BRPI0712934A2 - liquid detergent compositions with polysaccharide based polyacrylic acid based polidispercity polymers - Google Patents

Abstract

DETERGENT LIQUID COMPOSITIONS WITH LOW POLYDISPERSITY POLYRACYLIC ACID POLYMERS. The present invention relates to liquid detergent compositions comprising a polymer comprising polycrylic acid monomers having a low average numerical molecular weight in the range from about 1,000 am to about 10,000 amu, and a very low, low polydispersity. which is about 5, with the liquid detergent comprising less than about 50% of any aminofunctional solvent. The invention also relates to liquid detergent compositions comprising beneficial low molecular weight mixtures, very low polydispersity polycrylic acid based polymers with specific polymers.

Description

Report of the Invention Patent for "DETERGENT LIQUID COMPOSITIONS WITH LOW POLYDISPERSITY POLYRAYLIC ACID POLYMERS".

FIELD OF THE INVENTION The present invention relates to liquid detergent compositions.

liquid, and more especially liquid laundry or dishwashing detergent compositions, or surface cleaning detergents, which comprise a polymer or copolymer comprising low polydispersity polyacrylic acid monomers. These liquid detergents exhibit enhanced ability to be formulated in lower solvent vehicle contents and improved performance of polymeric detergent additives. BACKGROUND OF THE INVENTION

Fluid laundry products such as liquids, gels, pastes and the like are preferred by many consumers over solid detergents. Many of these consumers also want to conserve resources and eliminate what they understand as waste or unnecessary product without a noticeable reduction in product performance. Consequently, there is a renewed interest in concentrated products or also known as compact products. However, typical liquid detergent products cannot easily be formulated in lower water or other solvents due to the need to maintain detergent surfactants and polymeric additives that may become at least partially insoluble at higher concentrations. Typical builders, such as citrates and fatty acids, and additives may

Limerics such as polyacrylates and higher molecular weight molecules with high charge density molecules showed a tendency to precipitate into the solution with lower solvent contents, thus creating more instability in the end products. This instability may decrease the performance of the desired detergent products. Consequently, there remains a need for a concentrated liquid detergent that is comparable in performance to existing non-compact detergents. Ideally, any such comparable detergent will be easy to use and aesthetically pleasing to consumers.

Polyacrylic acid based polymers are known as builders or thickeners for detergent products. See US Patent No. 6,794,473 B2 to Yamaguchi et al. on September 21, 2004. However, it has been found that polymers comprising low molecular weight acrylic acid monomers and very low polydispersity create concentrated clear isotropic liquid detergents with sufficient physical stability and strong detergent performance. Separately, it was found that polymers comprising

Such low molecular weight and very low polydispersity acrylic acid monomers also improve the stability and performance of previously used additive polymers such as water-soluble or dispersible modified zwitterionic polyamines and / or polyamines. SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide improved liquid detergent compositions. Generally, the invention is directed to liquid detergent compositions comprising a polymer comprising polyacrylic acid monomers with a low average numerical molecular weight in the range of about 1000 to about 10,000 amu, and very low polydispersity. , less than about 5, with the liquid detergent comprising less than about 50% of any amino-functional solvent.

The invention also relates to liquid detergent compositions comprising beneficial mixtures of very low polydispersity and low molecular weight polyacrylic acid polymers with specific polymers. DETAILED DESCRIPTION OF THE INVENTION

Liquid detergent compositions of the present invention comprise acrylic acid-based polymers. By "acrylic acid-based polymers" is meant in the present invention a compound comprising repeating units called monomer units, wherein a fraction of the monomer units consists of acrylic acid or an acrylic acid salt. In selected embodiments of the present invention, the polymer may be an acrylic acid homopolymer wherein substantially 100% of the monomers are acrylic acids. In other embodiments of the invention, the polymer may be a copolymer comprising some acrylic acid monomers and some other monomers.

The size of the polymers of the present invention may be measured by standard measurement of average molecular weight. The molecular weight may be an average numerical molecular weight Mn, or a weight average molecular weight Mw. The polymers of the present invention may have a number average molecular weight in the range of from about 1,000 amu to about 10,000 amu. The molecular weight distribution of polymer-specific compounds may be reflected as the ratio of weight average molecular weight to number average molecular weight (Mw / Mn). This ratio is also called polymer polydispersity. The polymers of the present invention may have a polydispersity of less than about 5.0.

As discussed above, one embodiment of the polymer of the present invention may be a polyacrylic acid homopolymer. The embodiment may have a low average numerical molecular weight in the range of about 1,000 to about 4,000 and a polydispersity of less than about 5, with certain embodiments having an average numerical molecular weight in the range of about 1,100. at about 3,000 and a polydispersity of less than about 3,5.

The acrylic acid-based polymer of the present invention may also be a copolymer comprising acrylic acid monomers and 10% or less, based on the total polymer weight, of a hydrophilic asomer. Hydrophilic comonomers are monomers that when added to acrylic acid polymers make the copolymer less soluble in the liquid detergent composition. Typical hydrophilic monomers include polyethylene glycol acrylates, dicarboxylates, sulfonated monomers and mixtures thereof. Certain embodiments of polymers having hydrophilic comonomers may have a number average molecular weight of from about 1,000 to about 4,000 u, and a polydispersity of less than about 5, with certain embodiments having a numerical molecular weight. average in the range of about 1,100 to about 3,000 and a polydispersity of less than about 3,5.

Other embodiments of the acrylic acid-based polymer of the present invention may be a copolymer comprising acrylic acid monomers and 20% or less, based on the total weight of the polymer, of a hydrophobic comonomer. Hydrophobic comonomers are the monomers that when added to the acrylic acid polymers make the copolymer more soluble in the liquid detergent composition. Typical hydrophobic monomers include alkyl, aryl, silicone, propoxylated or butoxylated monomers and mixtures thereof. Certain embodiments of polymers having hydrophobic comonomers may have a number average molecular weight of from about 1,000 to about 10,000 µm, and a polydispersity of less than about 5, with certain embodiments having a number average molecular weight in the art. range from about 1,100 to about 3,000 and a polydispersity of less than about 5,0.

The liquid detergent compositions of the present invention may be any liquid detergent including, but not limited to, liquid laundry and childbearing detergent and surface cleaning compositions.

Liquid laundry detergent compositions

In a specific embodiment, the compositions are laundry detergent compositions, are in liquid form and comprise heavy duty liquid compositions. The compositions of the present invention comprise surfactants, together with other typical detergent ingredients, and a polymer comprising polyacrylic acid monomers with a low average numerical molecular weight and very low polydistitude.

The laundry detergent composition comprises a surfactant in an amount sufficient to achieve cleaning properties. In one embodiment, the laundry detergent composition comprises by weight from about 5% to about 90%, more specifically from about 5% to about 70%, and more specifically about 5%. % to about 40% of the surfactant. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises an anionic surfactant, a nonionic surfactant, or mixtures thereof.

Suitable anionic surfactants useful in the present invention may comprise any of the conventional types of anionic surfactant typically used in liquid detergent products. These include alkyl benzene sulfonic acids and their salts, as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C1-16 alkyl benzene sulphonic acids, preferably C1-14 alkyl benzene sulphonic acids. Preferably the alkyl group is Iine, and these linear alkyl benzene sulphonates. are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. These surfactants and their preparation are described, for example, in U.S. Patent Nos. 2,220,099 and 2,477,383. Especially preferred are straight chain sodium and potassium alkyl benzene sulfonates, where the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C 1 -C 14, for example C 12, LAS is a specific example of these surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. These materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, correspond to the formula: R1-O- (C2H4O) n-SO3M, where R 'is a C8 to C2O alkyl group, η is about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R 'is C1 to C18 alkyl, η is about 1 to 15, and M is sodium, potassium, ammonium, alkyl ammonium or ammonium alkanol. In more specific embodiments, R 'is a C 12 to C 16, η is about 1 to 6 and M is sodium.

Alkyl ether sulfates will generally be used in the form of mixtures comprising variable R 'chain lengths and varying degrees of ethoxylation. Often, these mixtures will also inevitably contain some non-ethoxylated alkyl sulfate materials, that is, surfactants of the ethoxylated alkyl sulfate formula, where n = 0. Non-ethoxylated alkyl sulfates may also be added separately from the compositions of this invention and used as or in any anionic surfactant components that may be present. Specific examples of non-alkoxylated, for example, non-ethoxylated alkyl ether sulfate surfactants are those produced by sulfation of higher C8 to C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: R0SO3 "M +, where R is typically a linear C8-C2O hydrocarbyl group, which may be straight chain or branched, and M is a water solubilization cation In specific embodiments, R is a C 10 to C 15 alkyl group, and M is alkali metal, more specifically, R is C 12a C 14 and M is some specific non-limiting examples of surfactants.

