WO1991011505A1 - Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol - Google Patents

Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol Download PDF

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Publication number
WO1991011505A1
WO1991011505A1 PCT/US1991/000337 US9100337W WO9111505A1 WO 1991011505 A1 WO1991011505 A1 WO 1991011505A1 US 9100337 W US9100337 W US 9100337W WO 9111505 A1 WO9111505 A1 WO 9111505A1
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group
hydrogen
composition
solvent
hydroxy
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PCT/US1991/000337
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English (en)
French (fr)
Inventor
Daniel Wayne Michael
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The Procter & Gamble Company
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Priority claimed from US07/628,064 external-priority patent/US5108660A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to KR1019920701779A priority Critical patent/KR927003772A/ko
Priority to DE69129981T priority patent/DE69129981T2/de
Priority to EP91905371A priority patent/EP0513240B1/en
Priority to BR919105962A priority patent/BR9105962A/pt
Priority to AU73426/91A priority patent/AU659994B2/en
Publication of WO1991011505A1 publication Critical patent/WO1991011505A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/92Sulfobetaines ; Sulfitobetaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/90Betaines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043For use with aerosol devices
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines

Definitions

  • This invention pertains to liquid detergent compositions for use in cleaning hard surfaces.
  • Such compositions typically contain detergent surfactants, solvents, builders, etc.
  • Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in neat or concentrated form so that a relatively high level of surfactant material and organic solvent is delivered directly to the soil. Moreover, it is a rather more straightforward task to incorporate high concentrations of anionic or nonionic surfactant in a liquid rather than a granular composition. For both these reasons, therefore, liquid cleaning compositions have the potential to provide superior soap scum, grease, and oflj soil removal over powdered cleaning compositions. Nevertheless, liquid cleaning compositions, and especially compositions prepared for cleaning glass, still suffer a number of drawbacks which can limit their consumer acceptability. They have to have good spotting/filming properties. In addition, they can suffer problems of product form, in particular, inhomogeneity, lack of clarity, or inadequate viscosity characteristics, or excessive "solvent" odor for consumer use.
  • An object of the present invention is to provide detergent compositions which provide good glass cleaning without excessive filming and/or streaking.
  • the present invention relates to an aqueous, liquid, hard surface detergent composition
  • an aqueous, liquid, hard surface detergent composition comprising: (a) zwitterionic detergent surfactant, containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably a carboxylate, sulfonate, or sulfate group, more preferably a sulfonate group; (b) solvent/buffer system that comprises either monoethanolamine, beta-aminoalkanol which contains from about three to about six carbon atoms, or mixtures thereof, preferably monoethanolamine; (c) optional detergent builder; and the balance being (d) aqueous solvent system and, optionally, minor ingredients.
  • compositions preferably does not contain amounts of materials, like conventional detergent builders, etc., that deposit on the surface being cleaned and cause unacceptable spotting/filming.
  • the compositions can be formulated at usage concentrations, or as concentrates, and can be packaged in a container having means for creating a spray to make application to hard surfaces more convenient.
  • superior aqueous liquid detergent compositions for cleaning shiny surfaces such as glass contain zwitterionic detergent surfactant (containing both cationic and anionic groups in substantially equivalent proportions so as to be electrically neutral at the pH of use, typically at least about 9.5, preferably at least about 10) and monoethanolamine and/or certain beta-amino alkanol compounds.
  • zwitterionic detergent surfactant containing both cationic and anionic groups in substantially equivalent proportions so as to be electrically neutral at the pH of use, typically at least about 9.5, preferably at least about 10.
  • aqueous, liquid hard surface detergent compositions herein contain from about 0.001% to about 15% of suitable zwitterionic detergent surfactant containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate.
  • suitable zwitterionic detergent surfactant containing a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, sulfate and/or sulfonate group, more preferably sulfonate.
  • Successively more preferred ranges of zwitterionic detergent surfactant inclusion are from about 0.02% to about 10% of surfactant, and from about 0.1% to about 5% of surfactant.
  • Zwitterionic detergent surfactants contain both a cationic group and an anionic group and are in substantial electrical neutrality where the number of anionic charges and cationic charges on the detergent surfactant molecule are substantially the same.
  • Zwitterionic detergents which typically contain both a quaternary ammonium group and an anionic group selected from sulfonate and carboxylate groups are desirable since they maintain their amphoteric character over most of thepH range of interest for cleaning hard surfaces.
  • the sulfonate group is the preferred anionic group.
  • Preferred zwitterionic detergent surfactants have the generic formula:
  • each y is preferably a carboxylate (COO-) or sulfonate (SO 3 -) group, preferably sulfonate; wherein each R 3 is a hydrocarbon, e.g., an alkyl, or alkylene, group containing from about 8 to about 20, preferably from about 10 to about 18, more preferably from about 12 to about 16 carbon atoms; wherein each (R 4 ) is either hydrogen, or a short chain alkyl, or substituted alkyl, containing from one to about four carbon atoms, preferably groups selected from the group consisting of methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl; wherein each (R 5 ) is selected from the group co sisting
  • the R 3 groups can be branched and/or unsaturated, and such structures can provide spotting/filming benefits, even when used as part of a mixture with straight chain alkyl R 3 groups.
  • the R 4 groups can also be connected to form ring structures.
  • hydrocarbylamidoalkylene betaines and, especially, hydrocarbylamidoalkylene sulfobetaines are excellent for use in hard surface cleaning detergent compositions, especially those formulated for use on both glass and hard-to- remove soils. They are even better when used with monoethanolamine and/or specific beta-amino alkanol as disclosed herein.
  • a more preferred specific detergent surfactant is a C 10-14 fatty acylamidopropylene(hydroxypropylene)sulf ⁇ betaine, e.g., the detergent surfactant available from the Sherex Company as a 40% active product under the trade name "Varion CAS Sulfobetaine.”
  • the level of zwitterionic detergent surfactant, e.g., HASB, in the composition is typically from about 0.001% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.2% to about 5%. The level in the composition is dependent on the eventual level of dilution to make the wash solution.
  • the composition when used full strength, or wash solution containing the composition, should contain from about 0.02% to about 1%, preferably from about 0.05% to about 0.5%, more preferably from about 0.1% to about 0.25%, of detergent surfactant.
  • the level can, and should be, higher, typically from about 0.1% to about 10%, preferably from about 0.25% to about 2%.
  • Concentrated products will typically contain from about 0.2% to about 10%, preferably from about 0.3% to about 5%. It is an advantage of the zwitterionic detergent, e.g., HASB, that compositions containing it can be more readily diluted by consumers since it does not interact with hardness cations as readily as conventional anionic detergent surfactants.
  • Zwitterionic detergents are also extremely effective at very low levels, e.g., below about 1%.
  • Other zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi, incorporated herein by reference.
  • Another detailed listing of suitable zwitterionic detergent surfactants for the detergent compositions herein can be found in U.S. Pat. No. 4,557,853, Collins, issued Dec. 10, 1985, incorporated by reference herein.
  • Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company, also incorporated herein by reference.
  • detergent surfactants e.g., anionic, and nonionic detergent surfactants
  • anionic, and nonionic detergent surfactants that can be used in small amounts in the composition of this invention as cosurfactants.
  • these are the alkyl- and alkylethoxylate- (polyethoxylate) sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the deter- gency art.
  • detergent surfactants that are amphoteric at a lower pH are desirable anionic detergent cosurfactants.
  • detergent surfactants which are C 12 -C 18 acylamido alkylene amino alkylene sulfonates, e.g., compounds having the formula R-C(O)-NH-(C 2 H 4 )-N(C 2 H 4 OH)- CH 2 CH(OH)CH 2 SO 3 M wherein R is an alkyl group containing from about 9 to about 18 carbon atoms and M is a compatible cation are desirable cosurfactants.
  • These detergent surfactants are available as Miranol CS, OS, JS, etc.
  • the CTFA adopted name for such surfactants is cocoamphohydroxypropyl sulfonate. It is preferred that the compositions be substantially free of alkyl naphthalene sulfonates.
  • detergent surfactants useful herei n contai n a hydrophobic group, typically containing an alkyl group in the C 9 -C 18 range, and, optionally, one or more linking groups such as ether or amido, preferably amido groups.
  • the anionic detergent surfactants can be used in the form of their sodium, potassium or alkanolammonium, e.g., triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
  • C 12 -C 18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • Suitable surfactants for use in such cleaners are one or more of the following: sodium linear C 8 -C 18 alkyl benzene sulfonate (LAS), particularly C 11 -C 12 LAS; the sodium salt of a coconut alkyl ether sulfate containing 3 moles of ethylene oxide; the adduct of a random secondary alcohol having a range of alkyl chain lengths of from 11 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties, several commercially available examples of which are Tergitol 15-S-3, Tergitol 15-S-5, Tergitol 15-S-7, and Tergitol 15-S-9, all available from Union Carbide Corporation; the sodium and potassium salts of coconut fatty acids (coconut soaps); the condensation product of a straight-chain primary alcohol containing from about 8 carbons to about 16 carbon atoms and having an average carbon chain length of from about 10 to about 12 carbon atoms with from about 4 to about 8 moles of ethylene oxide per
  • R 1 is a straight-chain alkyl group containing from about 7 to about 15 carbon atoms and having an average carbon chain length of from about 9 to about 13 carbon atoms and wherein each R 2 is a hydroxy alkyl group containing from 1 to about 3 carbon atoms; a zwitterionic surfactant having one of the preferred formulas set forth hereinafter; or a phosphine oxide surfactant.
