CN1224455A - Liquid detergent compositions comprising cotton soil release polymers and protease - Google Patents

Abstract

A liquid laundry detergent composition containing water-soluble and/or dispersible modified polyamines with functionalized main chain moieties, which has cotton detergency (optionally combined with non-cotton detergency agents) and protease.

Description

Liquid detergent composition containing cotton soil release polymer and protease

field of invention

The present invention relates to liquid laundry detergent compositions comprising a water-soluble and/or dispersible modified polyamine with a functionalized backbone for cotton soil removal (optionally with non- cotton stain remover binding).

Background Art of the Invention

The widespread use of soil release agents in domestic and industrial fabric treatment processes such as laundry, drying fabrics in hot air laundry dryers, etc. is known in the art. Various soil release agents have been produced commercially and are commonly used in detergent compositions, fabric softeners, antistatic articles and compositions. Such soil release polymers typically contain an oligomeric or polyester "backbone".

Soil release polymers are generally very effective on polyester or other synthetic fabrics when tallow, oil or similar hydrophobic stains spread to form a clinging film and are therefore not easily removed in aqueous laundering processes. Many soil release polymers have no appreciable effect on "hybrid" fabrics, that is to say fabrics comprising a mixture of cotton and synthetic materials, and have little or no effect on cotton items. The reason for the substantivity of many soil release agents on synthetic fabrics is that the backbone of polyester soil release polymers generally contains a mixture of terephthalate residues and ethyleneoxy or propyleneoxy polymer units; they are Identical or similar analogues of polyester fiber materials containing synthetic fabrics. The similar structure of this detergent and synthetic fabrics creates an inherent affinity between these compounds.

Extensive research in this area has greatly improved the efficiency of polyester soil release agents to produce substances with enhanced product properties and processability. Various polyester soil release polymers have been produced by varying the polymer backbone and selecting appropriate end-capping groups. For example, capping modifications, such as the use of sulfoaryl moieties, especially low-cost isethionate-derived capping units, have increased the solubility spectrum and compatibility of additive components for these polymers, while Does not reduce decontamination effect. Many polyester soil release polymers can now be formulated into liquid and solid (eg granular) detergents.

Unlike polyester soil release polymers, making oligomeric or polymeric materials that mimic the structure of cotton did not produce cotton oil-removing polymers. Although cotton and polyester fabrics are both made of long chain polymers, their chemical properties are different. Cotton contains cellulose fibers composed of 1-4 bonded anhydroglucose units. These glycoside chains characterize cotton cellulose as polysaccharides, whereas polyester soil release polymers are generally a combination of terephthalate and oxyethylene/oxypropylene residues. These differences in composition cause cotton and polyester fibers to have different fabric properties. Cotton is hydrophilic relative to polyester. Polyester is hydrophobic and absorbs oil or tallow stains and can be easily "dry cleaned". It is important that the terephthalate and ethyleneoxy/propyleneoxy backbones of polyester fibers have no reactive sites, such as the hydroxyl moieties of cotton, which interact with stains in a different way than synthetics. Many cotton stains become "set" and can only be resolved by bleaching the fabric.

To date, the development of effective cotton stain removers for use in laundry detergents has been inevitable. Some have attempted to adopt the convention of matching the structure of the soil release polymer to the structure of the fabric, and what has been successful in the field of polyester soil release polymers has also yielded decisive results when used in cotton soil release agents. The use of methylcellulose, raffinan with modified oligomeric units, proved to be more effective on polyester than cotton.

For example, UK 1314897, published 26 April 1973, discloses a hydroxypropylmethylcellulose material useful for preventing redeposition of warm stains and improving stain release on laundered fabrics. While the materials have some effect on polyester and blended fabrics, the disclosure states that these materials do not produce the desired effect on cotton fabrics.

Other attempts at producing soil release agents for cotton have generally taken the form of permanently changing the chemical structure of the cotton itself by reacting a substrate with the polysaccharide polymer backbone. For example US 3,897,026 to Kearney discloses fibrous fabric materials with improved soil release and stain repellency properties produced by reacting ethylene maleic anhydride copolymers with hydroxyl moieties of cotton polymers. An obvious disadvantage of this method is that the desired hydrophilicity of the cotton fabric is greatly altered by the process.

Non-permanent decontamination or finishing efforts have been made previously. US 3,912,681 to Dickson teaches a composition for applying a non-permanent stain release cover comprising a polycarboxylate polymer to cotton fabrics. However, this material must be used at a pH of less than 3, a method that is not suitable for consumer use and is not compatible with laundry detergents that typically have a pH greater than 7.5.

US3948838 to Hinton et al. describes high molecular weight (500,000 to 1,500,000) polyacrylate polymers for stain release. These substances may preferably be used in conjunction with other fabric treatments, such as durable press fabric agents such as formaldehyde. This method is also not suitable for consumers to use in general washing machines.

US4559056 to Leigh et al. discloses a method for treating cotton fabrics or synthetic fibers with a composition containing organopolysiloxane elastomers, organopolysiloxane oxyalkylene copolymer crosslinked agent and silicone vulcanization accelerator. Organopolysiloxane oligomers are known to those skilled in the art as suds suppressors.

Other soil release agents that do not contain terephthalate and polyoxyethylene/propylene mixtures are the vinyl caprolactam resins disclosed by Rupert et al. in US 4,579,681 and 4,614,519. The effectiveness of these disclosed vinylcaprolactam materials is limited to polyester fabrics, cotton and polyester blends and cotton fabrics made hydrophobic with a finish.

Examples of alkoxylated polyamines and quaternized alkoxylated polyamines are disclosed in European Patent Application 206513, which are useful as soil dispersants, but which are not disclosed as cotton soil release agents. Additionally, these materials are free of nitrogen oxides, which is the key improvement to the polyamines of the present invention and which is the component that enhances the bleach stability of the presently disclosed compounds.

It has now been unexpectedly found that effective soil release agents for cotton can be prepared from certain modified polyamines. This unexpected result produced a composition that was effective in providing stain release once applied to synthetic only and synthetic-cotton blend fabrics. When the cotton soil release polymers of the present invention are used in combination with non-cotton soil release agents, they provide soil release benefits on all types of fabrics.

The present invention provides liquid laundry detergent compositions which contain nonionic and anionic surfactants alone or in combination with effective proteases together with non-cotton soil release polymers and cotton soil release agents of the present invention. Such a combination results in a liquid laundry detergent composition which has stain removal benefits on all fabrics. The liquid detergents can come in a variety of viscosities and can include concentrates, pourable "off the shelf" detergents, or light duty fabric pre-treaters.

Background technique

In addition to the above documents, the following documents disclose various soil release polymers or modified polyamines; US4548744, issued October 22, 1985 to Connor; ; US4877896, granted Oct. 31, 1989 by Maldonado et al.; US4891160, granted Jan. 2, 1990 by Vander Meer; US4976879, granted Dec. 11, 1990 by Maldonado et al.; US5415807 granted on 1980; US4235735 granted by Marco et al. on November 25, 1980; UK1537288 published on December 29, 1978; UK1498520 published on January 18, 1978; published on November 30, 1995 WO95/32272; German patent DE2829022 granted on January 10, 1980; Japanese publication JP06313271 published on April 27, 1994.

Summary of the invention

The present invention relates to a liquid laundry composition having a cotton stain removal effect, comprising:

a) at least about 0.001% by weight protease;

b) at least about 0.01% by weight of a water-soluble or dispersible modified polyamide cotton soil release agent containing a polyamine backbone having the following general formula:

Modified polyamine general formula V _(n+1) W _m Y _n Z or polyamine main chain with the following general formula:

A modified polyamine having the general formula V _(n-k+1) W _m Y _n Y' _k Z, wherein k is less than or equal to n, said polyamine backbone having a mass greater than about 200 Daltons prior to modification molecular weight, where

或 或

i) The V unit is a terminal unit having the following general formula:

or or

或

或

ii) W units are backbone units having the following general formula:

or

or

或

和iii) Y units are branched units having the general formula: or

or

and

或

或

iv) The Z unit is a terminal unit having the following general formula:

or

or

Wherein the main chain linking R unit is selected from C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ - C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OR ² )CH ₂ O)(R ¹ O) _y -R ¹ O(CH ₂ CH(OR ² )CH ₂ ) _w -, -C(O)(R ⁴ ) _r C(O)-, -CH ₂ CH(OR ² )CH ₂ - and Their mixtures; wherein R ¹ is C ₂ -C ₆ alkylene and their mixtures; R ² is hydrogen, -(R ¹ O) _x B and their mixtures; R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof; R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ arylalkylene, C ₆ -C ₁₀ arylene and mixtures thereof; R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene , C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -C(O)-, -C(O)NHR ⁶ -NHC(O)-, -C(O)( R ⁴ ) _r C(O)-, -CH ₂ CH(OH)CH ₂ O(R ¹ O) _y R ¹ O-CH ₂ CH(OH)CH ₂ - and mixtures thereof; R ⁶ is C ₂ - C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E unit is selected from hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p -CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)-CO ₂ M, -(CH ₂ ) _p PO ₃ M, -(R ¹ O) _x B, -C(O)R ³ and their mixtures; as long as the E unit of any nitrogen is hydrogen, the nitrogen is not an oxide of nitrogen; B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q CH(SO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q CH(SO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M, -PO ₃ M and their mixtures; M is hydrogen or a water-soluble cation sufficient to satisfy charge balance; X is a water-soluble anion ; m is a number from 4 to about 400; n is a number from 0 to about 200; p is a number from 1 to 6, q is a number from 0 to 6; r is 0 or 1; w is 0 or 1; x is 1 a number to 100; y is a number from 0 to 100; z is 0 or 1; and

c) balancing carrier and additive components; wherein said laundry composition has a pH of from about 7.2 to about 8.9 when measured as a 10% solution in water.

All percentages, ratios and parts herein are by weight unless otherwise indicated. All temperatures are in degrees Celsius (° C.), unless otherwise stated. All cited documents are, in relevant part, incorporated by reference.

Detailed Description of the Invention

The present invention relates to liquid laundry detergent compositions suitable for use on cotton, non-cotton or blends of cotton and non-cotton fabrics. Such liquid laundry detergent compositions may optionally contain bleaching materials. The present invention therefore includes the following formulations.

A liquid laundry detergent composition comprising:

a) at least about 0.001% by weight protease;

b) at least about 0.01% by weight of the water-soluble or dispersible modified polyamide cotton soil release agent of the present invention; and

c) Equilibrium carrier and additive components; Equilibrium carrier and additive components; wherein said cleaning composition has a pH of about 7.2 to 8.9 when measured in a 10% aqueous solution.

A preferred composition of the invention contains:

a) at least about 0.01% by weight of a detersive surfactant;

b) at least about 0.001% by weight of a protease selected from the group consisting of Protease A, Protease B, Protease D, Subtilisin 309 variants and mixtures thereof;

c) optionally at least about 0.01% by weight of a non-cotton soil release agent;

d) at least about 0.01% by weight of the water-soluble or dispersible modified polyamide cotton soil release agent of the present invention; and

e) Equilibrium carrier and additive components; Equilibrium carrier and additive components; wherein said cleaning composition has a pH of about 7.2 to 8.9 when measured in a 10% aqueous solution.

Further preferred liquid laundry detergent compositions of the present invention comprise:

a) at least about 0.01% by weight of an anionic detersive surfactant;

b) at least about 0.01% by weight of a nonionic detersive surfactant;

c) at least about 0.001% by weight of an enzyme selected from the group consisting of Protease A, Protease B, Protease D, Subtilisin 309 variants and mixtures thereof;

d) at least about 0.01% by weight of non-cotton soil release agents;

e) at least about 0.01% by weight of the water-soluble or dispersible modified polyamide cotton soil release agent of the present invention; and

f) Equilibrium carrier and additive components; Equilibrium carrier and additive components; wherein said cleaning composition has a pH of about 7.2 to 8.9 when measured in a 10% aqueous solution.

More preferred liquid laundry detergent compositions of the present invention comprise:

a) at least about 0.01% by weight of an anionic detersive surfactant selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, and mixtures thereof;

b) at least about 0.01% by weight of a nonionic detersive surfactant;

c) at least about 0.001% by weight of an enzyme selected from the group consisting of Protease A, Protease B, Protease D, Subtilisin 309 variants and mixtures thereof;

d) at least about 0.01% by weight of non-cotton soil release agents;

e) at least about 0.01% by weight of the water-soluble or dispersible modified polyamide cotton soil release agent of the present invention; and

f) Equilibrium carrier and additive components; Equilibrium carrier and additive components; wherein said cleaning composition has a pH of about 7.2 to 8.9 when measured in a 10% aqueous solution.

Preferred liquid laundry detergent compositions of the present invention contain certain anionic and nonionic surfactants, enzymes and non-cotton soil release agents which, when used in combination with the cotton soil release polymers of the present invention, provide improved cleaning and removal of all fabrics. dirt effect. Preferred liquid laundry detergent compositions of the present invention comprise the following ingredients.

protease

Preferred liquid laundry detergent compositions herein also contain at least 0.001% by weight protease. However, an effective amount of protease is sufficient for use in the liquid laundry detergent compositions of the present invention. By "effective amount" is meant any amount capable of producing a cleaning, soil-removing, stain-removing, whitening, deodorizing, or color-improving effect on a substrate, such as fabric. In practice, typical amounts are up to about 5 milligrams by weight, usually 0.01 to 3 milligrams, of active enzyme per gram of detergent composition for current commercial practice. It should also be noted that the composition of the present invention generally contains 0.001-5%, preferably 0.01-1% by weight of industrially produced enzymes. In such industrial production, the protease of the invention is generally present in an amount sufficient to have an activity of 0.005 to 0.1 A Dalton (Anson) Units (AU) per gram of composition.

Preferred liquid laundry detergent compositions of the present invention contain an improved protease produced by Bacillus amyloliquefaciens or Bacillus lentus. For the purpose of the present invention, the protease derived from Bacillus amyloliquefaciens is further referred to as "subtilisin BPN'", also referred to as "protease A", and the protease derived from Bacillus lentus can be further referred to as "subtilisin 309". In order to achieve the purpose of the present invention, the order arrangement of Bacillus amyloliquefaciens subtilisin, as described in the patent of "Protease-Containing Cleaning Compositions" by A.Baeck et al. in US08/322676, plays the role of subtilisin The role of the amino acid sequence ranking system for BPN' and subtilisin 309.

Bacillus amyloliquefaciens subtilisin derivative-BPN' enzyme

Bleach stable variant of BPN' (Protease A-BSV)

A preferred protease for use in the present invention is a bleach-stable variant of Protease A (BPN'). This bleach-stable variant of BPN' is a non-naturally occurring carbonyl hydrolase that has different proteolytic activity, stability, substrate specificity, pH profile and/or performance characteristics. Such bleach-stable variants of BPN' are disclosed in EP130756A, Jan. 9, 1985. A specific protease A-BSV is BPN' in which Gly at position 166 is replaced by Asn, Ser, Lys, Arg, His, Gln, Ala or Glu; Gly at position 169 is replaced by Ser; Met at position 222 is replaced by Gln, Phe, Cys, His, Asn, Glu, Ala or Thr; or optionally Gly at position 166 by Lys; Met at position 222 by Cys; or optionally Gly at position 169 by Ala; position 222 Met is replaced by Ala.

Protease B

A preferred protease for use in the present invention is Protease B. Protease B is a non-naturally occurring variant of a carbonyl hydrolase that has a different proteolytic activity, stability, substrate specificity, pH profile, and/or performance characteristics. Protease B is a variant of BPN' in which the tyrosine at position +217 is replaced by leucine, which is disclosed in EP303761A, 28th April, 1987 and EP130756A, 9th January, 1985.

Bleach Stable Variant of Protease B (Protease B-BSV)

A preferred protease for use in the present invention is a bleach-stable variant of Protease B. A specific protease B-BSV is the following variant, wherein Gly at position 166 is replaced by Asn, Ser, Lys, Arg, His, Gln, Ala or Glu; Gly at position 169 is replaced by Ser; Met at position 222 is replaced by Gln, Phe, Cys, His, Asn, Glu, Ala or Thr are substituted; or optionally at 166 position Gly is substituted by Lys; at 222 position Met is substituted by Cys; or optionally at 169 position Gly is substituted by Ala; at 222 position Met is replaced by Ala.

Surface active variant of protease B

Preferred surface-active variants of Protease B contain the BPN' wild-type amino acid sequence in which the tyrosine is replaced by a leucine at position +217, wherein at positions 199, 200, 201, 202, 203, 204, 205, 206, 207, One or more wild-type amino acid sequences at 208, 209, 210, 211, 212, 213, 214, 215, 216, 218, 219 or 220 are substituted; wherein the BPN' variant is comparable to wild-type subtilis for insoluble substrates Compared to lysosin BPN', absorption was reduced and hydrolysis was increased. The position with a substituted amino acid is preferably 199, 200, 201, 202, 205, 207, 208, 209, 210, 211, 212 or 215; more preferably 200, 201, 202, 205 or 207.

Also preferred proteases derived from B. amyloliquefaciens subtilisins are the subtilisins BPN' enzymes which have been modified by altering the nucleotide sequence of the various recognition enzymes, thus altering the amino acid sequence of the enzyme. These modified subtilisin enzymes have reduced uptake and increased hydrolysis of insoluble material compared to wild-type subtilisin. Also applicable is the alteration of the genetic code for such BPN' variants.

Derivatives of subtilisin 309

Other preferred proteases for use in the present invention also include the "subtilisin 309" variant. These proteases include several subtilisin 309 variants described below.

Protease D

A preferred protease for use in the present invention is Protease D. Protease D is a carbonyl hydrolase variant derived from Bacillus lentus subtilisin whose amino acid sequence is not found in nature, and it is derived from the precursor carbonyl hydrolase through a position equivalent to the +76 position of said carbonyl hydrolase, It is also preferred to combine one or more equivalents selected from +99, +101, +103, +104, +107, +123, +27, +105, +109, + 126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or + The amino acid residue position of 274 was prepared by substituting different amino acids for multiple amino acid residues as described in WO 95/10615 published April 20, 1995 by Genencor International.

A． Variants of loop region 6 substitutions - these subtilisin 309 variants have a modified amino acid sequence of the subtilisin 309 wild-type amino acid sequence, wherein the modified amino acid sequence is comprised at 193, 194, 195, 196, 197 , 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213 or 214 have substituents at one or several positions; thus subtilisin 309 variant Compared to wild-type subtilisin 309, the uptake of insoluble material was reduced and its hydrolysis was increased. These proteases preferably have an amino acid substituted at position 193, 194, 195, 196, 199, 201, 202, 203, 204, 205, 206 or 209; more preferably at position 194, 195, 196, 199 or 200.

B． Polycyclic region substitution variants - These subtilisin 309 variants may also have a modified amino acid sequence of the subtilisin 309 wild-type amino acid sequence, wherein the modified amino acid sequence is included in the first, second, third, fourth Alternatively one or several positions of the fifth loop region are substituted; thus the subtilisin 309 variant reduces the uptake of insoluble material and increases its hydrolysis compared to wild type subtilisin 309.

C． Substitutions at positions in the non-loop region - Alternatively, one or several substitutions of wild-type subtilisin 309 may be made at positions in the non-loop region, for example at position 74. If other substitutions of subtilisin 309 are made at position 74 only, the substitutions are preferably with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro, preferably His or Asp. However, modifications can be made at one or more loop positions as well as position 74, eg residues 97, 99, 101, 102, 105 and 121.

Subtilisin BPN' variants and subtilisin 309 variants are also described in WO95/29979, WO95/30010 and WO95/30011, all of which were published on November 9, 1995, all of which are incorporated herein by reference.

Another preferred protease for use with the modified polyamines of the present invention is ALCALASE ^(R) supplied by Novo. Other suitable proteases are prepared from a Bacillus genus which has maximum activity in the pH range of 8-12, developed by Novo Industries A/S of Denmark, referred to herein as "Novo" as ESPERASE® ^and sell. The preparation of this and similar enzymes is described in GB1243784 to Novo. Other suitable enzymes include ^SAVINASE® supplied by Novo and International Bio-Synthetics, Inc. of the Netherlands. Provided by ^MAXATASE® . See also the high pH protease from Bacillus sp. NCIMB 40338 described in WO9318140A to Novo. Enzymatic detergents containing a protease, one or several other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those described in WO9510591A to Procter & Gamble. The proteases described in WO 9507791 to Procter & Gamble to reduce absorption and enhance hydrolysis may be used when desired. Recombinant trypsin-like proteases useful in the detergents of the present invention are described in WO9425583 to Novo.

In addition to the proteases described above, there are other enzymes described below which are suitable for use in the liquid laundry detergent compositions of the present invention.

non-cotton soil release polymer

Preferred non-cotton soil release polymers suitable for use in the liquid laundry detergent compositions of the present invention are as follows.

