WO2001060964A1

WO2001060964A1 - Methods for making laundry detergent compositions with an emulsified composition containing a skin conditioning oil and a polyamine emulsifier

Info

Publication number: WO2001060964A1
Application number: PCT/US2000/003794
Authority: WO
Inventors: Yunping Han; Ling Shi; Zhengyu Hu; Xiaoyan Ma
Original assignee: The Procter & Gamble Company
Priority date: 2000-02-14
Filing date: 2000-02-14
Publication date: 2001-08-23
Also published as: AU2000232314A1

Abstract

Methods for making detergent compositions that contain at least about 0.001 %, and no more than about 10 %, by weight, of an emulsified composition that contains an insoluble skin conditioning oil and a polyamine emulsifier. The detergent compositions can be produced by agglomerating the emulsified compositions with surfactants, detergent builders and other detergent ingredients. Additionally, detergent particles can be formed by spraying the emulsified composition onto detergent ingredients. These detergent particles can be admixed with other detergent ingredients, and particles and agglomerates thereof. The polyamine emulsifier is preferably an alkoxylated polyethyleneimine with a degree of alkoxylation from about 3 to about 20. And the skin conditioning oil is preferably polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, and mixtures thereof.

Description

METHODS FOR MAKING LAUNDRY DETERGENT COMPOSITIONS WITH AN EMULSIFIED COMPOSITION CONTAINING A SKIN CONDITIONING OIL AND A POLYAMINE EMULSIFIER

TECHNICAL FIELD

The present invention relates to methods for making detergent compositions in granular, liquid or tablet form, for use in laundry applications, wherein the compositions comprise an emulsified composition. The emulsified composition comprises an insoluble skin conditioning oil and a polyamine emulsifier. This emulsified composition imparts skin mildness benefits to washing solutions formed from such compositions.

BACKGROUND OF THE INVENTION

In many areas of the world, clothes are washed by hand. There are at least two ways to launder clothes by hand. In one method, the person washing the clothes, the "launderer", uses a solid laundry bar to rub a detergent composition directly onto a fabric article. The clothes are then manually washed in water, with additional detergent being rubbed onto the clothes as needed. A second manual washing method involves preparing a wash solution using water and a detergent composition that can be granular, liquid or in tablet form. The clothes are then washed in this wash solution. Unless gloves are worn, in both cases the hands of the launderer are in constant contact with a solution that contains detersive ingredients. These detersive ingredient can include, for example, surfactants, enzymes, bleaches and other common detergent ingredients. And these ingredient are, in general, not beneficial to human skin. To be more specific, hand laundering can be cause dryness and irritation to human skin.

Solid laundry bars have been formulated with skin conditioning ingredients that are added directly to the bar or sprayed on the exterior of the bar. Because the launderer holds the bar in their hand, the skin conditioning ingredients contact and condition their skin. Water insoluble oils and silicone containing components have been used for this purpose as they are especially useful for conditioning human skin. And, as discussed below, silicone materials are commonly used in laundry detergents for supressing suds.

But in the case of hand laundering in a wash solution made from detergent granules, tablets or liquids, the hands do not contact the detergent directly. Instead, the hands contact the dissolved detergent. Unfortunately, many skin conditioning ingredients are insoluble in water. Thus, if an insoluble skin conditioning ingredient is added to a laundry composition that is dissolved in water before use, the skin conditioning ingredient will segregate from the solution, usually by rising to the top. This results in little or no deposition of the skin conditioning ingredient on the hands of the launderer.

In fact, the segregation and rising to the surface of an insoluble component is how silicon suds suppressors work. For many years, detergent formulators have added small amounts of silicone containing materials to the detergent composition to suppress suds formation on the surface of the wash solution. When these compositions are dissolved in water the silicon materials raise to the surface of the wash solution. The presence of the silicon components changes the interfacial surface tension of the wash water such that fewer suds form on the surface.

Silicone suds suppressors are well known to the art, and there have been many efforts to improve their delivery and performance. These silicon materials have been encapsulated with, for example, starch, to segregate them from the other detergent ingredients during manufacture and storage. Likewise, emulsions of silicon materials and polyglycols have been used in laundry compositions, primarily to control the delivery timing of the silicon into the wash water. The amount and the molecular weight of the polyglycol can be adjusted to control the rate of solubiltiy of the polyglycol in the wash solution, and subsequently the delivery timing of the silicon component. But ultimately, the encapsulation and emulsification of silicone components for use in laundry compositions is designed to release the silicon when it is added to water so that it can rise to the surface of the solution where it controls the amount of suds formation. And, as discussed above, once on the surface of the wash solution, very little, if any, of the silicon materials deposit on the skin of the launderer. Therefore, there exists a need for a laundry detergent composition that when dissolved in water is not irritating to, and more preferably, beneficial to human skin. More specifically, there exists an need for a laundry detergent composition that contains a skin conditioning material that deposits readily on the skin of a person who immerse their hands in a wash solution made from such a detergent composition. And there exists a need for methods of making these detergent compositions. The methods of making detergent compositions of the present invention solve both of these problems by incorporating an emulsion that contains an insoluble skin conditioning oil and a polyamine emulsifier, such that the skin conditioning oil is readily deposited on human skin.

SUMMARY OF THE INVENTION

The present invention is directed to methods for producing detergent compositions or detergent particles. One such method comprises the steps of: a) preparing an emulsified composition comprising: i) an insoluble skin conditioning oil; and ϋ) a polyamine emulsifier; b) spraying the emulsified composition onto detergent particles which comprise from about 1% to about 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants and mixtures thereof, and from about 1 % to about 80% by weight of a builder material selected from the group consisting of inorganic salts, silicates, aluminosilicates, and mixtures thereof. Another method of the present invention is directed to producing detergent particles. This method comprises the step of agglomerating detergent ingredients comprising: a) from about 1 % to about 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants and mixtures thereof; b) from about 1 % to about 80% by weight of a builder material selected from the group consisting of inorganic salts, silicates, aluminosilicates, and mixtures thereof; -and c) at least about 0.001 %, preferably at least about 0.01 %, most preferably at least about 0.1 % and no more than about 10%, preferably no more than about 7.0%, most preferably no more than about 4.0%, by weight, of an emulsified composition comprising: i) an insoluble skin conditioning oil; and ϋ) a polyamine emulsifier. In the methods defined above the polyamine emulsifier is preferably an alkoxylated polyethyleneimine, and preferably the degree of alkoxylation is from about 3 to about 20. It is also preferred that the weight ratio of the insoluble skin conditioning oil to the polyamine emulsifier be from about 1000:1 to about 1 :1.

