EP1171561A1 - Reinigungsmittel enthaltend antidunstigheitsmittel - Google Patents

Reinigungsmittel enthaltend antidunstigheitsmittel

Info

Publication number
EP1171561A1
EP1171561A1 EP00926084A EP00926084A EP1171561A1 EP 1171561 A1 EP1171561 A1 EP 1171561A1 EP 00926084 A EP00926084 A EP 00926084A EP 00926084 A EP00926084 A EP 00926084A EP 1171561 A1 EP1171561 A1 EP 1171561A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
mol
molecular weight
hazing
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00926084A
Other languages
English (en)
French (fr)
Inventor
Robert Allen Godfroid
Nicola John Policicchio
Michael William Dusing
Kenneth William Willman
Christopher James Binski
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1171561A1 publication Critical patent/EP1171561A1/de
Withdrawn legal-status Critical Current

Links

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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/20—Mops
    • A47L13/22—Mops with liquid-feeding devices
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/20—Mops
    • A47L13/24—Frames for mops; Mop heads
    • A47L13/254—Plate frames
    • A47L13/256—Plate frames for mops made of cloth
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
    • A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
    • A47L13/50—Auxiliary implements
    • A47L13/51—Storing of cleaning tools, e.g. containers therefor
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • This application relates to detergent compositions containing an anti-hazing agent.
  • the detergent composition cleaning solution is also preferably suitable for use with a disposable cleaning pad.
  • This application also relates to a process of using the detergent composition with such a cleaning pad, and the provision of a kit containing the detergent composition and cleaning pad are disclosed.
  • the developer and formulator of surfactants for hard surface cleaning must consider a wide variety of possibilities with limited (sometimes inconsistent) information, and then strive to provide overall improvements in one or more of a whole array of criteria, including performance in the presence of free calcium and a wide variety of soils, in complex mixtures of surfactants and polymers, e.g. cationic polymers, formulation changes, enzymes , various changes in consumer habits and practices, and the need for biodegradability.
  • surfactants and polymers e.g. cationic polymers, formulation changes, enzymes , various changes in consumer habits and practices, and the need for biodegradability.
  • hard surface cleaning compositions One problem associated with hard surface cleaning compositions is the hazing of a surface after cleaning. This hazing is often associated by the consumer with residual soil, or unremoved stains. The hazing is usually the result of solution components combining with visible residues of any unremoved soil. These residues, when dried on a hard surface, such as a floor, can refract light instead of reflecting it and diminish the appearance of the surface. When haze is present after cleaning the consumer perception is that more product should be used or that the product does not work. Consequently, there remains the need for a hard surface cleaning composition suitable for providing grease and particulate soil removal which upon drying on a surface minimizes or totally eliminates haze .
  • a hard surface detergent composition that comprises: an effective amount of anti-hazing agent, preferably from about 0.001% to about 5%, more preferably from about 0.001% to about 2%, by weight of the composition of anti-hazing agent.
  • the anti-hazing agent being selected from the group consisting of organic diamine, having molecular weight of from greater than 61 g/mol to less than or equal to 400 g/mol, organic triamine having molecular weight less than or equal to 500 g/mol, organic tetramine having molecular weight less than or equal to 600 g/mol, and mixtures thereof, and wherein the anti-hazing agent has a pKa of at least about 8; and an effective amount, preferably from about 0.005% to about 0.5%, more preferably from about 0.01% to about 0.2% by weight of the composition of one or more detergent surfactants; wherein the weight ratio of the anti- hazing agent to the surfactants is from about 40: 1 to about 1:5, preferably from about 15:1 to about 1 :5, more preferably from about 11 : 1 to about 1 :5; and said composition has a pH greater than about 8, preferably greater than 9, more preferably from 9.5 to 12.5, more preferably from about 9.5 to about 11.7.
  • a process of cleaning a surface comprises the step of applying an effective amount of the detergent composition according to the first aspect to said surface and. optionally, but preferably, absorbing the composition in an absorbent structure preferably comprising a superabsorbent material.
  • a kit comprises an implement containing disposable cleaning pad containing superabsorbent material and detergent composition that provides effective cleaning and good filming/streaking, that is reduces hazing, when used with said disposable cleaning pad, optionally, but preferably, without rinsing, said composition according to the first aspect comprising an effective amount of anti-hazing agent.
