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
  • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0069—Laundry bars
• • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

• the subject invention involves hand wash laundry compositions, especially laundry bars, containing a certain mixture of anionic surfactants.
• a preferred form of cleansing product for hand washing of clothes is the laundry bar.
• Soaps are readily available in much of the world and are relatively inexpensive, and are therefore often a primary surfactant in hand wash laundry compositions.
• the cleaning performance of soap-based hand wash laundry compositions can be improved by inco ⁇ orating some synthetic surfactants in such compositions.
• the subject invention involves hand wash laundry compositions comprising: a) from about 35% to about 70% anionic surfactant, the anionic surfactant being a combination of surfactants such that the composition comprises:
• alkyl ethoxy ether sulfate surfactant having an average of from about 0.5 to about 5 mole ethoxy per mole surfactant; wherein the ratio of alkylbenzene sulfonate surfactant to alkyl ethoxy ether sulfate surfactant is from about 1.4:1 to about 2.8:1 ; b) from about 30% to about 65% other components.
• alkyl means a hydrocarbyl moiety which is straight (linear) or branched, saturated or unsaturated. Unless otherwise specified, alkyl are preferably saturated (“alkanyl”) or unsaturated with double bonds (“alkenyl”), preferably with one or two double bonds.
• tallow is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of 2% C14, 29% C-
• the tallow, as used herein, can also be hardened (i.e, hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
• coconut oil is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of about 8% C ⁇ , 7% C10, 48% C ⁇ , 17% C14, 9% Ci ⁇ , 2% C18. 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
• Other sources having similar carbon chain length distribution in their fatty acids, such as palm kernel oil and babassu oil, are included within the term coconut oil.
• Hand wash compositions of the subject invention comprise from about 35% to about 70% anionic surfactant, preferably from about 40% to about 60%, more preferably from about 43% to about 49%, also preferably from about 50% to about 58%.
• the anionic surfactant in the subject invention compositions is a combination of surfactants such that the compositions comprise from about 30% to about 65% soap, preferably from about 33% to about 52%, more preferably from about 35% to about 39%, also preferably from about 40% to about 46%.
• the subject invention compositions comprise from about 2% to about 15% alkylbenzene sulfonate surfactant, preferably from about 3% to about 10%, more preferably from about 4% to about 6%, also preferably from about 6% to about 8%. Also, as part of the anionic surfactant, the subject invention compositions comprise from about 1.4% to about 5.5% alkyl ethoxy ether sulfate surfactant, preferably from about 1.7% to about 4.5%, more preferably from about 2.0% to about 2.9%, also preferably from about 2.9% to about 4.0%.
• the ratio of alkylbenzene sulfonate surfactant to alkyl ethoxy ether sulfate surfactant is from about 1.4:1 to about 2.8:1 , preferably from about 1.5:1 to about 2.5:1, more preferably from about 1.6:1 to about 2.4:1, more preferably still from about 1.8:1 to about 2.2:1, also preferably about 2:1.
• the ratio of soap to alkylbenzene sulfonate surfactant is preferably from about 2:1 to about 25:1, more preferably from about 4:1 to about 15:1, more preferably still from about 5:1 to about 10:1.
• the anionic surfactant of the subject invention compositions consists essentially of soap, alkylbenzene sulfonate surfactant, and alkyl ethoxy ether sulfate surfactant.
• the surfactant of the subject invention compositions consists essentially of soap, alkylbenzene sulfonate surfactant, and alkyl ethoxy ether sulfate surfactant.
• salts of fatty acids means salts of fatty acids.
• the fatty acids are linear or branched containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
• the average carbon chain length for the fatty acid soaps is from about 12 to about 18 carbon atoms, preferably from about 14 to about 16 carbon atoms.
• Preferred salts of the fatty acids are alkali metal salts, such as sodium and potassium, especially sodium. Also preferred salts are ammonium and alkylolammonium salts.
• the fatty acids of soaps useful in the subject invention bars are preferably obtained from natural sources such as plant or animal esters; examples include coconut oil, palm oil, palm kernel oil, olive oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, grease, lard, and mixtures thereof.
• Preferred fatty acids are obtained from coconut oil, tallow, palm oil (palm stearin oil), palm kernel oil, and mixtures thereof.
