Surfactant compositions with enhanced soil release properties containing a cationic gemini surfactant

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions and methods of use of both novel and known cationic or amphoteric surfactants which allow for the better deposition of polymeric soil release agents with surfactant systems. More particularly, the present invention relates to compositions and methods of use of low concentrations of surfactants comprised of multiple hydrophilic and hydrophobic chains which allow for the improved deposition of polymeric soil release agents in the presence of typical detergent ingredients, especially highly anionic surfactant systems.

2. Background Discussion

Soil release agents are key ingredients in cleaning, e.g., textile laundry and hard surface such as carpet-cleaning; and textile treating.

These soil release agents are commonly applied during manufacture of clothing or textile fiber. The primary purpose of the soil release agents is to make it easier to clean the textile fibers by home cleaning methods using conventional household machines or cleaners.

For example, in laundering processes normally employed, such as washing in a conventional home washing machine or hand washing with detergent bars, it is usually very difficult to remove soil and/or oily stains from textile material. Moreover, assuming that the undesirable materials are removed from the textile and/or a fairly clean textile material is being washed, soil remaining in the wash water is often redeposited onto the textile material prior to the end of the wash cycle. Hence, when the textile material is removed from the washing machine and subsequently dried, it has not been properly cleaned. Thus, textile material after use rarely assumes a truly clean appearance, but instead tends to gray and/or yellow due to the soil and/or oily materials deposited or redeposited and remaining thereon.

Also, synthetic fibers, and, therefore, fabrics having synthetic fibers incorporated therein or made entirely of synthetic fibers, are hydrophobic and oleophilic. Therefore, the oleophilic characteristics of the fiber permit oil and grime to be readily embedded in the fiber, and the hydrophobic properties of the fiber prevent water from entering the fiber to remove the contaminants from the fiber.

One remedy to the soil removal and soil redeposition problem is to deposit a finish onto the fiber to impart a hydrophilic character to the fiber. Attempts have been made to reduce the oleophilic characteristics of these synthetic fibers by coating the fibers with a coating that is oleophobic, i.e., will hinder the attachment of soil and oil materials to the fibers. Many polymer systems have been proposed which are capable of forming a film around the fibers that constitute the textile material, particularly acid emulsion polymers prepared from organic acids having reactive points of unsaturation. These treating polymers are known as soil-release agents.

Typical of the soil release agents that have been developed for synthetic fibers and fabrics, are the copolymers of ethylene glycol and terephthalic acid for the treatment of Dacron, Fortrel, Kodel and Blue C Polyester, trademarks of various synthetic fibers and fabrics.

Among the leading soil release agents developed for laundering purposes are the polyesters exemplified in U.S. Pat. Nos. 3,962,152; 3,416,952; 4,132,680; 4,201,824; 4,423,557; 4,349,688; 3,959,230; 3,893,929; 3,712,873; and 4,116,885. Generally these agents are polyester polymers containing terephthalate and/or urethane groups to improve water compatibility.

The term “soil-release” in accordance with the present invention refers to the ability of the fabric to be washed or otherwise treated to remove soil and/or oily materials that have come into contact with the fabric. The present invention does not wholly prevent the attachment of soil or oil materials to the fabric, but hinders such attachment and improves the cleanability of the fabric.

Concentrated solutions of soil-release polymers have been padded onto fabrics by textile manufacturers to impart a permanent soil-release finish to the fabric. As the amount of soil-release polymer on the fabric is increased, the ability of the fabric to release soil is increased. However, fabrics with this permanent soil-release finish possess many disadvantages. As the amount of soil-release polymer on the fabric is increased, the fabric has a tendency to become stiff and lose the desirable hand characteristic of the fabric. Thus, the upper limit on the amount of soil-release polymer to be used is determined by economics and the resulting adverse effect on the fabric. Fabrics with a heavy application of soil-release polymer do not have the same desirable appearance and hand as the same fabrics without the soil-release coating. Thus, practically speaking, there is a set concentration range of soil-release agent that can be applied, dictated by commercial requirements.

Some soil-release polymers are effective fabric treating agents even at very low levels on the fabric, at which levels the appearance and hand of the fabric are not adversely affected. Thus, this property offers an ideal method of treating a synthetic fiber containing fabric which would be to reapply a very small amount of soil-release polymer to the fabric each time the fabric is washed.

Moreover, the soil release agent is preferably reapplied when the fabric is washed because the original soil release agent, applied to the fabric during manufacture, washes out after repeated washing by the consumer.

The problem is to get the soil release agent in the detergent solution to adequately deposit and remain on the clothing being washed. A number of theories have been proposed to explain the difficulties encountered when one tries to enhance this soil release agent deposition during wash process. One theory suggests that the surfactants in the detergent may complex with the soil release agent, thus inhibiting the deposition of the agent onto the fabric. Another theory has proposed that the surfactants in the detergent compositions compete with the soil release agents for sites on the fabric. This competition prevents the soil release agents from getting to the fabric.

Anionic surfactants such as alkylbenzenesulfonates, alkylether sulfates, etc., are known to have antagonistic effects on the polymer deposition. These antagonistic effects are further exacerbated because anionic surfactants are generally used at high concentrations for general soil and stain removal performance.

While conventional surfactants generally have one hydrophilic group and one hydrophobic group, recently a group of compounds having at least two hydrophobic groups and at least two hydrophilic groups per molecule have been introduced. These have become known as “gemini surfactants” in the literature, e.g.,

Chemtech,

March 1993, pp 30-33, and

J. American Chemical Soc.,

115, 10083-10090 (1993) and the references cited therein. Other gemini surfactant compounds, that is, compounds having at least two hydrophilic groups and at least two hydrophobic groups are also disclosed in literature, but often are not referred to expressly as gemini surfactants.

Prior to the present invention, many synergistic benefits of mixtures of gemini surfactants and other ingredients were unknown. It would be a major achievement to provide a detergent composition that would enhance deposition of soil release agents on textile material being washed by the consumer and, thus, provide lasting soil release properties for the life of the material.

OBJECTS OF THE INVENTION

An object of the present invention is to provide detergent compositions with enhanced soil release properties.

Another object of the present invention is to provide textile detergent compositions comprising conventional surfactants and soil release agents with both novel and known surfactants comprised of multiple hydrophilic/hydrophobic chains.

Another object of the present invention is to provide detergency and soil release benefits in compositions which also act as fabric softeners.

These and other objects will become apparent from the description of the invention in the present specification.

SUMMARY OF THE INVENTION

The present invention relates to detergent compositions having enhanced soil release properties. These compositions comprise a first surfactant, a second cationic or amphoteric surfactant and a soil release agent. The first surfactant referred to is a conventional surfactant and has a single hydrophobic group and a single hydrophilic group per molecule. The second surfactant is a cationic or amphoteric surfactant having at least two hydrophobic groups and at least two hydrophilic groups per molecule. Those comprised of two hydrophilic/hydrophobic chains are known as gemini surfactants. Preferably, the hydrophilic groups are the same and the hydrophobic groups are the same. The second surfactant may also consist of a novel class of cationic surfactants comprised of more than two hydrophilic/hydrophobic chains as well as the use of cationic and amphoteric gemini surfactants known in the art. The soil release agents useful in the compositions of the present invention can be any of the conventional soil release agents known by those skilled in the art. However, nonionic polymer soil release agents are preferred.

