MXPA99006231A - Thickened, highly aqueous liquid detergent compositions - Google Patents

Abstract

Low cost, highly aqueous, thickened heavy duty liquid laundry detergent compositions are provided. Such compositions contain relatively low levels of surfactant materials, certain viscosity-enhancing agents, and very large amounts of water. Only minimal amounts of other detergent composition adjuvants are permitted in such compositions.

Description

COMPOSITIONS DETERGENTS HIGHLY AQUEOUS AND THICKLY LIQUID FIELD OF THE INVENTION This invention relates to liquid heavy duty laundry detergent (HDL) products comprising relatively small amounts of detersive surfactants, very large amounts of water as a liquid carrier and minimal amounts of a relatively inexpensive viscosity enhancing agent (thickener). which increases the viscosity of the products.

BACKGROUND OF THE INVENTION Liquid detergent products are commonly considered more convenient to use than dry detergent products in powder or particulate form. Therefore, liquid detergents have been widely accepted by consumers. Said liquid detergent products are easily measurable, they dissolve rapidly in the wash water, they are capable of being easily applied in solutions or concentrated dispersions to dirty areas on garments that will be washed, and do not form dust. They also normally occupy less storage space than granulated products. In addition, liquid detergents may have incorporated in their formulations materials that could not support drying operations without deterioration, operations that are commonly used in the manufacture of detergent products in particles or granulates. Liquid detergent products in terms of their most basic components will essentially and generally comprise functional ingredients such as one or more surfactants that promote and facilitate the removal of stains and soils from washed fabrics in aqueous washing solutions formed from said liquid detergent products. . The liquid detergent products will also generally contain a liquid carrier such as water, which serves to dissolve or at least suspend the functional and essential surfactant ingredients. In addition to the surfactants and a liquid carrier, the heavy duty liquid detergent products also contain a wide variety of additional functional ingredients that serve to promote the fabric cleaning effectiveness of the products in which they are incorporated. Such additional functional ingredients may include, for example, various builders, chelating agents, bleaching agents, activators or bleach catalysts, detergent enzymes, enzyme stabilizers, fat / oil solvents, dye transfer inhibiting agents, controllers of pH, brighteners and the like. Although the additional components of the composition can improve the cleaning performance thereof, said additional functional materials can also be relatively expensive, then raising the manufacturing cost of said products and finally raising the cost of said products to the consumer. Liquid detergent products may also contain other types of additional ingredients that do not necessarily improve the cleaning performance of said products, but which may be useful for improving the physical stability or aesthetics of said products. Such non-functional ingredients include a wide variety of materials such as hydrotropes, additional solvents, phase stabilizers, thickeners, suds suppressors, perfumes, colorants and the like. Again, although said non-functional ingredients can beneficially affect the stability or appearance of the detergent products that contain them, said non-functional ingredients also add cost to the product without necessarily serving to improve the cleaning performance of fabrics thereof. An especially fruitful way to cheaply improve the aesthetics of HDL is found in the area of viscosity-increasing agents of the composition. Of course, it is advantageous to thicken diluted HDIs to avoid the thin and watery appearance that such highly aqueous products would normally have. Since using large amounts of thickener or using relatively expensive thickeners would undesirably raise the cost of such HDLs, it would be advantageous to identify thickening agents that were relatively inexpensive and / or that could be usefully employed at relatively low concentrations. It would also be desirable to identify compounds such as certain surfactants and / or perfume materials which, in addition to their normal function, could also serve to increase the viscosity of the product. HDL products using relatively inexpensive thickeners are described, for example, in Dauderman et al., US patent. 5,565,135, issued on October 15, 1996 and in Dauderman et al., Patent of E.U. 5,587,356, issued December 24, 1996. Given the above considerations, it is highly desirable when formulating liquid detergent products to reach an adequate balance of factors as important as the cost of the composition, the cleaning performance of the composition and the slity or aesthetics of the composition. Notwithstanding the existence of products such as those described in the US patents. '135 and' 356 mentioned above, there remains a continuing need to identify heavy-duty laundry liquid detergents with ingredients selected to provide adequately effective stain / dirt removal of fabrics washed therewith, and by providing an appropriate product viscosity and other aesthetics while keeping the cost of these products very low. Accordingly, an object of the present invention is to formulate heavy-duty laundry detergent liquid compositions containing relatively small amounts of surfactant and a selected product and cost-effective product thickener system, together with very high concentrations of liquid detergent vehicle more cash in costs - water. A further object of the invention is to provide such liquid detergent compositions containing only minimal amounts of additional, functional and relatively expensive cleaning performance enhancing ingredients. Another object of the present invention is to provide liquid detergent compositions that also contain minimal amounts of additional and relatively expensive non-functional slity or aesthetic enhancement ingredients.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to thickened heavy duty laundry detergent liquid compositions that provide highly cost effective stain and dirt removal performance when used in fabric washing operations. Said compositions contain A) a surfactant system comprising about 2% to 5% by weight of the composition of certain anionic alkyl ether sulfate surfactants and about 0.2% to 10% by weight of the composition of a nonionic surfactant component of two ingredients; B) about 0.1% to 3% by weight of the composition of a thickening agent of chloride, formate or polyacrylate and C) about 86% to 94% by weight of the composition of a non-surfactant and aqueous liquid vehicle comprising no more than 3% by weight of the composition of liquids that are not water. In the surfactant system, which is substantially free of anionic and nonionic surfactants of aromatic base, the anionic component comprises alkyl ether sulphates in which the alkyl group contains from 8 to 20 carbon atoms and the polyethoxylated chain thereof contains about 1 to 20 portions of ethylene oxide. The nonionic surfactant component comprises about 0.1% to 8% by weight of the composition of an ethoxylated fatty alcohol having an alkyl portion of about 8 to 16 carbon atoms and an ethylene oxide content of about 1 to 16 moles. . The nonionic surfactant component also comprises about 0.1% to 1.0% by weight of the composition of a surfactant amine material having the general formula R? -X- (CH2) nN (R3) (R4) wherein Ri is alkyl of C6-C? 2, n is 2 to 4, X is a bridging group which is NH, CONH, COO or O, or X may be absent, and R3 and R4 are each independently H, C1- alkyl C4 or (CH2-CH2-O (R5)) wherein R5 is H or methyl. The viscosity enhancing agent component comprises alkali metal and alkaline earth metal chlorides and formates. Polyacrylate materials having a molecular weight of about 500,000 to 1,000,000 may also be employed as the viscosity enhancing agent.