• Fatty acids can be synthetically prepared, for example, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
• Alkali metal soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps, and mixtures thereof.
• Preferred soap raw materials for the subject invention bars and processes are soaps made from mixtures of fatty acids from tallow and coconut oil. Typical mixtures have tallow: coconut fatty acid ratios of 85:15, 80:20, 75:25, 70:30, and 50:50; preferred ratios are about 85:15 to 70:30, more preferred about 80:20 to 75:25.
• Preferred soap raw materials for the subject invention are neat soaps made by kettle (batch) or continuous saponification.
• Neat soaps typically comprise from about 65% to about 75%, preferably from about 67% to about 72%, alkali metal soap; from about 24% to about 34%, preferably from about 27% to about 32%, water; and minor amounts, preferably less than about 5% total, of residual materials and impurities, such as alkali metal chlorides, alkali metal hydroxides, alkali metal carbonates, glycerin, and free fatty acids.
• Another preferred soap raw material is soap noodles or flakes, which are typically neat soap which has been dried to a water content of from about 10% to about 30%. The other components above are proportionally concentrated.
• alkylbenzene sulfonate surfactants or “alkylbenzene sulfonates” means salts of alkylbenzene sulfonic acid with an alkyl portion which is linear or branched, preferably having from about 8 to about 18 carbon atoms, more preferably from about 10 to about 16 carbon atoms.
• the alkyl chains of the alkylbenzene sulfonic acid preferably have an average chain length of from about 11 to about 14 carbon atoms, more preferably from about 11.5 to about 13 carbon atoms.
• Branched or mixed branched and linear alkylbenzene sulfonates are known as ABS.
• Linear alkylbenzene sulfonates, known as LAS are more biodegradable than ABS, and are preferred for the subject invention compositions.
• the acid forms of ABS and LAS are referred to herein as HABS and HLAS, respectively.
• the salts of the alkylbenzene sulfonic acids are preferably the alkali metal salts, such as sodium and potassium, especially sodium. Salts of the alkylbenzene sulfonic acids also include ammonium.
• a particularly preferred LAS surfactant has a saturated linear alkyl with an average of 11.5 to 12.5 carbon atoms, and is a sodium salt (Ci -j 5_ « i2. ⁇ LAS-Na).
• Alkylbenzene sulfonates and processes for making them are disclosed in U.S. Patent Nos. 2,220,099 and 2,477,383, incorporated herein by reference.
• the alkyl ethoxy ether sulfate (AES) surfactants useful in the subject invention compositions have the following formula:
• R is alkyl of from about 10 to about 20, preferably from about 12 to about 18, more preferably from 13 to 16, more preferably still from 14 to 15, carbon atoms. On average, R is from about 13 to about 16, preferably from 14 to 15, carbon atoms. R is preferably saturated. R is preferably linear. in the above structure, x represents the "degree of ethoxylation" (number of ethoxy moieties per molecule) which can have a broad distribution for the AES surfactant of the subject compositions.
• x typically varies from 0 to about 20, preferably from 0 to about 10, more preferably from 0 to about 7, more preferably still from 0 to about 4. More typically, degree of ethoxylation is given as an average number of ethoxy moieties per surfactant molecule.
• x is preferably on average from about 0.5 to about 10, more preferably from about 0.7 to about 7, also preferably from about 0.8 to about 1.5, more preferably from about 0.9 to about 1.2, also preferably from about 1.5 to about 5, more preferably from about 2 to about 4.
• the AES surfactants are typically obtained by sulfating mixtures of C-14. 15 alcohols and the lower ethoxylates of such alcohols with gaseous SO3 in a falling film reactor, followed by neutralization with NaOH, as is well known in the art.
• Alcohols and lower ethoxy alcohols which provide preferred average ethoxy moieties, are typically about 20-75% alcohol, about 5-50% monoethoxy alcohol, about 5-30% diethoxy alcohol, about 2-25% triethoxy alcohol, and about 0-40% ethoxy(4-12) alcohol; mixtures having an average ethoxylation number of about 1 are typically about 30-60% alcohol, about 20- 40% monoethoxy alcohol, about 5-15% diethoxy alcohol, about 2-7% triethoxy alcohol, and about 0-5% ethoxy(4-8) alcohol.