It has been unexpectedly found that blends of these multiple hydrophilic/hydrophobic chain surfactants with certain conventional anionic, nonionic, cationic and amphoteric surfactants provide synergistic effects with respect to the deposition and maintenance of soil release agents on the washed substrate, e.g., textiles. Serendipitously, the present invention not only promotes the deposition of soil release agents, but also enhances soil removal, general detergency, and secondary properties such as soil anti-redeposition.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The detergent compositions of the present invention achieve their unexpectedly superior soil release properties by combining a first surfactant, a second cationic or amphoteric surfactant comprised of multiple hydrophilic/hydrophobic chains and a soil release agent. The first surfactant is selected from conventional well known non-gemini surfactants discussed in detail below. The second surfactant is selected from certain cationic or amphoteric surfactants comprised of multiple hydrophilic/hydrophobic chains and the soil release agent is selected from conventional well known soil release agents also discussed in detail below.

I. First Conventional Surfactants

In contrast to second (gemini) surfactants, the first or conventional surfactants have only a single hydrophobic group (head) and a single hydrophilic group (tail). It should be apparent that even non-gemini amphoteric surfactants, having a hydrophilic group with both positive and negative charges, is defined as having only a single hydrophilic group.

A. Nonionic Surfactants

Nonionic surfactants, including those having an HLB of from 5 to 17, are well known in the detergency art. Examples of such surfactants are listed in U.S. Pat. No. 3,717,630, Booth, issued Feb. 20, 1973, and U.S. Pat. No. 3,332,880, Kessler et al., issued Jul. 25, 1967, each of which is incorporated herein by reference. Nonlimiting examples of suitable nonionic surfactants which may be used in the present invention are as follows:

(1) The polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-630, marketed by Rhone-Poulenc Inc. and Triton X-45, X-114, X-100, and X-102, all marketed by Union Carbide.

(2) The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms). Examples of commercially available nonionic surfactants in this type include Tergitol 15-S-9, marketed by Union Carbide Corporation, Neodol 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, marketed by Shell Chemical Company.

(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds typically has a molecular weight of from about 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic surfactants, marketed by Wyandotte Chemical Corporation.

(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, said moiety having a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds, marketed by Wyandotte Chemical Corporation.

(5) Semi-polar nonionic detergent surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbons atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.

Preferred semi-polar nonionic detergent surfactants are the amine oxide detergent surfactants having the formula

wherein R

1

is an alkyl, hydroxy alkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms. R

2

is an alkylene or hydroxy alkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to about 3 and each R

3

is an alkyl or hydroxy alkyl group containing from 1 to about 3 carbon atoms or a polyethylene oxide group containing from one to about 3 ethylene oxide groups and said R

3

groups can be attached to each other, e.g., through an oxygen or nitrogen atom to form a ring structure.

Preferred amine oxide detergent surfactants are C

10

-C

18

alkyl dimethyl amine oxide, C

8

-C

18

alkyl dihydroxy ethyl amine oxide, and C

8-12

alkoxy ethyl dihydroxy ethyl amine oxide.

Nonionic detergent surfactants (1)-(4) are conventional ethoxylated nonionic detergent surfactants and mixtures thereof can be used.

Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the liquid, powder, and gel applications are biodegradable and have the formula:

R(OC

2

H

4

)

n

OH ii)

wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to about 20 carbon atoms and n is an average of from about 2 to about 12, particularly from about 2 to about 9. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 15. HLB is defined in detail in

Nonionic Surfactants,

by M. J. Schick, Marcel Dekker, Inc., 1966, pages 606-613, incorporated herein by reference. In preferred nonionic surfactants, n is from 3 to 7. Primary linear alcohol ethoxylates (e.g., alcohol ethoxylates produced from organic alcohols which contain about 20% 2-methyl branched isomers, commercially available from Shell Chemical Company under the trademark Neodol) are preferred from a performance standpoint.

Particularly preferred nonionic surfactants for use in liquid, powder, and gel applications include the condensation product of C

10

alcohol with 3 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide; the condensation product of C

12

alcohol with 5 moles of ethylene oxide; the condensation product of C

12-13

alcohol with 6.5 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylate and nonethoxylated fractions; the condensation product of C

12-13

alcohol with 2.3 moles of ethylene oxide, and the same condensation product which is stripped so as to remove substantially all lower ethoxylated and nonethoxylated fractions; the condensation product of C

12-13

alcohol with 9 moles of ethylene oxide; the condensation product of C

14-15

alcohol with 2.25 moles of ethylene oxide; the condensation product of C

14-15

alcohol with 4 moles of ethylene oxide; the condensation product of C

14-15

alcohol with 7 moles of ethylene oxide; and the condensation product of C

14-15

alcohol with 9 moles of ethylene oxide. For bar soap applications, nonionic surfactants are preferably solids at room temperature with a melting point above about 25° C., preferably above about 30° C. Bar compositions of the present invention made with lower melting nonionic surfactants are generally too soft, not meeting the bar firmness requirements of the present invention.

Also, as the level of nonionic surfactant increases, i.e., above about 20% by weight of the surfactant, the bar can generally become oily.

Examples of nonionic surfactants usable herein, but not limited to bar applications, include fatty acid glycerine and polyglycerine esters, sorbitan sucrose fatty acid esters, polyoxyethylene alkyl and alkyl allyl ethers, polyoxyethylene lanolin alcohol, glycerine and polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol and sorbitol fatty acid esters, polyoxyethylene lanolin, castor oil or hardened castor oil derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidone, glucamides, alkylpolyglucosides, and mono- and dialkanol amides.

Typical fatty acid glycerine and polyglycerine esters, as well as typical sorbitan sucrose fatty acid esters, fatty acid amides, and polyethylene oxide/polypropylene oxide block copolymers are disclosed by U.S. Pat. No. 5,510,042, Hartman et al, incorporated herein by reference.

The castor oil derivatives are typically ethoxylated castor oil. It is noted that other ethoxylated natural fats, oils or waxes are also suitable.

Polyoxyethylene fatty acid amides are made by ethoxylation of fatty acid amides with one or two moles of ethylene oxide or by condensing mono-or diethanol amines with fatty acid.

Polyoxyethylene alkyl amines include those of formula: RNH—(CH

2

CH

2

O)

n

—H, wherein R is C

6

to C

22

alkyl and n is from 1 to about 100.

Monoalkanol amides include those of formula: RCONHR

1

OH, wherein R is C

6

-C

22

alkyl and R

1

is C

1

to C

6

alkylene. Dialkanol amides are typically mixtures of:

diethanolamide: RCON(CH

2

CH

2

OH)

2

;

amide ester: RCON(CH

2

CH

2

OH)—CH

2

CH

2

O(O)CR;

amine ester: RC(O)OCH

2

CH

2

NHCH

2

CH

2

OH;

and

amine soap: RC(O)

−

OH

2

N

+

(CH

2

CH

2

OH)

2

,

wherein R in the above formulas is an alkyl of from 6 to 22 carbon atoms.

Examples of preferred but not limiting surfactants for detergent bar products are the following:

Straight-chain Primary Alcohol Alkoxylates

The deca-, undeca-, dodeca-, tetradeca-, and pentadeca-ethoxylates of n-hexadecanol, and n-hexadecanol, and n-octadecanol having an HLB within the range recited herein are useful nonionics in the context of this invention. Exemplary ethoxylated primary alcohols useful herein as the conventional nonionic surfactants of the compositions are n-C

18

EO(10); n-C

14

EO(13); and n-C

10

EO(11). The ethoxylates of mixed natural or synthetic alcohols in the “tallow” chain length range are also useful herein. Specific examples of such materials include tallow-alcohol-EO(11), tallow-alcohol-EO(18), and tallow-alcohol-EO(25).