Preferred compositions of the present invention contain still larger amounts of water, i.e. 88% by weight or more. Said highly preferred compositions also contain protease and amylase enzymes and certain types of perfume materials which can serve to enhance the viscosity-increasing performance of the thickening agents that are employed.

DETAILED DESCRIPTION OF THE INVENTION As mentioned, the liquid laundry detergent compositions herein contain essentially a surfactant component, a thickener component and a very large amount of an aqueous liquid carrier. Each of these essential components, as well as optional ingredients for said compositions and methods for preparing and using said compositions are described in detail as follows: all concentrations and ratios described hereinafter are on a weight basis, unless otherwise indicated.

A) Surfactant component The detergent compositions herein contain a surfactant component which should comprise an anionic alkyl ether sulfate surfactant and a non-ionic component which should comprise ethoxylated alcohols and certain surfactant amines. Each of these different types of surfactant is described as follows: Anionic alkyl ether sulfate surfactant The detergent compositions herein will generally comprise about 2% to 5% by weight of an anionic surfactant component comprising alkyl ether sulphates. Most preferably, said compositions comprise about 3.0% to 4.5% by weight of this anionic surfactant component, more preferably about 3.8% to 4.2% by weight of this anionic surfactant component. The anionic surfactant component essentially comprises ethoxylated alkyl sulfate surfactants. Said materials, known as alkyl ether sulfates or polyethoxylated alkyl sulphates, are those corresponding to the formula: R'-O- (CH 2 H 4 O) n S 3 M wherein R 'is a C 8 -C 2 alkyl group, n is from about 1 to 20 and M is a salt-forming cation. Preferably, R 'is C-C-iß alkyl, n is from about 1 to 15 and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R 'is a C 2 -C 6; n is from about 1 to 6 and M is sodium. These alkyl ether sulfate materials can provide particularly desirable fabric cleaning performance benefits when used in combination with selected non-ionic surfactants and described below, in the highly aqueous laundry liquid detergents of this invention. The alkyl ether sulphates will generally be used in the form of mixtures comprising varying lengths of the R 'chain and varying degrees of ethoxylation. Frequently, said mixtures will also inevitably contain certain non-ethoxylated alkyl sulfate materials, ie surfactants of the above ethoxylated alkyl sulfate formula, wherein n = 0. The non-ethoxylated alkyl sulfates can also be added separately to the compositions of this invention, as will be described below. In addition to the alkylethersulfate surfactants described hereinbefore, the anionic surfactant component of the compositions herein may also contain optional and additional anionic surfactants, as long as said optional and additional anionic materials are compatible with other components of the composition and not substantially adversely affect the cost or performance of the composition, i.e., the fabric cleaning performance or the stability of the composition. A preferred type of optional anionic surfactant that can be used in the compositions herein comprises primary or secondary non-ethoxylated alkyl sulfate anionic surfactants. Said surfactants are those produced by sulfation of higher C8-C2o fatty alcohols. The conventional primary alkyl sulfate surfactants have the general formula: ROS03"M + wherein R is typically a linear C8-C2o hydrocarbyl group, which may be straight chain or branched chain and M is a water solubilizing cation. R is a C 1 or C 15 alkyl and M is alkali metal.

Most preferably R is C 12 -C 14 and M is sodium. The conventional secondary alkyl sulfates can also be used in the preferred anionic surfactant component of the compositions herein. Conventional secondary alkyl sulfate surfactants are those materials that have the sulfate portion distributed randomly along the hydrocarbyl "base structure" of the molecule. Such materials can be illustrated by the structure: CH2 (CH2) n (CHOS? 3-M +) (CH2) -n CH3 where m and n are integers of 2 or more, and the sum of m + n is typically from about 9 to 15 and M is a cation solubilizing in water. Especially preferred types of secondary alkyl sulphates are the alkyl sulfate surfactants (2,3) which can be represented by structures of the formulas A and B: (A) CH 2 (CH 2) x (CHOSO 3"M +) CH 3 and (B) CH 3 (CH2) and (CHOS? 3"M +) CH2CH3 for 2-sufate and 3-sulfate, respectively. In formulas A and B, xy (y + 1) are, respectively, integers of at least about 6, and may vary from about 7 to about 20, preferably about 10 to about 16. M is a cation, such as a cation of alkali metal, alkaline earth metal or the like. Sodium is typical for use as M to prepare the water-soluble alkyl sulfates (2,3), but potassium and the like can also be used. Other optional anionic surfactants that may be employed generally include carboxylate-type anionics. The anionics: ipo carboxylate include fatty acid soaps, e.g., of C10-C18, the alkylalkoxycarboxylates of C-C-is (especially the ethoxycarboxylates EO 1 a) and the sarcosinates of C-? 0-C18, especially oleoilsarcosinate. A common type of anionic surfactant that is not to be used in the compositions herein comprises the aromatic anionics, for example, alkylbenzene sulfonates. The alkylbenzene sulfonates are desirably avoided in the formulation of the liquid detergent products herein for processing and / or other reasons. Accordingly, any anionic surfactant of the detergent compositions herein will be substantially free of aromatic anionics such as alkylbenzene sulfonate anionic surfactants.