  • fluorocarbon surfactants examples of which are FC-129, a potassium fluorinated alkylcarboxylate and FC-170-C, a mixture of fluorinated alkyl polyoxyethylene ethanols, both available from 3M Corporation, as well as the Zonyl fluorosurfactants, available from DuPont Corporation. It is understood that mixtures of various surfactants can be used.
  • MONOETHANOLAMINE AND/OR BETA-AMINOALKANOL Monoethandlamine and/or beta-aminoalkanol compounds serve primarily as solvents when the pH is above about 10.0, and especially above about 10.7. They also provide alkaline buffering capacity during use. However, the most unique contribution they make is to improve the spotting/filming properties of hard surface cleaning compositions containing zwitterionic detergent surfactant, whereas they do not provide any substantial improvement in spotting/filming when used with conventional anionic or ethoxylated nonionic detergent surfactants. The reason for the improvement is not known. It is- not simply a pH effect, since the improvement is not seen with conventional alkalinity sources.
  • Monoethanol amine and/or beta-alkanol amine are used at a level of from about 0.05% to about 10%, preferably from about 0.2% to about 5%.
  • dilute compositions they are typically present at a level of from about 0.05% to about 2%, preferably from about 0.1% t 0 a bout 1.0%, more preferably from about 0.2% to about 0.7%.
  • concentrated compositions they are typically present at a level of from about 0.5% to about 10%, preferably from about 1% to about 5%.
  • beta-aminoalkanols have a primary hydroxy group.
  • Suitable beta-aminoalkanols have the formula:
  • each R is selected from the group consisting of hydrogen and alkyl groups containing from one to four carbon atoms and the total of carbon atoms in the compound is from three to six, preferably four.
  • the amine group is preferably not attached to a primary carbon atom. More preferably the amine group is attached to a tertiary carbon atom to minimize the reactivity of the amine group.
  • Specific* preferred beta-aminoalkanols are 2-amino,1- butanol; 2-amino,2-methylpropanol; and mixtures thereof.
  • the most preferred beta-aminoalkanol is 2-amino,2-methylpropanol since it has the lowest molecular weight of any beta-aminoalkanol which has the amine group attached to a tertiary carbon atom.
  • the betaaminoalkanols preferably have boiling points below about 175oC. Preferably, the boiling point is within about 5oC of 165oC.
  • Such beta-aminoalkanols are excellent materials for hard surface cleaning in general and, in the present application, have certain desirable characteristics.
  • the beta-aminoalkanols are surprisingly better than, e.g., monoethanolamine for hard surface detergent compositions that contain perfume ingredients like terpenes and similar materials.
  • monoethanolamine normally is preferred for its effect in improving the spotting/filming performance of compositions containing zwitterionic detergent surfactant.
  • the improvement in spotting/filming of hard surfaces that is achieved by combining the monoethanolamine and/or beta-aminoalkanol was totally unexpected.
  • Beta-aminoalkanols provide superior cleaning of hard-to-remove greasy soils and superior product stability, especially under high temperature conditions, when used in hard surface cleaning compositions, especially those containing the zwitterionic detergent surfactants.
  • Beta-aminoalkanols and especially the preferred 2-amino-2- methylpropanol, are surprisingly volatile from cleaned surfaces considering their relatively high molecular weights.
  • cosolvent that has cleaning activity in addition to the monoethanolamine and/or beta- aminoalkanol.
  • the cosolvents employed in the solvent/buffer system in the hard surface cleaning compositions herein can be any of the well-known "degreasing" solvents commonly used in, for example, the dry cleaning industry, in the hard surface cleaner industry and the metalworking industry.
  • ⁇ H 25 is the heat of vaporization at 25oC
  • R is the gas constant (1.987 cal/mole/deg)
  • T is the absolute temperature in °K
  • Tb is the boiling point in oK
  • T c is the critical temperature in oK
  • d is the density in g/ml
  • M is the molecular weight.
  • hydrogen bonding parameters are preferably less than about 7.7, more preferably from about 2 to about 7, and even more preferably from about 3 to about 6. Solvents with lower numbers become increasingly difficult to solubilize in the compositions and have a greater tendency to cause a haze on gl ⁇ ss. Higher numbers require more solvent to provide good greasy/oily soil cleaning.
  • Cosolvents are typically used at a level of from about 1% to about 30%, preferably from about 2% to about 15%, more preferably from about 4% to about 8%.
  • Dilute compositions typically have cosolvents at a level of from about 1% to about 10%, preferably from about 3% to about 6%.
  • Concentrated compositions contain from about 10% to about 30%, preferably from about 10% to about 20% of cosolvent.
  • Many of such solvents comprise hydrocarbon or halogenated hydrocarbon moieties of the alkyl or cycloalkyl type, and have, a boiling point well above room temperature, i.e., above about 20oC.
  • compositions of the present type will be guided in the selection of cosolvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations.
  • kerosene hydrocarbons function quite well for grease cutting in the present compositions, but can be malodorous. Kerosene must be exceptionally clean before it can be used, even in commercial situations. For home use, where malodors would not be tolerated, the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reasonably modified by perfuming.
  • the C 6 -C 9 alkyl aromatic solvents especially the C 6 -C 9 alkyl benzenes, preferably octyl benzene, exhibit excellent grease removal properties and have a low, pleasant odor.