And it is preferred that the emulsified composition comprising at least about 0.01%, preferably at least about 0.1%, most preferably at least about 0.5% and no more than about 20%, preferably no more than about 10.0%, most preferably no more than about 7.0%, by weight, of the detergent composition or detergent particle.

The methods of the present invention preferably further comprise the step of admixing the detergent composition or detergent particle with additional detergent ingredients selected from the group consisting of an inorganic peroxygen bleaching compound, a bleach activator, a detersive enzyme, an enzyme stabilizer, a dye transfer inhibitor ingredient, cyclic amine based polymer, oligomer or copolymer material, a hydrophobically modified cellulosic material, a perfume, a brightener and mixtures thereof.

The detergent compositions of the present invention can be granular, liquid or in tablet form, although granular form is most preferred.

Hand laundering of fabrics and textiles in washing solutions made from the detergent compositions or detergent particles made by the methods of the present invention results in less skin irritation for the launderer. In fact, the launderer may experience an improvement in skin condition when using the compositions of the present invention. The present invention utilizes ingredients that cause little or no reduction in detersive activity. That is, the compositions clean clothes effectively while simultaneously maintaining or even enhancing the skin condition of the launderer.

DETAILED DESCRIPTION OF THE INVENTION

All percentages are by weight unless other specified. While not wanting to be limited by any one theory, it is believed that the polyamine emulsifier of the emulsified composition of the present invention has an affinity for human skir . When the detergent compositions of the present invention, which contain the emulsified composition, is dissolved in water, the emulsified composition forms dropplets of less than about 40 microns, preferably less than about 30 microns and most preferably less than about 20 microns that are suspended in the wash solution. This allows the emulsified composition to deposit readily on human skin. Once on the skin, the insoluble skin conditioning oils of the emulsified composition can lubricate and condition the launderer's hands. This benefit is not noticed when the insoluble skin conditioning oils and polyamine emulsifer are used individually. Thus, it is only by preparing the emulsified composition of the present invention that the benefit of reduced skin irritation is achieved.

INSOLUBLE SKIN CONDITIONING OILS

The methods for making laundry detergents compositions of the present invention comprise as an essential component an insoluble skin conditioning oil. Nonlimiting examples of insoluble skin conditioning oils include those selected from the group consisting of polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, C7-C40 branched chain hydrocarbons, C1-C30 alcohol esters of C1-C30 carboxylic acids, C1-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycendes of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30 carboxylic acids, propylene glycol diesters of C1-C30 carboxylic acids, liquid polyol carboxylic acid esters and polyesters including C1-C30 carboxylic monoesters and polyesters of sugars, vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, mineral oil, petrolatum, and mixtures thereof. Preferred insoluble skin conditioning oils for use in the present invention are polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, and mixtures thereof. Suitable insoluble skin conditioning oils for use in the present invention are disclosed in U.S. Patent Number 5,916,575, which issued on June 29, 1999, to McAtee, et al., and which is assigned to the Procter & Gamble Company. The entire disclosure of US Patent No. 5,916,575 is incorporated herein by reference. Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes, and polyalkarylsiloxanes are preferred insoluble skin conditioning oils for use in the present invention. These silicones are disclosed in U.S. Pat. No. 5,069,897, to Orr, issued Dec. 3, 1991 , which is incorporated by reference herein in its entirety. The polyalkylsiloxanes correspond to the general chemical formula R3 SiO [R2 SiO]x SiR3 wherein R is an alkyl group, preferably R is methyl or ethyl, more preferably methyl, and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available polyalkylsiloxanes include the polydimethylsiloxanes, which are also known as dimethicones, nonlimiting examples of which include the Vicasil®series sold by General Electric Company and the Dow Corning®200 series sold by Dow Corning Corporation. Specific examples of polydimethylsiloxanes useful herein include Dow Corning®225 fluid having a viscosity of 10 centistokes and a boiling point greater than 200°C, and Dow Coming®200 fluids having viscosities of 50, 350, and 12,500 centistokes, respectively, and boiling points greater than 200°C. Also useful are materials such as trimethylsiloxysilicate, which is a polymeric material corresponding to the general chemical formula [(CH2)3 SiO1/2 ]x [SiO2 ]y, wherein x is an integer from about 1 to about 500 and y is an integer from about 1 to about 500. A commercially available trimethylsiloxysilicate is sold as a mixture with dimethicone as Dow Corning®593 fluid. Also useful herein are dimethiconols, which are hydroxy terminated dimethyl silicones. These materials can be represented by the general chemical formulas R3 SiO[R2 SiO]x SiR2 OH and HOR2 SiO[R2 SiO]x SiR2 OH wherein R is an alkyl group, preferably R is methyl or ethyl, more preferably methyl, and x is an integer up to about 500, chosen to achieve the desired molecular weight. Commercially available dimethiconols are typically sold as mixtures with dimethicone or cyclomethicone (e.g. Dow Corning® 1401 , 1402, and 1403 fluids). Also useful herein are polyalkylaryl siloxanes, with polymethylphenyl siloxanes having viscosities from about 15 to about 65 centistokes at 25°C. being preferred. These materials are available, for example, as SF 1075 methylphenyl fluid (sold by General Electric Company) and 556 Cosmetic Grade phenyl trimethicone fluid (sold by Dow Corning Corporation).