Straight-Chain Secondary Alcohol Alkoxylates

The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol having an HLB within the range recited herein are useful conventional nonionics in the context of this invention. Exemplary ethoxylated secondary alcohols useful herein are 2-C

16

(EO)

11

; 2-C

20

(EO)

11

; and 2-C

16

(EO)

14

Alkyl Phenol Alkoxylates

As in the case of the alcohol alkoxylates, the hexa- through octadeca-ethoxylates of alkylated phenols, particularly monohydric alkylphenols, having an HLB within the range recited herein are useful as conventional nonionic surfactants in the instant compositions. The hexa- through octadeca-ethoxylates of p-tridecylphenol, m-pentadecylphenol, and the like, are useful herein. Exemplary ethoxylated alkylphenols useful in the mixtures herein are: p-tridecylphenol EO(11) and p-pentadecylphenol EO(18). Especially preferred is Nonyl Nonoxynol-49 known as Igepal® DM-880 from Rhone-Poulenc Inc.

As used herein and as generally recognized in the art, a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms. For present purposes, nonionics containing a phenylene group are considered to contain an equivalent number of carbon atoms calculated as the sum of the carbon atoms in the alkyl group plus about 3.3 carbon atoms for each phenylene group.

Olefinic Alkoxylates

The alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immediately hereinabove can be ethoxylated to an HLB within the range recited herein and used as the conventional nonionic surfactants of the instant compositions.

Branched Chain Alkoxylates

Branched chain primary and secondary alcohols which are available can be ethoxylated and employed as conventional nonionic surfactants in compositions herein.

The above ethoxylated nonionic surfactants are useful in the present compositions alone or in combination, and the term “nonionic surfactant” encompasses mixed nonionic surface active agents.

Alkylpolysaccharides

Still further suitable nonionic surfactants of this invention include alkylpolysaccharides, preferably alkylpolyglycosides of the formula:

RO(C

n

H

2n

O)

t

(Z)

x

iii)

wherein

Z is derived from glycose;

R is a hydrophobic group selected from the group consisting of a C

10

-C

18

, preferably a C

12

-C

14

, alkyl group, alkyl phenyl group, hydroxyalkyl group, hydroxyalkylphenyl group, and mixtures thereof;

n is 2 or 3; preferably 2;

t is from 0 to 10; preferably 0; and

x is from 1.5 to 8; preferably 1.5 to 4; more preferably from 1.6 to 2.7.

These surfactants are disclosed in U.S. Pat. No. 4,565,647 to Llenado, issued Jan. 21, 1986; U.S. Pat. No. 4,536,318 to Cook et al., issued Aug. 20, 1985; U.S. Pat. No. 4,536,317, Llenado et al., issued Aug. 20, 1985; U.S. Pat. No. 4,599,188 to Llenado, issued Jul. 8, 1986; and U.S. Pat. No. 4,536,319 to Payne, issued Aug. 20, 1985; all of which are incorporated herein by reference.

The compositions of the present invention can also comprise mixtures of the above nonionic surfactants.

A thorough discussion of nonionic surfactants for detergent bar and liquid products is presented by U.S. Pat. No. 5,510,042 to Hartman et al., and U.S. Pat. No. 4,483,779 to Llenado, et al., incorporated herein by reference.

B. Anionic Surfactants

Anionic surfactants include any of the known hydrophobes attached to a carboxylate, sulfonate, sulfate or phosphate polar, solubilizing group including salts. Salts may be the sodium, potassium, ammonium and amine salts of such surfactants. Useful anionic surfactants can be organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group, or mixtures thereof. (Included in the term “alkyl” is the alkyl portion of acyl groups.) Examples of this group of synthetic detersive surfactants which can be used in the present invention are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C

8

-C

18

carbon atoms) produced from the glycerides of tallow or coconut oil; and alkyl benzene sulfonates.

Other useful anionic surfactants herein include the esters of alpha-sulfonated fatty acids preferably containing from about 6 to 20 carbon atoms in the ester group; 2-acyloxyalkane-1-sulfonic acids preferably containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates preferably containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; olefin sulfonates preferably containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates preferably containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

Anionic surfactants based on the higher fatty acids, i.e., “soaps” are useful anionic surfactants herein. Higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms and the coconut and tallow soaps can also be used herein as corrosion inhibitors.

Preferred water-soluble anionic organic surfactants herein include linear alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; branched alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; the tallow range alkyl sulfates; the coconut range alkyl glyceryl sulfonates; alkyl ether (ethoxylated) sulfates wherein the alkyl moiety contains from about 12 to 18 carbon atoms and wherein the average degree of ethoxylation varies between 1 and 12, especially 3 to 9; the sulfated condensation products of tallow alcohol with from about 3 to 12, especially 6 to 9, moles of ethylene oxide; and olefin sulfonates containing from about 14 to 16 carbon atoms.

Specific preferred anionics for use herein include: the linear C

10

-C

14

alkyl benzene sulfonates (LAS); the branched C

10

-C

14

alkyl benzene sulfonates (ABS); the tallow alkyl sulfates, the coconut alkyl glyceryl ether sulfonates; the sulfated condensation products of mixed C

10

-C

18

tallow alcohols with from about 1 to about 14 moles of ethylene oxide; and the mixtures of higher fatty acids containing from 10 to 18 carbon atoms.

It is to be recognized that any of the foregoing anionic surfactants can be used separately herein or as mixtures. Moreover, commercial grades of the surfactants can contain non-interfering components which are processing by-products. For example, commercial alkaryl sulfonates, preferably C

10

-C

14

, can comprise alkyl benzene sulfonates, alkyl toluene sulfonates, alkyl naphthalene sulfonates and alkyl poly-benzenoid sulfonates. Such materials and mixtures thereof are fully contemplated for use herein.

Other examples of the anionic surfactants used herein include fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonate salts, a-olefin sulfonate salts, sulfonate salts of higher fatty acid esters, higher alcohol sulfate ester or ether ester salts, alkyl, preferably higher alcohol phosphate ester and ether ester salts, and condensates of higher fatty acids and amino acids.

Fatty acid soaps include those having the formula: R—C(O)OM, wherein R is C

6

to C

22

alkyl and M is preferably sodium.

Salts of ether carboxylic acids and salts thereof include those having the formula: R—(OR

1

)

n

—OCH

2

C(O)OM, wherein R is C

6

to C

22

alkyl, R

1

is C

2

to C

10

, preferably C

2

alkyl, and M is preferably sodium.

Alkane sulfonate salts and a-olefin sulfonate salts have the formula: R—SO

3

M, wherein R is C

6

to C

22

alkyl or a-olefin, respectively, and M is preferably sodium.

Sulfonate salts of higher fatty acid esters include those having the formula:

RC(O)O—R

1

—SO

3

M, i)

wherein R is C

12

to C

22

alkyl, R

1

is C

1

to C

18

alkyl and M is preferably sodium.

Higher alcohol sulfate ester salts include those having the formula:

RC(O)O—R

1

—OSO

3

M, ii)

wherein R is C

12

-C

22

alkyl, R

1

is C

1

-C

18

hydroxyalkyl, M is preferably sodium.

Higher alcohol sulfate ether ester salts include those having the formula:

RC(O)(OCH

2

CH

2

)

x

—R

1

—OSO

3

M, iii)

wherein R is C

12

-C

22

alkyl, R

1

is C

1

-C

18

hydroxyalkyl, M is preferably sodium and x is an integer from 5 to 25.

Higher alcohol phosphate ester and ether ester salts include compounds of the formulas:

R—(OR

1

)

n

—OPO(OH)(OM);

(R—(OR

1

)

n

—O)

2

PO(OM);

and

(R—(OR

1

)

n

—O)

3

—PO, iv)

wherein R is alkyl or hydroxyalkyl of 12 to 22 carbon atoms, R

1

is C

2

H

4

, n is an integer from 5 to 25, and M is preferably sodium.

