WO1998023720A1

WO1998023720A1 - Laundry detergent compositions containing a combination of surfactants and optical brighteners

Info

Publication number: WO1998023720A1
Application number: PCT/US1997/021886
Authority: WO
Inventors: Ricardo Alfredo Prada-Silvy; Luisa Navarro-Cerda; Ronny Jose Soto
Original assignee: The Procter & Gamble Company
Priority date: 1996-11-26
Filing date: 1997-11-20
Publication date: 1998-06-04
Also published as: ZA9710511B; MA24406A1; AR003911A1

Abstract

A laundry detergent composition, preferably in granular form, comprising 5 % to about 40 % detergent surfactant consisting of a primary anionic surfactant selected from alkylbenzene sulfonate, alkyl sulfate, and mixtures thereof, and an alkyl ethoxy sulfate surfactant having an average of from about 1 to about 9 moles ethoxy per mole surfactant, the ratio of primary anionic surfactant to alkyl ethoxy sulfate surfactant being within the range of from about 38:1 to about 4:1, and optical brightener selected from triazinylaminostilbenes and distyrylbiphenyls, wherein the weight ratio of primary anionic surfactant plus alkyl ethoxy sulfate surfactant to optical brightener is about 50:1 and above. The composition optionally comprises an hydroxyalkyl quaternary ammonium cationic surfactant and an alkyl ethoxy alcohol surfactant. The composition provides improved brightener performance.

Description

LAUNDRY DETERGENT COMPOSITIONS CONTAINING A COMBINATION OF SURFACTANTS AND OPTICAL BRIGHTENERS

TECHNICAL FIELD

The subject invention involves laundry detergent compositions containing a certain mixture of surfactants, and an optical brightener.

BACKGROUND OF THE INVENTION

Throughout the world, many people clean fabrics by washing with compositions containing soap and/or detergent. An essential ingredient in such laundry detergents is a detergent surfactant, and in particular an anionic surfactant. Preferred anionic surfactants are the alkyl benzene sulfonates and alkyl sulfates, which provide very effective soil removal.

Another important laundry detergent ingredient is an optical brightener. The optical brightener deposits onto the clothes during the laundering process, thereby providing to the fabric an aesthetically preferred bluish bue, which can be perceived by the consumer to have made the clothes, particularly white clothes and fabrics, whiter and brighter.

It is known that there is an interaction between anionic surfactants and optical brighteners, whereby at high levels of anionic surfactant, the brightening benefit by the incremental addition of optical brightener levels off at higher concentrations in the laundry process. In typical phosphated laundry detergent compositions designed to provide a high level of suds and cleaning, and having an anionic surfactant level of about 20% by weight of the composition, the brightening benefit delivered by optical brightener levels off at about 0.1% by weight. Therefore, there remains a need to provide further improvement in the performance of optical brighteners in such high suds detergent compositions, at higher brightener usage levels.

It is an object of the subject invention to provide detergent laundry compositions which provide superior cleaning performance in laundry operations, and more particularly improved brightener performance in high suds detergent compositions.

SUMMARY OF THE INVENTION

The subject invention involves laundry detergent compositions, preferably in granular form, comprising: a) from about 5% to about 40% detergent surfactant, the detergent surfactant comprising: 1) from about 60% to about 97% of a primary anionic surfactant selected from alkylbenzene sulfonate, alkyl sulfate, and mixtures thereof;

2) from about 2.5% to about 18% alkyl ethoxy sulfate surfactant having an average of from about 1 to about 9 moles ethoxy per mole surfactant, the ratio of primary anionic surfactant to alkyl ethoxy sulfate surfactant being within the range of from about 38:1 to about 4:1 ;

3) from 0% to about 10% hydroxyalkyl quaternary ammonium cationic surfactant having the structure:

R R'_nR"_mN⁺ Z-, wherein R is long-chain alkyl, R' is short-chain alkyl, R" is hydroxyethyl or hydroxypropyl, n is 1 or 2, m is 1 or 2, n + m is 3, and Z" is an anion, the ratio of primary anionic surfactant to cationic surfactant being greater than about 6:1; and

4) from 0% to about 15% alkyl ethoxy alcohol surfactant having an average of from about 1 to about 10 moles ethoxy per mole surfactant, the ratio of primary anionic surfactant to alkyl ethoxy alcohol surfactant being greater than about 4.5:1 ; b) from about 0.05% to about 0.5% optical brightener selected from tnazinylaminostilbenes and distyrylbiphenyls, wherein the weight ratio of primary anionic surfactant plus alkyl ethoxy sulfate surfactant to optical brightener is about 50:1 and above; and c) from about 60% to about 95% other components.

DETAILED DESCRIPTION OF THE INVENTION All percentages used herein are weight percent unless otherwise specified. As used herein, the term "alkyl" means a hydrocarbyl moiety which is straight (linear) or branched, saturated or unsaturated. Unless otherwise specified, alkyl are preferably saturated ("alkanyl") or unsaturated with double bonds ("alkenyl"), preferably with one or two double bonds. As used herein "long-chain alkyl" means alkyl having about 8 or more carbon atoms, and "short-chain alkyl" means alkyl having about 3 or fewer carbon atoms.

The term "tallow" is used herein in connection with materials having alkyl mixtures derived from fatty acid mixtures from tallow which typically are linear and have an approximate carbon chain length distribution of 2% C14, 29% C-| Q, 23% C<\ Q, 2% palmitoleic, 41% oleic, and 3% linoleic (the first three listed being saturated). Other mixtures with similar alkyl distribution, such as those from palm oil and those derived from various animal tallows and lard, are also included within the term tallow. The tallow, as used herein, can also be hardened (i.e, hydrogenated) to convert part or all of the unsaturated alkyl moieties to saturated alkyl moieties.

The term "coconut" is used herein in connection with materials having alkyl mixtures derived from fatty acid mixtures from coconut oil which typically are linear and have an approximate carbon chain length distribution of about 8% Cβ, 7% C-|Q. 48% C-|2_> 17% C<|4, 9% Ci6. 2% C-|8. 7% oleic, and 2% linoleic (the first six listed being saturated). Other mixtures with similar alkyl distribution, such as palm kernel oil and babassu oil, are included within the term coconut.

Compositions of the subject invention are preferably in solid, granular form, although other forms of laundry detergents are also included.