Anionic anions useful in the present invention include: a) C 1-8 alkyl benzene sulfonates (LAS); b) C 1 to C 20 random branched primary chain alkyl (AS) sulfates; c) C10 to C18 secondary (2,3) alkyl sulfates having the formulas (I) and (II):

OSO3 "M + OSO3" M +

CH3 (CH2) x (CH) CH3 OR CH3 (CH2) y (CH) CH2CH3

(I) (II)

wherein M in formulas (I) and (II) is hydrogen or a charge-neutral cation, and all units M, whether associated with the surfactant or auxiliary ingredient, may be either a hydrogen atom or a cation, depending on the form isolated by the skilled artisan, or the relative pH of the system in which the compound is used, with some non-limiting examples of preferred cations including sodium, potassium, ammonium and combinations thereof, where χ is an integer of at least about 7, preferably at least about 9, and where y is an integer of at least 8, preferably at least about 9, d) C10 -C18 alkylalkoxy sulfates (AExS) wherein χ is preferably from 1 to 30, e) C1 -C8 alkylalkoxy carboxylates preferably comprising from 1 to 5 ethoxy units, f) branched chain alkyl sulfates, as discussed in US No. 6,020,303 and US No. 6,060,443, g) alkylal sulfates branched chain medium oxy as discussed in US Nos. 6,008,181 and US Nos. 6,020,303, h) Modified alkyl benzene sulfonate (MLAS) as discussed 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., I) methyl ester sulfonate (MES), and j) alpha olefin sulfonate (AOS).

Suitable nonionic surfactants usable herein may comprise any of the types of conventional nonionic surfactants typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Normally liquid nonionic surfactants are preferred for use in the liquid detergent products of the present invention. Nonionic surfactants suitable for use herein

invention include nonionic alcohol alkoxylate surfactants. Alcohol alkoxylates are materials corresponding to the general formula: R1 (CmH2mO) nOH, where R1 is a C1 to C16 alkyl group, m is 2 to 4, and η is in the range of about 2 to 12. Preferably R1 is a primary or secondary alkyl group containing from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials containing from about 2 to 12 portions of ethylene oxide per molecule, more preferably from about 3 to 10 portions of ethylene oxide per molecule.

The alkoxylated fatty alcohol materials useful in liquid detergent compositions will often have a hydrophilic-lipophilic balance (BHL) in the range of about 3 to 17. Most preferably, the HLB of this material will be in the range of about 6 to 15, most preferably from about 8 to 15. Alkylated fatty alcohol-based nonionic surfactants are commercially available under the names Neodol and Dobanol from the Shell Chemical Company. Another suitable type of nonionic surfactant usable herein comprises amine oxide surfactants. Amine oxides are materials often referred to in the art as "semipolar" nonionic. Amine oxides have the formula: R (EO) x (PO) y (BO) zN (O) (CH 2 R ') 2.qH 20. In this formula, R is a relatively long chain hydrocarbyl moiety that may be saturated or unsaturated, linear or branched, and may contain from 8 to 20, preferably from 10 to 16 carbon atoms, and more preferably consisting of C 1 to C 6 primary alkyl-R 'is a short-chain moiety preferably selected from hydrogen, methyl and -CH 2 OH. When x + y + z is different from O, EO is ethylene oxy, PO is propylene oxy and BO is butylene oxy. Amine oxide surfactants are illustrated by C1-14 alkyl dimethyl amine oxide.

Some non-limiting examples of nonionic surfactants include: a) C 12 -C 18 alkyl ethoxylates, such as NEO-DOL® nonionic surfactants available from Shell, b) Ce-C 12 alkyl phenol alkoxylates wherein alkoxylate units are a mixture of oxyethylene and oxypropylene units, c) C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide / propylene oxide block polymers such as Pluronic® available from BASF, d) alcohols C4 -C22 branched chain medium chain BA as discussed in US No. 6,150,322; e) C 14 -C22 branched chain medium alkyl alkoxylates where χ is from 1 to 30 as discussed in US no. No. 6,153,577, US No. 6,020,303 and US No. 6,093,856, f) alkyl polysaccharides, as discussed in US 4,565,647, issued to Llenado on January 26, 1986, specifically alkyl polyglycosides as discussed in US 4,483,780 and US 4,483,779, g) polyhydroxy fatty acid amides as U.S. Patent Nos. 5,332,528, WO 92/06162, WO 93/19146, WO 93/19038 and WO 94/09099, eh) polyethyl ether (oxyalkylated) terminated alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.

In the laundry detergent compositions of the present invention, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is the case, the ratio of anionic weight to nonionic weight will typically be in the range of 10:90 to 90:10, more typically from 30:70 to 70:30.

Cationic surfactants are well known in the art, and some nonlimiting examples thereof include quaternary ammonium surfactants, which may have up to 26 carbon atoms. Additional examples include a) quaternary ammonium alkoxylate (AQA) surfactants as discussed in US No. 6,136,769; b) quaternary dimethyl hydroxy ethyl ammonium as discussed in 6,004,922; c) polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005 and WO 98/35006; d) cationic ester surfactants as discussed in U.S. Patent Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and e) amino surfactants as discussed in US Nos. 6,221,825 and WO 00/47708, specifically dimethyl propylamine starch (ΑΡΑ).

Some non-limiting examples of zwitterionic surfactants include: secondary and tertiary amine derivatives, secondary and tertiary heterocyclic amine derivatives, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Patent No. 3,929,678 issued to Laughlin et al. On December 30, 1975, from column 19, line 38, to column 22, line 48, for examples of zwitterionic surfactants, betaine, including alkyl dimethyl betaine and cocodimethyl starch propyl betaine, Ce to C-β amine oxides (preferably C12 3 C 18) and sulfo and hydroxy betaines such as N-alkyl-N, N-dimethylamino-1-propane sulfonate, wherein the alkyl group may be from C8 to C18, preferably from C10 to C14.

Non-limiting examples of ampholytic surfactants include: aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of secondary or tertiary heterocyclic amines, wherein the aliphatic radical may be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilizing group, for example carboxy, sulfonate or sulfate. . See US Patent No. 3,929,678, Laughlin et al., Issued December 30, 1975, in column 19, lines 18 to 35, for examples of anpholytic surfactants. For use in the present invention, "non-amino functional solvent" refers to any solvent that contains no amino functional group. Non-amino-functional solvents include, for example: water, alkanols such as C1 to C5 methanol, ethanol, propanol and 1-ethoxypentanol; C2 to C3 diols, C3 to C8 alkylene glycols; C3 to C6 lower monoalkylene alkylene glycol ethers; di-alkyl glycol ether; lower molecular weight polyethylene glycols; triols such as C3 to C9 glycerol; and mixtures thereof. More specifically, non-amino functional solvents are liquids at room temperature and pressure (i.e. 210 ° C and 1 atmosphere), and comprise carbon, hydrogen and oxygen.

Generally in non-compacted product formulations, non-amino-functional all-solvents, including water, may comprise from about 5% to about 90%, more specifically from about 10% to about 70%, and more specifically about 100%. about 20% to about 60%. Newly developed liquid detergent formulas may comprise no more than about 50%, more specifically no more than 35%, more specifically no more than 30%, even more specifically no more than 25%, in particular. weight of the composition, and specifically is from 0% to 45%, specifically 1% to 30%, more specifically from about 2% to about 25%, more specifically from about 3% to about 20%, more specifically from about 5% to about 15% by weight of the composition of the non-amino-functional solvent.

The lowest cost non-amino-functional solvent type is, of course, water itself. Accordingly, the non-amino-functional solvent will generally be mostly, if not completely, comprised of water. While other types of water miscible liquids such as alkanols, diols, other polyols, ethers, amines, and the like have conventionally been added in liquid detergent compositions such as cosolvents or stabilizers, the use of these water miscible liquids should be minimized in order to keep the cost of composition low.

Liquid detergent compositions of the present invention may also include any amount of additional optional ingredients. These include conventional components of laundry detergent compositions such as detersive builders, enzymes, enzyme stabilizers (such as propylene glycol, boric and / or borax), foam suppressants, dirt suspending agents, dirt release, other tissue treatment benefit agents, pH adjusting agents, chelating agents, smectite clays, solvents, hydrotropes and phase stabilizers, structuring agents, pigment transfer inhibitors, optical brighteners, perfumes and coloring agents. The various optional ingredients of the detergent composition, if present in the compositions of the present invention, need to be used in conventionally employed concentrations to give the desired effect to the composition or washing operation. Frequently, the total amount of these optional ingredients of the detergent composition may be in the range of from about 0.1% to about 50% and more preferably from about 1% to about 30% by weight of the composition. . Specifically, it has been found that combinations of the polymer to

Polyacrylic acid base with certain previously known additive polymers provide improved benefits.