  • the glycol ethers useful herein have the formula R 6 O(R 7 O) m H wherein each R 6 is an alkyl group which contains from about 3 to about 8 carbon atoms, each R 7 is either ethylene or propyl ene, and m is a number from 1 to about 3.
  • the most preferred glycol ethers are selected from the group consisting of monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether, monopropyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether, monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and mixtures thereof.
  • a particularly preferred type of solvent for these hard surface cleaner compositions comprises diols having from 6 to about 16 carbon atoms in their molecular structure.
  • Preferred diol solvents have a solubility in water of from about 0.1 to about 20 g/100 g of water at 20oC.
  • the diol solvents are especially preferred because, in addition to good grease cutting ability, they impart to the compositions an enhanced ability to remove calcium soap soils from surfaces such as bathtub and shower stall walls. These soils are particularly difficult to remove, especially for compositions which do not contain an abrasive.
  • the diols containing 8-12 carbon atoms are preferred.
  • the most preferred diol solvent is 2,2,4-trimethyl-1,3-pentanediol .
  • Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C 1-4 alcohols, butoxy propanol, Butyl Carbitol® and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxy propanol or dipropylene glycol monobutyl ether), hexyl diglycol (Hexyl Carbitol®), butyl triglycol, diols such as 2,2,4-trimethyl-1,3-pentanediol, and mixtures thereof, can be used.
  • Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic acid esters of C 1-4 alcohols, butoxy propanol, Butyl Carbitol® and 1(2-n-butoxy-1-methylethoxy)propane-2-ol (also called butoxy propoxy
  • the butoxy-propanol solvent should have no more than about 20%, preferably no more than about 10%, more preferably no more than about 7%, of the secondary isomer in which the butoxy group is attached to the secondary atom of the propanol for improved odor.
  • the solvent/buffer system is formulated to give a pH in the product and, at least initially, in use of from about 9.5 to about 13, preferably from about 9.7 to about 12, more preferably from about 9.7 to about 11.5. pH is usually measured on the product.
  • the buffering system comprises monoethanol amine and/or betaaminoalkanol and, optionally, but preferably, cobuffer and/or alkaline material selected from the group consisting of: ammonia; other C 2 -C 4 alkanolamines; alkali metal hydroxides; silicates; borates; carbonates; and/or bicarbonates; and mixtures thereof.
  • the preferred cobuffering/alkalinity materials are alkali metal hydroxides.
  • the level of the cobuffer/alkalinity-source is from 0% to about 5%, preferably from 0% to about 5%.
  • Monoethanolamine and/or beta-aminoalkanol buffering material, in the system is important for spotting/filming. It is surprising that monoethanolamine and/or beta-aminoalkanol provides improved spotting/- filming when used with the zwitterionic detergent surfactant.
  • the balance of the formula is typically water and non-aqueous polar solvents with only minimal cleaning action like methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and mixtures thereof.
  • the level of non-aqueous polar solvent is greater when more concentrated formulas are prepared.
  • the level of non-aqueous polar solvent is from about 0.5% to about 40%, preferably from about 1% to about 10% and the level of water is from about 50% to about 99%, preferably from about 75% to about
  • compositions herein can also contain other various adjuncts which are known to the art for detergent compositions. Preferably they are not used at levels that cause unacceptable spotting/filming.
  • adjuncts are:
  • Enzymes such as proteases
  • Hydrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and potassium xylene sulfonate;
  • Aesthetic-enhancing ingredients such as colorants and perfumes, providing they do not adversely impact on spotting/- filming in the cleaning of glass.
  • the perfumes are preferably those that are more water-soluble and/or volatile to minimize spotting and filming.
  • Antibacterial agents can be present, but preferably only at low levels to avoid spotting/filming problems. More hydrophobic antibacterial/germicidal agents, like orthobenzyl-para-chlorophenol, are avoided. If present, such materials should be kept at levels below about 0.1%.
  • An optional ingredient for general cleaning purposes is from 0% to about 30%, preferably from about 1% to about 15%, more preferably from about 1% to about 12%, of detergent builder.
  • a level of builder of from about 0.1% to about 0.5%, preferably from about 0.1% to about 0.2%, is useful.
  • some examples of builders for use herein are sodium nitrilotriacetate, potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium ethane-1-hydroxyl-1,1-di2 phosphonate, the nonphosphorous chelating agents described in the copending U.S. Pat. Application of Culshaw and Vos, Ser. No.
  • R is selected from the group consisting of:
  • each M is hydrogen or an alkali metal ion.
  • DHPIDA dihydroxyisopropylimino-(N,N)-diacetic acid
  • MIDA methylimino-(N,N)-diacetic acid
  • MEIDA 2-methoxyethylimino-(N,N)-diacetic acid
  • amidoiminodiacetic acid also known as sodium amidonitrilotriacetic, SAND
  • acetamidoiminodiacetic acid (AIDA)
  • MEPIDA 3-methoxypropylimino-N,N-diacetic acid
  • TRIDA tris(hydroxymethyl)methylimino-N,N-diacetic acid
  • the levels of builder present in the wash solution used for glass should be less than about 0.5%, preferably less than about 0.2%. Therefore, dilution is highly preferred for cleaning glass, while full strength use is preferred for general purpose cleaning.
