MXPA01005245A - Process for forming a cleaning composition - Google Patents

Abstract

The present invention relates to a process for forming a cleaning composition containing the steps of providing at least one alkaline material and at least one acid active, and adding the acid active and the alkaline material to a mixer. The acid active is substantially neutralized within the mixer to form a neutralized detergent active. At least one acid-sensitive polymer is added to the neutralized detergent active to form a slurry, and the slurry is formedinto a cleaning composition. A cleaning composition as formed by the above process is also described herein.

Description

PROCEDURE TO FORM A COMPOSITION FOR CLEANING FIELD OF THE INVENTION The present invention relates to a process for making a cleaning composition, and a cleaning composition made by said process. Specifically, the present invention relates to a process for making a cleaning composition containing a polymer and a cleaning composition containing said polymer formed by said process.

BACKGROUND OF THE INVENTION A cleaning composition, especially a laundry composition, will typically contain an acid species present during the production process. For example, the production process can use the acidic form of an anionic surfactant, which is neutralized during the production process. Although certain anionic surfactants may be added as a preneutralized surfactant, in certain locations, said preneutralized surfactant may be either unavailable, of unreliable quality, or excessively expensive. Accordingly, a typical production process adds an acidic active, and neutralizes it therein.

The polymers are commonly added to a cleaning composition to provide soil dispersion properties, anti-redeposition properties, fabric modification properties, etc. Such polymers can, for example, complex with soils to remove clothes, capture dirt to reduce redeposition, and bond to the fabric to provide a smooth feel. One type of polymer that is especially useful in a cleaning composition is a modified polyamine polymer. Said modified polyamine polymer typically provides one or more of the desirable properties discussed above. Specifically, said modified polyamine polymer can provide, for example, improved soil dispersion, anti-redeposition, and cloth modification properties. The modified polyamine polymer may contain, for example, additional charged or uncharged groups connected to a polymer base structure. The desirable properties of these polymers typically depend on their molecular weight and the properties of any chemically modified groups adhered thereto. Said polymers, and especially the modified polyamine polymers, are typically expensive in comparison to other detergent ingredients and are therefore typically used at relatively low concentrations. However, the properties noted above are typically concentration dependent; while the concentration of the polymer is greater, it is more great the desired effect. In this way, it is desirable to add an effective concentration of the polymer, and yet maintain this concentration low enough so as not to excessively increase the cost of formulating the cleaning composition. Accordingly, a need remains for a process that incorporates a polymer in a cleaning composition at a concentration that maintains polymer properties and performance profiles without increasing formulation costs.

BRIEF DESCRIPTION OF THE INVENTION It has been discovered that an acidic active present in a detergent production process can degrade certain polymers, causing them to disintegrate into lower molecular weight fragments which are significantly less effective in providing the desired polymer properties. Said polymer is therefore described herein as an "acid sensitive polymer". Thus, the present invention relates to an improved process for forming a cleaning composition containing an acidic active and an acid-sensitive polymer, which reduces the degradation of the acid sensitive polymer and results in polymer properties and performance profiles. maintained without increasing formulation costs.

The present invention relates to a process for forming a cleaning composition containing the steps of providing at least one alkaline material and at least one acidic active and adding the active acid and the alkaline material to a mixer. The acidic active is substantially neutralized within the mixer to form a neutralized detergent active. At least one acid-sensitive polymer is added to the neutralized detergent active to form a suspension, and the suspension is formed in a detergent composition. Also described herein is a cleaning composition as formed by the aforementioned process. These and other features, aspects, and advantages of the present invention will be apparent to those skilled in the art from a reading of the present disclosure with the appended claims.

