Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D10/00—Compositions of detergents, not provided for by one single preceding group
  • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/18—Sulfonic acids or sulfuric acid esters; Salts thereof derived from amino alcohols
  • C11D1/20—Fatty acid condensates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention relates to fully-formulated detergent compositions containing a nonionic surfactant, an anionic surfactant and soaps, all of which are prepared from mainly renewable resources such as natural fats and oils, fatty esters and reducing sugars.
• the compositions yield extremely low interfacial tensions in aqueous media, especially in the presence of calcium ions, and are thus useful for cleaning operations.
• Most conventional detergent compositions contain mixtures of various detersive surfactants in order to remove a wide variety of soils and stains from surfaces.
• various anionic surfactants especially the alkyl benzene sulfonates, are useful for removing particulate soils
• various nonionic surfactants such as the alkyl ethoxylates and alkylphenol ethoxylates are useful for removing greasy soils.
• mixtures of anionic and nonionic surfactants are used in many modern detergent compositions.
• many such surfactants are prepared mainly from petrochemical feedstocks.
• Soaps i.e., the salts of fatty acids
• Soaps have the advantage that they are available via the hydrolysis of renewable resources such as plant and animal oils and fats.
• soaps are quite susceptible to the formation of "curd" in the presence of water hardness.
• soaps are not as effective across conditions of pH and water hardness for lowering solution interfacial tensions as are their synthetic counterpart surfact ⁇ ants, and are less effective cleaners, especially for grease and oil deposits.
• nonionic surfactants which can be prepared using mainly renewable resources, such as fatty acid esters and sugars.
• One such class of surfactants includes the polyhydroxy fatty acid amides.
• conventional anionic surfactants such as the alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, and the like, has also been studied.
• alkyl benzene sulfonate surfactants do provide superior cleaning over a wide variety of usage conditions, especially in home fabric laundering operations. It is understandable that the formulator would be disinclined to change from the alkyl benzene sulfonates to other detersive systems, if doing so would lower overall product per ⁇ formance and, as noted above, would also be economically disadvantageous.
• surfactant systems which comprise a mixture of nonionic and anionic surfactants, both of which can be prepared from renewable, non-petrochemical resources. It would additionally be advantageous to devise such mixed nonionic/anionic surfactant systems which are compatible with other detersive surfactants and other detersive ingredients in order to enable the formulator to provide superior detergent compositions. It would be of considerable additional economic advantage for such surfactant systems to be manufactured mainly from the same basic feedstock v materials.
• nonionic polyhydroxy fatty acid amides with their anionic sulfated analogs quickly and easily provides superior mixed nonionic/anionic surfactant systems which are derivable from the same feedstocks and which are available from renewable resources such as plants. It has further been unexpectedly found that the combination of such nonionic/anionic surfactant mixtures with soaps leads to overall polyhydroxy fatty acid amide/sulfated polyhydroxy fatty acid amide/soap surfactant systems which provide extremely low interfacial tensions in aqueous media.
• the mixed nonionic/anionic/soap combinations herein provide excellent removal of greasy and oily soils and stains from a variety of substrates, even in the absence of phosphate builders. To achieve this goal using surfactants made from renewable resources and without the use of phosphates has been a substantial challenge to detergent formulators heretofore.
• Such mixed nonphosphate-built, nonionic/anionic/soap combinations are the subject matter of the present invention.
• the present invention encompasses detergent compositions comprising a mixed nonionic/anionic surfactant system which comprises a polyhydroxy fatty acid amide (a) of the formula
• R2 - C - N - Z wherein R is H, Ci-C ⁇ hydrocarbyl, 2-hydroxyethyl, 2-hydroxy- propyl, or a mixture therein, R 2 is C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two (in the case of glyceraldehyde) or preferably at least three (in the case of other reducing sugars) hydroxyls directly connected to the chain; and
• an anionic surfactant which is a member selected from the group consisting of sulfated polyhydroxy fatty acid amides of said formula (a), at a weight ratio of (a):(b) of from about 10:1 to about 1:10; and
• compositions according to the present invention containing such soaps exhibit quite low .interfacial tensions and good grease removal properties, even at pH's near neutrality, i.e., over the range of ca. 7-11.0.