Straight and branched chain hydrocarbons having from about 7 to about 40 carbon atoms are also useful herein. Nonlimiting examples of these hydrocarbon materials include dodecane, isododecane, squalane, cholesterol, hydrogenated polyisobutylene, docosane (i.e. a C22 hydrocarbon), hexadecane, isohexadecane (a commercially available hydrocarbon sold as Permethyl®101A by Presperse, South Plainfield, N.J.). Also useful are the C7-C40 isoparaffins, which are C7-C40 branched hydrocarbons. Also useful are C1-C30 alcohol esters of C1-C30 carboxylic acids and of C2-C30 dicarboxylic acids, including straight and branched chain materials as well as aromatic derivatives.

Also useful are esters such as monoglycendes of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids, thglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30 carboxylic acids, and propylene glycol diesters of C1-C30 carboxylic acids. Straight chain, branched chain and aryl carboxylic acids are included herein. Also useful are propoxylated and ethoxylated derivatives of these materials. Nonlimiting examples include diisopropyl sebacate, diisopropyl adipate, isopropyl myristate, isopropyl palmitate, myristyl propionate, ethylene glycol distearate, 2- ethylhexyl palmitate, isodecyl neopentanoate, di-2-ethylhexyl maleate, cetyl palmitate, myristyl myristate, stearyl stearate, cetyl stearate, behenyl behenrate, dioctyl maleate; dioctyl sebacate, diisopropyl adipate, cetyl octanoate, diisopropyl dilinoleate, caprilic/capric triglyceride, PEG-6 caprylic/capric triglycehde, PEG-8 caprylic/capric triglyceride, and mixtures thereof.

Also useful are various liquid polyol carboxylic acid esters, including C1- C30 monoesters and polyesters of sugars and related materials. These esters are derived from a sugar or polyol moiety and one or more carboxylic acid moieties. Examples of liquid esters include glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids (unsaturated), the mannose tetraesters of mixed soybean oil fatty acids, the galactose tetraesters of oleic acid, the arabinose tetraesters of linoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitol tetraoleate, the sorbitol hexaesters of unsaturated soybean oil fatty acids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate, sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, and mixtures thereof. Other preferred materials include cottonseed oil or soybean oil fatty acid esters of sucrose. The ester materials are further described in, U.S. Pat. No. 2,831 ,854, U.S. Pat. No. 4,005,196, to Jandacek, issued Jan. 25, 1977; U.S. Pat. No. 4,005,195, to Jandacek, issued Jan. 25, 1977, U.S. Pat. No. 5,306,516, to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,306,515, to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,305,514, to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 4,797,300, to Jandacek et al., issued Jan. 10, 1989; U.S. Pat. No. 3,963,699, to Rizzi et al, issued Jun. 15, 1976; U.S. Pat. No. 4,518,772, to Volpenhein, issued May 21 , 1985; and U.S. Pat. No. 4,517,360, to Volpenhein, issued May 21 , 1985; all of which are incorporated by reference herein in their entirety.

Vegetable oils and hydrogenated vegetable oils are also useful herein. Examples of vegetable oils and hydrogenated vegetable oils include safflower oil, castor oil, coconut oil, cottonseed oil, menhaden oil, palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil, linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed oil, hydrogenated safflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated cottonseed oil, hydrogenated menhaden oil, hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated peanut oil, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenated linseed oil, hydrogenated rice bran oil, hydrogenated sesame oil, hydrogenated sunflower seed oil, and mixtures thereof.

Also useful are C4-C20 alkyl ethers of polypropylene glycols, C1-C20 carboxylic acid ^esters of polypropylene glycols, and di-C8-C30 alkyl ethers. Nonlimiting examples of these materials include PPG-14 butyl ether, PPG-15 stearyl ether, dioctyl ether, dodecyl octyl ether, and mixtures thereof.

Mineral oil and petrolatum can also be used in the compositions of the present invention. Mineral oil, which is also known as petrolatum liquid, is a mixture of liquid hydrocarbons obtained from petroleum. See The Merck Index, Tenth Edition, Entry 7048, p. 1033 (1983) and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1 , p.415-417 (1993), which are incorporated by reference herein in their entirety. Petrolatum, which is also known as petroleum jelly, is a colloidal system of nonstraight-chain solid hydrocarbons and high- boiling liquid hydrocarbons, in which most of the liquid hydrocarbons are held inside the micelles. See The Merck Index, Tenth Edition, Entry 7047, p. 1033 (1983); Schindler, Drug. Cosmet. Ind., 89, 36-37, 76, 78-80, 82 (1961 ); and International Cosmetic Ingredient Dictionary, Fifth Edition, vol. 1 , p. 537 (1993).

POLYAMINE EMULSIFIER

The methods for making the detergent compositions of the present invention comprise as an essential component an emulsifier that is preferably a polyamine material. Preferred polyamine materials for use herein are polyethyleneimine polymers. These polyethyleneimine polymers comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree. In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.

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

The linear or non-cyclic polyamine backbones that comprise the modified polyethyleneimine polymers of the present invention have the general formula:

H B

[H₂N-R]n₊ι-[N-R]_m-[N-R]n-NH₂ said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units. The cyclic polyamine backbones comprising the modified polyethyleneimine polymers of the present invention have the general formula:

H B R

[H₂N-R]n₊ι-[N-R]_m-[N-R]n-[N-R]_k-NH₂ said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units

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

H₂N-R- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit. However, for the purposes of the present invention, some or all of the primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain "terminal" units. Likewise, when a primary amine moiety, located at the end of the main polyamine backbone having the structure:

-NH₂ is modified according to the present invention, it is thereafter defined as a Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below. In a similar manner, secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units. For example, when a secondary amine moiety, the major constituent of the backbones and branching chains of the present invention, having the structure:

H — [ - ] — is modified according to the present invention, it is thereafter defined as a W "backbone" unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone" units. In a further similar manner, tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y

"branching" units. For example, when a tertiary amine moiety, which is a chain branch point of either the polyamine backbone or other branching chains or rings, wherein B represents a continuation of the chain structure by branching, having the structure:

B

— [N-R]- is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain "branching" units. The R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below. The final modified structure of the modified polyethyleneimine polymers of the present invention can be therefore represented by the general formula:

V(n₊1 )W_mY_nZ for linear modified polyethyleneimine polymers and by the general formula:

V(n-k₊1 )W_mY_nY^,kZ for cyclic modified polyethyleneimine polymers . For the case of modified polyethyleneimine polymers comprising rings, a Y' unit of the formula:

serves as a branch point for a backbone or branch ring. For every Y' unit there is a Y unit having the formula:

B

— [N-R]- that will form the connection point of the ring to the main polymer chain or branch. In the unique case where the backbone is a complete ring, the polyamine backbone has the formula:

H B ^s [H₂N-R]_n+ι-[N-R]_m-[N-R]_n— therefore comprising no Z terminal unit and having the formula:

Vn-kWmYnY'k wherein k is the number of ring forming branching units. Preferably the polyamine backbones of the present invention comprise no rings. In the case of non-cyclic modified polyethyleneimine polymers, the ratio of the index n to the index m relates to the relative degree of branching. A fully non-branched linear modified polyethyleneimine polymer according to the present invention has the formula:

VW_mZ that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule. Typically the value for m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value of the index n is very low or nearly 0, are also preferred. Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y units for the purposes of the present invention.

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

E-N-R— k b) quaternized units having the structure:

wherein X is a suitable counter ion providing charge balance; and c) oxidized units having the structure:

Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure:

-N-R-

» b) quaternized units having the structure:

Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure:

-N-R-

I b) quaternized units having the structure:

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

-N-E

b) quaternized units having the structure:

When any position on a nitrogen is unsubstituted of unmodified, it is understood that hydrogen will substitute for E. For example, a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula: (HOCH₂CH₂)HN-.

For the purposes of the present invention there are two types of chain terminating units, the V and Z units. The Z "terminal" unit derives from a terminal primary amino moiety of the structure -NH₂. Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units. The Z "terminal" unit can be substituted with any of the E units described further herein below, except when the Z unit is modified to form an N-oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be a hydrogen. The modified polyethyleneimine polymers of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone. R units comprise units that for the purposes of the present invention are referred to as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyl" R units are C₂-C-|₂ alkylene, C-4-C-|₂ alkenylene, C3-C-1;? hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4-C-|₂ dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; Cβ-C^ dialkylarylene which for the purpose of the present invention are arylene moieties having two alkyl substituent groups as part of the linking chain. For example, a dialkylarylene unit has the formula:

although the unit need not be 1 ,4-substituted, but can also be 1 ,2 or 1 ,3 substituted C₂-C-i₂ alkylene, preferably ethylene, 1 ,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy" R units comprise - (R¹ O)_XR5(OR¹ )_X-,-CH₂CH(OR2)CH₂O)_Z(R¹ O)_yRl (OCH₂CH(OR2)CH₂)_w-,- CH₂CH(OR²)CH₂-, -(R¹ O)_XR¹ -, and mixtures thereof. Preferred R units are C₂-C<| alkylene, C3-C-]₂ hydroxyalkylene, C4-Cι dihydroxyalkylene, C8-C-| dialkylarylene, -(Rl θ)_xR¹-, -CH₂CH(OR2)CH₂-,

(CH₂CH(OH)CH₂O)_z(Rl O)_yR¹ (OCH₂CH-(OH)CH₂)_w-, -(R1 O)_XR⁵(OR¹ )_X-, more preferred R units are C₂-C-|₂ alkylene, C3-C-|₂ hydroxy-alkylene, C4-C<|₂ dihydroxyalkylene, -(R1 O)_XR1 -, -(R1 O)_XR⁵(OR1 )_X-, (CH₂CH(OH)CH₂O)_z(RlO)_yR (OCH₂CH-(OH)CH₂)_w-, and mixtures thereof, even more preferred R units are C₂-Cι₂ alkylene, C3 hydroxyalkylene, and mixtures thereof, most preferred are C₂-Cs alkylene. The most preferred backbones of the present invention comprise at least 50% R units that are ethylene. R¹ units are C₂-Cβ alkylene, and mixtures thereof, preferably ethylene.

R² is hydrogen, and -(Rl θ)_xB, preferably hydrogen.

R5 is C-|-C<|₂ alkylene, C3-C-|₂ hydroxyalkylene, C-4-C-|₂ dihydroxyalkylene, Cs-Cι₂ dialkylarylene,-C(O)-,-C(O)NHR⁶NHC(O)-,-

C(0)(R4)_rC(0)-, -R¹ (ORl )-,-CH₂CH(OH)CH₂O(R 0)_yR¹ OCH₂CH(OH)CH₂-,- C(O)(R4)_rC(O)-,-CH₂CH(OH)CH₂-, R5 is preferably ethylene,-C(O)-,- C(O)NHR6NHC(O)-, -R¹ (OR¹ )-,-CH₂CH(OH)CH₂-,-

CH₂CH(OH)CH₂O(R¹ O)_yR¹OCH₂CH-(OH)CH₂-, more preferably- CH₂CH(OH)CH₂-.

R^ is C₂-C<ι₂ alkylene or Ce-C-| arylene.

The preferred "oxy" R units are further defined in terms of the R¹ , R², and R⁵ units. Preferred "oxy" R units comprise the preferred R¹ , R², and R5 units. The preferred modified polyethyleneimine polymers of the present invention comprise at least 50% R¹ units that are ethylene. Preferred R¹ , R², and R⁵ units are combined with the "oxy" R units to yield the preferred "oxy" R units in the following manner.

i) Substituting more preferred R⁵ into -(CH₂CH₂O)_xR⁵(OCH₂CH₂)_x- yields -(CH₂CH₂O)_xCH₂CHOHCH₂(OCH₂CH₂)_x-. ii) Substituting preferred R¹ and R² into -(CH₂CH(OR²)CH₂O)_z- (R¹O)_yR¹ O(CH₂CH(OR²)CH₂)_w- yields -(CH₂CH(OH)CH₂O)_z- (CH₂CH₂O)_yCH₂CH₂O(CH₂CH(OH)CH₂)_w-.

iii) Substituting preferred R² into-CH₂CH(OR²)CH - yields -CH₂CH(OH)CH₂-.