• M is a water-soluble cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium), an alkaline earth metal cation (e.g., calcium, magnesium), ammonium or substituted-ammonium cation.
• M is preferably sodium or potassium, especially sodium.
• a particularly preferred AES surfactant has a saturated linear alkyl which is a mixture of about 50-60% C14 and about 40-50% C15, and has an average of about one ethoxy unit per molecule, and is a sodium salt (C14.15E1 S Na).
• compositions of the subject invention comprise from about 30% to about 65%, preferably about 40-60%, also preferably about 51-57%, also preferably about 44-50%, by weight of other components commonly used in detergent products.
• a typical listing of the classes and species of other surfactants, builders and other ingredients that may be included in the subject compositions appears in U.S. Patent No. 3,664,961 , issued to Norn ' s on May 23, 1972, and EP 550,652, published on April 16, 1992, incorporated herein by reference. The following are representative of such materials, but are not intended to be limiting.
• Auxiliary Surfactants are representative of such materials, but are not intended to be limiting.
• compositions of the subject invention can contain optional surfactants commonly used in detergent products.
• surfactants commonly used in detergent products.
• a typical listing of the classes and species of such surfactants, e.g., anionic, nonionic, zwitterionic, and amphoteric surfactants appear in U.S. 3,664,961 and EP 550,652.
• Such auxiliary surfactants if present, can be included at levels up to a total of about 10%, preferably about 0.5-3%.
• hydrotrope or mixture of hydrotropes
• Preferred hydrotropes include the alkali metal, preferably sodium, salts of tolune sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof.
• the hydrotrope in either the acid form or the salt form, and being substantially anhydrous, is added to the linear alkylbenzene sulfonic acid prior to its neutralization.
• the hydrotrope if present, will preferably be from about 0.5% to about 5% of the subject compositions.
• compositions of the subject invention comprise from about 5% to about 25% water, preferably from about 10% to about 24% water, more preferably from about 15% to about 21% water, also preferably from about 18% to about 23% water.
• Detergent Builders preferably from about 10% to about 24% water, more preferably from about 15% to about 21% water, also preferably from about 18% to about 23% water.
• compositions of the subject invention comprise from 0% to about 25% detergent builder.
• Preferred compositions comprise from about 4% to about 19% builder, more preferably from about 5% to about 16%.
• These detergent builders can be, for example, water-soluble alkali-metal salts of phosphate, pyrophosphates, orthophosphates, tripolyphospha.es, higher polyphosphates, and mixtures thereof.
• Preferred builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate.
• the builder can also be a non-phosphate detergent builder. Specific examples of non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts.
• alkali metal e.g., sodium and potassium carbonates, bicarbonates, and silicates are particularly useful herein.
• Specific preferred examples of builders include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof.
• Other specifically preferred examples of builders include zeolites and polycarboxylates.
• Sodium carbonate is a particularly preferred ingredient in the subject invention compositions, since in addition to its use as a builder, it can also provide alkalinity to the composition for improved detergency, and also can serve as a neutralizing agent for acidic components added in the composition processing.
• Sodium carbonate is particularly preferred as a neutralizing inorganic salt for an acid precursor of an anionic surfactant used in such compositions, such as alkyl ethoxy ether sulfuric acid and alkylbenzene sulfonic acid.
• Co-polymers of acrylic acid and maleic acid are preferred in the subject compositions as auxiliary builders, since it has been observed that their use in combination with fabric softening clay and clay flocculating agents further stabilizes and improves the clay deposition and fabric softening performance.
• Excess Carbonate and Bicarbonate are preferred in the subject compositions as auxiliary builders, since it has been observed that their use in combination with fabric softening clay and clay flocculating agents further stabilizes and improves the clay deposition and fabric softening performance.
• Additional firmness can be imparted to the laundry bar compositions of the subject invention if desired, by incorporating a substantial excess of alkali metal carbonate in the compositions.
• a small amount of this residual alkali metal carbonate may exist as the bicarbonate form, due to incomplete local neutralization of surfactant acids.