The present inventors have found that the use of low levels of alkyl ethoxy sulfate surfactant in combination with the primary anionic surfactant can improve the performance of optical brightener in the subject laundry detergent compositions, particular at higher concentrations of the brightener. Without being bound by any particular theory, it is believed that the alkylbenzene sulfonate and alkyl sulfate surfactants have a potential interaction with the optical brightener which suppresses the brightener performance response at incrementally higher levels of optical brightener. The effect of this interaction is believed to be less deposition of the brightener on the fabric. It is believed that the alkyl ethoxy sulfate forms micelles with these primary anionic surfactants, thereby interfering with the tendency of the primary anionic surfactant to hold back brightener deposition, allowing more of the optical brightener to deposit onto clothes, and resulting in an increase in optical brightener performance response at the incrementally higher levels of optical brightener.

Detergent Surfactants

Compositions of the subject invention comprise from about 5% to about 40% detergent surfactant, preferably from about 10% to about 35% detergent surfactant, more preferably from about 15% to about 30% detergent surfactant, more preferably still from about 20% to about 25% detergent surfactant.

As used herein, "alkylbenzene sulfonate surfactant" or "alkylbenzene sulfonate" means a salt of alkylbenzene sulfonic acid with an alkyl portion which is linear or branched, preferably having from about 8 to about 18 carbon atoms, more preferably from about 9 tc about 16 carbon atoms. The alkyl of the alkylbenzene sulfonic acid preferably has an average chain length of from about 10 to about 14 carbon atoms, more preferably from about 11 to about 13 carbon atoms. The alkyl is preferably saturated. Branched or mixed branched and linear alkylbenzene sulfonate is known as ABS. Linear alkylbenzene sulfonate, known as LAS, is more biodegradable than ABS, and is preferred for the subject invention compositions. The acid forms of ABS and LAS are referred to herein as HABS and HLAS, respectively.

The salts of the alkylbenzene sulfonic acids are preferably the alkali metal salts, such as sodium and potassium, especially sodium. Salts of the alkylbenzene sulfonic acids also include ammonium.

A particularly preferred LAS surfactant has saturated linear alkyl with an average of 11.5 to 12.5 carbon atoms, and is a sodium salt (C-_j -| 5_<_|2.5LAS-Na).

Alkylbenzene sulfonates and processes for making them are disclosed in U.S. Patent Nos. 2,220,099 and 2,477,383, incorporated herein by reference.

As used herein, "alkyl sulfate" (AS) includes the salt of alkyl sulfuric acid, preferably having carbon chain lengths in the range of from about C-J Q to about C20- Alkyl sulfate having chain lengths from about 12 to about 18 carbon atoms is preferred. AS surfactant preferably has an average chain length from about 12 to about 14 carbon atoms. Especially preferred is the alkyl sulfate made by sulfating primary alcohol derived from coconut or tallow, or mixtures thereof.

Salts of alkyl sulfates include sodium, potassium, lithium, ammonium, and alkylammonium salts. Preferred salts of alkyl sulfates are sodium and potassium salts, especially sodium salts.

The detergent surfactant system of the subject compositions comprises from about 60% to about 97%, preferably from about 70% to about 95%, more preferably from about 80% to about 92%, a primary anionic surfactant selected from alkylbenzene sulfonate, alkyl sulfate, and mixtures thereof.

A preferred primary anionic surfactant contains alkyl benzene sulfonate and alkyl sulfate surfactants at a weight ratio of alkylbenzene sulfonate to alkyl sulfate surfactant of at least about 1 :1 , more preferably at least about 2:1 , more preferably still at least about 4:1. The primary anionic surfactant can be all alkylbenzene sulfonate.

The alkyl ethoxy sulfate (AES) surfactant useful in the subject invention compositions has the following structure: R'"O(C2H4O)_xSO3M.

In the above structure, R'" is alkyl of from about 10 to about 20 carbon atoms. On average, R"' is from about 11 to about 18, preferably from about 12 to about 15, carbon atoms. R"' is preferably saturated. R'" is preferably linear.

In the above structure, x represents the "degree of ethoxylation" (number of ethoxy moieties per molecule) which can have a broad distribution for the AES surfactant of the subject composition. This is because, when a raw material alkyl alcohol is ethoxylated with ethylene oxide to form the alkyl ethoxy (prior to sulfation), a broad distribution of the number of ethoxy moieties per molecule results. In the above structure, x is on average from about 1 to about 9, preferably from about 1 to about 7, more preferably from about 2 to about 5, especially about 3.

In the above structure, M is a water-soluble cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium), an alkaline earth metal cation (e.g., calcium, magnesium), ammonium or substituted-ammonium cation. M is preferably sodium or potassium, especially sodium.

The AES surfactant is typically obtained by sulfating alkyl ethoxy alcohols with gaseous SO3 in a falling film reactor, followed by neutralization with NaOH, as is well known in the art.

The detergent surfactant system of the subject compositions comprises from about 2.5% to about 18% AES surfactant, preferably from about 2.5% to about 12%, and more preferably from about 4% to about 8%.

In the subject development compositions, the weight ratio of primary anionic surfactant to alkyl ethoxy sulfate surfactant is within the range of from about 38:1 to about 4:1 , preferably from about 28:1 to about 6:1 , more preferably from about 22:1 to about 10:1 , more preferably still from about 19:1 to about 11 :1.

An hydroxyalkyl quaternary ammonium (HAQA) cationic surfactant useful in the subject invention compositions has the following structure: R R'_nR"_mN⁺ Z". R is a long-chain alkyl, linear or branched, having from about 8 to about 18, preferably from about 9 to about 16, carbon atoms. R preferably has an average of from about 10 to about 15, more preferably from about 12 to about 14, carbon atoms. R is preferably saturated. R is preferably linear. R' is a short-chain alkyl having from 1 to about 3 carbon atoms; R' is preferably methyl or ethyl, especially methyl. R" is hydroxyethyl or hydroxypropyl, preferably hydroxyethyl. n is 1 or 2, preferably 2. m is 1 or 2, preferably 1. n + m is 3. Z" is a water soluble anion, such as halide, sulfate, methyisulfate, ethylsulfate, phosphate, hydroxide, fatty acid (laurate, myristate, palmitate, oleate, or stearate), or nitrate anion. Preferably Z^" is chloride, bromide or iodide, especially chloride.

The compositions comprises from 0% to about 10% of the HAQA surfactants, preferably from about 2.5% to about 5.5% of the HAQA surfactants, more preferably from about 2.7% to about 4.5%, more preferably still from about 2.8% to about 4.0%, still more preferably from about 2.9% to about 3.5%. The weight ratio of primary anionic surfactant to HAQA surfactants is greater than about 6:1, preferably within the range of from about 38:1 to about 16:1, more preferably from about 35:1 to about 20:1, more preferably still from about 30:1 to about 25:1.