Other anionic surfactants herein are sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

C. Cationic Surfactants

Preferred cationic surfactants of the present invention are the reaction products of higher fatty acids with a polyamine selected from the group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and mixtures thereof.

A preferred component is a nitrogenous compound selected from the group consisting of:

(i) the reaction product mixtures of higher fatty acids with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said reaction product containing a composition having a compound of the formula:

wherein R

1

is an acyclic aliphatic C

15

-C

21

hydrocarbon group and R

2

and R

3

are divalent C

1

-C

3

alkylene groups; commercially available as Mazamide 6 from PPG;

(ii) the reaction product of higher fatty acids with dialkylenetriamines in a molecular ratio of about 2:1; said reaction product containing a composition having a compound of the formula:

wherein R

1

, R

2

and R

3

are as defined above; and mixtures thereof.

Another preferred component is a cationic nitrogenous salt containing one long chain acyclic aliphatic C

15

-C

22

hydrocarbon group selected from the group consisting of:

(iii) acyclic quaternary ammonium salts having the formula:

wherein R

4

is an acyclic aliphatic C

15

-C

22

hydrocarbon group, R

5

and R

6

are C

1

-C

4

saturated alkyl or hydroxyalkyl groups, and A [−] is an anion, especially as described in more detail hereinafter, examples of these surfactants are sold by Sherex Chemical Company under the Adgen trademarks;

(iv) substituted imidazolinium salts having the formula:

wherein R

1

is an acyclic aliphatic C

15

-C

21

hydrocarbon group, R

7

is a hydrogen or a C

1

-C

4

saturated alkyl or hydroxyalkyl group, and A [−] is an anion;

(v) substituted imidazolinium salts having the formula:

wherein R

2

is a divalent C

1

-C

3

alkylene group and R

1

, R

5

and A [−] are as defined above; an example of which is commercially available under the Monaquat ISIES trademark from Mona Industries, Inc.;

(vi) alkylpyridinium salts having the formula:

wherein R

4

is an acyclic aliphatic C

16

-C

22

hydrocarbon group and A [−] is an anion; and

(vii) alkanamide alkylene pyridinium salts having the formula:

wherein R

1

is an acyclic aliphatic C

15

-C

21

hydrocarbon group, R

2

is a divalent C

1

-C

3

alkylene group, and A [−] is an ion group; and mixtures thereof.

Another class of preferred cationic nitrogenous salts having two or more long chain acyclic aliphatic C

15

-C

22

hydrocarbon groups or one said group and an arylalkyl group are selected from the group consisting of:

(viii) acyclic quaternary ammonium salts having the formula:

wherein each R

4

is an acyclic aliphatic C

15

-C

22

hydrocarbon group, R

5

is a C

1

-C

4

saturated alkyl or hydroxyalkyl group, R

8

is selected from the group consisting of R

4

and R

5

groups, and A [−] is an anion defined as above; examples of which are commercially available from Sherex Company under the Adgen trademarks;

(ix) diamido quaternary ammonium salts having the formula:

wherein each R

1

is an acyclic aliphatic C

15

-C

21

hydrocarbon group, R

2

is a divalent alkylene group having 1 to 3 carbon atoms, R

5

and R

9

are C

1

-C

4

saturated alkyl or hydroxyalkyl groups, and A [−] is an anion; examples of which are sold by Sherex Chemical Company under the Varisoft trademark;

(x) diamino alkoxylated quaternary ammonium salts having the formula:

wherein n is equal to 1 to about 5, and R

1

, R

2

, R

5

and A [−] are as defined above;

(xi) quaternary ammonium compounds having the formula:

wherein each R

4

is an acyclic aliphatic C

15

-C

22

hydrocarbon group, each R

5

is a C

1

-C

4

saturated alkyl or hydroxyalkyl group, and A [−] is an anion; examples of such surfactants are available from Onyx Chemical Company under the Ammonyx® 490 trademark;

(xiii) substituted imidazolinium salts having the formula:

wherein each R

1

is an acyclic aliphatic C

15

-C

21

hydrocarbon group, R

2

is a divalent alkylene group having 1 to 3 carbon atoms, and R

5

and A [−] are as defined above; examples are commercially available from Sherex Chemical Company under the Varisoft 475 and Varisoft 445 trademarks; and

(vi) substituted imidazolinium salts having the formula:

wherein R

1

, R

2

and A − are as defined above; and mixtures thereof.

The more preferred cationic conventional surfactant is selected from the group consisting of an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkyldimethylbenzylammonium salt, an alkylpyridinium salt, an alkylisoquinolinium salt, benzethonium chloride, and an acylamino acid cationic surfactant.

Anion A

In the cationic nitrogenous salts herein, the anion A [−] provides electrical neutrality. Most often, the anion used to provide electrical neutrality in these salts is a halide, such as chloride, bromide, or iodide. However, other anions can be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate, and the like. Chloride and methylsulfate are preferred herein as anion A.

Cationic surfactants are commonly employed as fabric softeners in compositions added during the rinse cycle of clothes washing. Many different types of fabric conditioning agents have been used in rinse cycle added fabric conditioning compositions as disclosed by U.S. Pat. No. 5,236,615, Trinh et al. and U.S. Pat. No. 5,405,542, Trinh et al., both patents herein incorporated by reference in their entirety. The most favored type of agent has been the quaternary ammonium compounds. Many such quaternary ammonium compounds are disclosed for example, by U.S. Pat. No. 5,510,042, Hartman et al. incorporated herein by reference in its entirety. These compounds may take the form of noncyclic quaternary ammonium salts having preferably two long chain alkyl groups attached to the nitrogen atoms. Additionally, imidazolinium salts have been used by themselves or in combination with other agents in the treatment of fabrics as disclosed by U.S. Pat. No. 4,127,489, Pracht, et al., incorporated herein by reference in its entirety. U.S. Pat. No. 2,874,074, Johnson discloses using imidazolinium salts to condition fabrics; and U.S. Pat. No. 3,681,241, Rudy, and U.S. Pat. No. 3,033,704, Sherrill et al. disclose fabric conditioning compositions containing mixtures of imidazolinium salts and other fabric conditioning agents. These patents are incorporated herein by reference in their entirety.

D. Amphoteric Surfactants

Amphoteric surfactants have a positive or negative charge or both on the hydrophilic part of the molecule in acidic or alkaline media.

Examples of the amphoteric surfactants which can be used herein include amino acid, betaine, sultaine, phosphobetaines, imidazolinium derivatives, soybean phospholipids, and yolk lecithin. Examples of suitable amphoteric surfactants include the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyl amphocarboxy glycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates and alkyl amphopropionates wherein alkyl represents an alkyl group having 6 to 20 carbon atoms. Other suitable amphoteric surfactants include alkyliminopropionates, alkyl iminodipropionates and alkyl amphopropylsulfonates having between 12 and 18 carbon atoms, alkylbetaines and amidopropylbetaines and alkylsultaines and alkylamidopropylhydroxy sultaines wherein alkyl represents an alkyl group having 6 to 20 carbon atoms are especially preferred.

Particularly useful amphoteric surfactants include both mono and dicarboxylates such as those of the formulae:

wherein R is an alkyl group of 6-20 carbon atoms, x is 1 or 2 and M is hydrogen or sodium. Mixtures of the above structures are particularly preferred.

Other formulae for the above amphoteric surfactants include the following:

where R is an alkyl group of 6-20 carbon atoms.

Of the above amphoteric surfactants, particularly preferred are the alkali salts of alkyl amphocarboxyglycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates, alkyl amphopropyl sulfonates and alkyl amphopropionates wherein alkyl represents an alkyl group having 6 to 20 carbon atoms. Even more preferred are compounds wherein the alkyl group is derived from coconut oil or is a lauryl group, for example, cocoamphodipropionate. Such cocoamphodipropionate surfactants are commercially sold under the trademarks Miranol C2M-SF CONC. and Miranol FBS by Rhodia Inc.