Preferred Non-Cotton Stain Remover-A. Preferred non-cotton soil release polymers suitable for use in the liquid laundry detergent compositions of the present invention comprise:

a) The main chain contains:

i) at least one moiety having the general formula:

ii) at least one moiety having the general formula:

wherein R ⁹ is C ₂ -C ₆ linear alkylene, C ₃ -C ₆ branched alkylene, C ₅ -C ₇ cyclic alkylene and mixtures thereof; R ¹⁰ is independently selected from hydrogen Or -L-SO ₃ ^{-M +} ; wherein L is selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxygen alkenyl), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarylene, alkylene poly(oxyalkylene) and mixtures thereof; M is hydrogen or a salt-forming cation; i is a number of 0 or 1;

iii) at least one trifunctional ester-forming branched moiety;

iv) at least one 1,2-oxyalkylene oxygen moiety; and

b) one or more end-capping units containing:

i ⁾ Ethoxylated _{or propoxylated} hydroxyethanesulfonate _{or ethoxylated} or propoxylated Hydroxypropane sulfonate unit wherein M is a salt-forming cation, such as sodium or tetraalkylammonium, R ¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is 1 to 20 ;

ii) a sulfoaroyl group of the general formula -(O)C(C ₆ H ₄ )(SO ₃ ^{-M +} ), wherein M is a salt-forming cation;

iii) Modified poly(oxyethylene)oxy monoalkyl ether units of the general formula R ¹² O(CH ₂ CH ₂ O) _k -, wherein R ¹² contains 1 to 4 carbon atoms and k ranges from about 3 to about 100; and

iv) Ethoxylated or propoxylated phenol sulfonate capping units, the general formula of which is MO ₃ S(C ₆ H ₄ )(OR ¹³ ) _n O-, wherein n is 1 to 20; M is Salt-forming cation; R ¹³ is ethylene, propylene and mixtures thereof.

The preferred class of non-cotton soil release polymers of the present invention have the general formula:

[(Terminal)(R ⁴ ) _t ][(AR ¹ -AR ² ) _u (AR ¹ -AR ³ ) _v (AR ¹ -AR ⁵ ) _w -AR ¹ -A-][(R ⁴ ) _t ( end group)]

wherein A is a carboxyl linking moiety having the general formula,

^R is an arylene group, preferably a 1,4-phenylene moiety, the general formula is as follows:

Thus when the A units and ^R1 units are linked in the general formula ^AR1 -A, they form a terephthalate unit having the general formula:

The ^R unit is ethyleneoxy or 1,2-propyleneoxy. The R ² units combine with the terephthalate moiety to form (AR ¹ -AR ² ) units having the following general formula:

wherein R' and R" are hydrogen or methyl, as long as R' and R" are not both methyl.

The ^R unit is a trifunctional ester-forming branched moiety having the following general formula:

或者通式：

Preferred ^R3 units include a glycerol moiety which is located on the soil release polymer backbone to provide branching sites. When ^R3 units are combined with terephthalate moieties to form polymer backbone units, such as ( ^AR1 - ^AR3 ) ^-AR1 -A units, these units have the general formula:

or the general formula:

One of the terephthalate residues becomes part of a (AR ¹ -AR ³ ) unit, while the second terephthalate contains part of another backbone unit, such as (AR ¹ -AR ² ) units, ( AR ¹ -AR ⁵ ) unit, AR ¹ -A-[(R ⁴ ) _t (end group)] unit or a second (AR ¹ -AR ³ ) unit. The third functional group is the start of the branch chain, which is generally also connected to the terephthalate residue, and is also a (AR ¹ -AR ² ) unit, (AR ¹ -AR ⁵ ) unit, AR ¹ -A-[(R ⁴ ) _t (terminal)] unit or part of another (AR ¹ -AR ³ ) unit.

Examples of segments of soil release polymers containing "trifunctional ester-forming branched moiety" ^R units containing glycerol units are those having the general formula:

The R ⁴ unit is an R ² , R ³ or R ⁵ unit.

The R ⁵ unit has the following general formula:

Wherein R ⁹ is C ₂ -C ₆ linear alkylene, C ₃ -C ₆ branched alkylene and mixtures thereof; preferred R ¹⁰ is independently selected from hydrogen or -L-SO ₃ ^{-M +} ; wherein L is selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene side chain moieties of groups, poly(oxyalkylene)oxyarylene groups, alkylene poly(oxyalkylene groups) and mixtures thereof; M is hydrogen or a salt-forming cation; i is a number of 0 or 1;

Each carbon atom of the R ⁹ unit is replaced by an R ¹⁰ unit, and R ¹⁰ is independently selected from hydrogen or -L-SO ₃ ^{-M +} , as long as there is no more than one -L-SO ₃ ^{-M +} unit attached to R ⁹ On the unit; L is selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxyalkylene), oxyalkyleneoxy Side chain linking moieties of arylene groups, poly(oxyalkylene)oxyarylene groups, alkylene poly(oxyalkylene) groups, and mixtures thereof.

M is a cationic moiety selected from lithium, sodium, potassium, calcium and magnesium, preferably sodium and potassium.

Preferably the R ⁵ moiety is primarily an R ¹⁰ substituted C ₂ -C ₆ alkylene chain. The R ⁵ unit comprises a C ₂ -C ₆ alkylene chain substituted by one or several individually selected R ¹⁰ moieties (preferred), or two C ₂ -C ₆ alkylene chains, said alkylene The base chains are linked by ether oxygen, and each alkylene chain is substituted by one or several individually selected ^R10 moieties, that is, ^R5 may contain two separate ^R9 units, each of which is replaced by one or several individually selected R ¹⁰ partially substituted. It is preferred that each R ^moiety has only one carbon atom substituted with -L-SO ₃ ^{-M +} units, with the remaining ^R substituents containing hydrogen atoms. When the symbol i is equal to 1 (two R ⁹ units including R ⁵ units), the preferred general formula is:

wherein each R ⁹ includes a C ₂ alkylene moiety. A preferred ^R10 moiety is -L- _SO3 ^- M ⁺ , preferably a _C2 carbon atom is replaced by a -L- _SO3 ^- M ⁺ moiety, and the balance part is a hydrogen atom, thus having the general formula:

wherein L is a polyethyleneoxymethyl substituent and x is 0 to about 20.

As adopted here, the said "R ⁵ part mainly includes the unit:

i is equal to 0, wherein the R ¹⁰ units are hydrogen and one R ¹⁰ unit is -L-SO ₃ ^{-M +} , wherein L is selected from the group consisting of alkylene, alkenylene, alkoxyalkylene, oxyalkylene, alkylene Aryl, alkarylene, alkoxyarylene and their mixture side chain linking moiety" refers to the preferred compounds of the present invention, wherein the R ¹⁰ moiety includes a -L-SO ₃ ^{-M +} moiety, R The rest of the ¹⁰ moiety are hydrogen atoms, e.g.

It is capable of being inserted into the polymer backbone of the soil release polymers of the present invention as an ^-AR5 -A- backbone segment. This unit is readily incorporated into the oligomer or polymer backbone by employing starting materials having the following general formula:

wherein x is 0 to 20 in order to have the L moiety of the present invention.

Other suitable monomers capable of inserting the R ^moieties into the backbone of the preferred Class A non-cotton soil release polymers of the present invention include alkylene poly(oxyalkylene)oxyarylenes containing monomers having the general formula body:

其中x为0到约20；更优选的是单体：

where x is from 0 to about 20. Another example of a preferred monomer giving rise to the preferred R ^unit wherein i equals 0 is sodium sulfopoly(ethyleneoxy)methyl-1,2-propanediol having the general formula:

where x is from 0 to about 20; more preferred are monomers:

Preferred non-cotton soil release agents of the present invention comprise, in addition to the ^R1 , ^R2 , ^R3 , ^R4 and ^R5 units described above, one or more terminal groups - (endgroups). The end groups are individually selected from ethoxylated or propoxylated hydroxyethanesulfonate and propanesulfonate units of the general formula (MO3S)( _CH2 ) _m ( ^R11O ) _n- , wherein M is a salt-forming cation as described above, such as sodium or tetraalkylammonium, R is ^ethylene or propylene or a mixture thereof, m is 0 or 1, n is 1 to 20, preferably n is 1 to 20 about 4; a sulfaroyl unit of the general formula -(O)C(C ₆ H ₄ )(SO ₃ ^{-M +} ), wherein M is a salt-forming cation as described above; the general formula R ¹² O(CH ₂ CH ₂ O) _k -modified poly(oxyethylene)oxy monoalkyl ether units, wherein R ¹² contains 1 to 4 carbon atoms, R ¹² is preferably methyl, k is from about 3 to about 100, preferably about 3 to 50, more preferably 3 to about 30; and an ethoxylated or propoxylated phenolsulfonate capping unit of the general formula MO ₃ S(C ₆ H ₄ )(OR ¹³ ) _n O—, Wherein n is 1 to 20; M is a salt-forming cation; R ¹³ is ethylene, propylene and their mixtures.

The most preferred capping units are those of the isethionate type, which are hydroxyethane moieties, (MO ₃ S)(CH ₂ ) _m (R ¹¹ O) _n -, preferably R ¹¹ is ethyl, m is equal to 0, and n is from 2 to 4.

The value of t is 0 or 1; the value of u is about 0 to about 60; the value of v is about 0 to about 35; the value of w is 0 to 35.

Has the following general formula:

[(Cap)(R ⁴ ) _t ][(AR ¹ -AR ² ) _u (AR ¹ -AR ³ ) _v (AR ¹ -AR ⁵ ) _w

-AR ¹ -A-][(R ⁴ ) _t (Cap)]

下面的结构是本发明的优选非棉去污聚合物的一个实例： The preferred non-cotton soil release polymers of the present invention are generally conveniently represented by the following general formula:

The following structure is an example of a preferred non-cotton soil release polymer of the present invention:

The above preferred non-cotton detergents are fully described in US08/545351, granted November 22, 1995, which is a continuation-in-part of US08/355938, granted December 14, 1994, which are hereby incorporated as refer to. Other non-cotton soil release polymers suitable for use in the compositions of the present invention are described below.

Preferred non-cotton SRA's can be further described as oligomeric esters comprising: (1) a backbone comprising (a) at least one selected from dihydroxysulfonate, polyhydroxysulfonate, a At least trifunctional units of the chained oligomer backbone, and their combined units; (b) at least one unit of the terephthaloyl moiety and (c) at least one is 1,2-oxyalkyleneoxy part of unsulfonated units; and (2) one or several capping units selected from nonionic capping units, anionic capping units, for example alkoxylated, preferably ethoxylated isethionic acid Esters, alkoxylated propane sulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfaroyl derivatives and mixtures thereof. Preferred esters have the general formula:

{(CAP)x(EG/PG)y′(DEG)y″(PEG)y(T)z(SIP)z′(SEG)q(B)m} where CAP, EG/PG, PEG, T and SIP refer to terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units, capping groups (CAP ), poly(ethylene glycol) (PEG), (DEG) means di(oxyethylene) oxygen units, (SEG) means units derived from sulfonated ethyl ether of glycerol and related moiety units, (B) means branched Unit, which is at least trifunctional, through which ester groups are formed to produce a branched oligomer backbone, x is about 1 to about 12, y' is about 0.5 to about 25, y" is from 0 to about 12, y' from 0 to about 10, y'+y"+y' sum from about 0.5 to about 25, z from about 1.5 to about 25, z' from 0 to about 12; z+z' sum from 1.5 to About 25, q is about 0.05 to 12; m is about 0.01 to 10, x, y', y ", y, z, z', q and m represent the average number of moles per mole of said ester corresponding units, The esters have a molecular weight of about 500 to 5,000.

Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxy Ethoxy)ethoxy}ethanesulfonate ("SE3") and its homologs and mixtures thereof and products of ethoxylated and sulfonated allyl alcohol. Preferred SRA esters in this class include transesterification and oligomerization of sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or 2 -Sodium [2-{2-(2-hydroxyethoxy)ethoxy}-ethoxy]ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate , EG and PG, and can be expressed as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is (Na+O ₃ S[CH ₂ CH ₂ O ]3.5)- and B are units derived from glycerol, and the molar ratio of EG/PG is about 1.7:1 as determined by conventional gas chromatography after completion of the hydrolysis.

Preferred Non-Cotton Stain Remover-B. A second preferred class of suitable SRA's includes the sulfonation products of substantially linear ester oligomers comprising an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and covalent Allyl derivatized sulfonated terminal moieties attached to the backbone. Such ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate ("DMT") and 1 , 2-propanediol ("PG") is reacted in two transesterification/oligomerization steps; and (c) reacting the product of (b) with sodium metabisulfite in water.

Preferred non-cotton soil release polymers suitable for use in the laundry detergent compositions of the present invention include:

a) one or two terminal units selected from the following groups:

i) _- ( _CH2 ) _q ( _CHSO3M ) _CH2SO3M ,

_ii ) -( _CH2 ) _q ( _CHSO2M ) _CH2SO3M ,

iii _{) -CH2CH2SO3M ,}

iv) and mixtures thereof; wherein q is a value from 1 to about 4, and M is a water-soluble cation, preferably sodium;

b) A main chain, including:

i) Arylene units, preferably terephthalate units having the general formula:

ii) Ethyleneoxy units having the general formula:

-O(CH ₂ CH ₂ O) _n CH ₂ CH ₂ O-

where n has a value of approximately 1 to 20; and

iii) 1,2-propyleneoxy units having the general formula:

-O(CH ₂ CH(CH ₃ )O) _n CH ₂ CH(CH ₃ )O-

wherein n has a value of about 1 to 20, and wherein the preferred backbone of the preferred non-cotton soil release polymers has an arylene repeat unit alternating with ethyleneoxy and 1,2-propyleneoxy units backbone such that the molar ratio of ethyleneoxy to 1,2-propyleneoxy units is 0:1 to about 0.9:0.1, preferably about 0:1 to about 0.4:0.6, more preferably arylene units to main are 1,2-propyleneoxy units alternating.

However, other combinations of the above units may be used to form the non-cotton soil release polymers for preparing the compositions of the present invention. These combinations are described in more detail in US Patent 4,968,451, Scheibel et al., issued November 6, 1990, which is incorporated herein by reference.

Preferred Non-Cotton Stain Remover-C. Laundry detergent compositions suitable for use herein are preferred non-cotton soil release polymers having the general formula:

(Cap)[(AR ¹ -AR ² )u(AR ³ -AR ² )vAR ⁴ -A-](Cap)

Wherein A is a carboxyl linking moiety, preferably A is a carboxyl linking moiety having the following general formula: ^R is an arylene moiety, preferably a 1,4-phenylene moiety having the general formula: Wherein for ^R1 , the degree of substitution with an arylene moiety rather than a 1,4-phenylene moiety is such that the soil release performance of the compound is not greatly affected. In general, the degree of partial substitution that can be tolerated depends on the backbone length of the compound.

The ^R2 moiety is an ethylene moiety or a substituted ethylene moiety having a _C1 - _C4 alkyl or alkoxy substituent. As used herein, the term " ^R2 moieties are primarily ethylene moieties or substituted ethylene moieties having _C1 - _C4 alkyl or alkoxy substituents" means that when all ^R2 moieties Compounds of the invention when composed of ethylene or substituted ethylene moieties or partially substituted with other moieties which may be employed. Examples of these other moieties include 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene, 1,2-hydroxyalkylene and oxyalkylene.

For the ^R2 moieties, the degree of partial substitution by these other moieties should be such that the soil release properties of the compound are not substantially adversely affected. For example, _a molar ratio of diethylene glycol ( _{-CH2CH2OCH2CH2-} ) to ethylene glycol (ethylene) of _75:25 is sufficient for polyesters prepared according to the invention _. Detergency activity.

For the R ³ moiety, suitable substituted C ₂ -C ₁₈ alkylene moieties may include substituted C ₂ -C ₁₂ alkylene, alkenylene, arylene, alkarylene, etc. moieties. Substituted alkylene or alkenylene moieties can be linear, branched or cyclic. R ³ can also be the same (eg, fully substituted arylene) or a mixture (eg, a mixture of substituted arylene and substituted alkylene). Preferred ^R3 moieties are substituted 1,3-phenylene, preferably 5-sulfo-1,3-phenylene. The R ³ moiety is also A-[(R ² -AR ⁴ )]-capped, where R ⁴ is R ¹ , R ³ and mixtures thereof.

Preferred (terminal) moieties include units of the general formula:

-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]X

wherein R ⁵ is C ₁ -C ₄ alkylene, or the moiety -R ² -AR ⁶ , wherein R ⁶ is C ₂ -C ₁₂ alkylene, alkenylene, arylene or alkarylene, and X is C ₁ -C ₄ alkyl, preferably methyl; the symbols m and n are such that the moiety -CH ₂ CH ₂ O- contains at least 50% by weight of the moiety of the formula

-[(R ⁵ O) _m (CH ₂ CH ₂ O) _n ]X

As long as R ⁵ is the moiety -R ² -AR ⁶ -, m is at least 1; each n is at least about 10, symbols u and v are such that the sum of u+v is from about 3 to about 25; symbol w is 0 or at least 1; and when w is at least 1, the symbols u, v and w are such that the sum of u+v+w is about 3 to 25.

Examples of such non-cotton soil release block polyesters are those having the general formula:

wherein the ^R2 moieties are primarily ethylene moieties, 1,2-propylene moieties and mixtures thereof; the ^R3 moieties are all potassium or preferably sodium 5-sulfo-1,3-phenylene moieties; ^R4 Moiety is R ¹ or R ³ moiety, or their mixture; each X is ethyl, methyl, preferably methyl; each n is about 12 to about 43; when w is 0, u+v is 3 to about 10; when w is at least 1, u+v+w is from 3 to about 10.

has the general formula:

(Cap)[(AR ¹ -AR ² )u(AR ³ -AR ² )vAR ⁴ -A-](Cap)

The aforementioned non-cotton soil release polymers of ® are described in detail in US Patent 4,702,857, issued October 27, 1987 to Gosselink, and incorporated herein by reference.

In addition to the non-cotton soil release polymers described above, other suitable soil release polymers for use in the liquid laundry detergent compositions of the present invention include the following. Such known polymeric soil release agents may optionally be used in the compositions of the present invention. If employed, SRA's generally range from 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0% by weight of the composition. Preferred SRA's are those described above.

SRA's suitable for use in the compositions of the present invention generally contain hydrophilic segments to render the surface of hydrophobic fibers, such as polyester and nylon, hydrophilic, and hydrophobic segments to deposit on the hydrophobic fibers and remain attached to them through washing and cleaning operations. In this way, it plays the role of fixing the hydrophilic segment. This allows for easy removal of stains after SRA treatment in subsequent wash steps.

SRA's can include various charges, such as anions or even cations, see US4956447, issued September 11, 1990 to Gosselink, as well as uncharged monomeric units, and their structures can be linear, branched or even star shaped. They may include capping moieties, which are particularly effective in controlling molecular weight or adjusting physical properties or surface activity. The structure and charge distribution can be tailored to suit different fiber or fabric types and for various detergent or detergent additive products.

SRA's include oligomeric terephthalates, generally prepared by a process involving at least one transesterification/oligomerization reaction, usually using a metal catalyst such as titanium alkoxide (IV). Such esters may be prepared using other monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, of course without forming densely cross-linked overall structures.

Suitable SRA's include the sulfonation products of substantially linear ester oligomers containing an oligoester backbone of p-benzoyl and oxyalkyleneoxy repeat units and covalently bonded to the backbone Allyl derived sulfonated end group moieties such as those described in US 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate ("DMT") and 1,2 - reacting propylene glycol ("PG") in two transesterification/oligomerization steps; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters in US4711730, issued December 8, 1987 by Gosselink et al. ) transesterification/oligomerization of methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG"). Examples of other SRA's include: Gosselink et al., US4721580, issued January 26, 1988, partially and fully anion-terminated oligoesters, such as ethylene glycol ("EG"), PG, DMT, and 3,6 - oligomers prepared from sodium dioxa-8-hydroxyoctane sulfonate; non-ionic end-capped block polyester oligomeric compounds in US4702857, granted to Gosselink et al. on October 27, 1987, for example by DMT, Methyl (methyl)-terminated PEG and EG and/or PG or prepared in combination with DMT, EG and/or PG, methyl-terminated PEG and Na-dimethyl-5-sulfoisophthalate and anionic, especially sulfaroyl, end-capped terephthalates in US4877896, Maldonado, Gosselink et al., Oct. 31, 1989, which are typical SRA's for use in laundry and fabric conditioning products , an example is an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further containing added PEG, such as PFG3400.