Nonionic Surfactants The detergent compositions herein will also comprise about 0.2% to 10% by weight of a nonionic surfactant component. Most preferably, said compositions will comprise from about 0.5% to 3% by weight of this nonionic surfactant component. The nonionic surfactant component of the compositions herein will comprise two specific types of nonionic surfactant materials - ethoxylated fatty alcohols and certain surfactant amines - and may also include a number of optional nonionics. These materials are all described as follows: i) Ethoxylated fatty alcohols The ethoxylated fatty alcohol nonionic surfactant materials useful herein are those corresponding to the general formula: R 1 (C 2 H 4 O) n OH wherein R 1 in a C 8 -C 6 alkyl group and n varies from about 1 to 16. Preferably, R1 is an alkyl group, which may be primary or secondary, containing about 9 to 15 carbon atoms, most preferably about 10 to 14 carbon atoms. Preferably, the ethoxylated fatty alcohols will contain about 2 to 12 portions of ethylene oxide per molecule, most preferably about 3 to 10 portions of ethylene oxide per molecule.

The nonionic ethoxylated fatty alcohol surfactant will often have a hydrophilic-lipophilic balance (HLB) ranging from about 3 to 17. Most preferably, the HLB of this material will vary from about 6 to 15, more preferably about 10 to 15. Examples of ethoxylated fatty alcohols useful in any nonionic surfactant component of the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain about 7 moles of ethylene oxide. Such materials have been marketed under the trademarks Neodol 25-7 and Neodol 23-6.5 by Shell Chemical Company. Other useful Neodoles include Neodol 1-5, an ethoxylated fatty alcohol that averages 11 atoms in its alkyl chain with approximately 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C? 2-C-? 3 alcohol having approximately 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated Cg-Cp primary alcohol having approximately 10 moles of ethylene oxide . Ethoxylated alcohols of this type have also been marketed by Shell Chemical Company under the Dobanol brand. Dobanol 91-5 is a fatty alcohol of C9-Cn ethoxylated with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a fatty alcohol of Ci2-C15 ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol. Other examples of suitable nonionic ethoxylated alcohol surfactants include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are ethoxylated linear secondary alcohols which have been sold commercially by Union Carbide Corporation. The first is a mixed ethoxylation product of linear secondary alkanol from Cu to C-? 5 with 7 moles of ethylene oxide and the latter is a similar product but with 9 moles of ethylene oxide being reacted. Other types of nonionic ethoxylated alcohol surfactants useful in the present compositions are the higher molecular weight nonionics, such as Neodol 45-11, which are similar condensation products of ethylene oxide of higher fatty alcohols, having the higher fatty alcohol 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Said products have also been sold commercially by Shell Chemical Company. The ethoxylated fatty alcohol component of the nonionic surfactant will generally comprise about 0.1% to 8% by weight of the compositions herein. Most preferably, the ethoxylated fatty alcohol component will comprise about 0.1% to 1% by weight of the compositions. ii) Surfactant amines The second essential ingredient of the nonionic surfactant component of the compositions herein comprises surface active amines.

Suitable surfactant amines for use herein include amines according to the formula: wherein Ri is a group of C6-C? 2, n is from about 2 to about 4, X is a bridging group that is selected from NH, CONH, COO or O, or X may be absent and R3 and R4 are individually selected from H, C1-C4 alkyl or (CH2-CH2-0 (R5)) wherein R5 is H or methyl. Preferred surfactant amines include the following: R1- (CH2) 2-NH2; R? -O- (CH2) -NH2; R1- (0) -NH- (CH2) 3-N (CH3) 2; and CH2-CH (OH) -R5 and R1- N I CH2-CH (OH) -R5; wherein R1 is an alkyl group of C6-Ci2 and R5 is H or CH3. In a highly preferred embodiment, the surfactant amine is described by the formula: R? -C (0) -NH- (CH2) 3-N (CH3) 2 wherein R1 is C8-C-? 2 alkyl.

Particularly preferred surfactant amines include those selected from the group consisting of octylamine, hexylamine, decylamine, dodecylamines, C8-C2 bis (hydroxyethyl) amine, C8-C12 bis (hydroxyisopropyl) amine and C8-C amidopropyldimethylamine? 6, preferably C8-C? 2, and mixtures of these amines. The surfactant amine component of the nonionic surfactant will generally comprise about 0.1% to 1.0% by weight of the composition. Most preferably, the surfactant amine component will comprise from about 0.2% to 0.6% by weight of the composition. iii) Optional non-ionic alternatives In addition to the above types of ethoxylated fatty alcohol and surfactant amine nonionic surfactants, the nonionic surfactant component may also optionally include additional compatible non-interference surfactants, if cost considerations permit. . These may include, for example, C 0 -C 0 alkyl polyglycosides when high foaming compositions are desired; polyhydroxy fatty acid amides; ethylene oxide-propylene oxide block polymers of the Pluronic type and the like. If used, said nonionic ethoxylated alcohol surfactant materials should comprise no more than about 0.4% by weight of the detergent compositions herein.

One of the most preferred types of optional nonionic surfactants comprises the polyhydroxy fatty acid amides.

