EP0105063B1 - Liquid hard-surface cleaner - Google Patents

Liquid hard-surface cleaner Download PDF

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Publication number
EP0105063B1
EP0105063B1 EP82305211A EP82305211A EP0105063B1 EP 0105063 B1 EP0105063 B1 EP 0105063B1 EP 82305211 A EP82305211 A EP 82305211A EP 82305211 A EP82305211 A EP 82305211A EP 0105063 B1 EP0105063 B1 EP 0105063B1
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EP
European Patent Office
Prior art keywords
glycol mono
composition
ether
butyl
alkyl
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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.)
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EP82305211A
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German (de)
English (en)
French (fr)
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EP0105063A1 (en
Inventor
Ricardo Diez
Donald Brown Compton
Neil David Fraser
Michael Eugene Burns
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to CA000385586A priority Critical patent/CA1178160A/en
Priority to GR69130A priority patent/GR78090B/el
Priority to IE2215/82A priority patent/IE53499B1/en
Priority to SE8205171A priority patent/SE8205171L/xx
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP82305211A priority patent/EP0105063B1/en
Priority to DE8282305211T priority patent/DE3274882D1/de
Publication of EP0105063A1 publication Critical patent/EP0105063A1/en
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Publication of EP0105063B1 publication Critical patent/EP0105063B1/en
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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
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/43—Solvents

Definitions

  • This invention relates to novel homogeneous aqueous liquid detergent compositions intended for general purpose household usage for cleaning hard surfaces.
  • compositions intended for such purposes have been commercially manufactured for many years. They have been available in both liquid and granular form, and often have been formulated to perform especially well in accomplishing some specific household task, such as cleaning tile floors in kitchen and bath, or tile walls in the bath, or bathroom tubs, or kitchen sinks, or painted walls in the kitchen or elsewhere in the house, or glass and porcelain surfaces. In general, the requirements for these tasks differ sufficiently from one another that no single composition is ideal for all such usages.
  • the compositions of the present invention are effective across an unusually broad spectrum of these tasks.
  • Solvent-based liquids such as Pine Sol (TM American Cyanamid Co.) and Lestoil (TM Noxell Corp.) typically contain about 25 to 35% of a solvent such as pine oil together with about 10-15% surfactant, but with little or no sequestering builders or alkaline buffers. When used full strength they are effective on greasy soils, such as spots on kitchen walls, but clean poorly on bathroom soils. They are also poor when diluted with water for cleaning surfaces having a broad area such as floors or walls.
  • Liquid products of this type such as Mr. Clean (TM Procter & Gamble Inc.), typically contain up to about 18% builder, up to about 5% surfactant, and up to about 12% hydrotrope, with little or no solvent-perhaps levels up to 2% or thereabouts.
  • Windex TM Drackett Company
  • Fantastik TM Texize Chemicals, Inc.
  • Formula 409 TM Chlorox Co.
  • Windex TM Drackett Company
  • Fantastik TM Texize Chemicals, Inc.
  • Formula 409 TM Chlorox Co.
  • These products may also be used full strength for spots on walls. They typically contain from about 4% to about 7% solvent, about 1-10% surfactant, and about 1-3% sequestering builder/alkaline buffer.
  • Still other formulations such as Comet (TM Procter & Gamble Inc.) are sold as abrasive cleansers for use on sinks, tubs and the like. They are most commonly in dry form, and contain finely ground silica as abrasive, together with relatively low levels of chlorine bleach, surfactant, calcium sequestrant, and alkaline buffer. A liquid cleanser containing suspended abrasive has also appeared commercially. These cleanser formulations contain no solvent.
  • the gist of the present invention is a range of compositions in convenient liquid form which contain exceptionally high levels of both builders and of solvents specifically chosen for their superb cleaning abilities, together with surfactant and with other ingredients needed to make the compositions homogeneous and physically stable for convenient use and storage.
  • the compositions of this invention are novel and exhibit outstanding performance characteristics that have not hitherto been achieved in a single formula: cleaning of floors as well as commercial liquid or granular floor cleaners when both are used diluted; cleaning of greasy walls as well as commercial wall cleaners when both are used full strength; and cleaning of bathtub soil, when used full strength, as well as abrasive cleansers.