SRA's also include: simple block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polyoxypropylene terephthalate, see Hays May 25, 1976 US3959230 and US3893929 of Basadur on July 8, 1975; cellulose derivatives, such as hydroxyether cellulose polymers, such as METHOCEL provided by Dow; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkyl cellulose , see Nicol et al., US4000093, Dec. 28, 1976; and an average degree of substitution (methyl) per anhydroglucose unit of about 1.6 to 2.3 and a solution viscosity of about 80 as measured in 2% aqueous solution at 20° C. to 120 cps of methyl cellulose ether. Such materials are available under the names METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Useful SRA's characterized by poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl ester), such as C ₁ -C ₆ vinyl esters, preferably poly(vinyl acetate), in polyolefin Grafting on the oxide backbone. See EP0219048 published April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22 supplied by BASF of Germany. Other SRA's contain 10-15% by weight of ethylene terephthalate and 80-90% by weight of polyethylene terephthalate (polyoxyethylene glycol with an average molecular weight of 300-5000) derived) polyesters of repeating units. Industrial examples include ZELCON5126 by Dupont and MILEASE by ICI.

Another SRA is an oligomer with the general formula: (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ , which contains p-benzoyl (T), sulfoisobenzoyl (SIP) ), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units, and it is preferably capped with a capping group (CAP), preferably a modified isethionate, as in Same in oligomers containing one sulfoisobenzoyl unit, 5 p-benzoyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably 0.5:1 to about 10:1 ratio, and two capping units derived from sodium 2-(2-hydroxyethoxy)ethanesulfonate. Said SRA preferably further contains 0.5% to 20% by weight oligomer reducing crystallization stabilizers, such as anionic surfactants, such as linear sodium dodecylbenzenesulfonate or selected from xylene-, cumene- and A substance of toluene-sulfonate or mixture thereof, these stabilizers or modifiers can be added to the synthesis vessel, all of which are described in US5415807 issued May 16, 1995 by Gosselink, Pan, Kellett and Hall middle. Suitable monomers for the above SRAs include sodium 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, sodium dimethyl-5-sulfonate isophthalate, EG and PG.

Other types of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see US4201824 to Violland et al. and US4240918 to Lagasse et al; Carboxylate-terminated SRA's prepared by adding trimellitic anhydride to the SRA's to convert the terminal hydroxyl groups to trimellitate esters. With proper selection of the catalyst, the trimellitic anhydride bonds to the end of the polymer through the ester of the trimellitic anhydride's individual carboxylic acid rather than by opening the anhydride linkage. Nonionic or anionic SRA's can be used as starting materials as long as they have esterifiable hydroxyl groups. See US4525524 to Tung et al. Other types include: (III) anionic terephthalate-based SRA's in the urethane-linked form, see US4201824 to Violland et al; Related copolymers of methylaminoethyl methacrylate, including nonionic and cationic polymers, refer to US4579681 of Ruppert et al.; (Ⅴ) graft copolymers, in addition to the SOKALANs provided by BASF, there are also acrylic acid monomers prepared by grafting on sulfonated polyester. These SRA's should have soil removal and anti-redeposition activity similar to known cellulose ethers: see EP279134A, Rhone-Poulenc Chemie, 1988. Still other types include: (VI) grafting of vinyl monomers, such as acrylic acid and vinyl acetate, onto proteins, such as casein, see EP457205A of BASF (1991); and (VII) grafting of adipic acid, Polyester-polyamide SRA's prepared from caprolactam and polyethylene glycol are particularly useful for treating polyamide fabrics, see DE2335044, Bevan et al., Unilever N.V., 1974. Other useful SRA's are described in US4240918, 4787989 and 4525524.

Any other anionic non-cotton soil release agent is suitable for use in the compositions of the present invention, alone or in combination, with the exception of carboxymethylcellulose (CMC), which when used alone according to the present invention is preferably at a concentration greater than 0.2%, more preferably Greater than 0.5%.

cotton soil release polymer

The cotton soil release agents of the present invention are water soluble or dispersible modified polyamines. These polyamines contain a backbone which may be linear or cyclic. The polyamine backbone may also contain longer or shorter polyamine branches. In general, the polyamine backbone referred to herein is modified in such a way that each nitrogen of the polyamine chain is hereinafter described as a unit that is substituted, quaternized, oxidized, or a combination of these reactions.

For the purposes of the present invention, the term "modification" refers to replacing the main chain -NH hydrogen atom with an E unit (substitution), quaternizing the nitrogen of the main chain (quaternization) or oxidizing the main chain nitrogen to nitrogen oxides (oxidation). The terms "modification" and "substitution" are used interchangeably when referring to the replacement of a hydrogen atom attached to a backbone nitrogen with an E unit. Quaternization or oxidation can be performed with some absence of substitution, but preferably substitution is accompanied by oxidation or quaternization of at least one backbone nitrogen.

The linear or acyclic polyamine backbone containing the cotton soil release agent of the present invention has the following general formula:

The backbone contains, prior to subsequent modification, primary, secondary and tertiary amine nitrogens linked by R"linker"units. The cyclic polyamine backbone comprising the cotton soil release agents of the present invention has the general formula:

The backbone contains, prior to subsequent modification, primary, secondary and tertiary amine nitrogens linked by R"linker"units.

For the purposes of this invention, primary amine nitrogens containing backbone or branched chains are defined as V or Z "terminal" units once modified. For example, when located at the main polyamine backbone or at the end of a branch with the structure:

H ₂ NR]-

When the primary amine moiety of is modified according to the invention, it is then referred to as the V "terminal" unit, or simply the V unit. However, for the purposes of the present invention, some or all of the primary amine moieties may remain unmodified subject to the other limitations described below. These unmodified primary amine moieties remain "terminal" units due to their position on the backbone. Likewise, when having the structure:

-NH ₂

When the primary amine moiety at the end of the main primary amine backbone is modified in accordance with the present invention, it is hereinafter referred to as the Z "terminal" unit, or simply the Z unit. This unit may remain unmodified subject to other constraints specified below.

Similarly, secondary amine nitrogens containing backbone or branched chains, once modified, are defined as W "backbone" units. For example, when the secondary amine moiety, i.e. the main part of the backbone and branches of the present invention, has the following structure:

When modified according to the invention, it is hereafter defined as a W "backbone" unit, or simply a W unit. However, some or all of the secondary amine moieties may remain unmodified for the purposes of the present invention. These unmodified secondary amine moieties remain "backbone" units due to their position on the backbone.

Similarly, tertiary amine nitrogens containing backbone or branched chains, once modified, are defined as Y "branched" units. For example, when the tertiary amine moiety, which is the branching point of the polyamine main chain or other branched or cyclic chains, has the following structure:

When modified according to the present invention, it is hereafter defined as a Y "branch" unit, or simply a Y unit. However, some or all of the tertiary amine moieties may remain unmodified for the purposes of the present invention. These unmodified tertiary amine moieties remain "branched" units due to their position on the main chain. The R units associated with the V, W and Y unit nitrogens used to link the polyamine nitrogens are described below.

Therefore, the structure of the last modification of polyamine of the present invention can use general formula:

V _(n+1) W _m Y _n Z

Denotes the thread-like polyamide wool soil release polymer and the general formula:

V _(n-k+1) W _m Y _n Y'kZ

V _(n+k+1) W _m Y _n Y'kZ

Indicates cyclic polyamide wool soil release polymer. In the case of polyamines containing rings, the general formula:

The Y' unit of α acts as a branch position of the main chain or a branched ring. For each Y' unit, there is a Y unit with the general formula:

It will form the point of attachment of the ring to the main polymer chain or branch. In the specific case where the backbone is a complete ring, the polyamine backbone has the general formula: Therefore there is no Z-terminal unit and has the general formula:

V _nk W _m Y _n Y'k where k is the number of rings forming branched units. Preferably the polyamine backbone of the present invention does not contain rings.

In the case of acyclic polyamines, the ratio of the symbols n to the symbols m is related to the relative degree of branching. The linear modified polyamine without branching at all according to the present invention has the following general formula:

_V

That is, n is equal to 0. The larger the value of n (the smaller the ratio of m to n), the greater the degree of branching in the molecule. Values for m generally range from a minimum of 4 to about 400, however, larger values of m, especially when the value of sign n is very low or close to zero, is also preferred.

Each polyamine nitrogen, whether primary, secondary or tertiary, once modified in accordance with the present invention, can be redefined as one of three general types: simply substituted, quaternized or oxidized. These unmodified polyamine nitrogen units are classified as V, W, Y or Z units depending on whether they are primary, secondary or tertiary nitrogens. For the purposes of the present invention, unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units, and unmodified tertiary amine nitrogens are Y units.

A modified primary amine moiety refers to the V "terminal" unit, which has one of the following three forms:

a) A simple substitution unit having the following structure:

b) a quaternary ammonium unit having the following structure:

where X is a suitable counterion providing charge balance; and

c) an oxidized unit having the following structure:

Modified secondary amine moieties refer to W "backbone" units having one of the following three forms:

a) A simple substitution unit having the following structure:

b) a quaternary ammonium unit having the following structure:

where X is a suitable counterion providing charge balance; and

c) an oxidized unit having the following structure:

Modified tertiary amine moieties refer to Y "branched" units having one of the following three forms:

a) an unmodified unit having the following structure:

b) a quaternary ammonium unit having the following structure:

where X is a suitable counterion providing charge balance; and

c) an oxidized unit having the following structure:

Some modified primary amine moieties refer to Z "end group" units having one of the following three forms:

a) A simple substitution unit having the following structure:

b) a quaternary ammonium unit having the following structure:

where X is a suitable counterion providing charge balance; and

c) an oxidized unit having the following structure:

When any position on the nitrogen is unsubstituted or unmodified, a hydrogen is considered to replace E. For example, a primary amine unit containing _one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the general formula ( _HOCH2CH2 )HN-.

For the purposes of the present invention, there are two types of chain end units, V and Z units. The Z "terminal" unit is derived from the terminal primary amine moiety of the structure _-NH2 . The acyclic polyamine backbone of the present invention contains only one Z unit, while the cyclic polyamine may not contain Z units. The Z "terminal" unit may be substituted with any of the E units described below, except when the Z unit is modified to form a nitrogen oxide. In the case where the Z unit nitrogen is oxidized to form an oxide of nitrogen, the nitrogen must be modified and therefore E cannot be hydrogen.

The polyamines of the present invention contain backbone R "linking" units which serve to link the nitrogen atoms of the backbone. The R units contain units which for the purposes of this invention are referred to as "hydrocarbyl R" units and "oxy R" units. "Hydrocarbyl" R units are C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, where the hydroxy moiety can be anywhere on the R unit chain except directly attached A carbon atom on a polyamine backbone nitrogen; C ₄ -C ₁₂ dihydroxyalkylene, where the hydroxyl moiety can occupy any two carbon atoms in the chain of R units, except those directly attached to the polyamine backbone nitrogen atom; C ₈ -C ₁₂ dialkarylene, which according to the invention is an arylene moiety having two alkyl substituents as part of the linking chain. For example, a dialkarylene unit has the general formula:

Although the unit need not be 1,4-substituted, it can also be 1,2 or 1,3 substituted C ₂ -C ₁₂ alkylene, preferably ethylene, 1,2-propylene and mixtures thereof , more preferably ethylene. "Oxygen" R units include -(R ¹ O) _x R ⁵ (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 -, -CH ₂ CH(OR ² )CH ₂ -, -(R ¹ O) _x R ¹ - and mixtures thereof, preferably R units are C ₂ -C ₁₂ alkylene, C ₃ - C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ , -CH ₂ CH(OR ² )CH ₂ - , -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH-(OH)CH ₂ ) _w -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, more preferably R units are C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, -(R ¹ O) _x R ¹ -, -( R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH-(OH)CH ₂ ) _w - and their More preferred R units are C ₂ -C ₁₂ alkylene, C ₃ hydroxyalkylene and mixtures thereof, most preferably C ₂ -C ₆ alkylene. The most preferred backbones of the present invention comprise at least 50% R units that are ethylene.

R ¹ units are C ₂ -C ₆ alkylene and mixtures thereof, preferably ethylene. R ² is hydrogen and -(R ¹ O) _x B, preferably hydrogen.

R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkylene, C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof, preferably C ₁ - C ₁₂ alkyl, C ₇ -C ₁₂ arylalkylene, more preferably C ₁ -C ₁₂ alkyl, most preferably methyl. The ^R3 unit is part of the E unit referred to below.

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

R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -C(O)- , -C(O)NHR ⁶ NHC(O)-, -C(O)(R ⁴ ) _r C(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 ⁵ is preferably ethylene , -C(O)-, -C(O)NHR ⁶ 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 _-CH2CH (OH) _CH2- .

R ⁶ is a C ₂ -C ₁₂ alkylene group or a C ₆ -C ₁₂ arylene group.

Preferred "oxygen" R units may be further represented by R ¹ , R ² and R ⁵ units. Preferred "oxygen" R units contain preferred ^R1 , ^R2 and ^R5 units. Preferred cotton soil release agents of the invention contain at least 50% ^R1 units that are ethylene. Preferred R ¹ , R ² and R ⁵ units are combined with "oxy" R units in the following manner to form preferred "oxy" R units.

i) Substitution of the more preferred R ⁵ to -(CH ₂ CH ₂ O) _x R ⁵ (OCH ₂ CH ₂ ) _x - yields -(CH ₂ CH ₂ O) _x CH ₂ CHOHCH ₂ (OCH ₂ CH ₂ ) _x -.

ii) Substitution of the preferred R ¹ and R ² to -(CH ₂ CH(OR ² )CH ₂ O) _z (R ¹ O) _y R ¹ O(CH ₂ CH-(OR ² )CH ₂ ) _w - yields -(CH ₂ CH(OH)CH ₂ O) _z (CH ₂ CH ₂ O) _y CH ₂ CH ₂ O(CH ₂ CH(OH)CH ₂ ) _w -,

iii) Substitution of the preferred ^R2 to _-CH2CH ( ^OR2 ) _CH2- yields _-CH2CH (OH) _CH2- .

E units are selected from hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M, -(CH ₂ ) _p PO ₃ M, -(R ¹ O) _m B, -C(O)R ³ , preferably hydrogen, C ₂ -C ₂₂ hydroxyalkylene, benzyl, C ₁ -C ₂₂ alkylene, -(R ¹ O) _m B, -C(O)R ³ , -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M, more preferably C ₁ -C ₂₂ alkylene, -(R ¹ O) _x B, -C( O)R ³ , -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M, most preferably C ₁ -C ₂₂ alkylene, - (R ¹ O) _x B and -C(O)R ³ . When no modification or substitution is made to the nitrogen, then the hydrogen atom will remain as the moiety representing E.

或

When the V, W or Z units are oxidized, the E units do not include hydrogen atoms, ie nitrogen is an oxide of nitrogen. For example, the backbone or branch does not include units with the following structures: or

or

或 或 Additionally, when the V, W or Z units are oxidized, the E units do not include a carbonyl moiety directly bonded to the nitrogen atom, ie nitrogen is an oxide of nitrogen. According to the present invention, the E unit -C(O)R ^moiety is free of bonds to the modified nitrogen in the nitrogen oxide, i.e. no nitrogen oxide amides or mixtures thereof having the structure:

or or

B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, - (CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M, -PO ₃ M, preferably hydrogen, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M, more preferably hydrogen or -(CH ₂ ) _q SO ₃ M.

M is hydrogen or a water-soluble cation in an amount sufficient to satisfy charge balance. Sodium ions for example satisfy -(CH ₂ ) _p CO ₂ M and -(CH ₂ ) _q SO ₃ M equivalently, resulting in -(CH ₂ ) _p CO ₂ Na and -(CH ₂ ) _q SO ₃ Na moieties. More than one type of monovalent cation (sodium, potassium, etc.) can be combined to meet the desired chemical charge balance. However, the charge of more than one anionic group may be balanced by divalent cations, or more than one monovalent cation is required to satisfy the charge requirements of a multivalent anionic group. For example -(CH ₂ ) _p PO ₃ M moieties substituted by sodium atoms have the general formula: -(CH ₂ ) _p PO ₃ Na ₃ . Divalent cations, such as calcium ions (Ca ²⁺ ) or magnesium ions (Mg ²⁺ ), may replace or be combined with other suitable monovalent water-soluble cations. Preferred cations are sodium and potassium, more preferably sodium.

X is a water-soluble anion, such as chloride ion (Cl), bromide ion (Br) and iodide ion (I ^- ), or X can be any negatively charged group, such as sulfate ion (SO ₄ ^2- ) and formazan base sulfite ion (CH ₃ SO ₃ ).

The symbols of the general formula have the following values: p has a value of 1 to 6, q has a value of 0 to 6; r has a value of 0 or 1; w has a value of 0 to 1, x has a value of 1 to 100; y has a value of 0 to 100; z has a value of 0 or 1; m has a value of 4 to about 400, n has a value of 0 to about 200; m+n has a value of at least 5.

Preferred cotton soil release agents of the present invention comprise a polyamine backbone wherein less than about 50% of the R groups contain "oxygen" R units, preferably less than about 20%, more preferably less than 5%, and most preferably the R units contain no "oxygen" R units. "Unit R.

The most preferred cotton soil release agents that do not contain "oxygen" R units contain a polyamine backbone in which less than 50% of the R groups contain more than 3 carbon atoms. For example, ethylene, 1,2-propylene and 1,3-propylene contain 3 or fewer carbon atoms and are preferred "hydrocarbyl" R units. That is, when the main chain R unit is a C ₂ -C ₁₂ alkylene group, it is preferably a C ₂ -C ₃ alkylene group, most preferably an ethylene group.

The cotton soil release agents of the present invention contain a modified homogeneous or heterogeneous polyamine backbone in which 100% or less of the -NH units are modified. For the purposes of the present invention, a "homogeneous polyamine backbone" refers to a polyamine backbone having R units that are identical (ie, all ethylene). However, this same definition does not exclude polyamines containing other secondary units including secondary units of the polymer backbone present as a consequence of the chosen chemical synthesis method. For example, it is known to those skilled in the art that ethanolamine can be used as an initiator in the synthesis of polyethyleneimine, thus a sample of polyethyleneimine containing a hydroxyethyl moiety produced by a polymerization "initiator" would be considered to contain Homogeneous polyamine backbones which are the object of the present invention. A polyamine backbone containing ethylene R units all free of branched Y units is a homogeneous backbone. A polyamine backbone containing all ethylene R units is a homogeneous backbone regardless of the degree of branching or the number of cyclic branches present.

For the purposes of the present invention, the term "heterogeneous polymer backbone" refers to polyamine backbones of complexes of different R unit lengths and R unit types. For example, a heterogeneous backbone contains R units that are a mixture of ethylene and 1,2-propylene units. For the purposes of this invention, it is not necessary for the mixture of "hydrocarbyl" and "oxygen" R units to provide a heterogeneous backbone. Proper manipulation of these "chain lengths of R units" enables the formulator to vary the solubility and substantivity to fabrics of the cotton soil release agents of the present invention.

The preferred cotton soil release polymers of the present invention contain a homogeneous polyamine backbone which is fully or partially substituted with polyethyleneoxy moieties, fully or partially quaternized amines, fully or partially oxidized to oxidized Compound nitrogen and their mixtures. However, not all backbone amine nitrogens must be modified in the same manner, and the modification is selected according to the specific needs of the formulator. The degree of ethoxylation is also determined by the specific needs of the formulator.

Preferred polyamines containing the backbone of the compounds of the invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamines (PEA's), polyethyleneimines (PEI's) , or via partially linked PEA's or PEI's having longer R units than the original PAA's, PAI's, PEA's or PEI's. A typical polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are produced by a reaction involving ammonia and ethylene dichloride, followed by fractional distillation. Commonly prepared PEA's are tetraethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the aforementioned pentamines, ie hexamines, heptamines, octaamines and possibly nonamines, co-derived mixtures cannot be separated by distillation and may include other species such as cyclic amines and especially piperazines. Cyclic amines with side chains having nitrogen atoms in them may also be present. See US 2,792,372, issued May 14, 1957 to Dickinson, which describes the preparation of PEA's.

Preferred amine polymer backbones include R units, which are _C2 alkylene (ethylene) units, also known as polyethyleneimines (PEI's). Preferred PEI's have at least moderate branching, ie, an m to n ratio of less than 4:1, however, PEI's having an m to n ratio of about 2:1 are most preferred. Preferred backbones have the following general formula prior to modification:

where m and n are the same as above. Preferred PEI's have molecular weights greater than about 200 Daltons prior to modification.

In the polyamine backbone, particularly in the case of PEI's, the relative proportions of primary, secondary and tertiary amine units vary according to the method of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine backbone represents a site for subsequent substitution, quaternization, or oxidation.

These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid and the like. Specific methods for preparing these polyamine backbones are disclosed in US2182306, issued May 1939 by Ulrich et al; US3033746 issued May 8, 1962 by Mayle et al; US2208095, issued September 17, 1957 to Crowther; and US2553696 issued May 21, 1951 to Wilson; all of which are incorporated herein by reference.

