EP0460810B1 - Nichtwässerige flüssige Detergenszusammensetzung für Geschirrspülautomaten - Google Patents

Nichtwässerige flüssige Detergenszusammensetzung für Geschirrspülautomaten Download PDF

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Publication number
EP0460810B1
EP0460810B1 EP91304072A EP91304072A EP0460810B1 EP 0460810 B1 EP0460810 B1 EP 0460810B1 EP 91304072 A EP91304072 A EP 91304072A EP 91304072 A EP91304072 A EP 91304072A EP 0460810 B1 EP0460810 B1 EP 0460810B1
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EP
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Prior art keywords
composition
detergent
silica
agent
filming
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EP91304072A
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English (en)
French (fr)
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EP0460810A1 (de
Inventor
Fahim Uddin Ahmed
Charles E. Buck
Gary Jakubicki
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Colgate Palmolive Co
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Colgate Palmolive Co
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Priority to AT91304072T priority Critical patent/ATE103323T1/de
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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 an automatic dishwasher detergent composition having improved anti-filming and/or anti-spotting properties.
  • the present invention is particularly directed to a stable nonaqueous liquid dishwasher detergent composition containing an anti-filming and/or anti-spotting agent for use in an automatic dishwasher to clean dishware, glassware and the like.
  • the present invention more particularly relates to a nonaqueous liquid dishwashing detergent composition with improved anti-filming and anti-spotting properties and to a method of using the detergent composition to clean dishware, glassware, china and the like.
  • the dishwashing composition contains an anti-filming agent, or an anti-filming agent and polyacrylic acid polymer or salt anti-spotting agent, inorganic builder salts, bleach compound and detergent.
  • the detergent dishwashing composition of the present invention reduce filming and/or spotting on dishware, glassware, china and the like, particularly in hard water at low temperature.
  • the invention relates to the use of a nonabrasive amount of small substantially water insoluble silica particles, as an anti-filming agent and polyacrylic acid or salt polymer as an anti-spotting agent in nonaqueous liquid dishwashing detergent compositions to reduce filming and/or spotting.
  • the detergent compositions do not require an added rinse aid, are stable in storage and are readily dispersible in the wash bath.
  • the present invention specifically relates to nonaqueous liquid automatic dishwashing detergent compositions having improved anti-filming properties, which are readily dispersible in the washing medium to provide effective cleaning of dishware, glassware, china and the like.
  • the present invention also relates to an improved nonaqueous liquid composition and to a method of using the composition.
  • the present invention is directed to a nonaqueous liquid automatic dishwasher detergent composition having improved anti-filming and/or anti-spotting properties for cleaning of dishware, glassware, china and the like.
  • the detergent composition contains as an essential ingredient a nonabrasive amount of small substantially water insoluble silica, alumina or titanium dioxide particles as an anti-filming agent.
  • the compositions can additionally contain a polyacrylic acid polymer or salt as an anti-spotting agent.
  • the present invention specifically relates to nonaqueous liquid automatic dishwashing detergent compositions having improved anti-filming and/or anti-spotting properties for cleaning of dishware, glassware, china and the like.
  • the nonaqueous liquid compositions are stable in storage, do not settle, are readily pourable and are readily dispersed in water.
  • the commercially available formulated powder detergents frequently require a separate step of hand towel wiping and drying of the dishware, glassware, china and the like to avoid leaving undesirable traces or film.
  • the use of liquid detergent compositions present other problems.
  • the builder salts settle in storage and are not readily redispersed.
  • the compositions also frequently become thicker in storage and are not readily pourable.
  • the automatic dishwashing detergent hereinafter also designated ADD, contain (1) sodium tripolyphosphate (NaTPP) to soften or tie up hard-water minerals and to emulsify and/or peptize soil; (2) sodium silicate to supply the alkalinity necessary for effective detergency and to provide protection for dishware, such as fine china and protection against machine corrosion; (3) sodium carbonate, generally considered to be optional, to enhance alkalinity; (4) a chlorine-releasing agent to aid in cleaning; (5) a surfactant and (6) a defoamer to reduce foam, thereby enhancing machine efficiency.
  • NaTPP sodium tripolyphosphate
  • sodium silicate to supply the alkalinity necessary for effective detergency and to provide protection for dishware, such as fine china and protection against machine corrosion
  • sodium carbonate generally considered to be optional, to enhance alkalinity
  • a chlorine-releasing agent to aid in cleaning
  • U.S. Patent No. 3,985,668 describes abrasive scouring cleaners of gel-like consistency containing (1) suspending agent, preferably the Smectite and attapulgite types of clay; (2) abrasive, e.g. silica sand or perlite; and (3) filler comprising light density powdered polymer, expanded perlite and the like.
  • the perlite has a buoyancy and thus stabilizing effect on the composition in addition to serving as a bulking agent, thereby replacing water otherwise available for undesired supernatant layer formation due to leaking and phase destabilization.
  • Optional ingredients include hypochlorite bleach, bleach stable surfactant and buffer, e.g.
  • silicates, carbonates, and monophosphates can be included as further optional ingredients to supply or supplement building function not provided by the buffer, the amount of such builder not exceeding 5% of the total composition, according to the patent. Maintenance of the desired (greater than) pH 10 levels is achieved by the buffer/builder components. High pH is said to minimize decomposition of chlorine bleach and undesired interaction between surfactant and bleach. When present, NaTPP is limited to 5%, as stated. Foam killer is not disclosed.