  • the detergent compositions of the present invention are homogeneous aqueous liquids comprising the following components:
  • the surfactants of this invention are of two general types, each of which characterized separately herein.
  • the first such type is comprised of a wide range of non-soap anionic, zwitterionic, amphoteric and nonionic surfactants.
  • a typical listing of the classes and species of these surfactants is given in US-A-3,664,961.
  • These surfactants can be used singly or in combination at levels in the range from 0.9% to 10%, preferably at levels from 2% to 7% by weight of the compositions.
  • Non-soap surfactants as herein defined contribute cleaning performance to the compositions of this invention, especially when used in diluted form to clean broad surfaces such as floors and walls.
  • Suitable anionic non-soap surfactants are water-soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate.
  • a particularly suitable class of non-soap anionic detergents includes water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from 8 to 22, especially from 10 to 20, carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 10 ⁇ C 18 ) carbon atoms produced from the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • alkylbenzenes those of the type described in US-A-2,220,099 and US-A-2,477,383 and those preferred from alkylbenzenes obtained by alkylation with straight chain chloroparaffins (using aluminum trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis).
  • straight chain chloroparaffins using aluminum trichloride catalysis
  • straight chain olefins using hydrogen fluoride catalysis
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C " . s LAS.
  • non-soap anionic detergent compounds herein include the sodium C 10 ⁇ C 18 alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain 8 to 12 carbon atoms.
  • non-soap anionic detergent compounds herein include the water-soluble salts or esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl polethoxy sulfates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, more especially 1 to 4 moieties of ethylene oxide per fatty alcohol moiety; water-soluble salts of olefin sulfonates containing from 12 to 24, preferably 14 to 16, carbon atoms, especially those made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulfon
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal or alkanol-ammonium cations; or magnesium or calcium cations under circumstances described by CA-A-1,071,055.
  • a preferred mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and either an alkyl sulfate having 8 to 18, preferably 12 to 18, carbon atoms in the alkyl group, or an alkyl polyethoxy sulfate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.
  • Suitable ampholytic surfactants are water-soluble derivatives of aliphatic secondary and tertiary amines in which the aliphatic moiety is straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phosphonate.
  • Suitable zwitterionic surfactants are water soluble derivatives of aliphatic quaternary ammonium phosphonium and sulfonium cationic compounds in which the aliphatic moieties are straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group.
  • Preferred amphoteric and zwitterionic surfactants have the general formula: wherein X is CO 2 - or SO 3 - , R, is alkyl or alkenyl group having 8 to 22 carbon atoms, possibly interrupted by amide, ester or ether linkages, R 2 is a methylene, ethylene, propylene, isopropylene or isobutylene radical, R 3 and R 4 are independently selected from hydrogen, C ' - 3 alkyl or -R 2 -X, whereby one of the substituents R 3 and R 4 is hydrogen if the other one is represented by the group-R 2 X, n is an integer from 1 to 6, and A is an equivalent amount of a neutralizing anion, except that amphoteric surfactants include amine salts of the above formula and also the corresponding free amines.
  • Highly preferred surfactants according to the above formula include N-alkyl-2-aminopropionic acid, N-alkyl-2-imino-diacetic acid, N-aikyi-2-iminodipropionic acid, N-alkyl-2-amino-2-methyl-propionic acid, N-alkyl-propylenediamine-propionic acid, N-alkyl-dipropylene-triamine-propionic acid, N-alkyl- dipropylenetriamine dipropionic acid, N-alkylglycine, N - alkyl - amino - succinic acid, N - amidoalkyl - N' - carboxymethyl - N',N' - dimethyl-ammonio -ethylene diamine, N - alkyl - amino - ethane - sulfonic acid, N - alkyl - N,N - dimethyl - ammonio - hydroxy - propane - s
  • RTM Armeen
  • RTM Z marketed by Armour-Dial, Inc.
  • Amphoram RTM CP1, Diamphoram (RTM) CP1, Triamphoram (RTM) CP1, Triamphoram (RTM) C 2 P 1 and Polyamphorams (RTM) CP1, C 2 P, and C 3 P 1
  • Suitable nonionic surfactants are of several classes. Suitable semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms, and especially alkyl dimethyl amine oxides wherein the alkyl group contains from 11 to 16 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxalkyl moieties of from 1 to 3 carbon atoms.