Examples of modified cotton soil release polymers containing PEI's of the present invention are illustrated by the following general formulas I-V:

式ⅠFormula I illustrates _a preferred cotton soil release polymer comprising a PEI backbone wherein all substitutable nitrogen atoms are modified by replacing hydrogen with polyoxyalkylene oxygen units, i.e. -( _CH2CH2O ) _20H , It has the following general formula:

Formula Ⅰ

Formula II illustrates a cotton soil release polymer containing _a PEI backbone in which all substitutable nitrogens are modified by replacing hydrogens with polyoxyalkylene oxygen units, i.e. -( _CH2CH2O ) _7H , which has the following The general formula: Formula II

This is an example of a cotton soil release polymer fully modified with one class of groups.

式ⅢFormula III illustrates a cotton soil release polymer containing _a PEI backbone in which all substitutable amine nitrogens are modified by replacing hydrogen with polyoxyalkylene oxygen units, i.e. -( _CH2CH2O ) _7H , the molecule Subsequent to modification by subsequent oxidation of all oxidizable primary and secondary nitrogens to nitrogen oxides, the cotton soil release agent has the general formula:

Formula III

Formula IV illustrates cotton soil release polymers containing a PEI backbone in which all backbone hydrogen atoms have been substituted and a portion of the backbone amine units have been quaternized. Substituents are polyoxyalkylene oxygen units, ie -(CH ₂ CH ₂ O) ₇ H, or methyl. The modified PEI cotton soil release polymer has the following general formula: Formula IV

式ⅤFormula V illustrates a cotton soil release polymer containing _a PEI backbone in which the backbone nitrogen is substituted (i.e., replaced by -( _CH2CH2O ) _7H or methyl), quaternized, oxidized to nitrogen oxides or combinations of them. The resulting cotton soil release polymer has the general formula:

Formula Ⅴ

In the above examples, not all nitrogens of a type of unit were modified equally. The present invention allows the formulator to ethoxylate some of the secondary amine nitrogens while oxidizing other secondary amine nitrogens to nitrogen oxides. This also applies to primary amine nitrogens, where the formulator can choose to modify all or part of the primary amine nitrogens with one or a few substituents prior to oxidation or quaternization. Any possible combination of E groups may be substituted on primary and secondary amine nitrogens, except as strictly defined above.

The laundry detergent composition of the present invention contains an additive component and a carrier, said additive component is selected from the group consisting of builders, optical brighteners, bleaching agents, bleach boosters, bleach activators, other non-cotton soil release polymers, Dye transfer inhibitors, dispersants, enzyme activators, suds suppressors, dyes, fragrances, pigments, filler salts, hydrotropes and mixtures thereof, however, this listing is not meant to exclude or exclude any formulation design suitable substances for teachers to use.

detergent surfactant

In addition to the preferred anionic and nonionic detersive surfactants described herein, other detersive surfactants suitable for the present invention are cationic, anionic, nonionic, amphoteric, amphoteric surfactants and mixtures thereof, which are described below will be described further.

Non-limiting examples of other surfactants that can be used in the present invention generally at concentrations of about 1% to 55% by weight include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS"), C ₁₀ -C ₁₈ Secondary (2,3) alkyl sulfates with the general formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ )CH ₂ CH ₃ , wherein x and (y+1) are integers of at least about 7, preferably at least about 9, M is a water-soluble cation, especially a sodium ion, an unsaturated sulfate such as oleyl sulfate, C ₁₀ -C ₁₈ Alkyl alkoxy carboxylates (especially ethoxy carboxylates of EO1-5), C ₁₀ -C ₁₈ glyceryl ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides , and C ₁₂ -C ₁₈ α-sulfonated fatty acid esters. Conventional nonionic and zwitterionic surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE") include so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkyl ethoxylates, if desired. Phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ₁₂ -C ₁₈ betaines and sultaines ("sultains"), C ₁₀ -C ₁₈ amine oxides, etc. It may also be included in the above compositions. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. See WO9206154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. C ₁₀ -C ₂₀ conventional soaps may also be used. If high foam is required, branched chain C ₁₀ -C ₁₆ soap can be used. Mixtures of anionic and nonionic surfactants are particularly preferred. Other commonly used surfactants are listed in standard texts.

Other anionic surfactants useful for detersive purposes may also be included in the compositions herein. They include salts of soaps (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di-, and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ Primary- or secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oily glycerol sulfates, alkane Alkyl phenol oxide ethylene ether sulfates, paraffin sulfonates, alkyl phosphonates, isothionates, such as acyl isethionates, N-acyl taurates, methyl tauramide ( tauride), alkyl succinamic acid salts and sulfosuccinates, sulfosuccinic acid monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), sulfosuccinic acid diesters ( Especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates, sulfates of alkyl polysaccharides, such as alkyl polyglycosides, branched primary alkyl sulfates , Alkyl polyethoxy carboxylate, for example, the general formula is RO(CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ , wherein R is a C ₈ -C ₂₂ alkyl group, and k is an integer from 0 to 10 , M is a soluble salt-forming cation, a fatty acid esterified with hydroxysulfonate and neutralized with sodium hydroxide. Additional examples are given in Surface Active Agents and Detergents (Volumes I and II by Schwartz, Perry and Berch).

The compositions herein preferably contain at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to 95%, most preferably from about 1% to 80%, by weight, of anionic detersive surfactant. Alkyl sulfate surfactants, primary or secondary alkyl, are an important class of anionic surfactants useful in the present invention. The general formula of alkyl sulfate is ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbon group, preferably an alkyl straight or branched chain or a hydroxyalkyl group with a C ₁₀ -C ₂₀ alkyl moiety, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is hydrogen or water-soluble cations, such as alkali metal cations (such as sodium, potassium, lithium), substituted or unsubstituted ammonium cations, such as methyl-, dimethyl - and trimethylammonium and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium, and cations derived from alkanolamines, such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. _C12 - _C16 alkyl chains are generally preferred for lower wash temperatures (eg, below about 50°C) and _C16 - _C18 alkyl chains are preferred for higher wash temperatures (eg, about 50°C).

Alkyl alkoxylated sulfate surfactants are another preferred class of anionic surfactants. These surfactants are water soluble salts or acids, generally of formula RO(A) _m SO ₃ M, where R is unsubstituted C ₁₀ -C ₂₄ alkyl or has a C ₁₂ -C ₂₄ alkyl moiety Hydroxyalkyl, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is an integer greater than 0, generally Between about 0.5 and about 6, more preferably between about 0.5 and 3, M is hydrogen or a water-soluble cation, which can be, for example, a metal cation (such as sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium ion or a substituted ammonium cation. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are also contemplated. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and alkanolamines such as monoethanolamine, diethanolamine and cations derived from triethanolamine and mixtures thereof. Representative surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfates, C ₁₂ -C ₁₈ alkyl polyethoxylated (2.25) sulfates, C ₁₂ -C ₁₈ alkanes Alkyl polyethoxylated (3.0) sulfates and C ₁₂ -C ₁₈ alkyl polyethoxylated (4.0) sulfates, wherein M is generally selected from sodium and potassium.

The compositions herein preferably also contain at least about 0.01%, preferably at least 0.1%, more preferably from about 1% to 95%, most preferably from about 1% to 80%, by weight, of an anionic detersive surfactant. Preferred anionic surfactants, such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE") and C ₆ -C ₁₂ alkylphenol alkoxylates (especially are ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensates of C ₆ to C ₁₂ alkylphenols, alkylene oxide condensates of C ₈ -C ₂₂ alkanols and ethylene oxide Propylene oxide block polymers (Pluronic ^™ - BASF Corp.), as well as semi-polar nonionic surfactants such as amine oxides and phosphine oxides, are useful in the compositions of the present invention. Surfactants of these types are extensively disclosed in US Patent 3,929,678, Laughlin et al., issued December 30, 1975, which is incorporated herein by reference.

Alkyl polysaccharides, such as those disclosed in US 4,565,647 to Llenado, incorporated herein by reference, may also be preferred nonionic surfactants in the compositions of the present invention.

Further preferred nonionic surfactants are polyhydroxy fatty acid amides having the general formula:

Wherein R ⁷ is C ₅ -C ₃₁ alkyl, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ - C ₁₅ alkyl or alkenyl or mixtures thereof; R ⁸ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, preferably methyl or ethyl, more preferably methyl. Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof; preferred alkoxy groups are ethoxy or propoxy and their mixtures. Preferred Q is prepared from a reducing sugar in a reductive amination reaction. More preferably Q is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. High dextrose corn syrup, high levulose corn syrup and high maltose corn syrup may be used as raw materials as well as the individual sugars listed above. These corn syrups can generate a mixture of sugar components for Q. It is considered that this by no means excludes other suitable starting materials. Q is more preferably selected _{from -CH2} (CHOH) _nCH2OH , -CH( _CH2OH )(CHOH) _{n-1 CH2OH} , -CH2( _CHOH ) _2- (CHOR')(CHOH) _CH2 OH, and its alkoxylated derivatives, n is an integer from 3 to 5 inclusive, R' is hydrogen or a cyclic or fatty monosaccharide. The most preferred substituents for the Q moiety are _alditols where n is 4, especially _-CH2 (CHOH) _4CH2OH .

R ⁷ CO-N< can be, for example, cocoamide, stearylamide, oleamide, laurylamide, myristamide, capricamide, palmitamide, tallowamide, and the like.

^R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl.

Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl and the like.

A particularly desirable class of surfactants for use in the compositions of the present invention are alkyl-N-methylglucamides, compounds of the general formula above, wherein R ⁷ is alkyl (preferably C ₁₁ -C ₁₃ ) , R ⁸ is methyl, Q is 1-deoxyglucityl.

Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N-(3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamides can be used for low sudsing. C ₁₀ -C ₂₀ conventional soaps can be used. If high foam is required, branched C ₁₀ -C ₁₆ soaps can be used.

Bleaching Compounds - Bleach and Bleach Activators

The detergent compositions of the present invention may optionally contain a bleaching agent or contain a bleaching composition comprising a bleaching agent and one or more bleach activators. Bleaching agents, when present, will be present in amounts of from about 0.05% to about 30%, more preferably from about 1% to 30%, most preferably from about 5% to 20%, of the detergent compositions, especially for fabric laundering. Bleach activators, if present, will generally be present in amounts of from about 0.1% to 60%, more usually from about 0.5% to 40%, of the bleaching composition comprising bleach plus bleach activator.

The bleaching agent employed in the present invention may be any presently known or ever to be known bleaching agent useful in detergent compositions for fabric cleaning. They include oxygen bleaches, among other bleaching agents. Perborate bleaches such as sodium perborate (eg mono- or tetrahydrate) may be used.

Other non-limiting classes of bleaches include percarboxylic acid bleaches and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. These bleaching agents are disclosed in US4483781 granted by Hartman on November 20, 1984, US740446 obtained by Burns et al. on June 3, 1985, EPO133354 disclosed by Banks et al. on February 20, 1985, Chung et al. in 1983 In US4412934 granted on November 1st. Very preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Patent 4,634,551, issued January 6,1987 to Burns et al.

Peroxygen bleach can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg, OXONE, commercially available from DuPont) may also be used.

Preferred percarbonate bleaches contain dry particles having an average particle size in the range of about 500 microns to about 1000 microns, with not more than about 10% by weight of said particles smaller than about 200 microns and not more than about 10% by weight of all Particles are said to be larger than about 1250 microns. Optionally the percarbonate may be coated with a silicate, borate or water soluble surfactant. Percarbonate is available from various industrial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents may also be used.

Peroxygen bleaches, perborates, percarbonates and the like are preferably used in combination with bleach activators which can be prepared in situ (ie during the wash) in aqueous solutions of peroxyacids corresponding to the bleach activators. Various non-limiting examples of active agents are disclosed in US4915854 and US4412934, issued April 10, 1990 to Mao et al. Typical active agents are nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED), although mixtures thereof may also be used. See US4634551 for other types of bleaches and activators.

The general formula of highly preferred amide derived bleach activators is:

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L

wherein ^R1 is an alkyl group containing about 6 to 12 carbon atoms, ^R2 is an alkylene group containing about 1 to 6 carbon atoms, ^R5 is hydrogen or an alkyl group or aryl group containing 1 to 10 carbon atoms Or alkaryl, L is any leaving group used. A leaving group is any group that is displaced from the bleach activator as a result of the nucleophilic action of the perhydrolysis anion on the bleach activator. A preferred leaving group is benzenesulfonate.

Preferred examples of bleach activators having the general formula above include (6-octanoyl-caproyl)oxybenzenesulfonate, (6-nonanamidecaproyl)oxybenzenesulfonate, (6-decanoyl-caproyl) Oxybenzenesulfonates and mixtures thereof, which are described in US 4,634,551, incorporated herein by reference.

Other classes of bleach activators include the benzoxazine activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30, 1990, which is incorporated herein by reference. Highly preferred benzoxazine active agents are:

Yet another preferred class of bleach activators includes the acyl lactam activators, especially the acyl caprolactams and acyl valerolactams having the general formula:

wherein ^R6 is hydrogen or an alkyl, aryl, alkoxyaryl or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Amides, capryloyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US Patent 4,545,784, Sanderson, issued October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactams, absorbed in sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and may also be used in the present invention. A particularly advantageous class of non-oxygen bleaches includes light sensitized bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718, issued Jul. 5, 1977 to Holcombe et al. If employed, detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially zinc phthalocyanine sulfonates.

The bleaching compounds can be catalyzed by manganese compounds if desired. Such compounds are known in the art and include, for example, manganese-based catalysts disclosed in US5246621, US5244594, US5194416, US5114606 and EP549271A1, 549272A1, 544440A2 and 544490A1; preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1 ,4,7-Trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^Ⅲ ₂ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl base-1,4,7-triazacyclononane) 2-(ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^Ⅲ Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ -(1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ 、Mn ^Ⅳ (1, 4,7-Trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal based bleach catalysts include those disclosed in US4430243 and US5114611. The use of manganese with various complex ligands to promote bleaching is also disclosed in US Pat.

Indeed, and without limitation, the compositions and methods of the present invention can be adjusted to have an active bleach catalyst material concentration of at least one part per million in aqueous wash liquors, and preferably from about 0.1 ppm to about 700 ppm in laundry liquors , more preferably from about 1 ppm to about 500 ppm of catalytic species.

Many other ingredients useful in detergent compositions may be included in the composition, including other active ingredients, carriers, hydrotropes, processing aids, pigments or dyes, solvents for liquid formulations, solvents for stick compositions solid filler etc. If high foam is required, a foam booster, such as C ₁₀ -C ₁₆ alkanolamide, may be added to the composition, generally at 1%-10%. C ₁₀ -C ₁₄ simple alcohols and glycol amides illustrate the general class of such suds boosters. It is also advantageous to employ such suds boosters containing high sudsing additive surfactants such as amine oxides, betaines and the aforementioned sultaines. If desired, soluble magnesium salts, such as _MgCl2 , _MgSO4, etc., can be added at a concentration of 0.1%-2% to provide more foam and enhance oil removal performance.

Various detersive ingredients useful in the compositions of the present invention may optionally be further stabilized by absorbing said ingredients into a porous hydrophobic substrate, followed by coating said substrate with a hydrophobic coating. Preferably the detersive components are mixed with a surfactant prior to being absorbed into the porous substrate. In use, the cleaning composition is released from the substrate into the aqueous wash liquor where it performs its desired cleaning action.

To illustrate the technique in more detail, porous hydrophobic silica (trademark SIPERNATD10, DeGussa) was mixed with a hydrolytic protease solution containing 3%-5% of _C13 - _C15 ethoxylated alcohol (EO7) nonionic surfactant . Generally, the enzyme/surfactant solution is 2.5 times the weight of silica. The generated powder is dispersed in silicone oil (various silicone oils with a viscosity of 500-12500 can be used) under the condition of stirring. The resulting silicone oil dispersion is either emulsified or incorporated into the final detergent matrix. In this way, components such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photosensitizers, pigments, optical brighteners, fabric conditioners and hydrolyzable surfactants can be "protected" for use in Detergents, including liquid laundry detergent compositions.

Liquid detergent compositions contain water and other solvents as carriers. Low molecular weight primary and secondary alcohols, typically methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for enhancing the dissolution of surfactants, however, polyhydric alcohols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g. 1,3-propanediol, ethylene glycol, Glycerin and 1,2-Propanediol). The composition may contain from 5% to 90%, typically 10% to 50%, of such carriers.

The detergent compositions herein are preferably formulated so that, during use in aqueous laundering operations, the pH of the wash water is between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry products are generally pH 9-11. Techniques for controlling pH within the recommended range for use include the use of buffer solutions, bases, acids, etc., and are known to those skilled in the art.

enzyme

The detergent compositions of the present invention may contain enzymes other than proteases for various purposes including removal of protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as fabrics to prevent dye transfer (e.g. during laundry), and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures of any suitable source, eg vegetable, animal, bacterial, fungal and yeast origin. The preferred choice is influenced by factors such as pH activity and/or stability, thermostability and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detergent enzyme" refers to any enzyme having a cleaning, stain removal or other benefit in a laundry, hard surface cleaning or body care detergent composition. Preferred detergent enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for washing purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.

Enzymes are generally added to detergent or detergent additive compositions in an amount sufficient to provide a "detergency effective amount". By "detergency-effective amount" is meant any amount capable of producing a cleaning, stain-removing, soil-removing, whitening, deodorizing or color-improving effect on a substrate, such as fabric. In practice, for current commercial practice, typical amounts are up to 5 mg by weight, more typically 0.01 to 3 mg, of active enzyme per gram of detergent composition. It should also be noted that the composition of the present invention generally contains 0.001% to 5%, preferably 0.01% to 1% by weight of industrial enzyme preparations. Proteases are usually present in these commercial formulations in sufficient amounts to have an activity of 0.005 to 0.1 Dalton Units (AU) per gram of composition. For some detergents, it is desirable to increase the active enzyme content of commercial formulations to reduce the total amount of non-catalytically active species, thereby improving spotting/filming or other end results. Higher active concentrations are also desirable for high strength detergent formulations.

Amylases suitable for use in the present invention include, for example, α-amylases described in Novo's GB1296839; ^RAPIDASE® from International Bio-Synthetics, Inc and ^TERMAMYL® from Novo, ^FUNGAMYL® from Novo are particularly effective. The use of enzymes to enhance stability, such as oxidative stability, is known. See, eg, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Some preferred embodiments of the compositions of the present invention may employ amylases for improved stability in detergents, particularly improved oxidative stability relative to the 1993 commercially adopted reference point of TERMAMYL ^(R) . These preferred amylases of the present invention have the characteristics of "increased stability" amylases, which are characterized by greater improvement in at least one or more of the following: oxidative stability, such as hydrogen peroxide/tetraacetyl Ethylenediamine in a buffer solution of pH 9 to 10; thermal stability, such as at a typical wash temperature, such as about 60° C.; or alkali stability, such as at a pH of about 8 to about 11, measured relative to the above reference point Enzyme comparison. Stability can be determined using any of the techniques disclosed in the art. See eg reference WO9402597. Stability-enhancing enzymes are available from Novo or Genencor International. A highly preferred class of enzymes according to the invention has the commonality of being prepared using in situ mutagens from one or several Bacillus amylases, especially Bacillus alpha-amylases, regardless of one, two or more amylase strains Is it a transient precursor. Enzymes with improved oxidative stability are preferred for use in detergent compositions which are in particular bleached, more preferably oxygen bleached as opposed to chlorine bleached, compared to the above mentioned reference amylases. Preferred amylases of this type include (a) an amylase according to the previously described WO9402597 granted to Novo on February 3, 1994, further illustrated by a mutant wherein alanine or threonine are used Acid, preferably threonine, in place of a methionine residue at position 197 of the Bacillus licheniformis alpha-amylase known as ^TERMAMYL® , or similar parent amylases, such as Bacillus amyloliquefaciens, Bacillus subtilis Or variants at the corresponding positions of Bacillus licheniformis; (b) amylases with improved stability, as in the 207th American Chemical Society National Meeting on March 13-17, 1994, published by C.Mitchinson under the title "Oxidatively Resistant α -Amylases" as described in the paper. It should be noted that bleach inactivates alpha-amylases in automatic dishwashing detergents, but amylases with improved oxidative stability were prepared by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) was considered the most likely residue to be modified. Met is sometimes substituted at positions 8, 15, 197, 256, 304, 366 and 438, resulting in specific mutations, of particular importance are M197L and M197T, the M197T variant being the most stable variant. Stability was determined in ^CASCADE® and ^SUNLIGHT® ; (c) particularly preferred amylases include amylase variants further improved in the transient parent as described in WO9510603A and supplied as ^DURAMYL® by Applicant Novo. Other particularly preferred oxidative stability-enhancing amylases include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other oxidative stability-enhancing amylase may be used, for example prepared by direct mutagenesis from known chimera, hybrid or simple mutant parents of available amylases. Other preferred enzyme modifications can be made. See WO9509909 to Novo.