  • U.S. Patent 4,511,487 dated 16th April, 1985 describes a low-foaming detergent paste for dishwashers.
  • the composition is based on a mixture of finely divided hydrated sodium metasilicate, an active chlorine compound and a thickening agent which is a foliated silicate of the hectorite type. Small amount of nonionic tensides and alkali metal carbonates and/or hydroxides may be used.
  • the Laitem et al USP 4,753,748 discloses a nonaqueous liquid automatic dishwashing detergent composition
  • a liquid nonionic surfactant containing a stable or readily redispersible suspension of a polyphosphate builder and/or citrate salt and an alkylene glycol mono alkyl ether anti-gel agent.
  • Scott USP 4,438,014 discloses a powder formulation containing a novel nonionic surfactant for automatic dishwasher detergent compositions.
  • the nonionic surfactant consists of an alkyl group to which there is directly attached a propylene oxide polymer to which is attached an ethylene oxide-propylene oxide random copolymer.
  • the nonionic surfactant is described as providing optimum cleaning and good spotting and film results and good defoaming power.
  • nonaqueous liquid detergent compositions of the present invention overcome many of the prior art problems associated with powder and liquid detergents. Because of the addition of a small effective amount of a silica, alumina or titanium dioxide anti-filming agent or silica and polyacrylic acid polymer or salt anti-spotting agent to the composition an added rinse aid is not required and towel wiping and drying are not required to obtain dry sparkling clean dishes, glasses, cups and eating utensils.
  • the nonaqueous liquid automatic dishwashing detergent compositions of the present invention have the advantages of being stable, nonsettling in storage, and non-gelling in storage, and are readily dispersible in the dishwashing machine.
  • the liquid compositions of the present invention are easily pourable, easily measured and easily put into dishwashing machines.
  • the concentrated nature of the liquid detergent concentrate composition of the present invention allows placing in the dishwashing machine more active liquid detergent, e.g. more dispersed polyphosphate and other detergent builders.
  • nonaqueous liquid detergent compositions of the present invention with the exception of the anti-film agent, are readily soluble in the wash water in the dishwashing machine.
  • a further object of the invention is to provide a method of washing dishware, glassware, china and the like in an automatic dishwashing machine using a nonaqueous liquid detergent composition in which a separate rinse aid is not added or needed.
  • a still further object of the invention is to provide a method of washing dishware, glassware, china and the like in an automatic washing machine using a nonaqueous liquid detergent composition by which method the dishware, glassware, china and the like are machine dried with reduced film and/or spots.
  • a nonaqueous liquid automatic dishwashing detergent composition which has the advantage of improved film performance, comprises a nonaqueous liquid automatic dishwashing detergent composition comprising a nonaqueous organic carrier liquid and at least one ingredient selected from the group consisting of organic detergent, detergent builder, foam inhibitor and mixtures thereof, and a member selected from the group consisting of a nonabrasive 0.5 to 10.0% amount of small substantially water insoluble particles of silica, alumina or titanium dioxide, or mixtures thereof, as an anti-filming agent.
  • a nonaqueous liquid automatic dishwasher detergent composition in which is incorporated from about 0.5 to 10% of a silica anti-filming agent or silica anti-filming agent and 1 to 30% of a water soluble polyacrylic acid polymer or salt anti-spotting agent.
  • the silica anti-filming agent has a particle size of about 0.1 to 10 microns.
  • the water soluble polyacrylic acid or salt polymer has a molecular wight of about 1000 to 100,000.
  • nonaqueous liquid automatic dishwasher detergent composition which includes, on a weight basis:
  • the present invention also provides a method for cleaning dishware, glassware, china and the like in an automatic dishwashing machine with an aqueous wash bath containing an effective amount of the nonaqueous liquid automatic dishwasher detergent (LADD) composition as described above.
  • the LADD composition is stable in storage, is easily measured and can be readily poured into the automatic dishwashing machine.
  • an improved automatic dishwasher detergent composition is prepared by incorporating small amounts of a silica anti-filming agent or silica anti-filming agent and polyacrylic acid polymer or salt in a dishwasher composition.
  • the present invention is based upon the discovery that substantially improved anti-filming and/or anti-spotting properties can be obtained by adding to the nonaqueous liquid detergent composition a small effective amount of a silica anti-filming agent or silica anti-filming agent and polyacrylic acid polymer or salt anti-spotting agent.
  • a nonaqueous liquid automatic dishwashing detergent composition is prepared by dispersing a polyphosphate builder in an organic carrier liquid.
  • the polyphosphate builder may be replaced in whole or in part by an organic builder.
  • ingredients can be added to the composition such as anti-encrustation agents, anti-foam agents, optical brighteners, enzymes and perfume.
  • the organic carrier liquids that can be used in accordance with the present invention are carrier liquids, diluents and solvents that are compatible with the composition ingredients.
  • Suitable organic carrier liquids are polyethylene glycol M.W. 300, M.W. 400 and M.W. 4000, propylene glycol, propylene carbonate, polypropylene glycol M.W. 200 and M.W. 300, methoxy propylene glycol, Carbowax MPEG 350 (polyethylene glycol methyl ether), from Union Carbide, triethanol amine, Butyl Carbitol, from DuPont Co, Glyme (ethylene glycol dimethyl ether), Diglyme (diethylene glycol dimethyl ether).
