WO1996037597A1

WO1996037597A1 - Detergent formulations

Info

Publication number: WO1996037597A1
Application number: PCT/EP1996/002112
Authority: WO
Inventors: Sridhar Gopalkrishnan; Kathleen M. Guiney; John V. Sherman; David T. Durocher; Michael C. Welch
Original assignee: Basf Corporation; Basf Aktiengesellschaft
Priority date: 1995-05-23
Filing date: 1996-05-17
Publication date: 1996-11-28
Also published as: JPH11505867A; EP0850294A1; AU5898096A

Abstract

The present invention relates to detergent compositions containing hydrophilic copolymers of formula (I) wherein x, y, and z are integers, (x + y):z is from about 5:1 to about 1000:1, and y can be any value ranging from zero up to the value of x; M is an alkali metal or hydrogen; R1 is H or CH3; R2 is -COOM, -OCH3, -SO3M, -O-CO-CH3, -CO-NH2; W is selected from residues of formula (II), (III) or (IV) or mixtures of (III) and (IV); wherein R1 is as defined above; R3 is -CH2-O-, -CH2-N-, -COO-, -O-, (1), -CO-NH-; Q is (2), (3) or (4) wherein M is as defined above; a is an integer from 0 to about 516; b is an integer from 0 to about 680; with the proviso that the sum of a + b cannot be 0; R4 is a C3-C4 alkyleneoxy group; and R5 is -CH2-CH2-O-, G and G1 are end groups.

Description

Detergent formulations

FIELD OF THE INVENTION

The present invention relates to detergent crutcher slurry com¬ positions that contain hydrophilic copolymers which permit the reduction of viscosity of such slurries and facilitate their pro¬ cessing during the manufacture of commercial powder detergents, as well as to laundry detergent formulations containing said copolymers and showing improved anti-redeposition properties.

BACKGROUND OF THE INVENTION

Spray-drying is a typical method of manufacturing powder laundry detergents and involves combining inorganic builder mixtures such as alkali metal bicarbonate, alkali metal carbonate, alkali metal silicate or water-insoluble builders such as zeolite, with water, to form a concentrated slurry. Such slurries typically contain surfactants which are usually anionic in nature, such as linear alkylbenzene sulfonate, alcohol ether sulfates, alcohol sulfates, secondary alkane sulfonates, alphaolefin sulfonates etc. Non- ionic surfactants, although not normally included in the crutcher, can be incorporated in the crutcher in small amounts; however, particular attention needs to be devoted to environmen¬ tal concerns related to "pluming" associated with the spray dry¬ ing of such slurries. A crutcher composition typically consti¬ tutes about 45 % - 60 % solids although it is possible to have a solids content greater than 60 % in the crutcher.

Powder detergent compositions typically involve the addition of substantial amounts of alkali metal carbonates, such as sodium carbonate, to the crutcher mix. Alkali metal carbonates, in par¬ ticular sodium carbonate, can constitute a substantial percentage of the powder detergent formulation, and are added primarily to remove hardness ions such as calcium, via an ion exchange mecha¬ nism, and also to provide alkalinity to the wash liquor. In a typical powder detergent manufacturing process, the crutcher mix is processed through a spray tower at very high temperatures to form dry beads. If the detergent formulation contains nonionic surfactants or heat-sensitive ingredients, these additives are sprayed on and absorbed into the dried beads.

A common problem associated with crutcher slurries that contain significant amounts of alkali metal carbonates is their tendency to gel, particularly in the presence of anionic surfactants. This gelling significantly increases the viscosity of the crutcher slurry and makes the crutcher slurry very difficult to process.

In order to reduce the gelation of such slurries for processing, polymeric dispersants have been added to the crutcher mix. Exam¬ ples of such additives are polycarboxylate polymers such as acrylic polymers and acrylic/maleic copolymers which are added in small amounts, typically about 5 % based on the weight of the de¬ tergent composition. The addition of polycarboxylates results in the dispersion of solids in the crutcher and thereby reduces the viscosity of the crutcher slurry.

U.S. Patent No. 4,368,134 teaches the use of water-soluble citric acid salts along with magnesium sulphate to reduce the viscosity of aqueous detergent slurries. U.S. Patent No. 4,362,640 teaches a method for reducing the viscosity of carbonate based crutcher slurries during the addition of aqueous sodium silicate by adding CO₂ with the silicate solution. U.S. Patent No. 4,311,606 teaches a method of reducing the viscosity of carbonate based crutcher slurries through the addition of sodium sesquicarbonate along with citric acid. However, the additives listed in the prior art described above function merely as dispersants and the viscosity reduction achieved via these methods ist modest.

Redeposition of soil on to the fabrics during laundering poses another significant problem and the art is replete with a number of additives that are incorporated in laundry detergent formulation to minimize soil redeposition.

This art is inundated with examples of additives that offer anti- redeposition advantages in laundry detergent compositions, such as the use of cellulosic polymers, polyethylene glycols of vary¬ ing molecular weights, and synthetic polymers. Particularly pre¬ ferred are cellulosic polymers such as carboxymethyl cellulose (CMC) and synthetic polymers such as polyvinylpyrrolidone. More¬ over, U.S. patents 4,548,744, 4,622,378, and 4,676,921 teach the utility of amine ethoxylates as anti-redeposition agents in de¬ tergent compositions. In addition, polyacrylic acid polymers of certain molecular weights offer anti-redeposition benefits when incorporated in laundry detergents.

While the known anti-redeposition additives have adequate soil suspension properties, they do not have adequate performance when it comes to particulate soil suspension and anti-redeposition, in particular, clay soil. Cellulosic polymers such as hydroxypropyl methylcellulose offer good anti-redeposition advantages for oil- type soil, but also do not offer significant anti-redeposition benefits for particulate soil removal, specifically clay soil.

OBJECTS OF THE INVENTION

It is therefore a first object of the invention to provide hydro¬ philic copolymers allowing to remove the above-mentioned defi¬ ciencies of the art. In particular, said copolymers should be useful in reducing the viscosity of aqueous detergent slurries, in particular of concentrated, optionally soda ash based, deter¬ gent slurries. Moreover, copolymers with improved anti-redeposi¬ tion properties for incorporation into laundry detergents should be provided for the purpose of minimizing redeposition of par¬ ticulate soils, such als clay soil, during the laundering pro- cess.

A second object is to provide a method of reducing the viscosity of aqueous detergent slurries.

A third object is to provide a method of reducing the viscosity of aqueous soda ash based detergent slurries.

A fourth object of the invention is to provide a method of pre¬ venting redeposition of particulate soils, such as clay soil, during the laundering process.

SUMMARY OF THE INVENTION

The inventors have now found that said hydrophilic copolymers when incorporated in small amounts in the crutcher slurry com¬ position give a substantial decrease in the viscosity of the slurry compared to the viscosity reducers known in the art. The viscosity decrease with the hydrophilic polymers may be two to three orders of magnitude lower than the viscosity achieved with- out the polymer in the slurry.