  • alkyl mono- and di-alkanol amides are alkyl mono- and di-alkanol amides, the alkyl group of which contains from 10 to 18 carbon atoms, such as coconut monoethanol amide and oleyl diethanol amide. Particularly preferred are the C 10 to C 18 , more especially C 12 to C 14 , diethanol amides.
  • Alkoxylated nonionic surfactants are another class that is suitable for use in this invention, especially when used in mixtures at levels no more than 50% of the total non-soap surfactant system, preferably at levels from 5% to 35% thereof.
  • Alkoxylated nonionic surfactant materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants include (a) polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration reacted with ethylene oxide in amounts equal to from 1 to 25 mols of ethylene oxide per mol of alkyl phenol.
  • the alkyl substituent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene and nonene.
  • Examples include dodecylphenol condensed with 3 mols of ethylene oxide per mol of phenol; dinonylphenol condensed with 10 mols of ethylene oxide per mol of phenol; and nonylphenol and di-isooctylphenol condensed with 20 mols of ethylene oxide; (b) The condensation products of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 1 to 30 mols of alkylene oxide per mol of alcohol.
  • the aliphatic alcohol comprises between 9 and 15 carbon atoms and is ethoxylated with between 2 and 12, desirably between 3 and 9 mols of ethylene oxide per mol of aliphatic alcohol.
  • Preferred nonionic surfactants of this type are prepared from primary alcohols which are either linear (such as those derived from natural fats or prepared by the Ziegler process from ethylene, e.g.
  • nonionic surfactants include Dobanol (RTM) 45-4, Dobanol (RTM) 45-7, Dobanol (RTM) 45-9, Dobanol (RTM) 91-3, Dobanol (RTM) 91-6, Dobanol (RTM) 91-8, Synperonic (RTM) 6, Synperonic (RTM) 14, the condensation products of coconut alcohol with an average of between 5 and 12 mols of ethylehe oxide per mol of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 mols of ethylene oxide per mol of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms.
  • Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol (TM Union Carbide Corp.) series having from 9 to 15 carbon atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy residues per molecule; and (c) block polymers formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with either propylene glycol or ethylene diamine.
  • Such synthetic nonionic detergents are commercially available under the names “Pluronic” and “Tetronic", respectively [TM BASF Wyandotte Corp].
  • preferred alkoxylated nonionic surfactants have an average HLB (hydrophilic-lipophilic balance) in the range from 9.5 to 13.5, especially from 10 to 12.5.
  • Highly suitable nonionic surfactants of this type are ethoxylated primary or secondary C 9 _, S alcohols having an average degree of ethoxylation from 3 to 9.
  • Especially preferred non-soap surfactants are C la - 18 alkyl diethanol amide and the sodium salts of straight or branched chain C 9 - 15 alkyl benzene sulfonate, C 10 - 18 alkyl sulfate, and C 10 - 18 alkyl polyethoxy sulfate containing from 1 to 12 ethylene oxide moieties per fatty alcohol moiety.
  • soaps are specifically excluded from the surfactants disclosed hereinabove.
  • soaps derived from fatty acids, natural or syntheric, saturated or unsaturated, having alkyl chains ranging from about 10 to 18 carbon atoms in length are also useful in the compositions of the present invention.
  • preferred soaps are sodium and potassium laurate, myristate, palmitate, oleate and stearate; and sodium and potassium soaps derived from coconut and tallow fatty acids.
  • Soaps are effective not only as supplemental cleaning agents, but also aid in the solublization of other ingredients of the composition. In addition they control sudsing, which is highly desirable for compositions that are intended to not require rinsing. Accordingly, use of from 0.5% to 5% soap is preferred in the compositions of this invention. This usage is, however, by no means essential to obtain superb cleaning performance characteristics and the requisite product homogeneity, and the broad limits of soap usage are therefore from zero to 5%.
  • the builders of this invention are of two general types, each of which is characterized separately herein.
  • Materials useful as Sequestrants are hardness sequestering builders selected from the alkali metal salts of polyphosphates and polyphosphonates.