E units are selected from the group consisting of hydrogen, C-j-C ₂ alkyl, C3-C₂₂ alkenyl, C/-C₂ arylalkyl, C₂-C₂₂ hydroxyalkyl, -(CH₂)_pCO M, - (CH₂)_qSO3M,-CH(CH₂CO₂M)CO₂M, -(CH₂)_pPO3M, -(R¹O)_mB,-C(O)R³, preferably hydrogen, C -C₂₂ hydroxyalkylene, benzyl, C^-C₂ alkylene, - (R¹ O)_mB,-C(O)R³, -(CH₂)_pCO₂M, -(CH₂)_qSO₃M,-CH(CH₂CO₂M)CO₂M, more preferably C-|-C₂₂ alkylene, -(Rlθ)_xB,-C(O)R³, -(CH₂)_pCO₂M, -(CH₂)_qSO₃M,- CH(CH₂CO₂M)CO M, most preferably C<|-C₂₂ alkylene, -(R¹ O)_xB, and- C(O)R³. When no modification or substitution is made on a nitrogen then hydrogen atom will remain as the moiety representing E.

E unitέ do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides. For example, the backbone chain or branching chains do not comprise units of the following structure:

Additionally, E units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are

N-oxides. According to the present invention, the E unit-C(O)R³ moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure:

or combinations thereof. B is hydrogen, C-1-C5 alkyl, -(CH₂)_qSO3M, -(CH₂)_pCO M, -(CH₂)_q- (CHSO₃M)CH₂SO3M, -(CH₂)_q(CHSO₂M)CH₂SO₃M, -(CH₂)_pPO₃M, -PO3M, preferably hydrogen, -(CH₂)_qSO₃M, -(CH₂)_q(CHSO3M)CH₂SO₃M, -(CH₂)_q- (CHSO M)CH SO3M, more preferably hydrogen or -(CH )_qSO3M. M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance. For example, a sodium cation equally satisfies -(CH₂)_pCO₂M, and -(CH₂)_qSO3M, thereby resulting in -(CH₂)_pCO₂Na, and -

(CH₂)_qSO3Na moieties. More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, more than one anionic group may be charge balanced by a divalent cation, or more than one monovalent cation may be necessary to satisfy the charge requirements of a poly-anionic radical. For example, a -(CH₂) PO3M moiety substituted with sodium atoms has the formula -(CH₂)_pPO3Na3- Divalent cations such as calcium (Ca²⁺) or magnesium (Mg²⁺) may be substituted for or combined with other suitable monovalent water soluble cations. Preferred cations are sodium and potassium, more preferred is sodium.

X is a water soluble anion such as chlorine (Cl^"), bromine (Br) and iodine (I") or X can be any negatively charged radical such as sulfate (SO4^2") and methosulfate (CH3SO3-). The formula indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1 ; w has the value 0 or 1 , x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1 ; m has the value from 4 to about 400, n has the value from 0 to about 200; m + n has the value of at least 5. The preferred modified polyethyleneimine polymers of the present invention comprise polyamine backbones wherein less than about 50% of the R groups comprise "oxy" R units, preferably less than about 20% , more preferably less than 5%, most preferably the R units comprise no "oxy" R units.

The most preferred modified polyethyleneimine polymers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the R groups comprise more than 3 carbon atoms. For example, ethylene, 1 ,2- propylene, and 1 ,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C₂-C-j₂ alkylene, preferred is C₂-C3 alkylene, most preferred is ethylene. The modified polyethyleneimine polymers of the present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified. For the purpose of the present invention the term "homogeneous polyamine backbone" is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact of the chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator" in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the purposes of the present invention. A polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone. A polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless of the degree of branching or the number of cyclic branches present.

The preferred polyamines that comprise the backbone of the compounds of the present invention are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's. A common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.

Preferred amine polymer backbones comprise R units that are C₂ alkylene (ethylene) units, also known as polyethyleneimines (PEI's). Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1 , however PEI's having a ratio of m to n of about 2:1 are most preferred. Preferred backbones, prior to modification have the general formula:

H B

[H₂N-CH₂CH₂]n₊ι-[N-CH₂CH₂]_m-[N-CH₂CH₂]_n-NH₂ wherein m and n are the same as defined herein above. Preferred PEI's, prior to modification, will have a molecular weight greater than about 200 Daltons.

The relative proportions of primary, secondary and tertiary amine units in the polyamine backbone, especially in the case of PEI's, will vary, depending on the manner of preparation. Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.

These modified polyethyleneimine polymers can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued

December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962;

U.S. Patent 2,208,095, Esselmann et a!., issued July 16, 1940; U.S. Patent

2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696,

Wilson, issued May 21 , 1951 ; U.S. Patent 5,565,145, Watson et al., issued October 15, 1996; all herein incorporated by reference.

Examples of modified polyethyleneimine polymers of the present invention comprising PEI's, are illustrated in Formulas I - IV:

Formula I depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH₂CH₂O)7H, having the formula:

Formula This is an example of a modified polyethyleneimine polymer that is fully modified by one type of moiety.

Formula II depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH₂CH₂O)7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said modified polyethyleneimine polymer having the formula:

Formula II

Formula III depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized. The substituents are polyoxyalkyleneoxy units, -(CH₂CH₂O)7H, or methyl groups. The modified PEI soil release polymer has the formula:

Formula III

Formula IV depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH₂CH O)7H or metiyl), quaternized, oxidized to N-oxides or combinations thereof. The resulting modit'ed polyethyleneimine polymer has the formula:

Formula IV In the above examples, not all nitrogens of a unit class comprise the same modification. The present invention allows the formulator to have a portion of the secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides. This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion of the primary amine nitrogens with one or more substituents prior to oxidation or quaternization. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above. Additional description and further examples of modified polyethyleneimine polymers can be found in U.S. Patent No. 4,548,744 to Connor, issued October 22, 1985; U.S. Patent No. 4,597,898 to Vander Meer, issued July 1 , 1986; and U.S. Patent No. 5,565,145 to Watson, et al., issued October 15, 1996.