The alkyl ethoxy alcohol (AE) surfactant useful in the subject invention compositions is ethoxylated fatty alcohols. This surfactant has an alkyl of from about 10 to about 20 carbon atoms. On average, the alkyl is from about 11 to about 18, preferably from about 12 to about 15 carbon atoms. The alkyl is preferably saturated. The alkyl is preferably linear.

The alkyl ethoxy alcohol surfactant has a "degree of ethoxylation" (number of ethoxy moieties per molecule) which can have a broad distribution because, when a raw material alkyl alcohol is ethoxylated with ethylene oxide, a broad distribution of the number of ethoxy moieties per molecule results. For the AE surfactant, the degree of ethoxylation is, on average, from about 1 to about 10, preferably from about 3 to about 9, more preferably from about 5 to about 8, especially about 6.5 -7.

The surfactant system of the subject compositions comprises from 0% to about 15% alkyl ethoxy alcohol surfactant, preferably from about 1% to about 8%, more preferably from about 1.5% to about 4%, more preferably still from about 2% to about 3%.

In the subject development compositions, the weight ratio of primary anionic surfactant to alkyl ethoxy alcohol surfactant is greater than about 4.5:1, preferably from about 60:1 to about 10:1, more preferably from about 50:1 to about 20:1, more preferably still from about 45:1 to about 30:1.

The surfactant system of the subject compositions preferably includes only, or substantially only, the surfactants disclosed herein above, such that the surfactant system of the subject compositions consists of, or consists essentially of, alkylbenzene sulfonate and alkyl sulfate surfactant (more preferably alkylbenzene sulfonate surfactant), AES surfactants, optionally but preferably HAQA surfactant, and optionally AE surfactant.

Optical Brighteners

Optical brightener is the other essential ingredient in the present detergent composition. In general, any optical brightener or other brightening or whitening agent known in the art can be incorporated into the subject detergent composition. Such brighteners are disclosed in The Product and Application of Fluorescent Brightening Agents. M. Zahradnik, published by John Wiley & Sons, New York (1982); and in Ullmann's Encyclopedia of Industrial Chemistry. "Optical Brighteners", A.E. Siegrist, C. Eckhardt, J. Kaschig, E. Schmidt, Vol. A18, published by VCH Publishers, New York (1991), pp. 153-176. Optical brighteners can be classified into subgroups, which include, but are not necessarily limited to, carbocycles, such as distyrylbenzenes, distyrylbiphenyls, and divinylstilbenes; triazinylaminostilbenes; stilbenyl-2H-triazoles, such as stilbenyl-2H- naphthol[1 ,2-d]triazoles and bis(1,2,3-triazol-2-yl)stilbenes; benzoxazoles, such as stilbenyl benzoxazoles and bis(benzoxazoles); furans, benzofurans and benzimidazoles, such as bis(benzo[b]furan-2-yl)biphenyls and cationic benzimidizoles; 1,3-diphenyl-2-pyrazolines; coumarins; naphthalimides; 1,3,5-triazin-2-yl derivatives; methinecyanines; and dibenzothiphene-5,5-dioxide. Anionic brighteners are preferred, and are often sulfonated forms of such compounds.

Preferred optical brighteners useful in the subject invention compositions are bis-(triazinylamino)stilbenes, preferably sulfonated 4,4'-bis((1,3,5-triazin-2- yl)amino)stilbenes, particularly those having the structure:

In the above structure, R-| is substituted amino, preferably selected from anilino, p-sulfoanilino, N-2-hydroxyethyl and NH-2-hydroxyethyl; R-_| is more preferably anilino; R2 is preferably selected from chloro, hydroxy, amino and substituted amino; more preferably R2 is mono- or disubstituted amino (e.g., methylamino, N-2- bis(hydroxyethyl)amino, N-2-hydroxyethyl-N-methylamino, NH-2-methoxyethyl, anilino, morphilino); and M is H or a salt-forming cation such as sodium or potassium, preferably sodium. The trans form of the above structure is preferred.

When in the above structure, R-| is anilino, R2 is N-2-bis(hydroxyethyl)amino, and M is sodium, the brightener is 4,4'-bis((4-anilino-6-bis(2-hydroxyethyl)amino-1,3,5- triazin-2-yl)amino)stilbene-2,2'-disulfonic acid disodium salt. This particular brightener is a preferred species and is commercially marketed under the tradename TINOPAL UNPAO by Ciba-Geigy.

When in the above structure, R<| is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is sodium, the brightener is 4,4'-bis((4-anilino-6-(2-hydroxyethyl, methylamino)-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonic acid disodium salt. This particular brightener is a preferred species and is commercially marketed under the tradename TINOPAL 5BM® by Ciba-Geigy.

When in the above structure, R-j is anilino, R2 is morphilino and M is sodium, the brightener is 4,4'-bis((4-anilino-6-morphilino-1,3,5-triazin-2-yl)amino)stilbene-2,2'- disulfonic acid disodium salt. This particular brightener is a highly preferred species and is commercially marketed under the tradename TINOPAL AMS® by Ciba-Geigy.

Other commercial brighteners with the above structure include TINOPAL DCS® where R-j is p-sulfoanilino and R2 is N-2-bis(hydroxyethyl)amino (tetrasodium salt), TINOPAL LCS® where R-j is anilino and R2 is N-2-methoxyethylamino, TINOPAL TAS® where R-| and R2 are both anilino, and BLANKOPHOR HRS® (Miles) where R-_j is anilino and R2 is methylamino.

Preferred optical brighteners useful in the subject invention compositions are distyrylbiphenyls, preferably sulfonated 4,4'-bis(styryl)bisphenyls, particularly those having the structure:

In the above structure, M is H or a salt-forming cation such as sodium or potassium, preferably sodium. The ethenyl groups are preferably in trans configuration.

When in the above structure, M is sodium, the brightener is 4,4'-bis(2- sulfostyryl)biphenyl disodium salt. This particular brightener is a highly preferred species and is commercially marketed under the tradename TINOPAL CBS® by Ciba- Geigy.

In the subject invention compositions, principal optical brighteners selected from triazinylaminostilbenes, distyrylbiphenyls and mixtures thereof, particularly the preferred bis(triazinylamino)stilbene and bis(styryl)biphenyl brighteners above, are included in the compositions at levels of from about 0.1% to about 0.5%, preferably from about 0.14% to about 0.4%, more preferably from about 0.16% to about 0.34%. For the bis(triazinylamino)stilbenes, more preferred levels are from about 0.22% to about 0.32%. For the bis(styryl)biphenyls, more preferred levels are from about 0.18% to about 0.24%. For mixture of brighteners in the subject compositions, such mixtures are preferably from about 20% to about 80%, more preferably from about 30% to about 70%, bis(triazinylamino)stilbenes, and from about 80% to about 20%, more preferably from about 70% to about 30%, bis(styryl)biphenyls.