The inventors have also found that these copolymers when incorpo¬ rated in small amounts an aqueous soda ash based detergent slur¬ ries function as dispersants and give a substantial decrease in the viscosity of the slurry.

It was also observed by the inventors, that upon incorporation of said copolymers into laundry detergents redeposition of particu¬ late soils, such als clay soil, during the laundering process can be minimized. A second embodiment refers to an aqueous detergent slurry com¬ position with reduced viscosity which contains about 5 - 60 % of inorganic builder salts, about 5 - 70 % of detergent active mat¬ ter selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, and about 0.01 - 10 % of said hydrophilic copolymer comprising said unsaturated hydrophilic monomer copolymerized with an oxyalkylated monomer.

A third embodiment of the invention refers to an aqueous soda ash based detergent slurry composition with reduced viscosity which contains about 5 - 65 % of inorganic builder salt comprising soda ash, and about 0.01 - 20 % of said copolymer comprising an unsat¬ urated hydrophilic monomer copolymerized with an oxyalkylated monome .

A fourth embodiment of the invention refers to a laundry deter¬ gent composition comprising 0.01 to 10 % by weight of said copolymer comprising a hydrophilic monomer and an oxyalkylated monomer, which provides superior anti-redeposition benefits compared to conventional polycarboxylate polymers used in laundry detergents.

Also provided as part of the invention is a method of reducing the viscosity of aqueous detergent slurries which comprises ad- ding thereto about 0.01 - 10 % of at least one of the herein de¬ fined hydrophilic copolymer as well as a method of reducing the viscosity of aqueous soda ash based detergent slurries which com¬ prises adding thereto about 0.01 - 20 % of at least one of the herein defined copolymers.

A further embodiment of the invention concerns a method of pre¬ venting soil redeposition, comprising adding to a laundry deter¬ gent 0.01 to 10 % by weight of at least one of the herein defined copolymers.

The hydrophilic copolymer of the present invention is preferably of the formula (I)

wherein x, y, and z are integers, (x + y):z is from about 5:1 to about 1000:1, and y can be any value ranging from zero up to the value of x;

M is an alkali metal or hydrogen;

R_l is H or CH₃;

R₂ is -COOM, -OCH₃ -S0₃M, -O-CO-CH₃, -CO-NH₂;

W is selected from residues of formula (II), (III) or (IV)

(ID ( III ) ( IV)

or mixtures of (III) and (IV);

wherein

Ri is as defined above;

R₃ is -CH₂-0-, -CH₂-N-, -COO-, -0-, -CH₂-0-CH₂-CH-0-, -CO-NH-;

Q is

wherein

M is as defined above a is an integer from 0 to about 516 b is an integer from 0 to about 680 with the proviso that the sum of a + b cannot be 0; R₄ is a C₃-C alkyleneoxy group; R5 is -CH₂-CH₂-0-; and G and G¹ are end groups.

BRIEF DESCRIPTION OF THE DRAWINGS 5

Figure 1 shows the ability of the copolymers of the invention to reduce the viscosity of aqueous sodium carbonate slurries. The performance of the polymers of this invention is compared to com¬ mercially available polymers that are typically added to deter- 0 gent slurries during the commercial manufacture of powder laundry detergents.

Figures 2 and 3 illustrate the soil anti-redeposition properties of the copolymers of the invention as against known anti-rede- 5 position additives.

DETAILED DESCRIPTION OF THE INVENTION

The hydrophilic copolymer of the present invention is preferably 0 a compound of the formula (I)

G¹ (I)

wherein x, y, and z are integers, (x + y):z is from about 5:1 to about 30 1000:1, preferably about 50:1 to 800:1, and more preferably about 100:1 to about 500:1, as for example 125:1, and y can be any value ranging from zero up to the value of x, preferably zero;

M is hydrogen or an alkali metal, preferably sodium or potassium. 35

Ri is H or CH₃; preferably H;

R₂ is -COOM, -OCH₃, -SO₃M, -O-CO-CH3, -CO-NH₂, preferably -COOM;

W is selected from residues of formula (II), (III) or (IV) 40

45

( ID ( III ) ( IV)

or mixtures of. (Ill) and (IV); preferably a residue of formula (II); or (III),

wherein

Ri is as defined above;

R₃ is -CH₂-0-, -CH₂-N-, -COO-, -0-, -CH₂-0-CH₂-CH-0-, -CO-NH-;

preferably -CH₂-0-; preferably R₃ is linked to the polymer backbone via the left-hand free chemical bond;

Q is

wherein

M is as defined above a is an integer from 0 to about 516 b is an integer from 0 to about 680 with the proviso that the sum of a + b cannot be 0;

R is a C₃-C₄ alkyleneoxy group;

R₅ is -CH₂-CH -0-; and

G and G¹ are end groups such as OH, SH, SR₇, SO₃M, OR₇ or H, R₇ being alkyl or aryl. G and G¹ may have the same meaning. According to one preferred embodiment a copolymer of formula (I) is provided wherein a is 0 and b is an integer from about 3 to about 680; preferably from about 8 to about 225, more preferably from about 12 to about 135, most preferably about 15.

According to another preferred embodiment, the ratio of a : b is from about 5:95 to about 100:0 and preferably from about 20:80 to about 80:20.

Also preferred are copolymers, wherein a:b is from about 1:4 to about 1:99, preferably from about 1:5 to about 1:20 and in par¬ ticular about 1:5.

Preferably, the values of a and b in the sidechain are such that the combined weights of R₄ and R₅ are such that the oxalkylated monomer has a solubility of at least about 500 grams/liter in water, preferably at least about 700 grams/liter. R₄ and R₅ may be interchangeable or randomly distributed in the sidechain.

The total molecular weight of the copolmer should be within the range of about 500 to 500,000, as determined by gel permeation chromatography. Preferably, the molecular weight falls within the range of about 1,000 to 100,000; more preferably within the range of about 1,000 to 20,000 (weight average molecular weight - WAMW; unless otherwise specified, molecular weights herein are given in terms of WAMW) .

The hydrophilic copolymer of the present invention is prepared by copolymerizing at least two different kinds of monomers, an un- saturated hydrophilic monomer and an oxyalkylated monomer. These monomers may be randomly distributed in polymerized form as monomer units within the polymer backbone.

Examples of unsaturated hydrophilic monomers useful in the pres- ent invention include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, methacrylate esters and substituted methacrylate esters, vinyl acetate, vinyl acetate copolymerized with said oxyalkylated monomer and hydrolyzed to polyvinyl alco¬ hol, vinyl alcohol, polyvinyl alcohol, methylvinyl ether, cro- tonic acid, itaconic acid, vinyl acetic acid, and vinylsulpho- nate. Preferably, the unsaturated hydrophilic monomer component of the hydrophilic copolymer in formula I is acrylic acid.