  • detergent builders e.g., sodium citrate, sodium ethyl enediaminetetraacetate, etc.
  • Inclusion of a detergent builder improves cleaning, but harms spotting and filming and has to be considered as a compromise in favor of cleaning. Inclusion of a detergent builder is optional and low levels are usually more preferred than high levels.
  • perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. : 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel , issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Normally, the art recognized perfume compositions are not very substantive as described hereinafter to minimize their effect on hard surfaces.
  • the degree of substantivity of a perfume is roughly proportional to the percentages of substantive perfume material used.
  • Relatively substantive perfumes contain at least about 1%, preferably at least about 10%, substantive perfume materials.
  • Substantive perfume materials are those odorous compounds that deposit on surfaces via the cleaning process and are detectable by people with normal olfactory acuity. Such materials typically have vapor pressures lower than that of the average perfume material. Also, they typically have molecular weights of about 200 or above, and are detectable at levels below those of the average perfume material.
  • Perfumes can also be classified according to their volatility, as mentioned hereinbefore.
  • the highly volatile, low boiling, perfume ingredients typically have boiling points of about 250oC or lower. Many of the more moderately volatile perfume ingredients are also lost substantially in the cleaning process.
  • the moderately volatile perfume ingredients are those having boiling points of from about 250oC to about 300°C.
  • the less volatile, high boiling, perfume ingredients referred to hereinbefore are those having boiling points of about 300°C or higher. A significant portion of even these high boiling perfume ingredients, considered to be substantive, is lost during the cleaning cycle, and it is desirable to have means to retain more of these ingredients on the dry surfaces.
  • perfume ingredients along with their odor character, and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals),” Steffen Arctander, published by the author, 1969, incorporated herein by reference.
  • Examples of the highly volatile, low boiling, perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, iso-bornyl acetate, camphene, cis-citral (neral), citronellal, citronellol, citronellyl acetate, paracymene, decanal, dihydro!
  • inalool dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthyl acetate, menthone, iso-menthone, myrcene, myrcenyl acetate, myrcenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alphapinene, beta-pinene, gam
  • lavandin contains as major components: linalool; linalyl acetate; geraniol; and citronellol. Lemon oil and orange terpenes both contain about 95% of d-limonene.
  • moderately volatile perfume ingredients are: amyl cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin,. dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eugenol, flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamic aldehyde), gamma- methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta- selinene, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin, and veratraldehyde.
  • Cedarwood terpenes
  • Examples of the less volatile, high boiling, perfume ingredients are: benzophenone, benzyl salicylate, ethylene brassylate, galaxolide (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclo- penta-gama-2-benzopyran), hexyl cinnamic aldehyde, lyral (4-(4- hydroxy-4-methyl pentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyl dihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, musk ketone, musk tibetene, and phenylethyl phenyl acetate.
  • any particular perfume ingredient is primarily dictated by aesthetic considerations, but more water-soluble materials are preferred, as stated hereinbefore, since such materials are less likely to adversely affect the good spotting/- filming properties of the compositions. If the terpene types of perfume ingredients are used, the beta-aminoalkanols are preferred for product stability.
  • compositions have exceptionally good cleaning properties. They can also be formulated to have good "shine” properties, i.e., when used to clean glossy surfaces, without rinsing.
  • compositions can be formulated to be used at full strength, where the product is sprayed onto the surface to be cleaned and then wiped off with a suitable material like cloth, a paper towel, etc. They can be packaged in a package that comprises a means for creating a spray, e.g., a pump, aerosol propell ant and spray valve, etc.
  • Cocoamidipropyl-dimethyl- betaine 0.20 - -
  • Cocoamidopropyl-dimethyl-2- hydroxy-3-sulfopropylbetaine 0.19 0.15 0.18
  • the following example shows the Filming/Streaking performan for various formulations including the preferred zwitterionic alkanolamine combinations.
  • Propylene Glycol Monobutylether - - - Sodium Hydroxide - - - Deionized Water q.s. q.s. q.s. Ralufon® DL (Raschig Corp.) is Lauryl-dimethyl- ammonium-3-sulfopropyl 3-(lauryl,dimethyl,ammonium)- propylsulfonate)
  • Ralufon ® DL (Raschig Corp.) is Lauryl-dimethyl-ammonium- 3-sul fopropyl 3- (lauryl,dimethyl,ammoniurn)-propyl- sulfonate)
  • Example III the following test was used to evaluate the products' performance.
  • a paper towel is folded into eighths. Two milliliters of test product are applied to the upper half of the folded paper towel. The wetted towel is applied in one motion with even pressure from top to bottom of a previously cleaned window or mirror. The window or mirror with the applied product(s) is allowed to dry for ten minutes before grading by expert judges. Grading :
  • the least significant difference between mean ratings is 0.8 at 95% confidence level.