These materials are described in more detail in Pan / Gosselink; US patent 5,332,528, issued July 26, 1994 and incorporated herein by reference. These materials have the general structure of the formula: O R1 l i I wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R2 is C5-C3 hydrocarbyl? and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an aromatic derivative thereof. Examples of such surfactants include the N-methyl- or N-hydroxypropylglucamides of C? O-C? 8. The N-hexylglucamides of C? 2-C? 6 N-propyl-a can be used for low foaming performance. The polyhydroxy fatty acid amides, if used, may comprise about 0.1% to 0.4% of the compositions herein. A common type of nonionic surfactant that should not be used in any nonionic surfactant component of the compositions herein comprises aromatic based nonionic agents such as alkylphenols. Nonionic aromatic base materials are desirably avoided in the formulation of the liquid detergent products herein for possible environmental and / or other reasons. Accordingly, any nonionic surfactant component of the compositions detergents of the present should be substantially free of said nonionic surfactants with an aromatic base.

Cationic / amphoteric surfactants In addition to the anionic and nonionic agents above described herein, the detergent compositions herein may also contain other types of compatible surfactant materials. These include surfactants of the cationic and amphoteric types.

Examples of such materials include cationic surfactants of quaternary ammonium, the amine oxides of C? o-C18 and the betaines and sulfobetaínas of C12-C18. Of these optional surfactants, the most preferred ones include the quaternary ammonium cationics. Quaternary ammonium cationic surfactants include those that have the formula: T R4 \ / R1 X R { NR2 wherein R1 and R2 are individually selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and - (CH 2 H 4 O) x H wherein x has a value of 2 to 5; X is an anion and (1) R3 and R are each a C8-C-t4 alkyl or (2) R4 is a C8-C22 alkyl and R3 is selected from the group consisting of C -? - C10 alkyl, hydroxyalkyl CrC, o and - (C2H40) xH where x has a value from 2 to 5. the foregoing are preferred individual long chain quaternary alkylammonium surfactants wherein in the above formula Ri, R2 and R3 are each methyl and R4 is a C8-C-? 8 alkyl. The most preferred quaternary ammonium surfactants are the C8-C6 alkyltrimethylammonium chloride, bromide and methylisulfate salts and C8-Ci6 alkyldi (hydroxyethyl) methylammonium salts. Of the above, lauryltrimethylammonium chloride, myristyltrimethylammonium chloride and coconut trimethylammonium chloride and methylisulfate are particularly preferred. ADOGEN 412 ™, a lauryltrimethylammonium chloride commercially available from Witco, is a preferred quaternary ammonium cationic surfactant. It is known that the cationic quaternary ammonium surfactants of the above type are useful in detergent compositions as fabric softening agents. However, such materials, if used in the compositions of the present invention, are generally used at concentrations below those useful for such materials to provide fabric softening effects. When employed at concentrations of about 0.1% to 1% by weight, most preferably about 0.4% to 0.8% by weight of the composition, said cationic quaternary ammonium surfactants will provide a performance benefit of removing grease / oil dirt without undesirably raising the cost of the compositions herein. When employed at these relatively low concentrations, said cationic quaternary ammonium surfactants may also act as thickeners that increase the viscosity of the liquid detergent compositions herein.

C) Viscosity enhancing agent component The third essential component of the liquid detergent compositions herein comprises one or more viscosity enhancing agents of relatively low cost. Said viscosity enhancing agents, i.e., thickeners, will generally comprise about 0.05% to 3% by weight of the compositions herein, most preferably about 0.1% to 2% by weight of the compositions herein. The relatively low cost viscosity increasing agents which are especially suitable for use in the highly aqueous liquid detergents of this invention may include halide and formate salts, as well as polyacrylic copolymers. Combinations or mixtures of these types of viscosity increasing agents can also be used. Suitable halide and formate salts that can be used include the alkali metal, alkaline earth metal and magnesium salts of halides and formates. Examples of such materials include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, sodium formate, calcium formate and magnesium formate. More sodium chloride, sodium formate and calcium formate are preferred. The polyacrylic copolymers that can be used as the viscosity-increasing agents are those having a molecular weight of from about 500,000 to 1,000,000, most preferably about 750,000 to 1,000,000. Suitable co-monomers for use in the preparation of these materials include methacrylic acid and ethylene oxide. These polyacrylic thickeners may or may not be interlaced. Examples of suitable polyacrylic copolymer thickeners include those marketed under the names Acusol 820 and Acusol 880 by Rohm and Haas Company.

D) Aqueous liquid vehicle The fourth essential component of the liquid detergent compositions herein comprises a non-surfactant and aqueous liquid carrier. Since the object of the present invention is to use as little as possible of the functional components of the detergent composition, the amount of the non-surfactant and aqueous liquid carrier employed in the compositions herein will be very large. In general, the non-aqueous and non-aqueous liquid carrier component will comprise approximately 86% to 94% by weight of the compositions herein. Most preferably, this liquid carrier component will comprise about 88% to less than 90% by weight of the compositions herein. The most effective type in non-surfactant and aqueous liquid vehicle costs is, of course, the water itself. Accordingly, the non-surfactant and aqueous liquid carrier will generally comprise water, if not entirely. Although other types of water-miscible liquids, such as alkanols, diols, other polyols, ethers, amines and the like, conventionally have been added to liquid detergent compositions as co-solvents or stabilizers, for the purposes of the present invention, the use of Such water miscible liquids should be minimized, if not eliminated. In this manner, the non-surfactant and aqueous liquid carrier component of the compositions herein will generally contain no more than about 3% by weight of the composition of liquids other than water. Preferably, the liquid carrier will contain more than about 2% by weight of the composition of liquids other than water.