DETAILED DESCRIPTION OF THE INVENTION In accordance with the present invention it has been discovered that a cleaning composition can utilize an acidic active and an acid sensitive polymer and yet avoid degradation of the acid sensitive polymer induced by acid. Since there is no need to add extra sensitive polymer in order to compensate for the expected degradation, this improved process maintains the yield profile and benefits of the polymer without increasing formulation costs. This procedure Improved degradation reduces, and therefore improves the effectiveness of a given amount of acid sensitive polymer. All percentages, ratios and proportions herein are by weight of the composition for final cleaning, unless otherwise specified. All temperatures are in degrees Celsius (° C), unless specified otherwise. All the cited documents are incorporated herein by reference. As used herein, the term "alkyl" means a hydrocarbyl portion which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl portions are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds. Included in the term "alkyl" is the alkyl portion of acyl groups. The term "substantially neutralized", as used herein, indicates that at least 50%, preferably at least 80%, and more preferably at least 85% of the acidic active, is weight, has been neutralized. In accordance with the present invention, it has been recognized that an acidic active present in a typical cleaning composition production process can degrade certain polymers, causing them to disintegrate into lower molecular weight fragments that are significantly less effective. Said polymer is therefore described herein as an "acid sensitive polymer". Without wishing to be limited by theory, it is believed that an acidic active can react with the polymer acid sensitive to cause it to degrade, or otherwise lose its effectiveness in the formulation for cleaning. For example, an acidic active can react with an active group on the acid sensitive polymer to reduce the properties of the acid sensitive polymer in the cleaning composition. In another example, an acidic active can react with the base structure of the acid sensitive polymer to hydrolyze it and disintegrate it into smaller fragments that are significantly less effective in a cleaning composition. The present process also reduces the undesirable polymerization of the acid sensitive polymer. Without wishing to be bound by theory it is believed that certain acid sensitive polymers can undesirably form homopolymers or copolymers when exposed to acid. Such undesirable polymerization can destroy or reduce the effectiveness and yield profile of the polymer in the final composition. Accordingly, in the process of the present invention it reduces said undesirable reactions by substantially neutralizing the acidic asset before adding the acid-sensitive polymer. Additionally, this improved procedure also provides additional benefits. For example, since acid sensitive polymers are typically expensive, the present invention reduces formulation costs by requiring the addition of less acid sensitive polymer to provide the same beneficial effects. On the contrary, since the beneficial effects of said acid sensitive polymers typically depend on their concentration in the cleaning composition, the present process improves the overall effectiveness of a given level of acid sensitive polymer. In the process of the present invention, at least one alkaline material is provided with which to neutralize the acidic active. The alkaline material can be any of those useful in a cleaning composition, and especially a laundry composition. The alkaline material is typically selected from metaalkaline and alkaline earth metal salts of, for example, carbonate, phosphate, silicate, layered silicate, hydroxide and mixtures thereof. Preferred examples of the carbonate useful herein include the bicarbonates and sesquicarbonates, more preferably, sodium carbonate (i.e., soda ash), potassium carbonate, and mixtures thereof. Where permitted, alkali metal and alkaline earth metal phosphates are especially useful herein since they serve the dual purpose of acting as an alkaline material, as well as a builder. If present, the detergency builder can assist in controlling mineral hardness and removal of particulate soils. Preferred phosphates useful herein include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric meta-phosphates), phosphonates, and mixtures thereof. The alkali metal silicate and alkali metal noterreous and the layered silicate are also useful herein. Examples of breeders Silicate detergency are the alkali metal silicates, particularly those that have a ratio of Si? 2: Na2? in the scale of 1.6: 1 to 3.2: 1 and layered silicates, such as the sodium layered silicates described in the U.S. patent. 4,664,839, issued May 12, 1987 to Rieck. NaSKS-6 is the trademark for a stratified crystalline silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). NASKS-6 has the form of laye-Na2SiO5 morphology of stratified silicate. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix? 2x +? - and H 2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Several other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS- 11, as the alpha, beta and gamma forms. As noted above, the delta Na 2 SiO (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crisp agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component for foam control systems. The hydroxide useful herein is preferably sodium hydroxide, as used in a caustic neutralization process. Typically, an aqueous solution of caustic sodium hydroxide is added to the mixer, in order to neutralize the acidic active.

The alkaline material useful herein is typically provided in the cleaning composition in at least one sufficient stoichiometric molar ratio to completely neutralize the acidic active. Typically, the alkaline material is in stoichiometric excess. The stoichiometric molar ratio of alkaline to acidic material is at least 1: 1, preferably at least 1.2: 1. In certain processes, such as agglomeration processes, this stoichiometric molar ratio of alkaline material to acidic active can reach 8: 1, or more. The present process also provides at least one acidic active which is added to the mixer and neutralized by the alkaline material. The active acid useful herein is typically the acid form of an anionic surfactant. The anionic surfactant useful herein typically includes the acidic forms of sulphonated surfactants and sulfonated surface active materials. Acid forms of conventional Cu-Cie alkylbenzene sulfonates are especially useful herein. Said alkylbenzene sulphonates may be the branched alkyl sulfonates, the linear alkylbenzenesulfonates ("LAS") or mixtures thereof. Typically, the sulfuric and / or sulfonic acid form of the anionic surfactant is provided. For example, to provide linear alkylbenzenesulfonate in the final cleaning composition, alkylbenzenesulfonic acid can be provided and neutralized in the present process.