• the. improved qualities of the compositions herein appear to peak with soaps of about C12, and decrease somewhat with soaps which are longer than about C13 and shorter than about Cn, especially with respect to spontaneous e ulsification of greasy soils. Accordingly, the C12 soaps are preferred herein.
• the "soaps" can be employed in any water-soluble salt form, e.g., alkali metal, alkaline earth metals, ammonium, alkanolammonium, di-alkanolammonium, tri-alkanolammonium, C1-5 alkyl substituted ammonium, basic amino acid groups, and the like, all of which are well-known to manuf cturers.
• the sodium salt form is convenient, cheap and effective.
• the fatty acid form can also be used, but will usually be converted into ion form by pH adjustments which are made during processing of the compositions. Since water- soluble soaps are generally easier to work with, it is preferred that they be used, rather than the fatty add form.
• Nonlimiting examples of soaps useful herein include: deca- noate; undecanoate; laurate; undecyleneate; 2-dodecenoate; tridecanoate; and mixtures thereof.
• the soaps typically comprise at least about 1% by weight of the total compositions herein and preferably comprise from about 4% to about 10% by weight of the compositions. Stated otherwise, the weight ratio of soap (c) to the combined mixture nonionic/ani ⁇ onic (a + b) is in the range c:(a + b) from about 1:20 to about 1:2, preferably about 1:8 to about 1:3.
• Preferred compositions herein contain at least about 10%, preferably from about 25% to about 65%, by weight of said nonionic/anionic/soap surfactant system. Such compositions may comprise from about 3% to about 50% of the nonionic surfactant and from about 3% to about 50% of its sulfated anionic ocunterpart surfactant.
• compositions which additionally contain from about 2% to about 40% by weight of an additional detersive surfactant, as well as other optional detersive adjuncts as disclosed hereinafter.
• compositions which comprise from about 10% to about 65% by weight of said mixed nonionic/anionic/soap surfactant system, from about 1% to about 15% by weight of an ethoxylated C ⁇ -C24 alcohol, and optional builders and detersive enzymes.
• Such compositions exhibit especially good removal of cosmetic stains from fabrics.
• compositions herein will also contain from about 0% to about 2%, preferably from about 0% to about 1.0%, by weight, of calcium ions.
• High sudsing compositions will contain from about 0% to about 2%, preferably from about 0% to about 1.0%, by weight of magnesium ions.
• Sources of calcium and magnesium can be any convenient water-soluble and toxicologically acceptable salt, including but not limited to, CaCl2. MgCl2, Ca(0H)2, Mg(0H)2, CaBr2, MgBr2, Ca malate, Mg malate; Ca maleate, Mg maleate, calcium formate, CaS04, gS ⁇ 4 or the calcium and/or magnesium salts of anionic surfactants or hydrotropes.
• CaCl2 and MgCl2 are convenient and preferred herein.
• the invention therefore also encompasses an improved method for removing cosmetic stains from fabrics, comprising contacting the fabrics thus stained with an aqueous bath containing at least about 0.02% by weight of a composition which comprises said nonionic/anionic/soap surfactant system and, preferably also containing said C8-C24 alkoxylated (preferably ethoxylated) alcohol or alkoxylated C8-C24 alkyl phenol (preferably ethoxylated). All percentages, ratios and proportions herein are by weight, , unless otherwise specified. All documents cited are incorporated herein by reference.
• compositions and processes of this invention most prefer ⁇ ably employ high quality polyhydroxy fatty acid amide surfactants which are substantially free of cyclized and ester-amide by-products. While the polyhydroxy fatty acid amide-based sur ⁇ factants used herein can be prepared, for example, by the methods disclosed in the Schwartz references above, this invention most preferably employs high quality polyhydroxy fatty .add amide surfactants which are substantially free of cyclized by-products.
• the methods comprise reacting N-alkylamino polyols with, preferably, fatty acid methyl esters in a solvent using an alkoxide catalyst at temperatures of about 85"C to provide high yields (90-98%) of polyhydroxy fatty acid amides having desirable low levels (typically, less than about 1.0%) of sub-optimally degradable cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2.
• Use of N-methyl and N-hydroxyalkyl amine compounds provides high sudsing materials.
• N-C -C8 alkyl amine compounds provides low sudsers.
• the low sudsers e.g., n-butyl, iso-butyl, n-hexyl
• the methanol introduced with the catalyst or generated during the reaction provides sufficient fluidization that the use of additional reaction solvent may be optional.