E) Optional ingredients of the detergent composition The detergent compositions of the present invention may also include any number of additional optional ingredients. These include conventional components for detergent compositions such as builders, foam formers or suds suppressors, anti-grime and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, sources of alkalinity, non-builders, chelating agents, smectite clays, enzymes, enzyme stabilizers (such as propylene glycol, boric acid and / or borax), hydrotropes, additional thickeners, dye transfer inhibitors, brighteners and perfumes, including perfumes that can promote the thickening of the liquid detergent products of the present. To maintain the purpose of the present invention, said optional ingredients, if used, should be incorporated at relatively low levels, and in fact at levels generally below those to which they are conventionally employed, if it is desired to obtain cost-effective compositions. Accordingly, if used, said optional ingredients will generally comprise no more than about 5%, ie, about 0.001% to 4% by weight of the compositions herein. Some of the optional ingredients may be used are described in greater detail as follows: i) Detergent Enzymes An optional component that is preferred in the compositions herein comprises enzymatic detergent material containing one or more protease enzymes and / or one or more amylase enzymes. Said enzymatic component will generally comprise about 0.05% to 0.5% by weight of the compositions herein, most preferably about 0.15% to 0.4% by weight of the compositions herein. Within this enzyme component, one or more protease enzyme materials will generally be present in an amount sufficient to provide about 0. 005 to 0.1 Anson units (AU) of protease activity per gram of the composition. The amylase enzyme materials will be present to the extent of about 0.01% to 0.1% by weight of the composition. Examples of suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniforms. Said protease enzymes are described in greater detail in GB 1, 243,784; EP 130J56A, EP 303J61A; WO 97/18140A; WO 93/03529A; WO 95/10591A; WO 95.07791 and WO 94/25583. All of these patent publications are incorporated herein by reference. Suitable protease materials are marketed under the brand names Esperase® (Novo), Alcalase® (Novo), Savinase® (Novo) and Maxatase® (International Bio-Synthetics). Amylases (a and ß) can be used for the removal of carbohydrate-based stains. These amylase enzymes can have any subtilisin origin such as plant, animal, bacterial, fungal or yeast. Amylase enzymes are described in greater detail in WO 95/26397A; GB 1, 296,839; WO 94/02597A; WO 94/18314 and WO 95/09909A. All of these patent publications are incorporated herein by reference. Suitable amylase enzyme materials are marketed under the trademarks Termamyl® (Novo), Fungamyl® (Novo), BAN® (Novo), Rapidase® (International Bio-Synthetis) and Duramyl® (Novo).

Other types of detergent enzymes have also been widely employed in detergent compositions. Enzymes such as lipases, cellulases and peroxidases are well known. It is possible to add one or more of these types of enzymes other than protease or amylase to the detergent compositions herein to improve the effectiveness of the composition in removing certain types of stains / soils. However, for the purposes of the present invention, it has been determined that the incorporation of these enzymes that are not protease or amylase in the compositions herein is not especially cost effective. Accordingly, the enzymatic component of the detergent compositions of this invention will generally contain no more than about 0.01% by weight of the composition of enzyme materials other than protease or amylase. ii) Optional Organic Detergent Enhancers The detergent compositions herein may also optionally contain low levels of an organic builder material that counteracts the effects of calcium or another, the hardness of the water found during the use of the wash / bleaching of the compositions herein, etc. Examples of such materials include the alkali metals, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include the sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, C?-C22 fatty acids and citric acid. Other examples are organic phosphonate sequestering agents such as those sold by Monsanto under the trade name Dequest and alkanehydroxyphosphonates. Citrate salts and C ?2-C-β8 fatty acid soaps are highly preferred. Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include polyacrylic acid, polymaleic acid and suitable polyacrylic / polymaleic acid copolymers and their salts, such as those sold by BASF under the trade name Sokalan. If used, the optional organic builder materials will generally comprise about 0.1% to 3%, most preferably about 0.1% to 2%, more preferably about 0.1% to 0.4%, by weight of the compositions herein. Even at such concentrations that are generally lower than those conventionally used, organic builders can serve to increase the effective fabric washing performance in cost of the liquid detergent compositions herein. iii) Enzyme Stabilizers The detergent compositions herein may also optionally contain low levels of materials that serve to maintain the stability of the enzyme materials of the enzyme component. Said enzyme stabilizers may include, for example, polyols such as propylene glycol, boric acid and borax. Combinations of these enzyme stabilizers can also be used. If used, the enzyme stabilizers may comprise about 0.1% to 1.0% by weight of the compositions herein. iv) Phase stabilizers / co-solvents The detergent compositions herein may also optionally contain low levels of materials that serve as phase stabilizers and / or co-solvents for the liquid compositions herein. Materials of this type include lower C-α-C3 alkanois such as methanol, ethanol and / or propanol. Lower C-α-C3 alkanolamines such as mono-, di- and triethanolamines may also be used, either by themselves or in combination with the lower alkanols. If used, the phase stabilizers / co-solvents may comprise about 0.1% to 0.5% by weight of the detergent compositions herein. v) pH Control Agents The detergent compositions herein may also optionally contain low levels of materials which serve to adjust or maintain the pH of the aqueous detergent compositions herein at optimum levels. The pH of the compositions of this invention should vary from about 7.8 to 11, most preferably about 8.0 to 9.0.