For the purposes of the present invention the term "non-homogeneous polymer backbone" refers to polyamine backbones that are a composite of various R unit lengths and R unit types. For example, a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1 ,2-propylene units. For the purposes of the present invention a mixture of "hydrocarbyl" and "oxy" R units is not necessary to provide a non-homogeneous backbone. The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity of the modified polyethyleneimine polymers of the present invention.

Preferred modified polyethyleneimine polymers of the present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof. However, not all backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the formulator. The degree of ethoxylation is also determined by the specific requirements of the formulator.

The polyamine emulsifier of the present invention if included in the detergent composition, is included from about 0.01 % to about 5%; preferably about 0.3% to about 4%; more preferably about 0.5% to about 2.5%, by weight of the detergent composition.

DETERSIVE SURFACTANT

The detergent compositions herein comprise from about 1 % to 80% by weight of a detersive surfactant. Preferably such compositions comprise from about 5% to 50% by weight of surfactant. Detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types. Detergent surfactants useful herein are described in U.S. Patent 3,664,961 , Norris, issued May 23, 1972, U.S. Patent 3,919,678, Laughlin -et al., issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. All of these patents are incorporated herein by reference. Of all the surfactants, anionics and nonionics are preferred.

Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.

Additional non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C-| 1 _13 LAS.

Preferred nonionic surfactants are those of the formula R₁ (OC₂H4)_nOH, wherein R₁ is a C^ Q-C^ Q alkyl group or a C8-C-| ₂ alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C-| ₂-C-i 5 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., C-|₂-C<| 3 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable surfactants, including polyhydroxy fatty acid amides and amine based surfactants, are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference is incorporated herein by reference.

DETERGENT BUILDER

The detergent compositions herein may also comprise from about 0.1 % to 80% by weight of a detergent builder. Preferably such compositions in liquid form will comprise from about 1 % to 10% by weight of the builder component. Preferably such compositions in granular form will comprise from about 1 % to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders. Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so- called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. Examples of silicate builders are the alkali metal silicates, particularly those having a SiO₂:Na O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na₂Siθ5 morphology form of layered silicate. It can be prepared by methods such as those described in German . SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xO_2x+ι -yH₂O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms. As noted above, the delta-Na₂Siθ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 to Jacobsen, et al., published November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M_z(zAIO₂)_y] xH₂O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available.

These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669 to Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations ZeDlite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AIO₂)₁₂(SiO₂)₁₂] xH₂O wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

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

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071 , issued to Bush et al., on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679 to Rapko, issued December 2, 1975; 3,835,163 to Rapko, issued September 10, 1974; 4,158,635 to Crutchfield et al., issued June 19, 1979; 4,120,874 to Crutchfield et al., issued October 17, 1978; and 4,102,903 to Crutchfield et al., issued July 25, 1978.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisucci nates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1 ,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984 to Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C₂Q alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 200,263 to Barrat et al., published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also U.S. Patent 3,723,322 to Diehl, issued March 27, 1973.

Fatty acids, e.g., C-| -C-| 8 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1 ,1-diphosphonate and other known phosphonates (see,, for example, U.S. Patents 3,159,581 to Diehl, issued December 1 , 1964; 3,213,030 to Diehl, issued October 19, 1965; 3,400,148 to Quimby, issued September 3, 1968; 3,422,021 to Roy, issued January 14, 1969; and 3,422,137 to Quimby, issued January 14, 1969) can also be used.

CYCLIC AMINE BASED POLYMER. OLIGOMER OR COPOLYMER MATERIALS

An optional component of the compositions of the present invention comprises one or more cyclic amine based polymer, oligomer or copolymer. Such materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain these cyclic amine based polymer, oligomer or copolymer materials. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cyclic amine based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.

The cyclic amine based polymer, oligomer or copolymer component of the compositions herein may comprise combinations of these cyclic amine based materials. For example, a mixture of piperadine and epihalohydrin condensates can be combined with a mixture of morpholine and epihalohydrin condensates to achieve the desired fabric treatment results. Moreover, the molecular weight of cyclic amine based fabric treatment materials can vary within the mixture.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1 ,000. Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized. Copolymers of the present invention can include, for example, polymers or oligomers polymerized from a mixture of a primary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morpholine.

The cyclic amine based polymer, oligomer or copolymer compositions herein will generally comprise from about 0.001 % to about 10% by the weight of the detergent composition. More preferably, the cyclic amine based polymer, oligomer or copolymer will comprise from about 0.01 % to about 7% by weight of the detergent compositions, most preferably from about 0.1 % to about 4%.

A more complete description of cyclic amine based polymers, oligomers and copolymers suitable for use in the present invention can be found in co- pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference was incorporated by reference above.

DYE TRANSFER INHIBITING INGREDIENTS

An optional component of the compositions of the present invention is a dye transfer inhibitor ("DTI") ingredient to reduce or prevent diminishing of color fidelity and intensity in fabrics, and the transfer of dyes. A preferred DTI ingredient includes a traditional polymeric dye transfer inhibition material capable of binding fugitive dyes to prevent them from depositing on the fabrics, a decolorization dye transfer inhibition material capable of decolorizing the fugitives dye by oxidation, or a combination thereof Non-limiting, preferred examples of an DTI ingredient includes polyvinylpyrridine N-oxide (PVNO), polyvinylpyrrolidone (PVP), polyvinylimidazole, N-vinylpyrrolidone and N- vinylimidazole copolymers (referred to as "PVPI"), copolymers thereof, and mixtures thereof. The amount of DTI ingredient included in the subject compositions, is at least about 0.001 %, preferably at least about 0.01 %, most preferably at least about 0.1 % and no more than about 10%, preferably no more than about 7.0%, most preferably no more than about 4.0%, by weight.