Examples of the oxyalkylated monomer include compounds that have a polymerizable olefinic moiety with at least one acidic hydrogen and are capable of undergoing addition reaction with alkylene ox¬ ide. It is also possible to include monomers with at least one acidic hydrogen that are polymerized first, and then subsequently oxyalkylated to yield the desired pxoduct. For example, allyl al¬ cohol is especially preferred since it represents a mono¬ functional initiator with a polymerizable olefinic moiety having an acidic hydrogen on the oxygen, and is capable of adding to alkylene oxide. Similarly diallylamine represents another mono¬ functional initiator with polymerizable olefinic moieties, having an acidic hydrogen on the nitrogen, and is capable of adding to alkylene oxide. Other examples of the oxyalkylated monomer of the copolymer include reaction products of either acrylic acid, meth¬ acrylic acid, maleic acid, or 3-allyloxy-l,2-propanediol with alkylene oxide.

The molecular weight of the oxalkylated monomer according to the various embodiments of the invention should be within the range of about 200 to 30,000, preferably about 300 to 15,000, and more preferably about 600 to 5000.

Preferred is for example an oxyethylated monomer which is a ethylene oxide adduct of allyl alcohol. This monomer has a molec¬ ular weight of about 700, and R₄ is a oxyethylene group repre¬ sented by the formula -CH₂-CH₂-0.

A preferred hydrophilic copolymer results from the polymerization of ac:/lic acid monomer with the ethylene oxide adduct of allyl alcohol, i.e.. copolymer of Formula I, wherein y = 0, Ri = H, R₂ = COOM wherein M is sodium, W is a residue of formula (II) , wherein R₃ = CH₂ - 0, R₅ is -CH₂-CH₂-O, and b is about 15.

Another preferred oxyalkylated monomer is a propylene oxide and ethylene oxide adduct of allyl alcohol. This monomer has a molec¬ ular weight of about 3800, and R is a propyleneoxy group repre¬ sented by the formula -CH₂-CH(CH₃)-0 and R₅ is -CH₂-CH₂-0. In this monomer, Ri = H, R₂ = COOM, R₃ = CH₂ - 0, and y = 0. The weight ratio percent of a:b in the oxyalkylated monomer is preferably about 20:80.

Preferred oxyalkylated monomer is also a propylene oxide and ethylene oxide adduct of allyl alcohol. This monomer has a molec- ular weight of about 700, and R₄ is a propylene group and R₅ is -CH₂-CH -0. In this monomer, Ri = H, R₂ = COOM, R₃ = CH₂ - 0, and y = 0. The weight ratio recent of a:b in the oxalkylated monomer is preferably about 80:20.

Still another preferred oxyalkylated monomer is a propylene oxide and ethylene oxide adduct of allyl alcohol having a molecular weight of about 1500 to 3800. In this oxyalkylated monomer, Ri = H, R₂ = COOM, R₃ = CH₂ - O, and y - 0 and the ratio of a:b is about 1:5.

The oxyalkylated moiety represents the side chain of this oxyal- kylated monomer. The side chain is hydrophilic in nature; that is, the side chain when isolated from its linkage to the backbone carbon atom has extensive solubility in water. The monomer unit containing the hydrophilic side chain also has similar solubility characteristics as the side chain. Preferably, the side chain when isolated from its linkage to the backbone will have a solu¬ bility in water of at least about.500 grams/liter, and even more preferably about 700 grams/liter, or more. Moreover, the entire side chain is hydrophilic in nature by virtue of its .extensive solubility in water.

The above-described hydrophilic copolymers are added to detergent compositions, hereinafter described, preferably to reduce viscos¬ ity of the detergent slurry or to improve the anti-redeposition properties of the detergent.

A first preferred aqueous detergent slurry composition of the in¬ vention comprises

(A) about 5 - 60 %, preferably about 15 to 50 % and more prefera- bly about 25 to 40 % of inorganic builder salts;

(B) about 5 - 70 %, preferably about 10 to 45 % and more prefera¬ bly about 15 to 35 % of detergent active matter selected from the group consisting of anionic, nonionic, cationic, amphote- ric and zwitterionic surfactants; and

(C) about 0.01 - 10 % of said hydrophilic copolymer comprising a hydrophilic monomer copolymerized with an oxyethylated mono¬ mer. Preferably, the copolymer of the invention make up about 0.5 to 7 % of a typical laundry formulation, even more prefe¬ rably about 1 to 5 %. (Unless otherwise stated, all weight percentages are based upon the weight of the total detergent formulation) .

Preferably, this composition comprises at least one copolymer of one of the following formulas:

wherein

Ri, R2, R3 R5, M, G, G¹, x, y, and z are as defined above; R_δ is a residue of the above formulas (III) or (IV) or a mixture thereof, wherein Q is as defined Pbove, provided that a is 0 and R₅ and M are as defined jove; and b is an integer from about 3 to about 680.

Alternatively, this composition may comprise at least one copolymer of one of the following formulas:

or

wherein

Rι» 2» R ₃/ R₄» R51 M, G, Gⁱ, x, y, and z are as defined above; Re is a residue of the above formulas (III) or (IV) or a mixture thereof; and a:b is from about 1:4 to about 1:99.

Another preferred composition of the invention is an aqueous soda ash based detergent slurry composition comprising

(A) about 5 - 65 %, preferably about 15 to 55 % and more prefera¬ bly about 35 to 50 % of inorganic builder salt comprising soda ash (i.e. sodium carbonate) and

(B) about 0.01 - 20 % of a copolymer comprising a hydrophilic mo¬ nomer copolymerized with an oxyalkylated monomer.

Preferably, the copolymer of the invention is about 1 % to 14 % of a slurry composition; more preferably about 2 % to 5 % of the slurry composition. (Unless otherwise stated, all weight-percent¬ ages are based upon the weight of the total solids in the slurry composition) .

Optionally, the slurry composition may contain about 0 - 20 %, preferably about 10 - 15 %, of inorganic builder salts other than sodium carbonate, such that the total amount of inorganic builder salt including sodium carbonate is as defined above.

The aqueous soda ash slurry composition can also optionally con¬ tain small amounts of surfactants or detergent active matter, that are conventionally employed in cleaning compositions.

These soda ash based compositions preferably comprise at least one copolymer of one of the following formulas:

Ri

-f^CH2-βτf CH- CH J -Rβ ]- G (lb)

-ly l_ -J z

R2 COOM COOM wherein

Ri, R₂, R₃, M, G, G¹, x, y, and z are as defined above;

Re is a residue of the above formulas (III) or (IV) or a mixture thereof,

wherein Q is

and a:b is from about 5:95 to about 100:0

Still another preferred composition is a laundry detergent com- position comprising about 0.01 to 10 %, preferably about 0.5 to 6 % and more preferably about 2 % by weight, of an anti-redeposi¬ tion additive comprising a copolymer of a hydrophilic monomer and an oxyalkylated monomer.