  • alkylene glycol monoalkyl ethers there can also be used as organic carrier liquids the alkylene glycol monoalkyl ethers.
  • the alkylene glycol mono alkyl ethers are low molecular weight amphiphilic compounds, particularly a mono-, di- or tri lower (C2 to C3) alkylene glycol mono lower (C1 to C5) alkyl ether.
  • Suitable examples of such additive amphiphilic compounds are ethylene glycol monoethyl ether C2H5-O-CH2CH2OH, diethylene glycol monobutyl ether C4H9-O-(CH2CH2O)2H and dipropylene glycol monomethyl ether
  • organic carrier liquids can be used alone or in admixture in order to obtain a desired viscosity and stability of the product liquid.
  • compositions of the present invention have good viscosity and stability characteristics and remain stable and pourable at low temperatures.
  • liquid nonionic surfactant detergents that can be used in the practice of the present invention are preferably the low foam poly-lower alkoxylated lipophiles.
  • Useful nonionics are represented by the low foam Plurafac series from BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include a C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, a C13-C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide and a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide.
  • Neodol 25-7 and Neodol 23-6.5 are made by Shell Chemical Company, Inc.
  • the former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5.
  • the higher alcohols are primary alkanols.
  • Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 (Registered Trademarks), both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp.
  • the former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.
  • a nonionic surfactant that can be used is available from Union Carbide Corporation under the trademark Tergitol MDS-42.
  • This nonionic surfactant is a C12-C14 linear alcohol containing 55% by weight random distributed oxyalkyl groups of which 42% are ethoxy and 58% propoxy groups.
  • a preferred nonionic surfactant that can be used in accordance with the present invention has the following formula R-O-(PO) x -(EO/PO)H
  • R is an alkyl group having 8 carbon atoms
  • PO is a propylene oxide polymer attached directly to the oxygen of the alkyl group
  • x is 8 to 9
  • EO/PO represents a copolymer of ethylene oxide and propylene oxide in which the ethylene oxide and propylene oxide are randomly mixed.
  • the molar ratio of Eo/PO is about 2:1 to 5:1, e.g. about 3:1.
  • the total number of EO and PO groups in the copolymer are such that the number of EO and PO groups are 5 to 8 and the cloud point of the nonionic surfactant is about 20 to 30°C.
  • Nonionic surfactants are the Poly-Tergent S-LF surfactants available from Olin Corporation. These surfactants are low foaming, biodegradable linear fatty alcohols. Surfactants of this type are available under the tradenames Poly-Tergent S-LF 18, Poly-Tergent S-305-LF, Poly-Tergent S-405-LF and Poly-Tergent CS-1.
  • anionic surfactants can also be used.
  • anionic surfactants that can be used are the linear or branched alkali metal mono- and/or di-(C8 ⁇ 14) alkyl diphenyl oxide mono and/or disulphonates, commercially available for example as DOWFAX (Registered Trademark) 3B-2 and DOWFAX 2A-1.
  • Suitable surfactants include the primary alkylsulphates, alkylsulphonates, alkylaryl-sulphates and sec, alkylsulphates.
  • Examples include sodium C10 ⁇ 18 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C10 ⁇ 18 alkanesulphonates such as sodium hexadecyl-1-sulphonate and sodium C12 ⁇ 18 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates.
  • the corresponding potassium salts may also be employed.
  • the nonionic and anionic surfactants are used in amounts of 0.1 to 12%, preferably 0.5 to 10.0%, and more preferably about 1.0 to 8.0%, for example 2 to 7%.
  • the anti-filming agent comprises a nonabrasive amount of small substantially water insoluble silica particles.
  • anti-filming agents alumina and titanium dioxide particles.
  • the anti-filming agent accordingly can be a member selected from the group consisting of silica, alumina and titanium dioxide and mixtures thereof.
  • the silica anti-filming agent materials that can be used are fumed or precipitated synthetic or natural silica.
  • the silica may be amorphous or crystalline.
  • the silica material that is used may contain up to about 0.1 to 5% alumina (Al2O3), usually up to about 0.5 to 3% and more usually about 1% alumina, based on the weight of silica.
  • Al2O3 alumina
  • a preferred silica material is Syloid 244 which is amorphous silica, has a particle size of about 4 microns and is provided by W.R. Grace Co.
  • Another suitable silica material is Silox 15, also from W.R. Grace Co., which has a particle size of about 4 microns.
  • Huber Zeo 49 is amorphous silica and is provided by J.M. Huber Corporation and contains about 1% alumina (Al2O3).
  • the particle size of the silica material that is used is important in achieving the desired anti-filming properties.
  • the silica particles that are used are finely divided and can have a particle size of about 0.10 to 10 microns, preferably 0.50 to 8 microns and more preferably about 1.0 to 5.0 microns.
  • the silica particles of this size and the amount used herein are not abrasive.
  • the finely divided silica material particles in the dishwashing wash act to coagulate proteinaceous particulate soils and keeps them in suspension to prevent them from depositing on the clean glass and dishware to form a film.
  • alumina material that can be used as an anti-filming agent is commercially available and is insoluble in water and has the formula Al2O3. Suitable materials are available under the tradenames Alumina Oxide C, available from Degussa Company and Catapal D, available from Vista Corp. Preferred alumina materials are fumed alumina and a precipitated alumina.