  • the anti-hazing agent being selected from the group consisting of organic diamine, having molecular weight of from greater than 61 g/mol to less than or equal to 400 g/mol, organic triamines having molecular weight less than or equal to 500 g/mol, organic tetramines having molecular weight less than or equal to 600 g/mol, and mixtures thereof, the anti-hazing agent having a pKa of at least about 8; and an effective amount of one or more detergent surfactants; wherein the weight ratio of said anti-hazing agent to said surfactants is from about 40:1 to about 1:5, preferably from about 15: 1 to about 1 :5, more preferably from about 11:1 to about 1 :5; and said composition has a pH greater than about 8, preferably greater than 9, more preferably from 9.5 to 12.5, more preferably from about 9.5 to about 11.7.
  • the invention in a fourth aspect also comprises a detergent composition as disclosed herein in a container in association with instructions to use it with an implement comprising a disposable pad, preferably a disposable pad comprising an effective amount of a superabsorbent material, and, optionally, said container is in a kit comprising disposable pad and, optionally, the remainder of said implement, or, at least, a disposable cleaning pad comprising a superabsorbent material.
  • the invention also relates in a preferred fifth aspect to the use of the composition and a cleaning pad comprising a superabsorbent material (superabsorbent pad) to effect cleaning of soiled surfaces.
  • HSC compositions are different form other similar cleaning compositions, such as LDL's or laundry compositions, in that they are tpyically used neat or pre-diluted, low suds (unlike LDL's), non-rinse, higher pH. Furthermore, HSC compositions are designed to be applied to much larger surfaces, than other cleaning compositions, such as counter tops, and floors. They are also applied to a wide variety of both synthetic and natural surfaces, such as marble, slate, vinyl, linoleum, granite, Formica, aluminum, stainless steel and the like.
  • the anti-hazing agent of the present invention is selected from the group consisting of organic diamines, having molecular weights of from greater than 61 g/mol to less than or equal to about 400 g/mol; organic triamines having molecular weight less than or equal to about 500 g/mol; organic tetramines having molecular weight less than or equal to about 600 g/mol; and mixtures thereof, and wherein said anti-hazing agent has a pKa of at least about 8.
  • the pKa of the anti-hazing agent is specified in an all-aqueous solution at 25°C and for an ionic strength between 0.1 to 0.5 M.
  • the pKa is an equilibrium constant which can change with temperature and ionic strength; thus, values reported in the literature are sometimes not in agreement depending on the measurement method and conditions.
  • the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines".
  • the anti-hazing agent is an organic diamine it has the formula:
  • each R is independently selected from the group consisting of hydrogen, C ⁇ -C linear or branched alkyl, alkyleneoxy having the formula: (R2O) y R3
  • R " is C 2 -C linear or branched alkylene, and mixtures thereof;
  • R 3 is hydrogen, C ⁇ -C alkyl, and mixtures thereof;
  • y is from 1 to about 10;
  • X is a unit selected from: i) C 2 -C ⁇ o linear alkylene, C -C ⁇ o branched alkylene, C -C ⁇ o cyclic alkylene, C 3 - Cio branched cyclic alkylene, an alkyl eneoxyalkylene having the formula:
  • R and y are the same as defined herein above; ii) C -C ⁇ o linear, C -C ⁇ o branched linear, C -C ⁇ o cyclic, C -C ⁇ o branched cyclic alkylene, C- 5 -C10 arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties which provide said diamine with a pKa greater than about 8; and iii) mixtures of (i) and (ii).
  • the anti-hazing agent is selected from the group consisting of 1,3- bis(amino methyl)-cyclohexane(also known as 1, 3 cyclohexaneBis(methylamine) or 1, 3 BAC), N-cyclohexyl-l,3-propanediamine, 1,2-diaminocyclohexane, 1, 3 cyclohexane Bis[tetra(hydoxypropyl)-methylamine], 1,3 benzene dimethanamine, N-phenylethylene diamine, 1,3 bis[tris(hydroxymethyl)-methylamino]propane, N,N,N',N'tetrakis(2- hydroxypropyl)ethylenediamine, N.N'-bis bishydroxypropy ethylene diamine, N,N ⁇ - bis(bishydroxyethyll)ethylene diamine, N,N',N'tetrakis(2-hydroxyethyl)ethylenediamine, 1,3, Bis[tris(hydroxymethyl)-
  • the anti-hazing agent is l,3-bis(amino methyl)- cyclohexane, N,N,N',N'tetrakis(2-hydroxypropyl)ethylenediamine, N,N',N'tetrakis(2- hydroxyethyl)ethylenediamine, N,N,N',N'tetrakis(2-hydroxypropyl)ethylenediamine.