HYDROPHOBICALLY MODIFIED CELLULOSIC BASED POLYMERS OR OLIGOMERS

An optional component of the compositions of the present invention comprises one or more cellulosic based polymer or oligomer. Such materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such cellulosic based fabric treatment materials. Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cellulosic based fabric treatment materials used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1 ,000. One suitable type of cellulosic based polymer or oligomer fabric treatment material for use herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1 ,000,000.

The cellulosic based fabric treatment component of the detergent compositions herein will generally comprise from about 0.1 % to about 5% by the weight of the detergent composition. More preferably, such cellulosic based fabric treatment materials will comprise from about 0.5% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3%. However, as discussed above, when used as a washing solution additive, i.e. when the cellulosic based fabric treatment component is not incorporated into a detergent composition, the concentration of the cellulosic based component can comprise from about 0.1 % to about 80% by weight of the additive material. Examples of cellulosic based fabric treatment components suitable for use in the present invention can be found in PCT Publications WO/US99/14245 and WO/US99/14295, which were filed in the name of Leupin et al., and are assigned to the Procter & Gamble Co. The entire disclosures of both of these PCT publications are incorporated herein by reference.

OTHER OPTIONAL DETERGENT INGREDIENTS

In addition to the surfactants, builders and emulsified composition of insoluble skin conditioning oils and polyamine emulsifier hereinbefore described, the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes and perfumes.

A preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach. Such peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.

Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al., Issued November 1 , 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent 4,634,551 , Issued January 6, 1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa. Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1 , 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also the hereinbefore referenced U.S. 4,634,551 for other typical bleaches and activators useful herein. Other useful amido-derived bleach activators are those of the formulae: R¹ N(R⁵)C(O)R²C(O)L or Rl C(O)N(R5)R²C(O)L wherein R¹ is an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R^ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenol sulfonate. Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene- sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.

Another class of useful bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. If utilized, peroxygen bleaching agent will generally comprise from about

2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1 :1 to 10:1 , more preferably from about 1.5:1 to 5:1.

Additional suitable bleaching agents and bleach activators are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference was incorporated by reference above.

Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability, optimal 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.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations. Cellulases usable herein include those disclosed in U.S. Patent No.

4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028; GB-A- 2.095.275 and DE-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

The enzyme-containing compositions herein may optionally also comprise from about 0.001 % to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01 % to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

DETERGENT COMPOSITION PREPARATION

The detergent compositions according to the present invention can be in liquid, paste, tablet or granular form. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means. The forgoing description of uses for the compositions of the present invention are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention.

Granular compositions, for example, are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%). Alternatively, or in addition to .spray drying, the detergent compositions and particles can be produced by agglomeration with a builder, a surfactant, other detergent ingredients and mixtures thereof. A description of such agglomeration processes can be found in US Patent Nos. 5,691 ,297 and 5,489,392, both of which were filed in the name of Nassano et al., and are assigned to the Procter & Gamble Co. The entire disclosure of US Patent Nos. 5,691 ,297 and 5,489,392 are incorporated herein by reference. The remaining dry ingredients, e.g., granules of the essential mixture of a mixture of a cyclic amine based polymer, oligomer or copolymer and Dye Transfer Inhibiting ingredient, can be admixed in granular powder form with the spray dried granules in a rotary mixing drum. The liquid ingredients, e.g., solutions of the essential mixture of a mixture of a cyclic amine based polymer, oligomer or copolymer and Dye Transfer Inhibiting ingredient, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the mixture of a cyclic amine based polymer, oligomer or copolymer and Dye Transfer Inhibiting ingredient to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired mixture of a cyclic amine based polymer, oligomer or copolymer and Dye Transfer Inhibiting ingredient.

The methods and compositions heretofore disclosed may also be applied towards the production of particles that may be used as one of the component detergent granules in a granular detergent composition.

FABRIC LAUNDERING METHOD

The present invention also provides a method for laundering fabrics. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment.

Agitation is preferably provided in a washing machine, or by manual agitation of the fabrics in a wash solution for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.

EXAMPLES The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

EXAMPLE 1 Emulsified compositions

Emulsified compositions are prepared as shown in Table 1. The emulsified compositions can added to the detergent compositions as described herein, and as exemplified below.

TABLE 1

Polyamine I = Ethoxylated polyethyleneimine with a molecular weight of about

1800 and average degree of ethoxylation 7 per Nitrogen Polyamine I = Ethoxylated polyethyleneimine with a molecular weight of about

600 and an average degree of ethoxylation 20 per Nitrogen Polyamine I = Ethoxylated polyethyleneimine with a molecular weight of about

600 and average degree of ethoxylation 12 per Nitrogen and quaternized to a degree of 19% Skin Cond. Oil I = Polydimethyl siloxane fluid with a viscosity of 350 centistokes Skin Cond. Oil II = Polydimethyl siloxane fluid with a viscosity of 1000 centistokes Skin Cond. Oil III = Polydimethyl siloxane fluid with a viscosity of 200 centistokes

EXAMPLE 2 Granular Detergent Test Composition Preparation

Several heavy duty granular detergent compositions are prepared containing an emulsified composition as prepared in Example 1. These granular detergent compositions have the following formulae: TABLE 2

Component 2 A 2 B 2 C 2 D wt % wt. % wt. % wt. %

C-|2 Linear alkyl benzene 10 10 10 10 sulfonate ^c14-15 ^alk ' ether (0.35 EO) 13 13 13 13 sulfate