The polyacrylic acid-based polymer may be beneficially combined with modified release water-soluble or dispersible polyamine polymers. Such polymers are discussed in US Patent No. 3,087,316. These polyamines comprise main chains which may be both linear and cyclic. The polyamine backbones may also comprise branches to the polyamine chains to a greater or lesser extent. In general, the polyamine backbones described herein are modified such that each nitrogen in the polyamine chain is therefore described in terms of a unit that is substituted, quaternized, oxidized or combinations thereof.

For the purposes of the present invention, the term "modification" is defined as replacing a -NH-main chain hydrogen atom with an E (substitution) unit, quaternizing a main chain nitrogen (quaternization) or oxidizing a main chain nitrogen to N-oxide (oxidation). The terms "modification" and "substitution" are used interchangeably when referring to the process of replacing a hydrogen atom attached to a main chain nitrogen by a Ε unit. Quaternization or oxidation may occur in some circumstances without substitution, but substitution must be accompanied by oxidation or quaternization of at least one mainstream nitrogen.

The linear or non-cyclic polyamine backbones comprising the cotton dirt release agents of the present invention have the general formula:

¥ ι

[H2N-R] n + i- [N-R] m- [N-R] n-NH2

said main chains prior to subsequent modification comprise primary, secondary and tertiary amine nitrogen connected by "linker" units. The polyamine main chains comprising the cotton dirt release agents of the present invention have the general formula:

I

H | R

[H2N-R] n-k +] - [N-R] m- [N-R] n— [N-Rjk-NH2

said major chains prior to subsequent modification comprise primary, secondary and tertiary amine nitrogen connected by R-linker units.

For the purpose of the present invention, primary amine nitrogen comprising the backbone or chain branch, once modified, is defined as "terminal" V or Z units. For example, when a primary amine moiety located at the end of the polyamine backbone or at the branch of the chain having the structure

H2N-R] -

is modified in accordance with the present invention, it is therefore defined as a "terminal" V unit or simply a V unit. However, for purposes of the present invention, some or all of the primary amine moieties may remain unchanged, subject to the restrictions further described below. These unmodified primary amine moieties, by virtue of their positions in the main chain, remain "terminal" units. Similarly, when a primary amine moiety located at the end of the polyamine backbone having the structure

-NH2

is modified in accordance with the present invention, it is therefore defined as a "terminal" Z unit or simply a Z unit. This unit may remain unchanged, further subject to the restrictions described below.

Similarly, secondary amine nitrogen comprising the backbone or chain branch, once modified, is defined as "backbone" W units. For example, when a secondary amine moiety is the major constituent of the main chains and chain branch of the present invention having the structure

H

- [N-R] -

is modified in accordance with the present invention, it is therefore defined as a "main chain" unit W or simply a W unit. However, for the purposes of the present invention, some or all of the primary amino moieties may remain unchanged, but according to the present invention, some units of the main chain need to be modified. These unmodified secondary amine moieties, by virtue of their positions in the main chain, remain units of the "main chain".

Similarly, tertiary amine nitrogen comprising the backbone or branch of the chain, once modified, is further called Y-branching units. For example, when a tertiary amine moiety, which is a branch point of the chain, both the polyamine backbone and the chain or ring branch, which has the structure.

I

- [N-R] -

is modified in accordance with the present invention, it is therefore defined as a "branching" Y unit or simply a Y unit. However, for purposes of the present invention, some or all of the tertiary amine moieties may remain unchanged. These unmodified tertiary amine moieties, by virtue of their positions on the main chain, remain "branching" units. The R units associated with the nitrogen units V, W and Y, which serve to connect polyamine nitrogen are described later in this document.

The modified final structure of the polyamines of the present invention may therefore be represented by the general formula:

V (n + 1) WmYnZ

for linear or branched polyamine polymers for releasing cotton dirt, and for the general formula:

V (n-k + 1) WmYnYkZ

for cyclic polyamine polymers for releasing cotton dirt. In the case of polyamines comprising rings, a unit Y1 having the following formula:

I

R

- [N-R] -

serves as a branch point for a main chain or branch ring. Except in cases where the main chain comprises a ring A, then for each unit Y 'there is a unit Y having the following formula:

I

- [N-R] -

which will form the point of connection of the ring to the main polymeric chain or branch. In the exclusive case where the main chain is a full ring, the polyamine main chain has the formula:

¥ ι

[H2N-R] n- [N-R] m- [N-R] n—

therefore comprising no terminal Z unit and having the following formula

VrvkWmYnYk

where k is the number of rings that form the branch units. In the case of non-cyclic polyamines, the ratio between the index η and

The index m refers to the relative degree of branching. A complete unbranched linear modified polyamine according to the present invention has the formula:

VWmZ

that is, η is equal to 0. The higher the value of η (the smaller the ratio between m and n), the greater the degree of branching in the molecule. Typically the value of m is in the range of a minimum of 4 to about 400, however, larger values of m, especially when the value of the index η is too low or close to 0, are also preferred. As further defined below, when the ratio of m: η is approximately 2: 1, m is preferably less than 200. Each polyamine nitrogen, whether primary, secondary or tertiary.

Aria, once modified in accordance with the present invention, is further defined as a member of one of three general classes: substituted simple, quaternized or oxidized. These unmodified polyamine nitrogen units are classified into V, W, Y, or Z units, depending on whether they are primary, secondary or tertiary nitrogen. That is, unmodified primary amine nitrogen are V or Z units, unmodified secondary amine nitrogen are W units, and unmodified tertiary amine nitrogen are Y units for the purposes of the present invention.

Modified primary amine moieties are defined as V "terminal" moieties having one of three forms:

(a) simple replaced units having the structure:

E-N-R— I

AND

>

b) Quaternized units having the structure:

E-N-R— I

AND

ι

wherein X is a suitable counterion that provides charge balancing; and

c) oxidized units having the structure:

the t

E-N-R— Modified secondary amine moieties are defined as "main chain" W units having one of three forms:

(a) simple replaced units having the structure:

-N-R-

ι

AND

>

b) Quaternized units having the structure:

—N-R— I

AND

wherein X is a suitable counterion that provides charge balancing; and

c) oxidized units having the structure:

0 t

—N-R—

1

AND

Modified tertiary amine moieties are defined as "backbone" Y units having one of three forms:

a) unmodified units having the structure:

-N-R-

I

b) Quaternized units having the structure:

ux "

—N-R—

wherein X is a suitable counterion that provides charge balancing; and c) oxidized units having the structure:

The t

—N-R—

Certain primary amine moieties are defined as "terminal" Z units having one of three forms: a) simple substituted units having the structure:

-HUH

ι

And (b) quaternized units having the structure: —Ν — E

wherein X is a suitable counterion that provides charge balancing; and c) oxidized units having the structure:

0

t

-HUH

1

AND

When any position in a nitrogen is unsubstituted or unmodified, it is understood that hydrogen will be replaced by E. For example, a primary amine moiety comprising an E moiety as a hydroxy ethyl moiety is a V moiety terminal having the following formula (HOCH2CH2) HN-.

For purposes of the present invention, there are two types of chain terminating units, units V and units Ζ. The "terminal" Z unit is derived from a terminal primary amine moiety of the -NH2 structure. Non-cyclic polyamine backbones according to the present invention comprise only one Z-unit, whereas cyclic polyamines may not comprise unidades-units. The "terminal" Z unit may be replaced by any of the E units described later in this document, except when the Z unit is modified to form an N-oxide. In the event that the nitrogen unit Z is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be a hydrogen.

The polyamines of the present invention comprise backbone units R which serve to connect the backbone nitrogen atoms. R units comprise units which, for purposes of the present invention, are called "R hydrocarbyl" units and "Roxy" units. "Hydrocarbyl" R units are C 2 to C 12 alkylene, preferably ethylene, 1,2-prolene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise - (R 10) x R 3 (O R 1) x -, -CH 2 CH (O R 2) CH 20) z (R 10) y R 10 - (CH 2 CH (OR 2) CH 2) w -, -CH 2 CH (OR 2) CH 2 - , and mixtures thereof; preferred "oxy" R units are -CH 2 CH (OR 2) CH 2 -, - (CH 2 CH (OH) CH 2 O) z (R 10 O) y R 1 -O (CH 2 CH (OH) CH 2) w -, and mixtures thereof. The R chain units of the main chain of the present invention need to comprise at least one -CH 2 CH (OR 2) CH 2 -, - (CH 2 CH (OH) CH 2 O) OR 2) CH 2 -, or mixtures thereof.

R1 units are C2 to Οβ alkylene, and mixtures thereof, preferably ethylene.

R2 is hydrogen, and - (R10) xB, preferably hydrogen.