Preferably, this laundry composition comprises a copolymer having the following formula:

Y

wherein Q is

which is, unless otherwise stated, preferred, or

and Ri, R₂, R₃, R₄, R₅, M, G, G^l, x, y, z, a, and b are as defined above.

The inorganic builder salts as used in the compositions of the invention may be selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal sili¬ cates, alkali metal phosphates, and zeolites. Preferably the de¬ tergent slurry composition contains major amounts of alkali metal carbonates such as sodium or potassium carbonate as for example about 15 - 45 %, preferably about 25 - 35 %. The builder material sequesters the free calcium or magnesium ions in water and pro¬ motes better detergency. Additional benefits provided by the builder are increased alkalinity and soil suspending properties. Water-insoluble builders which remove hardness ions from water by an ion-exchange mechanism are the crystalline or amorphous alumi- nosilicates referred to as zeolites. Typical zeolites are univa- lent cation-exchanging compounds and examples of such crystalline types of zeolites are Zeolite A, Zeolite X or Zeolite Y. The above-mentioned zeolites are typically used as builders in deter¬ gent ocmpositions. A more detailed description of such types of zeolites can be found in the Zeolite Molecular Sieves (1984) au¬ thored by D.W. Breck. Secondary builders such as the alkali metal salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid can also be utilized in the detergent compositions of the inven¬ tion. Other secondary builders known to those skilled in the art may also be utilized.

The detergent active matter as used in the compositions of the invention may be selected from the group of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants known to the skilled artisan. Examples of these surfactants may be found in McCutcheon, Detergents and Emulsifiers (1993), incorporated herein by reference. Examples of nonionic surfactants will in¬ clude commonly utilized nonionic surfactants which are either linear or branched and have an HLB of from about 6 to 18, prefer- ably from about 10 to 14. Examples of such nonionic detergents are alk lphenol oxyalkylates (preferably oxyethylates) and alco¬ hol oxyethylates. Examples of the alkylphenol oxyalkylates in- elude C6 - Ci8 alkylphenols, preferably C to CQ , with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both. Examples of alcohol oxyalkylates include Cg - Cie alcohols with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both. Some of these types of nonionic surfactants are available from BASF Corp. under the trademark PLURAFAC. Other types of nonionic surfactants are available from Shell under the trademark NEODOL. in particular, a C₁₂ - C₁₅ alcohol with an aver¬ age of 7 moles of ethylene oxide under the trademark NEODOL ® 25 - 7 is especially useful in preparing the laundry detergent com¬ positions useful in the invention. Other examples of nonionic surfactants include products made by condensation of ethylene ox¬ ide and propylene oxide with ethylene diamine (BASF, TETRONIC ® AND TETRONIC ® R) . Also included are condensation products of ethylene oxide and propylene oxide with ethylene glycol and propylene glycol (BASF, PLURONIC ® and PLURONIC ® R) . Other non¬ ionic surface active agents also include alkylpolyglycosides, long chain aliphatic tertiary amine oxides and phosphine oxides.

Typical anionic surfactants used in the detergency art include the synthetically derived water-soluble alkali metal salts of organic sulphates and sulphonates having about 6 to 22 carbon atoms, preferably 12 to 15 carbon atoms. The commonly used anionic surfactants are sodium alkylbenzene sulphonates, sodium alkylsulphates and sodium alkylether sulphates. Other examples include N-alkylglucosamides, reaction products of fatty acids with isethionic acid neutralized with sodium hydroxide, sulphate esters of higher alcohols derived from tallow or coconut oil, and alpha-methylestersulfonates.

Examples of ampholytic detergents include straight or branched aliphatic derivatives of heterocyclic secondary or tertiary amines. The aliphatic portion of the molecule typically contains about 8 to 20 carbon atoms, preferably 12 to 15 carbon atoms. Zwitterionic detergents include derivatives of straight or branched aliphatic quaternary ammonium, phosphonium or sulfonium compounds.

The detergent slurry compositions heretofore described may be used to manufacture detergent compositions. The slurry can be spray dried and additional ingredients such as enzymes, anti-re¬ deposition agents, optical brighteners, as well as dyes and per¬ fumes known to those skilled in the art can be added. Other op¬ tional ingredients may include fabric softeners, foam suppres- sants, and oxygen or chlorine releasing bleaching agents. The hydophilic copolymer as part of the invention may be prepared by the skilled artisan according to the process below, in which the alkylene oxide adduct of allyl alcohol is copolymerized with acrylic acid by way of a non-limiting example.

EXAMPLES

The following examples will serve to demonstrate the efficacy of the hydrophilic copolymer according to various embodiments of the invention. These examples should not be construed as limiting the scope of the invention.

Example 1:

Preparation of a Hydrophilic Copolymer comprising an Oxyalkylated Monomer (Alkylene Oxide = Propylene Oxide and Ethylene Oxide)

(A) Preparation of Oxvalkvlated Monomer (Αlkvlene Oxide Adduct of Allvl Alcohol)

To a 2 gallon stainless steel autoclave equipped with steam heat, vacuum and nitrogen pressure capability and agitation, a homoge¬ nous mixture of 396.2 grams of allyl alcohol and 44.1 grams of potassium t-butoxide was charged. The vessel was sealed, purged with nitrogen and pressurized to 90 psig with nitrogen. The pres¬ sure was then relieved to 2 psig and the temperature of the ves¬ sel was adjusted to 80°C. The first 125 grams of propylene oxide was added over a 1 hour period. The temperature was maintained between 75-85°C and the pressure was maintained at <90 psig. The next 200 grams of propylene oxide was added over a 1 hour period and at 75-85°C and <90 psig pressure. The next 400 grams of propylene oxide was added over a 1 hour period at 100-110°C and <90 psig pressure. The remaining 4551.2 grams of propylene oxide was charged at 500 grams per hour and at 120-130°C and <90 psig pressure. After all of the propylene oxide was added, the mixture was reacted at 125°C for 2 hours and the vessel was vented to 0 psig. The material was stripped at <10mm Hg and 125°C for 1 hour then cooled to 50°C and discharged into an intermediate holding tank for analysis.