The present method includes the step of adding the acidic active and the alkaline material to a mixer. The acidic active is then neutralized substantially within the mixer to form a neutralized detergent active. Types of mixers useful herein include commercially available intermittent suspension mixers (also called a "holding" mixer), or any other type of liquid mixer. Said mixers can be operated continuously, for example, in a multi-stage process. The processing described herein can be performed in a single mixer, or in multiple mixers as desired. The active acid useful herein is typically provided at levels of from 10% to about 65%, preferably from 12% to about 45%, and more preferably from 15% to about 35%, by weight of the composition for final cleaning. In a preferred embodiment of the process described herein, the sodium silicate is added to the neutralized detergent active prior to adding the acid sensitive polymer. Without wishing to be bound by theory, it is believed that this ensures an alkaline environment, so as to further prevent any form of residual acidic asset from degrading the acid sensitive polymer. An acid sensitive polymer is also provided herein. The acid sensitive polymer useful herein, reacts with an acidic active to reduce the effectiveness of the acid sensitive polymer in the composition for cleaning. As noted above, this reduction in effectiveness can result, for example, from chemical modification of the active groups of the acid sensitive polymer, from current fragmentation of the base structure of the acid sensitive polymer, etc. Preferred acid-sensitive polymers useful herein include soil dispersion polymers, anti-redeposition polymers and fabric conditioning polymers, and mixtures thereof. The most preferred classes of polymers useful herein include modified polyamine polymers, polyacrylate polymers, acrylic and maleic acid copolymers, and mixtures thereof. Modified polyamine polymers are especially preferred herein as an acid sensitive polymer. These polymers have shown a high susceptibility to acid-induced degradation when added with an acidic active in the normal agglomeration process. These modified polyamine polymers are even more preferably modified polyethylene imine polymers comprising either linear or cyclic base structures. The polyamine base structures may also comprise polyamine branching chains 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 purposes of the present invention, the term "modification" is defined as replacing a hydrogen atom base structure -NH by an E unit (substitution), quaternizing a nitrogen base structure (quaternized) or oxidizing a base structure from nitrogen to N-oxide (oxidize). The terms "modification" and "substitution" are used interchangeably when referring to the procedure of replacing a hydrogen atom adhered to a nitrogen base structure with an E unit. Quaternization or oxidation may take place in some circumstances without substitution, but substitution is preferably achieved by oxidation or quaternization of at least one nitrogen base structure. The linear or non-cyclic polyamine base structures comprising the modified polyethylene imine polymers of the present invention have the general formula: said base structures before subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by "chaining" units R. The base structures of cyclic polylamines comprising the modified polyethyleneimine polymers of the present invention have the general formula: said base structures prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by "chaining" units R. For purposes of the present invention, primary amine nitrogens comprising the base structure or branching chain once modified they are defined as "terminal" units V or Z. For example, when a portion of primary amine, located at the end of the main polyamine base structure or branch chain having the structure: H2N-R] - is modified in accordance with the present invention, is thereafter defined as a "terminal" unit V, or simply a unit V. However, for purposes of the present invention, some or all of the primary amine portions may remain unchanged. modification subject to the restrictions that are further described below. Those unmodified primary amine portions by virtue of their position in the base structure chain remain as "terminal" units. Similarly, 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 then defined as a "terminal" Z unit, or simply a Z unit. This unit can remain unchanged subject to the restrictions that are further described below. In a similar manner, the secondary amine nitrogens comprising the base structure or branching chain once modified are defined as units of "base structures" W. For example, when a secondary amine portion, the main constituent of the base structures and branching chains of the present invention, having the structure: H - [N-R] - is modified according to the present invention, is defined thereafter as a "base structure" unit W, or simply a unit W.