R3 is C1 to C12 alkylene, hydroxy C3 to C12 alkylene, dihydoxy C4 to C12 alkylalkylene C8 to C12 dialkylene, -C (O) -, -C (O) NHR6 NHC (O) -, - C (O) ( R4) rC (O) -,

-R 1 (OR 1) -, -CH 2 CH (OH) CH 2 O (R 1 O) y R 1 OCH 2 CH (OH) CH 2 -, -C (O) (R 4) r C (O) -, -CH 2 CH (OH) CH 2 -, R 3 is preferably ethylene, -C (O) -, -C (O) NHR 5 NHC (O) -, -R 1 (OR 1) -, -CH 2 CH (OH) CH 2 -, -CH 2 CH (OH) CH 2 O (R 1 O) y R 1 OCH 2 CH- (OH) CH 2 -, more preferably -CH 2 CH (OH) CH 2 -.

R 4 is C 1 -C 12 alkylene, C 4a C 12 alkenylene, C 8a C 12 arylalkylene, C 6a C 10 arylene, preferably C 1 -C 10 alkylene, C 8a C 12 arylalkylene, more preferably C 2a C 8 alkylene, most preferably ethylene or butylene.

R5 is C2 to C12 alkylene or C6 to C12 arylene

Preferred "oxy" R units are further defined in terms of R1, R2 and R3 units. Preferred "oxy" R units comprise preferred R units R1, R2 and R3. Preferred cotton dirt release agents comprise at least 50% ethylene R1 units. Preferred R units, R1, R2and R3 are combined with R "oxy" units to produce R "oxy" units as follows:

i) More preferred substitutions of R3 in (CH2CH2O) xR3 (OCH2CH2) X- yield - (CH2CH20) xCH2CH0HCH2 (0CH2CH2) x-.

ii) Preferred substitutions of R1 and R2 in - (CH2CH (OR2) CH2O) z- (R1O) yR1O (CH2CH (OR2) CH2) w- produce (CH2CH (OH) CH2O) z- (CH2CH2O) yCH2CH2O (CH2CH (OH ) CH2) w-. iii) Preferred substitutions of R2 in -CH2CH (OR2) CH2-

produce

-CH 2 CH (OH) CH 2 -.

Units E are selected from the group consisting of - (CH2) pCO2M, - (CH2) q-SO3M1 -CH (CH2CO2M) CO2M, - (CH2) pPO3M, - (R1O) xBl preferably - (R1O) xB, - (CH2) pCO2M, - (CH2) qSO3M, CH (CH2CO2M) CO2M, more preferably - (R10) xB. When no modification or substitution is performed on a nitrogen, then the hydrogen atom will remain as the representative portion of E. Units E do not comprise hydrogen atom when

Since units V, W or Z are oxidized, that is, nitrogen is N-oxides. For example, the parent chain or branched chains are not

comprise units with the following structure:

? ? ?

—N-R OR H-N-R OR -N-H

I I I

HHH

B is hydrogen, - (CH2) pCO2M, - (CH2) qSO3M, - (CH2) qCH (SO3M) -CH2SO3M, - (CH2) qCH (SO2M) CH2SO3M, - (CH2) pPO3M, -PO3M, preferably hydrogen - (CH2) qSO3M, - (CH2) qCH (SO3M) CH2SO3M, - (CH2) qCH (SO2M) -CH2SO3M, more preferably hydrogen or - (CH2) qSO3M.

M is hydrogen or a water-soluble cation sufficient to satisfy the charge balance. For example, a sodium cation also satisfies - (CH2) pCO2M, and - (CH2) qSO3M1 and therefore results in portions - (CH2) pCO2Na, and - (CH2) qSO3Na. More than one modern cation (sodium, potassium, etc.) can be combined to meet the required chemical charge balance. However, more than one anionic group may be balanced by a divalent cation, or more than one monovalent cation may be required to satisfy the charge requirements of a polyanionic radical. For example, a - (CH2) pPO3M portion substituted with sodium atoms has the formula - (CH2) pPO3Na2. Divalent cations such as calcium (Ca2 +) or magnesium (Mg2 +) may be substituted for or in combination with other suitable water-soluble monovalent cations. Preferred cations are sodium and potassium, more preferred is sodium.

X is a water soluble anion such as chlorine (Cl "), bromine (Br") and iodine.

(Γ) or X may be any negatively charged radical, such as sulfate (SO42 "), methosulfate (CH3OSO3) and methanesulfonate (CH3SO3).

The indices of the formula have the following values: ρ has the value from 1 to 6; q has the value from 0 to 6; r is 0 or 1; w has the value of O or 1; χ has the value from 1 to 100; y has the value from 0 to 100; ζ has the value of O or 1; k is from 0 to about 20; m is from 4 to about 400; η has a value from 0 to about 200; preferably m + η has a value of at least 5.

Preferred cotton dirt release agents of the present invention comprise polyamine backbones, with less than about 100% of the R groups comprising "ό-χι" R units, preferably less than about 50% with more preferably less than 30%, and most preferably less than about 20% of the R units comprise "oxy" R units.

Preferred cotton dirt release agents of the present invention comprise polyamine backbones, with less than 50% of the "hydrocarbyl" R groups comprising more than 3 carbon atoms. For example, ethylene, 1,2-prolylene and 1,3-prolylene comprise 3 or less carbon atoms and are preferred "hydrocarbyl" R units. That is, when the R chain units of the backbone are C 2 -C 12 alkylene, C 2 -C 3 alkylene is preferred and ethylene is more preferable.

The cotton dirt release agents of the present invention comprise non-homogeneous polyamine backbones, with 100% or less of the -NH units being modified. For the purpose of the present invention, the term "homogeneous polyamine backbone" is defined as the polyamine backbone having equal (i.e. all ethylene) R units. However, this definition of similarity does not exclude polyamines that comprise other foreign units that comprise the main polymer chain that are present due to an artifact of the chosen chemical synthesis method. For example, it is known 10

15

20

those skilled in the art that ethanolamine can be used as an "initiator" in the synthesis of polyethylene imine, so a polyethylene imine sample comprising a hydroxy ethyl moiety that results from polymerization of the "initiator" would comprise, for purposes of the present invention. invention, a homogeneous polyamine backbone.

For the purposes of the present invention, the term "non-homogeneous polymer backbone" refers to polyamine backbones which are a composite of various R unit lengths and R unit types. Proper handling of this "R chain lengths" provides the formulator with the ability to modify the solubility and adherence to dirt release agents in cotton fabrics of the present invention.

An example of a polyamine backbone according to the present invention prior to modification has the formula:

OH

kO '

NH9

where 8 R units comprise ethylene units and 1 R unit comprises a portion

-CH 2 CH (OH) CH 2 O (R 1 O) y R 1 OCH 2 CH (OH) CH 2 - wherein R 1 is ethylene and y is 1.

A further example of a pre-modified polyamine backbone that is suitable for use as a cotton dirt release agent according to the present invention has the formula: wherein 12 R units comprise ethylene and 1 unit R comprises a portion

-CH 2 CH (OH) CH 2 O (R 10 O) y R 1 OCH 2 CH (OH) CH 2 - wherein R 1 is ethylene and y is 1. Structures similar to these two examples given above are, for the purposes of the present invention, commonly referred to as " blocks ". Typically, several blocks are combined to form the final main chain before modification.

As in the above examples, low molecular weight polyethylene imines (PEI's) and polyethylene amines (PEA's), typically below 9.9E to 22 g (600 Dalton), are bonded using the "oxide" R units that serve as convenient coupling agents. Depending on the desired properties of the cotton dirt release agent (e.g., solubility, tissue adhesion), a greater or lesser degree of "oxide" R units will comprise the polyamine backbone. It is more convenient for nitrogen modification to occur

after complete assembly of the main polyamine chain. However, the formulator may wish to have a polymer backbone with a high degree of unmodified nitrogen atoms. This may be accomplished by pre-modifying some or all of the "hydrocarbyl" moieties of the main chain polyalkyleneimine or polyalkylene amine prior to attachment via "oxy" R units.

An example of a procedure allowing a mixture of modified and unmodified blocks in the polymer to release cotton soils comprises the steps of i) modifying an imine polyethylene having, for example,

the formula: where the modification is

a) the replacement of the hydrogen atom of -NH by a

unit E;

b) quaternization;

c) oxidation of N-oxide; or

d) mixtures thereof;

resulting in an example of modified imine polyethylene having the following formula:

NMod

Mod9N.

wherein Mod represents one or more modifications according to the present invention;

ii) a modified polyethylene imine is coupled to a second molecule of the original unmodified polyethylene imine via a -CH 2 CH (OH) CH 2 O (R 10) yR 1 OCH 2 CH (OH) CH 2 - moiety, wherein R 1 is ethylene and y is equal to 1, for form a polyamine of the cotton dirt release agent having the following formula: NMod

Mod

I H

Mod9R. ^ I

NMod

NH9

Once this process is complete the above unit may be used "as is" or may be coupled to one or more modified or unmodified blocks.