To a 5 gallon stainless autoclave equipped with steam heat, vac¬ uum and nitrogen pressure capability and agitation, 2696.8 grams of the allyl alcohol propylene oxide intermediate was charged. The vessel was sealed and pressurized to 90 psig with nitrogen and vented to 2 psig. This was repeated two more times. The temperature was adjusted to 145°C and the pressure was readjusted to 34 psig with nitrogen. To the vessel, 10788.9 grams of ethylene oxide was charged at 1400 grams per hour. The temperature was maintained at 140-150°C and the pressure was main¬ tained at <90 psig. If the pressure rose above 85 psig, the ethylene "xide addition was slowed. If this failed to lower the pressure, :.he addition was halted and allowed to react at 145°C for 30 minutes. The vessel was slowly vented to 0 psig and re- padded to 34 psig with nitrogen. The addition was continued at 140-150°C and <90 psig pressure. After all of the ethylene oxide was added, the material was held at 145°C for 1 hour. It was then cooled to 90°C and 14.3 grams of 85% phosphoric acid was added. The material was mixed for 30 minutes and then vacuum stripped at 100°C for 1 hour. The batch was cooled to 70°C and discharged into a holding tank. The product was found to have a number average molecular weight of 4091 by phthalic anhydride esterification in pyridine.

(B) Polymerization of Oxvalkvlated Monomer With Hydrophilic Mono¬ mer (Acrylic Acid)

To a two liter, four necked flask equipped with a mechanical stirrer, reflux condenser, thermometer, and outlet for feed lines, were added 301 grams of distilled water and 2.6 grams of 70% phosphorous acid. This solution was heated to 95 degrees cen¬ tigrade at which time a monomer blend of 555.4 grams of glacial acrylic acid and 61.7 grams of an allyl alcohol initiated prop¬ oxylate ethoxylate (I) (molecular weight 3500), a redox initiator system consisting of 132 grams of a 38 % sodium bisulfite solu¬ tion and 155.4 grams of a 10.9 % sodium persulfate solution, were fed into the flask linearly and separately while maintaining the temperature at 95 ± 3 degrees centigrade. The sodium bisulfite solution and monomer blend feeds were added over 4 hours while the sodium persulfate solution was added over 4.25 hours. The three feeds were added via teflon 1/8 inch tubing lines connected to rotating piston pumps. Appropriately sized glass reservoirs attached to the pumps hold the monomer blend and initiator feeds on balances accurate to 0.1 gram to precisely maintain feed rates. When the additions were complete, the system was cooled to 80 degrees centigrade. At 80 degrees centigrade, 25.3 grams of a 2.4 % 2,2'-azobis (N,N'-dimethyleneisobutyramidine) dihydro- chloride solution was added to the system over 0.5 hours as a postpolymerizer. When addition was complete, the system was reacted for 2 hours at 80 degrees centigrade. After reaction, the system was cooled to 60 degrees centigrade and the solution pH was adjusted to about 7 with the addition of 658 grams of 50 % sodium hydroxide solution. The resultant neutral polymer solution had an approximate solids content of 40 %. Example 2 :

Preparation of a Hydrophilic Copolymer Comprising a Oxyethylated Monomer

(A) Preparation of Oxyethylated Monomer (Ethylene Oxide Adduct of Allyl Alcohol)

To a 1 gallon stainless steel autoclave equipped with steam heat, vacuum and nitrogen pressure capability and agitation, a homoge¬ nous mixture of 210.5 grams of allyl alcohol and 23.4 grams of potassium £. - butoxide were charged. The vessel was sealed, purged with nitrogen and pressurized to 90 psig with nitrogen. The pressure was then readjusted to 34 psig and the temperature of the vessel was adjusted to 80°C. The first 75 grams of ethylene oxide were charged over a 1 hour period at 75 - 85°C and < 90 psig pressure. The next 125 grams of ethylene oxide were charged over an hour period at 75 - 85°C and < 90 psig. The next 225 grams of ethylene oxide were charged over a 1 hour period at 100 - 110°C and < 90 psig. The remaining 2140.9 grams of ethylene oxide were added over an 8 hour period at 145 - 155°C and < 90 psig pressure.

After all of the ethylene oxide was added, the mixture was reacted at 150°C for 2 hours and the vessel was vented to 0 psig. The material was stripped at < 10 mm Hg and 125°C for 1 hour then cooled to 50°C and discharged into an intermediate holding tank for analysis. The mixture was then considered an allyl alcohol ethylene oxide intermediate.

To a 2 gallon stainless steel autoclave equipped with steam heat, vacuum, nitrogen pressure capability and agitation, 498.8 grams of the allyl alcohol ethylene oxide intermediate were charged. The vessel was sealed and pressurized to 90 psig with nitrogen and vented to 2 psig. This was repeated two more times. The temperature was adjusted to 145°C and the pressure was readjusted to 34 psig with nitrogen. To the vessel, 2198.3 grams of ethylene oxide were charged at 275 grams per hour. The temperature was maintained at 140 - 150°C and the pressure was maintained at < 90 psig. If the pressure rose above 85 psig, the ethylene oxide addition was slowed. If this action failed to lower the pressure, the addition was halted and allowed to react at 145°C for 30 min¬ utes. The vessel was slowly vented to a 0 psig and repadded to 34 psig with nitrogen. The addition was continued at 140 - 150°C and < 90 psig pressure. After all of the ethylene oxide was added, the material was held at 145°C for 1 hour. It was then cooled to 90°C and 2.9 grams of 85 % phosphoric acid were added. The material was mixed for 30 minutes and then vacuum stripped at 100°C for 1 hour. The batch was cooled to 70°C and discharged into a holding tank. The ethylene oxide adduct of allyl alcohol product was found to have a number average molecular weight of 4095 g/mol by phthalic anhydride esterification in pyridine.

(B) Copolvmerization of Oxvethvlated Monomer with Hydrophilic Mo¬ nomer (Acrvlic Acid)

To a two liter, four-necked flask equipped with a mechanical stirrer, reflux condenser, thermometer, and outlet for feed lines, were added 301 grams of distilled water and 2.6 grams of 70 % phosphorous acid. This solution was heated to 95°C at which time a monomer blend of 555.4 grams of glacial acrylic acid and 62.8 grams of an allyl alcohol initiated ethoxylate (molecular weight 3800) and a redox initiator system consisting of 132 grams of a 38 % sodium bisulfite solution and 155.2 grams of a 10.9 % sodium persulfate solution, were fed into the flask linearly a. d separately while maintaining the temperature at 95 (+/-3)°C. The sodium bisulfite solution and monomer blend feeds were added over 4 hours while the sodium persulfate solution was added over 4.25 hours. The three feeds were added via TEFLON ® 1/8 inch tubing lines connected to rotating piston pumps. Appropriately sized glass reservoirs attached to the pumps hold the monomer blend and initiator feeds on balances accurate to 0.1 grams to precisely maintain feed rates.

