WO1995016016A1

WO1995016016A1 - Detergent composition containing amine oxide surfactant in the form of agglomerates

Info

Publication number: WO1995016016A1
Application number: PCT/US1994/014274
Authority: WO
Inventors: Ronald Allen Swift
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1993-12-07
Filing date: 1994-12-07
Publication date: 1995-06-15
Anticipated expiration: 1996-06-07
Also published as: CN1142848A; MA23390A1; JPH09506389A; AU1339395A; CA2177678A1; BR9408264A; EP0733095A1

Abstract

A detergent composition in form of agglomerates is provided. The detergent composition contains from about 1 % to 50 % by weight of a detersive surfactant system. The surfactant system itself comprises, by weight of the surfactant system, (i) at least about 50 % of an amine oxide surfactant, and (ii) less than about 30 % of a linear alkylbenzene sulfonate surfactant. Also, the detergent composition includes at least about 1 % by weight of a detergency builder to enhance cleaning. The surfactant system and the builder are agglomerated to form detergent agglomerates which are substantially free of phosphates. The surfactants in the detergent composition have improved solubility in an aqueous laundering solution. Thus, the solubility of the amine oxide surfactant, the LAS surfactant and other surfactants, if included, is enhanced by at least 5 % over those same surfactants alone under the same test conditions.

Description

DETERGENT COMPOSITION CONTAINING AMINE OXIDE SURFACTANT IN THE

FORM OF AGGLOMERATES

FIELD OF THE INVENTION The present invention is generally directed to a detergent composition in the form of agglomerates having improved biodegradability and cleaning, especially in cold temperature laundering solutions. More particularly, the invention is directed to an agglomerated, nil-phosphate detergent composition containing an amine oxide surfactant as the principle surfactant and reduced levels of linear alkylbenzene sulfonate surfactant (also referenced herein as "LAS") so as to improve the overall biodegradability of the detergent composition. The detergent composition also achieves improved cleaning by increasing the solubility of the amine oxide surfactant and LAS. especially in cold temperature washing solutions (e.g. 5°C to 30°C) and high water hardness conditions (e.g. 7 grains/gallon). For purposes of producing a high density, compact detergent composition, and in order to achieve the benefits discussed herein, the detergent of the invention is in the form of detergent agglomerates rather than spray dried granules.

BACKGROUND OF THE INVENTION Typically, conventional detergent compositions contain mixtures of various surfactants in order to remove a wide variety of soils and stains from surfaces. For example, various anionic surfactants, especially the alkyl benzene sulfonates, are useful for removing particulate soils, and various nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates, are useful for removing greasy soils.

While the art is replete with a wide variety of surfactants for those skilled in the "art of detergent formulation, most of the available surfactants are specialty chemicals which are not suitable for routine use in low cost items such as home laundering compositions. The fact remains that many home-use laundry detergents still comprise one or more of the conventional alkyl benzene sulfonates or primary alkyl sulfate surfactants. While the conventional alkyl benzene sulfonates exhibit acceptable solubility properties in aqueous laundering solutions, they are generally regarded as possessing poor biodegradability characteristics. The primary alkyl sulfates, on the other hand, have acceptable biodegradability traits but generally do not exhibit acceptable solubility properties, especially in cold temperature washing solutions.

