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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38663—Stabilised liquid enzyme compositions
• • 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
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

• the present invention relates to a viscoelastic, thixotropic, liquid automatic dishwashing detergent composition which is substantially free of chlorine bleach and silicate.
• the automatic dishwashing composition contains enzyme, an enzyme stabilizing system, and detergent surfactant or detergent builder. It has a
• liquid and/or gel automatic dishwashing detergent 20 compositions are becoming an increasingly popular alternative to granular compositions among consumers.
• liquid and/or gel formulations often do not deliver the same effective cleaning, spotting and filming performance as a granular composition.
• dishwashing detergents contain chlorine bleach and have high alkalinity (i.e. silicate, carbonate and caustic). See, for example, U.S. Patents 4,116,849, Leikhim, issued September 26,
• liquid composition which is substantially free of chlorine and silicate exhibits enhanced cleaning, spotting and filming ability.
• the cleaning benefit is achieved via the presence of enzymes and surfactant and/or builder in the composition. Removal of chlorine bleach and a lower product pH results in a composition which is
• composition of this invention is a viscoelastic, thixotropic, liquid automatic dishwashing detergent composition comprising, by weight:
• composition is substantially free of chlorine bleach and silicate.
• a particularly preferred embodiment of this invention is a gel automatic dishwashing detergent composition further comprising, by weight, from about 0.01% to about 6% of a chlorine scavenger.
• the present invention encompasses viscoelastic, thixotropic, liquid automatic detergent compositions which exhibit enhanced cleaning performance in the absence of chlorine bleach and silicate.
• These detergent compositions contain the following components by weight of the composition:
• an enzyme stabilizing system selected from the group consisting of calcium ion, propylene glycol, short chain carboxylic acid, boric acid, boronic acid, polyhydroxyl compounds and mixtures thereof; 0 (4) from about 0.01% to about 40% of a detergent surfactant or a detergent builder or mixtures thereof; and
• a viscoelastic thixotropic liquid automatic dishwashing detergent with a product pH between about 7 and about 11.
• Various other optional ingredients such as fatty acids, oxygen bleaches, perfumes, dyes, suds control agents and organic dispersants, can be added to provide additional performance and aesthetic benefits.
• a particularly preferred composition is a gel formulation.
• thixotropic means the material exhibits a decrease
• a viscoelastic liquid exhibits a steady state flow behaviour after a constant stress has oeen applied for a sufficiently long period of time.
• compositions of this invention contain from about 0.001% to about 5%, more preferably from about 0.003% to about 4%, most preferably from about 0.005% to about 3%, by weight, of active detersive enzyme.
• the preferred detersive enzyme is selected from the group consisting of protease, amylase, lipase and mixtures thereof. Most preferred are protease or amylase or mixtures thereof.
• the proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus. Bacillus subtilis and/or Bacillus licheniformis.
• Suitable proteolytic enzymes include Alcalase ® , Esperase®, Savinase ® (preferred); Maxatase ® , Maxacal ® (preferred), and
• Maxapem ® 15 protein engineered Maxacal
• subtilisin BPN subtilisin BPN
• Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17,
• proteolytic enzymes are selected from the group consisting of
• Esperase ® is most preferred.
• Suitable upases for use herein include those of bacterial, animal, and fungal origin, including those from chemically or genetically modified mutants.
• Suitable bacterial upases include those produced by Pseduomonas, such as Pseudomonas stutzeri ATCC 19.154. as disclosed in British Patent 1,372,034, incorporated herein by reference.
• Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced the the microorganism Pseudomonas fluorescens IAM 1057. This. lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference.
• This lipase is available under the trade name Lipas P "Amano,” hereinafter referred to as "Amano-P.”
• Such lipases should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Oucheterlon (Acta. Med. Scan., 133, pages 76-79 (1950)).
• These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S.. Patent 4,707,291, Thorn et al . , issued November 17, 1987, incorporated herein by reference.
• Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. 1 ioolvticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum var. 1 ipolvticum NRRlb 3673, and further Chromobacter viscousm lipases, and lipases ex ⁇ Pseudomonas gladioli .
• Other lipases of interest are Amano AKG and Bacillis Sp lipase (e.g. Solvay enzymes).
• lipases which are of interest where they are compatible with the composition are those described in EP A 0 339 681, published November 28, 1990, EP A 0 385 401, published September 5, 1990, E0 A 0 218 272, published April 15, 1987, and PCT/DK 88/00177, published May 18, 1989, all incorporated herein by reference.
