. num. 5,576,282; 6,306,812 B1; and 6,326,348 B1, incorporated herein by reference.

Suitable bleach activators include, but are not limited to, perhydrolyzable esters and perhydrolysable imides such as tetraacetylethylenediamine, octanoylcaprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylvalerolactam, dodecanoyloxybenzenesulfonate. Suitable bleach builders include but are not limited to those described in U.S. Pat. no. 5,817,614. For practical reasons and not in the form of limitation, the detergent compositions and cleaning processes herein can be adjusted to provide at least about one part in one hundred million catalytic metal complex in the aqueous wash. When sources of hydrogen peroxide are included, their approximate concentration generally ranges between 1% and 30% by weight of the detergent composition. When peracids or bleach activators are included, their approximate concentration generally ranges between 0.1% and 60% by weight of the detergent composition. For practical reasons and not in the form of limitation, the detergent compositions and cleaning processes herein can be adjusted to provide at least about one part in one hundred million of the bleach enhancer in the aqueous wash. Method of use The present application includes a method for cleaning a site, for example a surface or fabric. These methods include the steps of contacting a mode of the applicant's detergent composition in simple or diluted form in a scrubbing liquid, with at least a portion of a surface or fabric, then rinsing this surface or fabric. The surface or fabric is preferably washed before the rinsing step. For the purposes of the present application, washing includes but is not limited to scrubbing and mechanical agitation. As will be appreciated by one skilled in the industry, the detergent compositions of the present application are ideally suited for use in laundry applications. Accordingly, the present application includes a method for washing fabrics. The method includes the steps of placing the fabric to be washed in contact with a laundry solution comprising at least one embodiment of a detergent composition, cleaning additive or mixture thereof comprising the present application. Any fabric that the consumer usually launders under normal conditions can be used. The approximate pH of the solution preferably ranges from 8 to 10. The approximate concentration of the composition in the solution ranges from 500 ppm to 10., 000 ppm. Water temperatures preferably range from about 5 ° C to about 60 ° C. The water to fabric ratio is preferably from about 1: 1 to about 20: 1. Test methods The amine number is determined according to the method described in DGF Einheitsmethoden-Abteilung H-Tenside, Methode H-lll 20a (98) "Potentiometrische Titration des Gesamtbasenstickstoffs von Tensiden" (DGF standard methods - section H - surfactants , method H-lll 20a (98) "Potentiometric titration of the total basic nitrogen I surfactants"). The acid number is determined according to the method described in Europáisches Arzneibuch 4. Ausgabe 2002 S. 127 (Pharmacopoea Europaea, 4. ed. 2002, page 127) or DGF Einheitsmethoden - Abteilung C -Fette, Methode CV (DGF standard methods - section F - fats, method CV) Alkylation is tested by means of the procedure described in R. Preussmann et al. Arzneim.-Forschung 19, 1059 (1969). Synthesis examples Step I. Synthesis of unmodified polyaminoamides Charge a polyalkylene polyamine at room temperature (15-20 ° C), in a 2-liter round-bottomed glass flask equipped with a distillation bridge. Purge the reactor with nitrogen and add x g (x is defined later in Table 1) of deionized water. The temperature will rise to approximately 50 ° C. Heat the mixture to 60 ° C and add adipic acid within 5 minutes. The temperature will rise to approximately 100 ° C. Heat the reaction mixture to 120 ° C and stir one hour at this temperature. Slowly increase the temperature to 180-190 ° C and distill off the water and the unreacted amine for at least 3 hours until the quantity of condensed water has reached at least the theoretical value for a fully condensed product and the acid number is less than 10 mg KOH / g. Cool the reaction mixture to a temperature of 120 ° C to 180 ° C and dilute it with yg (and defined below) of deionized water to produce a white or slightly yellow polyaminoamide solution with an active content of 60 to 90% in weigh. The product is a liquid of high viscosity or a solid depending on the active content, the degree of condensation and the identity of the amine and the acid component. The raw material and the quantities used are indicated in Table 1.