  • Sequestrants are used in amounts from 10.5% to 19% by weight of the composition, preferably from 12% to 16%. It has been found that amounts up to 10.5% do not fully meet the multipurpose cleaning objectives of this invention while amounts over 19% are unnecessary to meet these objectives, difficult to solubilize, and add to costs not only directly but also indirectly by increasing hydrotrope requirements.
  • Potyphosphonates suitable for use herein can be exemplified by the Na, K and Li salts of methylene diphosphonic acid; ethylene diphosphonic acid; ethane-1, 1,2-triphosphonic acid; and ethane-1-hydroxy-1,1-diphosphonic acid.
  • Suitable polyphosphates include pyrophosphates such as tetrasodium pyrophosphate decahydrate and tetrapotassium pyrophosphate; tripolyphosphates such as pentapotassium tripolyphosphate; and higher polyphosphates and metaphosphates such as sodium pentapolyphosphate and sodium hexametaphosphate.
  • pyrophosphates such as tetrasodium pyrophosphate decahydrate and tetrapotassium pyrophosphate
  • tripolyphosphates such as pentapotassium tripolyphosphate
  • higher polyphosphates and metaphosphates such as sodium pentapolyphosphate and sodium hexametaphosphate.
  • alkali metal salts more particularly the sodium and potassium salts, of pyrophosphoric acid and tripolyphosphoric acid.
  • the potassium salt of pyrophosphoric acid is particularly preferred.
  • Alkaline pH Buffers are a second type of builder. These materials include alklia metal carbonate, bicarbonate, orthophosphate, borate and silicate salts and ethanolamines. Buffers are not essential ingredients of the compositions of this invention. However they are preferably used in amounts from 0.5% to 6% by weight of the composition to provide a source of reserve alkalinity. They are selected according to the conventional wisdom of the detergent arts to provide pH buffering from 8.5 to 11.0 for a 1 % aqueous solution of the complete composition of this invention. The lower pH boundary was selected in relation to cleaning effectiveness and the upper boundary in relation to mildness and safety to surfaces.
  • composition has the proper pH as defined herein, it is an effective cleaner without the presence of buffer for soils that do not contain an acidic component.
  • the broad limits for buffer are zero to 6% by weight of the composition.
  • the total of Sequestering Builder plus pH Buffer be not greater than 21 % by weight of the composition; this limitation is in relation to solubilization requirements for the homogeneous liquids of this invention.
  • the solvents of this invention are of two types that are characterized separately herein.
  • the first is a Principal Solvent that is required to meet the detergency objectives.
  • the second is an Auxiliary Solvent that under certain circumstances as described herein is utilized to solubilize the Principal Solvent in the composition in order to prepare a clear, homogeneous finished product.
  • the Principal Solvent of this invention is used in an amount from 6% to 15% by weight of the composition, preferably from 8% to 12%, more preferably from 10% to 12%. It has the following physical properties at 25°C:
  • the molar volume of a compound is the quotient of its molecular weight divided by its density. This has metric units of (grams per g. mol) divided by (grams per cubic centimeter) which results in a unit of volume per gram mol of the compound in question.
  • solubility parameters defined above are those of Hansen and Beerbower, "Solubility Parameters", Kirk-Othmer Encyclopedia of Chemical Technology, second ed., Supplementary Volume pp. 889-910, John Wiley & Sons, N.Y. (1971). Hansen characterized the solubility behavior of liquids according to three modes of interaction between molecules: (1) dispersion (London) forces arising from fluctuating atomic dipoles caused by electrons rotating about a nucleus; (2) interaction between permanent or induced molecular dipoles; and (3) hydrogen bonds. These are frequently identified as 5 c , 6p and 6 H respectively, and are herein designated by the terms dispersion parameter, polarity parameter, and hydrogen bonding parameter, respectively.
  • the Auxiliary Solvents of this invention can be used in an amount up to 10% of the composition by weight, i.e. from zero to 10%. When used, preferred amounts are from 2% to 10% by weight of the composition. Because of solubilization requirements, the total of Principal Solvent plus Auxiliary Solvent should not be greater than 22% of the composition by weight.
  • an Auxiliary Solvent is in general not necessary for solubilization and preferably is used in an insignificant amount if at all; i.e. less than 2% by weight of the composition.