• the preferred calculated excess amount of alkali metal carbonate incorporated in the subject invention bars is from about 2% to about 18% (bar weight basis), more preferably from about 4% to about 15%, more preferably still from about 6 1 / 2 % to about 12%, still more preferably from about 7% to about 10%, also preferably from about 5% to about 9%.
• the percentages of the preceding paragraph are calculated values in that they assume that each carbonate ion involved in a neutralization reaction reacts with 2 hydrogens from the acids. Sometimes a carbonate ion reacts with only one hydrogen resulting in formation of a bicarbonate ion. Of the above calculated excess alkali metal carbonate, less than about 2% (bar weight basis) typically exists in the bars as alkali metal bicarbonate, more typically less than 1 %.
• alkali metal carbonate in the subject invention bars results in a high pH wash solution, when the bar is used to wash clothes.
• Such high pH wash solution can be harsh to human skin.
• Such harshness can be reduced by inco ⁇ orating an alkali metal bicarbonate in the subject invention bars, in addition to the residual bicarbonate mentioned above.
• alkali metal bicarbonates include sodium bicarbonate and potassium bicarbonate, especially sodium bicarbonate.
• the amount of additional alkali metal bicarbonate incorporated in the subject bars is from 0% to about 8% (bar weight basis), preferably from about 0.5% to about 5%, more preferably from about 1% to about 4%.
• the preferred amount of additional alkali metal bicarbonate incorporated in the subject bars is from about 1% to about 2%, especially about 1.5%, alkali metal bicarbonate for each additional 4% of excess alkali metal carbonate over 4% (all %'s are bar weight basis). For example, if the excess alkali metal carbonate is about 8%, the most preferred amount of additional alkali metal bicarbonate is about 1.5%; if the excess alkali metal carbonate is about 12%, the most preferred amount of additional alkali metal bicarbonate is about 3%.
• the pH of a 1% aqueous solution of a bar composition of the subject invention is preferably from about 9 to about 11.5, more preferably from about 10.0 to about 11.0.
• a water-soluble inorganic strong-electrolyte salt helps provide improved firmness in the subject invention laundry bars, especially when included in conjunction with the excess alkali metal carbonate described hereinabove.
• strong-electrolyte salt excludes carbonates, bicarbonates, builders, and other inorganic materials disclosed herein as subject bar components, but which are water-soluble inorganic weak electrolyte salts.
• Preferred water-soluble inorganic strong-electrolyte salts suitable for incorporation in the subject invention bars include the alkali metal, preferably sodium and potassium, sulfates and halides, preferably chlorides, and mixtures thereof. Particularly preferred salts include sodium sulfate and sodium chloride, and mixtures thereof.
• Sodium sulfate is particularly preferred because it is less corrosive to equipment than sodium chloride.
• the amount of such salts incorporated in the subject bars, if any, is from about 0.2% to about 20%, preferably from about 0.4% to about 12%, more preferably from about 2% to about 10%, more preferably still from about 3% to about 8%. Soil Dispersing Agent
• a preferred ingredient in the subject compositions is a soil dispersing agent which is a water soluble or dispersible alkoxylated polyalkyleneamine material.
• a soil dispersing agent which is a water soluble or dispersible alkoxylated polyalkyleneamine material.
• Such material can be included in the subject compositions at a level up to about 1%, preferably from about 0.1% to about 0.8%, more preferably from about 0.3% to about 0.6%.
• the alkoxylated polyalkyleneamine material has a polyalkyleneamine backbone of amine units having the general formula:
• each (H 2 N-R 1 -) unit is bonded to (-NH-R 1 -) or (>N-R 1 -);
• each (-NH-R 1 -) unit is bonded to any two units, provided that each is bonded to no more than one of (H 2 N-R 1 -) and (-NH 2 );
• each (>N-R 1 -) unit is bonded to any three units, provided that each is bonded to no more than two of (H 2 N-R 1 -) and (-NH 2 );
• the (-NH 2 ) is bonded to (-NH-R 1 -) or (>N-R1-); provided that each bond described in (i), (ii), (iii) and (iv) is between N of one unit and R ⁇ of another unit.
• n is on average from 0 to about 250, preferably from about 1 to about 100, more preferably from about 3 to about 40, more preferably still from about 5 to about 25, still more preferably from about 7 to about 15.