Another class of surfactants which has found use in various compositions where emulsification is desired comprises the secondary alkyl sulfates (also referenced herein as "SAS"). The conventional secondary alkyl sulfate surfactants are available as generally pasty, random mixtures of sulfated linear and/or partially branched alkanes. For example, Rossall et al. U.S. Patent No. 4,235,752, disclose a detergent surfactant which is a C_jo__jg secondary alkyl sulfate containing 50% of 2/3 sulfate isomers and 40% of various other effective isomers. The surfactant materials disclosed by Rossall et al is for use primarily in dishwashing operations. Such materials have not come into widespread use in laundry detergents, since they do not offer any advantages over alkyl benzene sulfonates, especially with respect to water solubility and cleaning performance. Accordingly, Rossall et al do not provide a high density laundry detergent having improved solubility in either cold temperature wash solutions or high hardness water conditions. Tosaka et al, U. S. Patent No. 5,096,621 (Kao Corp.), is directed to a detergent composition containing an amine oxide surfactant, anionic surfactant and a nonionic surfactant, together which achieve improved cleaning performance. Tosaka et al also exemplifies only "liquid" dishwashing detergent compositions and hard surface cleaning compositions, although powdered forms of such compositions are also contemplated. Moreover, the Tosaka et al patent does not incorporate amine oxide surfactants directly into detergent agglomerates for increased solubility in cold temperature washing solutions. Rather. Tosaka et al combine discrete amine oxide particles with spray dried granules to form their detergent composition. Thus, the Tosaka et al patent does not speak to the solubility problem associated with cold temperature laundering solutions, a problem particularly prevalent when using detergents having sulfate-based (i.e. AS, SAS. AES, etc.) surfactant systems comprising less than about 30% of LAS.

The limited solubility of alkyl sulfate surfactants including both primary and secondary alkyl sulfates is especially prevalent in modern granular laundry detergents which are typically used in cold temperature (e.g. 5°C to 30°C) washing solutions and are formulated in "condensed" or "compact" form for low dosage usage. For the consumer, the smaller package size attendant with compact detergent products provides for easy storage and handling. For the manufacturer, unit storage costs, shipping costs and packaging costs are lowered.

The manufacture of acceptable compact or condensed granular detergents has its difficulties. In a typical compact detergent formulation, the so-called "inert" ingredients such as sodium sulfate are substantially eliminated. However, such ingredients do play a role in enhancing solubility of conventional detergents. As a consequence, compact detergents often suffer from solubility problems, especially in cold temperature laundering solutions. Moreover, conventional compact or low density detergent granules are usually prepared by spray drying processes which result in extremely porous detergent particles that are quite amenable to being dissolved in aqueous washing solutions. By contrast, compact detergents are typically comprised of less porous, high density detergent particles which are less soluble. Thus, since the compact form of granular detergents typically comprise particles or granules which contain high levels of detersive ingredients with little or no room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in- use solubility. Accordingly, despite the disclosures in the art, there remains a need for a detergent composition which has improved cleaning performance, especially in cold temperature washing solutions. This need is especially prevalent in the art of compact or high density detergents currently being used by consumers. There is also a need for such a detergent composition which achieves these benefits by way of exhibiting improved solubility of the surfactants in the composition under high hardness and cold temperature water conditions. Also, there is a need for such a detergent composition which exhibits improved biodegradability. SUMMARY OF THE INVENTION

The present invention meets the needs identified above by providing a detergent composition in the form of agglomerates which exhibit improved solubility or dissolution of the surfactants in cold temperature washing solutions as well as under high water hardness conditions. The detergent composition comprises a surfactant system having a high level of an amine oxide surfactant in combination with a low level of linear alkylbenzene sulfonate surfactant. The low level, i.e. less than about 30% of the surfactant system, and the omission of phosphates in the detergent composition is maintained for purposes of achieving improved biodegradability. Other adjunct detergent ingredients may also be included in the agglomerates which form the detergent composition. For example, high active (high surfactant levels) particles (e.g. SAS and AS) may be optionally included to enhance cleaning.

As used herein, the phrase "improved solubility" means that the solubility of the surfactants of the detergent composition is enhanced by at least 5% in the laundering solution when employed in the manner of this invention, as compared to the solubility of the same surfactants per se, under the same test conditions (i.e. water temperature and pH, stirring speed and time, particle size, water hardness, and the like). As used herein, the term "agglomerates" refers to particles formed by agglomerating particles which typically have a smaller mean particle size than the formed agglomerates. All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference. In accordance with one aspect of the invention, a detergent composition in form of agglomerates is provided herein. The detergent composition comprises from about 1% to 50% by weight of a detersive surfactant system. The surfactant system itself comprises, by weight of the surfactant system, (i) at least about 50% of an amine oxide surfactant, and (ii) less than about 30% of a linear alkylbenzene sulfonate surfactant. Also, the detergent composition includes at least about 1% by weight of a detergency builder to enhance cleaning. The surfactant system and the builder are agglomerated to form detergent agglomerates which are substantially free of phosphates. The surfactants in the detergent composition have improved solubility in an aqueous laundering solution. Thus, the solubility of the amine oxide surfactant, the LAS surfactant and other surfactants, if included, is enhanced by at least 5%. preferably 10 to 50%, over those same surfactants alone under the same test conditions in aqueous washing solutions at cold temperatures, i.e. 5°C to 30°C.