Materials such as NaOH may be added to alter the pH of the composition, if necessary. vi) Perfumes Perfumes can be added to the compositions herein for their conventional purpose, that is, to improve the aesthetics of the products by providing a pleasing odor to liquid products, both before and during use. Certain types of perfume compounds, in addition to acting as perfumes, also serve to unexpectedly increase the viscosity of the highly aqueous, formate-containing detergent compositions herein. Not all conventional perfume compounds act in this way, but a number of conventional ones do. The perfume component of the compositions herein will comprise about 0.01 to 0.5% by weight of the composition. Most preferably, the perfume compounds will comprise from about 0.1% to about 0.4% by weight of the compositions herein. The perfume compositions that are preferred to be used in the compositions herein are those that significantly increase the viscosity of a certain type of aqueous test composition containing formate and containing surfactant. Said aqueous test composition is one comprising about 1% to 14% (e.g., about 12%) of surfactant including about 0.5% lauryltrimethylammonium chloride, from 1% to 2% (vgr ., approximately 1.25%) of sodium formate and approximately 0.3% of the perfume compound or compounds. It is preferred to use in the compositions herein these perfume compounds, which in said test composition increase the Brookfield viscosity of said composition over that of the test composition which does not contain perfume compounds and at a value of about 140 cps or less. plus. Most preferably, the perfume composition that is preferred to be used in this invention will increase the viscosity of the test composition to a value of about 165 cps or more. The procedure for evaluating perfume compounds in this test composition is described in greater detail in Example III below. As described in Example III, a number of common perfume compounds satisfy the viscosity increase test described herein and accordingly are preferred to be used in the compositions herein. These include the perfume materials described as follows in Table A.

TABLE A Common name Chemical name Formula Benzyl o-hydroxybenzoate benzyl salicylate Citronelol 3,7-dimethyl-6-octen-1 -ol Citronelal nitrile 3J-dimethyl-6-octene nitrile p.t. bucinal aldehyde p-butyl-a-methylhydrocinnamic hexylcinnamic aldehyde or a-n-hexyl cinnamic aldehyde jasmonal H acetate acetate hexahydro-4,7-acetate or ciclacet methano-iden-5 (or 6) -yl linalool 3J-dimethyl-1, 6-octadien-3-ol vii) Clay dirt removal / anti-redeposition agents The compositions herein may also optionally contain water-soluble ethoxylated amines having removal and anti-redeposition properties of clay soils. If used, said materials may comprise about 0.01% to 3% by weight of the composition.

The most preferred clay removal / antiredeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in VanderMeer, US patent. 4,597,898, issued July 1, 1986. Another group of clay soiling removal / antiredeposition agents that is preferred comprises the cationic compounds described in Oh and Gosselink, European Patent Publication EP-A-111, 965, published on 27 June 1984. Other agents of this type include the ethoxylated amine polymers described in Gosselink, European Patent Publication EP-A-111, 984, published June 27, 1984. All of these patent publications are incorporated herein. as a reference.

F) Form, preparation and use of the composition The liquid detergent compositions herein are in the form of an aqueous solution or uniform dispersion or suspension of surfactants, thickeners and certain other optional ingredients, many of which are normally in solid form, and have been combined with the normally liquid components of the composition in a manner, such as the liquid ethoxylated alcohol nonionic surfactant, the aqueous liquid carrier and any other normally liquid optional ingredient such as perfume. Said solution, dispersion or suspension will be acceptably stable in phase and will typically have a viscosity ranging from about 100 to 300 cps, most preferably about 150 to 250 cps. For the purposes of this invention, the viscosity is measured with a Brookfield LVTDV-11 viscometer apparatus using a RV # 2 spindle at 12 rpm. The liquid and aqueous detergent compositions herein can be prepared by combining the essential and optional components thereof in any convenient order and mixing, that is, by stirring, the resulting combination of components to form the thickened and stable phase compositions of the present . In a preferred process for preparing said compositions, the essential and certain optional components that are preferred will be combined in a particular order. In said preferred preparation process, a liquid matrix is formed which contains at least a major portion, and preferably substantially all, of the liquid components, eg, the nonionic ethoxylated alcohol surfactant, the liquid carrier non-surfactant and aqueous and other optional liquid components, mixing the liquid components carefully imparting shear agitation to this liquid combination. For example, rapid agitation with a mechanical agitator can be used very useful. While the shear agitation is maintained, substantially all of the preferred anionic surfactants, the viscosity enhancing agents, the preferred cationic surfactants and the optional builders can be added in the form of particles ranging in size from about 0.2 to 1. , 000 microns. Agitation of the mixture is continued, and if necessary, it can be increased at this point to form a solution or uniform dispersion of insoluble solid phase particles within the liquid phase. After all the materials in solid form have been added to this stirred mixture, the particles of the enzyme material that is preferred, ie the enzyme pellets, are incorporated. In this way, the enzyme component is preferably added to the aqueous liquid matrix at the end. As a variant of the method of preparing the composition described hereinabove, one or more of the solid components may be added to the stirred mixture as a solution or suspension of premixed particles with a minor portion of one or more of the liquid components. In another variant of the preparation process, the viscosity enhancing agent can be added by combining it with the anionic surfactant during the preparation of the preferred anionic surfactant component. In this manner, the formate viscosity enhancing agent (such as sodium formate) can be introduced into the compositions herein by means of the anionic surfactant when the anionic surfactant is combined with the rest of the components of the detergent composition. After the addition of all the components of the composition, stirring of the mixture is continued for a period sufficient to form compositions having the necessary characteristics of viscosity and phase stability. This will frequently involve agitation for a period of about 30 to 60 minutes. The compositions of this invention, prepared as described above, can be used to form aqueous wash solutions that will be used in fabric washing. In general, an effective amount of said compositions is added to the water, preferably in a conventional automatic fabric washing machine, to form said aqueous washing solutions. The aqueous washing solution formed in this way is then put in contact, preferably under agitation, with the fabrics that will be washed therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous wash solutions may comprise sufficient amounts to form about 500 to 7,000 ppm of the composition in an aqueous wash solution. Most preferably, about 1,000 to 3,000 ppm of the detergent compositions herein will be provided to the aqueous wash solution.