TABLE 1 1 diethylenetriamine: diethylenetriamine, N4-amine: N, N'-bis (3-aminopropyl) ethylene diamine Step II. Alkoxylation of the unmodified polyaminoamide Option 1. Reaction with 1 mole of ethylene oxide per mole of NH groups Charge the aqueous solution of the polyaminoamide in a 2 L metal reactor and make it inert by applying 300 to 500 kPa (3 to 5) bar) of nitrogen 3 times. Heat the reactor contents to 90-130 ° C and add the required amount of ethylene oxide in portions (the total amount is equimolar to the amino hydrogens present in the polyaminoamide) so that the pressure increases slowly. Increase the pressure further by adding nitrogen to a pressure of 500-800 kPa (5-8 bar) and then stir the reaction mixture at 90-130 ° C until the pressure remains constant. Cool the reaction mixture to 70-80 ° C. Wash the reactor with 300 kPa (3 bar) of nitrogen and remove the residual ethylene oxide in a rotary evaporator. The resulting alkoxylated polyaminoamide is yellow or light brown and the product is a liquid of high viscosity or a solid depending on the active content, the degree of condensation and the identity of the amine and the acid component. Option 2. Methods A to C Method A: Obtain the aqueous solution of the modified polyaminoamide in accordance with step I, charge the catalyst and the xylene in an inert 2 I metal reactor as described above in option 1. Heat the mixture to 130-160 ° C under a stream of nitrogen to remove water from the reaction mixture. Cool the reactor contents to 120-150 ° C and then add portions of ethylene oxide so that the pressure increases slowly. Increase the pressure further by adding nitrogen to a pressure of 500-800 kPa (5-8 bar). Stir the reaction mixture at 120-150 ° C until the pressure remains constant. Cool up to 80 ° C. Wash the reactor with 300 kPa (3 bar) of nitrogen to remove the residual ethylene oxide. Eliminate xylenes at 120 ° C by introducing 400 kPa (4 bar) of hot stream. The obtained alkoxylated polyaminoamide is a dark brown aqueous solution with an active content of 67% and a pH of 10.5.

Method B: Obtain the aqueous solution of the polyaminoamide according to step 1 and mix the catalyst. Remove water and other volatile components at 80-120 ° C at reduced pressure. Charge the mixture in an inert 2 I metal reactor as described above in option I. Add the alkylene oxide in portions at 120-150 ° C so that the pressure increases slowly. Increase the pressure even more by adding nitrogen to a pressure of 500-800 kPa (5-8 bar). Shake the reaction mixture to 120-150 ° C until the pressure remains constant. When different alkylene oxides are added gradually, a minimum period of 2 hours must pass during which the pressure remains constant after the addition of each alkylene oxide and before adding the following alkylene oxide. After adding all the alkylene oxides, cool to 80-90 ° C. Wash the reactor with 300 kPa (3 bar) of nitrogen and remove the residual ethylene oxide (alkylene oxide) in a rotary evaporator. Method C: Remove water from the aqueous solution of the polyaminoamide obtained according to step 1 at 80-120 ° C under reduced pressure. Cool the mixture to 50 ° C and add the catalyst under a nitrogen atmosphere. Remove volatile compounds from the mixture at 80-120 ° C under reduced pressure. Charge the mixture in an inert 2 I metal reactor as described above in option I. Add the alkylene oxide in portions at 120-150 ° C so that the pressure increases slowly. Increase the pressure further by adding nitrogen to a pressure of 500-800 kPa (5-8 bar). Stir the reaction mixture at 120-150 ° C until the pressure remains constant. Cool to 80-90 ° C. Wash the reactor with 300 kPa (3 bar) of nitrogen and remove the residual ethylene oxide in a rotary evaporator. The raw materials and the amounts used for the modified polyaminoamides obtained are indicated in Table 2.