• Suitable fungal lipases include those produced by Humicola lanuqinosa and Thermomvces lanuoinosus.
• lipase obtained by cloning the gene from Humicola lanuqinosa and expressing the gene in Asper ⁇ illus orvzae as described in European Patent Application 0 258 068, incorporated herein by reference, commercially available under the trade name Lipolase ® from Novo-Nordisk.
• Any amylase suitable for use in a liquid detergent composition can be used in these compositions.
• Amylases include for example, ⁇ -amylases obtained from a special strain of B_ ⁇ I cheniforms, described in more detail in British Patent Specification No. 1,296*839.
• Amylolytic enzymes include, for example, RapidaseTM, MaxamylTM, Terma yTTM and BANTM.
• active amylase in a preferred embodiment, from about 0.001% to about 5%, preferably 0.005% to about 3%, by weight of active amylase can be used. Preferably from about 0.005% to about .3% by weight of active protease can be used.
• amylase is MaxamylT and/or TermanylTM and the protease is Esperase ® and/or Savinase®.
• the viscoelastic, thixotropic thickening agent in the compositions of the present invention is from about 0.1% to about 10%, preferably from about 0.25% to about 5%, most preferably from about 0.5% to about 3%, by weight of the detergent composition.
• the viscoelastic, thixotropic thickening agent is free of any enzymatically reactive species.
• the enzyme(s) present in the automatic detergent composition could degrade the thickening agent which contains such species, resulting in a rheolog cally unstable product.
• the thickening agent is a polymer with a molecular weight from about 500,000 to about 10,000,000. more preferably from about 750,000 to about 4,000,000.
• the preferred cross-! nkedpolycarboxylate polymer is preferably a carboxyvinyl polymer.
• carboxyvinyl polymer Such compounds are disclosed in U.S. Patent 2,798,053, issued on July 2, 1957, to Brown, the specification of which is hereby incorporated by reference. Methods for making carboxyvinyl polymers are also disclosed in Brown. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
• Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of
• oligosaccarides reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, an pentaerythritol; most preferred is sucrose or pentaerythritol.
• the hydroxyl groups of the modified polyol be etherified with ally! groups, the polyol having at least two ally! ether groups per polyol molecule.
• sucrose it is preferred that
• the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2% to about 2.5%.
• Preferred monomeric olefinically unsaturated carboxylic acids 3 for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable, alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric onoolefinic acrylic acids of the structure
• R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
• Various carboxyvinyl polymers, nomopolymers and copolymers o are commercially available from B.F. Goodrich Company, New York, N.Y., under the trade name Carbopol ® . These polymers are also known as carbomers or polyacrylic acids.
• Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 750,000, Carbopol 941 _ • having a molecular weight of about 1,250,000, and Carbopols 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respectively. More preferred are the series of Carbopols which use ethyl acetate and cyclohexane in the manufacturing process, Carbopol 981, 2984, 980, and 1382.
• Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.
• polyacrylic acid available from BASF Corporation
• Carbopol 600 series resins available from B.F. Goodrich
• Polygel DK available from 3-V Chemical Corporation.
• Mixtures of polycarboxylate polymers as herein described may also be used in the present invention.
• the polycarboxylate polymer thickening agent is preferably utilized with essentially no clay thickening agents since the presence of clay usually results in a less desirable product having phase instability.
• the polycarboxylate polymer is preferably used instead of clay as a thickening agent in the present compositions, although clay can be used if so desired.
• the preferred clay thickening agent can be either naturally occurring or synthetic.
• a preferred synthetic clay is the one disclosed in U.S. Patent 3,843,598, incorporated herein by reference.
• Naturally occurring clays include some smectite and attapulgite clays as disclosed in U.S. Patent 4,824,590, incorporated herein by reference.
• the cellulosic type thickeners hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCEL® available from Oow Chemical) can also be used.
• the polycarboxylate polymer thickening agent provides an apparent viscosity at high shear of greater than about 250 centipoise and an apparent yield value of from about 40 to about 800, and most preferably from about 60 to about 600, dynes/cm ⁇ to the composition.
• Viscosity is a measure of the internal resistance to flow exhibited by a fluid in terms of the ratio of the shear stress to the shear rate.