Preferred polyamine "blocks" having "hydrocarbyl" R units that comprise the backbone of the compounds of the present invention are generally polyalkyl amine (PAA's), polyalkylene imine (PAI's) units, preferably polyethylene amines (PEA's) ), polyethylene imine (PEI1S). An example of a polyalkylene amine (PAA) is tetrabutylene penamine. PEA1S are obtained from polyalkylene amines by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. Commonly obtained PEAs are triethylene tetramine (TETA) and tetraethylene pentamine (TEPA). Above pentamines, that is, hexamines, heptamines, octamines and possibly nonamines, the derived mixture generally does not appear to be distilled off and may include other materials such as cyclic amines and especially piperazines. Cyclic amines with side chains may also be present in which nitrogen atoms appear. See U.S. Patent No. 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.

PEI blocks comprising the preferred main chains of the polyamines of the present invention may be prepared, for example, by ethylene imine polymerization in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydroxide peroxide. - drogen, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEI1S are set forth in US Patent No. 2,182,306, issued to Ulrich et al., On December 5, 1939, US No. 3,033,746, issued to Mayle et al., On 8 May 2, 1962, US No. 2,208,095, issued to Esselmann et al., on July 16, 1940, US No. 2,806,839, issued to Crowther, September 17, 1957, and US No. 2,553. 696, issued to Wilson, May 21, 1951 (all incorporated herein by reference). In addition to the linear and branched PEIs, the present invention also includes cyclic amines that are typically formed as synthesis artifacts. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.

However, the polyamine backbones of the present invention may comprise 100% of the "oxide" moieties, for example, a pre-modification polyamine backbone comprising R -CH 2 CH (OH) CH 2 O (R 10) y R 1 OCH 2 CH ( OH) CH2 -, where R1 is ethylene and y is 1, has the formula

An example of a dirt release agent according to the present invention has the formula:

OH

H3Cv

THE

r1

Here"

ο

OH

OH OH.

Ν, O ^ Ο.

r1 rV r1 S S S <7 "r» „S S

, 1V A xS »

^ O ^ VJ C \

Hi

SS

HO

HO HOv

, O ^ O '

Nv

Cl "

CH3- Ov

Ov

OH OH

cr

HOv

sOH

Ov

O ^ I ^ O

CH,

OH

* Oh

wherein R units are ethylene and -CH 2 CH [(CH 2 CH 20) 2H] CH 2 - and the units E are - (CH 2 CH 2 O) 2 H and -CH 3.

Examples of preferred but non-limiting polyamine-based polymers of the present invention are shown below - PEI60 (EO) io (PO) 7 and PEI60 (EO) 2o, respectively.

Off-0Iv O ^ 0L

laugh

LoJu / * \ ^ Zol

Hi 7 ', γ, 27

The polyacrylic acid-based polymers of the present invention may also be beneficially combined with zwitterionic polyamine additives set forth in US 6,660,711. These zwitterionic polyamines of the present invention have the formula:

[J — RJn-J

wherein [J-R] units represent amino units, which comprise the main chain and any branch of the chains. Preferably, the zwitterionic polyamines prior to modification, among others, quaternization, substitution of an amino moiety hydrogen for an alkylenhoxy moiety, have major chains comprising from 2 to about 100 amino moieties. The index η describing the number of units present in the main chain is further described below.

The units J are the amino units of the main chain, said units are selected from the group consisting of:

(i) primary amino units having the following formula:

(R1) 2N-

(ii) secondary amino units having the following formula:

—R1N- j

iii) tertiary amino units having the following formula:

B

I

- N- »formula:

formula:

formula:

formula:

iv) primary quaternary amino units having the following

(R1) 2Ijj

Q;

v) secondary quaternary amino units having the following

- R1N

I

Q;

vi) tertiary quaternary amino units having the following

B I

Q;

vii) N-oxide amino units having the following formula:

(R1) 2N T

THE·

J

viii) secondary amino N-oxide units having the following

—R1N

I

The

(ix) tertiary amino N-oxide units having the following formula:

over there:

B

- N

I

THE-

)

x) and mixtures thereof; Units B that have the formula:

[J — R] -

represent a continuation of the main chains of the branching zwitterionic polyamines. The number of B units present, as well as any amino units comprising the branches, reflect the total value of index n. The amino units of the main chain of zwitterionic polymers are connected by one or more R units, said R units are selected from the group consisting of:

(i) linear C 2 to C 12 alkyl, branched C 3 to C 12 alkylene, or mixtures thereof; preferably C3 to C6 alkylene. When two nitrogen

Adjacent areas of the polyamine backbone are N-oxides, preferably the backbone alkylene moiety which separates said units is larger C40O units.

(ii) alkylene oxyalkylene units having the following formula:

- (R2O) w (Rs)

wherein R2 is selected from the group consisting of ethylene, 1,2-prolylene, 1,3-prolylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; R3 is linear C2 to Ce alkylene, branched C3 to Ce alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25. R2 and units R3 may also comprise other units in the main chain. When comprising alkylene oxyalkyl units, in one embodiment, R 2 and R 3 units are preferably ethylene or mixtures of ethylene, prolene and butylene, more preferably ethylene; in another embodiment R2 and R3 units are preferably mixtures of ethylene, prolene and butylene; the index w is preferably from about 2 to about 10, preferably about 6.

iii) hydroxy alkylene units having the following formula:

OR4

- (CH2) x (CH) y (CH2) -

wherein R4 is hydrogen, C1 to C6 alkyl, - (CH2) u (R20) t (CH2) uY, and mixtures thereof. When R units comprise hydroxy alkylene units, R 4 is preferably hydrogen or - (CH 2) u (R 2 O) t (CH 2) u Y, wherein t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is preferably hydrogen or an anionic unit, more preferably -SO3M. Indices x, y and ζ are independently from 1 to 6, preferably indices are 1 and R4 is hydrogen (2-hydroxy propyl unit) or (R2O) tY, or for polyhydroxy units y is preferably A preferred hydroxy alkylene unit is 2-hydroxy propylene which may, for example, be suitably formed of glycidyl ether forming reagents, among others epihalohydrin.

iv) hydroxy alkylene units or oxyalkylene units having the following formula:

OR4

OR4

I

- (CH2) x (CH) y (CH2) z (X) r -] - (RzO) w ^ (CH2) x (CH) y (CH2) z (X) r-I-

where R21 R41 and the indices w, x, y and ζ are equal, as previously

defined in this document. X is oxygen or the amino unit -NR4-, the index r is

O or 1. Indices j and k are independently from 1 to 20. When units

alkylenoxy are absent, the index w is 0. Some non-limiting examples of

Preferred hydroxy alkylene units or preferred oxyalkylene units have the formula:

OH OH

I I

—CH2CHCH2O- (CH2CH2CH2O) 2- CH2CHCH2- ■

OH

- CH2CHCH2O- (CH2CH2O) 3-

OH

OH

OH

CH2CHCH2O - CH2CHCH2-

OH I

CH2CHCH2O- (CH2CH2O) - - CH2CHCH2

OH

OH

—CH2CHCH2O- (CH2CH2CH2O) 4- - CH2CHCH2-

(v) alkylenoxycarboxy units having the following formula:

o o

- (R3O) w (R3) w (X) r -C- (X) r- R3- (X) r -C- (X) 1 (R3) w (OR3) w-;

wherein R2, R31 X, r and w are the same as previously defined in this document. Some non-limiting examples of alkyl carboxy units

Preferred lenoxy include:

THE

THE

■ CH2 - C - O - CH2CH2CH2CH2 - O - C - CH2 -. THE

Il

-CH9-C-NH

- (CH2CH2CH2O) 4-C

THE

Il

NH — C — CHo

C— (OCH2CH2CH2) 4-

(vi) main chain branch units having the following formula:

R4

- (CH2) x (C) y (CH2) z (X) r R4

R4

(R2O) w (CH2) x (C) y (CH2) z (X) r-I-R4

wherein R4 is hydrogen, C1 to C6 alkyl, - (CH2) u (R2O) t (CH2) uY, and mixtures thereof. When R units comprise main chain branch units, R 4 is preferably hydrogen or - (CH 2) u (R 2 O) t- (CH 2) u Y, wherein t is greater than 0, preferably 10 to 30; the index is 0 to 6, Y is hydrogen, linear alkyl C1 to C4, - N (R1) 2, an anionic unit, and mixtures thereof; preferably Y is hydrogen, or -N (R1) 2. A preferred embodiment of main chain branch units comprises R4 equal to - (R2O) tH. The indices x, y and ζ are independently from 0 to 6.

vii) The formulator may suitably combine any of the R units described above to manufacture a zwitterionic polyamine having a greater or lesser degree of hydrophilic character. R1 units are the nitrogen-linked units of the

main hate. Units R1 are selected from the group consisting of:

i) hydrogen; which is the unit typically present prior to any major chain modification.

ii) C1 -C22 alkyl, preferably C1 -C4 alkyl, most preferably methyl or ethyl, most preferably methyl. A preferred embodiment of the present invention is in the example where R 1 units are attached to quaternary units (iv) or (v), R 1 are equal to quaternization unit Q. For example, a unit J that has the following formula: (CH3) 2N CH3.

iii) C7 to C22 arylalkyl, preferably benzyl.

iv) - [CH 2 CH (O R 4) CH 2 O] s (R 20), Y; wherein R2 and R4 are equal as hereinbefore defined, preferably when R1 units comprise R2 units, R2 is preferably ethyl.