The present invention is effective wherein the weight ratio of primary anionic surfactant plus alkyl ethoxy sulfate to the principal optical brightener is about 50:1 and above, preferably about 60:1 and above, more preferably from about 80:1 to 200:1 , and even more preferably from about 90:1 to about 120:1.

Other optical brighteners which are optionally also included, but preferably not included, in the subject compositions include PHORWHITE® brighteners from Verona, other TINOPAL® brighteners from Ciba-Geigy, other BLANKOPHOR® brighteners from Miles, and ARTIC WHITE brighteners from Hilton-Davis. Particular brighteners include 2-(4-styrylphenyl)-2H-naphtho[1 ,2-d]triazoles; 4,4'-bis-(1 ,2,3-triazol-2-yl)stilbenes; and aminocoumarins. Specific examples include 4-methyl-7-diethylamino coumarin; 1 ,2- bis(benzimidazol-2-yl)ethylene; 1 ,3-diphenylphrazolines; 2,5-bis(benzoxazol-2- yl)thiophene; 2-stryl-naphtho[1 ,2-d]oxazole; 2-(4-styryl-3-sulfophenyl)-2H-naphtho[1 ,2- djtriazole; and 2-(stilben-4-yl)-2H-naphtho[1 ,2-d]triazole.

Such other optical brighteners, or mixtures thereof, can be included at levels by weight in the compositions from 0% (preferred) to about 1%, also from about 0.01% to about 0.5%, also from about 0.03% to about 0.3%.

Other Components

The compositions of the subject invention comprise from about 60% to about 95%, preferably from about 65% to about 90%, more preferably from about 70% to about 85%, more preferably still from about 75% to about 80%, other components commonly used in laundry detergent products. A typical listing of the classes and species of other surfactants, builders and other ingredients that may be included in the subject compositions appears in U.S. Patent No. 3,664,961 , issued to Norris on May 23, 1972, incorporated herein by reference, and EP 550,652, published on April 16, 1992. The following are representative of such materials, but are not intended to be limiting. Detergent Builders

The compositions of the subject invention preferably comprise detergent builders which assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1 % builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

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), and aluminosilicates. Non-phosphate builders are required in some locales. Importantly, the subject compositions 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, or with low levels of P-containing builders.

In situations where phosphorus-based builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates (STPP), 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; 3,213,030, 3,422,021 ; 3,400,148 and 3,422,137) can also be used.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range of about 1.6:1 to about 3.2:1 , preferably about 1.6:1 ; and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to Rieck. 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 alkali metal carbonates and bicarbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973. Preferred is sodium carbonate.

Aluminosilicate builders are useful in the subject compositions. Aluminosilicate builders are of great importance in many currently marketed granular detergent compositions. Aluminosilicate builders include those having the empirical formula: M_z(zAIO2)y VH2O 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 v 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, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2((^A'°2)l2(Siθ2)i2)"^vH2⁰ wherein v is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (v = about 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns rn diameter.

Organic detergent builders suitable for the subject compositions 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 builders can generally be added to the compositions in acid form, but can also be added in the form of neutralized salts. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders available from renewable resources and are biodegradable. Citrates can be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also useful in such compositions and combinations.

Also suitable in the subject detergent compositions are the 3,3-dicarboxy-4-oxa- 1 ,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkanyl 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 preferred builders of this group, and are described in European Patent Application 200 263, 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 Diehl U.S. Patent 3,723,322.

Fatty acids, e.g., C<|2^_C 8 monocarboxylic acids, can also be incoφorated 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.

The compositions of the subject invention comprise from 0% to about 70% builders, preferably from about 10% to about 50%, more preferably from about 13% to about 40%, more preferably from about 20% to about 35%. The compositions preferably comprise from about 5% to about 40%, more preferably from about 7% to about 30% of builders other than carbonates (including bicarbonates) and silicates (excluding zeolites), preferably selected from inorganic phosphate and zeolite builders (more preferably from inorganic phosphate builders), more preferably from about 10% to about 20%, more preferably still from about 12% to about 16%; STPP is preferred among such builders.

The subject compositions also preferably comprise from about 5% to about 19% sodium carbonate, more preferably from about 7% to about 15%, more preferably still from about 8% to about 12%. The subject compositions also preferably comprise from about 5% to about 12% silicates, more preferably from about 6% to about 10%, more preferably still from about 7% to about 8%. Chelating Agents

The subject detergent compositions may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelating agents and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. These agents are also useful in stabilizing bleaching components of the subject compositions.

Amino carboxylates useful as optional chelating agents include ethylenediamine tetracetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexacetates, diethylenetriamine pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the subject compositions, when at least low levels of total phosphorus are permitted in detergent compositions. Preferably, these amino phosphonates do not contain alkanyl or alkenyl groups with more than about 6 carbon atoms. Preferred amino phosphonates are diethylenetriamine penta(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof. Particularly preferred are sodium, zinc, magnesium, and aluminum salts and complexes thereof, and mixtures thereof. Preferably such salts or complexes have a molar ratio of metal ion to chelant molecule of at least about 1 :1 , preferably at least about 2:1.

Such chelants can be included in the subject compositions at a level up to about 5%, preferably from about 0.1% to about 2%, more preferably from about 0.2% to about 1.5%, more preferably still from about 0.5% to about 1%. Polymeric Dispersing Agents The subject compositions preferably comprise polymeric dispersing agents. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates of monomeric segments, containing no carboxylate radicals such as vinyimethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to about 10,000, more preferably from about 4,000 to about 7,000 and most preferably from about 4,000 to about 5,000. Water- soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to about 100,000, more preferably from about 5,000 to about 75,000, most preferably from about 7,000 to about 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to about 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application 066915, published December 15, 1982, as well as in EP 193 360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193 360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal- antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1 ,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have an average molecular weight of about 10,000.

Another type of preferred antiredeposition agent includes the carboxymethylcellulose (CMC) materials. There materials are well-known in the art.

The above polymeric dispersing agents, if included, are typically at levels up to about 5%, preferably from about 0.2% to about 2.5%, more preferably from about 0.5% to about 1.5%. Polyacrylate and acrylic/maleic copolymer dispersing agents are preferably included in the subject compositions at a level of from about 0.3% to about 2%, more preferably from about 0.5% to about 1.5%. A CMC-type dispersing agent is preferably included in the subject compositions at a level of from about 0.1% to about 1.5%, more preferably from about 0.2% to about 1%.