  • the titanium dioxide material that can be used as an anti-filming agent is insoluble in water and has the formula TiO2. Suitable materials are available under the tradenames Titanium Dioxide P25, available from Degussa Co. Preferred titanium dioxide materials are fumed titanium dioxide and precipitated titanium dioxide.
  • the particle size of the alumina and titanium dioxide material that are used is important in achieving the desired anti-filming properties.
  • the alumina or titanium dioxide particles that are used are finely divided and can have a particle size of about 0.01 to 10 microns, preferably 0.01 to 8 microns and more preferably about 0.020 to 4.0 microns.
  • a suitable particle size is about 0.01 to 0.50 microns.
  • the alumina and titanium dioxide particles of this size and in the amount used herein are not abrasive.
  • the finely divided alumina or titanium dioxide material particles in the dishwashing wash act to coagulate proteinaceous particulate soils and keeps them in suspension to prevent them from depositing on the clean glass and dishware.
  • the alumina and titanium dioxide anti-filming agents function in the following manner.
  • the surface of vitreous glassware contains negatively charged sites through the Si-O bonds. Usually the oxygen atoms carry these charges. It is postulated that these negatively charged ions will attract positively charged particles and thereby will form an "artificial soil" layer. This protective mono-layer will then repel the regular food soil and will increase the anti-redeposition property of the automatic dishwashing detergent.
  • the alumina and titanium dioxide particles, respectively, will generate positively charged particles which will bond themselves to the glassware surface to form the artificial soil layer which will prevent the formation of film.
  • silica, alumina or titanium dioxide anti-filming agent that can be used to achieve the desired improvement in film will depend on the hardness of the water, detergent active compound, inorganic salts and other ADD ingredients.
  • the silica, alumina or titanium dioxide anti-filming agents are particularly effective in hard wash water of, for example, 300 ppm hardness or more.
  • the amount of each of the silica, alumina or titanium dioxide anti-film agent that is used can be about 0.5 to 10%, preferably about 1 to 8% and more preferably about 1.5 to 6% by weight based on the weight of the entire composition.
  • the silica, alumina and titanium dioxide can each be used alone or one or more of them can be used mixed together.
  • the weight percent amounts mentioned above are the total for the anti-film agent ingredients used in the mixture.
  • polyacrylic acid polymers and salts thereof anti-spotting agents that can be used are generally commercially available and are briefly described as follows.
  • the polyacrylic acid polymers and salts thereof that can be used comprise water soluble low molecular weight polymers having the formula wherein the R1, R2 and R3 can be the same or different and can be hydrogen, C1-C4 lower alkyl, or combinations thereof.
  • the value of n is 5 to 1000, preferably, 10 to 500, and more preferably 20 to 100.
  • M represents hydrogen, or an alkali metal such as sodium or potassium. The preferred substituent for M is sodium.
  • the preferred R1, R2 and R3 groups are hydrogen, methyl, ethyl and propyl.
  • Preferred acrylic acid monomer is one where R1 to R3 are hydrogen, e.g. acrylic acid, or where R1 and R3 are hydrogen and R2 is methyl, e.g. methyl acrylic acid monomer.
  • the degree of polymerization i.e. the value of n, is generally determined by the limit compatible with the solubility of the polymer in water.
  • the terminal or end groups of the polymer are not critical and can be H, OH, CH3 or a low molecular weight hydrocarbon.
  • the polyacrylic acid polymers and salts thereof can have a molecular weight of 500 or 1,000 to 100,000, preferably 1,500 to 80,000 and especially preferably 2,000 to 50,000.
  • polyacrylic acid polymers which can be used include the Acrysol LMW acrylic acid polymers from Rohm and Haas, such as the Acrysol LMW-45N, a neutralized sodium salt, which has a molecular weight of about 4,500 and Acrysol LMW-20NX, a neutralized sodium salt, which has a molecular weight of about 2,000.
  • Other polyacrylic acid polymers or salts thereof that can be used are: Alcosperse 149, molecular weight 2000, Alcosperse 123, molecular weight 4500, Alcosperse 107, molecular weight 3000, Alcosperse 124, molecular weight 2000, and Alcosperses 602N molecular weight 4500, all of which are available from Alco Chemical Corp.
  • the low molecular weight acrylic acid polymers can, for example, have a molecular weight of about 1,000 to 10,000.
  • Another polyacrylic acid polymer that can be used is Alcosperses 110 (from Alco) which is a sodium salt of an organic polycarboxylate and which has a molecular weight of about 100,000.
  • polyacrylic acid polymers or salt that can be used to achieve the desired improvement in anti-filming and anti-spotting properties will depend on the hardness of the water, detergent active compound, inorganic salts and other ADD ingredients.
  • the polyacrylic acid or salt anti-spotting agent is particularly effective in reducing spotting in hard water of, for example, 300 ppm hardness or more.
  • the amounts of the polyacrylic acid polymer or salt anti-spotting agent that can be used are in the range of from about 1.0 to 30%, preferably from about 2.0 to 25%, especially preferably about 4 to 20%.
  • ADD effectiveness is related to (a) oxygen bleach levels; (b) alkalinity; (c) solubility in washing medium; and (d) foam inhibition. It is preferred herein that the pH of the aqueous wash bath after addition of the liquid ADD composition be at least about 9,5, more preferably from about 10,5 to 13,5 and most preferably at least about 11.5.