Other commercially useful amphoteric surfactants are available from Rhodia Inc. and include:

cocoamphoacetate

(sold under the trademarks MIRANOL CM

CONC. and MIRAPON FA),

cocoamphopropionate

(sold under the trademarks MIRANOL CM-

SF CONC. and MIRAPON FAS),

cocoamphodiacetate

(sold under the trademarks MIRANOL

C2M CONC. and MIRAPON FB),

lauroamphoacetate

(sold under the trademarks MIRANOL HM

CONC. and MIRAPON LA),

lauroamphodiacetate

(sold under the trademarks MIRANOL

H2M CONC. and MIRAPON LB),

lauroamphodipropionate

(sold under the trademarks MIRANOL

H2M SF CONC. AND MIRAPON LBS),

lauroamphodiacetate

(sold under the trademark MIRANOL BM

obtained from a mixture

CONC.), and

of lauric and myristic

acids

cocoamphopropyl

(sold under the trademark MIRANOL CS

sulfonate

CONC.)

Somewhat less preferred are:

caproamphodiacetate

(sold under the trademark MIRANOL S2M

CONC.),

caproamphoacetate

(sold under the trademark MIRANOL SM

CONC.),

caproamphodipropionate

(sold under the trademark MIRANOL S2M-

SF CONC.), and

stearoamphoacetate

(sold under the trademark MIRANOL DM).

II. Gemini Surfactants

Gemini surfactants form a special class of surfactant. These surfactants have the general formula:

A—G—A

1

i)

and get their name because they comprise two surfactant moieties (A,A

1

) joined by a spacer (G), wherein each surfactant moiety (A,A,

1

) has a hydrophilic group and a hydrophobic group. Generally, the two surfactant moieties (A,A

1

) are twins, but they can be different.

The gemini surfactants are advantageous because they have low critical micelle concentrations (cmc) and, thus, lower the cmc of solutions containing both a gemini surfactant and a conventional surfactant. Lower cmc causes better solubilization and increased detergency at lower surfactant use levels and unexpectedly enhances the deposition of the soil release polymers as claimed by this invention with demonstrated results to follow herein. Soil removal agents adhere to the fabric being laundered, much better than when mixed with only non-gemini, conventional surfactants.

Also, the gemini surfactants result in a low pC

20

value and low Krafft points. The pC

20

value is a measure of the surfactant concentration in the solution phase that will reduce the surface tension of the solvent by 20 dynes/cm. It is a measure of the tendency of the surfactant to adsorb at the surface of the solution. The Krafft point is the temperature at which the surfactant's solubility equals the cmc. Low Krafft points imply better solubility in water, and lead to greater latitude in making formulations.

Unexpectedly, the mixture of gemini surfactant with the above mentioned conventional surfactant, and the above-mentioned polymeric soil release agent, dramatically enhances the deposition of the soil release agent. The aforementioned mixture is far more effective than conventional surfactant and soil release agent formulations without the gemini surfactants.

A number of the gemini surfactants are reported in the literature, see for example, Okahara et al., J. Japan Oil Chem. Soc. 746 (Yukagaku) (1989); Zhu et al., 67 JAOCS 7,459 (July 1990); Zhu et al., 68 JAOCS 7,539 (1991); Menger et al., J. Am. Chemical Soc. 113, 1451 (1991); Masuyama et al., 41 J. Japan Chem. Soc. 4,301 (1992); Zhu et al., 69 JAOCS 1,30 (January 1992); Zhu et al., 69 JAOCS 7,626 July 1992); Menger et al., 115 J. Am. Chem. Soc. 2, 10083 (1993); Rosen, Chemtech 30 (March 1993); and Gao et al., 71 JAOCS 7,771 (July 1994), all of this literature incorporated herein by reference.

A number of gemini surfactants have also been disclosed in the patent literature including U.S. Pat. No. 5,160,450 to Okahara et al., U.S. Pat. No. 3,244,724 to Guttman, U.S. Pat. Nos. 2,524,218 and 2,530,147 to Bersworth (three hydrophilic heads) and U.S. Pat. No. 2,374,354 to Kaplan.

The present invention then, is comprised of the discovery of novel cationic surfactants comprised of multiple hydrophilic/hydrophobic chains and their use along with other known cationic and amphoteric gemini surfactants in combination with a second conventional surfactant and a polymeric soil release agent so as to provide enhanced cleaning and soil release properties in laundry detergents and the like.

The novel cationic surfactants useful in the practice of the present invention are composed of trimeric and tetrameric hydrophilic/hydrophobic chains or tails as represented by the structures below:

wherein R is a C

5

-C

22

alkyl, aryl, alkylaryl and the perfluorinated- and hydroxy-substituted derivatives thereof; R

1

is a C

1

-C

4

alkyl and R

2

is a C

2

-C

12

alkylene, arylene or alkylarylene and Y independently represents an anion such as Br

−

, Cl

−

, methosulfate, alkosulfate and the like.

Specific trimeric and tetrameric cationic gemini surfactants of the present invention may be represented as follows:

wherein R has been hereinbefore defined. Preferred compounds comprise methylalkyl-bis(3-(dimethyl-alkylammonio)propyl) ammonium tribromide.

wherein R has been hereinbefore defined. Preferred compounds comprise methylalkyl-bis(6-(dimethyl-alkylammonio)hexyl) ammonium tribromide.

wherein R has been hereinbefore defined. Preferred compounds comprise methyldodecyl-bis(3-(dimethyldodecylammonio)propyl]ammonium tribromide and methyldodecyl-bis[6-(dimethyldodecylammonio)hexyl]ammonium tribromide.

The trimer and tetramer gemini species can be prepared as follows:

A second trimeric cationic structure can be prepared as follows:

The tetrameric cationic gemini surfactant is prepared by the same pathways utilizing H

2

N—(CH

2

)

3

—NH—(CH

2

)

6

—NH—(CH

2

)

6

—NH

2

as the starting material. Similar pathways are disclosed in two articles by Zana et al., Langmuir 7 1072-1075 (1991) and Langmuir 10 1448-1457 (1995) which are hereby incorporated by reference.

These new tetrameric cationic surfactants can be used together with the conventional linear surfactant as discussed, supra, in combination with the polymeric soil release agent to surprisingly and unexpectedly provide enhanced and superior cleaning and soil release properties in laundry detergents and other like compositions. Other known cationic gemini surfactants can be used in place of the novel trimer and tetranier species if desired. Generically, these gemini surfactants can be represented by the structure:

wherein R is a C

5

-C

22

alkyl, aryl, alkylaryl and the perfluorinated- and hydroxy-substituted derivatives thereof and carboxyalkyl; R

1

is a C

1

-C

4

alkyl; X independently represents —O—; —S—; (—CH

2

—)

n

; or

wherein n is a number of from about 1-25; m is a number of from about 1-4 and p is a number of from about 1 to 50 and Y is a halogen, CH

3

SO

4

−

and CH

2

CH

2

SO

4

−

.

More specifically, the cationic gemini surfactants useful in the compositions of the present invention include compounds with the structures:

wherein R, R

1

, p and Y have been hereinbefore defined.

wherein R, R

1

and Y have been hereinbefore defined.

wherein R, R

1

and Y have been hereinbefore defined.