Cellulases usable in the present invention include bacterial and fungal species, preferably preferably at a pH between 5 and 9.5. Barbesgoard et al. disclosed fungal cellulase or cellulase 212 produced by Humicola insolens or Humicola DSM1800 in US4435307 on March 6, 1984 - produced by fungi belonging to the genus Aeromonas, and by the hepatopancreas of shipworms Extracted cellulase Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832. ^CAREZYME® (Novo) is particularly effective. See WO9117243 to Novo.

Suitable lipases for laundry use include those produced by microorganisms of the genus Pseudomonas, eg Pseudomonas stilgiformis ATCC 19.154, as disclosed in GB1372034. See also Japanese Patent Application No. 5320487 published on February 24, 1978 for lipases. This lipase is supplied by Amano Pharmaceutical Co. Lth., Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P". Other suitable industrial lipases include Amano-CES, a lipase produced by Chromobacter viscosum, such as Chromobacter viscosum var.lipolyticumNRRLB3673 provided by Toyo Jozo Co.Tagata of Japan; USBiochemical Corp. of the United States. and Disoynth Co. of the Netherlands. Chromobacter viscosum lipase provided, as well as lipase produced by Pseudomonas gladioli. The LIPOLASE ^(R) enzyme derived from Humicola lanuginosa and produced by Novo Industries, see EP341947, is the preferred lipase herein. Lipase and amylase variants stabilized by peroxidases are described in WO9414951A to Novo. See WO9205249 and RD94359044.

Cutinase enzymes suitable for use in the present invention are described in WO8809367A to Genencor.

Peroxidase can be combined with oxygen raw materials, such as percarbonate, perborate, hydroxide, etc., to perform "solution bleaching" or to prevent dye transfer or pigment transfer from the substrate to the washing solution during the wash process. Other substrates present in . Known peroxidases include horseradish peroxidase, ligninase, haloperoxidase, such as chloro- or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO89099813A, Novo, October 19, 1989 and WO8909813A, Novo.

A range of enzyme materials and methods for their incorporation into synthetic detergent compositions are described in WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139, issued January 5, 1971 to McCarty et al. Enzymes are also disclosed in US 4,101,457, Place et al., Jul. 18, 1978, and US 4,507,219, Mar. 26, 1985, Hughes. Enzymes useful in liquid detergent formulations and methods for their incorporation into such formulations are disclosed in US Patent 4,261,868, issued April 14,1981 to Hora et al. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and representatively in US3600319, Gedge et al., August 17, 1971, EP199405, October 29, 1986, Venegas, and EP200586. Enzyme stabilization systems are also described, eg in US3519570. A potent subtilisin AC13 producing proteases, xylanases and cellulases is described in WO9401532A to Novo.

enzyme stabilization system

The liquid enzyme-containing compositions of the present invention, but not limited thereto, may contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to 6%, by weight of the enzyme stabilizing system. This enzyme stabilization system can be any stabilization system compatible with the detergent enzyme. Such systems are originally provided by active substances in other formulations or added separately by formulators or by manufacturers of finished detergent enzymes. Such stabilizing systems may, for example, contain calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids and mixtures thereof, and are designed for different stabilization problems depending on the type and physical state of the detergent composition.

One stabilizing approach is to use water-soluble materials of calcium and/or magnesium ions in the final composition so that the enzymes contain such ions. Calcium ions are generally more effective than magnesium ions and are preferred in the present invention, and if only one is present, calcium ions may be used. Typical detergent compositions, especially liquid ones, contain from about 1 to about 30, preferably from about 2 to 20, more preferably from about 8 to 12 millimoles of calcium ions per liter of finished detergent composition, according to including diversity, type And the concentration of added enzyme can be varied. Water-soluble calcium and magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; calcium sulfate or the corresponding typical calcium salts can usually be used of magnesium salts. It is of course useful to further increase the calcium and/or magnesium concentration, eg to enhance the degreasing action of certain types of surfactants.

Another method of stabilization is the use of borates. See US4537706 to Severson. When borate stabilizers are used, their concentrations can be as high as 10% or more of the composition, and generally up to about 3% by weight of boric acid or other borate compounds, such as borax or orthoborate, are suitable for use in Use of liquid detergents. Substituted boric acids, such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid, etc. can be used in place of boric acid and the total amount of boron in detergent compositions can be reduced by using such substituted boron derivatives.

Stabilizing systems of some detergent compositions may further contain from 0 to about 10%, preferably from about 0.01% to about 6%, by weight, of a chlorine bleach scavenger to prevent the presence of chlorine bleaching substances in many water sources from acting on enzymes and rendering them useless. live, especially under alkaline conditions. When the concentration of chlorine in the water is small, typically in the range of about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of all water contacting the enzyme, for example in a fabric washing process, can be considerable; Stability is sometimes problematic. Since perborate or percarbonate, which can react with chlorine bleach, may be present in certain instant compositions in amounts isolated from the stabilizing system, the use of other chlorine-resistant stabilizers may be of lesser importance, although Use them for improved results. Suitable chlorine scavenger anions are known and readily available and, if used, may be salts containing ammonium cations with sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. Antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may also be used. Likewise, special enzyme inhibition systems can be added for maximum compatibility with the various enzymes. Other conventional scavengers such as hydrogen sulfate, nitrates, chlorides, raw materials of hydrogen peroxide, such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, and phosphates, concentrated phosphates, Acetates, benzoates, citrates, formates, laurates, malates, tartrates, salicylates, etc. and mixtures thereof can also be employed if desired. In general, since the action of the chlorine scavenger can be performed by separately listed components (such as hydrogen peroxide feed) which are considered to be better performing, there is no need to add a separate chlorine scavenger unless it has the desired degree of action. Compounds are not included in the enzyme-containing embodiments of the invention; rather, scavengers are added only for optimal results. Also, it is a common practice for chemists to avoid the use of any enzyme scavengers or stabilizers which, if used, are highly incompatible with the other reaction components when formulated. As far as ammonium salts are employed, such salts can be simply mixed with detergent compositions, but tend to absorb water and/or release ammonia during storage. Therefore, such materials, if present, need to be protected in the particles, as described in US 4,652,392 to Baginski et al.

Auxiliary

Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic additives can be used. Adjuncts are generally used in fabric washing compositions to aid in the removal of particulate soils.

The level of adjuvants can vary widely depending on the end use of the composition and its desired physical form. When present, the compositions generally contain at least about 1% of adjuvants. Liquid formulations generally contain from about 5% to about 50%, more usually from about 5% to about 30%, by weight, of detergent builder. Granular formulations generally contain from about 10% to about 80%, more usually from about 15% to about 50%, by weight, of detergent builder. However, lower or higher levels of adjuvants are not meant to be excluded.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphoric acids (typically tripolyphosphonates, pyrophosphates, and glassy polymeric metaphosphates) , phosphates, phytates, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. In some cases, however, non-phosphate builders are required. What is important is that the compositions of the invention work surprisingly well even in the presence of so-called "weak" builders (compared to phosphates), such as citrates, or in the so-called The same is true for "bad auxiliaries" that occur in the case of salt auxiliaries.

Examples of silicate builders are alkali metal silicates, especially those with SiO ₂ :Na ₂ O ratios between 1.6:1 and 3.2:1 and phyllosilicates, eg HPRieck in 1987 Layered sodium silicates described in US4664839, granted May 12, 2009. NaSKS-6 is the trade designation for a crystalline layered silicate supplied by Hoechst (commonly abbreviated "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is a phyllosilicate in the form of δ-Na ₂ SiO ₅ . It can be prepared, for example, by the methods described in DE-A-3417649 and DE-A-3742043 of Germany. SKS-6 is a very preferred silicate for use in the present invention, but other such phyllosilicates, such as those of the general formula _{NaMSixO2x +1} · _yH2O , where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, y is a number from 0 to 20, preferably 0 can be used in the present invention. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as alpha, beta and gamma forms. As noted above, δ- _Na2SiO5 (NaSKS-6 form) is the most preferred for the present invention _. Other silicates are also effective, such as magnesium silicate, which acts as a crisping agent in granular formulations, as a stabilizing agent for oxygen bleaches and as a component of suds suppressing systems.

Examples of carbonate builders are alkaline earth metal and alkali metal carbonates, as disclosed in German Patent 2321001, 15.11.1973.

Aluminosilicate builders are effective in the present invention. Aluminosilicate builders are of importance in most currently marketed high performance granular detergent compositions, and can also be an important builder ingredient in liquid detergent compositions. Aluminosilicate builders include those having the general formula:

M _z (zAlO ₂ ) _y ·xH ₂ O

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to 0.5, and x is an integer of from about 15 to about 264.

Effective aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be natural or synthetic. A method for preparing aluminosilicate ion exchange materials is disclosed in US 3,985,669, issued October 12, 1976 to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are those designated Zeolite A, Zeolite P(B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the general formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O

wherein x is a number from about 20 to about 30, especially about 27. This material is known as Zeolite A. The present invention can also use dehydrated zeolite (x=0-10). Preferred are aluminosilicates having a particle diameter of about 0.1 to 10 microns.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. The polycarboxylate builder can generally be incorporated into the composition in the acid form, but also in the form of its neutralized salt. When employed in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a wide variety of effective materials. An important class of polycarboxylate additives includes ether polycarboxylates, including oxydisuccinates, such as Berg. in US3128287 granted on April 7, 1964 and Lamberti et al. on January 18, 1972 It is disclosed in the US3635830 that obtained the right on the date. See also US 4,663,071, Bush et al., issued May 5, 1987 for the "TMS/TDS" adjuvant. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds, such as those disclosed in US Pat.

Other effective detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and Carboxymethyloxysuccinic acid, polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid various alkali metal, ammonium and substituted ammonium salts, and polycarboxylates such as mellitic acid, butyric acid Diacids, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate builders such as citric acid and its soluble salts (especially the sodium salt) are particularly important polycarboxylate builders for high performance liquid detergent formulations because they are renewable raw materials and their Biodegradable and available. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly effective in these compositions and combinations.

Also suitable for use in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in Bush, January 28, 1986. Right of US4566984. Useful succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinates include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate Carbenyl succinate, etc. Lauryl succinate is a preferred adjuvant of this type and is described in EP86200690.5/0200263 published November 5, 1986.

Other suitable polycarboxylates are disclosed in US 4,144,226, Crutchfield et al., March 13, 1979 and US 3,308,067, March 7, 1967, Diehl. See also US3723322 to Diehl.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, can also be added to the composition alone or in combination with the above-mentioned adjuvants, especially citrate and/or succinate adjuvants, so that they have additional adjuvant activity . Such use of fatty acids will generally reduce foam, which will be up to the formulator.

Where phosphorus-based builders are employed, and particularly in stick formulations for handwashing operations, various alkali metal phosphates such as the known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, eg, US3159581, 3213030, 3422021, 3400148 and 3422137) may also be employed.

Chelating agent

The detergent compositions of the present invention may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are described hereinafter. While not wishing to be bound by theory, it is believed that the action of these materials is due in part to their unexpected ability to remove iron and manganese ions from wash solutions by forming soluble chelates.

Amino carboxylates useful as selective chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetraacetate, Amine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylene diamine tetrakis (methylene phosphonate ), such as DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, eg 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly the [S,S] isomer, as described by Hartman and Perkins on November 3, 1987 Documented in authorized US4704233.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, chelating agents, if used, comprise from about 0.1% to about 3.0% by weight of the composition.

Agents for Clay Removal/Anti-Redeposition

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay-removing and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Representative ethoxylated amines are described in US 4,597,898, issued Jul. 11, 1986, to VanderMeer. Another class of preferred clay-removing-anti-redeposition agents are cationic compounds which are disclosed in EP111965, June 27, 1984 by Oh and Gosselink. Other clay removal/anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in EP111984, published June 27, 1984, by Gosseink; Amphoteric polymers in EP112592; and amine oxides disclosed in US4548744, published October 22, 1985 by Connor. Other clay removal and/or anti-redeposition agents known in the art may also be used in the compositions of the present invention. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These substances are known in the art.

polymer dispersant

Polymeric dispersants are advantageously used in amounts of from 0.1% to about 7% by weight of the compositions of the present invention, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not wishing to be bound by theory, that when used in combination with other builders, the polymeric dispersant enhances overall detergent builder performance by inhibiting crystal growth, dispersing particulate soil and resisting redeposition.

The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and Methylenemalonic acid. The presence of polymeric polycarboxylates or monomeric segments that do not contain carboxylate groups such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided such segments do not exceed about 40% by weight.

Particularly useful polymeric polycarboxylates can be prepared from acrylic acid. Such acrylic acid-based polymers useful in the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such acid form polymers is preferably from 2,000 to 10,000, more preferably from 4,000 to 7,000, most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium, and substituted ammonium salts. Such soluble polymers are known substances. The use of such polyacrylates in detergent compositions has been disclosed, for example, in US Patent 3,308,067, issued March 7,1967 to Diehl.

Acrylic/maleic based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such acid form copolymers is from 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in the polymer is generally from 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Aqueous salts of such acrylic acid/maleic acid copolymers include, for example, alkali metal, ammonium, and substituted ammonium salts. Such water-soluble acrylate/maleate copolymers are known materials and are described in EP66915 published on December 15, 1982 and in EP193360 published on September 23, 1986, which also describes Polymer containing hydroxypropyl acrylate. Other effective dispersants include maleic/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP193360 and include, for example, 45/45/10 maleic/acrylic acid/vinyl alcohol terpolymers.

Another polymer that may be included is polyethylene glycol (PEG). PEG has a dispersing effect and acts as a clay removal-anti-redeposition agent. For this reason they generally have a molecular weight in the range of about 500 to about 100,000, preferably about 1,000 to about 50,000, more preferably about 1,500 to 10,000.

Polyaspartic acid and polyglutamic acid dispersants can also be used, especially in combination with zeolite builders. Dispersants such as polyaspartic acid preferably have a molecular weight (average) of about 10,000.

brightener

Any optical brighteners or other brighteners known in the art can be incorporated into the detergent compositions of the present invention at levels generally from 0.05% to about 1.2% by weight. Commercially available optical brighteners useful in the present invention can be divided into subclasses which include, but are not limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, thiofluorene-5,5-di Oxides, pyrroles, 5- and 6-membered heterocycles, and other mixed reagents. Examples of these brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agents" by M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are described in US Patent 4,790,856, issued December 13,1988 to Wixon. These brighteners include the PHORWHITE series of brighteners supplied by Verona. Other brighteners disclosed in these documents include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; supplied by Ciba-Geigy; Artic White CC and ArticWhite CWD supplied by Hilton-Davis in Italy; 2-(4-stryl -phenyl)-2H-naphthol[1,2-d]triazole; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbene; 4,4'-bis( stryl) biphenyl; and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis(-venz imidazol-2-yl)ethene; 1,3-diphenyl-phroxazoline ; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-naphtho-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphthalene- [1,2-d]triazole. See US3646015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners are preferred herein.

Foam suppressor

Compounds for reducing or inhibiting foam formation may be added to the compositions of the present invention. Suds suppressors are of particular importance in so-called "high concentration cleaning processes" as described in US4489455 and 4489574 and in front loading European style washing machines.

Various substances and suds suppressors which can be used as suds suppressors are known to those skilled in the art. See, eg, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Sons., Inc., 1979). A particularly effective class of suds suppressors contains monocarboxylic fatty acids and soluble salts thereof. See US2954347, patented Sep. 27, 1960, to Wayne St. John. The monocarboxylic fatty acids and salts thereof useful as suds suppressors contain hydrocarbyl chains of 10 to about 24, preferably 12 to 18, carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium and lithium salts and ammonium salts, and alkanolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant suds suppressors. They include, for example: high molecular weight hydrocarbons, such as paraffin, fatty acid esters (such as fatty acid triglycerides), fatty acid esters of monohydric alcohols, fatty C ₁₈ -C ₄₀ ketones (such as stearyl ketone), and the like. Other suds suppressors include N-alkylated aminotriazines such as tri- to hexa-alkyl melamine or cyanuric chloride with two or three moles of primary or secondary amines containing 1 to 24 carbon atoms Products Di- to tetra-alkyldiamine chlorotriazines, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl dialkali metal (such as K, Na and Li) phosphate and phosphates. Hydrocarbons such as paraffins and halogenated paraffins may be employed in their liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, have a pour point of about -40°C to about 50°C, and a minimum boiling point of not less than about 110°C (at atmospheric pressure). It is also known to employ waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US 4,265,779, Gandolfo et al., issued May 5,1981. Hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. In discussing the suds suppressor the term "paraffin" as used herein refers to a mixture of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersants or emulsifiers for polyorganosiloxane oils or resins, combinations of polyorganosiloxane and silica particles, where polyorganosiloxane Siloxanes are chemisorbed or dissolved on silica. Silicone suds suppressors are known in the art, for example as disclosed in US 4,265,779, Gandolfo et al., issued May 5, 1981, and EP 89307851.9, Starch, M.S., issued February 7, 1990.

Other silicone suds suppressors are disclosed in US 3,455,839, which relates to compositions and methods for preparing aqueous defoaming solutions by adding small amounts of polydimethylsiloxane fluid thereto.

Mixtures of siloxanes and silanized silicas are described, for example, in German patent DOS2124526. Silicone defoamers and suds suppressors disclosed in granular detergent compositions are disclosed in US 3,933,672 to Bartolotta et al. and US 4,652,392, Baginski et al.

A typical silicone based suds suppressor employed in the present invention is a suds suppressor in a suds suppressing amount, consisting essentially of:

(i) polydimethylsiloxane fluids having a viscosity of 20 cs. to about 1500 cs. at 25°C;

(ii) A ratio of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units to (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units per 100 parts by weight of (i) from about 5 to about 50 parts Silicone resins having a composition of 0.6:1 to about 12:1;

(iii) from about 1 to about 20 parts by weight of solid silica gel per 100 parts by weight of (i).

In the preferred silicone suds suppressor used in the present invention, the solvent used for the continuous phase is composed of some polyethylene glycol or polyethylene glycol-polypropylene glycol copolymer or their mixture (preferred), or polypropylene glycol . Primary silicone suds suppressors are branched/crosslinked and preferably not linear.

To illustrate further, conventional liquid laundry detergent compositions containing a suds suppressor optionally contain from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 percent by weight of the silicone suds suppressor An agent comprising (1) a non-aqueous emulsifier of a basic antifoam agent, the antifoam agent being a polysiloxane compound prepared from (a) a polyorganosiloxane, (b) a resinous siloxane, or a polysiloxane resin , (c) a mixture of well-dispersed fillers and (d) a catalyst that promotes the reaction of the mixture components (a) (b) and (c) to form silanolates; (2) at least one nonionic siloxane and (3) polyethylene glycol or a polyethylene glycol-polypropylene glycol copolymer having a solubility in water at room temperature of greater than about 2% by weight; and no polypropylene glycol. Similar amounts can be used for granular compositions, gels, and the like. See US4978471 issued Dec. 18, 1990 by Starch, 4983316 issued Jan. 8, 1991 by Starch, 5288431 issued Feb. 22, 1994 by Huber et al., and US4639489 and 4749740 issued by Aizawa et al. column, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers, each having an average molecular weight of less than about 1000, preferably between 100 and 800. The polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers of the present invention have a solubility at room temperature of greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents of the present invention are polyethylene glycols having an average molecular weight of less than about 1000, more preferably between 100 and 800, most preferably between 200 and 400, and copolymers of polyethylene glycol/polypropylene glycol, preferably PPG200/PEG300 things. Preferably the weight ratio of polyethylene glycol:polyethylene glycol/polypropylene glycol copolymer is between about 1:1 and 1:10, more preferably between 1:3 and 1:6.

Preferred silicone suds suppressors for use herein do not contain polypropylene glycol, especially those having a molecular weight of 4,000. They are also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors of the invention contain secondary alcohols such as 2-alkyl alkanols and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US4798679, 4075118 and EP150872. Such secondary alcohols include _C6 - _C16 alkyl alcohols containing a _C1 - _C16 chain. A preferred alcohol is 2-butyloctanol, which is supplied by Condea under the trade name ISOFOL12. A mixture of secondary alcohols is supplied by Enichem under the trade name ISALCHEM123. Mixed suds suppressors generally contain a mixture of alcohol + silicone in a weight ratio of 1:5 to 5:1.

For any detergent composition useful in automatic washing machines, suds should not form to the extent that they overflow the washing machine. When a suds suppressor is used, it is preferably present in a suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition selects the amount of suds suppressor sufficient to control suds to produce a low sudsing laundry detergent for use in automatic washing machines.