• any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, to minimize the overall level of amines in the product.
• cyclized by-products herein is meant the undesirable reaction by-products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures which may not be readily biode ⁇ gradable. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substitu- ents) is naturally "capped" by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein.
• compositions and processes herein use polyhydroxy fatty acid amide surfactants of the formula:
• R is H, Ci-C ⁇ hydrocarbyl, 2-hydrox eth 1, 2-hydroxy- propyl, or a mixture thereof, preferably C1-C4 alkyl, more prefer ⁇ ably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C ⁇ -Cig alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxyl- ated derivative (preferably ethoxy
• Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
• Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceralde- hyde.
• high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
• Z preferably will be selected from the group consisting of -CH2- (CHOH) n -CH2 ⁇ H, -CH(CH2 ⁇ H)-(CHOH) n -i-CH2 ⁇ H, -CH2-(CH0H)2(CH0R')- (CHOH)-CH2 ⁇ H, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
• R 1 can be, for example, N-methyl, N-ethyl, N-n-propyl, N-isopropyl, N-n-butyl, N-isobutyl, N-n-hexyl, N-2- ethylhexyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
• R2-C0-N ⁇ can be, for example, coca ide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
• Z can be 1-deoxyglucityl, 2-deoxyfructityl , 1-deoxyxylityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyman- nityl, 1-deoxymaltotriotityl, 2,3-dihydroxypropyl (from glyceral ⁇ dehyde), etc.
• polyhydroxy fatty acid amide surfactants used herein as the nonionic surfactant component can be mixtures of materials having various substituents R 1 and R 2 .
• the sulfation products herein are believed to be mainly mono-sulfates on the terminal hydroxyl substituent of the polyhydroxy fatty acid amides.
• the amides do contain multiple hydroxyl groups where sulfation can occur, the di-, tri-, tetra-, etc. sulfates can be formed in varying amounts and be co-present in the compositions. Indeed, it appears that using the syntheses disclosed herein, approximately
• the pH is monitored to assure that it remains basic at all times.
• a mixture with a final pH of 9.0 is achieved with a total of 157 ml IN sodium hydroxide and 400 ml water.
• the mixture is evaporated at ambient in a dish in hood-air stream for one week with occasional stirring to remove chloroform. Up to 8560 g is made with water to give approximately 1% solution at pH 8.6.
• Cationic SO3 analysis indicates 0.13 mole fraction sulfation.
• the resulting product is a mixed nonionic/anionic surfactant according to this invention.
• the polyhydroxy fatty acid amide is sulfated as follows.
• Step 1 Two hundred grams of the C12-14 N-methyl glucamide are dissolved in one liter of methylene chloride and transferred to a 2 1 reaction flask.
• Step 2 66.8 grams of a 1:1 (mole basis) pyridine/S03 complex obtained from Aldrich Chemical Company are added to the reaction flask. The reaction is allowed to proceed at room temperature foe three days (a matter of convenience; other reaction times can be used, depending on temperature, etc.).
• Step 3 25 grams of sodium carbonate are dissolved in 80 mis. water and added to the reaction flask with mixing for four hours.
• Step 4 The crude reaction mixture is evaporated and the residue taken up in methanol (total volume 1.4 1).
• Step 5 The methanol is dried over MgS ⁇ 4 and the solids removed by vacuum filtration.
• Step 6 The methanol solution is decolorized with charcoal; the charcoal is removed by filtration through a Celite bed.
• Step 7 Excess methanol is evaporated on a rotary evaporator (60 * C; vacuum). The residue is slurried with ethyl acetate (slightly warm).
• Step 8 The ethyl acetate slurry is cooled to room temperature and the solids allowed to settle. The ethyl acetate containing the desired sulfated glucamide surfactant is decanted from the solids and the solvent removed by evaporation.
• Step 9 The solids remaining after evaporation of the ethyl acetate are ground by mortar and pestle and dried in a vacuum oven (25 * C; 20 mm pressure). The yield is 205 g/84.7% of theoretical.
• Tallow (C16-C18) N-methylglucamide is sulfated similarly, except that pyridine is used in place of methylene chloride as the solvent in the first step. A precipitate forms in Step 5, and is removed by filtration. The sulfated tallow N-methyl glucamide requires no decolorization.