  • Auxiliary solvents used in this manner have sometimes been described in the prior art as "coupling agents". This term is avoided herein, as the solubilizing function can often be accomplished not only by Auxiliary Solvents as defined herein, but also by Principal Solvents of relatively high Polarity and Hydrogen Bonding Parameters. So doing not only accomplishes the solubilizing function but also contributes effectively to cleaning. According to these principles, it may be preferred, for example, to solubilize xylene with diethylene glycol mono-n-butyl ether than with isopropyl alcohol.
  • Orange terpenes and limonenes also, are mixtures of chemicals derived from naturally occurring materials that vary somewhat according to source. These three values for both substances are estimated to be approximately those appearing in the foregoing table for solvent L.
  • Solvents meeting the criteria herein expressed for Principal Solvents of this invention that ordinarily do not require the use of Auxiliary Solvents, include ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, isopropylene glycol mono ethyl ether, isopropylene glycol mono propyl ether, isopropylene glycol mono butyl ether, methyl cyclohexane, butyl acetate, amyl acetate, butyl butyrate, butyl lactate, diethyl carbonate, diethyl succinate, methyl i-amyl ketone, morpholine, and anisole.
  • Solvents meeting the criteria herein expressed for Principal Solvents of this invention include n-hexane, n-decane, cyclohexane, toluene, xylene, naphthalene, diethyl benzene, chlorobenzene, trichloroethylene, pine oil, alpha terpineol, d-limonene, and orange terpene.
  • Solvents which can be used as Auxiliary Solvents in this invention, that do not meet the criteria for Principal Solvents, include propylene carbonate, methyl ethyl ketone, acetone, ethylene glycol mono methyl ether, ethylene glycol mono ethyl ether, diethylene glycol mono methyl ether, diethylene glycol mono ethyl ether, benzyl alcohol, diethylene glycol, glycerol, hexylene glycol, propylene glycol, ethylene glycol, 1-butanol, 1-propanol, and ethanol.
  • the Principal Solvents of this invention can be selected from among aliphatic, aromatic and chlorinated hydrocarbons; alcohols; esters; ethers; glycol ethers; ketones; and amines.
  • Preferred Principal Solvents are ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol, mono-n-hexyl ether, isopropylene glycol mono ethyl ether, mixed isopropylene glycol mono-butyl, ethyl and propyl ethers, pine oil, alpha terpineol, orange terpene, methyl cyclohexane, toluene, xylene, butyl acetate and amyl acetate.
  • diethylene glycol mono-n-butyl ether used in the essential absence of an Auxiliary Solvent.
  • hydrotropes Water soluble salts of low molecular weight organic acids are suitable hydrotropes. Among such materials are sodium and potassium salts of toluene, benzene and cumene sulfonic acids, and sodium and potassium sulfosuccinate. Urea is also a suitable hydrotrope. Hydrotropes are used in amounts from 3% to 25% by weight of the composition, preferably from 6% to 14%.
  • compositions of the present invention can optionally contain minor amounts of colorants; perfumes; soil suspending agents such as carboxymethyl cellulose, sodium polyacrylate, and polyethylene glycols having a molecular weight from 400 to 10,000; fluorescers; suds boosters; suds regulants; opacifiers; enzymes and enzyme stabilizers; germicides; antioxidants such as sodium sulfite; and other materials known to the liquid detergent arts.
  • chelating agents for heavy metals such as nitrilotriacetic acid, ethylene diamine tetraacetic acid and N-hydroxyethyl ethylene diamine triacetic acid, added in the form of free acids or alkali metal salts thereof; in quantities so low as to make a negligible contribution as hardness sequestering builder (e.g. at or below 1 % by weight of the compositions); for the purpose of improving the clarity and/or color stability of the liquid product.
  • heavy metals such as nitrilotriacetic acid, ethylene diamine tetraacetic acid and N-hydroxyethyl ethylene diamine triacetic acid
  • compositions of this invention and the benefits derived therefrom. They are illustrative of the invention and are not to be construed as limiting thereof.
  • Composition A was prepared by mixing the following components together in the order listed:
  • NaAE 3 S designates the sodium salt of the condensation product of 3 mols of ethylene oxide with coconut fatty alcohol.
  • TKPP designates tetrapotassium pyrophosphate.
  • KTS designates potassium toluene sulfonate.
  • the coconut fatty acid was neutralized during the mixing process to form coconut soap.