Another group of cationic gemini surfactants useful in the detergent compositions of the present invention include quaternary cationic surfactants having two imidazoline groups that are connected by an alkylene bridge. These surfactants may be structurally represented as follows:

wherein R

1

independently represents alkyl, hydroxy-substituted or perfluorinated alkyl of from about 5 to about 22 carbon atoms; R

2

represents alkylene and the hydroxy-substituted derivatives thereof, alkylaryl of 1 to about 10 carbon atoms and the hydroxy-substituted derivatives thereof or R

3

—D—R

3

wherein R

3

independently represents alkylene of from 1 to about 6 carbon atoms and the hydroxy-substituted derivatives thereof as well as aryl, and D represents —O—, —S—, —SO

2

—, a polyether group [—O(R

4

)

x

—] or aryl wherein R

4

independently represents about C

2

to about C

4

alkyl with x being a number from 1 to 20 and X independently represents an alkyl of 1 to 10 carbon atoms and the hydroxy-substituted derivatives thereof and alkylaryl; and Y independently represents an anion.

These surfactants and the process for their preparation are more specifically described in U.S. Pat. No. 5,643,498 to Li et al. which is hereby incorporated by reference.

Some of the compounds such as those described above are set forth more fully in U.S. Pat. No. 5,534,197 to Schiebel et al. which description is incorporated herein by reference.

A second group of gemini surfactants that are amphoteric in nature also exhibit surprising and unexpectedly good soil release properties when used with the aforementioned polymers. These surfactants may be structurally represented as follows:

wherein R is a C

6

to C

18

alkyl, aryl and the hydroxy-substituted derivatives thereof, preferably derived from coconut fatty acid, (—CH

3

(CH

2

)

n

COOH wherein n is a number of from 6 to 18), stearyl (CH

3

(CH

2

)

16

COOH) or palmityl (CH

3

(CH

2

)

14

COOH). More preferably, the compounds are selected from the group consisting of N′N′bis(2-lauramidoethyl)ethylenediamine diamine; -N′N′di(acetate)-N′N′bis(2- lauramidoethyl)ethylenediamine-N′N′di(propionate);N′N′bis(2-lauramidoethylethylenediamine-N′N′-di(-2-hydroxy-propyl sulfonate).

With respect to the compounds useful in the present invention, many of the moieties can be derived from natural sources which will generally contain mixtures of different saturated and unsaturated carbon chain lengths. The natural sources can be illustrated by coconut oil or similar natural oil sources such as palm kernel oil, palm oil, soy oil, rapeseed oil, castor oil or animal fat sources such as herring oil and beef tallow. Generally, the fatty acids from natural sources in the form of the fatty acid or the triglyceride oil can be a mixture of alkyl radicals containing from about 5 to about 22 carbon atoms. Illustrative of the natural fatty acids are caprylic (C

8

), capric (C

10

), lauric (C

12

), myristic (C

14

), palmitic (C

16

), stearic (C

18

), oleic (C

18

, mono-unsaturated), linoleic (C

18

, di-unsaturated), linolenic (C

18

, tri-unsaturated), ricinoleic (C

18

, mono-unsaturated) arachidic (C

20

), gadolic (C

20

, mono-unsaturated), behenic (C

22

) and erucic (C

22

). These fatty acids can be used per se, as concentrated cuts or as fractionations of natural source acids. The fatty acids with even numbered carbon chain lengths are given as illustrative though the odd numbered fatty acids can also be used. In addition, single carboxylic acids,e.g., lauric acid, or other cuts, as suited for the particular application, may be used.

Where desired, the cationic gemini surfactants used in the present invention can be oxyalkylated by reacting the product with an alkylene oxide according to known methods, preferably in the presence of an alkaline catalyst. The free hydroxyl groups of the alkoxylated derivative can then be sulfated, phosphated or acylated using normal methods such as sulfation with sulfamic acid or sulfur trioxide-pyridine complex, or acylation with an acylating agent such as a carboxylic acid, ester, and the naturally occurring triglyceride esters thereof.

For alkylation conditions and commonly used alkylating agents, see Amphoteric Surfactants Vol. 12, Ed. B. R. Bluestein and C. L. Hilton,

Surfactant Science Series

1982, pg. 17 and references cited therein, the disclosures of which are incorporated herein by reference.

For sulfation and phosphation, see Surfactant Science Series, Vol. 7, Part 1, S. Shore & D. Berger, page 135, the disclosure of which is incorporated herein by reference. For phosphating review, see Surfactant Science Series, Vol. 7, Part II, E. Jungermann & H. Silbertman, page 495, the disclosure of which is incorporated herein by reference.

The surfactant compositions of the invention are extremely effective in aqueous solution at low concentrations as defined herein. The surfactants of the invention can be used in any amount needed for a particular application which can be easily determined by a skilled artisan without undue experimentation.

III. Polymeric Soil Release Agents

Soil release agents, usually polymers, are especially desirable additives for releasing hydrophobic stains from textile fibers especially synthetics and also are used as effective particle suspending agents for liquid detergent, and fabric softener systems. Suitable soil release agents are disclosed in U.S. Pat. Nos.: 4,956,477; 4,702,857; 4,713,194; and 4,711,730 all to Gosselink et al.; U.S. Pat. No. 4,877,896 to Maldonado, et al.; U.S. Pat. No. 4,873,003 to O'Lenick et al.; U.S. Pat. No. 4,999,128 to Sonenstein; U.S. Pat. No. 4,749,596 to Evans, and U.S. Pat. No. 5,236,615 to Trinh et al., said patents being incorporated herein by reference. Typical soil release agents include nonionic or anionic polymers, or mixtures thereof.

Especially effective polymeric soil release agents are the block copolymers of polyalkylene terephthalate and polyoxyethylene terephthalate, and block copolymers of polyalkylene terephthalate and polyethylene glycol. The polyalkylene terephthalate blocks preferably comprise ethylene and/or propylene alkylene groups. Many of such soil release polymers are nonionic. More specifically, these polymers are comprised of repeating units of ethylene and/or propylene terephthalate and polyethylene oxide terephthalate, preferably at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from about 25:75 to about 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of these polymeric soil release agents is in the range of from about 4,000 to about 55,000. Other useful soil release polymers include, but are not limited to, sulfonated polyethylene terephthalate, polyester urethane, and acetic acid ethenyl esters; the polyethylene terephthalate/polyoxyethylene terephthalate (PET—POET) polymer being most preferable. Typically, molecular weight ranges of these polymers are from 500 to 120,000, preferably, 2000 to 35,000, and most preferably 2000 to 25,000.

U.S. Pat. No. 4,976,879 to Maldonado et al. discloses specific preferred soil release agents which can also provide improved antistatic benefits; said patent being incorporated herein by reference.

Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available materials Zelcon 4780 (from DuPont) and Milease T (from ICI).

A more complete disclosure of these highly preferred soil release agents is contained in European Patent Application 185,427, Gosselink, published Jun. 25, 1986, incorporated herein by reference.

A preferred nonionic soil release polymer has the following average structure:

Such soil release polymers are described in U.S. Pat. No. 4,849,257, Borcher, et al., this patent being incorporated herein by reference.

Another preferred nonionic soil release polymer has the following average structure:

wherein n is preferably between about 50 to about 150.

Another preferred nonionic soil release polymer is described in now abandoned U.S. patent application Ser. No. 07/676,682, filed Mar. 28, 1991, by Pan, et al., for Nonionic Soil Release Agents.

The most preferred nonionic soil release agents are the REPEL-O-TEX line of soil release agents sold by Rhône-Poulenc Inc., Cranbury, N.J. These products include REPEL-O-TEX SRP3, REPEL-O-TEX SRP4, REPEL-O-TEX QCJ product and REPEL-O-TEX QCX products. VELVETOL 251C is a 100% active hydrophilic polyester from which REPEL-O-TEX SRP3, SRP4, AND QCJ are manufactured at different polymer concentrations. The polymers have a molecular weight of from about 3,000 to about 10,000. REPEL-O-TEX QCJ product is a 15 weight percent active dispersion of the above mentioned polymer for liquid laundry detergents, whereas SRP3 and SRP4 are diluted with sodium sulfate for powder detergent applications. The polymers of the REPEL-O-TEX products are nonionic polyester-polyether (PET—POET) transesterification co-polymers. The REPEL-O-TEX QCX is a higher molecular weight hydrophilic polyester polymer with a molecular weight range of from about 10,000 to about 35,000.