• the yield value is an indication of the shear stress at which the gel strength is exceed and flow is initiated. Yield value can be measured herein with a Brookfield RVT model viscometer with a T-bar B spindle at about 77 ⁇ F (25 ⁇ C) utilizing a Helipath drive during associated readings.
• the system is set to 0.5 rpm and a torque reading is taken for the composition to be tested after 30 seconds or after the system is stable.
• the system is stopped and the rpm is reset to 1.0 rpm.
• a torque reading is taken for the same composition after 30 seconds or after the system is stable.
• Apparent viscosities at high shear are determined with a Brookfield RVT viscometer with spindle #6 at 100 rpm, reading the torque at 30 seconds.
• a preferred method herein for measuring viscosity and yield value is with a Contraves Rheomat 115 viscometer which utilizes a Rheoscan 100 controller, a DINI 45 spindle and cup at 25°C.
• the shear rate is increased from 0 to 150 sec-1 over a 30 second time period.
• the viscosity, measured in centipoise is taken at a shear rate of 150 sec-1.
• the shear rate for yield value measurements is increased linearly from 0 to 0.4 sec-1 over a period of 500 seconds after an initial 5 minute rest period.
• Enzyme Stabilizing System The preferred compositions herein comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight, of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme of the present invention.
• Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof.
• the level of calcium ion should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, etc., in the composition.
• Any water-soluble calcium salt can be used as the source of calcium ion. including calcium chloride, calcium formate, and calcium acetate.
• a small amount of calcium ion generally from about 0.05 to about 0.4 mill i oles per liter, is often also present in the composition due to calcium in the enzyme and formula water.
• Calcium ions can be used with boric acid or a suitable salt of boric acid, described herein below, in a composition with a product pH between about 7 and about 9.
• calicum ions and the salt of boric acid can associate to from calcium borate which is insoluble in cold water and under certain product conditions can be insoluble above about pH 9. This precipitate can lead to phase instability, decrease in effective enzyme stabil zation and undesired product aesthetics. Therefore, a sufficient amount of calcium ion and boric acid or the salt of boric acid should be used to achieve enzyme stability without affecting phase stability, enzyme stability, or aesthetics. From about 0.03% to about 0.6%, more preferably from about 0.05% to about 0.45% of calcium formate is preferred.
• Suitable enzyme stabilizing systems comprise polyols containing only carbon, hydrogen and oxygen atoms. They preferably contain from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups. Examples include propylene glycol (especially 1,2-propanediol , which is preferred), 1,2- butanediol, ethylene glycol, glycerol, sorbitol, mannitol , and glucose.
• the polyol generally represents from about 0.5% to about 10%, preferably from about 1.5% to about 8%, by weight of the composition.
• the weight ratio of polyol to a boric acid added is at least 1, most preferably at least about 1.3.
• compositions can also contain the water-soluble short chain carboxylates described in U.S. Patent 4,318,818, Letton et al . , issued March 9, 1982, incorporated herein by reference.
• the formates are preferred and can be used at levels from about 0.05% to about 5%, preferably from about 0.075% to about 2.5%, most preferably from about 0.1% to about 1.5%, by weight.
• Sodium formate is preferred.
• Another stabilizing system comprises from about 0.05% to about 7%, preferably from about 0.1% to about 5%, by weight of
• the boric acid may be, but is preferably not, formed by a comDound capable of forming boric acid in the composition. - i l -
• Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, eta- and pyroborate, and sodium pentaborate) are suitable.
• alkali metal borates e.g., sodium ortho-, eta- and pyroborate, and sodium pentaborate
• Still another enzyme stabilizing system includes polyhydroxyl compounds, such as sugar alcohols, monosaccharides and discaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-soluble sodium or potassium salts and water-soluble hydroxy alcohols, as disclosed in U.S. Published Patent Application B-458,819, Weber, published April 13, 1976; o diamines and polyamines, as disclosed in German Pat. No. 2,058,826; amino acids, as disclosed in German Pat. No. 2,060,485; and reducing agents, as disclosed in Japanese Pat. No. 72-20235.
• polyhydroxyl compounds such as sugar alcohols, monosaccharides and discaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-soluble sodium or potassium salts and water-soluble hydroxy alcohols, as disclosed in U.S. Published Patent Application B-458,819, Weber, published April 13, 1976
• o diamines and polyamines as disclosed in German Pat. No. 2,058,826
• amino acids as disclosed
• the enzyme mixture may be incorporated into the detergent composition in a 5 coated, encapsulated, agglomerated, prilled, or noodled form in accordance with, e.g., U.S. Patent 4,162,987, Maguire et al, issued July 31, 1979.