• m is on average from about 3 to about 700, preferably from about 4 to about 200, more preferably from about 6 to about 80, more preferably still from about 8 to about 50, still more preferably from about 15 to about 30.
• the ratio n:m is preferably from 0 to about 1:4, more preferably from about 1:1.5 to about 1:2.5, more preferably still about 1 :2.
• R 1 is linear alkanylene having from 2 to about 12 carbon atoms, preferably from 2 to about 4 carbon atoms.
• less than about 50% of the R 1 moieties have more than 3 carbon atoms, more preferably less than about 25% R 1 moieties have more than 3 carbon atoms, more preferably still less than about 10% R 1 moieties have more than 3 carbon atoms.
• More preferred R 1 is selected from ethylene, 1 ,2-propylene, 1,3-propylene, and mixtures thereof
• substantially all R 1 units are the same.
• Most preferred R 1 is ethylene.
• the polyalkyleneamine backbone described above has a molecular weight of at least about 180 daltons, preferably has a molecular weight of from about 600 to about 5000 daltons, more preferably has a molecular weight of from about 1000 to about 2500 daltons.
• the method for calculating the total number of NH substituent sites is as follows. Each NH function capable of being substituted is considered one equivalent. Primary amine moieties (-NH 2 ) comprise two mole equivalents of substituent sites; secondary amine moieties (-NH-) comprise one mole equivalent of substituent sites.
• Primary amine moieties (-NH 2 ) comprise two mole equivalents of substituent sites; secondary amine moieties (-NH-) comprise one mole equivalent of substituent sites.
• polyethyleneamine wherein R 1 is ethylene, having the structure:
• Substituents for the hydrogens bonded to the nitrogens are poly(alkyleneoxy) units having the formula
• R 3 is alkanylene having from 2 to about 6 carbon atoms, preferably from 2 to about 4 carbon atoms.
• R 3 is preferably selected from ethylene, 1 ,2-propylene, and mixtures thereof More preferably R 3 is ethylene.
• R2 is selected from hydrogen, alkanyl having from 1 to about 4 carbon atoms, and mixtures thereof Preferably R2 is hydrogen.
• p is on average from about 1 to about 50, preferably from about 3 to about 10. In general, p preferably increases with increasing molecular weight of the polyalkyleneamine backbone.
• degree of ethoxylation is defined as the average number of alkoxylations per nitrogen atom substituent site and may be expressed as a fractional number.
• a polyalkyleneamine may have a degree of ethoxylation equal to 1 or greater and still have less than 100% of the polyalkyleneamine backbone nitrogen substituent sites substituted.
• polyalkyleneamine backbones include both polyalkyleneamines (PAA's) and polyalkyleneimines (PAI's); preferred backbones are polyethyleneamine (PEA's) and polyethyleneimines (PEI's).
• PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. Common PEA's include triethylenetetramin ⁇ (TETA), tetraethylenepentamine (TEPA), and tetrabutylenepentamine. Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cog ⁇ nerically derived mixture does not readily separate by distillation and can include other materials such as cyclic amines and piperazin ⁇ s. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, incorporated herein by reference, which describes the preparation of PEA's.
• the PEI's include the preferred polyalkyleneamine backbones useful herein. They can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEI's are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S.
• Patent 2,553,696, Wilson issued May 21, 1951 (all herein incorporated by reference).
• the compounds useful herein also include the cyclic amines that are typically formed as artifacts of synthesis. The presence of these materials may be increased or decreased depending on the conditions chosen by the formulator.
• PEI 1800 E7 has a polyethyleneimine backbone having an average molecular weight of about 1800, a ratio of n:m of about 1 :2, and an average degree of ethoxylation of about 7.
• Ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and introduction of ethylene oxide as a liquid.
• a -20 lb. net weight cylinder of ethylene oxide is set up to deliver ethylene oxide as a liquid by pumping to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder can be monitored.
• a 750 g portion of PEI (Nippon Shokubai, Epomin SP-018 having a listed average molecular weight of 1800 and a ratio of n:m of about 1 :2), equating to about 0.417 moles of polymer and 17.4 moles of nitrogen substitution sites, is added to the autoclave.