Leno. The value of the index s is from 0 to 5. For the purposes of the present invention, the index t is expressed as an average value, said average value of about 0.5 to about 100. The formulator may alkylene oxylate lightly the main chain nitrogen so that not all nitrogen atoms comprise an R1 unit which is an alkylenoxy unit which makes the t-index value less than 1.

v) Anionic units as described in the present invention below.

vi) The formulator may suitably combine one or more of the R1 units described above by substituting the main chain of the

zwitterionic compounds of the present invention.

Q is a quaternization unit selected from the group consisting of C1 to C4 linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described above in the present invention, preferably Q is equal to R1 when R1 comprises an alkyl moiety. For each N + unit of the main chain (quaternary nitrogen) there will be an anion to provide charge neutrality. The anionic groups of the present invention include both units that are covalently bonded to the polymer as well as external anions that are present to achieve charge neutrality. Some non-limiting examples of anions suitable for use include halogen, among others, chloride; methylsulfate; hydrogensulfate and sulfate. The formulator will recognize by the examples described in the present invention that the anion will typically be a unit which is part of the quaternization reagent, among others methyl chloride, dimethyl sulphate, benzyl bromide. X is oxygen, -NR 4 -, and mixtures thereof preferably

oxygen.

Y is hydrogen, C1 to C4 linear alkyl, -N (R1) 2, or an anionic unit. Y is -N (R1) 2, preferably when Y is part of a unit R which is a main chain branch unit. Anionic units are defined herein as "units or portions capable of having a negative charge". For example, a carboxylic acid unit, -CO2H1 is neutral, however, under deprotonation, the unit becomes an anionic unit, -CO2 ", the unit is therefore" capable of having a negative charge. " - anionic Y unit limiters include - (CH2) fCO2M1 -C (O) (CH2) fCO2M, - (CH2) fPO3M1 - (CH2) fOPO3M1 - (CH2) fSO3M1 -CH2 (CHSO3M) - (CH2) fSO3M1 - CH2 ( CHSO 2 M) (CH 2) f SO 3 M, -C (O) CH 2 CH (SO 3 M) CO 2 M, -C (O) CH 2 CH (CO 2 M) NHCH (CO 2 M) CH 2 CO 2, -C (0) CH 2 CH (CO 2 M) NHCH 2 CO 2 M, -CH 2 CH (OZ) CH 2 O (R10) tZl - (CH2) fCH [0 (R20) tZ] -CHf0 (R20) tZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit, some non-limiting examples of which include - (CH2) fCO2M1 -C (O) (CH2) fCO2M1 - (CH2) fPO3M1 - (CH2) fOPO3M1 - (CH2) fSO3M1 -CH2 (CHSO3M) - (CH2) fSO3M1 -CH2 (CHSO2M) (CH2) fSO3M, -C (O) CH 2 CH (SO 3 M) CO 2 M, -C (O) CH 2 CH (CO 2 M) NHCH (CO 2 M) CH 2 CO 2 M 1 and mixtures thereof, M is a cation that provides charge neutrality.

Y units may also be oligomeric or polymeric,

for example, the anionic Y unit that has the formula:

OH SO3Na

-CH2CHCH2O-CH2CHCH2SO3Na

may be oligomerized or polymerized to form units of the general formula:

THE-

SO3Na

- CH2CHCH2O- CH2CHCH2SO3Na

-H

η

where the index η represents a number greater than 1.

Some other non-limiting examples of Y units that may be suitably oligomerized or polymerized include: OH SO 2 Na

I I

—CH2CHCH2O- CH2CHCH2SO3Na

and

OH

I

—CH2CHCH2O- CH2CH2CH2SO3Na

and

OSO3Na

I

—CH2CHCH2O— CH2CH2CH2OSO3Na

As previously described in the present invention, that a variety of factors, among others, the overall polymer structure, the nature of the formulation, the wash conditions and the target cleaning benefit, can all influence the best values for Qr. of the formulator, Δ0, and Q (+).

For liquid laundry detergent compositions preferably less than about 90%, more preferably less than 75%, even more preferably less than 50%, most preferably less than 40% of said units. Y comprise an anionic moiety, among others, units comprising -SO 3 M. The number of units comprising an anionic unit will vary from modality to modality. M is hydrogen, a water-soluble cation, and mixtures thereof; The index f is from 0 to 6.

The index η represents the number of units of the main chain, and the number of amino units in the main chain is η + 1. For the purposes of the present invention, the index η is from 1 to about 99. Units B branches are included in the total number of units in the main chain.

Some non-limiting examples below indicate how the main chains of the present polyamines are assembled and defined.

The following is a non-limiting example of a backbone according to the present invention prior to quaternization. On

χ

OH, OH.

THE

OH

, Ο. J2 NH2

NH2

Ο "

OH

THE

* H 'H OH

Ό "

,THE

~ ΟΗ

NH2

which has an index η of 4.

The following is also a non-limiting example of a backbone according to the present invention prior to quaternization.

NH2

H2N

N I

H

.NH2

which has an index η of 4.

Following is a non-limiting example of a fully quaternized polyamine backbone.

OH

+ N (CH3) 3

L ^ OH

OH

^ OH

, Ov

I "^ o CH3

On

, N (CH3) 3

CH3

I

+ N '

THE

THE

CH3 OH

,THE

~ OH

N (CH3) 3

Following is a non-limiting example of a fully quaternized polyamine backbone. (CH3) 3N

N (CH3) 3

The CH3

The following is a non-limiting example of a

final zwitterionic mine according to the present invention.

OH

Nt (CH2CH2O) 2OSO3Mh CH3

CH3 - N [(CH2CH2O) 20SO3M] 2 OH

OH

(CH2CH2O) 20SO3M]

N [(CH 2 CH 2 O) 20 SO 3 M] 2 CH 3

Following is a non-limiting example of a final zwitterionic polyamine according to the present invention.

N [(CH 2 CH 2 O) 20 SO 3 M] 2 CH 3

CH3-N

N

ι CH3

[(CH2CH2O) 20SO3M] 2

N [(CH 2 CH 2 O) 20 SO 3 M] 2 CH 3

O [(CH2CH2O) 20SO3MI2

Preferred zwitterionic polymers of the present invention have the formula:

(RO) tY Hl

[Y (ORz) t J 2 -N-R 3 -N-R-

+

N-

m

- [(RzO) tYJ2

wherein R units have the formula - (R 2 O) w R 3 - wherein R 2 and R 3 are independently selected from the group consisting of C 2 to C 8 linear alkylene, C 3 to C 8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof. R2 units of the above formula which comprise - (R2O) tY units are each ethylene; Y is hydrogen, -SO3M1 and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, even more preferably from 0 to 3, most preferably from 0 to 2; the index w is preferably from about 2 to about 10, preferably about 6.

Some non-limiting major chain examples according to the present invention include 1,9-diamino-3,7-dioxanonane;

1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane; 1,14-diamino-3,12-dioxatetradecane. However, the main chains comprising more than two nitrogen may comprise one or more repeating units having the formula:

H2N- [R-NH] -

for example, a unit that has the formula:

H2N- [CH2CH2OCH2CH2NH] - is described in the present invention as 1,5-diamino-3-oxapentane. A main chain comprising two 1,5-diamino-3-oxapentane units has the formula:

H2NCH2CH2OCH2CH2Nhch2CH2OCH2CH2NH2.

Other suitable repeat units include: 1,8-diamino-3,6-diaxaoctane, 1,11-diamino-3,6,9-trioxaundecane, 1,5-diamino-1,4-dimethyl-3-oxaheptane 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane, 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.