  • N,N'-bis(bishydroxypropyl)ethylene diamine N ⁇ -bis ishydroxyethyOethylene diamine, 1 ,3 benzene dimethanamine and mixtures thereof.
  • the anti-hazing agent can provide additional functions and/or benefits.
  • the preferred anti-hazing agents provide alkalinity, especially to provide a pH of greater than about 8, preferably greater than about 9, and more preferably from about 9.5 to about 12.5, even more preferably from about 9.5 to about 11.7 to improve cleaning, stabilize the formula, and/or neutralize anionic materials like surfactants and carboxylate polymers that are present.
  • the preferred anti-hazing agents for example, l,3-bis(amino methyl)- cyclohexane, in addition to providing improved cleaning and product stability help reduce the incidence of, or severity of marks on the floor after cleaning the surface with a composition according to the present invention.
  • the preferred amines have surprisingly low odor compared to other amines, which allow them to be used at relatively higher levels in compositions while maintaining consumer-acceptable odor characteristics in the finished product.
  • compositions of the present invention contain one or more detergent surfactants. It is preferred that these surfactants are selected from the group consisting of anionic, nonionic, zwitterionic, cationic, amphoteric and mixtures thereof, more preferably the detergent surfactant has a linear or branched structure and is selected from the group consisting of anionic and nonionic detergent surfactants, even more preferably anionic and nonionic detergent surfactants having hydrophobic chains containing from about 8 to about 18, preferably from about 8 to about 15, carbon atoms. Examples of anionic surfactants include, but are not limited to, linear alkyl sulfates, alkyl sulfonates, and the like.
  • nonionic surfactants include alkylethoxylates and the like.
  • zwitterionic surfactants include betaines and sulfobetaines.
  • amphoteric surfactants include alkylampho glycinates, and alkyl imino propionate. Further example of suitable surfactants are described in McCutcheon's Vol. 1 : Emulsifiers and Detergents, North American Ed., McCutheon Division, MC Publishing Co., 1995, which is incorporated herein by reference
  • Highly preferred surfactants include alcohol ethoxylate detergent surfactant (e.g., Neodol 1-5®, available from Shell Chemical Co.) and an alkyl sulfonate (e.g., Witconate NAS-8, a linear Cg sulfonate available from Witco Co.) and mixtures thereof.
  • alcohol ethoxylate detergent surfactant e.g., Neodol 1-5®, available from Shell Chemical Co.
  • an alkyl sulfonate e.g., Witconate NAS-8, a linear Cg sulfonate available from Witco Co.
  • Soil Suspending Agents The hard surface cleaning compositions of the present invention can optionally
  • the soil suspending agents preferably water soluble polymers, for use in the detergent composition and/or cleaning solution of this invention are preferably selected from a group consisting of, ethoxylated and/or propoxylated polyalkylamines, carboxylate polymers, nitrogen-based zwitterionic polymers, polyethyleneoxides, polyphosphates, and cellulosic polymers.
  • Preferred soil suspending agents are ethoxylated polyalkylamines. Such agents are disclosed in U. S. Pat. Patent Number: 4,891,160, issued January 2, 1990, entitled Detergent compositions containing ethoxylated amines having, clay soil removal/anti- redeposition properties, by Vander Meer, James M.
  • Preferred ethoxylated polyamines can be derived from polyamino amides and/or polyaminopropyleneoxide materials.
  • Preferred ethoxylated amine polymers are the ethoxylated C 2 -C polyalkyleneamines and polyalkyleneimines.
  • Particularly preferred ethoxylated polyalkyleneamines and polyalkyleneimines are the ethoxylated polyethyleneamines (PEAs) and polyethyleneimines (PEIs).
  • PEAs polyethyleneamines
  • PEIs polyethyleneimines
  • Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation.
  • Preferred have a molecular weight of from about 140 to about 310, preferably from about 140 to about 200.
  • PEAs can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation.
  • the common PEAs obtained are tri ethyl enetetramine (TETA) and tetraethylenepentamine (TEPA).
  • TETA tri ethyl enetetramine
  • TEPA tetraethylenepentamine
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines.
  • cyclic amines with side chains in which nitrogen atoms appear See U.S. Pat. No. 2,792,372 to Dickson, issued May 14, 1957, which describes the preparation of PEAs.
  • the minimum degree of ethoxylation required for preferred soil suspension performance can vary depending upon the number of units in the PEA.
  • the PEIs used in preparing the compounds of the present invention have a molecular weight of at least about 600 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these compounds have an average molecular weight of from about 600 to about 2600.