In accordance with another aspect of the invention, a method for laundering soiled fabrics is provided. The method comprises the step of contacting soiled fabrics with an effective amount of a detergent composition as described herein in an aqueous laundering solution. An effective amount is typically on the order of 1000 to 1500 ppm.

Accordingly, it is an object of the present invention to provide a detergent composition which has improved cleaning performance as a result of increasing the solubility of the surfactants. especially in cold temperature washing solutions. It is also an object of the invention to provide such a detergent composition which has improved biodegradability. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The invention is directed to a detergent composition having improved solubility in cold temperature laundering solutions. A multitude of consumers around the world launder soiled clothes in conventional washing machines unique to their particular geographic location. Typically, these conventional washing machines launder the soiled clothes in water supplied at relatively cold temperatures, for example in range of 5°C to 30°C, and at high hardness concentrations, e.g. 7 grains/gallon (rich with Ca and Mg ions). Most of the modern day consumers also use compact or condensed laundry detergents to accomplish their laundering needs. Under the aforementioned conditions, solubility of current detergents in aqueous laundering solutions has been a problem. This problem is especially exacerbated when the detergent composition has high levels of alkyl sulfates, alkyl ethoxy sulfate and/or secondary alkyl sulfates which are not particularly amenable to dissolution in cold aqueous laundering solutions. Such surfactants are particularly useful in modern laundry detergents since they minimize the need for linear alkylbenzene sulfate surfactants which generally have poor biodegradability. Another approach to this problem has been to use cationic surfactants such as amine oxide but such surfactants are generally included as a separate component, i.e. admix, apart from the detergent granules which have been spray dried.

It has now been found that the solubility of a detergent composition can be increased by incorporating amine oxide surfactant with a minimal amount (less than 30% of the surfactant system) of linear alkylbenzene sulfonate surfactant directly into the detergent by way of agglomeration. By having the detergent composition in the form of agglomerates, the solubility of the overall surfactant system in the laundering solution is improved, especially those solutions kept at cold temperatures (e.g. 5°C to 30°C). To that end, the preferred detergent composition of the invention comprises from about 1% to about 50%, preferably from about 15% to about 40%, by weight a surfactant system of which at least 50%, preferably from about 50% to about 100%. is an amine oxide surfactant and less than about 30%, preferably from about 0% to about 15%, is a linear alkylbenzene sulfonate (LAS) surfactant. Optionally, the surfactant system may include nonionic surfactants and/or anionic surfactants such as those selected from the group consisting of alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof While the level of these adjunct surfactants can vary, generally they comprise from about 0.01% to about 50% of the surfactant system.

Preferably, the detergent composition of the invention also comprises at least about 1%, preferably from about 10% to about 40%. of a detergency builder. The detergent composition may also include one or more of adjunct detergent ingredients. Nonlimiting examples of the detergency builder and such adjunct ingredients are described in detail hereinafter. Preferably, the detergent composition herein is formulated and processed to achieve a density of at least 650 g/1 for purposes of producing a "compact" detergent product.