  • the pH of the composition was measured to be 9.5 when measured full strength and 9.3 when measured as a 1% aqueous solution.
  • composition was tested for cleaning performance against 5 kinds of artificial soil designed to simulate in a reproducible manner a like number of natural soils found around a house:
  • liquid cleaning compositions were used full strength on both bathroom soils and on the greasy kitchen wall soil; while the liquid compositions were used in dilute form on both kitchen soils; making 5 tests in all. These practices simulated consumer practices in cleaning these surfaces, either full strength from the bottle or diluted in a scrub bucket.
  • 2 grams of the liquid compositions were applied to each Gardner test sponge and used for full strength cleaning; while a mixture of 0.15 grams of the liquid composition with 9.85 grams of water was used for dilute cleaning.
  • 2 grams of the composition plus 2 grams of water was applied to the sponge.
  • Mr. Clean (TM Procter & Gamble Inc.) is a built liquid composition sold commercially for hard surface cleaning, containing sodium nitrilotriacetate and mixed diethanol amide/ethoxylated nonionic surfactant as principal cleaning ingredients
  • Pine Sol (TM American Cynamid Co.) is a liquid composition sold commercially for hard surface cleaning, containing pine oil, isopropanol and soap
  • Comet (TM Procter & Gamble Inc.) is an abrasive cleanser sold for scouring tubs and sinks, containing finely divided silica as the scouring agent, and lesser amounts of anionic surfactant, chlorine bleach, and builder.
  • composition A formulated according to this invention, was approximately equal to or was superior to each of these commercial products in every application. This same conclusion was also reached by a panel of graders who visually examined the tile surfaces after cleaning.
  • a second composition of this invention, B was prepared that differed from A only in that 2% diethanolamine was used as buffer, replacing the mixture of 1.55% Na 2 CO 3 plus 1.25% NaHC0 3 , with a minor adjustment in the water content. The cleaning tests were repeated with approximately the same results.
  • Composition C of this invention was like that of Composition A except that it contained 6% instead of 10% of diethylene glycol mono-n-butyl ether, with the difference made up by water.
  • Composition C was tested on the two bathroom soils in the manner hereinbefore described, and in the same series of tests, with the following results: 75% removal of simulated bathtub soil and 46% removal of simulated shower wall soil. It is apparent that the 6% solvent level, which is at the lower end of the formulation range of the compositions of this invention, while it reduces performance against both types of soil, is still well within the range of commercial products against bathtub soil and remains superior to all commercial products against shower wall soil.
  • Compositions A, B and C were homogeneous and were stable indefinitely at room temperature.
  • Composition D is the only one of the foregoing that is according to this invention. It is clearly apparent from the above results that removal of surfactant or reduction of builder to a level outside the scope of this invention caused a significant reduction in cleaning when the compositions were used in dilute form on either simulated floor soil or wall soil; builder reduction diminished effectiveness against simulated shower wall soil as well. It is also clear that reduction of a solvent to a level outside the scope of this invention caused a significant reduction in cleaning when the compositions were used full strength on all three soils: simulated kitchen wall, bathroom tub and shower wall soils. These data demonstrate both the need and the effectiveness of concurrent high levels of both builder and solvent, in liquid compositions containing surfactant and other ingredients, to obtain the multiple cleaning objectives of this invention: a standard of accomplishment that has not been achieved heretofore.
  • compositions are prepared like Composition D except for the following differences:
  • compositions H and I were prepared according to this invention as follows:
  • compositions were homogeneous and stable indefinitely at room temperature.
  • a number of other compositions were prepared that were identical to Composition H except for differences in solvent. They too were homogeneous and stable indefinitely at room temperature.
  • These solvents were: a mixture of 3% n-decane and 7% diethylene glycol mono-n-butyl ether (hereinafter referred to as DGBE); a mixture of 3% cyclohexane and 7% DGBE; a mixture of 3% xylene and 7% DGBE; a mixture of 5% xylene and 5% DGBE; a mixture of 2.2% diethyl benzene and 7.8% DGBE; 10% butyl acetate; 10% amyl acetate; 10% diethyl carbonate; 8% diethyl succinate; 7.5% methyl i-amyl ketone; 10% methyl i-amyl ketone; 10% ethylene glycol mono-n-butyl ether; 10%
  • compositions H and I were tested for cleaning performance on both bathroom soils in the manner described hereinbefore. Results were comparable to those of compositions A and D.