• the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
• the autoclave contents are heated to 130°C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
• Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
• the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
• the temperature is maintained between 100 and 110°C while the total pressure is allowed to gradually increase during the course of the reaction to a maximum of about 350 psia.
• Vacuum is removed and the autoclave is cooled to 105°C while it is being charged with nitrogen to 250 psia and then vented to atmospheric pressure.
• the autoclave is charged to 200 psia with nitrogen.
• Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110°C and limiting any temperature increases due to reaction exotherm.
• 4500 g of ethylene oxide resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen substituent site
• the temperature is increased to 110°C and the mixture stirred for an additional hour.
• the reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
• the reaction mixture is then deodorized by sparging with inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture for about V ⁇ hour while agitating and heating the mixture to about 100-130°C.
• inert gas argon or nitrogen
• the preferred fabric softening clay is a smectite-type clay.
• the smectite- type clays can be described as expandable, three-layer clays; i.e., alumino ⁇ silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g of clay.
• the clay particles are of a size that they cannot be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes.
• the fabric softening clay if it is included, can be added to the subject invention compositions to provide about 0.1% to about 20% by weight of the composition, more preferably from about 0.2% to about 15%, and more preferably still about 0.3% to 10%.
• smectite-type clays While any of the smectite-type clays are useful in the subject invention compositions, certain clays are preferred.
• Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white detergent compositions.
• Volclay BC which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe 2 ⁇ 3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in the instant compositions from the standpoint of product performance.
• certain smectite-type clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the requisite range; such clays are not preferred in the subject compositions.
• the polymeric clay flocculating agent is selected to provide improved deposition of the fabric softening clay.
• Such materials have a high molecular weight, greater than about 100,000. Examples of such materials can include long chain polymers and copoiymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums, are suitable as well.
• the preferred clay flocculating agent is a polyethylene oxide) polymer.
• the amount of clay flocculating agent included in the subject compositions, if any, is about 0.2%-2%, preferably about 0.5%-1%. Chelant
• a preferred optional component of the subject invention compositions is a detergent chelant.
• Such chelants are able to sequester and chelate alkali cations (such as sodium, lithium and potassium), alkali metal earth cations (such as magnesium and calcium), and most preferably, heavy metal cations such as iron, manganese, zinc and aluminum.
• Preferred cations include sodium, magnesium, zinc, and mixtures thereof
• the detergent chelant is particularly beneficial for maintaining good cleaning performance and improved surfactant mileage, meaning that for a given level of anionic surfactant and level of detergent chelant, equivalent sudsing and cleaning performance can be achieved compared to a similar composition containing a higher level of the anionic surfactant but without the detergent chelant.
• the detergent chelant is preferably a phosphonate chelant, particular one selected from diethylenetriamine penta(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof; or an acetate chelant, particularly one selected from diethylenetriamine penta(acetic acid), ethylene diamine tetra(acetic acid), and mixtures and salts and complexes thereof Particularly preferred are sodium, zinc, magnesium, and aluminum salts and complexes of diethylenetriamine penta(methylene phosphonate), diethylenetriamine pentaacetate, and mixtures thereof.
• such salts or complexes have a molar ratio of metal ion to chelant molecule of at least about 1:1, preferably at least about 2:1.
• the detergent chelant can be included in the subject compositions at a level up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, more preferably still from about 0.5% to about 1.0%.
• Another preferred additional component of the subject compositions is fatty alcohol having an alkyl chain of about 8-22 carbon atoms, more preferably about 12-18 carbon atoms.
• Fatty alcohol is effective at reducing bar wear rate and smear (mushiness) of laundry bars.
• a preferred fatty alcohol has an alkyl chain predominantly containing and averaging about 16-18 carbon atoms, so-called "high-cut fatty alcohol,” which can exhibit less base odor of fatty alcohol relative to broad cut fatty alcohols.
• fatty alcohol in the compositions, if any, is present at up to a level of about 10%, preferably from about 0.75% to about 6%, more preferably from about 2% to about 5%.
• Free fatty alcohol can also serve as a suds booster, for reinforcing and extending suds generation and longevity.