When the additions are complete, the system was cooled to 80°C. At this temperature, 25.3 grams of a 2.4 % 2,2' - azobis (N,N'-dime- thyleneisobutylramidine)dihydrochloride solution were added to the system over 0.5 hours as a postpolymerizer. When addition was complete, the system was reacted for 2 hours at 80°C. After reaction, the system was cooled to 60°C and the solution pH was adjusted to about 7 with the addition of 658 grams of 50 % sodium hydroxide solution. The resultant neutral polymer solution had an approximate solid content of about 40 %. Example 3 :

Viscosity-Reducing Properties of Oxyalkylated Copolymers in an Aqueous Detergent Slurry Composition

The examples describe the viscosity reducing properties of the hydrophilic copolymers of this invention when added in small amounts to aqueous detergent slurry compositions. The numbers in each column in Table 1 refer to the active weight percentage of each component in the detergent formulation. The viscosity values reported in Table 1 are Brookfield viscosities measured with a Brookfield Viscometer (RVT Model) using spindle # 4 at 20 rpm. All viscosity measurements were immediately measured after sample preparation at 25°C. The viscosity reducing properties of the hy- drophilic copolymers of this invention were evaluated in a con¬ centrated aqueous detergent composition built with different builders such as sodium silicate, sodium carbonate, alkali metal phosphate, and zeolite. The performance of Polymers C & D, copolymers that fall within the scope of the invention, are compared to conventional polycarboxylates (Polymers A & B) that are widely used in detergent formulations.

The nonionic surfactant used in the formulations shown in the Table 1 is NEODOL ® 25-7, a product of Shell. The linear alkyl- benzene sulfonic acid, sodium salt (LAS) was obtained from Vista under the name Vista C-560 slurry. The zeolite was "ZEOLITE A", also known as VALFOR ® 100, available from the PQ Corp of Valley Forge, PA. The sodium carbonate was obtained from the FMC corpo¬ ration under the name "FMC Grade 100". The sodium citrate used was sodium citrate dihydrate obtained from Mallinckrodt Specialty Chemicals Company. Tetrapotassiu pyrophosphate was obtained from the Stauffer Chemical Company. Polymers A and B shown in Table 1 are used for comparative purposes. Polymer A is a sodium salt copolymer of acrylic acid with maleic acid with a weight average molecular weight of 70,000 available from BASF Corporation under the tradename SOKALAN CP5. Polymer B is a sodium salt homopolymer of acrylic acid with a weight average molecular weight of 8000, available from the BASF Corporation under the tradename SOKALAN PA39CL.

Polymer C shown in Table 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, within the scope of the invention and is prepared according to Example 2 ratio by weight of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1. The oxyalkylated monomer compo¬ nent had a molecular weight of about 3800. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - O, R₄ = -CH₂-CH(CH₃) -0, R₅ = -CH₂-CH₂-0 and y = 0. The ratio of a:b was about 1:5. The average molecular weight of Polymer C is about 16000.

Polymer D shown in Table 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, within the scope of the invention and is prepared according to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 85:15 by weight, while the molar ratio was about 123:1. The oxyalkylated monomer component had a molecular weight of about 1500. In this monomer, Ri = H,

R₂ = COONa, R₃ = CH₂ - 0, R₄ = -CH₂-CH(CH₃)-0, R₅ = -CH -CH -0 and y = 0. The ratio of a:b was about 1:5. The average molecular weight of Polymer D was 9280.

Table 1 illustrates that the copolymers of this invention are able to reduce the viscosity of aqueous detergent slurries con¬ taining surfactants and inorganic builders by several orders of magnitude compared to conventional polycarboxylates such as

Sokalan CP5 polymer and Sokalan PA30C1 polymer typically used as dispersants for reducing the viscosity of crutcher slurries. The viscosity reducing properties of Polymers C and D of this inven¬ tion are also compared to the viscosity of detergent slurried that do not contain a polymer.

Example 4:

Viscosity-Reducing Properties of Oxyalkylated Copolymers in an Aqueous Soda Ash based Detergent Composition

The following experimentation describes the viscosity reducing properties of the copolymers of this invention when added in small amounts to aqueous soda ash based detergent slurry. These examples should not be construed as limiting the scope of the in¬ vention.

The sodium carbonate was obtained from the FMC corporation under the name "FMC Grade 100". Polymer E shown in Figure 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, of Formula I within the scope of the invention and is prepared ac¬ cording to Example 2 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1. The oxyalkylated monomer component had a molecular weight of about 3800, and R was a propyleneoxy group represented by the formula -CH₂-CH(CH₃)-0 and R₅ was -CH₂-CH₂-0. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, y = 0, and the ratio of a:b is 20:80.

Polymer F shown in Figure 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, of Formula I within the scope of the invention and is prepared according to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 93:7, while the molar ratio was about 123:1. The oxyalkylated monomer component had a molecular weight of about 700. Q is of the structure such that R₅ is bonded directly to R₃; R was a pro¬ pyleneoxy group represented by the formula -CH₂-CH(CH₃)-0 and R₅ was -CH₂-CH₂-0. The ratio of a:b was 80:20 by weight. In this monomer, Ri = H, R₂ = COONa, R = CH₂ - 0, and y = 0. Sokalan® PA30C1 polymer used in Figure 1 is a polyacrylic, sodium salt sold with a molecular weight of 8000, commercially by BASF Corporation. Sokalan® PA75 polymer is also a polyacrylic acid so¬ dium salt with a molecular weight of 90,000 available commer- cially from the BASF Corporation. Sokalan® CP5 polymer is a copolymer of acrylic acid and maleic acid with a molecular weight of 70000, also available from BASF Corporation.

Figure 1 shows the ability of the copolymers of this invention to reduce the viscosity of aqueous sodium carbonate slurries. The performance of the polymers of this invention is compared to com¬ mercially available polymers that are typically added to deter¬ gent slurries during the commercial manufacture of powder laundry detergents. The dispersing properties of the copolymers of this invention was evaluated as follows: To a one liter stainless bea¬ ker, was added 600 grams of FMC Grade 100 soda ash followed by 400 grams of tap water. The resulting slurry was mixed using a Lightnin"® mixer equipped with a digital read out of the rota¬ tional speed of the impeller as well as the torque. The torque read out reflects the power in watts required to stir the slurry at a fixed rpm. The rpm in this example was set at 1200. Thus by using this technique one can measure the power drawn by the motor which would be directly proportional to the viscosity of the slurry. The initial torque in the absence of the polymer is noted. Thereafter the polymer additive is added in small incre¬ ments ranging from 0.5 % to 3.8 % by weight of the solids in the slurry, to the stirred slurry and the torque readout is then noted. In order to eliminate the effects of dilution, all polymer additives shown in Figure-1 had the same active polymer content. All evaluations were done at 25°C.

Figure 1 shows the performance of three commercial polymers available from BASF Corporation under the SOKALAN trade name. Figure-1 also shows the superior dispersing properties of two copolymers of this invention.