For purposes of enhancing biodegradability, the detergent agglomerates which form the detergent composition of the invention preferably do not contain phosphates and contain little or no LAS. Further, it is important for the detergent composition to be in the form of "agglomerates" as opposed to spray dried granules. This is particularly important since most amine oxide surfactants cannot be readily subjected to spray drying processes without causing or creating extremely adverse plumes from the spray drying towers. The same is true for alkyl sulfate and alkyl ethoxy sulfate surfactants. As a consequence, past as well as current detergents only incorporate amine oxide surfactants as a "separate" adjunct ingredient. This, however, does not provide the detergent composition with satisfactory solubility characteristics.

By contrast, the detergent composition of the present invention incorporates the amine oxide directly "into" the individual agglomerates by way of an agglomeration process technique as described hereinafter. While not intending to be limited by theory, it is believed that the amine oxide is brought into the aqueous laundering solution more rapidly and more completely as a result of being intimately bound within the agglomerates. In agglomerated form, the amine oxide apparently is extremely hygroscopic and has very little crystallinity tendencies so as to be very soluble, especially in cold temperature washing solutions. Furthermore, by utilizing an amine oxide surfactant along with other adjunct surfactants such as AS, AES and SAS, the overall solubility of the detergent agglomerates in cold washing solutions and high hardness conditions is improved, thereby resulting in improved cleaning performance.

The "improved solubility" achieved by the detergent composition is concerned with enhanced solubility of the surfactant system of which at least 50% is an amine oxide surfactant. Preferably, the improvement represents at least a 5% increase in solubility of the surfactant system in the wash solution over the solubility of the same surfactants if they were dissolved alone or without being contained in a detergent composition as defined herein. More preferably, the solubility improvement is from about 10% to about 50%. As those skilled in the art will appreciate, any comparison of the surfactant system solubility should be completed under the same laundering conditions, e.g. water temperature, hardness and pH, stirring speed and time, and particle size. Typical surfactant system solubility improvements are set forth in the Examples hereinafter. Those skilled in the art should also appreciate the numerous ways in which the amount of the surfactant system in the washing solution can be determined. For example, the amount of amine oxide surfactant dissolved can be determine by way of a titration technique during which samples of the aqueous laundering solution containing the detergent composition are taken after one minute and filtered with 0.45 mm nylon filter paper, after which a cationic titrant, which can be commercially purchased, e.g. from Sigma Chemical Company under the trade name Hyamine. is added to the filtered solution. The filtered solution is then titrated with an anionic titrant such as sodium dodecyl sulfate. From the foregoing, the amount of cationic surfactant, i.e. amine oxide, which was dissolved in the washing solution can be determined. The solubility of the other optional surfactants contained in the surfactant system can be determined by well known techniques such as the so-called "catSO_β" titration technique. The Examples presented hereinafter illustrate the improved solubility of the amine oxide surfactant as well as the aforementioned titration technique.

Surfactant System In the broadest aspect of the invention, the agglomerated detergent composition contains a surfactant system including at least 50% of an amine oxide surfactant and less than about 30% of LAS. Optionally, the surfactant system may include additional surfactants, nonlimiting examples of which are provided hereinafter.

The amine oxide surfactants suitable for used herein have the general formula

wherein R_j is a Cg_24 alkyl group or a substituted C _24 alkyl group. R2 and R3 are H, a C1.3 alkyl group or a substituted C_]_3 alkyl group, and n is from 0 to about 10.

Nonlimiting examples of the amine oxide surfactant include C_jo-i8 amine oxides, secondary amine oxides, and tertiary amine oxides. The tertiary amine oxide surfactant may be in hydrated form and have the general formula R1R2R3NO n^O wherein Ri , R2 and R3 are the same as above and n is 1 or 2. Examples of other tertiary amines suitable for use herein include those containing one or two short-chain groups independently selected from methyl, ethyl, and 2- hydroxyethyl groups, with the remaining valences of the amino nitrogen being satisfied with long- chain groups independently selected from primary alkyl groups containing 8-24 carbons, e.g., octyl. decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, and tetracosyl groups. The primary alkyl groups may be branched-chain groups, but the preferred amines are those in which at least most of the primary alkyl groups have a straight chain.