A preferred ingredient in the subject compositions is a soil dispersing agent which is a water soluble or dispersible alkoxylated polyalkyleneamine material. Such material can be included in the subject compositions at a level up to about 1%, preferably from about 0.1% to about 0.8%, more preferably from about 0.3% to about 0.5%.

The alkoxylated polyalkyleneamine material has a polyalkyleneamine backbone of amine units having the general formula:

(H₂N-Rl-)_q+1 (-NH-Rl-)_r (>N-Rl-)_q (-NH₂) wherein:

(i) each (H₂N-R¹-) unit is bonded to (-NH-R¹-) or (>N-R¹-);

(ii) each (-NH-R¹-) unit is bonded to any two units, provided that each is bonded to no more than one of (H2N-R¹-) and (-NH2); (iii) each (>N-R^-) unit is bonded to any three units, provided that each is bonded to no more than two of (H2N-R¹-) and (-NH2); (vii) the (-NH2) is bonded to (-NH-R¹-) or (>N-R1-); provided that each bond described in (i), (ii), (iii) and (iv) is between N of one unit and R1 of another unit.

In the above general formula, q is on average from 0 to about 250, preferably from about 1 to about 100, more preferably from about 3 to about 40, more preferably still from about 5 to about 25, still more preferably from about 7 to about 15.

In the above general formula, r is on average from about 3 to about 700, preferably from about 4 to about 200, more preferably from about 6 to about 80, more preferably still from about 8 to about 50, still more preferably from about 15 to about 30.

In the above general formula, the ratio q:r is preferably from 0 to about 1:4, more preferably from about 1:1.5 to about 1:2.5, more preferably still about 1:2.

In the above general formula, R^ is linear alkanylene having from 2 to about 12 carbon atoms, preferably from 2 to about 4 carbon atoms. For preferred polyalkyleneamine backbones, less than about 50% of the R^ moieties have more than 3 carbon atoms, more preferably less than about 25% R1 moieties have more than 3 carbon atoms, more preferably still less than about 10% R^ moieties have more than 3 carbon atoms. More preferred R^"1 is selected from ethylene, 1,2-propylene, 1,3- propylene, and mixtures thereof. For most preferred backbones, substantially all R^ units are the same. Most preferred R^ is ethylene.

The polyalkyleneamine backbone described above has a molecular weight of at least about 180 daltons, preferably has a molecular weight of from about 600 to about 5000 daltons, more preferably has a molecular weight of from about 1000 to about 2500 daltons.

On the above polyalkyleneamine backbone, from about 50% to about 100% of the hydrogens bonded to the nitrogens are substituted; preferably from about 90% to about 100% of the hydrogens bonded to the nitrogens are substituted; more preferably substantially all of the hydrogens bonded to the nitrogens are substituted.

Substituents for the hydrogens bonded to the nitrogens are poly(alkyleneoxy) units having the formula

In the above formula, R³ is alkanylene having from 2 to about 6 carbon atoms, preferably from 2 to about 4 carbon atoms. R³ is preferably selected from ethylene, 1 ,2-propylene, and mixtures thereof. More preferably R³ is ethylene.

In the above formula, R² is selected from hydrogen, alkanyl having from 1 to about 4 carbon atoms, and mixtures thereof. Preferably R² is hydrogen. ln the above formula, p is on average from about 1 to about 50, preferably from about 3 to about 10. In general, p preferably increases with increasing molecular weight of the polyalkyleneamine backbone.

Those skilled in the art of alkoxylation of polyalkyleneamines recognize that the "degree of ethoxylation" is defined as the average number of alkoxylations per nitrogen atom substituent site and may be expressed as a fractional number. A polyalkyleneamine may have a degree of ethoxylation equal to 1 or greater and still have less than 100% of the polyalkyleneamine backbone nitrogen substituent sites substituted.

The relative proportion of primary, secondary, and tertiary amine units in the polyalkyleneamine backbone will vary, depending on the manner of preparation of the backbone.

Preferred "polyalkyleneamine backbones" herein include both polyalkyleneamines (PAA's) and polyalkyleneimines (PAI's); preferred backbones are polyethyleneamine (PEA's) and polyethyleneimines (PEI's).

PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. Common PEA's include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and tetrabutylenepentamine. Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not readily separate by distillation and can include other materials such as cyclic amines and 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, incorporated herein by reference, which describes the preparation of PEA's.

The PEI's include the preferred polyalkyleneamine backbones useful herein. They can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfate, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEI's 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 al., 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 (all herein incorporated by reference). In addition to the linear and branched PEI's, the compounds useful herein also include the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator. The following is a non-limiting example of the synthesis of a preferred soil dispersing agent. Preparation of PEI 1800 E7:

"PEI 1800 E7" has a polyethyleneimine backbone having an average molecular weight of about 1800, a ratio of q:r of about 1 :2, and an average degree of ethoxylation of about 7.

Ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and introduction of ethylene oxide as a liquid. A ~20 lb. net weight cylinder of ethylene oxide is set up to deliver ethylene oxide as a liquid by pumping to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder can be monitored.

A 750 g portion of PEI (Nippon Shokubai, EPOMIN SP-018® having a listed average molecular weight of 1800 and a ratio of q:r of about 1 :2), equating to about 0.417 moles of polymer and 17.4 moles of nitrogen substitution sites, is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure). The autoclave contents are heated to 130°C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm. The temperature is maintained between 100 and 110°C while the total pressure is allowed to gradually increase during the course of the reaction to a maximum of about 350 psia. After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen substitution site), the temperature is increased to 110°C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide. (If a degree of ethoxylation of 1 was desired, the process would now proceed directly to the deodorization step below.)