TABLE 2 1) modified polyaminoamide from step I. 2) unmodified polyaminoamide raw material in accordance with step I used in option I 3) amount of polyaminoamide obtained in accordance with step 1 as an aqueous solution 4) EO = ethylene; PO = propylene oxide 5) mol of alkylene oxide per mole of hydrogen atoms bound to the amino in the unmodified polyaminoamide Step III. Quaternization (Examples 1 to 7): a) Reaction with dimethisulphate Example 1: (polyaminoamide D1: PETA: AA 20:19) + 24 mol EO / NH 75% methylcuat [% nitrogen in amino quaternized with methyl groups]) Obtain 390 g of the aqueous solution of the modified polyaminoamide C1 in accordance with step II (66% active content). Charge the modified polyaminoamide in a 0.5 ml reaction flask in a nitrogen atmosphere. Heat the mixture to 60-70 ° C and add 25.3 g of dimethisulfate (1 mole per mole of amino groups) in portions within 4 hours. Maintain the reaction mixture at 60-70 ° C until the Preussmann test is performed to determine that the alkylation of the substances is negative. A modified polyaminoamide with a degree of quaternization of 75% (calculated from the amine number) is obtained with the appearance of a dark brown liquid with a pH of 5.5.

Examples 2 to 6: general procedure (modified polyaminoamides D2 to D6) Obtain the resulting modified polyaminoamide according to step II (100% active content). Charge the polyaminoamide in a 1 L reaction flask in a nitrogen atmosphere. Heat the mixture to 60 ° C and add dimethisulfate in portions which produces an approximate increase in temperature to 70 ° C after the first addition of the largest amount of dimethisulfate. Keep the reaction mixture at 70 ° -80 ° C until the result of the Preußmann test is negative. A modified polyaminoamide with a degree of quaternization greater than 90% (calculated from the number of amine) is obtained with the appearance of a dark brown viscous solid or liquid with an acidic pH. The raw material and the amount of dimethisulfate used is included in Table 3.

TABLE 3 calculated from the amine number b) Quaternization with benzyl chloride Example 7: (polyaminoamide D7: [N4-Amin: AA 3: 2] + 24 EQ / NH 68% Benzilcuat f% nitrogen in the amino quaternized with benzyl groups]) Obtain 365 g of the modified polyaminoamide C7 prepared in accordance with step II (100% active content). Charge the polyaminoamide in a 1 L reaction flask in a nitrogen atmosphere and dilute with 56.4 g of distilled water. Heat the solution to 90 ° C and add 28.6 g of benzyl chloride (0.75 mol per mol of amine functional groups) within 15 minutes. Maintain the reaction mixture 90 minutes at 90 ° C and then add 2.5 g of a 50% by weight aqueous sodium hydroxide solution. Stir the reaction mixture at 90 ° C for a further 3 hours. To destroy residual benzyl chloride, add a solution of 4.7 g of sodium acetate in 38 g of distilled water to the reaction mixture and stir the obtained mixture for a further 4 hours at 90 ° C. Step IV Introduction of acid groups (Examples 8 to 14) a) Tras-sulfation process Examples 8 to 11: general procedure (modified polyaminoamides E1, E3, E5 and E6) Obtain the modified polyaminoamide D1, D3, D5 or D6 according to Examples 1, 3, 5 and 6 of step III (as an aqueous solution or material with an active content greater than 98%). Introduce the polyaminoamide in a 1 l reaction flask in a nitrogen atmosphere and heat to 60 ° C. Add concentrated sulfuric acid in portions, thus lowering the pH of the mixture to 2.4 or less. Stir the reaction mixture 3 hours at 90 ° C, at a pressure of 2 kPa (20 mbar) or less, passing nitrogen through the mixture to remove the water and the methanol formed. Decompress with nitrogen and cool to 60 ° C. Add zg (z defined below) of a 50% by weight aqueous sodium hydroxide solution in portions to obtain the product as a brown aqueous solution (active content greater than 95% by weight) with a pH of 8 to 9. The product is a high viscosity liquid or a waxy solid. The type of raw material and the relative amounts of reactants are indicated in Table 4.