The compositions of the present invention generally contain from 0% to about 5% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and their salts generally comprise up to about 5% by weight of the detergent compositions. Preferably, from about 0.5% to about 3% fatty monocarboxylate suds suppressor is employed. Silicone suds suppressors are typically used at levels up to 2.0% by weight of the detergent composition, although higher levels can be used. The upper limit is practically feasible due to the main balance of cost reduction and the effectiveness of smaller volumes to effectively control foam. Preferably, from about 0.01% to about 1%, more preferably from about 0.25% to about 0.5%, silicone suds suppressor is employed. As used herein, these weight percent values include all silica used in combination with the polyorganosiloxane, as well as all additive materials that may be employed. Monostearyl phosphate suds suppressors are generally used at levels of from about 0.1% to 2% by weight of the composition. Hydrocarbon suds suppressors are typically used at levels of from about 0.01% to about 5.0%, although higher levels can also be used. Alcohol suds suppressors generally range from 0.2% to 3% by weight of the finished composition.

fabric softener

Various laundering universal fabric softeners, particularly US4062647 issued December 13, 1977 to Storm and Nirschl, and other softener clays known in the art may optionally be present in the compositions of the present invention at 0.5% to about Used in an amount of 10% by weight, it provides fabric softener action while washing fabrics. Clay softeners may be used in combination with amine and cationic softeners such as those disclosed in US 4,375,416, Crisp et al., March 1, 1983 and US 4,291,071, Harris et al., issued September 22, 1981.

dye transfer inhibitor

The compositions of the present invention may also contain one or more substances which inhibit the transfer of dyes from one fabric to another during the laundering process. Generally, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and their mixtures. If employed, these agents will generally be present in amounts of from about 0.01% to about 10%, preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2%, by weight of the composition.

More specifically, preferred polyamine N-oxide polymers for use in the present invention contain units having the following general structure: RA _x -P; where P is a polymerizable unit to which NO groups may be attached or NO groups The group may form part of a polymerizable unit or the NO group may be attached to both units; A has one of the following structures: -NC(O)-, -C(O)O-, -S-, - O-, -N=; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, on which the NO group can be connected Nitrogen or NO groups are part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidone, piperidine and derivatives thereof.

The NO group can be represented by the following structural formula:

Wherein R ¹ , R ² , R ³ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the NO group can be connected to the above groups or Forms part of any of the above groups. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably a pKa<7, most preferably a pKa<6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are vinyls, polyolefins, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random polymers or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymer typically has a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer may vary according to appropriate copolymerization or according to the appropriate degree of N-oxidation. Polyamine oxides can be prepared in almost any degree of polymerization. Generally, the average molecular weight is from 500 to 1,000,000; more preferably from 1,000 to 500,000; most preferably from 5,000 to 100,000. Such preferred materials may be represented by "PVNO".

The most preferred polyamine N-oxide in the detergent compositions of the present invention is poly(4-vinylpyridine-N-oxide) having an average molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about It is 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI") are also preferred for use in the present invention. Preferably the PVPVI has an average molecular weight of 5,000 to 1,000,000, more preferably 5,000 to 200,000, most preferably 10,000 to 20,000. (The average molecular weight range is described by Barth et al. in "Modern Methods of Polymer Characterization" in Chemical Annlysis Vol. The molar ratio is 1:1 to 0.2:1, more preferably 0.8:1 to 0.3:1, most preferably 0.6:1 to 0.4:1. These copolymers may be linear or branched.

The compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to 400,000, preferably from about 5,000 to about 200,000, most preferably from about 5,000 to about 50,000. PVP's are known to those skilled in the detergent art; see for example EP-A-262897 and EP-A-256696, which are hereby incorporated by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP in ppm in the wash solution is from about 2:1 to about 50:1, more preferably from 3:1 to about 10:1.

The detergent compositions of the present invention may also optionally contain from about 0.005% to 5% by weight of some type of hydrophilic optical brightener which also has dye transfer inhibiting effect. If such brighteners are employed, the compositions of the present invention will preferably contain from about 0.01% to 1% by weight of such optical brighteners.

The hydrophilic fluorescent whitening agent that can be used in the present invention has following general structural formula:

Wherein R ¹ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ² is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morpholino, chlorine and amino; and M is a salt-forming cation, such as sodium or potassium.

When in the above general formula, R ¹ is anilino, R ² is N-2-bis-hydroxyethyl, and M is a cation, such as sodium, the whitening agent is 4,4'-bis[(4-anilino -6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and its disodium salt. This particular brightener class is sold under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener for use in the detergent compositions of the present invention.

When in the above general formula, R ¹ is anilino, R ² is N-2-hydroxyethyl-N-2-methylamino, M is a cation, such as sodium, the whitening agent is 4,4'-bis [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener is sold under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above general formula, R ¹ is anilino, R ² is morpholino, and M is a cation, such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino -s-Triazin-2-yl)amino]-2,2'-stilbene disulfonic acid, its sodium salt. This particular brightener is sold under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

Particular optical brighteners useful herein have particularly effective dye transfer inhibiting effects when used in combination with selected polymeric dye transfer inhibiting agents described above. Such selected polymers (such as PVNO and/or PVPVI) in combination with such selected optical brighteners (such as Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) will provide better performance in aqueous wash solutions than alone. The dye transfer inhibiting effect was more pronounced with one of the two detergent composition ingredients. Without being bound by theory, it is believed that such brighteners do this due to their strong affinity for fabrics in the wash solution, and thus deposit relatively quickly on fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be determined by the so-called "exhaustion coefficient" parameter. The exhaustion factor is generally the ratio of (a) the brightener deposited on the fabric to (b) the original concentration of brightener in the wash liquor. Brighteners with relatively high exhaustion coefficients are most suitable for the dye transfer inhibiting agents of the present invention.

Of course, it is contemplated that other conventional optical brightener-type compounds may optionally be used in the compositions of the present invention to impart a "brightening" effect to conventional fabrics rather than a true dye transfer inhibiting effect. Such use is conventional and known for detergent formulations.

Preparation of cotton soil release polymer

Example 1

Ethoxylated polyethyleneimine with an average molecular weight of 1800

Add polyethyleneimine MW1800 to a 250 ml three-neck round bottom flask equipped with a Claisen head, a thermometer connected to a temperature controller (Therm-O-Watch ^™ , I ² R), sparge tube and mechanical stirrer (Polyscience, 50.0 g, 0.028 mol). Ethylene oxide gas (Liquid Carbonics) was passed through the sparge tube at about 140° C. under an argon atmosphere with rapid stirring until the weight gained 52 grams (equivalent to 1.2 ethoxy units). 50 g of a yellow gel-like substance were collected. Potassium hydroxide (Baker, 0.30 g, 0.0053 moles) was added to the remaining material and after the potassium hydroxide had dissolved, ethylene oxide was passed as above until a weight gain of 60 g (equivalent to a total of 4.2 ethoxylated unit). 53 grams of this brown viscous liquid were collected. Ethylene oxide was bubbled through the remaining material as above until a weight gain of 35.9 grams (equivalent to a total of 7.1 ethoxylated units) was obtained to give 94.9 grams of a dark brown liquid. The potassium hydroxide in the latter two samples was neutralized by adding the theoretical amount of methanesulfonic acid.

Example 2

Quaternization of PEI1800E ₇

Into a 500-mL Erlenmeyer flask equipped with a mechanical stirring bar was charged polyethyleneimine with an average molecular weight of 1800, which had been ethoxylated to approximately 7 ethylene oxide residues per nitrogen (PEI1800, E ₇ ) (207.3 g, 0.590 mole nitrogen, as prepared in Example 1), and acetonitrile (120 g). Dimethyl sulfate (28.3 g, 0.224 mol) was added to the rapidly stirred solution in one portion, then stopped and stirred at room temperature overnight. Acetonitrile was removed by rotary evaporation at about 60°C, followed by further stirring at about 80°C using a Kugelrohr apparatus. The solvent was stripped until 220 g of the desired partially quaternized dark brown viscous liquid material was obtained. ¹³ C-NMR (D ₂ O) spectra obtained on a sample of the reaction product showed no carbon resonance at -58 ppm corresponding to dimethyl sulfate. ^{The 1} H-NMR (D ₂ O) spectrum indicated that the partial shift of the resonance of the methylene attached to the non-quaternized nitrogen at about 2.5 ppm had shifted to about 3.0 ppm. This is consistent with the required quaternization of about 38% of the nitrogen.

Example 3

Formation of Amine Oxide by PEI1800E ₇

Into a 500 ml Erlenmeyer flask equipped with a mechanical stirring bar was charged polyethyleneimine (PEI 1800, E ₇ ) (209 grams, 0.595 moles of nitrogen, as prepared in Example 1) and hydrogen peroxide (120 grams of a 30% solution in water, 1.06 moles). The Erlenmeyer flask was capped and, after an initial exotherm, stirred overnight at room temperature. ¹ H-NMR (D ₂ O) obtained on a sample of the reaction mixture indicated complete conversion. The resonance for the methylene proton attached to the unoxidized nitrogen has shifted from its original position at -2.5 ppm to -3.5 ppm. About 5 grams of 0.5% Pd on alumina flakes was added to the reaction solution, and the solution was left at room temperature for about 3 days. The solution was tested and found to be free of peroxide by dipstick. The material obtained is suitable for storage as a 51.1% active solution in water.

Example 4

Formation of Amine Oxide of Quaternized PEI1800E ₇

Into a 500 ml Erlenmeyer flask equipped with a mechanical stirring bar was charged polyethyleneimine with an average molecular weight of 1800, which was ethoxylated to approximately 7 ethylene oxide groups per nitrogen (PEI1800, E ₇ ). and then further modified by quaternization to about 38% with dimethyl sulfate (130 g, ~0.2 moles of oxidizable nitrogen, prepared in Example II), also adding hydrogen peroxide (48 gram for a 30% by weight solution in water, 0.423 moles) and water (-50 grams). The Erlenmeyer flask was capped and, after an initial exotherm, stirred overnight at room temperature. ¹ H-NMR (D ₂ O) obtained on a sample of the reaction mixture showed that the resonance associated with the previously observed methylene peak at 2.5-3.0 ppm was completely converted to contain the methylene at a chemical shift of approximately 3.7 ppm substance. About 5 grams of 0.5% Pd on alumina flakes was added to the reaction solution, and the solution was left at room temperature for about 3 days. The solution was tested and found to be free of peroxide by dipstick. The material obtained is suitable for storage as a 51.1% active solution in water.

Example 5

Preparation of PEI1200E ₇

The ethoxylation reaction was carried out in a 2 gallon stirred stainless steel reactor equipped with temperature and control, pressure measurement, vacuum and inert gas purge, sampling devices and added liquid ethylene oxide. A -20 lb ethylene oxide (ARC) mesh cylinder was set up to pump liquid ethylene oxide into the reactor with the cylinder placed on a weighing pan to monitor the weight change of the cylinder.

A 750 gram portion of polyethyleneimine (PEI) (listed average molecular weight of 1200 equals about 0.625 moles of polymer and 17.4 moles of nitrogen functional groups) was added to the kettle. The autoclave was then sealed and the air vented (vacuum reduced to 28" Hg, followed by nitrogen to 250 psia, then atmospheric pressure). The contents of the autoclave were heated to 130°C under vacuum. Approx. 1 After 1 hour, the reactor was filled with nitrogen to 250 psia while the reactor was cooled to about 105° C. Ethylene oxide was then gradually added to the reactor while accurately measuring the reactor pressure, temperature, and ethylene oxide flow rate The ethylene oxide pump was turned off and cooled to limit the temperature rise due to the reaction exotherm. The temperature was maintained between 100 and 110° C. while gradually increasing the total pressure during the reaction. After a total of 750 grams of epoxy After ethane was added to the kettle (approximately 1 mole of ethylene oxide per PEI nitrogen functional group), the temperature was increased to 110°C and the kettle was stirred for an additional hour. At this point, vacuum was used to remove any remaining untreated Reactive ethylene oxide.

Next, 376 grams of 25% sodium methoxide in methanol (1.74 moles to give a 10% loaded PEI nitrogen-functional catalyst) was added while the autoclave was cooled to approximately 50°C while vacuum was continuously applied. The methanol solution was drawn into the autoclave under vacuum, and the set point of the autoclave temperature controller was raised to 130°C. A device is used to measure the pressure of the stirrer. Stirrer pressure was measured as a function of temperature and pressure. As the methanol was removed from the kettle, the pressure and temperature values of the agitator gradually increased, and the viscosity of the mixture increased and stabilized for about 1 hour indicating that most of the methanol had been removed. The mixture was heated further and stirred under vacuum for another 30 minutes.

The vacuum was removed and the autoclave was cooled to 105°C while purging nitrogen to 250 psia and returned to atmospheric pressure. The autoclave was filled with nitrogen to 200 psia. Add ethylene oxide gradually to the reactor as above, while maintaining the temperature between 100 and 110°C and controlling any temperature rise due to the exothermic reaction, accurately measure the pressure, temperature and environment of the reactor. Oxygen flow rate. After adding 4500 grams of ethylene oxide over the course of several hours (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen functionality), the temperature was raised to 110° C. and the mixture was stirred for another hour.

The reaction mixture was then collected in a nitrogen purged vessel and finally transferred to a 22 liter three necked round bottom flask equipped with heating and stirring. 167 grams of methanesulfuric acid (1.74 moles) was added to neutralize the strongly basic catalyst. Then deodorize by passing 100 cubic feet of inert gas (argon or nitrogen) through a gas dispersion plate and through the reaction mixture while stirring, and heat the mixture to 130°C.

The final reaction product was cooled slowly and collected in a nitrogen-purged glass container.

In another preparation, neutralization and deodorization are done in the reactor prior to product withdrawal.

Another preferred example, such as PEI1200E15 and PEI1200E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used for the reaction.

Example 6

9.7% quaternization of PEI1200E7

Into a 500 ml Erlenmeyer flask equipped with a mechanical stirrer was charged polyethyleneimine with a degree of ethoxylation of 7 at MW 1200 (248.4 g, 0.707 moles of nitrogen, prepared as in Example 5) and acetonitrile (Baker, 200 ml). Dimethyl sulfate (Aldrich, 8.48 g, 0.067 mol) was added immediately to the rapidly stirring solution, which was then capped and stirred overnight at room temperature. Evaporation of acetonitrile in a rotary evaporator at ~60°C followed by a Kugelroho apparatus (Aldrich) at ~80°C gave ~220 g of the desired material as a dark brown viscous liquid. ¹³ C-NMR (D ₂ O) spectrum showed no peak corresponding to dimethyl sulfate at ~58 ppm. ^{The 1} H-NMR (D ₂ O) spectrum showed a partial shift of the peak at 2.5 ppm (methylene group attached to the non-quaternized nitrogen) to ~3.0 ppm.

Example 7

Preparation of PEI600E ₂₀

The ethoxylation reaction was carried out in a 2 gallon stirred stainless steel reactor equipped with the necessary equipment for temperature and control, pressure measurement, vacuum and inert gas purge, sampling and addition of liquid ethylene oxide. A -20 lb ethylene oxide reticulated cylinder (ARC) was set up to pump liquid ethylene oxide into the reactor with the cylinder placed on a weighing pan to monitor the cylinder weight change.

A 250 gram portion of polyethyleneimine (PEI) (Nippon Shokubai, listed with an average molecular weight of 600 equals about 0.417 moles of polymer and 6.25 moles of nitrogen functionality) was added to the kettle. The autoclave was then sealed and the air vented (reduce vacuum to 28"Hg, followed by nitrogen to 250 psia, then return to normal pressure). The contents of the autoclave were heated to 130°C under vacuum. About 1 hour Afterwards, the reactor was filled with nitrogen to 250 psia, and the reactor was cooled to about 105° C. Then, ethylene oxide was gradually added to the reactor while accurately measuring the pressure, temperature and flow rate of ethylene oxide in the reactor The ethylene oxide pump was turned off and cooled to limit the temperature rise due to the reaction exotherm. The temperature was maintained between 100 and 110° C. while gradually increasing the total pressure during the reaction. After a total of 275 grams of ethylene oxide After the alkanes were added to the kettle (approximately 1 mole of ethylene oxide per PEI nitrogen functional group), the temperature was increased to 110°C and the kettle was stirred for an additional hour. At this point, vacuum was used to remove any remaining unreacted Ethylene oxide.

Next, while the autoclave was cooled to approximately 50° C. with vacuum applied continuously, 135 grams of 25% sodium methoxide in methanol (0.625 moles based on PEI nitrogen functionality to achieve a 10% loading of catalyst) were added. The methanol solution was drawn into the autoclave under vacuum, and the set point of the autoclave temperature controller was raised to 130°C. A device was used to measure the power consumed by the stirrer. Stirrer power was determined as a function of temperature and pressure. As the methanol was removed from the kettle, the stirrer power and temperature values were gradually increased, and the viscosity of the mixture increased and stabilized for about 1 hour indicating that most of the methanol had been removed. The mixture was heated further and stirred under vacuum for another 30 minutes.

The vacuum was removed and the autoclave was cooled to 105°C while purging nitrogen to 250 psia and returned to atmospheric pressure. The autoclave was filled with nitrogen to 200 psia. Add ethylene oxide gradually to the reactor as above, while maintaining the temperature between 100 and 110°C and controlling any temperature rise due to the exothermic reaction, accurately measure the pressure, temperature and environment of the reactor. Oxygen flow rate. After adding approximately 5225 grams of ethylene oxide over the course of several hours (resulting in a total of 20 moles of ethylene oxide per mole of PEI nitrogen functionality), the temperature was raised to 110° C. and the mixture was stirred for an additional hour.

The reaction mixture was then collected in a nitrogen purged vessel and finally transferred to a 22 liter three necked round bottom flask equipped with heating and stirring. 60 grams of methanesulfonic acid (0.625 mol) was added to neutralize the strongly basic catalyst. Then deodorize by passing 100 cubic feet of inert gas (argon or nitrogen) through a gas dispersion plate and through the reaction mixture while stirring, and heat the mixture to 130°C.

The final reaction product was cooled slowly and collected in a nitrogen-purged glass container.

In another preparation, neutralization and deodorization are done in the reactor prior to product withdrawal.

Preparation of non-cotton soil release polymer

Example 8

Synthesis of Sodium 2-(2,3-Dihydroxypropoxy)ethanesulfonate Monomer

Into a 500 ml three necked round bottom flask equipped with mechanical stirrer, modified Claisen head, condenser (set up for distillation), thermometer and temperature controller (Therm-O-Watch ^™ , ^I2R ) was charged with ethyl hydroxyethyl Sulfonic acid, sodium salt (Aldrich, 50.0 g, 0.338 moles), sodium hydroxide (2.7 g, 0.0675 moles), and glycerin (Baker, 310.9 g, 3.38 moles). The solution was heated at 190°C overnight under argon atmosphere to distill off water from the reaction mixture. ¹³ C-NMR (DMSO-d ₆ ) virtually disappeared the isethionic acid peaks at ~53.5 ppm and ~57.4 ppm, indicating that the reaction was complete. Product peaks appeared at ~51.4 _ppm ( _-CH2SO3Na ) and ~ _{67.5 ppm} ( _CH2CH2SO3Na ). The solution was cooled to -100°C and neutralized to pH 7 with methanesulfonic acid (Aldrich). The desired pure starting material was obtained by adding 0.8 mol% potassium phosphate, monobasic as buffer solution, and heating in a Kugelrohr apparatus (Aldrich) at 200°C, ~1 mmHg for ~3 hours to yield 77 g of a yellow wax solid. Alternatively, a portion of the glycerol is removed prior to use in the preparation of oligomers. The use of SEG in glycerol facilitates the handling of sulfonated monomers.