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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)
  • Detergent Compositions (AREA)
PCT/US1991/000337 1990-01-29 1991-01-22 Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol WO1991011505A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR1019920701779A KR927003772A (ko) 1990-01-29 1991-01-22 쯔비터이온성 세정 계면활성제 및 모노에탄올아민 및/또는 β-아미노알칸올을 함유하는 액체 경질 표면 세제 조성물
DE69129981T DE69129981T2 (de) 1990-01-29 1991-01-22 Zusammensetzung flüssiger reinigungsmittel für harte oberflächen, amphoterisches tensid und monoethanolamin und/oder beta-aminoalkanol enthaltend
EP91905371A EP0513240B1 (en) 1990-01-29 1991-01-22 Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol
BR919105962A BR9105962A (pt) 1990-01-29 1991-01-22 Composicoes de detergente liquido para superficies rigidas,contendo tensoativo detergente zwitterionico e monoetanolamina e/ou beta aminoalcanol
AU73426/91A AU659994B2 (en) 1990-01-29 1991-01-22 Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
US47190990A 1990-01-29 1990-01-29
US47190890A 1990-01-29 1990-01-29
US471,909 1990-01-29
US471,908 1990-01-29
US49985890A 1990-03-27 1990-03-27
US499,858 1990-03-27
US62806690A 1990-12-21 1990-12-21
US62806790A 1990-12-21 1990-12-21
US62806590A 1990-12-21 1990-12-21
US628,065 1990-12-21
US628,064 1990-12-21
US628,067 1990-12-21
US07/628,064 US5108660A (en) 1990-01-29 1990-12-21 Hard surface liquid detergent compositions containing hydrocarbyl amidoalkylenesulfobetaine
US628,066 1990-12-21