Next, vacuum is continuously applied while the autoclave is cooled to about 50° C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen substituent sites). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130°C. A device is used to monitor the power consumed by the agitator. The agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105°C while it is being charged with nitrogen to 250 psia and then vented to atmospheric pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110°C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen substituent site) is achieved over several hours, the temperature is increased to 110°C and the mixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by sparging with inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture for about VA hour while agitating and heating the mixture to about 100- 130°C. Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter "SRA", can optionally be employed in the subject detergent compositions. If utilized, SRA's will generally comprise up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.5% to about 1.5%, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cationic species, see U.S. 4,956,447, issued September 11 , 1990 to Gosselink, et al., as well as noncharged monomer units, and their structures may be linear, branched or even star- shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , issued November 6, 1990 to Scheibel et al. Other SRA's include the nonionic end-capped 1 ,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711 ,730, issued December 8, 1987 to Gosselink et al. Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, issued January 26, 1988 to Gosselink, such as oligomers from ethylene glycol (EG), 1 ,2-propylene glycol (PG), dimethyl terephthalate (DMT), and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, issued October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, issued October 31, 1989 to Maldonado et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

Another preferred SRA is an oligomer having empirical formula (CAP)2(EG/PG)5(T)5(SIP)ι which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy- 1 ,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two- end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Such SRA preferably further comprises from about 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabilizer, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in U.S. 5,415,807, Gosselink et al., issued May 16, 1995, incorporated herein by reference. A preferred SRA of this type, designated SRA-1 herein, is made from sodium 2-(2-hydroxyethoxy)-ethanesulfonate, dimethyl terephthalate, dimethyl 5-sulfoisophthalate, sodium salt, ethylene glycol and propylene glycol. SRA-1 is a doubly end-capped ester with 12% by weight of linear sodium dodecylbenzenesulfonate as a stabilizer. SRA-1 and a method for making it are described in Example V of U.S. 5,415,807, columns 19-20.

Yet another group of preferred SRA's are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxy sulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1 ,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are esters of the empirical formula:

((CAP)a(EG/PG)_b(DEG)_cPEG)_d(T)_e(SIP)f(SEG)g(B)_h) wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, DEG represents di(oxyethylene)oxy units, SEG represents units derived from the sulfoethyl ether of glycerin and related moiety units, B represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, a is from about 1 to about 12, b is from about 0.5 to about 25, c is from 0 to about 12, d is from 0 to about 10, b+c+d totals from about 0.5 to about 25, e is from about 1.5 to about 25, f is from 0 to about 12; e + f totals from about 1.5 to about 25, g is from about 0.05 to about 12; h is from about 0.01 to about 10, and a, b, c, d, e, f, g, and h represent the average number of moles of the corresponding units per mole of the ester; and the ester has a molecular weight ranging from about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters include Na-2-(2-3- dihydroxypropoxy)ethanesulfonate (SEG), Na-2-(2-(2-hydroxyethoxy)ethoxy) ethanesulfonate (SE3) and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-(2-(2-hydroxy-ethoxy)ethoxy) ethanesulfonate and/or sodium 2-(2-(2-(2-hydroxyethoxy)ethoxy)- ethoxy)ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)₂(T)₅(EG/PG)-| (SEG)₂.5(B)o.i3 wherein CAP is (NaO₃S(CH₂-CH2θ)₃ 5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, issued May 25, 1976 and U.S. 3,893,929 to Basadur, issued July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL® from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, issued December 28, 1976 to Nicol et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM100® and METOLOSE SM200®, which are the trade names of methyl cellulose ethers manufactured by Shinetsu Kagaku Kogyo KK.

Suitable SRA's characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C<\ -CQ vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 of Kud et al. Commercially available examples include SOKALAN® SRA's such as SOKALAN HP-22®, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol of average molecular weight about 300-5,000. Commercial examples include ZELCON 5126® from DuPont and MILEASE T® from ICI.

Additional classes of SRA's include: nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201 ,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anyhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al. Other classes of SRA's include: anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201 ,824, Violland et al.; poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681 , Ruppert et al.; graft copolymers, in addition to the SOKALAN® types from BASF, made by grafting acrylic monomers onto sulfonated polyesters. These SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP 279 134 A, 1988, to Rhone-Poulenc Chemie. Still other SRA classes include: grafts of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as caseins, see EP 457 205 A to BASF (1991); and polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N.V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989 and 4,525,524. All of the patent publications on SRA's referred to hereinabove are incorporated herein by reference. Enzymes

Enzymes can be included in the subject compositions for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes which may be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures of two or more thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability in the presence of active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

The subject compositions typically comprise up to about 5%, preferably from about 0.01% to about 2%, more preferably about 0.2% to about 1%, of commercial enzyme preparations.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE®. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1 ,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130 756, published January 9, 1985) and Protease B (see European Patent Application 251 446, published January 7, 1988).

Protease enzymes in commercial preparations are included in the subject compositions at levels sufficient to provide from about 0.004 to about 2 Anson units (AU) of activity per gram of the compositions, preferably from about 0.006 to about 0.1 AU, also from about 0.005 to about 0.02 AU.

Amylases include, for example, α-amylases described in British Patent Specification No. 1 ,296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo Industries. Amylase is preferably included in the subject compositions such that the activity of the amylase is from about 0.02 KNU to about 5 KNU per gram of the composition, more preferably from about 0.1 KNU to about 2 KNU, more preferably still from about 0.3 KNU to about 1 KNU. (KNU is a unit of activity used commercially by Novo Ind.)

The cellulases usable in the subject compositions include both bacterial and fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800, a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabelia Auricula Solander). Suitable cellulases are also disclosed in British Patent Spec. Nos. 2,075,028 and 2,095,275 and German Patent Spec. No. 2,247,832. Cellulases disclosed in PCT Patent Application No. WO 91/17243, such as CAREZYME® (Novo), are especially useful cellulases.

Cellulase is preferably included in the subject compositions such that the activity of the cellulase is from about 0.1 CEVU to about 20 CEVU per gram of the composition, more preferably from about 1 CEVU to about 10 CEVU, more preferably still from about 2 CEVU to about 5 CEVU. (The activity of a cellulase material (CEVU) is determined from the viscosity decrease of a standard CMC solution as follows. A substrate solution is prepared which contains 35g/l CMC (Hercules 7 LFD) in 0.1 M tris buffer at pH 9.0. The cellulase sample to be analyzed is dissolved in the same buffer. 10ml substrate solution and 0.5ml enzyme solution are mixed and transferred to a viscosimeter (e.g., Haake VT 181 , NV sensor, 181 rpm), thermostated at 40°C. Viscosity readings are taken as soon as possibly after mixing and again 30 minutes later. The activity of a cellulase solution that reduces the viscosity of the substrate solution to one half under these conditions is defined as 1 CEVU/liter.)

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such a Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034. See also lipases in Japanese Patent Application 53/20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P. Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341 947) is a preferred lipase.

Lipase is preferably included in the subject compositions such that the activity of the lipase is from about 0.001 KLU to about 1 KLU per gram of the composition, more preferably from about 0.01 KLU to about 0.5 KLU, more preferably still from about 0.02 KLU to about 0.1 KLU. (KLU is a unit of activity used commercially by Novo Ind.)

Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101 ,457, Place et al., issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985.

Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge et al., and European Patent Application No. 199 405, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. Bleaching Compounds - Bleaching Agents and Bleach Activators

The subject detergent compositions may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels up to about 20%, preferably from about 1 % to about 5%, of the subject compositions. If present, the amount of bleach activators will typically be up to about 70%, preferably from about 0.5% to about 5% of the subject compositions.

The bleaching agents can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra- hydrate) can be used. A preferred level of perborate bleach in the subject composition is from about 1% to about 2%, more preferably from about 1.2% to about 1.5%.

Another category of bleaching agent that can be used encompasses 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 133 354, Banks et al., published February 20, 1985, and U.S. Patent 4,412,934 Chung et al., issued November 1 , 1983. Bleaching agents also include 6-nonylamino-6- oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium 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.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of such particles being smaller than about 200 micrometers and not more than about 10% by weight of such particles being larger than about 1 ,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) 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. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) activators are typical, and mixtures thereof can also be used. A preferred level of NOBS or TAED bleach activator in the subject compositions is from about 0.5% to about 2%, more preferably from about 0.8% to about 1.5%, more preferably still from about 1% to about 1.3%.

See also U.S. 4,634,551 for other typical bleaches and activators. Fabric Softening Clay

A preferred fabric softening clay is a smectite-type clay. The smectite-type clays can be described as expandable, three-layer clays; i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g of clay. Preferably the clay particles are of a size that they cannot be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes. The fabric softening clay, if it is included, can be added to the subject invention compositions to provide about 0.1% to about 20% by weight of the composition, more preferably from about 0.2% to about 15%, and more preferably still about 0.3% to 10%.

While any of the smectite-type clays are useful in the subject invention compositions, certain clays are preferred. For example, Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white detergent compositions. Volclay BC, which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe2θ3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in the instant compositions from the standpoint of product performance. On the other hand, certain smectite-type clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the requisite range; such clays are not preferred in the subject compositions. Clay Flocculating Agent

It has been found that the use of a clay flocculating agent in a composition containing softening clay provides improved softening clay deposition onto the clothes which results in better clothes softening performance, compared to that of compositions comprising softening clay alone. The polymeric clay flocculating agent is selected to provide improved deposition of the fabric softening clay. Typically such materials have a high molecular weight, greater than about 100,000. Examples of such materials can include long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrroiidone, and ethylene imine. Gums, like guar gums, are suitable as well. The preferred clay flocculating agent is a poly(ethylene oxide) polymer. The amount of clay flocculating agent included in the subject compositions, if any, is about 0.2%-2%, preferably about 0.5%-1%. Dye Transfer Inhibiting Ingredient

Another preferred optional component in the subject compositions is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics. A preferred DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitive dyes by oxidation. An example of a decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate. Non-limiting examples of polymeric DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N- vinylimidazole polymers (referred to as "PVPI") are also preferred. The amount of DTI included in the subject compositions, if any, is about 0.05%-5%, preferably about 0.2%- 2%. Photobleaches

A preferred optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by reference. Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals. Such photobleaches are available, for example, under the tradename TINOLUS. Zinc phthalocyanine sulfonate is available commercially under the tradename QUANTUM® from Ciba Geigy. The photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%, preferably from about 0.001% to about 0.015%, more preferably from about 0.002% to about 0.01%. Fillers Sodium sulfate and calcium carbonate (also known as Calcarb) are well known and often used as filler components of the subject compositions. Fillers also include minerals, such as talc and hydrated magnesium silicate-containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Sodium sulfate is a preferred filler material. Filler materials, if included, are typically at levels up to about 60%, preferably from about 25% to about 50%. Auxiliary Surfactants

The compositions of the subject invention can contain optional surfactants commonly used in detergent products. A typical listing of the classes and species of such surfactants, e.g., anionic, nonionic, zwitterionic, and amphoteric surfactants appear in U.S. 3,664,961 and EP 550,652. Such auxiliary surfactants may include C-|o-C-|8 ^a'M alkoxy carboxylates (especially the ethoxy 1.5 carboxylates) C^<|rj-C-18 glycerol ethers, C10-C-18 ^a"^<y' polyglycosides and their corresponding sulfated polyglycosides, and C12-C-18 α-sulfonated fatty acid esters. Such auxiliary surfactants may include one or more of CQ-C-\2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylates/propoxylates), C12-C18 betaines and sulfobetaines (sultaines), and C10-C18 amine oxides. Such auxiliary surfactants may include C10-C18 N-alkyl polyhydroxy fatty acid amides, such as C12-C18 N-methyl glucamides (see PCT Application WO 92/06154); other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides, such as C<ιo-Cl8 N-(3-methoxy propyl) glucamide. Conventional C10-C-20 ^{attv ac}'^c' ^soaP^{s are a}'^so possible auxiliary surfactants. Such auxiliary surfactants, if present, can be included at levels up to a total of about 10%, preferably about 0.5-3%.

In addition, a hydrotrope, or mixture of hydrotropes, can be present in the subject compositions. Preferred hydrotropes include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope, in either the acid form or the salt form, and being substantially anhydrous, is added to the linear alkylbenzene sulfonic acid prior to its neutralization. The hydrotrope, if present, is preferably from about 0.5% to about 5% of the subject compositions. Water

The compositions of the subject invention typically comprise from about 3% to about 15% water, preferably from about 4% to about 12% water, more preferably from about 5% to about 9% water. Miscellaneous Dyes, pigments, germicides, perfumes, polyethylene glycol, glycerine, sodium hydroxide, alkylbenzene, fatty alcohol, and other minors, some of which are impurities carried in from surfactant-making processes, can also be incorporated in the subject compositions. If included, they are typically at levels up to about 3%.

EXAMPLES

The following exemplify compositions of the subject invention, but are not intended to be limitations of the scope of the subject invention. The examples are granular detergents which may be made by well-known processes, such as spray drying of a paste or slurry, and agglomerating or dry blending in mixers.

The following list of components are utilized in the examples. LAS: linear C-| 1-C13 alkylbenzene sulfonate, sodium salt. AS: linear C-14 alkyl sulfate, sodium salt. AES: linear C-12-C15 ethoxy(3) sulfate, sodium salt.

HDQA: linear C12-C14 dimethyl hydroxyethyl quaternary ammonium chloride. AE: linear C14-C 15 ethoxy (7) alcohol. STPP: sodium tripolyphosphate. Silicate: sodium silicate having a SiO2:Na2O ratio of 1.6. Carbonate: sodium carbonate. DTPA: diethylenetriaminepentacetate, sodium salt.

SOKALAN®: copolymer of acylic and maleic acids, designated HP-22 from BASF. CMC: carboxymethyl cellulose having an average molecular weight of 63,000. SRA-1 : polymeric soil release agent described hereinabove.