EXAMPLES The following examples illustrate the compositions of the present invention, but do not necessarily attempt to limit or otherwise define the scope of the present invention.

EXAMPLE A composition of the present invention is prepared by mixing is listed in Table I in the proportions shown.

TABLE I Liquid detergent composition Component% By weight of active C12-15 polyethoxylated alkylsulfate 4.0 (2.5) (27%) C12-? 3 ethoxylated alcohol * (EO = 9) 0.4 C8-16 amidopropyl dimethylamine 0.5 Citric acid (50%) 1.9 Protease enzyme (34 g / l) 0.23 Ethoxylated tetraethylenepentamine 0.5 Enzyme amylase 0.05 Propylene glycol 0.26 Monoethanolamine 0.32 Borax (38%) 0.63 NaOH (50%) 1.22 Calcium formate 0.07 Sodium formate (30%) 1.25 Coloring 0.02 Perfume including benzyl salicylate 0.30 Brightener 0.05 Water 88.3 100%? Eodol 23-9 The liquid detergent composition of Table I provides a very effective fabric cleaning performance when used to form aqueous wash solutions for conventional fabric washing operations. Said performance is provided and the composition is stable, even though the composition is relatively low cost thanks to the incorporation only of very small amounts of the surfactants and other auxiliaries of the composition. By virtue of the use of sodium and calcium formate and perfume based on benzyl salicylate in the composition of Table I, this liquid detergent product is also thick enough to be used as a pretreatment product when applied fully concentrated directly on the stains from the fabric before washing stained fabrics. Compositions with substantially similar viscosity characteristics can be obtained if, in the composition of Table I, the perfume is replaced with an equivalent amount of other perfumes comprising citronellol, citronellal nitrile, hexyl cinnamic aldehyde, flower acetate, p.t. bucinal or linalool.

EXAMPLE II The composition of Example I is tested to verify its ability to remove selected types of enzyme sensitive spots from soiled fabrics. Said test compares the stain removal performance, both during washing (TTW) and in pretreatment (PT), with a highly aqueous but similar high cost detergent composition as described in Example I of a US application. copendiente and assigned commonly related that has the serial number of E.U. 08 / 744,721, filed October 29, 1996. This composition of Example I of USSN 08 / 744,721 uses a surfactant system similar to that of Example I herein, but does not use a surfactant amine, and the product of USSN 08 / 744,721 it is not so diluted (water content = 83.7%) as the compositions of this invention. The image analysis tests show the relative stain removal performance between the product described in Example I of USSN 08 / 744,721 and the product of example I above. The results are shown in table II: TABLE II Stain removal performance (image analysis - 21"C, 1.027 grams per liter) Bold number = Example I of Example I significance USSN 721 previous 95% statistic TTW Clay 47 51 Chop pudding 85 87 Sauce 71 71 Fat bacon 82 83 El Pasto 90 78 Blood 89 84 Pudding of choc. 89 93 Sauce 75 83 Hamburger fat 78 73 The data in Table II indicate that for the spots tested, the product of example I of the present invention provides a comparable (and, for some spots, superior) stain removal performance in relation to with a similar product that is of higher cost and is not so diluted.

EXAMPLE III This example illustrates a method for determining the relative effectiveness of various perfume compounds in increasing the viscosity of liquid laundry detergent compositions, highly aqueous and formate-containing formate of this invention are preferred. In said process, a liquid detergent base and test composition containing formate is prepared and splashed with 0.3% by weight of a number of conventional perfume compounds or other reference components. Said spattered test composition is mixed well using a vortexer and maintained at 21 ° C for 36 hours. The viscosity of each of the spattered compositions is then measured with a Brookfield LVTDV-11 viscometer using a # 2 spindle at 12 rpm. The test compositions have the formula shown in Table III.

TABLE III Component% in Active Weight Total surfactant agent 12.2 (Surfactant component) (% by weight of Active) C12-14 alkylsulfonic acid polyethoxylated (3.0) (27%) 5.25 C12-14 alkylsulfate 5.25 Ethoxylated alcohol of C12-13 * (EO = 9) 1.0 N-methylglucamide of C12-14 0.2 Lauryltrimethylammonium chloride ** (37%) 0.5 Citric acid (50%) 0.75 Protease enzyme (34 g / l) 0.23 Propylene glycol 0.29 Monoethanolamine 0.32 Borax (38%) 0.63 Ethanol (97%) 0.04 NaOH (50 %) 1.51 Sodium formate 1.25 Minor components (polish, preservative, dye, foam suppressant) 0.14 TABLE III (CONTINUED) Composition of perfume or other test material 0.3 Water 82.34 Total 100% * Neodol 23-9 ** Adopt 412 The viscosity characteristics of the test compositions in Table III having various components of perfume compound or other test material are establish in table IV.

TABLE IV Perfume composition Brookfield viscosity (cps) or other test material Citronelol 284.0 Hexycinnamic aldehyde 240.0 Citronellol nitrile 230.0 P.T. Bucinal 229.0 Linalool 200.0 Benzyl salicylate 163.0 Ciclal C 155.0 Flower acetate 145.0 Frutene 145.0 Cis-3-hexenyl salicylate 135.0 Linalyl acetate 125.0 Pentanyl acetate 100.0 Phenylethyl alcohol 83.0 Galaxolide 80.5 H2O 47.0 Dipropylene glycol 42.6 The viscosity test data Table IV indicates that certain common perfume compounds are especially effective in increasing the thickening of highly aqueous liquid detergent products containing formate. Said relatively effective thickening perfumes can, in general, be characterized as aldehydes, nitriles, ketones and secondary alcohols. Other common perfume compositions are not as effective in thickening these compositions. These tend to be primary esters and alcohols. The perfume compounds which are preferably employed in the present invention are those which increase the viscosity (as compared to the H2O test material) of the detergent compositions of the type in Table III to a value of 140 cps or more.