Emulsified composition, 1.0 0 0 0 Example 1 A

Emulsified composition, 0 2.0 0 0 Example 1 B

Emulsified composition, 0 0 2.5 0 Example 1 C

Emulsified composition, 0 0 0 1.0 Example 1 D

Phosphate Builder 28 28 28 28

Sodium Carbonate 27 27 27 27

PEG 4000 1.6 1.6 1.6 1.6

Dispersant 2.3 2.3 2.3 2.3

Ci -13 Alcohol Ethoxylate (9 EO) 1.5 1.5 1.5 1.5

Sodium Perborate 1 1 1 1

Enzymes 0.6 0.6 0.6 0.6

Cyclic Amine Based Polymers 3.0 0.2 0.5 1.0

Dye Transfer Inhibiting 1.0 0.2 0.1 0.5 ingredient

Hydrophobically Modified 1.0 3.0 10.0 10.0 Cellulosic Based Polymers

Perfume, Brightener, Suds Balance Balance Balance Balance Suppressor, Other Minors, Moisture, Sulfate

100% 100% 100% 100% EXAMPLE 3 Liquid Detergent Test Composition Preparation

Several heavy duty liquid detergent compositions are prepared with an emulsion composition according to Example 1. These liquid detergent compositions have the following formula:

TABLE 3

Component wt. % 12-15 alkyl ether (2.5) sulfate 38

C<|2 glucose amide 7

Citric Acid 5

C-12-1 Fatty Acid 2

Emulsified composition, 1 Example 1 E

Enzymes 1

MEA 1

Propanediol 0.4

Borax 7

Dispersant 1.5

Na Toluene Sulfonate 6

Cyclic Amine Based Polymer 1

Dye Transfer Inhibitor 0.5

Hydrophobicaliy Modified 0.1 Cellulosic Based Polymer

Dye, Perfume, Brighteners, Balance Preservatives, Suds Suppressor, Other Minors, Water

100% EXAMPLE 4 A detergent agglomerate containing an emulsified composition according to Example 1 , and which may be used as a particulate component in a detergent composition, is prepared according to the following formulas and ranges. The granule may be manufactured by agglomeration methods known to those skilled in the art; some of which are described in the present application.

TABLE 4

1 : Dispersant is Na Polyacrylate 4500, Polyethylene Glycol or a mixture of both.

EXAMPLE 5 Granular laundry detergent compositions are made according to the following formulae:

Claims

WHAT IS CLAIMED IS:

1. A method for producing a detergent composition, the method comprising the steps of: a) preparing an emulsified composition comprising: i) an insoluble skin conditioning oil; and ϋ) a polyamine emulsifier; b) spraying the emulsified composition onto detergent particles which comprise from about 1 % to about 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants and mixtures thereof, and from about 1 % to about 80% by weight of a builder material selected from the group consisting of inorganic salts, silicates, aluminosilicates, and mixtures thereof; and wherein the emulsified composition comprising at least about 0.01 %, preferably at least about 0.1 %, most preferably at least about 0.5% and no more than about 20%, preferably no more than about 10.0%, most preferably no more than about 7.0%, by weight, of the detergent composition.

2. The method according to claim 1 , further comprising the steps of admixing the detergent composition with additional detergent ingredients selected from the group consisting of an inorganic peroxygen bleaching compound, a bleach activator, a detersive enzyme, an enzyme stabilizer, a dye transfer inhibitor ingredient, cyclic amine based polymer, oligomer or copolymer material, a hydrophobically modified cellulosic material, a perfume, a brightener and mixtures thereof.

3. A method for producing detergent particles, the method comprising the step of agglomerating detergent ingredients comprising: a) from about 1 % to about 80% by weight of surfactants selected from the group consisting of nonionic, anionic, cationic, amphoteric zwitterionic surfactants and mixtures thereof; b) from about 1 % to about 80% by weight of a builder material selected from the group consisting of inorganic salts, silicates, aluminosilicates, and mixtures thereof; and c) at least about 0.001 %, preferably at least about 0.01 %, most preferably at least about 0.1 % and no more than about 10%, preferably no more than about 7.0%, most preferably no more than about 4.0%, by weight, of an emulsified composition comprising: i) an insoluble skin conditioning oil; and ϋ) a polyamine emulsifier.

4. The method according to claim 3, further comprising the step of admixing the detergent particles with detergent ingredients selected from the group consisting of an inorganic peroxygen bleaching compound, a bleach activator, a detersive enzyme, an enzyme stabilizer, a dye transfer inhibitor ingredient, cyclic amine based polymer, oligomer or copolymer material, a hydrophobically modified cellulosic material, a perfume, a brightener and mixtures thereof.

5. The method according to any of claims 1 through 4, wherein the polyamine emulsifier is an alkoxylated polyethyleneimine, and preferably the degree of alkoxylation is from about 3 to about 20.

6. The method according to any of claims 1 through 5, wherein the insoluble skin conditioning oil is selected from the group consisting of polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, C7-C40 branched chain hydrocarbons, C1-C30 alcohol esters of C1-C30 carboxylic acids, C1-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycerides of C1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30 carboxylic acids, propylene glycol diesters of C1-C30 carboxylic acids, liquid polyol carboxylic acid esters and polyesters including C1-C30 carboxylic monoesters and polyesters of sugars, vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, mineral oil, petrolatum, and mixtures thereof.

7. The method according to any of claims 1 through 5, wherein the insoluble skin conditioning oil is selected from the group consisting of polydialkylsiloxanes, polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms, and mixtures thereof.

8. The method according to either of claims 2 and 4, wherein the cyclic amine based polymer, oligomer or copolymer material is an adduct selected from the group consisting of piperazine, piperadine, epichlorohydrin, epichlorohydrin benzyl quat, epichlorohydrin methyl quat, morpholine and mixtures thereof.

9. The method according to either of claims 2 and 4, wherein the inorganic peroxygen bleaching compound is selected from the group consisting of alkali metal salts of perborate, percarbonate and mixtures thereof, and the bleach activator is nonanoyloxybenzene sulfonate.

10. The method according to any of claims 1 through 7, wherein the weight ratio of the insoluble skin conditioning oil to the polyamine emulsifier is from about 1000:1 to about 1 :1.

11. The method according to either of claims 1 and 2, wherein the emulsified composition forms dropplets of less than about 40 microns, preferably less than about 30 microns and most preferably less than about 20 microns when the detergent composition is dissolved in water.