However, for purposes of the present invention, some or all of the secondary amine portions may remain unchanged. These unmodified secondary amine portions by virtue of their position in the base structure chain remain as "base structure" units. In a further similar manner, the tertiary amine nitrogens comprising the base structure or the branching chain once modified are further referred to as "branching" units Y. For example, when a tertiary amine portion, which is a chain branching point of the base structure of polyamine or other branching chains or rings, in which B represents a continuation of the chain structure by branching, which has the structure: - [NR] - is modified in accordance with the present invention, is hereinafter defined as a "branching" unit Y, or simply a unit Y. However, for purposes of the present invention, some or all of the amine moieties tertiary can remain without modification. Those portions of tertiary amine without modification by virtue of their position in the base structure chain remain as "branching" units. The R units associated with the nitrogens of units V, W, and Y which serve to connect the polyamine nitrogens are described hereinafter. The final modified structure of the modified polyethylene imine polymers of the present invention can therefore be represented by the general formula: V (n + l) WmYnZ for polymers of linear modified polyethylenimine and by the general formula: V (n-k + 1) WmYnY 'Z for cyclic modified polyethyleneimine polymers. In the case of modified polyethyleneimine polymers comprising rings, a unit Y 'of the formula: R - [N-R] - serves as a branch point for a base structure or branching ring. For each unit Y 'there exists a unit Y that has the formula: B - [N-R] - which will form the connection point of the ring to the main polymer chain or branch. In the unique case where the base structure is a complete ring, the polyamine base structure has the formula: thereby comprising no terminal unit Z and having the formula: Vn-kWmYnY'k in which k is the number of branching units forming ring. Preferably the polyamine base structures of the present invention do not comprise rings. In the case of non-cyclic modified polyethyleneimine polymers, the ratio of the index n to the index m refers to the relative degree of branching. A completely unbranched linear modified polyethyleneimine polymer according to the present invention has the formula: VWmZ ie n is equal to 0. While the value of n is larger (while the ratio of man is lower), it is more the degree of branching in the molecule. Typically the value for m is on the scale of a minimum value of 4 to about 400, however larger values for m, especially when the value of index n is very low or close to 0, are also preferred. Each polyamine nitrogen, whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simply 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 unmodified primary amine nitrogens are V or Z units, the unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y units for purposes of the present invention. The modified primary amine moieties are defined as "terminal" V units having one of three forms: a) simply substituted units having the structure: E-N-R- I E b) quaternized units that have the structure: X "E-N + -R- in which X is a suitable counterion that provides load balance; and c) oxidized units having the structure: O t E-N- R- Modified secondary amine portions are defined as "base structure" units W having one of three forms. a) simply replaced units that have the structure: - N-R- I E b) quaternized units that have the structure: in which X is a suitable counterion that provides load balancing; and c) oxidized units having the structure: O - N t - R - I E Portions of modified tertiary amine are defined as "branching" units AND having one of three forms: a) unmodified units having the structure: -N- R- b) quaternized units that have the structure: -N + - R - in which X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: O f - N- R - Certain portions of modified primary amine are defined as "terminal" Z units that have one of three forms: a) simple substituted units that have the structure: -N-E I E b) quatemized units that have the structure: in which X is an adequate counter-ion that provides load balance; and c) oxidized units having the structure: O T -N-E When any position on a nitrogen is unsubstituted 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 V terminal unit having the formula : (HOCH2CH2) HN-. For purposes of the present invention there are two types of chain termination units, units V and Z. The unit "terminal" Z is derived from a terminal primary amino portion of the structure - H2. The non-cyclic polyamine base structures according to the present invention comprise only one unit Z while the cyclic polyamines can not comprise any unit Z. The "terminal" unit Z can be substituted with any of the units E that are further described. immediately, except when unit Z is modified to form an N-oxide. In the case where the nitrogen unit Z is oxidized to an N-oxide, the nitrogen must be modified and therefore E can not be a hydrogen. The modified polyethylenemine polymers of the present invention comprise "chaining" units of base structure R which serve to connect the nitrogen atoms of the base structure. R units comprise units that for purposes of this invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" units R are C2-Ci2 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkenylene in which the hydroxyl portion can take any position on the chain of the R unit except the carbon atoms