Claims (8)

NOVELTY OF THE INVENTION CLAIMS

1. - A heavy duty, highly aqueous laundry detergent liquid composition that provides cost effective stain and dirt removal performance when used in fabric washing operations and which has an acceptable viscosity for use in laundry operations. fabrics at home, said composition comprising: (A) about 2% to 5% by weight of the composition of an anionic surfactant component that is substantially free of anionic surfactants of aromatic base and which comprises alkyl polyethoxylated sulfates in which the group alkyl contains about 8 to 20 carbon atoms and the polyethoxylated chain contains from about 1 to 20 portions of ethylene oxide; (B) about 0.2% to 10% by weight of the composition of a nonionic surfactant component that is substantially free of aromatic base nonionic surfactants and which comprises: i) from about 0.1% to 8% by weight of the composition of ethoxylated fatty alcohols of the formula R1 (OC2H4) nOH, wherein R1 is a C8-C6 alkyl group and n is from about 1 to 16 and ii) about 0.1% to 1.0% by weight of the composition of a surfactant amine that has the formula: R3 R? -X- (CH2) nN R4 wherein R1 is a C6-C? 2 alkyl group, n is from about 2 to about 4, X is a bridging group that is selected from NH, CONH, COO or O , or X may be absent and R3 and R4 are individually selected from H, C1-C4 alkyl or (CH2-CH2-0 (R5)) wherein R5 is H or methyl; (C) from about 0.1% to 3% by weight of the composition of a viscosity-increasing agent component comprising alkali metal and alkaline earth metal chlorides and formates, polyacrylic compositions having a molecular weight of from about 500,000 to 1,000,000 and combinations of said viscosity-increasing agents and (D) from about 86% to 94% by weight of the composition of a liquid non-surfactant and aqueous vehicle comprising not more than 3% by weight of the composition of liquids other than water. 2. A composition according to claim 1, further characterized in that (A) the alkyl ether sulfate contains from about 12 to 16 carbon atoms and from about 1 to 6 moles of ethylene oxide; (B) the ethoxylated fatty alcohol contains from about 10 to 14 carbon atoms and from about 3 to 10 moles of ethylene oxide; (C) the surfactant amine is selected from R? - (CH2) 2-NH2; R O- (CH 2) 2-NH 2; R1- (0) -NH- (CH2) 3-N (CH3) 2; and CH2-CH (OH) -R5 R-N I CH2-CH (OH) -R5; wherein Ri is a C6-C2 alkyl group and R5 is H or CH3 and (D) the agent

The viscosity enhancer is selected from sodium formate, calcium formate and mixtures thereof.

3. A composition according to claim 2, which further contains about 0.05% to 0.5% by weight of an enzyme component comprising both protease and amylase enzymes.

4. A composition according to claim 3, which further contains about 0.1% to 1% by weight of the composition of one or more enzyme stabilizing agents selected from propylene glycol, boric acid and borax.

5. A composition according to claim 2, which further contains from about 0.01% to 0.5% by weight of the composition of one or more perfume compounds that alone or in combination increase the Brookfield viscosity of an aqueous composition that it comprises 11% to 14% surfactant including about 0.5% lauryltrimethylammonium chloride, from 1% to 2% sodium formate and 0.3% perfume, at a value of about 140 cps or more.

6. - A composition according to claim 2, which further contains from about 0.1% to 3% by weight of the composition of a carboxylate builder selected from C10-C22 fatty acids and their salts, and citric acid and its you go out;

7. A heavy-duty, highly aqueous laundry detergent liquid composition that provides cost effective stain and dirt removal performance when used in fabric washing operations and which has an acceptable viscosity to be used in water treatment operations. washing fabrics at home, said composition comprising: (A) from about 3.8% to 4.2% by weight of the composition of an anionic surfactant component which is substantially free of aromatic base anionic surfactants and which comprises sodium alkyl ether sulfates of C12- C16 containing from about 1 to 6 moles of ethylene oxide; (B) from about 0.5% to 3% by weight of the composition of a nonionic surfactant component which is substantially free of aromatic base nonionic surfactants and which comprises: i) from about 0.1% to 1% by weight of the composition of C10-C14 ethoxylated fatty alcohols containing from about 3 to 10 moles of ethylene oxide and i) from about 0.2% to 0.6% by weight of the composition of a selected surfactant amine of C8-C amidopropyldimethyl amines 6; (C) from about 0.1% to 2% by weight of the composition of a carboxylate builder selected from C10-C22 fatty acids and salts, and citric acid and its salts; (D) from about 0.05% to 0.5% by weight of the composition of an enzyme component comprising one or more protease detergent enzymes and one or more amylase detergent enzymes but containing not more than about 0.01% by weight of said composition of other types of detergent enzymes; (E) from about 0.1% to 2% by weight of the compositions of a viscosity increasing agent of sodium chloride, sodium formate or calcium formate and (F) of about 88% or less than 90% by weight of the composition of a liquid non-surfactant and aqueous vehicle comprising not more than 2% by weight of the composition of liquids other than water.

8. A composition according to claim 7, which further contains from about 0.1% to 0.4% by weight of the composition of perfume compositions selected from benzyl salicylate, citronellol, citronellal nitrile, p.t. bucinal, flower acetate, linalool, hexyl cinnamic aldehyde and combinations thereof.