  • composition was prepared; was homogeneous and stable at room temperature; and cleans well according to the tests described hereinbefore.
  • Solvents not meeting the criteria herein for principal solvent methyl ethyl ketone-18; 1-butanol-20; diethylene glycol mono ethyl ether-35; ethanol-40; acetone-more than 45; methanol-more than 45; dimethylformamide-more than 45.
  • compositions of this invention were prepared in greater quantity for the purpose of stability testing:
  • Composition N was prepared identical to that of Composition K except that its solvent was 10% ethylene glycol mono-n-butyl ether.
  • Compositions K and N were clear, homogeneous liquids and remained so after storage for 3 months at 4°, 21° and 49°C. Both fully recovered to their original homogeneous appearance after 3 cycles alternating between 24 hours at -18°C. and 72 hours at +10°C.
  • Composition 0 was prepared identical to that of Composition L except that the KTS level was 12%.
  • Compositions L, M and 0 were tested using procedures and obtaining results the same as for Compositions K and N except that the storage tests at 4°, 21° and 49°C. were discontinued after 2 weeks, with no visible changes having occurred during that time.
  • compositions containing higher or lower amounts of builder and/or solvent within the scope of this invention can be stabilized by adjusting levels of KTS and fatty acid within the ranges specified herein, according to principles known in the art.
  • Diethanolamine is preferred to inorganic buffers from the standpoint of increasing stability under severe storage conditions.
  • compositions were prepared according to the method of Composition A for the purpose of comparing the inorganic builder of this invention with an aminopolycarboxylate builder, another common type of sequestering builder. Cleaning tests were run according to the methods of Example 1, using all compositions at full strength.
  • Composition Q as compared with Composition P, represents equimolar substitution of trisodium nitrilotriacetate for TKPP, with all other ingredients remaining the same. Because sequestration is a chemical process and because costs are roughly comparable when examined in this way, this is a common, useful and valid type of comparison. It is apparent from the foregoing figures that the performance of Composition Q is seriously deficient in removal of both bathtub and shower soil.
  • Composition R as compared with Composition P, represents equiponderant substitution of trisodium nitrilotriacetate for TKPP. Although Composition R cleans somewhat better than Composition Q as might be expected, its performance in removal of bathroom tub soil is still seriously deficient in comparison with that of Composition P.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP82305211A 1981-09-10 1982-09-30 Liquid hard-surface cleaner Expired EP0105063B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA000385586A CA1178160A (en) 1981-09-10 1981-09-10 Liquid hard-surface cleaner
GR69130A GR78090B (enrdf_load_stackoverflow) 1981-09-10 1982-08-26
IE2215/82A IE53499B1 (en) 1981-09-10 1982-09-09 Liquid hard-surface cleaner
SE8205171A SE8205171L (sv) 1981-09-10 1982-09-10 Flytande rengoringsmedel for harda ytor
EP82305211A EP0105063B1 (en) 1981-09-10 1982-09-30 Liquid hard-surface cleaner
DE8282305211T DE3274882D1 (en) 1982-09-30 1982-09-30 Liquid hard-surface cleaner

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA000385586A CA1178160A (en) 1981-09-10 1981-09-10 Liquid hard-surface cleaner
EP82305211A EP0105063B1 (en) 1981-09-10 1982-09-30 Liquid hard-surface cleaner

Publications (2)

Publication Number Publication Date
EP0105063A1 EP0105063A1 (en) 1984-04-11
EP0105063B1 true EP0105063B1 (en) 1986-12-30