directly connected to the hydroxyl groups. polyamine base structure nitrogens; C4-C12 dihydroxyalkylene in which the hydroxyl portions can occupy any two of the carbon atoms of the chain of unit R except those carbon atoms directly connected to the polyamine base structure nitrogens; C8-C12 dialkylarylene which for purposes of the present invention are arylene portions having two alkyl substituent groups as part of the linking chain. For example, a dialkylarylene unit has the formula: although the unit does not need to be 1, 4-substituted alkylene, but can also be substituted C2-C12 alkylene, 1-2 or 1.3 substituted, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise (R1O) xR5 (OR1) x-, CH 2 CH (OR 2) CH 2 O) z (R 1 O) and R 1 (OCH 2 CH (OR 2) CH 2) w-, -CH 2 CH (OR 2) CH 2 -, - (R 1 O) x R 1 -, and mixtures thereof. Preferred R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C125 dialkylarylene - (R1O) xR1-, -CH2CH (OR2) CH2-, (CH2CH (OH) CH2O) z (R1O) and R1 (OCH2CH- (OH) CH2) w-, - (R1O) xR5 (OR1) x-, the most preferred R units are C2-C12 alkylene, C3- hydroxyalkylene C12, C4-C12 dihydroxyalkylene, - (R1O) xR1-, - (R1O) xR5 (OR1) x-, (CH2CH (OH) CH2?) Z (R10) and R1 (OCH2CH- (OH) CH2) -, and mixtures thereof, the most preferred R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures thereof, more preferred are C2-C6 alkylene. The most preferred base structures of the present invention comprise at least 50% of R units that are ethylene. The R1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene. R2 is hydrogen, and - (R1O) xB, preferably hydrogen. R 3 is C 1 -C 18 alkyl, C 7 -C 12 arylalkylene, aryl substituted by C 7 Cl 2 alkyl, C 6 -C 12 aryl, and mixtures thereof, preferably C 1 -C 12 alkyl, C 7 -C 12 arylalkylene, more preferably C 1 -C 12 alkyl, C-1-C12, more preferably methyl. The R3 units serve as part of E units that are described below. R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-Ci2 arylalkylene, C6-C6 arylene, preferably C1-C10 alkylene, C8-C12 arylalkylene, more preferably C2-C8 alkylene, more preferably ethylene or butylene. R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C2 dialkylarylene) -C (O) -, C (O) NHR6NHC (O) -, -C (O) (R4) rC (O) -, -R1 (OR1) -, CH2CH (OH) CH2O (R1O) and R1OCH2CH (OH) CH2-, -C (O) (R4) rC (O) -, CH2CH (OH) CH2-, R5, is preferably ethylene, -C (O) -, - C (O) NHR6NHC (0) -, -R1 (OR1) -, -CH2CH (OH) CH2-, -CH2CH (OH) CH2O (R1O) and R1OCH2CH- (OH) CH2-, more preferably CH2CH (OH) CH2- . R6 is C2-C12 alkylene or C6-C12 arylene. The preferred "oxy" R units are further defined in terms of the units R1, R2 and R5. The preferred "oxy" R units comprise the preferred R1, R2 and R5 units. The preferred modified polyethyleneimine polymers of the present invention comprise at least 50% of R1 units that are ethylene. The preferred R1, R2 and R5 units are combined with the "oxy" R units to produce the preferred "oxy" R units in the following manner. i) substituting more preferred R5 in - (CH2CH2O) xR5 (OCH2CH2) x -produces - (CH2CH2?) xCH2CHOHCH2 (OCH2CH2) x-. ii) substituting preferred R1 and R2 in - (CH2CH (OR2) CH20) z- (R1O) and R1O (CH2CH (OR2) CH2) w- produces - (CH2CH (OH) CH2O) z- (CH2CH20) and CH2CH20 (CH2CH (OH ) CH2) w-. iii) substituting preferred R2 in -CH2CH (OR2) CH2- produces -CH2CH (OH) CH2-. The units E are selected from the group consisting of hydrogen, C?-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) pCO M, - (CH2) qSO3IVI, - CH (CH2CO2M) CO2M, - (CH2) pPO3M, - (R1O) mB, -C (O) R3, preferably hydrogen, hydroxyalkylene of C2-C22, benzyl, C? -C22 alkylene, - (R1O) mB, -C (O) R3, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, more preferably alkylene C? -C22, - (R1O) xB, -C (O) R3, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, more preferably C1-C22 alkylene, - (R1O) xB , and -C (O) 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, ie the nitrogens are N-oxides . For example, the base structure chain or branch chains do not comprise units of the following structure: O O O T T T -N- R or H- N- R or -N-H H H H Additionally, the units E do not comprise carbonyl moieties directly attached to a nitrogen atom when the units V, W or Z are oxidized, that is, the nitrogens are N-oxides. According to the present invention, the portion -C (0) R3 of unit E is not bound to a nitrogen modified by N-oxide, that is, there are no N-oxide amides having the structure: or combinations thereof. B is hydrogen, C? -C6 alkyl, - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) q- (CHS? 3M) CH2S? 3M, - (CH2) q (CHSO2M) CH2S? 3M, - (CH2) pPO3M, -P03M, preferably hydrogen, - (CH2) qSO3M, - (CH2) q- (CHSO3M) CH2SO3M, - (CH2) q- (CHS02M) CH2SO3M, more preferably hydrogen or - (CH2) qS03M. M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge equilibrium. For example, a sodium cation also satisfies - (CH2) PC02M, and - (CH2) qSO M, thus resulting in portions - (CH2) pC02Na, and (CH2) qSOsNa. More than one monovalent cation (sodium, potassium, etc.) can be combined to satisfy the required chemical charge equilibrium. However, a charge balance of more than one cationic group can be balanced by a divalent cation, or more than one monovalent cation may be necessary to satisfy the loading requirements of a polyanionic radical. For example, a - (CH2) pP? 3M portion substituted with sodium atoms has the formula - (CH2) pP03Na3. Divalent cations such as calcium (Ca2 +) or magnesium (Mg2 +) can be replaced by or combined with other suitable water-soluble monovalent cations. The preferred cations are sodium and potassium, more preferred is sodium.