• a preferred fatty alcohol has an alkyl chain length predominantly of about 12-14 carbon atoms, and is preferably included in the composition at a level from about 1 % to about 3%. More preferably, a narrow-cut Cj 2 alkyl alcohol is included at a level of about 0.5%-2%.
• compositions based on coconut fatty alkyl ether sulfate can contain, as unreacted starting material, from about 0.1%-3.5%, more typically from about 2%-3%, by weight of free coconut fatty alcohol.
• starch An optional ingredient for incorporation in the subject invention laundry bars is starch.
• Starch helps provide additional firmness for such bars.
• Preferred starches for incorporation in the bars include whole-cut corn starch, tapioca-type starches, and other starches with similar properties and which are not pregelatinized, collectively referred to herein as "whole-cut" starches.
• Non- limiting examples of whole-cut powdered starches useful in the subject invention are Pearl® corn starch from A. E. Staley Manufacturing Company and Argo® corn starch from CPC International.
• the amount incorporated in the subject development bars is from 0% to about 4%, preferably from about 1 % to about 3%.
• Starch derivatives such as pregelatinized starches, amylopectins, and dextrins, referred to herein as "other starches", can also be used to give the bars of the subject invention some additional firmness and particular physical properties, as described in U.S. Patent 4,100,097 issued to O'Roark July 11, 1978 and assigned to Hewitt Soap Co.
• the amount of other starches incorporated in the subject bars is from 0% to about 10%.
• a preferred DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolohzation DTI materials capable of decolorizing the fugitive dyes by oxidation.
• An example of a decolonization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate.
• Non-limiting examples of polymeric DTI materials include poiyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof.
• Copoiymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred.
• the amount of DTI included in the subject compositions, if any, is about 0.05%-5%, preferably about 0.2%-2%.
• Another preferred optional component in the subject compositions is a secondary fabric softener component in addition to the softening clay.
• Such materials are typically at levels of about 0.1%-5%, preferably about 0.3%-3%.
• Such materials can include amines of the formula R4R5R6N, wherein R4 is about C5-C22 a'kyl.
• R5 and R ⁇ are independently about C1-C10 alkyl.
• One preferred amine is ditallowmethyl amine.
• Such materials can include cyclic amines such as imidazolines of the general formula 1 -(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline, where higher alkyl is about 12-22 carbons and lower alkyl is about 1-4 carbons, such as described in UK Patent Application GB 2,173,827.
• quaternary ammonium compounds of the formula R10R11R12R13N + X _ , wherein Rio is alkyl having about 8-20 carbons, Ru is alkyl having about 1-10 carbons, R-
• Exemplary materials include alkyl trimethyl ammonium and dialkyl dimethyl ammonium salts. Bleaches
• the bleaching component can be a source of "OOH group, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate.
• Sodium percarbonate (2Na 2 C03-3H 2 0 2 ) is preferred since it has a dual function as both a source of HOOH and a source of sodium carbonate.
• Another optional bleaching component is a peracid per se, such as that having a formula:
• the bleaching component can contain, as a bleaching component stabilizer, a chelating agent of polyaminocarboxylic acids, polyaminocarboxylates such as ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, and ethylenediaminodisuccinic acid, and their salts with water-soluble alkali metals.
• the bleach components can be added to the compositions, if included, at a level up to about 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.
• a preferred optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by reference.
• Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals.
• Such photobleaches are available, for example, under the tradename TINOLUS or as zinc phthalocyanine sulfonate.
• the photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%, preferably from about 0.001% to about 0.015%, more preferably from about
• Calcium carbonate (also known as Calcarb) is a well known and often used filler component of the subject compositions.
• Fillers include minerals, such as talc and hydrated magnesium silicate-containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Filler materials, if included, are typically at levels up to about 40%, preferably from about 5% to about 25%. Binding Agents
• Binding agents for holding the bar together in a cohesive, soluble form can also be used, and include natural and synthetic starches, gums, thickeners, and mixtures thereof. Such materials, if included, are typically at levels up to about 3%, preferably about 0.5% - 2%.
• Glycerine is commonly inco ⁇ orated in laundry bar compositions. If included, it is typically at concentrations up to about 3%, preferably about 0.5%- 1.5%. Glycerine can affect bar brittleness. Soil Release Polymers
• the subject compositions can include soil release polymers.