  • linear polymer backbones are possible, branched chains can also occur.
  • the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation.
  • PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing PEIs are disclosed in U.S. Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No. 3,033,746 to Mayle et al., issued May 8, 1962; U.S. Pat. No. 2,208,095 to Esselma-nn et al., issued July 16, 1940; U.S. Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957; and U.S. Pat. No.
  • the minimum degree of ethoxylation required for suitable soil suspension performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800.
  • the degree of ethoxylation for preferred compounds increases as the molecular weight of the PEI increases.
  • the degree of ethoxylation is preferably at least about 1, with a more preferred range of from about 12 to about 42.
  • the degree of ethoxylation is preferably at least about 2, with a typical range of from about 10 to about 40.
  • the level at which the ethoxylated amine(s) can be present in the detergent compositions herein can vary depending upon the compounds used. Generally, the ethoxylated amines can be included in an amount of from about
  • composition 0.001% to about 1% by weight of the composition, with the preferred range being from about 0.005% to about 0.5% by weight, and a more preferred range of about 0.01% to 0.1%.
  • polyalkyleneamines comprise a nitrogen-containing backbone with an average molecular weight of from about 600 to about 10,000, preferably from about 1,000 to about 3,000.
  • polyalkylamine has the general formula:
  • m has an average value of about 20. What is meant herein by an average value of 20 is that sufficient ethylene oxide or other suitable reagent is reacted with the polyethyleneimine starting material to fully ethoxylate each N-H unit in the polyethyleneamine to an average degree of 20 ethoxy groups.
  • the units which make up the polyalkyleneimine backbones are derived from primary amine units having the formula:
  • B [N-CH 2 CH 2 ]— which are the branching points of the main and secondary backbone chains, B representing a continuation of the chain structure by branching.
  • the tertiary units have no replaceable hydrogen atom and are therefore not modified by substitution with ethyleneoxy units.
  • an amount of cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture.
  • Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of alkyleneoxy units in the same manner as linear and branched polyalkyleneimines.
  • the indices w, x, and y have values such that the average molecular weight of the polyethyleneimine backbone prior to modification is about 600 daltons.
  • each branch chain must terminate in a primary amine unit, therefore the value of the index w is y + 1 in the case where no cyclic amine backbones are present.
  • the average molecular weight for each ethylene backbone unit, - NCH2CH2-, is approximately 43 daltons.
  • soil suspending materials include polyvinyl pyrrolidone and/or cellulose derivatives.
  • Polyvinyl pyrrolidone is not a single individual compound but can be obtained in almost any degree of polymerization. The degree of polymerization, which is most easily expressed in terms of average molecular weight, is not critical provided the material has the desired water solubility and soil-suspending power.
  • suitable soil-suspending vinyl pyrrolidone polymers are linear in structure, and have an average molecular weight within the range of about 5,000 to about 100,000, and preferably from about 15,000 to about 50,000. Suitable polymers will also, generally, have a water solubility of greater than 0.3% at normal usage temperatures.
  • any well-known nonionic cellulose ether can be used in the detergent composition according to the invention.
  • the cellulose ether is an alkyl or an alkyl/ hydroxyalkyl cellulose derivative.
  • the alkyl group should contain from 1 to 4, preferably from 1 to 3 carbon atoms
  • the hydroxyalkyl group should contain from 2 to 4, preferably from 2 to 3 carbon atoms.
  • Particularly preferred materials include methyl hydroxyethyl cellulose, methyl hydroxylpropyl cellulose and ethyl hydroxyethyl cellulose.
  • the total level of the polyvinyl pyrrolidone and/or cellulose derivatives in the detergent composition is preferably in the range of about 0.001% to about 1% by weight of the composition, a more preferred range being from about 0.005% to about 0.5% by weight, and a more preferred range of about 0.01 % to 0.1 %.
  • An improvement in soil suspension can be achieved at all mixing ratios of the vinyl pyrrolidone polymer and the nonionic cellulose ether.
  • the ratio of the vinyl pyrrolidone polymer to the nonionic cellulose ether in the detergent composition is within the range from about 8:2 to about 2:8, most preferably from about 6:4 to about 4:6, by weight.
  • Mixtures of this type are disclosed in U. S. Pat. Patent Number: 4,999,129, entitled Process and composition for washing soiled polyester, fabrics, by Michael Hull.
  • Other soil suspending agents can be anionic polymers. Examples of these anionic polymers are disclosed in, e.g., U. S. Pat.