Example 5:

Anti-Redeposition Properties

The following examples described in Figures 2 and 3 will serve to demonstrate the efficacy of the copolymer according to various embodiments of the invention. The example should not be construed as limiting the scope of the invention. All tests were performed using a six-pot Terg-O-Tometer obtained from US Testing Corp. of New Jersey. A 10 minute wash and a 5 minute rinse cycle was employed. The wash and rinse temperature was set a 95F. Nine clay cotton swatches obtained from Scientific Services of New Jersey were used in each pot to provide a signif- icant clay soil load in the wash cycle. In addition, the wash li¬ quor in each pot was spiked with an additional 300 mg of Bandy Black Clay soil. The anti-redeposition performance of the copolymers of this invention were measured over three wash and rinse cycles, using six clean cotton swatches in the first cycle. These swatches are carried over through three wash and rinse cycles. After each wash and rinse cycle, the clay soiled cotton swatches used to provide the clay soil load to the wash liquor were discarded and a fresh set of nine clay swatches were added at the beginning of each wash cycle. At the end of the third rinse cycle, the cotton swatches were dried in a Whirlpool dryer for 90 minutes. The reflectance of the dried swatches were then measured using a Hunter calorimeter. The difference in the re¬ flectance values between the initial clean cotton swatch and the reflectance value of the cotton swatch after three wash and rinse cycles are reported in Figures 2 and 3.

The nonionic surfactant used in the formulation is NEODOL ® 25-7, a product of Shell. The linear alkylbenzene sulfonic acid, sodium salt (LAS) was obtained from Vista under the name Vista C-560 slurry. The zeolite was "ZEOLITE A", also known as VALFOR ® 100, available from the PQ Corp of Valley Forge, PA. The sodium carbonate was obtained from the FMC Corporation under the name "FMC Grade 100". The sodium silicate used was sodium silicate pentahydrate obtained from Mayo Products. SOKALAN ® PA30C1 (Poly¬ acrylic acid, sodium salt) is a product of BASF Corp. SOKALAN ® HP 22 (nonionic graft copolymer) is a product of BASF Corp.

Polymer G is a copolymer of acrylic acid with an oxyalkylated al- lyl alcohol, within the scope of the invention and is prepared according to Example 1 exept that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 85:15 by weight, while the mo¬ lar ratio was about 123:1. The oxyalkylated monomer component had a molecular weight of about 1500, and R₄ was a propyleneoxy group represented by the formula -CH₂-CH(CH₃)-O and R₅ was -CH₂-CH₂-O. The percent ratio of a:b was 20:80. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - O, and y = 0.

Polymer H is a copolymer of acrylic acid with an oxyethylated al- lyl alcohol, within the scope of the invention and prepared ac¬ cording to Example 2 except that the ratio of acrylic acid to the oxyethylated allyl alcohol was 70:30 by weight, while the molar ratio was about 131:1. The oxyethylated monomer component had a molecular weight of about 4100, a = 0 (R is absent), R₅ is - CH₂-CH₂-0, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, and y = 0.

Polymer E is a copolymer of acrylic acid with an oxyalkylated al¬ lyl alcohol, within the scope of the invention and prepared ac¬ cording to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1. The oxyalkylated monomer component had a molecular weight of about 3800, and R was a propyleneoxy group represented by the formula -CH₂-CH(CH₃)-0 and R₅ was -CH₂-CH₂-0. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, and y = 0. The percent ratio of a:b is 20:80.

Polymer F is a copolymer of acrylic acid with an oxyalkylated al¬ lyl alcohol, within the scope of the invention and prepared ac¬ cording to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 93:7, while the molar ratio was about 123:1. The oxyalkylated monomer component had a molecular weight of about 700. Q is of the structure such that R₅ is bonded directly to R₃; R₄ is a propyleneoxy group represented by the for¬ mula -CH₂-CH(CH₃)-0 and R₅ was -CH -CH₂-0. The percent ratio of a:b is 80:20. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, and y = 0.

Polymer J is a copolymer of acrylic acid with an oxyethylated al¬ lyl alcohol, within the scope of the invention and prepared ac¬ cording to Example 1 except that the ratio of acrylic acid to the oxyethylated allyl alcohol was 92.3:7.7 by weight, while the mo- lar ratio was about 116:1. The oxyethylated monomer component had a molecular weight of 700, a = 0 (R₄ is absent), R₅ is -CH₂-CH₂-0, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, and y = 0.

Figures 2 and 3 show the anti-redeposition performance of commer- cial polymers such as Sokalan PA30C1 and Sokalan HP22 polymers as well as polymers of the invention, in anionic and nonionic based detergent formulas. Both of these charts demonstrate the signif¬ icant anti-redeposition benefits provided by the polymers of this invention when compared to conventional anti-redeposition polymers used in detergent formulations. Example 6 :

Viscosity-Reducing Properties of an Oxyethylated Copolymer in an Aqueous Detergent Slurry Composition

The following example describes the viscosity reducing properties of the hydrophilic copolymers of the invention when added to aqueous detergent slurry compositions. The numbers in each column in Table 2 refer to the active weight percentage of each compo- nent in the detergent formulation. The viscosity values reported in Table 2 are measured with a Brookfield Viscometer (RVT Model) using spindle # 4 at 20 rpm. All viscosity measurements were im¬ mediately measured after sample preparation at 25°C. The viscosity reducing properties of the hydrophilic copolymers of this inven- tion were evaluated in a concentrated aqueous detergent composi¬ tion built with different builders such as sodium silicate, so¬ dium carbonate, alkali metal phosphate, and zeolite. The nonionic surfactant used in the formulations shown in the Table 2 is NEO¬ DOL ® 25-7, a product of Shell. The linear alkylbenzene sulfonic acid, sodium salt (LAS) was obtained from Vista under the name Vista C-560 slurry. The zeolite was "ZEOLITE A", also known als VALFOR ® 100, available from the PQ Corp of Valley Forge, PA. The sodium carbonate was obtained from the FMC corporation under the name "FMC Grade 100". The sodium silicate used was sodium meta- silicate pentahydrate obtained from Mayo Products Company. Tetra- potassium pyrophosphate was obtained from the Stauffer Chemical Company.

The performance of Polymer J, a copolymer within the scope of this invention, is compared to conventional polycarboxylates

(Polymers A & B) that are widely used in detergent formulations. Polymer A is a sodium salt copolymer of acrylic acid with maleic acid with a weight average molecular weight of 70,000, available from BASF Corporation under the tradename SOKALAN CP5. Polymer B is a sodium salt homopolymer of acrylic acid with a weight aver¬ age molecular weight of 8000, available from the BASF Corporation under the tradename SOKLAN PA30CL.

Polymer J shown in Table 2 is a copolymer of acrylic acid with an oxyethylated allyl alcohol, within the scope of the invention. The weight ratio of acrylic acid to the oxyethylated allyl alco¬ hol was 92.3:7.7, while the molar ratio was about 116:1. The ox¬ yethylated monomer component had a molecular weight of about 700, and ₅ was -CH₂-CH₂-O. In this monomer, Ri = H, R₂ = COONa, R₃ = CH₂ - 0, and y = 0. The weight average molecular weight of Polymer J is about 17,000.