Exemplary of these tert-amines are N-octyldimethylamine, N,N-didecylmethylamine, N- decyl-N-dodecylethylamine. N-dodecyldimethylamine, N-tetradecyldimethylamine, N-tetradecyl-N- ethylmethylamine. N-tetradecyl-N-ethyl-2-hydroxyethylamine, N,N-di-tetradecyl-2- hydroxyethylamine. N-hexadecyldimethylamine, N-hexadecyldi-2- hdroxyethylamine N-

SUBSTltUTE SHEET (RULE 26) octadecyldimethylamine. N.N-dieicosylethylamine, N-docosyl-N-2-hydroxyethylmethylamine. N- tetracosyldimethylamine, etc.

Other examples of tertiary as well as secondary amine oxides suitable for use herein include dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide. bis-(2- hydroxyethyl) dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide. (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2- hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds. Preferred amine oxide surfactants for use herein include C12-14 dimethylamine oxides. Most preferred is dimethyldodecylamine oxide.

Additional amine oxide surfactants and methods of making the same, all of which are suitable for use herein, are disclosed by Borland et al. U.S. Patent No. 5,071,594 and Tosaka et al. U.S. Patent No. 5.096,621. incorporated herein by reference. Further amine oxides suitable for use herein are described by Almstead et al, U.S. Patent No. 3,351.557; Davis, U.S. Patent No.

3,341.459; Zimmerer et al. U.S. Patent No. 3.202,714; Drew et al, U.S. Patent No. 3.441.611: and. Drew, U.S. Patent No. 3,441612, all of which are incorporated herein by reference.

Optionally, the surfactant system can include conventional Ci _j-C_jg alkyl benzene sulfonates (also referenced herein as "LAS) as long as the level does not exceed about 30% of the surfactant system. While the biodegradability of the so-called "LAS" surfactants have been the subject of some concern, the surfactant system herein may include a small amount of (i.e. less than 30%) LAS for purposes of improving the overall solubility of the detergent composition without substantially decreasing the overall biodegradability of the present detergent composition.

Adjunct Surfactants The surfactant system may also include a variety of adjunct surfactants wherein the aggregate amount of the adjuncts do not exceed 50% of the surfactant system. Nonlimiting examples are presented herein and include conventional primary alkyl sulfate surfactants have the general formula

ROS03-M+ wherein R is typically a linear C₁₀-C20 hydrocarbyl group and M is a water-solubilizing cation.

Branched-chain primary alkyl sulfate surfactants (i.e., branched-chain "PAS") having 10-20 carbon atoms can also be used herein; see, for example, European Patent Application 439,316, Smith et al, filed 21.01.91, the disclosure of which is incorporated herein by reference (Included in the term "alkyl" is the alkyl portion of acyl groups). Included in the surfactant system are the C_jo-C_j alkyl alkoxy sulfates ("AE_XS"; especially EO 1-7 ethoxy sulfates). Conventional secondary alkyl sulfate surfactants can also be used herein and include those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure

CH₃(CH2)_n(CHOSθ3-M⁺)(CH₂)_mCH3 wherein m and n are integers of 2 or greater and the sum of m + n is typically about 9 to 17, and M is a water-solubilizing cation.

More preferably, a selected secondary (2,3) alkyl sulfate surfactant is used herein which comprises structures of formulas A and B