  • the total molecular weight of the copolymer disclosed in said patent are within the range of about 1000 to 100,000, as determined by gel permeation chromatography. More preferably, the weight average molecular weight falls within the range of about 1,000 to 30,000; most preferably within the range of about 1,000 to 20,000.
  • the hydrophilic copolymer can be prepared by copolymerizing two monomers, an unsaturated hydrophilic monomer and a hydrophilic oxyalkylated monomer.
  • unsaturated hydrophilic monomers disclosed include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, methacrylate esters and substituted methacrylate esters, vinyl acetate, vinyl alcohol, methylvinyl ether, crotonic acid, itaconic acid, vinyl acetic acid, and vinylsulphonate.
  • the unsaturated hydrophilic monomer component of the hydrophilic copolymer is preferably acrylic acid.
  • hydrophilic oxyalkylated monomer examples include compounds that have a polymerizable olefinic moiety with at least one acidic hydrogen and are capable of undergoing addition reaction with alkylene oxide. It is also possible to include monomers with at least one acidic hydrogen that are polymerized first, and then subsequently oxyalkylated to yield the desired product.
  • allyl alcohol is especially preferred since it represents a monofunctional initiator with a polymerizable olefinic moiety having an acidic hydrogen on the oxygen, and is capable of adding to alkylene oxide.
  • hydrophilic oxyalkylated monomer of the copolymer examples include reaction products of either acrylic acid, methacrylic acid, maleic acid, or 3-allyloxy-l,2-propanediol with alkylene oxide.
  • Preparation of oxyalkylated monomers is disclosed in U.S. Pat. No. 5,162,475 and U.S. Pat. No. 4,622,378 both incorporated herein by reference.
  • the hydrophilic oxyalkylated monomer which is a propylene Is oxide and ethylene oxide adduct of allyl alcohol. This monomer has a molecular weight of about 3800.
  • the molecular weight of the hydrophilic oxyalkylated monomer according to the various embodiments of the invention should be preferably within the range of about 600 to 30,000, more preferably about 700 to 15,000, and most preferably about 700 to 5000.
  • the hydrophilic oxyalkyated monomer preferably has a solubility of about 500 grams/liter, more preferably about 700 grams/liter in water.
  • polymeric polycarboxylates that are suitable include, for example, the polymers disclosed in U. S. Pat. 5,574,004, incorporated herein by reference.
  • Such polymers include homopolymers and/or copolymers (composed of two or more monomers) of an alpha, beta-ethylenically unsaturated acid monomer such as acrylic acid, methacrylic acid, a diacid such as maleic acid, itaconic acid, fumaric acid, mesoconic acid, citraconic acid and the like, a monoester of a diacid with an alkanol, e.g., having 1-8 carbon atoms, and mixtures thereof.
  • an alpha, beta-ethylenically unsaturated acid monomer such as acrylic acid, methacrylic acid, a diacid such as maleic acid, itaconic acid, fumaric acid, mesoconic acid, citraconic acid and the like
  • the polymeric polycarboxylate when it is a copolymer, it can be a copolymer of more than one of the foregoing unsaturated acid monomers, e.g., acrylic acid and maleic acid, or a copolymer of at least one of such unsaturated acid monomers with at least one non-carboxylic alpha, beta-ethylenically unsaturated monomer which can be either relatively non-polar such as styrene or an olefinic monomer, such as ethylene, propylene or butene-1, or which has a polar functional group such as vinyl acetate, vinyl chloride, vinyl alcohol, alkyl acrylates, vinyl pyridine, vinyl pyrrolidone, or an amide of one of the delineated unsaturated acid monomers, such as acrylamide or methacrylamide.
  • unsaturated acid monomers e.g., acrylic acid and maleic acid
  • copolymers can be prepared by after treating a homopolymer or a different copolymer, e.g., copolymers of acrylic acid and acrylamide by partially hydrolyzing a polyacrylamide.
  • Copolymers of at least one unsaturated carboxylic acid monomer with at least one non-carboxylic co-monomer should contain at least about 50 mol % of polymerized carboxylic acid monomer.
  • the polymeric polycarboxylate should have a number average molecular weight of, for example about 1000 to 10,000, preferably about 2000 to 5000. To ensure substantial water solubility, the polymeric polycarboxylate is completely or partially neutralized, e.g., with alkali metal ions, preferably sodium ions.
  • the total level of the polymeric polycarboxylate in the detergent composition is preferably in the range of about 0.001% to about 1% by weight of the composition, a more preferred range being from about 0.005% to about 0.5% by weight, and a more preferred range of about 0.01% to 0.1%.