• the sulfated polyhydroxy fatty acid amides used herein as the anionic surfactant component can also comprise the sulfated reaction product of polyhydroxy fatty acid amides having a mixture of R 1 and R 2 substituents.
• Mq/Ca Salts Mq/Ca Salts
• the sul ared polyhydroxy fatty acid amide surfactants herein are conventionally prepared in their acid or alkali metal (e.g., Na, K) salt forms, or as ammonium or alkanolammonium salts, e.g., triethanolammonium.
• These counterion salts are non-limiting examples of typical sulfated detergents.
• the formulator may find it advantageous to incorporate at least about 0.5%, preferably from about 0.6% to about 2%, by weight of magnesium ions, calcium ions, or mixtures thereof, into the finished detergent composition. This can be done by simply adding various water-soluble salts such as the chlorides, sul- fates, acetates, etc.
• magnesium and/or calcium salts of the sulfated polyhydroxy fatty acids herein byreacting Mg(0H)2 or Ca(0H)2 with the acid form of the sulfated polyhydroxy fatty acid amide, and this can conveniently be done in situ during the formulation of the finished detergent compositions or as a separ ⁇ ate step during the manufacture of the sulfated surfactant, itself.
• Low Sudsing Compositions Under some circumstances the formulator of detergent composi ⁇ tions may find it desirable to provide low sudsing compositions. For example, low sudsing is a desirable feature of window clean- ers, floor and wall cleansers, and other hard surface cleansers where excess sudsing would require inconvenient rinsing steps in the overall cleaning process. Dishwashing detergents for use in automatic machines must be formulated to have essentially no suds, since excess suds can actually spill out of the machines. Like- wise, European-style front loading fabric washing machines require low sudsing detergents to avoid suds spillage. Low sudsing can also be advantageous in concentrated laundering processes such as described in U.S. Patents 4,489,455 and 4,489,574.
• the polyhydroxy fatty acid amides of formula (I) herein having H, hydroxyalkyl and/or methyl substitu- ents as group R 1 are high sudsers, whereas the compounds with R 1 as C3-C8 (straight-chain, branched chain or cyclic) are low sudsers.
• the low sudsers, especially C2 and C3 alkyl, still lower interfacial tensions ver substantially and are thus quite active detersive surfactants.
• the formulator may wish to employ compounds of formula (II), conveniently and preferably with their corresponding sulfates,
• Low sudsers preferably are substantially free of N-hydrogen, N-methyl, N-ethyl and N-hydroxyalkyl substituents.
• the sulfates with shorter alkyl chains can be used with these longer chain polyhydroxy fatty acid amides, but this is less convenient from a manufacturing stand ⁇ point.
• the synthesis of such compounds follows the steps noted above.
• the formulator may opt not to conduct the hereinbefore described steps ("Secondary Reaction") to diminish the levels of fatty acids in the reaction products, since the fatty acids can, themselves, help control suds.
• preferred compositions herein are those wherein the total number of carbon atoms in the N-alkyl substituent plus fatty acid substituent is no greater than about 20-21. This is espe- daily true when formulating homogeneous liquid compositions.
• low sudsing herein is meant a suds height or suds volume for the low sudsing detergent compositions herein containing the N-C3-C8 alkyl polyhydroxy fatty acid amide surfactant which is substantially less than that which is achieved in comparable compositions containing the N-methyl polyhydroxy fatty acid amide surfactant.
• the compositions herein provide sudsing which is no greater, on average, than about 70%, preferably no greater than about 50%, of that produced with the N-methyl sur ⁇ factants.
• the sudsing can be still further reduced by means of standard suds control agents such as the silicones, various fatty materials and the like.
• a useful test procedure for comparing the sudsing of the low-suds compositions herein is provided hereinafter.
• the test comprises agitating aqueous solutions containing the detergent being tested in a standardized fashion and comparing sudsing against equivalent detergents containing the N-methyl polyhydroxy fatty acid amide.
• This particular test is run at ambient temperature ⁇ ca. 23 * C) and at 60*C, and at water hardness (3:1 Ca:Mg) levels of 10.4 gr/gal (179 ppm) and 25 gr/gal (428 ppm) to mimic a wide variety of prospective usage conditions.
• the formulator may modify the test conditions to focus on prospective usage conditions and user habits and practices throughout the world.