Publications (1)

Publication Number Publication Date
WO1991011505A1 true WO1991011505A1 (en) 1991-08-08

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ID=27569798

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PCT/US1991/000337 WO1991011505A1 (en) 1990-01-29 1991-01-22 Liquid hard surface detergent compositions containing zwitterionic detergent surfactant and monoethanolamine and/or beta-aminoalkanol

Country Status (14)

Country Link
EP (1) EP0513240B1 (es)
JP (1) JPH05503547A (es)
KR (1) KR927003772A (es)
CN (1) CN1036073C (es)
AR (1) AR245202A1 (es)
AU (1) AU659994B2 (es)
BR (1) BR9105962A (es)
CA (1) CA2074823C (es)
DE (1) DE69129981T2 (es)
ES (1) ES2119773T3 (es)
MX (1) MX173001B (es)
MY (1) MY107342A (es)
NZ (1) NZ236922A (es)
WO (1) WO1991011505A1 (es)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503219A1 (en) * 1991-03-11 1992-09-16 THE PROCTER & GAMBLE COMPANY Method and diluted cleaning composition for the cleaning of hard surfaces
WO1993015173A1 (en) * 1992-01-23 1993-08-05 The Procter & Gamble Company Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner
EP0595383A1 (en) * 1992-10-26 1994-05-04 The Procter & Gamble Company Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant
EP0630965A1 (en) * 1993-06-23 1994-12-28 The Procter & Gamble Company Concentrated liquid hard surface detergent compositions containing maleic acid-olefin copolymers
WO1995013345A1 (en) * 1993-11-12 1995-05-18 The Procter & Gamble Company Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume
WO1995018210A1 (en) * 1993-12-30 1995-07-06 The Procter & Gamble Company Liquid hard surface detergent compositions containing builders
US5468423A (en) * 1992-02-07 1995-11-21 The Clorox Company Reduced residue hard surface cleaner
EP0691397A2 (en) 1994-07-07 1996-01-10 The Clorox Company Antimicrobial hard surface cleaner
US5523024A (en) * 1992-02-07 1996-06-04 The Clorox Company Reduced residue hard surface cleaner
WO1996026263A1 (en) * 1995-02-23 1996-08-29 Unilever Plc Process and composition for cleaning surfaces
US5585342A (en) * 1995-03-24 1996-12-17 The Clorox Company Reduced residue hard surface cleaner
US5817615A (en) * 1992-02-07 1998-10-06 The Clorox Company Reduced residue hard surface cleaner
CN104194967A (zh) * 2014-09-19 2014-12-10 山东华亚环保科技有限公司 一种具有杀菌除油作用的高效玻璃清洗剂
CN113528253A (zh) * 2021-07-08 2021-10-22 福建省佑达环保材料有限公司 一种用于OLED掩膜版及坩埚表面LiF材料清洗的组合物

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TWI446400B (zh) * 2007-10-05 2014-07-21 Schott Ag Fluorescent lamp with lamp cleaning method
WO2012160462A2 (en) * 2011-05-20 2012-11-29 Ecolab Usa Inc. Non-corrosive oven degreaser concentrate

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US4257907A (en) * 1979-05-21 1981-03-24 Monsanto Company Disinfectant cleaning compositions
US4259217A (en) * 1978-03-07 1981-03-31 The Procter & Gamble Company Laundry detergent compositions having enhanced greasy and oily soil removal performance
US4414128A (en) * 1981-06-08 1983-11-08 The Procter & Gamble Company Liquid detergent compositions
US4698181A (en) * 1986-06-30 1987-10-06 The Procter & Gamble Company Detergent compositions containing triethylenetetraminehexaacetic acid
US4769169A (en) * 1985-09-10 1988-09-06 Amphoterics International Limited Amphoteric surfactants for use in antimicrobial cleaning compositions
US4810421A (en) * 1986-04-03 1989-03-07 The Procter & Gamble Company Liquid cleaner with organic solvent and ternary builder mixture
US4948531A (en) * 1988-11-22 1990-08-14 Sterling Drug Incorporated Liquid one-step hard surface cleaning/protector compositions

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US3876563A (en) * 1972-09-22 1975-04-08 Procter & Gamble Liquid detergent compositions
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US4421680A (en) * 1981-09-18 1983-12-20 Irving Shivar Cleaning and degreasing composition
US4554098A (en) * 1982-02-19 1985-11-19 Colgate-Palmolive Company Mild liquid detergent compositions
US4690779A (en) * 1983-06-16 1987-09-01 The Clorox Company Hard surface cleaning composition
DE3512535A1 (de) * 1985-04-06 1986-10-16 Henkel KGaA, 4000 Düsseldorf Verfahren zum manuellen reinigen von gegenstaenden mit harten oberflaechen
US4921629A (en) * 1988-04-13 1990-05-01 Colgate-Palmolive Company Heavy duty hard surface liquid detergent