(A) CH₃(CH₂)_x(CHOS0₃-M⁺) CH₃ and (B) CH3(CH₂)_y(CHOS0₃-M⁺)CH2CH3 for the 2-sulfate and 3-sulfate. respectively. Mixtures of the 2- and 3-sulfate can be used herein. In formulas A and B. x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16. M is a cation, such as an alkali metal, ammonium, alkanolammonium, alkaline earth metal, or the like. Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but ethanolammonium, diethanolammonium, triethanolammonium, potassium, ammonium, and the like, can also be used. It is preferred that the secondary (2,3) alkyl sulfates be substantially free (i.e., contain less than about 20%, more preferably less than about 10%, most preferably less than about 5%) of such random secondary alkyl sulfates. The preparation of the secondary (2,3) alkyl sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefms. A typical synthesis using -olefins and sulfuric acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5,075,041, Lutz, granted December 24. 1991, both of which are incorporated herein by reference. The synthesis, conducted in solvents which afford the secondary (2,3) alkyl sulfates on cooling, yields products which, when purified to remove the unreacted materials, randomly sulfated materials, unsulfated by-products such as C_]Q and higher alcohols, secondary olefin sulfonates, and the like, are typically 90+% pure mixtures of 2- and 3-sulfated materials (up to 10% sodium sulfate is typically present) and are white, non-tacky, apparently crystalline, solids. Some 2,3-disulfates may also be present, but generally comprise no more than 5% of the mixture of secondary (2,3) alkyl mono-sulfates. Such materials are available as under the name "DAN", e.g., "DAN 200" from Shell Oil Company.

If increased solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formulator may wish to employ mixtures of such surfactants having a mixture of alkyl chain lengths. Thus, a mixture of Ci 2-C1 g alkyl chains will provide an increase in solubility over a secondary (2,3) alkyl sulfate wherein the alkyl chain' is, say. entirely C_jg. The solubility of the secondary (2,3) alkyl sulfates can also be enhanced by the addition thereto of other surfactants such as the material which decreases the crystallinity of the secondary (2,3) alkyl sulfates. Such crystallinity-interrupting materials are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate.

Additional nonlimiting examples of surfactants useful in conjunction with the surfactants described herein are the Ciø-C_j alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Ci ._j glycerol ethers, the C_jQ-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and C_j2-C_jg alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the

alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C -C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C_j^-C_jg betaines and sulfobetaines ("sultaines"), can also be included in the overall compositions. The CJ_Q-C _j N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C^-C_j N-methylglucamides. See WO 9,206.154. The N-propyl through N-hexyl C_j^-C_jg glucamides can be used for low sudsing. C1Q-C20 conventional soaps may also be used. If high sudsing is desired, the branched- chain C_jo-Ci6 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.

Builder The detergent composition of the invention also includes a detergency builder material to 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 paniculate soils. Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates). sulphates, and aluminosilicates.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2-Na2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Siθ5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3 ,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xθ2_X+ι yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20. preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5. NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Siθ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crisping agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15. 1973. Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M_z(zA10₂)y] xH₂0 wherein z and y are integers of at least 6. the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3.985.669. 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:

Na₁₂l(A10₂)i2(Siθ2)i2] xH2θ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

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

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4.663.071. issued to Bush et al. on May 5. 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120.874 and 4.102,903.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used, however, in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy- 4-oxa-l,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 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate. myristylsuccinate, palmitylsuccinate. 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent

Application 86200690.5/0.200.263, 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., Ci2-C_jg monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

Detergent Adjunct Ingredients The detergent composition can also include any number of additional ingredients in an amount from 0% to about 75% by weight of the detergent composition. These ingredients include bleaches, bleach activators, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued

November 1, 1983. and in U.S. Patent 4.483,781, Hartman. issued November 20, 1984. both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071. Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672. issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference. Suitable smectite clays for use herein are described in U.S. Patent 4,762.645. Tucker et al. issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent. Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.

Enzymes can be included in the formulations herein 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 to be incorporated include proteases, amylases, Upases, cellulases. and peroxidases, as well as mixtures 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 versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. sub tilts and B.lichenifo ms. 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 trade names 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 Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130.756, Bott et al, published January 9, 1985).

Amylases include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo). RAPID ASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulase usable in the present invention include both bacterial or 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 or a cellulase 212-producing fungus belonging to the genus Aeromonas. and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372.034. See also Upases 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 "Amano," hereinafter referred to as "Amano-P." Other commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.. Tagata. Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. 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 Intemational Application WO 89/099813, published October 19, 1989, by O. 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, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4.261,868, Hora et al, issued April 14, 1981. 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 Publication No. 0 199 405, Application No. 86200586.5, published October 29. 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519.570. Additionally, dye transfer inhibiting agents may also be included, for example, polyvinylpyrrolidone, polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinylimidazole are a suitable dye transfer inhibiting polymers for use in the present detergent composition. The level of such additional dye transfer inhibiting agents may vary, but typically will be from about 0.01% to about 10% by weight of the detergent composition.