• soil release polymers if included, can be at levels up to about 5%, preferably about 0.05%-3%, more preferably about 0.2%-1%.
• a soil release polymer can improve the multi-cycle cleaning of clothes washed with the subject compositions.
• detergent enzymes are cellulase, lipase, protease, amylase, and mixtures thereof Enzymes, if included, are typically at levels up to about 5%, preferably about 0.2-2%. Soil Suspending Agents
• Soil suspending agents can be included in the subject invention compositions. Their use is balanced with the fabric softening clay/clay flocculating agent combination, if any, to provide optimum cleaning and fabric softening performance. Soil suspending agents can also include water-soluble salts of carboxymethylcellulose and carboxyhydroxymethylceiluiose.
• a preferred soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokalan®, from BASF Co ⁇ .
• Other soil suspending agents include polyethylene glycols having a molecular weight of about 400-10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof. Such materials, if included, are typically at levels up to about 5%, preferably about 0.1% - 1%.
• Optical Brighteners are typically at levels up to about 5%, preferably about 0.1% - 1%.
• optical brighteners are also preferred optional ingredients in compositions of the subject invention.
• Preferred optical brighteners are diamino stilbene, distyrilbiphenyl-type optical brighteners.
• Preferred as examples of such brighteners are 4,4'-bis((4-anilino-6-bis(2-hydoxyethyl) amino-1,3,5-trizin-2- yl)amino)stilbene-2,2'-disulfonic acid disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4 , -bis((4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino)stilbene- 2,2'-disulfonic acid disodium salt.
• Such optical brighteners, or mixtures thereof, if included, are typically at levels in the compositions up to about 1%, preferably about 0.01 %-0.08%. Miscellaneous
• Dyes, pigments, germicides, perfumes, polyethylene glycol, glycerine, sodium hydroxide, alkylbenzene, fatty alcohol, and other minors, some of which are impurities carried in from surfactant-making processes, can also be incorporated in the subject compositions. If included, they are typically at levels up to about 3%.
• the detergent laundry bars of the subject invention can be processed using conventional soap or detergent bar making equipment with some or all of the following key equipment: blender/mixer, mill or refining plodder, two-stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.
• the raw materials are mixed in the blender.
• Alkylbenzene sulfonic acid is added into a mixture of alkaline inorganic salts, strong electrolyte salts, and fillers (preferably including sodium carbonate) and the resulting partially neutralized mixture is mechanically worked to effect homogeneity and complete neutralization of the mixture.
• the soap and alkyl ethoxy ether sulfate surfactant are added, followed by the remaining other ingredient materials.
• the mixing can take from about 1 minute to about 1 hour, with the usual mixing time being about 5-30 minutes.
• the blender mix is discharged to a surge tank.
• the product is conveyed from the surge tank to the mill or refining plodder via a multi-worm transfer conveyor.
• the product is then conveyed to a double stage vacuum plodder, operating at a high vacuum, e.g. about 400-740 millimeters of mercury vacuum, so that entrapped air is removed.
• a high vacuum e.g. about 400-740 millimeters of mercury vacuum
• the product is extruded and cut to the desired bar length, and printed with the product brand name.
• the printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
• compositions of the subject invention are listed hereafter by wa of exem lification, and not by way of limitation.
• the surfactant can be replaced, for example, by the same amount of C ⁇ 2 _i8Ei ⁇ S-Na, C ⁇

Applications Claiming Priority (2)

Publications (1)

Family

ID=21779116

Family Applications (1)

Country Status (6)

Cited By (2)

Citations (4)

• 1997
  • 1997-04-29 ZA ZA9703718A patent/ZA973718B/xx unknown
  • 1997-05-01 WO PCT/US1997/007204 patent/WO1997042298A1/en active Search and Examination
  • 1997-05-02 CO CO97023452A patent/CO4950590A1/es unknown
  • 1997-05-02 ID IDP971464A patent/ID18776A/id unknown
  • 1997-05-02 PE PE1997000342A patent/PE85698A1/es not_active Application Discontinuation
  • 1997-05-05 AR ARP970101840A patent/AR006962A1/es unknown

Patent Citations (4)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events