The zwitterionic polymers of the present invention comprise

preferably have polyamine backbone derived from two types of backbone units:

(i) Normal oligomers comprising R units of type (i), which are preferably polyamines having the formula:

H2N- (CH2) Jn +, - [NH- (CH2) Jm- [NB- (CH2) Jn-NH2

wherein B is a continuation of the branch polyamine chain, η is preferably O, m is from 0 to 3, χ is 2 to 8, preferably from 3 to 6; and

(ii) hydrophilic oligomers comprising R units of type (ii), which are preferably polyamines having the formula:

H2N- [(CH2) x OJy (CH2) J— [NH - [(CH2) xOJy (CH2) Jm -NH2 where m is from 0 to 3; each χ is independently from 2 to 8, preferably

from 2 to 6; y is preferably from 1 to 8. Depending on the degree of hydrophilic character required in the zwitterionic main chains, the formulator may assemble higher oligomers from these constituent parts by using R units of type (iii), (iv) and (v). Some non-limiting examples include epihalohydrin condensate having the formula:

H H OH H H

I Ill I

H2N- (CH2) 6- N- (CH2) 6-N-CH2CHCH2 -N- (CH2) 6- N— (CH2) 6- NH2

or the hybrid oligomer having the formula:

OH OH

I I

H2N (CH2) 3O (CH2) 4O (CH2) 3N-CH2Chch2O- (CH2) 4O-CH2CHCH2-N (CH2) 3O (CH2) 4O (CH2) 3NH2

each main chain comprising a mixture of R units.

As previously described in the present invention, the formulator may form zwitterionic polymers that have an excess charge (Qr less than 1 or greater than 1) or an equivalent amount of type charge (Qr equal to 1). An example of a preferred zwitterionic polyamine according to the present invention having an excess of animal units

charged charges, Qr equal to 2, has the formula:

[CH2CH2OI20SO3 "

I [CH2CH2OI20SO3 "

CH3-IsT CL I

I ^^ ^^ ^^ ^^ O ^^ N-CH3 [CH2CH2O120SO3 +1

[CH2CH2O120SO3-

wherein R is a 1,3-propylene-oxy-1,4-butylene-oxy-1,3-prolylene moiety, w is 2; R1 is - (R2O) tY, where R2 is ethylene, each Y is -SO3 ", Q is methyl, m is O, η is O, t is 20. For the zwitterionic polyamines of the present invention, it will be recognized by the formulator that Not all R1 units will have a -S03 "portion termination in said R1 unit. For the above examples, the final zwitterionic polyamine blend comprises at least about 90% of Y units which are -SO 3 "units.

As previously described in the present invention, the formulator may form zwitterionic polymers that have an excess charge or an equivalent amount of charge type. An example of a preferred zwitterionic polyamine according to the present invention which has an excess of quaternized units in the backbone has the formula: (CH2 CH2o) 2 OH

(CH2CH2O) 20H

(CH2CH2O) 20H

+

N

CH3

N-CH3

(CH2CH20) 20SO3M

(CH2CH2O) 20SO3M

wherein R is 1,5-hexamethylene, w is 2; R1 is - (R2O) tY, where R2 is ethyl, Y is hydrogen or -SO3M1 Q is methyl, m is 1, t is 20. For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not all of the compounds are present. - of the units R1 will have a -SO3 portion denomination in said unit R1.

For the above example, the final zwitterionic polyamine mixture comprises at least about 40% Y units which are -SO 3 "units.

in the form of an aqueous solution, uniform dispersion or suspension of surfactant, polymer and other optional ingredients, some of which may normally be in solid form and have been combined with the normally liquid components of the composition as a non-surfactant. amino-functional and any other optional normally liquid ingredients. Such a solution, dispersion or suspension must have acceptable phase stability and typically will have a viscosity in the range of from about 0.1 to 0.6 Pa.s (100 to 600 cps), more preferably about 0.15 to 0.4 Pa.s (150 to 400 cps). For the purposes of this invention, viscosity is measured by a Brookfield LVDV-II + viscometer using a # 21 spindle.

They may be prepared by combining their components in any convenient order and by mixing, for example by stirring, the resulting component combination to form a stable phase liquid detergent composition. In a preferred process for the preparation of these compositions, a liquid matrix is formed containing at least a large proportion and preferably substantially all of the liquid components such as nonionic surfactant, non-active liquid carriers. surface and other optional liquid components, said liquid components being thoroughly mixed by applying shear stirring to that liquid combination. For example, rapid stirring with the aid of a mechanical stirrer may usefully be employed. While shear agitation is maintained,

The liquid detergent compositions of the present invention are

The liquid detergent compositions of the present invention comprise substantially all anionic surfactants and solid ingredients. Stirring of the mixture is continued and, if necessary, may be increased at this point to form a solution or uniform dispersion of insoluble solid phase particles in the liquid phase. After some or all of the solid form materials are added to this stirred mixture, particles of any enzyme material to be included, for example enzyme nuggets, are incorporated. As a variation of the preparation procedure for the composition described above, one or more of the solid components may be added to the mixture in the form of a premixed solution or paste with a minimum portion of one or more liquid components. . After the addition of all components of the composition, the mixture is continued to stir for a sufficient time to form compositions with the indispensable viscosity and phase stability characteristics. Often this will comprise agitation over a period of about 30 to 60 minutes.

The compositions of this invention prepared as described hereinbefore may be used to form aqueous wash solutions for use in fabric wash. Generally, an effective amount of these compositions is added to the water, preferably in a conventional automatic washing machine, to form these aqueous laundry solutions. The aqueous wash solution thus formed is then brought into contact, preferably under agitation, with the fabrics to be washed. An effective amount of the liquid detergent compositions of the present invention, added to water to form aqueous laundry solutions, may comprise sufficient amounts to form from about 500 to 7,000 ppm of composition in an aqueous wash solution. More preferably, from about 1,000 to 3,000 ppm of the detergent compositions of the present invention will be provided in an aqueous wash solution. Examples

The following examples illustrate the compositions of the present invention, but are not necessarily intended to limit or otherwise define the scope of the present invention. Example 1

The following liquid formulas are within the scope of the present invention.

Ingredient 1a 1b 1c 1d 1e% wt% wt% wt% weight weight weight weight alkyl ether sodium sulfate 20.5% 20.5 20.5 branched alcohol sulfate 5.8% 5.8 5.8 linear alkyl benzene sulfonic acid 2.5% 2.5 2.5 alkyl ethoxylate 0.8% 0.8 0.8 amine oxide citric acid 3.5% 3.5 3.5 fatty acid 2.0 % 2.0 2.0 protease 0.7% 0.7 0.7 amylase 0.37% 0.37 0.37 Iipase borax 3.0% 3.0 3.0 sodium calcium formate 0.22% 0.22 0.22 formic acid 1.2% amine ethoxylate polymers 1.2 1.2 zwitterionic amine ethoxylate polymer 1.6% 1.6 1.6 sodium polyacrylate1 0.6% polyacrylate copolymer sodium2 0.6 sodium polyacrylate copolymer3 1.6 DTPA4 0.25% fluorescent whitening agent 0.2% continued

Ingredient 1a 1b 1c 1d 1e ethanol 2.9% propanediol 5.0% diethylene glycol 2.56 polyethylene glycol 4000 0.11% ethanolamine 2.7% sodium hydroxide 3.67% cumene sodium sulfonate based foam suppressor in silicone 0.01% perfume 0.5% Acid Blue 75 0.01% opacifier6 water qsp 100% qsp 100% qsp 100% qsp 100% qsp 100%

1. Polyacrylic acid sodium salt, Mn = 1000-4000 u, PD <5.

2. Polyacrylic acid ethylene copolymer sodium salt 90:10, Mn = 1000-4000 u, PD <5.

Polyacrylic acid-polyethylene glycol acrylate copolymer sodium salt 90:10, Mn = 1000-4000 u, PD <5.

4 Diethylene triamine pentaacetic acid sodium salt

a non-toning dye used to adjust the color of the formula

6 Acusol OP 301

All documents cited in the Detailed Description of the Invention are, in their relevant part, incorporated herein by reference, and the citation of any document shall not be construed as an admission that this prior art represents a relationship with respect to the present invention.

While specific embodiments of the present invention have been illustrated and described, it should be obvious to those skilled in the art that various other changes and modifications may be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.