Agglomeration Process The following describes and exemplifies the agglomeration process by which the detergent composition of the invention is produced. The parameters noted herein are exemplary only and should not be considered as limiting in any way.

Step A - Preparation of Surfactant Paste - The objective is to combine the surfactants including the amine oxide surfactant and liquids in the compositions into a common mix in order to aid in surfactant solubilization and agglomeration. In this Step, the surfactants and other liquid components in the composition are mixed together in a Sigma Mixer at 140°F (60°C) at about 40 rpm to about 75 rpm for a period of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20.000-40,000 centipoise. Once thoroughly mixed, the paste is stored at 140°F (60°C) until agglomeration Step (B) is ready to be conducted.

Step B - Agglomeration of Powders with Surfactant Paste - The purpose of this Step is to transform the base formula ingredients into flowable detergent agglomerates having a mean particle size range of from about 800 microns to about 1600 microns. In this Step, the powders (including materials such as zeolite, citrate, citric acid builder, layered silicate builder (as SKS-6), sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical brightener) are charged into the Eirich Mixer (R-Series) and mixed briefly (ca. 5 seconds - 10 seconds) at about 1500 rpm to about 3000 rpm in order to mix the various dry powders fully. The surfactant paste from Step A is then charged into the mixer and the mixing is continued at about 1500 rpm to about 3000 rpm for a period from about 1 minute to about 10 minutes, preferably 1-3 minutes, at ambient temperature. The mixing is stopped when course agglomerates (average particle size 800-1600 microns) are formed.

Step C - The purpose of this Step is to reduce the agglomerates' stickiness by removing/drying moisture and to aid in particle size reduction to the target particle size (in the mean particle size range from about 800 to about 1600 microns, as measured by sieve analysis). In this Step, the wet agglomerates are charged into a fluidized bed at an air stream temperature of from about 41°C to about 60°C and dried to a final moisture content of the particles from about 4% to about 10%.

Step D - Coat Agglomerates and Add Free-Flow Aids - The objective in this Step is to achieve the final target agglomerate size range of from about 800 microns to about 1600 microns, and to admix materials which coat the agglomerates, reduce the caking/lumping tendency of the particles and help maintain acceptable flowability. In this Step, the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5μm) during the mixing. The mixing is continued until the desired median particle size is achieved (typically from about 5 seconds to about 45 seconds). At this point, from about 0.1% to about 1.5% by weight of precipitated silica (average particle size 1-3 microns) is added as a flow aid and the mixing is stopped.

In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope. EXAMPLE I Several detergent compositions (A-E) are made in accordance with the agglomeration process described above. Compositions A. B and C are within the scope of the invention and compositions D and E are outside of the invention and are presented for purposes of comparison as described in Example II hereinafter. The relative proportions of compositions A-E, in agglomerate form, are listed in Table I below.

A

Component Surfactants % ( t.) % ( t.) % ( t.) % ( t.) % ( t.)

C i4_ι 5 primary alkyl sulfate - 2.5 - 19.2 16.9 ^c12" 15 ^ky^{1 ethoχ}y O^**3) sulfate - 1.5 - 10.8 9.5

C_jo-i ^linear alkylbenzene sulfonate. Na - - - - 3.6

Nonionic* 3.3 - - - -

Amine Oxide^ 24.7 23.5 31.7 - -

Builders

Zeolite 4A 37.9 36.9 37.0 40.0 40.0

Carbonate (Na) 18.3 17.8 17.9 16.1 16.1

Additives

Polyethylene glycol (M.W. 4000) - 1.0 1.2 - -

Misc. (water, perfume and minors) 15.8 16.8 12.2 13.9 13.9

100.0 100.0 100.0 100.0 100.0

* nonionic surfactant commercially available from Shell Chemical Company under the trade name Neodol

(23-9).