• Substituted boric acids e.g. phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
• a particularly preferred boronic acid is an aryl boronic acid of the structure:
• x is selected from Cj-C6 alkyl, substituted Cj-C ⁇ alkyl, aryl, substituted aryl, hydroxyl, hydroxyl derivative, amine Ci-C ⁇ alkylated amine, amine derivative, halogen, nitro, thiol, thio derivative, aldehyde, acid, acid salt, ester, sulfonate or phosphonate; each Y is independently selected from hydrogen, Cj-C ⁇ alkyl, substituted ⁇ -Z ⁇ alkyl, aryl, substituted aryl, hydroxyl, hydroxyl derivative, halogen, amine, alkylated amine, amine derivative, nitro, thiol.
• ⁇ In addition to the above listed enzyme stabilizers, from 0 to about 10%. preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers can be added to prevent chlorine bleacn species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
• Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbamate, ascorbate, etc.. organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
• EDTA ethylenediaminetetracetic acid
• MEA monoethanolamine
• scavenging anions like sulfate, bisulfate, carbonate, bicarbonate, percarbonate, nitrate, chloride, borate, sodium perborate tetrahydrate, sodium perborate monohydrate, phosphate, condensed phosphate, acetate, benzoate. citrate, formate, lactate, malate, tartrate, salicyiate, etc. and mixtures thereof can also be used.
• the preferred ammonium salts can be simply admixed with the detergent composition, they are prone to adsorb water and/or give off ammonia gas. Accordingly, it is better if they are protected in a particle like that described in U.S. Patent 4,652,392, Baginski et al , which is incorporated herein by reference.
• the preferred ammonium salts or other salts of the specific chlorine scavenger anions can either replace the suds controlling agent or be added in addition to the suds controlling agent.
• one or more buffering agents can be included which are capable of maintaining the pH of the compositions within the desired alkaline range.
• the pH of the undiluted composition (“as is") is determined at room temperature (about 20 * C) with a pH meter. It is in the low alkaline pH range
• composition pH between about 7 and about 11, preferably between about 8 and about 11.5, minimizes undesirable degradation of the active enzymes. Maintenance of this particular pH range also maximizes the soil and stain removal properties and prevents spotting and filming during utilization of the present compositions.
• the pH adjusting agents are generally present in a level from about 0.001% to about 25%, preferably from about 0.5% to about 20% by weight of the detergent composition.
• any compatible material or mixture of materials which has the effect of maintaining the composition pH within the pH range of about 7 to about 11, preferably about 8 to about 11, most preferably about 9 to 11, can be utilized as the pH adjusting agent in the instant invention.
• Such agents can include, for example, various water-soluble, inorganics salts such as the carbonates, bicarbonates, sesquicarbonates, pyrophosphates, phosphates, tetraborates, and mixtures thereof. Silicates are not included because of their high alkaline buffering properties.
• Examples of preferred materials which can be used either alone or in combination as the pH adjusting agent herein include sodium carbonate, sodium bicarbonate, potassium carbonate, sodium sequicarbonate, sodium pyrophosphate, tetrapotassium pyrophos- phate, tripotassium phosphate, trisodium phosphate, organic amines and their salts such as monoethanol amine (MEA), anhydrous sodium tetraborate, sodium tetraborate pentahydrate, potassium hydroxide, sodium hydroxide, and sodium tetraborate decahydrate. Combinations of these pH adjusting agents, which include both the sodium and potassium salts, may be used.
• compositions of this invention can contain from about
• the detergent surfactant is low foaming or which in combination with other components (i.e. suds suppressors) is low foaming.
• the surfactant is a low foaming surfactant.
• the surfactant employed is preferably enzyme stable (enzyme compatible) and free of enzymatically reactive species.
• the surfactant should be free of peptide or glycosidic bonds.
• Desirable detergent surfactants include nonionic, am ' onic, amphoteric and zwitterion c detergent surfactants, and mixtures thereof.
• nonionic surfactants examples include:
• condensation product of 1 mole of a saturated or unsaturated, straight or branched chain, alcohol or fatty acid containing from about 10 to about 20 carbon atoms with from about 4 to about 40 moles of ethylene oxide is particularly preferred.