  • the amount of alkali metal silicate added and the amount of alkali metal TPP added can be used to obtain the desired alkalinity in the wash bath.
  • the sodium carbonate can be added to act as a buffer to maintain the desired pH level in the wash bath.
  • the sodium carbonate can be added in an amount of 0 to 25 wt.%, preferably 5 to 20 wt.% and typically about 5 to 15 wt.% of the detergent composition.
  • compositions of the present invention can contain inorganic builder salts such as NaTPP or organic builder salts such as the alkali metal salts of polycarboxylic acids.
  • a preferred solid builder salt is an alkali metal polyphosphate such as sodium tripolyphosphate (TPP).
  • TPP sodium tripolyphosphate
  • Suitable other builder salts are alkali metal borates, phosphates and bicarbonates.
  • Such builder are sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, potassium bicarbonate and sodium or potassium zeolites.
  • the detergent builders e.g. NaTPP may be employed in the nonaqueous liquid ADD composition in a range of 20 to 60%, preferably about 20 to 55 wt.%, and more preferably about 20 to 45 wt.%.
  • the NaTPP may be anhydrous or hydrated, including the stable hexahydrate with a degree of hydration of 6 corresponding to about 18% by weight of water or more.
  • anhydrous NaTPP is preferred.
  • the NaTPP may be replaced in whole or in part by organic builder salts. Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as an alkali metal polycarboxylic acid.
  • Suitable alkali metal polycarboxylic acids are alkali metal salts of citric and tartaric acid, e.g. monosodium and disodium citrate (anhydrous). The sodium salts of citric and tartaric acids are preferred.
  • Foam inhibition is important to increase dishwasher machine efficiency and minimize destabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be sufficiently reduced by suitable selection of the type and/or amount of detergent active material, the main foam-producing component. The degree of foam is also somewhat dependent on the hardness of the wash water in the machine whereby suitable adjustment of the proportions of NaTPP which has a water softening effect may aid in providing the desired degree of foam inhibition. However, it is generally preferred to include a foam depressant or inhibitor.
  • alkyl phosphonic acid esters of the formula available, for example, from BASF-Wyandotte (PCUK-PAE), and especially the alkyl acid phosphate esters of the formula available, for example, from Hooker (SAP) and Knapsack (LPKN-158), in which one or both R groups in each type of ester may represent independently a C12 ⁇ 20 alkyl group.
  • SAP Hooker
  • LNKN-158 Knapsack
  • R groups in each type of ester may represent independently a C12 ⁇ 20 alkyl group.
  • Mixtures of the two types or mixtures of mono- and di-esters of the same type may be employed.
  • a mixture of mono- and di-C16 ⁇ 18 alkyl acid phosphate esters such as monostearyl/distearyl acid phosphates 1.2/1 (Knapsack).
  • proportions of 0.01 to 6wt.%, preferably 0.1 to 5 wt.%, especially about 0.5 to 4.5 wt.%, of foam depressant in the composition is typical, the weight ratio of detergent active component to foam depressant generally ranging from about 10:1 to 1:1 and preferably about 4:1 to 1:1.
  • Other defoamers which may be used include, for example, the known silicones, such as Dow Corning 1400 and 1500, which are polysiloxanes mixed with dispersed silica.
  • the peroxygen bleach compounds are preferably used in the compositions of the present invention.
  • the oxygen bleaches are well known and are represented by percompounds which liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulfate.
  • the perborates, particularly sodium perborate monohydrate, are preferred.
  • the peroxygen compounds can be used in an amount of 3 to 15, preferably 4 to 12 and more preferably 4 to 8% by weight.
  • the peroxygen compound is preferably used in admixture with an activator therefor.
  • Suitable activators which can lower the effective operating temperature of the peroxide bleaching agent are used.
  • Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine (TAED) and pentaacetyl glucose are particularly preferred.
  • the bleach activators can be used in an amount of 0 to 8, preferably 1 to 8 and more preferably 2 to 6 wt. percent, for example 2 to 4 wt. percent.
  • the bleach activators interact with the peroxygen compounds to form a peroxyacid bleaching agent in the wash water.
  • acetylsalicyclic acid derivatives include, for example, acetylsalicyclic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these.
  • acetylsalicyclic acid derivatives ethylidene benzoate acetate and its salts
  • ethylidene carboxylate acetate and its salts include alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these.
  • TAGU tetraacetylglycouril
  • the conventionally used dishwasher detergent composition chlorine bleach compounds such as dichloro-isocyanurate, alkali metal, e.g. potassium and sodium, hypochlorite should not be used because they are unstable in the organic carrier liquids used in the compositions of the present invention. That is compounds that contain hypochlorite or that generate hypochlorite in the product liquid should not be used. Compounds that are stable in the product liquid, but that develop hypochlorite ion in the dishwasher water can however be used. For example, a combination of sodium chloride and Oxone (TM for potassium monopersulfate) which develop hypochlorite ion in the dishwasher water can be used.
  • TM sodium chloride and Oxone
  • the sodium silicate which provides alkalinity and protection of hard surfaces, such as fine china, is employed in an amount ranging from about 5 to 30% wt.%, preferably about 7 to 26% wt.%, and more preferably about 8 to 24 wt.%, in the composition.
  • the composition can contain 8 to 15% sodium silicate.
  • the sodium silicate also protects the washing machine from corrosion.