TABLE 4 b) Sulphation with sulfuric acid Example 12: Synthesis of E2: [DETA: AA1Q: 9] + 44 EO / NH, 93% methylcuat, 100% sulfation: Obtain 202 g of the modified polyaminoamide D2 prepared according to Example 2 of step III. Place it in a 0.5 L reaction flask in a nitrogen atmosphere and heat to 60 ° C. Add 4 g of concentrated sulfuric acid and stir the reaction mixture for 8 hours at 90 ° C and at a pressure of < 2 kPa (20 mbar) passing nitrogen through the mixture to remove the methanol and the condensation water formed. Decompress with nitrogen and cool to 60 ° C. Adjust the pH to 8.5 by adding an aqueous solution of 50% by weight sodium hydroxide. The product is obtained as a brown liquid of high viscosity. c) Reaction with polyphosphoric acid Examples 13 and 14, general procedure (modified polyaminoamides E4 and E7) Obtain the modified polyaminoamide D4 or D7 prepared according to Examples 4 and 7 of step III. Introduce the polyaminoamide in a reaction flask of 0.25-0.5 I in a nitrogen atmosphere and heat to 65 ° C. (For example, water from E7 evaporated first.) Add polyphosphoric acid within 10 to 30 minutes and at the same time increase the temperature to 75 ° C. Stir 6 hours at 75 ° C. The product is obtained as a dark brown waxy solid with a pH of 2 to 3.5. The amount of reactants and the degree of phosphating are included in Table 5.

TABLE 5 polyphosphoric acid An example of a suitable detergent composition, indicated as LD5, is included in Table 6. LD4 is included as a reference detergent composition.

TABLE 6 "One or more polymers in accordance with U.S. Patent No. 4,891, 160 to VanderMeer et al 2 One or more polymers in accordance with WO 00/105923 of Price et al., Polymer in accordance with any of the examples of polyaminoamide of the present application included above.

All documents cited in the Detailed Description of the invention are, in their relevant part, incorporated herein by reference.

The mention of any document should not be construed as an admission that it corresponds to a prior industry with respect to the present invention. While specific embodiments of the present application have been illustrated and described, it will be apparent to those skilled in the industry that various changes and modifications may be made without departing from the spirit and scope of the application. Therefore, it has been intended to cover all possible changes and modifications within the scope of this application in the appended claims.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. A detergent composition comprising: (I) from about 0.01% to about 90% by weight of the detergent composition, of a surfactant system; (II) from about 0.01% to about 20% by weight of the detergent composition, of a modified polyaminoamide comprising Formula (I) (0 wherein n of Formula (I) is an integer from 1 to 500; R3 of formula (I) is selected from a C2-C8 alkanediyl, preferably, 1,2-ethanediyl or 1,3-propanediyl; of the formula (I) is selected from a chemical bond, C -? - C20 alkanediyl, C -? - C20 alkanediyl comprising 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, alkanediyl of CrC2o comprising 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical and mixtures thereof, wherein Formula (I) comprises secondary amino groups of the polymer backbone, the amino hydrogens are selectively substituted in the modified polyaminoamide such that the modified polyaminoamide comprises partial quaternization of the secondary amino groups by selectively replacing at least one hydrogen from the amino or with at least one alkoxy entity of the Formula (II): - (CH2-CR1R2-0-) pA (II) wherein A of the Formula (II) is selected from hydrogen or an acid group; the acid group is selected from B1-PO (OH) 2, -B1-S (0) 2OH and -B2-COOH; such that B 1 of Formula (II) is a single bond or alkanediyl of C-i-Cd, 'and B2 of Formula (II) is an alkanediyl of CrC6; R of Formula (II) is independently selected from hydrogen, C 1 -C 2 alkyl, C 2 -C 8 alkenyl, C 6 -C 6 aryl or C 6 -C 16 aryl C 1 -C 4 alkyl; R2 of Formula (II) is independently selected from hydrogen or methyl; and p of Formula (II) is an integer comprising an average of at least 10; the rest of the amino hydrogens of the secondary amino groups is selected from the group comprising electron pairs, hydrogen, C6 alkyl, C6-Ci6 aryl, d-C4 alkyl and Alk-OA of the formula (III) , wherein: A of the Formula (III) is hydrogen or an acid group; the acid group is selected from B1-PO (OH) 2, -B1-S (0) 2OH and -B2-COOH; such that B1 of Formula (III) is selected from a single bond or an alkanediyl of CrC6; and B2 of Formula (III) is selected from C6 alkanediyl and Alk of Formula (III) is C2-C6-1, 2-diyl alkane; secondary amino groups of Formula (I) are also selected to contain at least one alkylation moiety of Formula (IV): -RX (IV) wherein R of Formula (IV) is selected from the group consisting of : C?-Cß alkyl, C 6 -C 16 aryl-C 4 alkyl and Alk-OA of the formula (III), and - (CH 2 -CR 1 R 2 -O-) pA of the formula (II); and X of Formula (IV) is a leaving group selected from a halogen, an alkyl-halogen, a sulfate, an alkylsulfonate, an arisulfonate, an alkyl sulfate and mixtures thereof.