• Sudsing Test Suds cylinders having the dimensions 12 inch (30.4 cm) height and 4 inch (10.16 cm) diameter are releasably attached to a machine which rotates the cylinders 360 * around a fixed axis.
• a typical test uses four cylinders, two for the standard comparison detergent product and two for the low sudsing detergent test product.
• aqueous solution of the respective detergents 500 mL is placed in the cylinders.
• the solutions comprise 3 g of the detergent, but other amounts can be used.
• the temperature of the solutions and their hardness are adjusted as noted above.
• CaCl2 and MgCl2 salts are used to supply hardness.
• the cylinders are sealed and the 500 ml level marked with tape. The cylinders are rotated through two complete revolutions, stopped and vented.
• a suds "volume” is calculated by taking the average suds height over the test time (10 minutes) and can be expressed as suds volume per minute (cm), which conforms with: suds volume per minute - sum of suds height at each time of measurement divided by total time (10 minutes).
• adjunct materials preferably used in fully- formulated detergent compositions containing the surfactants of the present invention will vary, depending on the intended end-use of the final compositions. The following are intended only to be nonlimiting illustrations of such adjuncts, more examples of which will readily come to mind of the skilled formulator.
• compositions herein are designed to provide good cleaning. However, if the formulator wishes, various additional surfactants can be incorporated into the compositions to provide various auxiliary cleaning benefits. Typically, such additional surfactants will be used at levels up to 30% by weight of the final, fully-formulated compositions.
• Nonlimiting examples of optional surfactants useful herein include the conventional Cn-C 6 alkyl benzene sulfonates, the Cl2 ⁇ Cl8 primary and secondary alkyl sulfates and C12-C18 unsaturated (alkenyl) sulfates such as oleyl sulfate, the Cio-C ⁇ alkyl alkoxy sulfates (especially ethoxy sulfates), the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglyco- sides, C12-C18 alpha-sulfonated fatty acid esters, C12-C18 betaines and sulfobetaines, C10-C 8 amine oxides, and the like, having due regard for the effects on sudsing noted above.
• nonionic alcohol- and alkylphenol- ethoxylates are preferred for use in the present composi ⁇ tions to remove "non-polar, greasy” stains such as cosmetics, lipstick, and the like, from various fabrics and surfaces.
• Enzymes - Detersive enzymes can optionally be included in the detergent formulations for a wide variety of purposes, especially for fabric laundering, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
• the enzymes to be incorpor ⁇ ated include proteases, amylases, Upases, cellulases, and per- oxidases, 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.
• Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 g to about 3 mg, of active enzyme per gram of the composition.
• Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
• Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
• Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
• Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application 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, or-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
• the cellulases 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 Aero onas, 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-0S-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.
• Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
• Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
• Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application W089/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S.
• Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
• compositions herein can option- ally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
• Builders - Detergent builders can optionally be included in the compositions herein 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 particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder.
• Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder.
• Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder.
• Lower or higher levels of builder, however, are not meant to be excluded.
• Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbon- ates), sulphates, and aluminosilicates.
• non-phosphate builders are required in some locales.
• the composi ⁇ tions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
• silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2: a2 ⁇ 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.
• layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
• other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
• 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 especially useful in the present invention.
• Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent composi ⁇ tions, and can also be a significant builder ingredient in liquid detergent formulations.
• Aluminosilicate builders include those having the empirical formula: M z (zAl ⁇ 2-ySi ⁇ 2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC ⁇ 3 hardness per gram of anhydrous aluminosili- cate.
• Preferred aluminosilicates are zeolite builders which have the formula:
• aluminosilicate ion exchange materials are commer ⁇ cially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosili ⁇ cates or synthetically derived. A method for producing alumino- silicate 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), and Zeolite X. In an especially preferred ⁇ embodiment, the crystalline aluminosilicate ion exchange material has the formula:
• 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.
• polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
• Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
• polycarboxylate builders include 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
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
• ether hydrox - polycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxymethyloxysuccinic acid
• various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
• polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular composi ⁇ tions, especially in combination with zeolite and/or layered silicate builders.
• 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.
• succinate builders include: laurylsuc- cinate, yristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
• Fatty acids e.g., C12- 18 monocarboxylic acids
• the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
• Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
• the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophos- phates can be used.