  • the sodium silicate can have a Na2O:SiO2 ratio of 1.6/1 to 1/3.2.
  • the sodium silicate can be added in the form of a dry powder or as a nonaqueous dispersion, preferably having an Na2O:SiO2 ratio of from 1/1 to 1/2.8, for example, 1/2.4. Potassium silicates of the same ratios can also be used.
  • the preferred alkali metal silicates are anhydrous sodium disilicate and sodium metasilicate.
  • foam depressant can be added in the form of dry powders or nonaqueous dispersions or solutions.
  • the detergent active materials used in the present invention can be either the nonionic or anionic detergents.
  • the nonionic detergents are, however, preferred.
  • compositions may be included in small amounts, generally less than about 4 wt.%, e.g. 0.5 to 4% such as perfume, hydrotropic agents such as the sodium benzene, toluene, xylene and cumene sulphonates, preservatives, dyestuffs and pigments and the like.
  • hydrotropic agents such as the sodium benzene, toluene, xylene and cumene sulphonates
  • preservatives dyestuffs and pigments and the like.
  • dyestuffs and pigments and the like Especially preferred for colouring are the chlorinated phthalocyanines and polysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints.
  • nonaqueous liquid ADD compositions of this invention are readily employed in known manner for washing dishes, glasses, cups, eating utensils and the like in an aqueous wash bath, in an automatic dishwasher, containing an effective amount of the composition.
  • the composition may also include conventional organic or inorganic thickening agents in amounts sufficient to obtain a product consistency of a cream or a paste.
  • the thickening agents i.e. thickeners or suspending agents which provide thickening properties
  • the thickening agents may be organic or inorganic, water soluble or insoluble, dispersible or colloid-forming, and monomeric or polymeric, and should of course be stable in these compositions, e.g. stable to alkalinity.
  • the preferred thickeners generally comprise the inorganic, colloid-forming clays of smectite and/or attapulgite types. These materials are generally used in amounts of about 1.5 to 10, preferably 2 to 5 wt.%, to confer the desired thickening properties to the formulation.
  • Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite, and the like. Montmorillonite clays are preferred and are available under tradenames such as Thixogel (Registered Trademark) No. 1 and Gelwhite (Registered Trademark) GP, H, ect., from Georgia Kaolin Company; and ECCAGUM (Registered Trademark) GP, H, ect., from Luthern Clay Products.
  • Attapulgite clays include the materials commercially available under the tradename Attagel (Registered Trademark), i.e.
  • Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Bentonite 27 and Betone 38 from NL Chemicals can also be used. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1:5 are also useful. Thickening or suspending agents of the foregoing types are well known in the art, being described, for example, in USP 3,985,668, which is incorporated herein by reference thereto.
  • nonaqueous liquid ADD compositions of this invention are readily employed in known manner for washing dishes, glasses, cups, cookware, eating utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath containing an effective amount of the composition.
  • an automatic dishwashing detergent concentrate composition is formulated using the below named ingredients.
  • the nonaqueous liquid dishwasher detergent compositions of the present invention can contain conventional dishwashing detergent composition additives.
  • the formulations can be prepared with commercially available detergent builders, peroxygen bleach compounds and bleach activators and surfactant compounds.
  • the formulations can be prepared using the conventional blending and mixing procedures used for the preparation of liquid detergent compositions as briefly described below.
  • compositions of the present invention can be prepared in two stages.
  • silica, alumina or titanium dioxide anti-film agent, powdered silicate and low molecular weight polyacrylate powder (when used) are premilled using a ceramic ball mill.
  • the premilled materials are then mixed using a standard rotary mixer. This mixed material is then transferred to an attritor and milled for 30 minutes at 500 rpm using 1/4 inch stealite grinding media.
  • the organic carrier liquid and Neodol 25-6.5 are mixed, and the defoamer and phosphate builder salts are added.
  • the premilled anti-film agent and polyacrylate are then added to the organic carrier liquid and nonionic surfactant mixture followed by the addition of sodium carbonate, oxygen bleach and bleach activator and the remaining ingredients. After mixing the liquids solids mixture is vigorously stirred to obtain a stable dispersion of the solids in the organic carrier liquid.
  • One or more of the ingredients can be omitted or additional ingredients such as perfumes and anti-foam agents can be added to the composition.
  • nonaqueous liquid compositions as used herein is intended to include compositions containing 0-8% water, typically 2-6% and more typically 1-2% water.
  • the water can be present in the form of hydrated compounds, i.e. bound water, for example, sodium tripolyphosphate hexahydrate, hydrated sodium carbonate, hydrated sodium sulfate, sodium perborate monohydrate and/or in the form of moisture, i.e. unbound water. It is preferred, however, that the composition contain less than 1% moisture as unbound water.
  • an aqueous liquid automatic dishwasher detergent composition was formulated using the below named ingredients in the amounts indicated and is compared with a prior art commercial powder detergent.
  • the commercial powder gave more film than the invention nonaqueous liquid ADD composition. There was- no difference in the spot scores.
  • nonaqueous liquid automatic dishwasher detergent compositions were formulated using the below named ingredients in the amounts indicated.
  • Test I 100 ppm hardness, 120°F data show that the polyacrylate in the formulations B and C provides substantially improved spot performance as compared to the comparison formulation A without polyacrylate.
  • the film performance for the formulations A, B and C were similar.