2. The detergent composition according to claim 1, further characterized in that the modified polyaminoamide also comprises aliphatic, aromatic or cycloaliphatic diamines to produce the general Formula (VII): (VI) wherein R3, R4 and n of Formula (VI) are the same as in Formula (I); R7 of the Formula (VI) is a divalent organic radical carrying from 1 to 20 carbon atoms, alkanediyl of CrC20 comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen; alkanediyl of CrC2o, alkanediyl of C? -C2u comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical and mixtures thereof.

3. The detergent composition according to claim 1 or 2, further characterized in that the modified polyaminoamide also comprises an esterification portion of the alkoxy portion, the alkylation portion and mixtures thereof, provided there is a hydroxyl group in the alkoxy portion and in the alkylation portion.

4. The detergent composition according to claim 3, further characterized in that the esterification portion is selected from chlorosulfonic acid, sulfur trioxide, amidosulfonic acid, polyphosphate, phosphoryl chloride, phosphorus pentoxide, and mixtures thereof.

5. The detergent composition according to claim 1 or 2, further characterized in that the polyaminoamide comprises primary amino groups of the main polymer chain 6.

The detergent composition according to claim 5, further characterized in that the primary amino groups of the main polymer chain comprises modified amino hydrogens since they comprise at least one alkoxy portion of Formula (II) and the rest of the amino hydrogens of the secondary amino groups are also modified with some element from the group consisting of electron pairs , hydrogen, alkyl CrC6, aryl of C6-C-? 6-alkyl of d-C4 and Alk-OA of the formula (III) and the primary amino groups are also modified since they comprise at least one portion of alkylation of the Formula (II) 7.

The detergent composition according to claim 6, further characterized in that the modified polyaminoamide also en comprises an esterification portion of the alkoxy portion, the alkylation portion and mixtures thereof when the alkoxy portion and the alkylation portion comprise a hydroxyl group.

The detergent composition according to claim 6, further characterized in that the modified polyaminoamide also comprises an etherification portion of the alkoxy portion, the alkylation portion and mixtures thereof when the alkoxy portion and the alkylation portion comprise a group hydroxyl

9. The detergent composition according to claim 8, further characterized in that the etherification portions are selected from L-B3-A 'of the Formula (XV), wherein A' of the Formula (XV) is selected from -COOH , -S03H, and -PO (OH) 2, B3 of the Formula (XV) is selected from alkanediyl of d-C6; and L of the Formula (XV) is a leaving group that can be replaced with nucleophiles.

10. The detergent composition according to claim 1, further characterized in that it additionally comprises from about 1% to about 80% of a weight additive of the detergent composition.

11. The detergent composition according to claim 1, further characterized in that the detergent composition is a laundry detergent composition.