X is a water-soluble anion such as chlorine (CI-), Bromine (Br-) and iodine (I ") or X can be any negatively charged radical such as sulfate (S042") and methosulfate (CH3S03"). The formula has the following values: p has the value of 1 to 6, q has the value of 0 to 6, r has the value 0 or 1, w has the value 0 or 1, x has the value of 1 to 100; and has the value from 0 to 100, z has the value 0 or 1; m has the value of 4 to about 400, n has the value of 0 to 200; m + n has the value of at least 5. The preferred modified polyethyleneamine polymers of the present invention comprise polyamine base structures in which less than 50% of the R groups comprise "oxy" R units, preferably less than 20% , more preferably less than 5%, more preferably the R units do not comprise "oxy" R units. The most preferred modified polyethylene imine polymers not comprising "oxy" R 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 "hydrocarbyl" units R preferred. That is, when the R units of base structure are C2-C12 alkylene, the C2-C3 alkylene is preferred, more preferred is ethylene. The modified polyethylene imine polymers of the present invention comprise homogeneous and non-homogeneous modified polyamine base structures, in which 100% or less of the units -NH are modified. For purposes of the present invention the term "homogeneous polyamine base structure" is defined as a polyamine base structure having R units that are the same (i.e., all ethylene). However, this definition of equality does not exclude polyamines comprising other foreign units comprising the polymer base structure that is present due to an artifact of the selected method of chemical synthesis. 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 purposes of the present invention. A polyamine base structure comprising all R units of ethylene in which non-branching Y units are present is a homogeneous base structure. A polyamine base structure comprising all the R units of ethylene is a homogeneous base structure regardless of the degree of branching or the number of cyclic branches present. For purposes of the present invention the term "non-homogeneous polymer base structure" refers to polyamine base structures that are a mixed body of various lengths of unit R and types of unit R. For example, a base structure does not homogeneous comprises R units which are a mixture of ethylene and 1,2-propylene units. For purposes of the present invention, a mixture of "hydrocarbyl" units and "oxy" R is not necessarily to provide a non-homogeneous base structure. Proper handling of those "chain lengths of unit R" provides the formulator with the ability to modify the fabric solubility and substantivity of the modified polyethyleneimine polymers of the present invention. Preferred modified polyethyleneamine polymers of the present invention comprise homogeneous polyamine base structures that are totally or partially substituted by polyethyleneoxy moieties, fully or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof . However, not all basic structure amine nitrogens should be modified in the same way, the selection of modification is left 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 in general polyalkonamine (PAAs), polyalkyleneamines (PAIs), preferably polyethyleneamine (PEAs), polyethyleneimines (PEIs), or PEAs or PEIs connected by portions having units R longer than PAA's, PAI's, PEA's or original PEI's. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEAs are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's that are obtained are triethylenetetramine (TETA) and tetraetienphenimine (TEPA). Above the pentamines, that is, they are examined, heptamines, octamines and possibly nonamines, the cogenically 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 the 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. Preferred amine polymer base structures comprise R units which are C2 alkylene (ethylene) units, also known as polyethylene imines (PEI's). Preferred PEIs have at least moderate branching, ie 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 preferred base structures, before modification, have the general formula: wherein m and n are the same as defined herein above. The PEI's preferred before modification will have a molecular weight greater than 200 Daltons. The relative proportions of primary, secondary and tertiary amine units in the polyamine base structure, especially in the case of PEI's, will vary, depending on the manner of preparation. Each hydrogen atom attached to each nitrogen atom of the chain of Polyamine base structure represents a potential site for substitution, quaternization or subsequent oxidation. These modified polyethyleneimine polymers 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 patent of E. U. A. 2,182,306, Ulrich et al., Issued December 5, 1939; U.A. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent No. 2,208,095, Esselmann et al., issued July 16, 1940; U.A. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent No. 2,553,696, Wilson, issued May 21, 1951; all incorporated herein by reference. Examples of modified polyethyleneimine polymers of the present invention comprising PEI's are illustrated in formulas l-IV: Formula I illustrates a modified polyethyleneimine polymer comprising a PEI base structure in which all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkylenoxy unit, - (CH 2 CH 2 O) 7 H, having the formula: Formula This is an example of a modified polyethyleneimine polymer that is completely modified by a type of portion. Formula II illustrates a modified polyethyleneimine polymer comprising a PEI base structure in which all the substitutable primary amine nitrogens are modified by hydrogen replacement with a polyoxyalkylene glycol unit, - (CH2CH2O) 7H, the molecule is then modified by Subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said modified polyethyleneimine polymer has the formula: Formula II The formula III illustrates a modified polyethyleneimine polymer comprising a PEI base structure in which all the 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?) H, or methyl groups. The modified PEI dirt release polymer has the formula: Formula lll Formula IV illustrates a modified polyethyleneimine polymer comprising a PEI base structure in which the nitrogens of the base structure are modified by substitution (ie, by - (CH2CH2?) 7H or methyl), quaternized, oxidized to N-oxides or combinations thereof. The resulting modified polyethyleneimine polymer has the formula: Formula IV In the previous examples, not all the nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides. This also applies to primary amine nitrogens, in which the formulator can select to modify all or a portion of the primary amine nitrogens with one or more substituents before oxidation or quaternization. Any possible combination of E groups can be substituted over the primary and secondary amine nitrogens, except for the restrictions described herein above. The acid sensitive polymer useful herein is typically provided at levels from 0.05% to 15%, preferably from 0.1% to 10%, and more preferably from 0.2% to 7%, by weight of the cleaning composition. If the acid sensitive polymer herein is a modified polyethyleneimine polymer, it is typically provided at levels of 0.05% to 2%, preferably from 0.1% to 1%, and more preferably from 0.2% to 0.8% by weight of the cleaning composition. In a preferred embodiment of the invention, a carrier is provided, in which the acid sensitive polymer is dispersed to form a premix. Because the acid-sensitive polymer is typically a viscous solid or liquid, and because of the typically low concentration at which the acid sensitive polymer is used, a carrier is normally required in order to uniformly disperse the sensitive polymer to the acid through the neutralized detergent active. The carrier is typically a liquid, and can serve either only as a carrier, or it can serve a dual purpose. As the acid sensitive polymer to be dispersed therein to form the premix, the carrier is preferably non-acidic, such as water. Also useful herein is a non-aqueous carrier, or a basic carrier. Sufficient carrier must be provided so that the acid sensitive polymer disperses easily, preferably dissolves, therein to form the premix. The weight ratio of carrier to acid-sensitive polymer in the premix is typically at least about 1: 1, preferably from 1: 1 to about 8: 1. The acid sensitive polymer or, in the preferred embodiment, the premix containing the acid sensitive polymer is added to the neutralized detergent active to form a suspension. This typically takes place within a mixer or apparatus that homogenizes the suspension.