Example 9

Synthesis of Sodium 2-[2-(2-Hydroxyethoxy)ethoxy]ethanesulfonate Monomer

Into a 1 liter three necked round bottom flask equipped with mechanical stirrer, modified Claisen head, condenser (set up for distillation), thermometer and temperature controller (Therm-O-Watch ^™ , ^I2R ) was charged with hydroxyl Ethylsulfonic acid, sodium salt (Aldrich, 100.0 g, 0.675 mol) and distilled water (-90 mL). After dissolution, a drop of hydrogen peroxide (Aldrich, 30% by weight in water) was added to oxidize traces of bisulfite. The solution was stirred for 1 hour. The peroxide indicator strip was very weakly positive. Sodium hydroxide (MCB, 2.5 g, 0.0625 mol) was added followed by diethylene glycol (Fisher, 303.3 g, 2.86 mol). The solution was heated at 190°C overnight under an argon atmosphere to distill water from the solution mixture. ¹³ C-NMR (DMSO-d ₆ ) indicated that the reaction was complete by virtually disappearing the isethionic acid peaks at ~53.5 ppm and ~57.4 ppm. The solution was cooled to room temperature and neutralized to pH 7 with 57.4 g of a 16.4% solution of p-toluenesulfonic acid monohydrate in diethylene glycol. (Optionally methanesulfonic acid can be used.) ¹³ C-NMR spectrum of the product indicated the remaining 4 methylene groups at ~51 _ppm ( _-CH2SO3Na ), ~60 ppm ( _-CH2OH ) and at ~69 ppm , ~72ppm and ~77ppm have resonance. A small amount of resonance can also be seen due to the formation of sodium p-toluenesulfonate during neutralization. The reaction yielded 451 grams of a 35.3% solution of sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate in diethylene glycol. Excess diethylene glycol was removed by adding 0.8 mole % monobasic potassium phosphate (Aldrich) as a buffer solution and heating at 150°C, ~1 mmHg for ~3 hours in a Kugelrohr apparatus (Aldrich), resulting in a rather viscous Oily or glassy desired "SE3" (as above).

Example 10

Synthesis of Sodium 2-{2-[2-(2-Hydroxyethoxy)ethoxy]ethoxy}ethanesulfonate Monomer

To a 1 liter three necked round bottom flask equipped with a mechanical stirrer, modified Claisen head, condenser (set up for distillation), thermometer and temperature controller (Therm-O- ^WatchTM , ^I2R ) was added Isethionic acid, sodium salt (Aldrich, 205.0 g, 1.38 mol) and distilled water (~200 mL). After dissolution, a drop of hydrogen peroxide (Aldrich, 30% by weight in water) was added to oxidize traces of bisulfite. The solution was stirred for 1 hour. The peroxide indicator strip was very weakly positive. Sodium hydroxide (MCB, 5.5 g, 0.138 mol) was added followed by diethylene glycol (Aldrich, 448.7 g, 3.0 mol). Triethylene glycol is optionally purified by heating with a strong base, such as NaOH, until the color is stable, followed by distillation of the pure alcohol for synthesis. The solution was heated at 190°C overnight under an argon atmosphere to distill water from the solution mixture. ¹³ C-NMR (DMSO-d ₆ ) is through the isethionic acid peaks that practically disappear at ~53.5ppm and ~57.4ppm, and appear at ~51ppm (-CH ₂ SO ₃ Na), ~60ppm (-CH ₂ OH ) and product peaks at ~67ppm, ~69ppm, and ~72ppm of residual methylene to indicate completion of the reaction. The solution was cooled to room temperature and neutralized to pH 7 with methanesulfonic acid (Aldrich). The reaction yielded 650 g of a 59.5% solution of sodium 2-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}ethanesulfonate in triethylene glycol. Excess triethylene glycol was removed by addition of 0.8 mole % potassium monobasic phosphate (Aldrich) as a buffer solution and heated at 180° C., Need material. A more soluble buffer solution was found to be more effective in controlling pH during removal of excess triethylene glycol. An example of such a more soluble buffer solution is the salt of methanesulfonic acid and N-methylmorpholine. Optionally the pH can be controlled by frequent or continuous addition of an acid, such as methanesulfonic acid, to keep the pH near neutral during the removal of excess alcohol.

It is believed that this material contains a small amount of disulfonate resulting from the reaction of the two ends of triethylene glycol with isethionate. However, the crude material can be used as anionic capping group for polymer preparation without further purification.

Other preparations employ large amounts of triethylene glycol, such as 5 to 10 moles per mole of isethionic acid.

Example 11

Sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, Dimethylterephthalate, Sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate , Glycerin, Ethylene Glycol and Propylene Glycol Oligomer Synthesis

^{Add 2} -Sodium [2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (14.4 g, 0.074 mol), 2-(2, Sodium 3-dihydroxypropoxy)ethanesulfonate (3.3 g, 0.015 mol), glycerin (Baker, 1.4 g, 0.015 mol), ethylene glycol (Baker, 14.0 g, 0.225 mol), and propylene glycol (Fisher, 17.5 grams, 0.230 moles) and titanium (IV) propoxide (0.01 grams, 0.02% by weight of the total reactants). The mixture was heated to 180° C. and maintained at this temperature overnight under an argon atmosphere to distill methanol and water from the reaction vessel. The material was transferred to a 500 ml single necked round bottom flask and gradually heated to 240° C. in a Kugelelrohr apparatus (Aldrich) at about 2 mmHg over about 20 minutes and held for 1.5 hours. The reaction flask was air cooled and rapidly cooled to near room temperature in vacuo (~30 min). The reaction yielded 21.3 g of the desired oligomer as a brown glass. ¹³ C-NMR (DMSO-d ₆ ) shows a resonance of -C(O)OCH ₂ CH ₂ O(O)C at ~63.2ppm (diester) and -C(O)C at ~59.4ppm (monoester) ) OCH ₂ CH ₂ OH resonance. The ratio of the peak height of the diester resonance to the peak height of the monoester resonance is about 10. Resonances at -51.5 ppm and _-51.6 ppm representing sulfoethoxy groups ( _-CH2SO3Na ) also appeared. ¹ H-NMR (DMSO-d ₆ ) showed a resonance representing the aromatic hydrogen of terephthalate at ~7.9 ppm. Analysis by hydrolysis gas chromatography indicated a molar ratio of unbound ethylene glycol to unbound propylene glycol of 1.7:1. It also indicates that approximately 0.9% of the final polymer is glycerol. If all the glycerol monomers are incorporated in the form of glycerides, this is about 4% by weight of the final oligomer. Solubility was tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and stirring the vial vigorously. The material dissolves readily under these conditions.

Example 12

Sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl terephthalate, Sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate , Synthesis of Oligomers of Ethylene Glycol and Propylene Glycol

Add ² -Sodium [2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (14.4 g, 0.074 mol), 2-(2, 3-dihydroxypropoxy) sodium ethanesulfonate (6.6 g, 0.030 mole), ethylene glycol (Baker, 14.0 g, 0.225 mole) and propylene glycol (Fisher, 18.3 g, 0.240 mole) and titanium propoxide (IV ) (0.01 g, 0.02% of the total weight). The mixture was heated to 180°C and held at this temperature overnight to distill methanol and water from the reaction vessel. The material was transferred to a 500 ml single necked round bottom flask and gradually heated to 240° C. in a Kugelelrohr apparatus (Aldrich) at about 0.1 mm Hg over about 20 minutes and held for 110 minutes. The reaction flask was air cooled under vacuum and rapidly cooled to near room temperature (-30 min). The reaction yielded 24.4 g of the desired oligomer as a brown glass. 13C-NMR (DMSO-d ₆ ) shows -C(O)OCH ₂ CH ₂ O(O)C- resonance at ~63.2ppm (diester) and -C(O) at ~59.4ppm (monoester) _{OCH2CH2OH resonance} . The ratio of diester peak to monoester peak was determined to be about 8. Resonances at -51.5 ppm and _-51.6 ppm representing sulfoethoxy groups ( _-CH2SO3Na ) also appeared. ¹ H-NMR (DMSO-d ₆ ) showed a resonance at ~7.9 ppm representing the aromatic hydrogen of terephthalate. Analysis by hydrolysis gas chromatography indicated a molar ratio of unbound ethylene glycol to unbound propylene glycol of 1.6:1. Solubility was tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and stirring the vial vigorously. The material dissolves readily under these conditions.

Example 13

Sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl terephthalate, Sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate , Glycerin, Ethylene Glycol and Propylene Glycol Oligomer Synthesis

Add ² -Sodium [2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (7.0 g, 0.030 mol), dimethyl terephthalate (9.6 g, 0.049 mol), 2-(2, Sodium 3-dihydroxypropoxy)ethanesulfonate (2.2 g, 0.010 mole), glycerol (Baker, 1.8 g, 0.020 mole), ethylene glycol (Baker, 6.1 g, 0.100 mole), and propylene glycol (Fisher, 7.5 grams, 0.100 moles) and titanium (IV) propoxide (0.01 grams, 0.02% of the total weight). The mixture was heated to 180° C. and maintained at this temperature overnight under an argon atmosphere to distill methanol and water from the reaction vessel. The material was transferred to a 250 ml single necked round bottom flask and gradually heated to 240° C. in a Kugelelrohr apparatus (Aldrich) at about 3 mmHg over about 20 minutes and held for 1.5 hours. The reaction flask was rapidly cooled to near room temperature (-30 min) under vacuum with air cooling. The reaction yielded 18.1 g of the desired oligomer as a brown glass. ¹³ C-NMR (DMSO-d ₆ ) indicated a -C(O)OCH ₂ CH ₂ O(O)C-(diester) resonance at -63.2 ppm. At -59.4 ppm - C(O) _OCH2CH2OH ( _monoester ) resonance was undetectable and 12 times smaller than the diester peak. Resonances at -51.5 ppm and _-51.6 ppm representing sulfoethoxy groups ( _-CH2SO3Na ) also appeared. ¹ H-NMR (DMSO-d ₆ ) showed a resonance at -7.9 ppm representing the aromatic hydrogen of terephthalate. Analysis by hydrolysis gas chromatography indicated a molar ratio of unbound ethylene glycol to unbound propylene glycol of 1.6:1. It was also found that 0.45% by weight of the final polymer was glycerol. Solubility was tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and stirring the vial vigorously. The material dissolves readily under these conditions.

Example 14

Sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, Dimethyl terephthalate, Sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate , Glycerin, Ethylene Glycol and Propylene Glycol Oligomer Synthesis

Add ² -Sodium [2-(2-hydroxyethoxy)ethoxy]ethanesulfonate (2.7 g, 0.011 mol, as in Example 2), dimethyl terephthalate (12.0 g, 0.062 mol, Aldrich ), 2-(2,3-dihydroxypropoxy) sodium ethanesulfonate (5.0 grams, 0.022 moles, as in Example 1), glycerin (Baker, 0.50 grams, 0.0055 moles), ethylene glycol (Baker, 6.8 g, 0.110 moles) and propylene glycol (Fisher, 8.5 g, 0.112 moles) and titanium(IV) propoxide (0.01 g, 0.02% of total weight). The mixture was heated to 180° C. and maintained at this temperature overnight under an argon atmosphere to distill methanol and water from the reaction vessel. The material was transferred to a 500 ml single necked round bottom flask and gradually heated to 240° C. in a Kugelelrohr apparatus (Aldrich) at about 0.5 mmHg over about 20 minutes and held for 150 minutes. The reaction flask was rapidly cooled to near room temperature (-30 minutes) with air cooling under vacuum. The reaction yielded 16.7 g of the desired oligomer as a brown glass. ¹³ C-NMR (DMSO-d ₆ ) showed -C(O)OCH ₂ CH ₂ O(O)C-(diester) resonance at ~63.2ppm and -C(O)OCH ₂ at ~59.4ppm Resonance of _CH2OH (monoester). The ratio of the peak height of the diester resonance to the peak height of the monoester resonance is about 6.1. Peaks at ~51.5 ppm and ~ _51.6 ppm representing sulfoethoxy groups ( _-CH2SO3Na ) also appeared. ¹ H-NMR (DMSO-d ₆ ) showed a resonance at ~7.9 ppm representing the aromatic hydrogen of terephthalate. Analysis by hydrolysis gas chromatography indicated a molar ratio of unbound ethylene glycol to unbound propylene glycol of 1.42:1. Solubility was tested by weighing a small amount of material into a vial, adding enough distilled water to make a 35% by weight solution, and stirring the vial vigorously. The material dissolves readily under these conditions. A -9 gram sample of this material was then heated in the Kugelelrohr apparatus at 0.5 mmHg at 240°C and held for 80 minutes. ¹³ C-NMR (DMSO-d ₆ ) indicated no detectable monoester peak at 59.4 ppm. The diester peak at -63.2 ppm is at least 11 times larger than the monoester peak. The solubility of this material was tested as above and it was also found to dissolve readily under these conditions.

The high density liquid detergent composition of the present invention is described below. Table I components weight% 15 16 17 18 Polyhydroxy Coconut Fatty Acid Amide 2.50 2.50 - - C ₁₂ -C ₁₃ alcohol ethoxylates E ₉ - - 3.65 0.80 Sodium C ₁₂ -C ₁₅ Alcohol Sulfate - - 6.03 2.50 C ₁₂ -C ₁₅ Alcohol Ethoxylate E _1.8 Sodium Sulfate 20.15 20.15 - - C ₁₄ -C ₁₅ Alcohol Ethoxylate E _2.25 Sodium Sulfate - - 18.00 18.00 Alkyl N-methyl glucamide - - 4.50 4.50 C ₁₀ amidopropylamine 0.50 0.50 1.30 - citric acid 2.44 3.00 3.00 3.00 Fatty acids (C ₁₂ -C ₁₄ ) - - 2.00 2.00 NEODOL23-9 ¹ 0.63 0.63 - - ethanol 3.00 2.81 3.40 3.40 monoethanolamine 1.50 0.75 1.00 1.00 Propylene Glycol 8.00 7.50 7.50 7.00 boric acid 3.50 3.50 3.50 3.50 Ethoxylated Tetraethylene Pentamine ² 0.50 - - - Tetraethylenepentamine - 1.18 - - Sodium toluenesulfonate 2.50 2.25 2.50 2.50 NaOH 2.08 2.43 2.62 2.62 Protease ³ 0.78 0.70 - - Protease ⁴ - - 0.88 - ALCALASE ⁵ - - - 1.00 Cotton Stain Release Polymer ⁶ 0.50 0.50 - - Cotton Stain Release Polymer ⁷ - - 2.00 1.00 Non-cotton soil release polymer ⁸ 0.33 0.22 - 1.00 Non-cotton soil release polymer ⁹ - - 1.00 - water 10 balance balance balance balance

1. E ₉ ethoxylated alcohol sold by Shell Oil Co.

2. Ethoxylated tetraethylenepentamines (PEI189E15-E18) according to US4597898, issued Jul. 1, 1986 to Vander et al.

3. Bleach stable variant of BPN' (Protease A-BSV) disclosed in EP130756A, Jan. 9, 1985.

4. Subtilisin 309 loop region 6 variant.

5. Proteolytic enzymes sold by Novo.

6. Cotton soil release polymer of Example 7 ( _PEI600E20 ).

7. Cotton soil release polymer of Example 5 ( _PEI1200E20 ).

8. The non-cotton soil release polymer of Example 11.

9. The non-cotton soil release polymer of Example 12.

10. Balanced to 100% may contain, for example, minor amounts of optical brighteners, fragrances, suds suppressors, detergents, chelating agents, dye transfer inhibitors, added water and fillers including calcium carbonate, talc, silicates and the like. Table II components weight% 19 20 twenty one twenty two Polyhydroxy Coconut Fatty Acid Amide 3.65 3.50 - - C ₁₂ -C ₁₃ alcohol ethoxylates E ₉ 3.65 0.80 - - Sodium C ₁₂ -C ₁₅ Alcohol Sulfate 6.03 2.50 - - C ₁₂ -C ₁₅ Alcohol Ethoxylate E _2.5 Sodium Sulfate 9.29 15.10 - - C ₁₄ -C ₁₅ Alcohol Ethoxylate E _2.25 Sodium Sulfate - - 18.00 18.00 Alkyl N-methyl glucamide - - 4.50 4.50 C ₁₀ amidopropylamine - 1.30 - - citric acid 2.44 3.00 3.00 3.00 Fatty acids (C ₁₂ -C ₁₄ ) 4.23 2.00 2.00 2.00 NEODOL23-9 ¹ - - 2.00 2.00 ethanol 3.00 2.81 3.40 3.40 monoethanolamine 1.50 0.75 1.00 1.00 Propylene Glycol 8.00 7.50 7.50 7.00 boric acid 3.50 3.50 3.50 3.50 Tetraethylenepentamine - 1.18 - - Sodium toluenesulfonate 2.50 2.25 2.50 2.50 NaOH 2.08 2.43 2.62 2.62 Protease ² 0.78 0.70 - - Protease ⁴ - - 0.88 - ALCALASE ⁴ - - - 1.00 Cotton Stain Release Polymer ⁴ 0.50 0.50 - - Cotton Stain Release Polymer ⁵ - - 2.00 1.00 Non-cotton soil release polymer ⁶ 0.33 0.22 - 1.00 Non-cotton soil release polymer ⁷ - - 1.00 - water 8 balance balance balance balance

1. E ₉ ethoxylated alcohol sold by Shell Oil Co.

2. A bleach-stable variant of BPN' (Protease A-BSV) disclosed in EP130756A of January 9, 1985.

3. Subtilisin 309 loop region 6 variant.

4. Proteolytic enzymes sold by Novo.

5. Cotton soil release polymer of Example 1 ( _PEI1200E7 ).

6. Cotton soil release polymer of Example 7 ( _PEI600E20 ).

7. The non-cotton soil release polymer of Example 10.

8. The non-cotton soil release polymer of Example 11.

9. Balanced to 100% may contain, for example, minor amounts of optical brighteners, fragrances, suds suppressors, detergents, chelating agents, dye transfer inhibitors, added water and fillers including calcium carbonate, talc, silicates and the like. Table III components weight% twenty three twenty four 25 26 C ₁₄ -C ₁₅ Alcohol Ethoxylate E _2.25 Sodium Sulfate 13.00 - - 8.43 C ₁₂ -C ₁₅ Alcohol Ethoxylate E _2.5 Sodium Sulfate - 18.00 13.00 - Sodium C ₁₂ -C ₁₃ linear alkylbenzene sulfonate 9.86 - - 8.43 Fatty acids (C ₁₂ -C ₁₄ ) - 2.00 2.00 2.95 C ₁₂ -C ₁₃ alcohol ethoxylates E ₉ - - - 3.37 C ₁₀ amidopropylamine - - 0.80 - NEODOL23-9 ¹ 2.22 2.00 1.60 - Alkyl N-methyl glucamide - 5.00 2.50 - citric acid 7.10 3.00 3.00 3.37 ethanol 1.92 3.52 3.41 1.47 monoethanolamine 0.71 1.09 1.00 1.05 Propylene Glycol 4.86 8.00 6.51 6.00 boric acid 2.22 3.30 2.50 - Ethoxylated tetraethylenepentamine 1.18 1.18 - 1.48 Sodium cumene sulfonate 1.80 3.00 - 3.00 Sodium toluenesulfonate - - 2.50 - NaOH 6.60 2.82 2.90 2.10 Dodecyltrimethylammonium Chloride - - - 0.51 Sodium tartrate mono and disuccinic acid - - - 3.37 sodium formate - - - 0.32 Protease D ² 0.88 0.88 - - Protease subtilisin 309 variant ⁵ - - 0.78 0.56 Cotton Stain Release Polymer ⁴ 0.50 2.00 - - Cotton Stain Release Polymer ⁵ 1.50 - 2.00 3.00 Non-cotton soil release polymer ⁶ 1.50 - 2.00 - Non-cotton soil release polymer ⁷ - 1.15 - 1.50 water ⁸ balance balance balance balance

1. _E9 ethoxylated alcohol sold by Shell Oil Co.

2. Protease B variant of BPN' in which Try217 is replaced by Leu.

3. Subtilisin 309 variant, which has a modified amino acid sequence of the wild-type amino acid sequence of subtilisin 309, wherein the substituents occur at one or several positions of 194, 195, 196, 199 or 200.

4. Cotton soil release polymer of Example 4.

5. Cotton soil release polymer of Example 7.

6. The non-cotton soil release polymer of Example 10.

7. The non-cotton soil release polymer of Example 11.

8. Balanced to 100% may contain, for example, minor amounts of optical brighteners, fragrances, suds suppressors, detergents, chelating agents, dye transfer inhibitors, added water and fillers including calcium carbonate, talc, silicates and the like. Table IV components weight% 27 28 29 30 C ₁₄ -C ₁₅ Alcohol Ethoxylate E _2.25 Sodium Sulfate 13.00 - - 8.43 C ₁₂ -C ₁₅ Alcohol Ethoxylate E _2.5 Sodium Sulfate - 18.00 13.00 - Sodium C ₁₂ -C ₁₃ linear alkylbenzene sulfonate 9.86 - - 8.43 Fatty acids (C ₁₂ -C ₁₄ ) - 2.00 2.00 2.95 C ₁₂ -C ₁₃ alcohol ethoxylates E ₉ - - - 3.37 C ₁₀ amidopropylamine - - 0.80 - NEODOL23-9 ¹ 2.22 2.00 1.60 - Alkyl N-methyl glucamide - 5.00 2.50 - citric acid 7.10 3.00 3.00 3.37 ethanol 1.92 3.52 3.41 1.47 monoethanolamine 0.71 1.09 1.00 1.05 Propylene Glycol 4.86 8.00 6.51 6.00 boric acid 2.22 3.30 2.50 - Ethoxylated tetraethylenepentamine 1.18 1.18 - 1.48 Sodium cumene sulfonate 1.80 3.00 - 3.00 Sodium toluenesulfonate - - 2.50 - NaOH 6.60 2.82 2.90 2.10 Dodecyltrimethylammonium Chloride - - - 0.51 Sodium tartrate mono and disuccinic acid - - - 3.37 sodium formate - - - 0.32 Protease D ² 0.88 0.88 - - Protease subtilisin 309 variant ³ - - 0.78 0.56 Cotton Stain Release Polymer ⁴ 0.50 2.00 - - Cotton Stain Release Polymer ⁵ 1.50 - 2.00 3.00 Non-cotton soil release polymer ⁶ 1.50 - 2.00 - Non-cotton soil release polymer ⁷ - 1.15 - 1.50 water ⁸ balance balance balance balance 1. E ₉ ethoxylated alcohol sold by Shell Oil Co.