  • Test II 300 ppm hardness, 120°F show that the addition of silica anti-film agent to invention formulation D, which also contains polyacrylate, improves the spot and film performance as compared to the formulation C which contains only the polyacrylate.
  • Test I data show that the addition of polyacrylate to the formulation improves spot performance
  • Test II data show that the further addition of silica improves spot and film performance.
  • a nonaqueous liquid automatic dishwashing detergent composition is formulated from the following ingredients in the amounts specified.
  • the formulation is tested by washing glassware at 130°F in hard water (300 ppm hardness) in a Kenmore automatic dishwasher to clean glass tumblers using the procedure described in ASTMD 3566-79, except that only four cleaning cycles are used.
  • the spotting and filming are evaluated as in Example 1.
  • the clean tumblers are found to have reduced film as compared to commercial powder formulations not containing alumina anti-film agent.
  • Example 3 is repeated with the difference that 2.00 wt.% titanium dioxide is substituted for the alumina anti-filming agent.
  • the formulation is tested by washing glassware at 130°F in hard water (300 ppm hardness) as before. The clean tumblers are found to have reduced film as compared to commercial powder formulations not containing titanium dioxide anti-film agent.
  • the nonaqueous liquid automatic dishwasher detergent compositions of the present invention provide improved film and/or improved spot properties on glassware and dishware.

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Claims (14)

  1. Nicht-wäßrige, flüssige Reinigungsmittelzusammensetzung für Geschirrspülmaschinen, die eine nicht-wäßrige, organische Trägerflüssigkeit und mindestens einen Bestandteil ausgewählt aus der Gruppe bestehend aus organischem Reinigungsmittel, Reinigungsmittel-Builder, Schauminhibitor und Mischungen derselben sowie einen Bestandteil ausgewählt aus der Gruppe bestehend aus einer nicht-scheuernden Menge von 0,5 bis 10 % von kleinen, im wesentlichen wasserunlöslichen Teilchen aus Siliciumdioxid, Aluminiumoxid oder Titandioxid oder Mischungen derselben als Anti-Filmbildungsmittel umfaßt.
  2. Nicht-wäßrige, flüssige Reinigungsmittelzusammensetzung für Geschirrspülmaschinen, die bezogen auf das Gewicht umfaßt:
    (a) 20 bis 60 % organische Trägerflüssigkeit,
    (b) 20 bis 60 % anorganischen oder organischen Reinigungsmittel-Builder,
    (c) 5 bis 30 % Natriumsilikat,
    (d) 0 bis 25 % Alkalimetallcarbonat,
    (e) 0,1 bis 12 % in Wasser dispergierbares, organisches, reinigungsaktives Material,
    (f) 0 bis 6 % Schaumunterdrückungsmittel,
    (g) 3 bis 15 % Persauerstoffbleichverbindung,
    (h) 0 bis 8 % Bleichaktivator und
    (i) eine nicht-abreibend wirkende Menge von 0,5 bis 10 % eines Anti-Filmbildungsmittels, das ein Mittel ausgewählt aus der Gruppe bestehend aus Siliciumdioxid, Aluminiumoxid, Titandioxid und Mischungen derselben mit einer Teilchengröße von 0,01 bis 10 µm ist.
  3. Nicht-wäßrige, flüssige Reinigungsmittelzusammensetzung für Geschirrspülmaschinen, die bezogen auf das Gewicht umfaßt:
    (a) 25 bis 55 % organische Trägerflüssigkeit,
    (b) 20 bis 55 % Alkalimetalltripolyphosphat,
    (c) 7 bis 26 % Natriumsilikat,
    (d) 5 bis 20 % Alkalimetallcarbonat,
    (e) 0,5 bis 10 % in Wasser dispergierbares, organisches, nichtionisches, reinigungsaktives Material,
    (f) 0,1 bis 5 % Schaumunterdrückungsmittel,
    (g) 4 bis 12 % Persauerstoffbleichverbindung,
    (h) 2 bis 6 % Bleichaktivator und
    (i) eine nicht-scheuernde Menge von 1 bis 8 % eines Anti-Filmbildungsmittels, das ein Mittel ausgewählt aus der Gruppe bestehend aus Siliciumdioxid, Aluminiumoxid, Titandioxid und Mischungen derselben mit einer Teilchengröße von 0,01 bis 8 µm ist.
  4. Flüssige, nicht-wäßrige Reinigungsmittelzusammensetzung für Geschirrspülmaschinen, die bezogen auf das Gewicht umfaßt:
    (a) 30 bis 45 % organische Trägerflüssigkeit,
    (b) 20 bis 45 % Alkalimetalltripolyphosphat,
    (c) 10 bis 24 % Natriumsilikat,
    (d) 5 bis 15 % Alkalimetallcarbonat,
    (e) 0,5 bis 4,5 % Schaumunterdrückungsmittel,
    (f) 1 bis 8 % in Wasser dispergierbares, organisches, nichtionisches Reinigungsmittel,
    (g) 4 bis 12 % Persauerstoffbleichverbindung,
    (h) eine nicht-scheuernde Menge von 1,5 bis 6 % eines Ant-Filmbildungsmittels, das ein Mittel ausgewählt aus der Gruppe bestehend aus Siliciumdioxid, Aluminiumoxid, Titandioxid und Mischungen derselben mit einer Teilchengröße von 0,01 bis 8,0 µm ist, und
    (i) 4 bis 20 % in Wasser lösliches Polyacrylsäurepolymer oder -salz.