Table 2 illustrates that the copolymers of this invention are able to reduce the viscosity of aqueous detergent slurries con¬ taining surfactants and inorganic builders by several orders of magnitude compared to conventional polycarboxylates such as Sokalan CP5 polymer and Sokalan PA30C1 polymer typically used as dispersants for reducing the viscosity of crutcher slurries. The viscosity reducing properties of Polymer C of this invention are also compared to the viscosity of detergent slurries that do not contain a polymer.

While the invention has been described in each of its various em¬ bodiments, it is to be expected that certain modifications thereto may occur to those skilled in the art without departing from the true spirit and scope of the invention as set forth in the specification and the accompanying claims.

Claims

30

Claims

1. An aqueous detergent slurry composition comprising

(A) about 5 - 60 % of inorganic builder salts;

(B) about 5 - 70 % of detergent active matter selected from the group consisting of anionic, nonionic, cationic, am- photeric and zwitterionic surfactants; and

(C) about 0.01 - 20 % of a hydrophilic copolymer of the for¬ mula (I)

wherein x, y, and z are integers, (x + y) :z is from about 5:1 to about 1000:1, and y can be any value ranging from zero up to the value of x;

M is an alkali metal or hydrogen; Ri is H or CH₃;

R₂ is -COOM, -OCH₃, -S0₃M, -0-CO-CH₃, -C0-NH₂;

W is selected from residues of formula (II) , (III) or (IV)

( ID ( III ) ( IV)

or mixtures of (III) and (IV) ;

wherein

R_\ is as defined above; R₃ is -CH₂-O-, -CH₂-N-, -C00-, -0-, -CH₂-0-CH₂-CH-O-, o I

-CO-NH-; I

Q is

wherein M is as defined above a is an integer from 0 to about 516 b is an integer from 0 to about 680 with the proviso that the sum of a + b cannot be 0;

R₄ is a C₃-C₄ alkyleneoxy group; R₅ is -CH₂-CH₂-0-; and

G and G¹ are end groups.

2. The composition of claim 1, comprising at least one copolymer of one of the following formulas:

or

wherein

R_lf R₂, R₃, R₅, M, G, G¹, x, y, and z are as defined in claim

1;

R_ξ is a residue of the above formulas (III) or (IV) or a mixture thereof, wherein Q is as defined above, provided that a is 0 and R₅ and M are as defined above; and b is an integer from about 3 to about 680.

3. The composition of claim 1, comprising at least one copolymer of one of the following formulas:

or

wherein

Rii ₂« 3 4 Rs M, G, G¹, x, y, and z are as defined in claim 1; R₆ is a residue of the above formulas (III) or (IV) or a mixture thereof; and a:b is from about 1:4 to about 1:99.

An aqueous soda ash based detergent slurry composition com¬ prising

(A) about 5 - 65 % of inorganic builder salt comprising soda ash, and

(B) about 0.01 - 20 % of a copolymer comprising a hydrophilic monomer copolymerized with an oxyalkylated monomer.

5. The composition of claim 4, comprising at least one copolymer of one of the following formulas:

or

wherein

Ri, R₂, R₃, M, x, y, and z are as defined in claim 1;

R₆ is a residue of the above formulas (III) or (IV) or a mixture thereof, G and G¹ are end groups, wherein Q is

and a:b is from about 5:95 to about 100:0

6. A laundry detergent composition comprising 0.01 to 10% by weight of an anti-redeposition additive having the following formula:

wherein Q is

and Ri, R₂, R₃, R₄ 5 M, G, G¹, x, y, z, a, and b are as defined in claim 1.

7. The composition of anyone of claims 1 to 6 wherein said copolymer has a molecular weight within the range of about 500 to 500,000.

8. The composition of claim 7, wherein said copolymer has a mo¬ lecular weight within the range of about 1000 to 100,000.

9. The composition of claim 8, wherein said copolymer has a mo¬ lecular weight within the range of about 1000 to 20,000.

10. The composition of claim 2 comprising a copolymer of formula (la) wherein Ri = H, R₂ = COOM, wherein M is sodium, R₃ = -CH₂-O-, R₅ = -CH₂-CH₂-O-, y = 0, and b is about 15.

11. The composition of of claim 3 comprising a copolymer of for¬ mula (Ic) wherein Ri = H, R₂ = COOM, wherein M is sodium, R₃ = -CH₂-O-, y = O, a:b is about 1:5, and the oxyalkylated monomer has a molecular weight of about 1000-5000.

12. The composition of claim 5 or 6 comprising a copolymer of formula (Id) , wherein Ri = H, R₂ = COOM, wherein M is sodium, R₃ = -CH₂-0-, a:b is from about 20:80 to 80:20, and the oxyal- kylated monomer has a molecular weight of from about 600 to 5000.

13. A method of reducing the viscosity of aqueous detergent slur¬ ries comprising the steps of adding thereto about 0.01 - 10 % of a hydrophilic copolymer selected from a copolymer as defi¬ ned in anyone of claims 1, 2 or 3.

14. A method of reducing the viscosity of aqueous soda ash based detergent slurries comprising the steps of adding thereto about 0.01 - 10 % of a copolymer as defined in anyone of claims 1 or 5. 15. A method of preventing soil redeposition, comprising adding to a laundry detergent 0.01 to 10% by weight of a copolymer as defined in anyone of claims 1 or 6.

5 16. The method of anyone of claims 13 to 15 wherein said copolymer has a molecular weight within the range of about 500 to 500,000.

17. The method of claim 16, wherein said copolymer has a molecu- 10 lar weight within the range of about 1000 to 100,000.

18. The method of claim 17, wherein said copolymer has a molecu¬ lar weight within the range of about 1000 to 20,000.

15 19. The method of claim 13, wherein a copolymer of formula (la) is applied, wherein Ri = H, R₂ = COOM, wherein M is sodium, R₃ = -CH₂-O-, R₅ is -CH₂-CH₂-0-, y = O, and b is about 15.

20. The method of claim 13, wherein a copolymer of formula (Ic) 20 is applied, wherein R_\ = H, R₂ = COOM, wherein M is sodium,

R₃ = -CH₂-0-, y = O, a:b is about 1:5, and the oxyalkylated monomer has a molecular weight of about 1000-5000.

21. The method of claim 14 or 15, wherein a copolymer of formula 25 (Id) is applied, wherein i = H, R₂ = COOM, wherein M is so¬ dium, R₃ = -CH₂-O-, y = O, a:b is from about 20:80 to 80:20, and the oxyalkylated monomer has a molecular weight of from about 600 to 5000.

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