SAVINASE/BAN®: protease and amylase enzyme product designated 6/1 OOT from Novo Industries A/S.

CAREZYME®: cellulase enzyme product designated 5T from Novo Industries A/S, having an activity of 5000 CEVU/g. Perborate: sodium perborate monohydrate. NOBS: nonanoyloxybenzene sulfonate. ZPS: zinc phtalocyanine sulfonate.

TINOPAL CBS®: 4,4'-bis(2-sulfostyryl)biphenyl disodium salt.

TINOPAL AMS®: 4,4'-bis((4-anilino-6-morphilino-1 ,3,5-triazin-2-yl)amino)-stilbene-2,2- disulfonic acid disodium salt. Sulfate: sodium sulfate.

The numbers in the following table are weight percents.

Additional examples of the present invention include:

The subject invention includes processes for laundering fabrics using the compositions described hereinabove. Preferred processes are hand washing operations and machine-assisted hand washing operations using such compositions.

The subject processes include incorporating the subject compositions in water, typically at concentrations of from about 1000 ppm to about 9000 ppm, preferably from about 1500 ppm to about 7500 ppm, more preferably from about 2000 ppm to about 6000 ppm, in which fabrics are washed. The subject washing operations preferably are carried out at wash solution temperatures of from about 10°C to about 60°C, more preferably from about 12°C to about 40°C. The subject wash solutions are preferably within the pH range of from about 8 to about 11 , more preferably from about 9.8 to about 10.5.

While particular embodiments of the subject invention have been described hereinabove, it will be obvious to those skilled in the art that various changes and modifications to the subject invention can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of this invention.

Claims

WHAT IS CLAIMED IS:

1. A detergent composition comprising: a) from 5% to 40% detergent surfactant, the detergent surfactant comprising:

1) from 60% to 97% of a primary anionic surfactant selected from alkylbenzene sulfonate, alkyl sulfate, and mixtures thereof;

2) from 2.5% to 18% alkyl ethoxy sulfate surfactant having an average of from 1 to 9 moles ethoxy per mole surfactant, the ratio of primary anionic surfactant to alkyl ethoxy sulfate surfactant being within the range of from 38:1 to 4:1 ;

3) from 0% to 10% hydroxyalkyi quaternary ammonium cationic surfactant having the structure:

R R^, _nR"_mN⁺ Z-, wherein R is long-chain alkyl, R' is short-chain alkyl, R" is hydroxyethyl or hydroxypropyl, n is 1 or 2, m is 1 or 2, n + m is 3, and Z~ is an anion, the ratio of primary anionic surfactant to cationic surfactant being greater than 6:1 ; and

4) from 0% to 15% alkyl ethoxy alcohol surfactant having an average of from 1 to 10 moles ethoxy per mole surfactant, the ratio of primary anionic surfactant to alkyl ethoxy alcohol surfactant being greater than 4.5:1 ; b) from 0.05% to 0.5% optical brightener, wherein the weight ratio of primary anionic surfactant plus alkyl ethoxy sulfate to optical brightener is 50:1 and above; and c) from 60% to 95% other components.

2. The composition according to Claim 1 wherein the detergent surfactant comprises from 2.5% to 5.5% hydroxyalkyi quaternary ammonium cationic surfactant, the ratio of primary anionic surfactant to cationic surfactant being within the range of from 38:1 to 16:1.

3. The composition according to Claim 2 wherein the composition comprises from 15% to 30% detergent surfactant, the detergent surfactant comprising:

(1) from 70% to 95% alkylbenzene sulfonate surfactant, the alkyl being alkanyl or alkenyl or a mixture thereof and having an average of from 10 to 14 carbon atoms; (2) from 6% to 12% alkyl ethoxy sulfate surfactant having an average of from 1 to 7 moles ethoxy per mole surfactant, the alkyl being alkanyl or alkenyl or a mixture thereof having an average of from 11 to 18 carbon atoms, the ratio of alkylbenzene sulfonate surfactant to alkyl ethoxy sulfate surfactant being within the range of from 19:1 to 11 :1 ;

(3) from 2.7% to 4.5% of the hydroxyalkyi quaternary ammonium cationic surfactant, R being alkanyl or alkenyl having an average of from 10 to 15 carbon atoms, each R' being methyl, the ratio of alkylbenzene sulfonate surfactant to such cationic surfactant being within the range of from 35:1 to 20:1 ;

(4) from 0% to 8% alkyl ethoxy alcohol surfactant having an average of from 3 to 10 moles ethoxy per mole surfactant, the alkyl being alkanyl or alkenyl or a mixture thereof having an average of from 11 to 18 carbon atoms, the ratio of alkylbenzene sulfonate surfactant to alkyl ethoxy alcohol surfactant being greater than 10:1.

4. The composition according to Claim 1 wherein the optical brightener is selected from: i) 0.16% to 0.4% brightener which is 4,4'-bis((1 ,3,

5-triazin-2- yl)amino)stilbene having the structure:

wherein R^ and R2 are both substituted amino, and M is H or a salt- forming cation; ii) from 0.16% to 0.34% brightener which is 4,4'-bis(sulfostyryl)biphenyl disodium salt; and iii) mixtures thereof.

The composition according to Claim 4 wherein R1 is anilino or p- sulfoanilino, and R2 is selected from the group consisting of N-2- bis(hydroxyethyl)amino, N-2-hydroxyethyl-N-2-methylamino, morpholino, N- 2-methoxyethylamino, anilino, and methylamino.

6. The composition according to Claim 5 wherein the optical brightener i) is from 0.22% to 0.32% of 4,4'-bis((4-anilino-6-morpholino-1 ,3,5-triazin-2- yl)amino)stilbene-2,2-disulfonic acid disodium salt.

7. The composition according to Claim 4 wherein the composition comprises from 0.16% to 0.4% optical brightener consisting of from 20% to 80% bis(triazinylamino)stilbene and from 80% to 20% bis(styryl)biphenyl.

8. The composition according to Claim 1 wherein the primary anionic surfactant comprises alkylbenzene sulfonate and alkyl sulfate surfactant at a weight ratio of alkylbenzene sulfonate to alkyl sulfate surfactant of at least 4:1.

9. The composition according to Claim 1 wherein the weight ratio of primary anionic surfactant plus alkyl ethoxy sulfate surfactant to optical brightener is from 90:1 to 120:1.

10. The composition according to Claim 9 wherein the weight ratio of primary anionic surfactant to alkyl ethoxy sulfate surfactant is from 22:1 to 10:1.