  5. Zusammensetzung nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß sie eine nicht-scheuernde Menge von 1,0 bis 8 % des Anti-Filmbildungsmittels enthält.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie 1 bis 30 %, z.B. 2 bis 25 %, wasserlösliches Polyacrylsäurepolymer oder -salz als Anti-Fleckenbildungsmittel enthält.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Persauerstoffbleichverbindung ein Alkalimetallperborat, -monopersulfat, -percarbonat, -monoperoxyphthalat oder eine Mischung derselben ist, z.B. Natriumperborat, Kaliummonopersulfat, Natriumpercarbonat, Monoperoxyphthalat oder Mischungen derselben.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß der Bleichaktivator Tetraacetylethylendiamin (TAED) ist.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie außerdem 2 bis 25 % Polyacrylsäurepolymer- oder -salz-Anti-Fleckenbildungsmittel enthält, das die Formel:
    Figure imgb0016
     aufweist, in der R¹, R² und R³ gleich oder verschieden sein können und Wasserstoff oder niederes C₁-C₄-Alkyl sein können, M Wasserstoff oder Alkalimetall bedeutet, n = 5 bis 1000 ist und das Polymer ein Molekulargewicht von 1000 bis 100 000 aufweist.
  10. Zusammensetzung nach Anspruch 9, dadurch gekennzeichnet, daß das wasserlösliche Polyacrylsäurepolymer- oder -salz-Anti-Fleckenbildungsmittel die Formel:
    Figure imgb0017
     aufweist, in der R¹ und R³ ein Wasserstoff sind und R² ein Wasserstoffatom oder eine Methylgruppe ist, M ein Wasserstoff-, Natrium- oder Kaliumatom ist, n = 10 bis 500 ist und das Polymer ein Molekulargewicht von 1500 bis 50 000 aufweist.
  11. Zusammensetzung nach Anspruch 9 oder Anspruch 10, dadurch gekennzeichnet, daß das Polyacrylsäurepolymer oder -salz ein Molekulargewicht von etwa 2000 oder etwa 4500 aufweist.
  12. Zusammensetzung nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß das Siliciumdioxid-Anti-Filmbildungsmittel bezogen auf das Gewicht des Siliciumdioxids 0,1 bis 5 % Aluminiumoxid enthält.
  13. Zusammensetzung nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß das Anti-Filmbildungsmittel eine Teilchengröße von 0,01 bis 5 µm aufweist.
  14. Verfahren zur Reinigung von fester Glasware und Geschirr, bei dem die Glasware und das Geschirr in einer Geschirrspülmaschine mit einem wäßrigen Waschbad kontaktiert wird, in dem eine wirksame Menge der Zusammensetzung gemäß einem der Ansprüche 1 bis 13 dispergiert ist, um saubere Glasware und sauberes Geschirr mit weniger Film und/oder Flecken zu erhalten.
EP91304072A 1990-05-07 1991-05-07 Nichtwässerige flüssige Detergenszusammensetzung für Geschirrspülautomaten Expired - Lifetime EP0460810B1 (de)

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WO1993021298A1 (en) * 1992-04-13 1993-10-28 The Procter & Gamble Company Process for preparing thixotropic liquid detergent compositions
PT101284A (pt) * 1992-06-08 1994-12-30 Colgate Palmolive Co Agente de viscosificacao polimerico aquoso e solucao polimerica contendo o referido agente
GB9306901D0 (en) * 1993-03-31 1993-05-26 Unilever Plc Liquid cleaning products
US5607503A (en) * 1993-09-03 1997-03-04 Refract-A-Gard Pty Limited Silica-based binder
DE4436151A1 (de) * 1994-08-16 1996-05-02 Henkel Kgaa Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
AU6925796A (en) * 1995-09-05 1997-03-27 Unilever N.V. Liquid detergent composition comprising dispersed hydrophilic silica
DE19822939A1 (de) * 1998-05-22 1999-11-25 Henkel Kgaa Nichtwäßrige viskose Geschirreinigungsmittel
WO2002008370A2 (en) * 2000-07-19 2002-01-31 The Procter & Gamble Company Cleaning composition
WO2002008371A2 (en) * 2000-02-17 2002-01-31 The Procter & Gamble Company Cleaning composition
DE10311886A1 (de) * 2003-03-18 2004-10-07 Henkel Kgaa Nichtwäßrige flüssige Geschirreinigungsmittel
DE102007014875A1 (de) * 2007-03-26 2008-10-02 Henkel Ag & Co. Kgaa Reinigungsmittel
GB201818827D0 (en) * 2018-11-19 2019-01-02 Reckitt Benckiser Finish Bv Composition
CN115074173B (zh) * 2021-03-16 2023-03-14 宝山钢铁股份有限公司 一种抗斑迹轧制油及其在单机架冷轧机轧制过程中的应用

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NZ226709A (en) * 1987-11-05 1990-10-26 Colgate Palmolive Co Al 2 o 3 or tio 2 and polyacrylic acid polymer in thixotropic dishwashing compositions
JPH05504158A (ja) * 1990-02-16 1993-07-01 ユニリーバー・ナームローゼ・ベンノートシヤープ 液体洗浄製品

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BR9101818A (pt) 1991-12-17

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