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EP82305211A Expired EP0105063B1 (en) 1981-09-10 1982-09-30 Liquid hard-surface cleaner

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Country Link
EP (1) EP0105063B1 (enrdf_load_stackoverflow)
CA (1) CA1178160A (enrdf_load_stackoverflow)
GR (1) GR78090B (enrdf_load_stackoverflow)
IE (1) IE53499B1 (enrdf_load_stackoverflow)
SE (1) SE8205171L (enrdf_load_stackoverflow)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0137616B1 (en) * 1983-08-11 1988-01-27 The Procter & Gamble Company Liquid detergents with solvent
GB8409054D0 (en) * 1984-04-07 1984-05-16 Procter & Gamble Stabilized oil-in-water cleaning microemulsions
US4749509A (en) * 1986-11-24 1988-06-07 The Proctor & Gamble Company Aqueous detergent compositions containing diethyleneglycol monohexyl ether solvent
US5202050A (en) * 1987-04-06 1993-04-13 The Procter & Gamble Company Method for cleaning hard-surfaces using a composition containing organic solvent and polycarboxylated chelating agent
NZ224148A (en) * 1987-04-10 1991-02-26 Colgate Palmolive Co Pre-spotting composition for food residue removal
US5102573A (en) * 1987-04-10 1992-04-07 Colgate Palmolive Co. Detergent composition
GB8802106D0 (en) * 1988-01-30 1988-02-24 Procter & Gamble Hard-surface cleaning compositions
GB8805448D0 (en) * 1988-03-08 1988-04-07 Bp Chem Int Ltd Liquid detergent compositions
US4921629A (en) * 1988-04-13 1990-05-01 Colgate-Palmolive Company Heavy duty hard surface liquid detergent
US4954286A (en) * 1988-04-14 1990-09-04 Lever Brothers Company Fabric pretreatment cleaning compositions
DE3836369C2 (de) * 1988-10-26 1997-10-02 Basf Lacke & Farben Verfahren zur Reinigung von Rohrleitungssystemen
US5254290A (en) * 1991-04-25 1993-10-19 Genevieve Blandiaux Hard surface cleaner
ZA925727B (en) * 1991-08-09 1993-03-10 Bristol Myers Squibb Co Glass cleaning composition.
JPH07507584A (ja) * 1992-06-18 1995-08-24 ユニリーバー・ナームローゼ・ベンノートシヤープ 洗浄組成物の改良
AU671895B2 (en) * 1993-04-12 1996-09-12 Colgate-Palmolive Company, The Tricritical point composition
SE504143C2 (sv) * 1995-03-21 1996-11-18 Akzo Nobel Nv Alkaliskt rengöringsmedel innehållande nonjonisk tensid och komplexbildare samt användning av en amfotär förening som solubiliserande medel
AU728470B2 (en) * 1996-02-14 2001-01-11 Stepan Company Reduced residue hard surface cleaner comprising hydrotrope
US6395103B1 (en) * 1997-05-23 2002-05-28 Huntsman Petrochemical Corporation Degreasing compositions
US5935918A (en) * 1998-03-06 1999-08-10 Pomp; Paul R. Firearm cleaning agent for cleaning a firearm bore
EP1080169A1 (en) 1998-05-22 2001-03-07 The Procter & Gamble Company Acidic cleaning compositions with c10 alkyl sulfate detergent surfactant
US6596677B1 (en) * 2000-09-25 2003-07-22 Huntsman Petrochemical Corporation Propylene carbonate based cleaning compositions
GB2400375A (en) * 2003-04-09 2004-10-13 Hassan Scott Lisa Non-emulsifying aqueous cleaner-degreaser
PL2041255T3 (pl) * 2006-07-14 2011-02-28 Ecolab Inc Alkaliczna kompozycja do czyszczenia podłogi i sposób czyszczenia podłogi
TWI446400B (zh) * 2007-10-05 2014-07-21 Schott Ag Fluorescent lamp with lamp cleaning method
CN114480029B (zh) * 2021-12-22 2024-09-13 宁波小懒科技有限公司 一种清洁剂

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2709690B1 (de) * 1977-03-05 1978-05-11 Henkel Kgaa Fluessiges Reinigungsmittel
GB1579668A (en) * 1977-05-10 1980-11-19 Colgate Palmolive Co Cleaning compositions
EP0040882B1 (en) * 1980-05-27 1985-01-30 THE PROCTER & GAMBLE COMPANY Liquid detergent compositions

Also Published As

Publication number Publication date
GR78090B (enrdf_load_stackoverflow) 1984-09-26
IE822215L (en) 1983-03-10
IE53499B1 (en) 1988-11-23
SE8205171L (sv) 1983-03-11
CA1178160A (en) 1984-11-20
SE8205171D0 (sv) 1982-09-10
EP0105063A1 (en) 1984-04-11

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