Suitable anionic polymeric or oligomeric soil release agents are disclosed in U.S. Pat. No. 4,018,569 to Trinh, and U.S. Pat. No. 4,787,989 to Fanelli, et al. Other suitable polymers are disclosed in U.S. Pat. No. 4,808,086 to Evans et al.; all of these patents being incorporated herein by reference.

Cationic polymeric soil release agents are also useful in the present invention. Suitable cationic soil release polymers are described in U.S. Pat. No. 4,956,447 to Gosselink, et al. and U.S. Pat. No. 4,873,003 to O'Lenick, et al.; and U.S. Pat. No. 5,405,542 to Trinh et al. These patents are also incorporated by reference.

IV. Auxiliary Detergent Ingredients

A. Detergency Builders

Compositions of the present invention may include detergency builders selected from any of the conventional inorganic and organic water-soluble builder salts, including neutral or alkaline salts, as well as various water-insoluble and so-called “seeded” builders.

Builders are preferably selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates. Most preferred are the alkali metal, especially sodium, salts of the above.

Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphate having a degree of polymerization of from about 6 to 21, and orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene-1, 1-diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.

Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SIO

2

to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.

Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.

Highly preferred polycarboxylate builders herein are set forth in U.S. Pat. No. 3,308,067 to Diehl, issued Mar. 7, 1967 which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other builders include the carboxylated carbohydrates of U.S. Pat. No. 3,723,322 to Diehl that is incorporated herein by reference.

Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate phloroglucinol trisulfonate, water-soluble polyacrylates (having molecular weights of from about 2,000 to about 200,000 for example), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979 and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979 both to Crutchfield et al., which are incorporated herein by reference.

“Insoluble” builders include both seeded builders such as 3:1 weight mixtures of sodium carbonate and calcium carbonate; and 2.7:1 weight mixtures of sodium sesquicarbonate and calcium carbonate. Amphorus and crystalline alumino silicates such as hydrated sodium Zeolite A are commonly used in laundry detergent applications. They have a particle size diameter of 0.1 micron to about 10 microns depending on water content of these molecules. These are referred to as ion exchange materials. Crystalline alumino silicates are characterized by their calcium ion exchange capacity. Amphorus alumino silicates are usually characterized by their magnesium exchange capacity. They can be naturally occurring or synthetically derived.

A detailed listing of suitable detergency builders can be found in U.S. Pat. No. 3,936,537, supra, incorporated herein by reference.

B. Miscellaneous Detergent Ingredients

Detergent composition components may also include hydrotropes, enzymes (e.g., proteases, amylases and cellulases), enzyme stabilizing agents, pH adjusting agents (monoethanolamine, sodium carbonate, etc.) halogen bleaches (e.g., sodium and potassium dichloroisocyanurates), peroxyacid bleaches (e.g., diperoxydodecane-1,12-dioic acid), inorganic percompound bleaches (e.g., sodium perborate), antioxidants as optional stabilizers, reductive agents, activators for percompound bleaches (e.g., tetraacetylethylenediamine and sodium nonanoyloxybenzene sulfonate), soil suspending agents (e.g., sodium carboxymethyl cellulose), soil anti-redisposition agents, corrosion inhibitors, perfumes and dyes, buffers, whitening agents, solvents (e.g., glycols and aliphatic alcohols) and optical brighteners. Any of other commonly used auxiliary additives such as inorganic salts and common salt, humectants, solubilizing agents, UV absorbers, softeners, chelating agents, static control agents and viscosity modifiers may be added to the detergent compositions of the invention.

For bar compositions, processing aids are optionally used such as salts and/or low molecular weight alcohols such as monodihydric, dihydric (glycol, etc.), trihydric (glycerol, etc.), and polyhydric (polyols) alcohols. Bar compositions may also include insoluble particulate material components, referred to as “fillers” such as calcium carbonate, silica and the like.

V. Composition Concentrations

The total weight percentages of the conventional surfactants of the present invention, all weight percentages being based on the total active weight of the compositions of this invention consisting of conventional surfactant(s), gemini surfactant(s), soil release agent(s), and (optionally) detergency builder(s) are about 10 to about 99.9 weight percent, preferably about 15-75 weight percent.

The gemini surfactants are suitably present at a level of about 0.005 to about 50, preferably from about 0.02-15.0, active weight percent of the composition.

The polymeric soil release agents, are suitably employed at a level of from about 0.05 to about 40, preferably from about 0.2-15 active weight percent.

The optional detergency builders are suitably present at a level of from about 0 to about 70 weight percent, preferably from about 5 to about 50 weight percent.

VI. Detergent and/or Fabric Softener Compositions

In the preparation of detergent and/or fabric softening compositions, other optional ingredients such as bleaches, enzymes, antioxidants, reductive agents, perfumes, fabric brighteners and the like may be included in amounts each of from about 0 to about 5 weight percent based on the active weight of the composition.

Specific to fabric softener compositions, they generally comprise from about 10 to 80 active weight percent cationic conventional surfactant; about 0.005 to about 20, preferably 0.02-10 active weight percent gemini surfactant. The gemini surfactant may be cationic, nonionic, amphoteric or mixtures thereof. They also contain about 0.1 to about 5, preferably about 0.2-3.0, most preferably about 0.2 to about 1.5 weight percent of polymeric soil release agent. Gemini/polymer synergy enhances soil release and general detergency boosting benefits, and improves suspending/stabilizing properties of the polymeric suspending agents.

Other optional ingredients for liquid detergents include liquid carriers and adjuvants as disclosed by U.S. Pat. No. 5,402,542 to Trinh et al. which is incorporated herein by reference in its entirety.

The liquid carrier is preferably selected from the group consisting of water and mixtures of the water and short chain C

1

-C

4

monohydric alcohols. The water used can be distilled, deionized, or tap water. Mixtures of water and up to about 15% of a short chain alcohol such as ethanol, propanol, isopropanol or butanol, and mixtures thereof, are useful as the carrier liquid.

Adjuvants can be added to the softener compositions for their known purposes. Such adjuvants include, but are not limited to, clays, viscosity control agents, perfumes, emulsifiers, preservatives, anti-foaming agents, antioxidants, bactericides, fingicides, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, and agents to provide ease of ironing. These adjuvants, if used, are added at their usual levels, generally each of up to about 5% by active weight of the composition.

The fabric softener compositions can be prepared by conventional methods such as those disclosed in U.S. Pat. No. 5,405,542 to Trinh et al.

The present invention is further illustrated by the following non-limiting examples.

EXAMPLES

To explore the benefits of employing the cationic gemini surfactants together with conventional surfactants and soil release polymers, the following examples were run. Tables in the present specification list the resulting data. In the examples, the TERG-O-TOMETER, which is a laboratory scale apparatus designed to simulate the washing process under controlled conditions, was used to evaluate soil release performance. It is manufactured by United Testing Company of Hoboken, N.J.

The soil release test procedure of these examples involved a prewash cycle (cloths repeatedly being washed before staining). Clean fabrics, two DACRON single knit (DSK), two DACRON double knit (DDK) and two DACRON/cotton blend (D65/C35) from Scientific Services, or two pieces of cotton fabric, were prewashed for 12 minutes at 120° F., with 150 ppm (2/1 Ca++/Mg++) water hardness and cold water rinse.