• the condensation product of a fatty alcohol containing from 17 to 19 carbon atoms, with from about 6 to about 15 moles, preferably 7 to 12 moles, most preferably 9 moles, of ethylene oxide provides superior spotting and filming performance. More particularly, it is desirable that the fatty alcohol contain 18 carbon atoms and be condensed with from about 7.5 to about 12, preferably about 9 moles of ethylene oxide.
• Polyoxypropylene, polyoxyethylene condensates having the formula HO(C2H6 ⁇ ) x (C3H6 ⁇ ) x H or HO(C3H6 ⁇ ) y (C2H4 ⁇ ) x (C3H6 ⁇ ) y H where total y equals at least 15 and total (C2H4O) equals 20% to 90% of the total weight of the compound and the molecular weight is from about 2,000 to about 10,000, preferably from about 3,000 to about 6,000.
• These materials are, for example, the PLUR0NICS ® which are o well known in the art.
• Useful surfactants in detergent compositions are those having the formula RO-(C H4 ⁇ ) x R 1 wherein R is an alkyl or alkylene group containing from 17 to 19 carbon atoms, x is a number from about 6 to about 15, preferably from about 7 to about 12, and R is selected from the group consisting of: preferably, hydrogen, C1-5 0 alkyl groups, C2-5 acyl groups and groups having the formula -(CyH2yO) n H wherein y is 3 or 4 and n is a number from one to about 4.
• Particularly suitable surfactants are the low-sudsing compounds of (4), the other compounds of (5), and the C17.-C19 5 materials of (1) which have a narrow ethoxy distribution.
• Certain of the block co-polymer surfactant compounds designated PLURONIC, PLURAFAC® and TETRONIC® by the BASF Corp., Parsippany, N.J. are suitable as the surfactant for use herein.
• a particularly preferred embodiment contains from about 40% to about 70% of a 0 polyoxypropylene, polyoxethylene block polymer blend comprising about 75%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 mole of propylene oxide; and about 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and _ ⁇ z polyoxypropylene, initiated with tri-methylol propane, containing .99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylol propane.
• nonionic type surfactants which may be employed have melting points at or above ambient temperatures, such as octyldimethylamine N-oxide dihydrate, decyldimethylamine N-oxide dihydrate, C8-C12 N-methyl-glucamides and the like.
• Such surfactants may advantageously be blended in the instant compositions with short-chain anionic surfactants, such as sodium octyl sulfate and similar alkyl sulfates, though short-chain sulfonates such as sodium cumene sulfonate could also be used.
• Anionic surfactants which are suitable for the compositions of the present invention include, but are not limited to, water so uble-alkyl sulfates and/or sulfonates, containing from about 8 to about 18 carbon atoms.
• Natural fatty alcohols include those produced by reducing the glycerides of naturally occurring fats and oils. Fatty alcohols can be produced synthetically, for example, by the Oxo process. Examples of suitable alcohols which can be employed in alkyl sulfate manufacture include decyl, lauryl, myristyl, palmityl and stearyl alcohols and the mixtures of fatty alcohols derived by reducing the glycerides of tallow and coconut oil .
• alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alkyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, magnesium coconut alkyl sulfate, calcium coconut alkyl sulfate, potassium coconut alkyl sulfate and mixtures thereof.
• alkyl sulfates are sodium coconut alkyl sulfate, potassium coconut alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.
• a preferred sulfonated anionic surfactant is the alkali metal salt of secondary alkane sulfonates, an example of which is the Hostapur SAS from Hoechst Celanese.
• surfactants operable in the present invention are the water-soluble betaine surfactants. These materials have the general formula:
• R3 wherein Rj is an alkyl group containing from about 8 to 22 carbon atoms; R2 and R3 are each lower alkyl groups containing from about 1 to 5 carbon atoms, and R4 is an alkylene group selected from the group consisting of methylene, propylene, butylene and pentylene. (Propionate betaines decompose in aqueous solution and hence are not included in the instant compositions).
• betaine compounds of this type include dodecyldimethylammonium acetate, tetradecyldimethylammonium acetate, hexadecyldimethylammonium acetate, alkyldimethylammonium acetate wherein the alkyl group averages about 14.8 carbon atoms in length, dodecyldimethylammonium butanoate, tetradecyldimethyl- ammonium butanoate, hexadecyldimethylammonium butanoate, dodecyl- dimethylammonium hexanoate, hexadecyldimethylammonium hexanoate, tetradecyldiethylammonium pentanoate and tetradecyldipropyl- ammonium pentanoate.