2. Protease B variant of BPN' in which Try217 is replaced by Leu.

3. Subtilisin 309 variant, which has a modified amino acid sequence of the wild-type amino acid sequence of subtilisin 309, wherein the substituents occur at one or several positions of 194, 195, 196, 199 or 200.

4. Cotton soil release polymer of Example 7.

5. Cotton soil release polymer of Example 1.

6. The non-cotton soil release polymer of Example 10.

7. The non-cotton soil release polymer of Example 11.

8. Balanced to 100% may contain, for example, minor amounts of optical brighteners, fragrances, suds suppressors, detergents, chelating agents, dye transfer inhibitors, added water and fillers including calcium carbonate, talc, silicates and the like. Table V components 31 32 33 34 35 Polyhydroxy Coconut Fatty Acid Amide 3.50 3.50 3.15 3.50 3.00 NEODOL23-9 ¹ 2.00 0.60 2.00 0.60 0.60 _C25 Alkyl Ethoxylated Sulfate 19.00 19.40 19.00 17.40 14.00 _C25 Alkyl Sulfate - - - 2.85 2.30 C ₁₀ -aminopropylamide - - - 0.75 0.50 citric acid 3.00 3.00 3.00 3.00 3.00 tallow fatty acid 2.00 2.00 2.00 2.00 2.00 ethanol 3.41 3.47 3.34 3.59 2.93 Propylene Glycol 6.22 6.35 6.21 6.56 5.75 monomethanolamine 1.00 0.50 0.50 0.50 0.50 sodium hydroxide 3.05 2.40 2.40 2.40 2.40 Sodium p-toluenesulfonate 2.50 2.25 2.25 2.25 2.25 Borax 2.50 2.50 2.50 2.50 2.50 Protease ² 0.88 0.88 0.88 0.88 0.88 lipolytic enzyme ³ 0.04 0.12 0.12 0.12 0.12 Duramyl ⁴ 0.10 0.10 0.10 0.10 0.40 CAREZYME 0.053 0.053 0.053 0.053 0.053 Fluorescent whitening agent 0.15 0.15 0.15 0.15 0.15 cotton stain remover ⁵ 1.18 1.18 1.18 1.18 1.75 Non-cotton stain remover ⁶ 0.22 0.15 0.15 0.15 0.15 fumed silica 0.119 0.119 0.119 0.119 0.119 A small amount, beauty products, water balance balance balance balance balance

1. _C12 - _C13 alkyl E9 ethoxylates were supplied by Shell Oil Co.

2. Bacillus amyloliquefaciens subtilisins described in WO 95/10615, Genencor International, published April 20, 1995.

3. Prepared from Humicola lanuginosa and commercially available from Novo.

4. Disclosed in WO9510603A and commercially available from Novo.

5. Soil release polymer according to example 7.

6. Terephthalate copolymers are disclosed in US Patent 4,968,451, Scheibel et al., issued November 6, 1990.

Claims (9)

1. A liquid laundry composition comprising: a) at least 0.001% by weight of protease; b) at least 0.01% by weight of a water-soluble or dispersible modified polyamide cotton soil release agent containing a polyamine backbone having the following general formula:

Modified polyamine general formula V _(n+1) W _m Y _n Z or polyamine main chain with the following general formula:

A modified polyamine with the general formula V _(n-k+1) W _m Y _n Y' _k Z, wherein k is less than or equal to n, and the main chain of the polyamine has a value greater than 200 Daltons before modification Molecular weight, of which i) The V unit is a terminal unit having the following general formula:

or

or

ii) W units are backbone units having the general formula: or

or

iii) Y units are branched units having the following general formula: or or

and iv) The Z unit is a terminal unit having the following general formula:

or

or

Wherein the main chain linking R unit is selected from C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ - C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OR ² )CH ₂ O) _z - (R ¹ O) _y R ¹ (O CH ₂ CH(OR ² )CH ₂ ) _w , -C(O)(R ⁴ ) _r C(O)-, -CH ₂ CH(OR ² )CH ₂ - and Their mixtures, preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ , -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH) CH ₂ ) _w -, -CH ₂ CH(OR ² )CH ₂ - and mixtures thereof, more preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy Alkylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z -(R ¹ O) _y R ¹ (O CH ₂ CH(OH)CH ₂ ) _w -, and mixtures thereof, most preferably C ₂ -C ₁₂ alkylene and mixtures thereof, wherein R ¹ is C ₂ -C ₆ alkylene, Preferred are ethylene, and mixtures thereof; R ² is hydrogen, -(R ¹ O) _x B and mixtures thereof, preferably hydrogen; R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ aryl alkyl C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof, C ₁ -C ₆ alkyl and mixtures thereof, more preferably methyl; R ⁴ is C ₁ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ aryl alkylene, C ₆ -C ₁₀ arylene and their mixtures, preferably C ₂ -C ₁₂ alkylene, C ₈ -C ₁₂ arylalkylene and their mixtures, more preferably ethylene, butylene and their mixtures; R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ )-, - C(O)(R ⁴ ) _r C(O)-, -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 - and their mixtures, preferably ethylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ ) _y -, -(CH ₂ CH(OH )CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH)CH ₂ ) _w -, -CH ₂ CH(OH)CH ₂ - and mixtures thereof, more preferably -CH ₂ CH(OH) )CH ₂ -; R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E unit is selected from hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M , -(CH ₂ )PPO ₃ M, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, preferably hydrogen, C ₃ -C ₂₂ hydroxyalkyl, benzyl, C ₁ -C ₂₂ Alkyl, -(R ¹ O) _x B, -C(O)R ³ , -(CH ₂ ) _P CO ₂ ^- M ⁺ , -(CH ₂ ) _q SO ₃ ^- M ⁺ , -CH(CH ₂ CO ₂ M) CO ₂ M and mixtures thereof, more preferably hydrogen, C ₁ -C ₂₂ alkyl, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, most preferably -(R ¹ O) _x B; as long as the E unit of any nitrogen is hydrogen, said nitrogen is not an oxide of nitrogen; B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M, -PO ₃ M and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _q (CHSO ₃ M)-CH ₂ SO ₃ M, -( _CH2 ) _q ( _CHSO2M ) _-CH2SO3M and mixtures thereof, more preferably hydrogen _, -( _CH2 ) _qSO3M and _mixtures thereof, most preferably hydrogen; M is hydrogen or Water-soluble cation sufficient to satisfy charge balance; X is a water-soluble anion; m is a number from 4 to 400; n is a number from 0 to 200; p is a number from 1 to 6, q is a number from 0 to 6; r is 0 or 1; w is 0 or 1; x is a number from 1 to 100; y is a number from 0 to 100; z is 0 or 1; and c) balanced carrier and additive components, wherein said additive components are selected from the group consisting of self-agents, optical brighteners, bleaching agents, bleach accelerators, bleach activators, dye transfer inhibitors, dispersants, enzyme active agents, foam suppressors Agents, dyes, fragrances, pigments, filler salts, hydrotropes and mixtures thereof; wherein said laundry composition has a pH of 7.2 to 8.9 when measured as a 10% aqueous solution. 2. A liquid laundry detergent composition comprising: a) at least 0.01% by weight of a detersive surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates, alkyl alkoxylates, fatty acid amides, the general formula of which is as follows:

Wherein R ⁷ is C ₇ -C ₂₂ alkyl, R ⁸ is independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, -(C ₂ H ₄ O) _j H and their Mixtures; wherein j is from 1 to 3; and mixtures of said surfactants; b) at least 0.001% by weight protease; c) at least 0.01% by weight of non-cotton stain removers; d) at least 0.01% by weight of a water-soluble or dispersible modified polyamide cotton soil release agent containing a polyamine backbone having the following general formula:

Modified polyamine general formula V _(n+1) W _m Y _n Z or a polyamine main chain with the following general formula:

A modified polyamine with the general formula V _(n-k+1) W _m Y _n Y' _k Z, wherein k is less than or equal to n, and the main chain of the polyamine has a value greater than 200 Daltons before modification Molecular weight, of which i) The V unit is a terminal unit having the following general formula: or or

ii) W units are backbone units having the general formula:

or

or iii) Y units are branched units having the general formula:

or

or

and iv) The Z unit is a terminal unit having the following general formula: or

or

Wherein the main chain linking R unit is selected from C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ - C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OR ² )CH ₂ O) _z - (R ¹ O) _y R ¹ (O CH ₂ CH(OR ² )CH ₂ ) _w -, -C(O)(R ⁴ ) _r C(O)-, -CH ₂ CH(OR ² )CH ₂ - and mixtures thereof, preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ , -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH )CH ₂ ) _w -, -CH ₂ CH(OR ² )CH ₂ - and mixtures thereof, more preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ di Hydroxyalkylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH)CH ₂ ) _w -, and mixtures thereof, most preferably C ₂ -C ₁₂ alkylene and mixtures thereof, wherein R ¹ is C ₂ -C ₆ alkylene, preferably Ethylene, and mixtures thereof; R ² is hydrogen, -(R ¹ O) _x B and mixtures thereof, preferably hydrogen; R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl , C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof, C ₁ -C ₆ alkyl and mixtures thereof, more preferably methyl; R ⁴ is C ₁ -C ₁₂ Alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ aryl alkylene, C ₆ -C ₁₀ arylene and mixtures thereof, preferably C ₂ -C ₁₂ alkylene, C ₈ - C ₁₂ arylalkylene and their mixtures, more preferably ethylene, butylene and their mixtures; R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ - C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ )-, -C (O)(R ⁴ ) _r C(O)-, -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 - and mixtures thereof, preferably ethylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ ) _y -, -(CH ₂ CH(OH) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH)CH ₂ ) _w -, -CH ₂ CH(OH)CH ₂ - and mixtures thereof, more preferably -CH ₂ CH(OH) CH ₂ -; R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E unit is selected from hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CHXCO ₂ M)CO ₂ M, -( CH ₂ )PPO ₃ M, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, preferably hydrogen, C ₃ -C ₂₂ hydroxyalkyl, benzyl, C ₁ -C ₂₂ alkyl , -(R ¹ O) _x B, -C(O)R ³ , -(CH ₂ ) _p CO ₂ ^- M ⁺ , -(CH ₂ ) _q SO ₃ ^- M ⁺ , -CH(CH ₂ CO ₂ M ) CO ₂ M and mixtures thereof, more preferably hydrogen, C ₁ -C ₂₂ alkyl, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, most preferably -(R ¹ O) _x B; as long as the E unit of any nitrogen is hydrogen, said nitrogen is not an oxide of nitrogen; B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M , -PO ₃ M and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -( CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M and mixtures thereof, more preferably hydrogen, -(CH ₂ ) _q SO ₃ M and mixtures thereof, most preferably hydrogen; M is hydrogen or sufficient for charge balance Water-soluble cation; X is a water-soluble anion; m is a number from 4 to 400; n is a number from 0 to 200; p is a number from 1 to 6, q is a number from 0 to 6; r is 0 or 1; w is 0 or 1; x is a number from 1 to 100; y is a number from 0 to 100; z is 0 or 1; and e) Balanced carrier and additive components; wherein said laundry composition has a pH of 7.2 to 8.9 when measured as a 10% aqueous solution. 3. A liquid laundry detergent composition comprising: a) at least 0.01% by weight of an anionic surfactant selected from the group consisting of alkyl alkoxy sulfates, alkyl sulfates and mixtures thereof; b) at least 0.01% by weight of a nonionic surfactant selected from the group consisting of alkyl alkoxylates, fatty acid amides of the general formula:

Wherein R ⁷ is C ₇ -C ₂₂ alkyl, R ⁸ is independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, -(C ₂ H ₄ 0) _j H and their Mixtures; wherein j is from 1 to 3; and mixtures of said nonionic surfactants; c) at least about 0.001% by weight protease; d) at least 0.01% by weight of non-cotton stain removers; e) at least 0.01% by weight of a water-soluble or dispersible modified polyamide cotton soil release agent containing a polyamine backbone having the following general formula:

Modified polyamine general formula V _(n+1) W _m Y _n Z or a polyamine main chain with the following general formula:

A modified polyamine with the general formula V _(n-k+1) W _m Y _n Y' _k Z, wherein k is less than or equal to n, and the main chain of the polyamine has a value greater than 200 Daltons before modification Molecular weight, of which i) The V unit is a terminal unit having the general formula: or

or

ii) W units are backbone units having the following general formula:

or or

iii) Y units are branched units having the following general formula:

or

or and iv) The Z unit is a terminal unit having the following general formula: or or

Wherein the main chain linking R unit is selected from C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ - C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (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 -, -C(O)(R ⁴ ) _r C(O)-, -CH ₂ CH(OR ² )CH ₂ - and Their mixtures, preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -(R ¹ O) _x R ¹ , -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH) CH ₂ ) _w -, -CH ₂ CH(OR ² )CH ₂ - and mixtures thereof, more preferably C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxy Alkylene, -(R ¹ O) _x R ¹ -, -(R ¹ O) _x R ⁵ (OR ¹ ) _x -, -(CH ₂ CH(OH)CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH)CH ₂ ) _w -, and mixtures thereof, most preferably C ₂ -C ₁₂ alkylene and mixtures thereof, wherein R ¹ is C ₂ -C ₆ alkylene, preferably Ethylene, and mixtures thereof; R ² is hydrogen, -(R ¹ O) _x B and mixtures thereof, preferably hydrogen; R ³ is C ₁ -C ₁₈ alkyl, C ₇ -C ₁₂ arylalkyl , C ₇ -C ₁₂ alkyl substituted aryl, C ₆ -C ₁₂ aryl and mixtures thereof, C ₁ -C ₆ alkyl and mixtures thereof, more preferably methyl; R ⁴ is C ₁ -C ₁₂ Alkylene, C ₄ -C ₁₂ alkenylene, C ₈ -C ₁₂ aryl alkylene, C ₆ -C ₁₀ arylene and mixtures thereof, preferably C ₂ -C ₁₂ alkylene, C ₈ - C ₁₂ arylalkylene and their mixtures, more preferably ethylene, butylene and their mixtures; R ⁵ is C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ - C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkarylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ )-, -C (O)(R ⁴ ) _r C(O)-, -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 - and mixtures thereof, preferably ethylene, -C(O)-, -C(O)NHR ⁶ NHC(O)-, -R ¹ (OR ¹ ) _y -, -(CH ₂ CH(OH) CH ₂ O) _z (R ¹ O) _y R ¹ (OCH ₂ CH(OH)CH ₂ ) _w -, -CH ₂ CH(OH)CH ₂ - and mixtures thereof, more preferably -CH ₂ CH(OH) CH ₂ -; R ⁶ is C ₂ -C ₁₂ alkylene or C ₆ -C ₁₂ arylene; E unit is selected from hydrogen, C ₁ -C ₂₂ alkyl, C ₃ -C ₂₂ alkenyl, C ₇ -C ₂₂ arylalkyl, C ₂ -C ₂₂ hydroxyalkyl, -(CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q SO ₃ M, -CH(CH ₂ CO ₂ M)CO ₂ M, -(CH ₂ )PPO ₃ M, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, preferably hydrogen, C ₃ -C ₂₂ hydroxyalkyl, benzyl, C ₁ -C ₂₂ Alkyl, -(R ¹ O) _x B, -C(O)R ³ , -(CH ₂ ) _p CO ₂ ^- M ⁺ , -(CH ₂ ) _q SO ₃ ^- M ⁺ , -CH(CH ₂ CO ₂ M) CO ₂ M and mixtures thereof, more preferably hydrogen, C ₁ -C ₂₂ alkyl, -(R ¹ O) _x B, -C(O)R ³ and mixtures thereof, most preferably -(R ¹ O) _x B; as long as the E unit of any nitrogen is hydrogen, said nitrogen is not an oxide of nitrogen; B is hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, - (CH ₂ ) _p CO ₂ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -(CH ₂ ) _q (CHSO ₂ M)CH ₂ SO ₃ M, -(CH ₂ ) _p PO ₃ M, -PO ₃ M and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -(CH ₂ ) _q SO ₃ M, -(CH ₂ ) _q (CHSO ₃ M)CH ₂ SO ₃ M, -( _CH2 ) _q ( _CHSO2M ) _CH2SO3M and mixtures thereof, more preferably hydrogen, -( _CH2 ) _qSO3M and mixtures thereof, _most preferably hydrogen; M is hydrogen or sufficient to satisfy the _charge Balanced water-soluble cation; X is a water-soluble anion; m is a number from 4 to 400; n is a number from 0 to 200; p is a number from 1 to 6, q is a number from 0 to 6; r is 0 or 1; w is 0 or 1; x is a number from 1 to 100; y is a number from 0 to 100; z is 0 or 1; and f) Balancing the carrier and additive components; wherein said laundry composition has a pH of 7.2 to 8.9 when measured as a 10% aqueous solution. 4. The composition described in any one of claims 1 to 3, wherein said protease is selected from the group consisting of protease A derived from Bacillus amyloliquefaciens, protease B derived from Bacillus amyloliquefaciens, protease D derived from Bacillus amyloliquefaciens, and Bacillus lentus Derived subtilisin 309 variants and mixtures thereof. 5. The composition of claim 4, wherein said Protease D is a carbonyl hydrolase variant of Protease A derived from Bacillus proteolyticus whose amino acid sequence is not found in nature, and which carbonyl hydrolyzes from a precursor The enzyme combines one or more equivalents selected from +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 , +274 and their mixed amino acid residue positions are derived by replacing multiple amino acid residues with different amino acids, where the numbering is based on the numbering of Bacillus amyloliquefaciens subtilisin. 6. The composition of any one of claims 1-5, wherein said subtilisin 309 is derived from a Bacillus lentus variant having a wild-type amino acid sequence at 199, 200, 201, 202, 203, 204 , 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 218, 219, 220 or a mixture of one or more positions are substituted, the number of which is according to Bacillus amyloliquefaciens Subtilisin number. 7. The composition of any one of claims 1-6, wherein the non-cotton soil release polymer contains: a) backbone: i) at least one moiety having the general formula: ii) at least one moiety having the general formula: wherein R ⁹ is C ₂ -C ₆ linear alkylene, C ₃ -C ₆ branched alkylene, C ₅ -C ₇ cyclic alkylene and mixtures thereof; R ¹⁰ is independently selected from hydrogen Or -L-SO ₃ ^{-M +} ; wherein L is selected from the group consisting of alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, alkyleneoxyarylene, poly(oxygen alkenyl), oxyalkyleneoxyarylene, poly(oxyalkylene)oxyarylene, alkylene poly(oxyalkylene) and mixtures thereof; M is hydrogen or a salt-forming cation; i is a number of 0 or 1; iii) at least one trifunctional ester-forming branched moiety; iv) at least one 1,2-oxyalkylene oxygen moiety; and b) one or more end-capping units containing: i ⁾ Ethoxylated _{or propoxylated} hydroxyethanesulfonate or _{ethoxylated or} propoxylated Hydroxypropane sulfonate unit wherein M is a salt-forming cation, such as sodium or tetraalkylammonium, R ¹¹ is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is 1 to 20 ; ii) sulfoaroyl units of general formula -(O)C(C ₆ H ₄ )(SO ₃ ^{-M +} ), wherein M is a salt-forming cation; iii) Modified poly(oxyethylene)oxy monoalkyl ether units of the general formula R ¹² O(CH ₂ CH ₂ O) _k -, wherein R ¹² contains 1 to 4 carbon atoms and k is from 3 to 100 ;and iv) Ethoxylated or propoxylated phenol sulfonate capping units, the general formula of which is MO ₃ S(C ₆ H ₄ )(OR ¹³ ) _n O-, wherein n is 1 to 20; M is Salt-forming cation; R ¹³ is ethylene, propylene and mixtures thereof. 8. The composition of any one of claims 1 to 7, further comprising amylases, cellulases, peroxidases, lipases and mixtures thereof. 9. A method of decontaminating cotton fabrics comprising contacting cotton fabrics to be cleaned with an effective amount of a liquid laundry composition according to any one of claims 1-8.