• Phosphonate builders such as ethane-1- hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patent 3,159,581; 3,213,030; 3,422,021; 3,400,148; and 3,422,137) can also be used.
• Bleaching Compounds - Bleaching Agents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
• bleaching agents When present, bleaching agents will typically be at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
• the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
• Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein, but, under some conditions, may undesirably interact with the polyol nonionic surfactant.
• bleaching agent that can be used without restriction encompasses percarboxylic (“percarbonate”) acid bleaching agents and salts therein. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
• percarboxylic (“percarbonate”) acid bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hart an, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S
• Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
• Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxy- hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
• Persulfate bleach e.g., 0X0NE, manufactured commercially by DuPont
• Mixtures of bleaching agents can also be used.
• Peroxygen bleaching agents and the perborates are preferably combined with bleach activators, which lead to the in situ produc ⁇ tion in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
• bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
• NOBS nonanoyloxybenzene sulfonate
• TAED tetraacetyl ethylene diamine
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non- oxygen bleaching agent of particular interest includes photo- activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al.
• detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
• Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
• Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
• compositions will comprise from about 0.01% to about 10%, by weight, of the polymeric soil release agent, typically from about 0.1% to about 5%, and from about 4% to about 50%, more typically from about 5% to about 30% of anionic surfactant.
• Such compositions should generally contain at least about 1%, preferably at least about 3%, by weight, of the mixed nonionic/anionic surfactant of this invention, though it is not intended to necessarily be limited thereto.
• the polymeric soil release agents for which performance is enhanced herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxy- propylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (111) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient, amount of oxyethylene units such that the hydrophile component has hydro- philicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50%
• the polyoxyethylene segments of (a)(1) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more prefer ⁇ ably from 6 to about 100.
• Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as ⁇ 3S(CH2)n CH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
• Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METH0CEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al .
• Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
• poly(vinyl ester) e.g., C1-C6 vinyl esters
• poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
• Commercially available soil release agents of this kind include the S0KALAN type of material, e.g., S0KALAN HP-22, available from BASF (West Germany).
• One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
• This polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
• Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
• this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
• Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
• Suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
• Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo- aroyl, end-capped terephthalate esters.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi ⁇ tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• Chelating Agents may also optionally contain one or more iron and/or manganese chelating agents.
• Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenedi- aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri- onates, triethylenetetraaminehexaacetates, diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent composi ⁇ tions, and include ethylenediaminetetrakis (methylenephosphon- ates), nitrilotris (methylenephosphonates) and diethylenetriamine- pentakis (methylenephosphonates).
• these amino phos ⁇ phonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
• a preferred biodegradable chelator for use herein is ethyl- enediamine disuccinate ("EDDS"), as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
• EDDS ethyl- enediamine disuccinate
• these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi ⁇ tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
• compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
• Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%.
• the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
• Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds dis ⁇ closed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
• Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
• Patent 4,548,744, Connor, issued October 22, 1985 Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
• Another type of preferred anti- redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
• CMC carboxy methyl cellulose
• Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein. These materials can also aid in calcium and magnesium hardness control.
• Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
• polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
• Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
• Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
• Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
• Such materials include the water-soluble salts of copolymers of acrylic add and maleic acid.
• the average molecular weight of such copolymers in the acid form preferably ranges, from about
• the ratio of aer late to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
• Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982.
• PEG poly ⁇ ethylene glycol
• PEG can exhibit dispersing agent perform ⁇ ance as well as act as a clay soil removal/antiredeposition agent.
• Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
• Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
• Briqhtener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
• Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
• optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighten ⁇ ers include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphtho1[l,2-d]- triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes ⁇ 4,4'-bis- (styryl)bisphenyls; and the y-aminocoumarins.
• these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzi idazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-y1)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.
• Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention.
• the incorporation of such materials, herein ⁇ after "suds suppressors,” can be desirable to further reduce the already-low sudsing of the mixed nonionic/anionic surfactants herein.
• Additional suds suppression can be of particular import ⁇ ance when the detergent compositions herein optionally include a relatively high sudsing surfactant in combination with the low- sudsing mixed nonionic/anionic surfactants of this invention.
• suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
• One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
• the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
• Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts,, and ammonium and alkanolammonium salts.
• the detergent compositions herein may also contain non- surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
• suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters.