After drying for 45 minutes on a “high” dryer setting, swatches were stained with three drops of dirty motor oil. Swatches were allowed to wick overnight. The stained swatches were washed once under the same prewash conditions. The same formulas used in the prewash were used in the final wash.

Evaluation was performed by making the following measurements:

Rd

1

=Average reflectance of prewashed fabric

Rd

2

=Average reflectance of wicked cloth

Rd

3

=Average reflectance of cleaned cloth

Then % soil removed scores listed on the Tables for the examples was calculated as follows:

% soil removal=((

Rd

3

−Rd

2

)/(

Rd

1

−Rd

2

))×100%.

It is noted that in all the examples, all like ingredient abbreviations or designations indicate like ingredients.

Examples 1-3 and Comparative Examples 1-3

Compositions of the present invention were tested for effectiveness by measuring reflectance. A higher reflectance number means a cleaner fabric. According to the above test procedure, samples of the fabric were each washed five (5) times at 120° F. for 12 minutes. Detergent concentration was used at 1 gm. per liter which is usually the recommended commercial use level. Dirty motor oil was then added to the fabric and the fabric was allowed to wick overnight. Afterwards, the oily fabric was washed once in a washing solution having the same composition used previously (in the prewash) and the fabric's reflectance was measured using Spectrogard equipment, common in the industry and available from BYK-Gardner.

In these Examples 1-3 and Comparative Examples 1-3, the base detergent is an anionic detergent having an all anionic surfactant package except for Neodol 25-9 (1.3%). The composition is listed in TABLE A. These examples and comparative examples all employ 1 active weight percent REPEL-O-TEX SRP3 polymeric soil release polymer. This SRP is composed of 50% VELVETOL 251C (polymer having a molecular weight range of 3,000-10,000) and 50% sodium sulfate.

TABLE A

Ingredients of Anionic

Detergent Base A

Weight %

LAS

1

6.0%

PS-603

2

6.6

NEODOL 25-9

3

1.3

Na-Sulfate

4

8.3

LSB

5

8.1

Na-Carbonate

9

30.0

Silicate

7

1.2

Zeolite

8

29.3

Perborate

9

0.6

Water

10

2.3

Additives

11

QS

Notes:

1

Linear alkyl benzene sulfonate

2

Linear ether sulfate-12-15 C's chain, 3EO

3

Linear alcohol ethoxylate, 12-15 C's

4

Sodium sulfate

5

Sodium lauryl sulfate

6

Sodium carbonate

7

Sodium silicate

8

Builder Zeolite A

9

Bleach

10

Deionized

11

Additives

The amount of the gemini surfactant is listed as active weight percent employed. The soil release polymer, gemini surfactants, etc., were formulated as detergent compositions with Base A above. In the following tables, SRP is the abbreviation for soil release polymer, DK means double knit, SK means single knit and cotton/poly refers to cotton/polyester fabrics. The numbers given for the respective detergent formulations and clothing material represent the percentages of soil removed from the clothing. The higher the number, the greater the degree of soil removed from the fabric indicating the greater amount of soil release polymer deposited thereon. The washing conditions at which the formulations were tested are also given. Pre-wash refers to washing the fabric before staining so that the copolymer is deposited on the fabric. 5×, 8× etc., means the number of times the fabric was pre-washed.

Example 1

Soil Removal: Detergent Base A+SRP3 w/quaternary Cationic Geminis

Washing Conditions:

150 ppm Water

Temp 100° F.

% based on active

TABLE 1

5x Pre-Wash

Dacron/

Dacron/

Cotton/

Sample

DK

SK

Poly

Base A + 1.0% SRP3 + 1.5% ethylene bis-

−2

82

37.5

(methyl laurimidazoline)dimethosulfate

Base A + 1.0% SRP3 + 1.5% conventional

2.1

7

2

non-gemini amphoteric surfactant

Base A + SRP3

2.0

8.0

9.0

Example 2

Soil Removal: Gemini Surfactants (Linear Alcohol Ethoxylates) w/SRP3 in Detergent Base A (15%)

Washing Conditions:

150 ppm Water

Temp 120° F.

% based on active

TABLE 2

5x Pre-Wash

Dacron/

Dacron/

Cotton/

Sample

DK

SK

Poly

1% SRP3 + 1% Methyldodecyl-bis[3-

39.5

81

50

(dimethyldodecylammonio)propyl]-

ammonium tribromide

Base A + SRP3

2.0

8.0

9.0

Example 3

Soil Removal: Linear Alcohol Ethoxylates and Trimeric Gemini Surfactants @ Lower Temp. (100° F.) in Detergent Base A

Washing Conditions:

150 ppm Water

Temp 100° F.

% based on active

TABLE 3

8x Pre-Wash

Dacron/

Dacron/

Cotton/

Sample

DK

SK

Poly

1% SRP3 + 1% Hexanediyl-1,6-

39.5

91.5

48

bis(dodecyldimethylammonium bromide)

Base A + SRP3

2.0

8.0

9.0

Examples 1-3 are summarized as Table 1 and the respective soil release polymer and gemini surfactants were formulated with the other ingredients as set forth above. The numbers given are the percentages of the soil removed from the various articles of clothing. The washing conditions for each example are given.

As can be seen from the high levels of soil release that were achieved, the combination of the gemini surfactants or the multiple hydrophilic/hydrophobic chain surfactants with the soil release polymer and conventional surfactant provides superior soil release properties that surprisingly and unexpectedly enhances the cleaning efficacy of these compositions at different washing conditions when compared to the known laundry detergents of the prior art. In other words, the data clearly shows that the addition of the cationic or amphoteric gemini surfactant as well as the multiple hydrophilic/hydrophobic chain surfactants dramatically increase the deposition and effectiveness of the soil release polymer on the fabric and hence results in cleaner clothes.

Although the subject matter has been described with respect to the preferred embodiments, it will be readily apparent to those having ordinary skill in the art to which the invention pertains that changes and modifications may be made thereto without departing from the spirit or scope of the present invention as defined by the following claims.

Number	Name	Date	Kind
3416952	McIntyre et al.	Dec 1968	A
3712873	Zenk	Jan 1973	A
3893929	Basadur	Jul 1975	A
3959230	Hays	May 1976	A
3962152	Nicol et al.	Jun 1976	A
4116885	Derstadt et al.	Sep 1978	A
4132680	Nicol	Jan 1979	A
4201824	Violland et al.	May 1980	A
4349688	Sandler	Sep 1982	A
4423557	Westelaken	Jan 1984	A
4661267	Dekker et al.	Apr 1987	A
5643498	Li et al.	Jul 1997	A

Surfactant compositions with enhanced soil release properties containing a cationic gemini surfactant

Information

Patent Number

Date Filed

Date Issued

Inventors

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

US Referenced Citations (12)

Non-Patent Literature Citations (5)

Entry
R. Zana et al., “Micellization of Two Triquaternary Ammonium Surfactants in Aqueous Solution”; Langmuir. Jul. 5, 1995.
R. Zana et al., “Alkanediyl-A,W-bis(dimethylalkylammonium bromide) Surfactants. 1. Effect of the Spacer Chain Length on the Critical Micelle Concentration and Micelle Ionization Degree”; Langmuir (1991); 7, 1072-1075.
M. Rosen et al., “Gemini Surfactants”, Journal of Surfactants and Detergents, vol. 1, No. 4 (Oct. 1998), pp. 547-554.
M. Rosen, “Geminis: A New Generation of Surfactants”; Chemtech, Mar. 1993, pp. 30-33.
F. M. Menger et al., “Gemini Surfactants: A New Class of Self-Assembling Molecules”; J. American Chemical Soc., 115, pp. 10083-10090 (1993).