• Especially preferred betaine surfactants include dodecyldimethylammonium acetate, dodecyldimethylammonium hexanoate, hexadecyldimethylammonium acetate, and hexadecyldi ⁇ methylammonium hexanoate.
• Other surfactants include amine oxides, phosphine oxides, and sulfoxides. However, such surfactants are usually high sudsing.
• a disclosure of surfactants can be found in published British Patent Application 2,116,199A; U.S. Patent 4,005,027, Hartman; U.S. Patent 4,116,851, Rupe et al ; U.S. Patent 3,985,668, Hartman; U.S.
• Patent 4,271,030 Brierley et al ; and U.S. Patent 4,116,849, • Leikhim, all of which are incorporated herein by reference.
• Other desirable surfactants are the alkyl phosphonates, taught in U.S. Patent 4,105,573 to Jacobsen issued August 8, 1978, incorporated herein by reference.
• Still other preferred anionic surfactants include the linear or branched alkali metal mono- and/or di-(Cs-i4) alkyl diphenyl oxide nomo- and/or disulfonates, commercially available under the trade names DOWFAX ® 3B-2 (sodium n-decyl diphenyloxide disulfonate) and DOWFAX ® 2A-1. These and similar surfactants are disclosed in published U.K. Patent Applications 2,163,447A; 2,163,448A; and 2,164,350A, said applications being incorporated herein by reference.
• Detergencv Builder Detergency builders can be added to the present invention in levels from about 0.01% to about 40%, preferably from about 0.1% to about 30%, most preferably from about 2% to about 25% by weight of the composition.
• the builders reduce the free calcium and/or magnesium ion concentration in a surfactant-containing aqueous solution, enhancing stain removal and providing additional cleaning benefits.
• the detergency builder can be any of the detergent builders known in the art which include trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium pyrophosphate, potassium tripolyphosphate, potassium hexametaphosphate, sodium carbonate, sodium bicarbonate, sodium hydroxide, borax, sodium nitrilotriacetate, potassium nitrilotriacetate, sodium carboxymethyloxysuccinate, sodium carboxy ethyloxymalonate, oxydisuccinate, polyphosphonates, salts of low molecular weight carboxylic acids, such as citrate builders, particularly sodium citrate, and polycarboxylates, such as polyacrylates or polymaleates, copolymers and mixtures thereof.
• detergent builders known in the art which include trisodium phosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate,
• Suitable builders include ether carboxylates such as tartrate monodisuccinate and tartrate disuccinate, which can be found in the disclosures of U.S. Patents 3,566,984 and 4,663,071, both incorporated herein by reference.
• the preferred builder is citric acid or an alkali metal •citrate such as sodium citrate in levels from about 2% to about 25%, preferably from about 3% to about 20% by weight of the composition.
• Some of the above-described detergency builders additionally serve as buffering (pH adjusting) agents. It is preferred that the buffering agent contain at least one compound capable of additionally acting as a builder.
• compositions can contain organic dispersant which overcomes the problem of unsightly films which form on china and especially on glassware due to calcium- or magnesium-hardness-induced precipitation of pH-adjusting agents, especially carbonates, used herein.
• the organic dispersants herein can be used at levels of 0 to about 20%, typically from about 0.5% to about 17%, most preferably from about 1% to about 15% of the automatic dishwashing composition. Such organic dispersants are preferably water-soluble sodium polycarboxylates.
• Polycarboxylate dispersants herein generally contain truly polymeric numbers of carboxylate groups, e.g., 8 or more, as distinct from carboxylate builders, sometimes called “polycarboxylates” in the art when, in fact, they have relatively low numbers of carboxylate groups such as four per molecule.
• the organic dispersants are known for their ability to disperse or suspend calcium and magnesium "hardness", e.g., carbonate salts.
• Organic dispersants are polyacrylates or acrylate-containing copolymers.
• SOKALAN Polymeric Dispersing Agents
• polyanionic materials are, as noted, usually available as viscous aqueous solutions, often having •dispersant concentrations of about 30-50%.
• the organic dispersant is most commonly fully neutralized; e.g., as the sodium salt form. While the foregoing encompasses preferred organic dispersants for use herein, it will be appreciated that other oligomers and polymers of the general polycarboxylate type can be used, according to the desires of the formulator.