^dimethyl amine oxide surfactant commercially available from Procter & Gamble. EXAMPLE II

This Example illustrates the surprisingly improved solubility achieved by the detergent composition of the invention. Specifically, standard dosages of compositions A-E (1170 ppm) are dissolved in an aqueous laundering solution having a water temperature of 10°C and a water hardness of 7 grains/gallon (Ca:Mg ratio of 3: 1). The laundering solution is continuously agitated at a rate of 75 rpm and samples of the wash solution were taken at various time intervals as shown in Table I below. For purposes of illustrating the improved solubility of the detergent composition according to the invention, the amount of surfactant in the laundering solution is determined by conducting the titration technique described previously wherein samples are taken from individual wash solutions containing one of the compositions A-E and titrated to determine the cationic surfactant concentration. More specifically, the amount of cationic surfactant dissolved in the laundering solution is determined by filtering the aforementioned samples through 0.45 nylon filter paper to remove the insolubles and thereafter, adding a cationic titrant. such as Hyamine™ which is commercially available from Sigma Chemical Company, to the filtered solution. The filtered solution is then titrated with an anionic titrant to determine the cationic concentration. From the foregoing, the relative amount of surfactant dissolved in the wash solution can be determined. This technique is well known and others may be used if desired, especially if concentrations of anionic and nonionic surfactants are desired. The results are shown in Table II below. TABLE π

(% total of cationic or anionic dissolved)

Time (Minutes) A B C D E

0 0.0% 0.0% 0.0% 0.0% 0.0%

1 88.5% 71.0% 80.0% 22.0% 30.0%

3 92.3% 90.0% 97.0% 34.0% 39.0%

10 93.3% 97.0% 97.0% 34.0% 48.0%

From the results in Table II. it is quite clear that compositions A, B and C which are within the scope of the invention surprisingly have improved solubility over compositions D and E which are outside the scope of the invention.

Having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

What is Claimed is:

1. A detergent composition characterized by:

(a) from 1% to 50% of a detersive surfactant system characterized, by weight of said surfactant system, (i) at least 50% of an amine oxide surfactant, and

(ii) less than 30% of a linear alkylbenzene sulfonate surfactant; and

(b) at least 1% of a detergency builder; wherein said surfactant system and said builder are agglomerated to form detergent agglomerates which are substantially free of phosphates; wherein said amine oxide surfactant and said linear alkylbenzene sulfonate surfactant of said surfactant system have improved solubility in an aqueous laundering solution.

2. The detergent composition of claim 1 further characterizing an adjunct surfactant selected from the group selected from alkyl sulfates, alkyl ethoxy sulfate, secondary alkyl sulfates and mixtures thereof.

3. The detergent composition according to any of claims 1-2 wherein said detergency builder is in an amount from 10% to 40% by weight.

4. The detergent composition according to any of claims 1-3 wherein said linear alkylbenzene sulfonate surfactant is present in an amount of from 0% to 15% of the said surfactant system.

5. The detergent composition according to any of claims 1-4 wherein said aqueous laundering solution is at a temperature from 5°C to 30°C.

6. The detergent composition according to any of claims 1-5 further characterizing adjunct ingredients selected from the group characterized by bleaches, bleach activators, suds suppressers and soil release agents.

7. The detergent composition according to any of claims 1-6 wherein said detergency builder is selected from the group characterized by sodium carbonate, zeolites and mixtures thereof.

8. The detergent composition according to any of claims 1-7 wherein the density of said detergent composition is 650 g/1.

9. The detergent composition according to any of claims 1-8 further characterizing by weight of said surfactant system, from 1% to 50% of a Ci_Q-C_jg N-alkyl polyhydroxy fatty acid amide for use as an adjunct surfactant.

10. The detergent composition according to any of claims 1-9 wherein said amine oxide surfactant is at least 5% more soluble in said detergent composition as compared to said amine oxide surfactant dissolved alone in said aqueous laundering solution.