The mixer can be the same mixer that was used in the previous neutralization step, or a different mixer. The suspension is then formed into a composition for cleaning by, for example, spray drying, or agglomeration procedures known in the art. In a preferred process, the suspension is formed in spray-dried granules in a conventional spray-drying tower operated at an inlet temperature in the range of 180 ° C to about 450 ° C. Said known apparatus operates by sprinkling the suspension by means of nozzles towards a flow of hot air countercurrent (or co-current) which dries the suspension and finally forms the spray-dried porous granules. Examples of the invention are set forth below by way of illustration and are not intended to be in any way limiting the invention.

EXAMPLE 1 A cleaning composition is formed according to the following procedure. Approximately 20-25% of acidic active is provided corresponding to the acid form of LAS. Approximately 1.2 times the stoichiometrically required amount of dilute caustic hydroxide solution is supplied to neutralize the acidic active. The acidic active and the alkaline material are added to a mixer, and neutralized therein to form a neutralized detergent active. Approximately 8% silicate is also added to the neutralized detergent active. An acid-sensitive polymer (a modified polyletyleneimine polymer, having a base structure of MW 1800 and an ethoxylation degree of about 7) is provided and mixed with water at a weight ratio of 1: 1 to about 8: 1 to form a pre-mix. The pre-mix is then added to the mixer, where it is mixed for 10 seconds to form a suspension. At this point, other detergent ingredients, such as phosphate, sulfate, etc., are also added. The suspension is then poured into a drip tank and pumped at a pressure of 40-70 bar, through a pressure nozzle in a spray tower to form spray-dried granules. The spray tower uses counterflow airflow with an inlet temperature of approximately 320-350 ° C.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for forming a cleaning composition comprising the steps of: A) providing at least one alkaline material and at least one acidic active; B) add the acidic active and the alkaline material to a mixer; C) substantially neutralizing the acidic active in the mixer to form a neutralized detergent active; D) adding at least one acid sensitive polymer to the neutralized detergent active to form a suspension; and E) forming the suspension in a cleaning composition.

2. The process according to claim 1, further characterized in that the acid sensitive polymer comprises a polyamine base structure before modification by means of quaternization, substitution, or oxidation corresponding to the formula: H B [^ -Rj ^ -O -RÍ ^ -tN - ^ - N ^ having a modified poiiamine of formula V (n + i) WmYnZ or a polyamine base structure before modification through quaternization, substitution, or oxidation corresponding to the formula: which has a modified polyamine formula V (n-k + i) WmYnY '? < Z, in which k is less than or equal to n, said polyamine base structure before the modification has a molecular weight greater than 200 daltons, in which: i) units V are terminal units having the formula: O x- E-N-R- E-N ^ -R- or E-N-R- I I E E E ii) units W are base structure units that have the formula: O? + X "-N-R- -N + -R- -N-R- I E iii) units Y are branching units that have the formula: iv) Z units are terminal units that have the formula: O X "T -N-E or - N + -E or -N-E I E wherein the R units of base structure bond are selected from the group consisting of C2-C12 alkylene, C4-C2 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, - (R10) xR1-, - (R1O) xR5 (OR1)? -, (CH2CH (OR2) CH2O) z (R1O) and R1 (OCH2CH (OR2) CH2) w-, -C (O) (R4) rC (0) -CH2CH (OR2) CH2-, and mixtures thereof; wherein R1 is C2-C2 alkylene and mixtures thereof, R2 is hydrogen, - (R1O)? B, and mixtures thereof; R3 is C1-C18 alkyl. C7-Ci2 arylalkyl, aryl substituted by C7-C2 alkyl, C6-C2 aryl, and mixtures thereof; R 4 is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 8 -Ci arylalkylene, Ce-C 1 arylene, and mixtures thereof; R5 is C1-C12 alkylene, C3-C2 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -C (O) -, C (O) NHR6NHC (O) -, -R1 (OR1) -, -C (O) (R4) rC (O) -, CH2CH (OH) CH2-, -CH2CH (OH) CH2? (R1O) and R1OCH2CH (OH) CH2-, and mixtures thereof; R6 is C2-C12 alkylene or CQ-C12 arylene; the E units are selected from the group consisting of hydrogen, C1-C22 alkyl. C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, - (CH2) pCO2M, - (CH2) qSO3M, -CH (CH2C? 2M) CO2M, - (CH2) PP? 3M, - (R1O ) xB, -C (O) R3, and mixtures thereof; with the proviso that when any unit E of a nitrogen is a hydrogen, said nitrogen is also not an N-oxide; B is hydrogen, C? -C6 alkyl > - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) q (CHSO3M) CH2SO3M, (CH2) q- (CHS? 2M) CH2SO3M, - (CH2) PPO3M, -PO3M, and mixtures thereof; M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge equilibrium; X is a water-soluble anion; m has the value of 4 to 400; n has the value from 0 to 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; and has the value from 0 to 100; z has the value of 0 or 1.