• Suitable polymers are generally at least partially neutralized in the form of their alkali metal, ammonium or other conventional cation salts. The alkali metal, especially sodium salts, are most preferred.
• the molecular weight of such dispersants can vary over a wide range, it preferably is from about 1,000 to about 500,000, more preferably is from about 2,000 to about 250,000, and most preferably is from about 3,000 to about 100,000.
• Nonlimiting examples of such materials are as follows.
• suitable organic dispersants include those disclosed in U.S. Patent 3,308,067 issued March 7, 1967, to Diehl, incorporated herein by reference.
• Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• the presence of monomeric segments containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable, preferably when such segments do not constitute more than about 40% by weight of the polymer.
• Suitable organic dispersants for use herein are copolymers of acrylamide and acrylate having a molecular weight of from about 3,000 to about 100,000, preferably from about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20%, by weight of the polymer. Most preferably, the polymer has a molecular weight of from about 4,000 to about 10,000 and an acrylamide content of from about 1% to about 15%, by weight of the polymer.
• Still other useful organic dispersants include acrylate/ aleate or acrylate/fumarate copolymers with an average molecular weight in acid form of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 2:1.
• Other such suitable copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982, incorporated herein by reference.
• Yet other organic dispersants are useful herein, as illustrated by water-soluble oxidized carbohydrates, e.g., oxidized starches 5 prepared by art-disclosed methods.
• Other Optional Materials include acrylate/ aleate or acrylate/fumarate copolymers with an average molecular weight in acid form of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 2:1.
• compositions of the present invention may optionally comprise certain esters of phosphoric acid (phosphate ester).
• Phosphate esters are any materials of the general formula: o o o
• R and R' are C6-C20 alkyl or ethoxylated alkyl groups.
• R and R' are of the general formula: alkyl-(OCH2CH2) ⁇ wherein the alkyl substituent is C12-C18 and Y is between 0 and about 4. Most preferably the alkyl substituent of that formula is 0 C 2-C 8 and Y is between about 2 and about 4.
• Such compounds are prepared by known methods from phosphorus pentoxide,' phosphoric acid, or phosphorus oxy halide and alcohols or ethoxylated alcohols.
• phosphate esters will generally comprise mixtures of the mono- and di-esters, together with some proportion of tri-ester.
• Typical commercial esters are available under the trademarks "Phospholan” PDB3 (Diamond Shamrock), “Servoxyl” VPAZ (Servo), PCUK-PAE (BASF-Wyandotte) , 0 SAPC (Hooker).
• Preferred for use in the present invention are KN340N and KL340N (Hoescht) and monostearyl acid phosphate (Occidental Chemical Corp.). Most preferred for use in the present invention is Hostophat-TP-2253 (Hoescht).
• phosphate esters useful herein provide protection of
• the phosphate ester .component also acts as a suds suppressor in the anionic surfactant-containing detergent compositions disclosed herein. If a phosphate ester component is used in the compositions of the present invention, it is generally present from about 0.1% to about 5%, preferably from about 0.15% to about 1.0% by weight of the composition.
• Metal salts of long chain fatty acids and/or long chain hydroxy fatty acids have been found to be useful in automatic dishwashing detergent compositions to inhibit tarnishing caused by repeated exposure of sterling or silver-plate flatware to bleach-containing automatic dishwashing detergent compositions (U.S. Patent 4,859,358, Gabriel et al ) .
• long chain is meant the higher aliphatic fatty acids or hydroxy fatty acids having from about 6 to about 24 carbon atoms, preferably from about 8 to 22 carbon atoms, and most preferably from about 10 to 20 carbon atoms and most preferably from about 12 to 18, inclusive of the carbon atom of carboxyl group of the fatty acid, e.g., stearic acid, and hydroxy stearic acid.
• metal salts of the long chain fatty acids and/or hydroxy fatty acids is meant both monovalent and polyvalent metal salts, particularly the sodium, potassium, lithium, aluminum, and zinc salts, e.g., lithium salts of the fatty acids.
• this component generally comprises from about 0.01% to about 2%, preferably from about 0.05% to about 0.2% by weight of the composition.
• An alkali metal salt of an amphoteric metal salt of an a photeric metal anion (metalate), such as aluminate, can be added to provide additional structuring to the polycarboxylate polymer thickening agent. See U. S. Patent 4,941,988, Wise, issued July 17, 1990, incorporated herein by reference.