• the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
• the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40 * C and about 5*C, and a minimum boiling point not less than about 110 * C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100*C.
• the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
• the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
• the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
• Non-surfactant suds suppressors comprises silicone suds suppressors.
• This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
• Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
• An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
• polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25*C;
• the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol.
• the primary silicone suds suppressor is branched/crosslinked and not linear.
• typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from abut 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a non- aqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
• a primary antifoam agent which is a mixture of (a) a poly
• the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/poly ⁇ propylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
• the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
• the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
• Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.
• the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLUR0NIC L101.
• suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
• the secondary alcohols include the C6-C16 alkyl alcohols having a Ci-Ci ⁇ chain.
• a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark IS0F0L 12.
• Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
• Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
• Suds suppressors when utilized, are preferably present in a "suds suppressing amount.”
• Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
• compositions herein will generally comprise from 0% to about 5% of suds suppressor.
• monocarboxylic fatty acids, and salts therein will- be present typically in amounts up to about 5%, by weight, of the detergent composition.
• from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
• Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due pri arly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
• from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
• these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
• Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition.
• Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
• the surfactant compositions herein can also be used with a variety of other adjunct ingredi ⁇ ents which provide still other benefits in various compositions within the scope of this invention.
• the following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.
• Various through-the-wash fabric softeners especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can be used typically at levels of from about 0.5% to about 10% by weight in the present composi ⁇ tions to provide fabric softener benefits concurrently with fabric cleaning.
• the polyhydroxy fatty acid amides of the present invention cause less interference with the softening performance of the clay than do the common polyethylene oxide nonionic sur ⁇ factants of the art.
• Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
• Hair Care Ingredients - Shampoo compositions formulated in the manner of this invention can contain from about 0.05% to about 10% by weight of various agents such as: conditioners, e.g., silicones (see, for example, U.S. Patents 4,152,416 and 4,364,847); antidandruff agents such as the pyridinethiones, especially zinc pyridinethione (see U.S. Patents 4,379,753 and 4,345,080), selenium compounds such as selenium sulfide and 0CT0PIR0X; hair styling polymers (see U.S. Patents 4,012,501 and 4,272,511); and pediculicides (anti-lice agents) such as LINDANE and various pyrethrins (see British Patent 1,593,601 and U.S. Patent 4,668,666).
• conditioners e.g., silicones
• antidandruff agents such as the pyridinethiones, especially zinc pyridinethione (see U.S. Patent
• compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
• detersive ingredients employed in the present compositions advantageously can be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
• the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
• the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
• a porous hydro ⁇ phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol E0(7) nonionic surfactant.
• the enzyme/surfact ⁇ ant solution is 2.5 X the weight of silica.
• the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
• silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
• the result- ing silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
• ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in deter- gents, including liquid laundry detergent compositions.
• Liquid detergent compositions can contain water and other solvents as carriers.
• Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
• Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2- propanediol) can also be used.
• Formulations - The formulation of effective, modern detergent compositions poses a considerable challenge, especially in the absence of phosphate builders.
• the formulator is required to address the removal of a wide variety of soils and stains, many of which are termed "greasy/oily" soils, such as foods, cosmetics, motor oil, and the like, from a wide variety of fabric surfaces and under a spectrum of usage condi ⁇ tions, ranging from boil wash temperatures preferred by some users to laundering temperatures as cold as 5 * C preferred by others.
• Local factors especially water hardness levels and the presence or absence of metal cations such as iron in local wash water supplies, can dramatically impact detergency performance.
• the formulator of hand dishwashing compositions must provide compositions which remove high loads of greasy food residues, but which do so under conditions which are not irritating to the user's skin nor damaging to the articles being washed. It is especially difficult to provide good grease removal at near- neutral pH's.
• spontaneous emulsifica ⁇ tion may be achievable with some specialized surfactants only at relatively high pH's in the range of 10-11, whereas this desirable result is also achievable with the present compositions even in the near-neutral pH range of about 7-9, as well as from 9-11. This is particularly important for hand-washing operations, for example, hand dishwashing, where skin mildness is of concern to the user.