3. The process according to claim 1, further comprising the step of dispersing the acid-sensitive polymer in a carrier to form a premix before forming the suspension.

4. The method according to claim 1, further characterized in that it further comprises the step of spray drying the suspension to form a cleaning composition.

5. The method according to claim 1, further characterized by additionally comprising the step of adding sodium silicate to the neutralized detergent active prior to forming the suspension.

6. The process according to claim 1, further characterized in that the alkaline material is selected from the group consisting of a carbonate, a phosphate, silicate, layered silicate, hydroxide, and mixtures thereof.

7. A cleaning composition as formed by the method according to claim 1.

8. The method according to claim 3, further characterized in that the weight ratio of carrier to acid sensitive polymer is at least approximately 1: 1.

9. The method according to claim 3, further characterized in that the carrier comprises water.

10. A method for forming a cleaning composition comprising the steps of: A) providing at least one material alkaline and at least one acid active; B) adding the acidic active and the alkaline material to a mixer, the alkaline material is selected from the group consisting of a carbonate, a phosphate, silicate, layered silicate, hydroxide, and mixtures thereof; C) substantially neutralizing the acidic active in the mixer to form a neutralized detergent active; D) dispersing the acid sensitive polymer in a carrier to form a premix; E) adding the pre-mix to the neutralized detergent active to form a suspension; and forming the suspension in a cleaning composition; wherein the weight ratio of carrier to acid-sensitive polymer is at least 1: 1 and in which the acid sensitive polymer comprises a polyamine base structure before modification by means of quaternization, substitution, or oxidation that corresponds to the formula: having a modified polyamine of formula V (n + i) WmYnZ or a pollamine base structure before modification by means of quaternization, substitution or oxidation corresponding to the formula: H B R [H2N-R] H? T- [N-R] FT- [N-R] n- [N-R] j ^ NH2 having a modified polyamine of formula V (n-k + i) WmYnY'kZ, in which k is less than or equal to n, said pollamine base structure before modification has a molecular weight greater than 200 daltons, in which: i) units V are terminal units that have the formula: O? + X "E-N-R- E-N-R- I E ii) units W are base structure units that have the formula: O? + X "* -N-R- or -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: O? + X "4 -N-E -N + -E -N-E I I E wherein the base structure chaining units R are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, dialkarylene-C2-Ci2, - ( R1O)? R1-, (R1O) xR5 (OR1)? -, (CH2CH (OR2) CH2?) Z (R10) and R1 (OCH2CH (OR2) CH2) w-, -C (0) (R4) rC (0 ) -, -CH2CH (OR2) CH2-, and mixtures thereof; wherein R1 is C2-Ce alkyiene and mixtures thereof; R2 is hydrogen, - (R1O)? B and mixtures thereof; R3 is C1-C18 alkyl, arylalkyl of C -C2, aryl substituted by C7-C12 alkyl, C6-C12 aryl, and mixtures thereof; R 4 is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, C 8 -C 12 arylalkylene, Ce-C-1 arylene, and mixtures thereof; R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C2 dihydroxyalkylene, C8-Ci2 diacylarylene, -C (O) -, C (O) NHR6NHC (O) -, -R1 (OR1 ) -, -C (O) (R4) rC (O) -, -CH2CH (OH) CH2-, -CH2CH (OH) CH2O (R1O) and R1OCH2CH (OH) CH2-, and mixtures thereof; Rd is C2-C12 alkylene or C6-C12 arylene; the units E are selected from the group consisting of hydrogen, C1-C22 alkyl. C3-C22 alkenyl, C7-C22 arylalkio, C2-C22 hydroxyalkyl, - (CH2) PCO2M, - (CH2) qS03M, -CH (CH2CO2M) C? 2M, - (CH2) pPO3M, - (R1O) xB , -C (O) R3, and mixtures thereof; with the proviso that when any unit E of a nitrogen is a hydrogen, said nitrogen is also not an N-oxide; B is hydrogen, C? -C6 alkyl, - (CH2) qS03M, - (CH2) pCO2M, - (CH2) q (CHSO3M) CH2S03M, - (CH2) q- (CHSO2M) CH2S? 3M, - (CH2) PPO3M, -PO3M, and mixtures thereof; M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge equilibrium; X is a water-soluble anion; m has the value of 4 to 400; n has the value from 0 to 200; p has the value of 1 to 6, q has the value of 0 to 6J r has the value of 0 or 1; w has the value of 0 or 1; x has the value of 1 to 100; and has the value from 0 to 100; z has the value of 0 or 1.