• Suitable nonchlorine bleaches in the present compositions are solid, water-soluble peroxygen compounds in levels from 0 to about 15%, preferably from about 0.2% to about 12% by weight of the composition.
• Preferred compounds include perborates, persulfates, peroxydisulfates, perphosphates and the crystalline peroxyhydrates. 2,124,526, U.S. Patent 3,933,672, Bartolotta et al., and U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987. All are incorporated herein by reference.
• compositions hereof will .generally comprise from 0% to about 5% of suds suppressor.
• 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., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
• compositions hereof A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, draining promoting agents, processing aids, corrosion inhibitors, perfumes, dyes or pigments, oxygen bleaches, bleach activators, etc.
• the above-described other optional materials generally are enzyme compatible and comprise no more than about 10% by weight of the total composition and are dissolved, suspended, or emulsified in the present compositions.
• composition Preferred viscoeleastic, thixotropic, liquid automatic dishwashing detergent compositions hereof will preferably be •formulated such that during use in aqueous operations, the wash water will have a pH of between about 7 and 11, preferably between about 8 and 10.5.
• This invention further provides a method for cleaning dishware (i.e. glass, china, flatware, silverware and the like) by contacting the dishware with a liquid detergent composition comprising detersive enzyme, detersive surfactant, viscoelastic thixotropic thickening agent, enzyme stabilizing system, and buffering agent. Agitation is preferably provided for enhanced cleaning.
• a liquid detergent composition comprising detersive enzyme, detersive surfactant, viscoelastic thixotropic thickening agent, enzyme stabilizing system, and buffering agent.
• Agitation is preferably provided for enhanced cleaning.
• Preferred herein are gel and/or paste automatic dishwashing detergent compositions, more preferably gel automatic dishwashing detergent compositions.
• This invention also allows for concentrated gel automatic dishwashing detergent compositions. By “concentrated” is meant that these compositions will deliver to the wash the same amount of active detersive ingredients at a lower dosage.
• Concentrated gel automatic detergent compositions herein contain about 10 to 100 weight % more active detersive ingredients than regular gel automatic dishwashing detergent compositions.
• a preferred method for preparing a final product of the present invention comprises:
• step (d) adding surfactant and other suitable agents
• the polymer may be added as either a powder or slurry.
• the enzyme stabilizing system should be added prior to the addition of builder. Without being bound by theory, it is believed the enzyme stabilizing system added after the builder will associate with the builder and lose its effectiveness; whereas, if added prior to the builder it will form an effective compound which will not associate with the builder. In addition, enzymes are added last to minimize degradation due to temperature and pH changes resulting during the process.
• compositions prepared as above described exhibit a viscoelastic, thixotropic nature, and have good phase stability. Good rheology can be obtained both by the method of formulation and by the use of all sodium components, which this invention allows to be achieved.
• Viscoelastic, thixotropic liquid automatic dishwashing detergent compositions are as follows:
• Compositions 1-4 demonstrate the use of various enzyme stabilizing systems, i.e. boric acid (composition 1), boric acid 0 and 1,2-propanediol (composition 4), and calcium/sodium formate (compositions 2 and 3). All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40'F (4.4'C) to about 120'F (48.9'C).
• various enzyme stabilizing systems i.e. boric acid (composition 1), boric acid 0 and 1,2-propanediol (composition 4), and calcium/sodium formate (compositions 2 and 3). All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40'F (4.4'C) to about 120'F (48.9'C).
• Block co-polymer surfactant(3) 7.00 1.50 1.50 1.50 Sodium n-decydiphenyloxide disulfonate( 4 ) Boric acid 1,2-propanediol Protease enzyme(5) Amylase enzyme( 6 ) Lipase enzyme(7) C12-14 fatty acid Monoethanolamine (MEA) Suds suppressor(S) Water and trim
• MSAP, Hooker Chemical or LPKN, Knapsack Compositions 5-12 demonstrate the use of chlorine scavengers in viscoelastic, thixotropic liquid automatic dishwashing- detergent compositions. All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40'F (4.4 * C) to about 120'F (48.9'C).
• Concentrated gel automatic dishwashing detergent compositions with chlorine scavengers are shown below.
• Viscoelastic, thixotropic liquid automatic dishwashing detergent compositions are as follows: Ta le 5
• Amylase enzyme Water and minors
• a paste dishwashing detergent composition is as follows:

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• 1993
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