  • Still other polycarboxylate materials include those disclosed in U. S. Pat. Patent
  • the polymers can be derived from L-glumatic acid, D-glumatic acid or mixtures, e.g. racemates, of these L and D isomers.
  • the L isomer and D, L racemate are currently preferred.
  • the polymers include not only the homopolymers of glutamic acid but also copolymers, such as block, graft or random copolymers, containing glutamic acid. Thus, copolymers of glutamic acid with at least one other (preferably biodegradable) monomer, oligomer or polymer come into consideration.
  • copolymers containing at least one other amino acid such as aspartic acid, ethylene glycol, ethylene oxide, (or an oligymer or polymer of any of these) or polyvinyl alcohol.
  • Glutamic acid can, of course, carry one or more substituents and the polymers useful as component (a) include those in which a proportion or all of the glutamic acid monomers are substituted.
  • Substituents include, for example, alkyl, hydroxy alkyl, aryl and arylalkyl, commonly with up to 18 carbon atoms per group, or polyethylene glycol attached by ester linkages.
  • soil suspending agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.
  • the total level of cellulose derivatives in the detergent composition is preferably in the range of about 0.001% to about 1% by weight of the composition, a more preferred range being from about 0.005% to about 0.5% by weight, and a more preferred range of about 0.01% to 0.1%.
  • Further useful organic polymeric compounds are the polyethylene glycols, particularly those of average molecular weight of 1,000-100,000, more particularly 2000 to 10,000 and most preferably 4,000. These can be used alone or in combination with the polycarboxylate polymers disclosed herewithin.
  • the total level of these polymers in the detergent composition is preferably in the range of about 0.001% to about 1% by weight of the composition, a more preferred range being from about 0.005%) to about 0.5% by weight, and a more preferred range of about 0.01% to 0.1%.
  • the composition preferably contains a polymer that has hydrophilic and shear-thinning characteristics that is capable of inhibiting molecular aggregation of surfactant solution on floors during the dry-down process to provide one, or more, of the benefits of: strippability; avoidance of build-up; easy spreading of solution on hard surfaces such as floors; and maintaining a sufficient amount of water on the surface to level the ingredients remaining on the surface.
  • the polymer allows formulation at even low surfactant levels and allows for addition of solvents to aid in cleaning without hurting filming/streaking.
  • hydrophilic, shear-thinning polymer that is capable of inhibiting molecular aggregation of surfactant solution on floors during the dry-down process, is present in an amount of from about 0.0001% to about 0.2%, more preferably from about 0.0001% to about 0.1%, even more preferably from about 0.0005% to about 0.08%, by weight of the composition. It is preferred that hydrophilic, shear- thinning polymer has a molecular weight of at least about 100,000, preferably at least about 1,000,000.
  • the hydrophilic, shear-thinning polymer is selected from the group of polymers consisting of xanthan gum, guar gum, gum arabic, pectin and mixtures thereof, preferably xanthan gum.
  • composition of the present invention can optionally contain a suds suppressor.
  • W ⁇ hen present the suds suppressor is preferably present from about 0.0005% to about 0.02%, more preferably from about 0.001% to about 0.01%), by weight of the composition.
  • Suitable suds suppressors include, silicone suds suppressor such as silicone polymers and linear or branched C ⁇ Q-CI S fatty acids or alcohols, with silicone suds suppressor being preferred. Further examples of suitable suds suppressors can be found in co-pending U.S.
  • the composition of the present invention can optionally contain a corrosion inhibitor.
  • the corrosion inhibitor is preferably present from about 0.0001% to about 0.2%), preferably from about 0.0001% to about 0.1%, more preferably from about 0.0005% to about 0.08% by weight of the composition.
  • One suitable group of corrosion inhibitors include the crystalline layered silicates as disclosed, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline layered sodium silicates of general formula
  • Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called ⁇ -layered structure, as described in EP 0 164514 and EP 0 293640.
  • the most preferred crystalline layered sodium silicate compound has the formula ⁇ -Na Si 2 O5 , known as NaSKS-6 (trade name), available from Hoechst AG.
  • a preferred alkali metal silicate is sodium silicate having an SiO 2 :Na 2 O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0.
  • Sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to 12% by weight of SiO 2 .
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • alkali or alkaline earth metal metasilicate more preferably alkali metal metasilicate, even more preferably sodium metasilicate, present at a level of at least 0.4% SiO 2 by weight.