• the polyhydroxy fatty acid amides employed in the practice of this invention are, structurally, nonionic-type surfactants and are referred to herein as "nonionics". It now appears that the conformation of the polyhydroxy fatty acid amide may be changed due to interaction between water hardness ions, especially calcium cations, and the soap or anionic surfactant. This may increase the molecular packing of the polyhydroxy fatty acid amides at the air/water interface. Whatever the explanation at the molecular level, the net result is the lower interfacial tensions and improved cleaning benefits which are associated with the composi ⁇ tions of this invention, especially with respect to removal of greasy soils.
• the formulator may advantageously employ both calcium and magnesium ions in such compositions to provide dual cleaning/sudsing benefits. If lower-sudsing compositions are desired, the magnesium ions may be deleted. Calcium and magnesium ions, if used, can be incorporated into the present compositions in the form of their chloride, sulfate, bromide, formate, acetate, malate, or maleate salts, or as salts of anionic hydrotropes or anionic surfactants.
• Usage levels are typically from about 0.5% to about 2% of the total compositions. When such cations are desired to be present, and if a builder is present, it is preferred that the builder be a non-phosphate builder such as citrate, zeolite or layered silicate.
• the formulator may determine that it is acceptable prac ⁇ tice to rely on natural water hardness to provide such ions to the compositions under in-use situations. This may be a reasonable expedient, since as little as 2 gr/gal calcium hardness can provide substantial benefits. However, the formulator will most likely decide to add the calcium and/or optional magnesium ions directly to the compositions, thereby assuring their presence in the in-use situation.
• the calcium and/or magnesium may be added to the compositions in the form of a lightly complexed chelate, such as calcium malate or maleate, magnesium malate or maleate, or the like.
• the detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.0 and about 10.5.
• Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0.
• Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
• a liquid detergent composition heresin comprises the following.
• a granular detergent herein comprises the following.
• Detersive enzyme** 1.0 c 12-14 alkyl sulfate, Na 5.0
• Example III The compositions of Example I and II are each modified by including 0.5% of a commercial proteolytic enzyme preparation (ESPERASE) therein.
• ESPERASE a commercial proteolytic enzyme preparation
• TERMAMYL a commercial amylase preparation
• LIPOLASE a commercial lipolytic enzyme preparation
• the composition of Example III can be further improved by the addition of 1.2% CaCl2>
• EXAMPLE IV A dishwashing composition with high grease removal properties is as follows.
• EXAMPLE V A shampoo composition is prepared according to Example IV by deleting the magnesium ions.
• compositions are especially useful for removing cosmetic stains from fabrics. This is an especially important technical improvement in deter- gency performance.
• Cosmetics, or facial "make-up", lipstick and the like typically comprise a complex mixture of finely-ground, highly colored particulate material which is intimately admixed with a greasy or waxy carrier. Cosmetics are specifically formu ⁇ lated to remain on the surface to which they are applied, and for this reason their carriers are water-insoluble and/or water repellent. As is well-known, once a lipstick or other cosmetic smear is established on a fabric, its removal can prove extremely difficult. By comparison, the removal of cosmetic stains from fabrics is substantially more difficult than is the removal of common greasy stains such as lard.
• compositions according to the present invention which additionally comprise from about 1% to about 20% by weight of an ethoxylated (EO 1-7; preferably 2-3) C12-C18 alcohol or alkyl phenol are preferably used in such formulations to further boost performance.
• EO 1-7 ethoxylated
• C12-C18 alcohol or alkyl phenol ethoxylated phenol
• compositions herein will typically be used in aqueous media at concentrations of at least about 200 ppm, e.g., for lightly-soiled fabrics and/or hand dishwashing. Higher usage concentrations in the range of 1,000 ppm to 8,000 ppm, and higher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user, soil loads, soil types, and the like. Wash temperatures can range from 5 * C to the boil.

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• 1993
  • 1993-11-24 EP EP94902398A patent/EP0670886A1/en not_active Withdrawn
  • 1993-11-24 WO PCT/US1993/011455 patent/WO1994012610A1/en not_active Application Discontinuation
  • 1993-11-24 JP JP6513378A patent/JPH08503735A/ja active Pending
  • 1993-11-24 CA CA002148096A patent/CA2148096A1/en not_active Abandoned
  • 1993-11-24 AU AU56785/94A patent/AU5678594A/en not_active Abandoned
  • 1993-11-29 MX MX9307500A patent/MX9307500A/es unknown
  • 1993-11-30 CN CN 93121557 patent/CN1090878A/zh active Pending

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