Claims (16)

1. A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers having a number average molecular weight of from about 1,000 to about 10,000 amu, and a polydispersity of less than about 5, wherein: The liquid detergent comprises less than about 50% of any non-amino functional solvent. A liquid detergent composition according to claim 1, wherein the liquid detergent comprises less than about 40% of any amino-functional solvent. A liquid detergent composition according to claim 1, wherein the polymer is a polyacrylic acid monomer homopolymer. Liquid detergent composition according to claim 3, characterized in that the polyacrylic acid homopolymer has a number average molecular weight of from about 1,000 to about 4,000 amu. Liquid detergent composition according to claim 4, characterized in that the polyacrylic acid homopolymer has a number average molecular weight of from about 1,100 to about 3,000 amu. Liquid detergent composition according to claim 1, characterized in that the polymer is a copolymer comprising a mixture of acrylic acid monomers and hydrophilic monomers, wherein such copolymer has a number average molecular weight of about 1,000. at about 4,000 am a polydispersity less than about 3.5. Liquid detergent composition according to Claim 6, characterized in that the copolymer comprises a mixture of acrylic acid monomers and hydrophilic monomers selected from the group consisting of polyethylene glycol acrylates, dicarboxylates, sulphonated monomers and mixtures thereof. Liquid detergent composition according to Claim 1, characterized in that the copolymer comprises a mixture of acrylic acid monomers and hydrophobic monomers, such copolymer having a number average molecular weight of about 1,000. at about 10,000 am a polydispersity less than about 5.0. Liquid detergent composition according to Claim 8, characterized in that the copolymer comprises a mixture of acrylic acid monomers and hydrophobic monomers selected from the group consisting of alkyl, aryl, silicone monomers. , propoxy, butoxy and mixtures thereof. A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers having a number average molecular weight of from about 1,000 to about 10,000 u, a polydispersity of less than about 5 and a compound of modified, soluble or dispersible polyamine. Liquid detergent composition according to Claim 10, characterized in that the water-soluble or dispersible modified polyamine compound comprises a polyamine backbone corresponding to the formula: ¥ ι [HzN-Rntnti- EN-Rmm-tN-Rln-NHz which has a modified polyamine of formula V (n + i) WmYnZ, or a polyamine backbone that corresponds to the formula: <formula> formula see original document page 45 </formula> which has a modified polyamine of formula V (ri-k + i) WmYnYkZ, where k is less than or equal to n, said polyamine backbone prior to modification has a molecular weight greater than about 3.3E-22 g (200 daltons) where i) V units are terminal units having the formula: <formula> formula see original document page 45 </formula> ii) W units are main chain units having the formula: <formula> formula see original document page 45 </formula> <formula> formula see original document III) Y units are branch units that have the formula: <formula> formula see original document page 46 </formula> iv) Z units are terminal units that have the formula: <formula> formula see original where the R chain-binding units R are selected <formula> formula see original document page 46 </formula> from the group consisting of C 2 to C 2 alkylene, - (R 0) XR ( OR) x -, - (CH 2 CH (OR 2) CH 2 O) z (R 1 O) y R 1 (OCH 2 CH (OR 2) CH 2) w -, -CH 2 CH (OR 2) CH 2 - and mixtures thereof; provided that when R comprises C1 to C12 alkylene R also comprises at least one - (R 1 O) x R 3 (OR 1) x -, - (CH 2 CH (OR 2) CH 2 O) z (R 1 O) y R 1 - (OCH 2 CH (OR 2) CH 2) w-, or -CH 2 CH (OR 2) CH 2 -; R1 is C2 to C6 alkylene and mixtures thereof; R2 is hydrogen, - (R10) XB and mixtures thereof; R 3 is C 1 to C 12 alkylene, hydroxy C 3 to C 12 alkylene, dihydroxy C 4 to C 12 alkylene, C 8 to C 12 dialkylene, -C (O) -, -C (O) NHR 5 NHC (O) -, -C (O) (R 4 ) rC (O) -, - and CH2 CH (OH) CH2 O- (R10) yR1 OCH2 CH (OH) CH2 -, and mixtures thereof; R4 is C1 -C12 alkylene, C4 -C12 alkenylene, C8 -C12 arylalkylene, C6 -C10 arylene and mixtures thereof; R5 is C2 -C12 alkylene or C6 -C12 arylene; Units E are selected from the group consisting of hydrogen, - (CH2) p-CO2M, - (CH2) qSO3M, -CH (CH2CO2M) CO2M, - (CH2) pPO3M, - (R1O) xB, and mixtures thereof; provided that when any E unit of a nitrogen is a hydrogen, said nitrogen is not also an N-oxide; B is hydrogen, - (CH2) qSO3M, - (CH2) pCO2M, - (CH2) qCH (SO3M) -CH2SO3M, - (CH2) qCH (SO2M) CH2SO3M, - (CH2) pPO3M, -PO3M, and mixtures thereof ; M is hydrogen or a water-soluble cation in sufficient quantity to satisfy the charge balance; X is a water soluble anion; k has a value from 0 to about 20; m has a value from 4 to about 400; η has a value from 0 to about 200; ρ has a value from 1 to 6, q has a value from 0 to 6; r has a value of 0 or 1; w has a value of 0 or 1; χ has a value from 1 to 100; y has a value from 0 to 100; and ζ has a value of 0 or 1. Liquid detergent composition according to Claim 11, characterized in that the modified polyamine compound is selected from the group consisting of compounds having the formulas <formula> formula see original document page 47 </formula> and mixtures thereof, A liquid detergent composition comprising a polymer comprising polyacrylic acid monomers having an average number molecular weight of from about 1,000 to about 10,000 amu and a polydispersity of less than about 5 and a zwitterionic polyamine. Liquid detergent composition according to claim 13, characterized in that the zwitterionic polyamine has the formula: wherein J is selected from the group consisting of: : i) primary amino units having the formula: <formula> formula see original document page 48 </formula> ii) secondary amino units having the formula: <formula> formula see original document page 48 </formula> iii) units tertiary amino having the formula: <formula> formula see original document page 48 </formula> (iv) quaternary amino units having the formula: <formula> formula see original document page 48 </formula> ν) secondary quaternary amino units which have the formula: <formula> formula see original document page 49 </formula> vi) tertiary quaternary amino units having the formula: <formula> formula see original document page 49 </formula> vii) primary N-oxide amino units which have formula: <formula> formula see original document page 49 </formula> viii) secondary amino acid N-oxide units having the formula: <formula> formula see original document page 0 </formula> ix) tertiary amino N-oxide units which have the formula: <formula> formula see original document page 0 </formula> (x) and mixtures thereof; in B is a continuation of the main chain by the branch having the formula: [J — R] -; R is a hydrophilic moiety of the main chain selected from the group consisting of: i) linear C 2 -C 12 alkylene, branched C 3 -C 12 alkylene or mixtures thereof; ii) alkylene oxyalkylene units having the formula: <formula> formula see original document page 0 </formula> iii) hydroxy alkylene units having the formula: <formula> formula see original document page 0 </formula> - (CH2) x (CH) y (CH2) i- iv) hydroxy alkylene units or oxyalkylene units having the formula: <formula> formula see original document page 50 </formula> (CH2) x (CH) y (CH2) z (X ) R4 (R2O) OR4 (CH2) x (CH) y (CH2) z (X) r- v) carbenoxy alkylenoxy units having the formula: - (R3O) w (R3) w (X) rC- (X ) r-R3- (X) rC- (X) 1 (R3) w (OR3) w- · vi) and mixtures thereof; R1 is selected from the group consisting of: i) hydrogen; ii) C1 to C22 alkyl; iii) C7 to C22 arylalkyl; iv) - [CH 2 CH (O R 4) CH 2 O] s (R 20) t Y; v) anionic units; vi) and mixtures thereof; R 2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and mixtures thereof; R 3 is C 2 to C 8 linear alkylene, C 3 to C 8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; R4 is hydrogen, C1 to C4 alkyl, - (R2O) tY1 and mixtures thereof; Q is a quaternization unit selected from the group consisting of linear C1 to C4 alkyl, hydroxy C1 to C4 alkyl, benzyl, (R2 O) t Y, and mixtures thereof; X is oxygen, -NR 4 -, and mixtures thereof; Y is hydrogen, C1 to C4 linear alkyl, an anionic unit, and mixtures thereof; index j is from 0 to 20; the index k is from 1 to 20; η is from 1 to 99; the index r is 0 or 1; the index s is from 0 to 5; the index t has an average value of about 0.5 to about 100; the index w is from 0 to 25; indices x, y, and ζ are independently from 0 to 6. Liquid detergent composition according to claim 14, characterized in that the zwitterionic polyamine has the formula: wherein R units have the formula - (R2O ) wherein R 2 and R 3 are independently selected from the group consisting of C 2 to C 8 linear alkylene, C 3 to C 8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; Y is an anionic unit selected from the group consisting of - (CH2) fCO2M1 -C (O) (CH2) fCO2M1 - (CH2) fPO3M, - (CH2) fOPO3M, - (CH2) fSO3M1 - CH2 (CHSO3M) (CH2) fSO3M1 -CH2 (CHSO2M) (CH2) fSO3M1 and mixtures thereof; M is hydrogen, a water-soluble cation, and mixtures thereof; the index f is from 0 to 10; Q is a quaternization unit selected from the group consisting of linear C1 to C4 alkyl, hydroxy C1 to C4 alkyl, benzyl, (R2 O) t Y, and mixtures thereof; the index m is from 0 to 20; The t-index is from 15 to 25. Cation 14, further comprising a modified water-soluble or dispersible polyamine compound. 16. Liquid detergent composition according to claim