  • Sodium metasilicate has a nominal SiO : Na 2 O ratio of 1.0.
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO 2 is preferably from 50:1 to 5:4, more preferably from 15: 1 to 2: 1, most preferably from 10:1 to 5:2.
  • Suitable corrosion inhibitors include paraffin, and nitrogen-containing corrosion inhibitor compounds. Nitrogen-containing corrosion inhibitor compounds are disclosed in copending European Application no. EP-A-634,478. Mn(-Q) compounds for use in corrosion inhibition are described in copending European Application No. EP-A- 672 749.
  • Suitable corrosion inhibitor herein include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valeric acid, lactic acid, glycolic acid and ⁇ , ⁇ '- dihydroxyisobutyric acid.
  • suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • the glycerol esters are also highly preferred. These are the mono-, di- or tri- esters of glycerol and the fatty acids as defined above.
  • Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowyl proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Suitable corrosion inhibitor include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil. Waxes, including microcrystalline waxes are suitable corrosion inhibitor herein.
  • Preferred waxes have a melting point in the range from 35°C to 110°C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • One preferred corrosion inhibitor is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C 2 5_45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 : 10 to 2: 1 , preferably from 1:5 to 1:1.
  • a paraffin oil, hydrocarbons or the like as a corrosion inhibitor as this would increase the hazing of the hard surface to which it is applied.
  • an oil or similar material is to be used in the compositions of the present invention they are selected so as to minimize, and if possible eliminate, any haze produced on the hard surface which is attributable to the paraffin oil or the like.
  • Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and British Patent GB-A-1, 137,741, which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents Ri , R3, R4 and R5 where R ⁇ is any of H, CH OH, CONH3, or COCH3, R3 and R 5 are any of C ⁇ -C 2 n alkyl or hydroxyl, and R is any of H, NH 2 or NO 2 .
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, l-phenyl-5-mercapto-l,2,3,4-tetrazole, thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol.
  • mercaptans and diols especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol.
  • saturated or unsaturated C ⁇ o- 2 o fatty acids, or their salts especially aluminium tristearate, zinc distearate.
  • the C ⁇ 2 -C 2 o hydroxy fatty acids, or their salts are also suitable.
  • Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
  • Copolymers of butadiene and maleic acid particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.
  • Another preferred anticorrosion inhibitor for use in the present invention is a hydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons having a number of carbon atoms in the range of from 20 to 50; preferred hydrocarbons are saturated and/or branched; preferred hydrocarbon oil selected from predominantly branched C 5_45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 :10 to 2:1, preferably from 1:5 to 1:1.
  • a preferred hydrocarbon oil is paraffin.
  • a paraffin oil meeting the characteristics as outlined above, having a ratio of cyclic to noncyclic hydrocarbons of 32:68, is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
  • the water-soluble bismuth compound may be essentially any salt or complex of bismuth with essentially any inorganic or organic counter anion.
  • Preferred inorganic bismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • Suitable corrosion inhibitors can also be found in U.S. Patent No. 4,199,483; U.S. Patent No. 4,992,195; U.S. Patent No. 4,098,720; U.S. Patent No. 5,736,495; U.S. Patent No. 3,981,780; U.S. Patent No. 4,292,190; all of which are hereby incorporated by reference.
  • Corrosion inhibitors particularly useful under alkaline compositions include sorbitan monooleate; morpholines; 3-fluoroaniline; sodium benzoate; benzoic acid; p-tert- butylbenzoic acid; sodium nitrate; sodium nitrite; salicylic acid; thiosalicylic acid; resorcinol; sodium phosphates; polyphosphates; sodium silicates; sodium borates; borax; sodium chromate; benzenesulfonic acid; benzotriazole; tolytriazole; octadecylamine; hexadecylamine; sodium molybdate; and sodium tungstate.
  • the corrosion inhibitor when present in the composition is selected from the group consisting of alkali metal or alkaline earth salts of silicate, alkali metal or alkaline earth salts of metasilicate, polyvalent ion salts of fatty acids, alkyl phosphates, paraffin, benzotriazole, inorganic salts of Bi" + , organosilicates, inorganic salts of Zn" + , and mixtures thereof. It is also preferable to minimize the amount of chloride ions present in the composition as higher levels of chloride ions are believed to increase corrosion.
  • Other optional composition ingredients are also preferable to minimize the amount of chloride ions present in the composition as higher levels of chloride ions are believed to increase corrosion.
  • the detergent composition may further comprise other optional ingredients. Suitable ingredients include, but not limited to: hydrophobic cleaning solvents, detergent builders, dyes, detergent enzymes, and/or perfumes etc.
  • Suitable hydrophobic cleaning solvents include short chain (e.g., C ⁇ -C ⁇ ) derivatives of oxyethylene glycol and oxypropylene glycol, such as mono- and di-ethylene glycol n-hexyl ether, mono-, di- and tri-propylene glycol n-butyl ether, and the like.
  • the level of hydrophobic cleaning solvent e.g., solvent having a solubility in water of less than about 3%, is in the cleaning composition at less than about 3%, more preferably less than about 2% by weight of the composition.
  • Suitable detergent builders include those derived from phosphorous sources, such as orthophosphates, pyrophosphates, tripolyphosphates, etc., and those derived from non- phosphorous sources, such as nitrilotriacetates; and the like.
  • Suitable detergent enzymes include lipases, proteases, amylases and other enzymes known to be useful for catalysis of soil degradation.
  • the total level of such optional ingredients is low, preferably less than about 0.1%, more preferably less than about 0.05%>, to avoid causing hazing or filming/streaking problems.
  • any water in the composition such as in premixed or ready to use solutions, the water used is deionized or softened water.
  • a kit in another aspect of the present invention, comprises an implement containing a pad containing superabsorbent material and a detergent composition that provides effective cleaning and good hazing streaking when used with a disposable cleaning pad and without rinsing comprising an effective amount of an anti- hazing agent.
  • the implement comprises: a. a handle; and b. a removable cleaning pad preferably containing an effective amount of a superabsorbent material, and having a plurality of substantially planar surfaces, wherein each of the substantially planar surfaces contacts the surface being cleaned, more preferably said pad is a removable cleaning pad having a length and a width, the pad comprising i. a scrubbing layer; and ii.
  • an absorbent layer comprising a first layer and a second layer, where the first layer is located between the scrubbing layer and the second layer (i.e., the first layer is below the second layer) and has a smaller width than the second layer.
  • An important aspect of the cleaning performance provided by the preferred pad is related to the ability to provide multiple planar surfaces that contact the soiled surface during the cleaning operation. In the context of a cleaning implement such as a mop, these planar surfaces are provided such that during the typical cleaning operation (i.e., where the implement is moved back and forth in a direction substantially perpendicular to the pad's width), each of the planar surfaces contact the surface being cleaned as a result of "rocking" of the cleaning pad.
  • Soil suspending agent 0.001 to 1.0
  • Anti-corrosion agent 0.0 to 0.1
  • Neodol 1-5 Shell Chemical
  • Witconate NAS-89(Witco) 2: l,3-bis(methylamine)-cyclohexane, (Mitsubishi Gas Products);

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP00926084A 1999-04-19 2000-04-18 Reinigungsmittel enthaltend antidunstigheitsmittel Withdrawn EP1171561A1 (de)

Applications Claiming Priority (3)

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US12994999P 1999-04-19 1999-04-19
US129949P 1999-04-19
PCT/US2000/010385 WO2000063333A1 (en) 1999-04-19 2000-04-18 Detergent composition comprising anti-hazing agent

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ES2704092T3 (es) * 2014-04-30 2019-03-14 Procter & Gamble Composición limpiadora
ES2704090T3 (es) * 2015-07-16 2019-03-14 Procter & Gamble Composición detergente líquida
US20170015951A1 (en) * 2015-07-16 2017-01-19 The Procter & Gamble Company Cleaning compositions containing a cyclic amine and a fabric shading agent and/or a brightener
US20170015948A1 (en) * 2015-07-16 2017-01-19 The Procter & Gamble Company Cleaning compositions containing a cyclic amine and a silicone
US20170015949A1 (en) * 2015-07-16 2017-01-19 The Procter & Gamble Company Cleaning compositions containing a cyclic amine and an encapsulated perfume
EP3165593B1 (de) * 2015-10-29 2019-01-23 The Procter and Gamble Company Flüssige reinigungsmittelzusammensetzung
EP3162878A1 (de) * 2015-10-29 2017-05-03 The Procter and Gamble Company Flüssige reinigungsmittelzusammensetzung
JP7007833B2 (ja) * 2017-08-09 2022-01-25 大日本除蟲菊株式会社 防錆・清掃シート

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CN108024496A (zh) * 2015-09-28 2018-05-11 巴斯夫欧洲公司 中和棉籽的方法
CN108024496B (zh) * 2015-09-28 2021-07-27 巴斯夫欧洲公司 中和棉籽的方法

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