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Publication number Priority date Publication date Assignee Title
US3928065A (en) * 1973-12-19 1975-12-23 Lever Brothers Ltd Composition for cleaning metal cookware
US4259217A (en) * 1978-03-07 1981-03-31 The Procter & Gamble Company Laundry detergent compositions having enhanced greasy and oily soil removal performance
US4257907A (en) * 1979-05-21 1981-03-24 Monsanto Company Disinfectant cleaning compositions
US4414128A (en) * 1981-06-08 1983-11-08 The Procter & Gamble Company Liquid detergent compositions
US4769169A (en) * 1985-09-10 1988-09-06 Amphoterics International Limited Amphoteric surfactants for use in antimicrobial cleaning compositions
US4810421A (en) * 1986-04-03 1989-03-07 The Procter & Gamble Company Liquid cleaner with organic solvent and ternary builder mixture
US4698181A (en) * 1986-06-30 1987-10-06 The Procter & Gamble Company Detergent compositions containing triethylenetetraminehexaacetic acid
US4948531A (en) * 1988-11-22 1990-08-14 Sterling Drug Incorporated Liquid one-step hard surface cleaning/protector compositions

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503219A1 (en) * 1991-03-11 1992-09-16 THE PROCTER & GAMBLE COMPANY Method and diluted cleaning composition for the cleaning of hard surfaces
TR26347A (tr) * 1992-01-23 1995-03-15 Procter & Gamble MELEZ IYONIK VE KATYONIK DETERJAN YüZEY AKTIF CISIMLERI VE MONOETANOLAMIN VE BETA-AMINOALKANOL ICEREN SERT YüZEY TEMIZLEYICI SIVI DETERJAN BILESIMLERI.
WO1993015173A1 (en) * 1992-01-23 1993-08-05 The Procter & Gamble Company Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol
US5817615A (en) * 1992-02-07 1998-10-06 The Clorox Company Reduced residue hard surface cleaner
CN1040455C (zh) * 1992-02-07 1998-10-28 克罗洛斯公司 减少残余物的硬表面除垢剂和方法
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner
US5523024A (en) * 1992-02-07 1996-06-04 The Clorox Company Reduced residue hard surface cleaner
US5468423A (en) * 1992-02-07 1995-11-21 The Clorox Company Reduced residue hard surface cleaner
US5437807A (en) * 1992-02-07 1995-08-01 The Clorox Company Reduced residue hard surface cleaner
EP0595383A1 (en) * 1992-10-26 1994-05-04 The Procter & Gamble Company Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant
EP0630965A1 (en) * 1993-06-23 1994-12-28 The Procter & Gamble Company Concentrated liquid hard surface detergent compositions containing maleic acid-olefin copolymers
WO1995013345A1 (en) * 1993-11-12 1995-05-18 The Procter & Gamble Company Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume
WO1995018210A1 (en) * 1993-12-30 1995-07-06 The Procter & Gamble Company Liquid hard surface detergent compositions containing builders
EP0691397A2 (en) 1994-07-07 1996-01-10 The Clorox Company Antimicrobial hard surface cleaner
WO1996026263A1 (en) * 1995-02-23 1996-08-29 Unilever Plc Process and composition for cleaning surfaces
US5585342A (en) * 1995-03-24 1996-12-17 The Clorox Company Reduced residue hard surface cleaner
US5714448A (en) * 1995-03-24 1998-02-03 The Clorox Company Reduced residue hard surface cleaner
US5851981A (en) * 1995-03-24 1998-12-22 The Clorox Company Reduced residue hard surface cleaner
CN104194967A (zh) * 2014-09-19 2014-12-10 山东华亚环保科技有限公司 一种具有杀菌除油作用的高效玻璃清洗剂
CN113528253A (zh) * 2021-07-08 2021-10-22 福建省佑达环保材料有限公司 一种用于OLED掩膜版及坩埚表面LiF材料清洗的组合物
CN113528253B (zh) * 2021-07-08 2023-04-11 福建省佑达环保材料有限公司 一种用于OLED掩膜版及坩埚表面LiF材料清洗的组合物

Also Published As

Publication number Publication date
CA2074823C (en) 1998-01-20
DE69129981T2 (de) 1999-04-15
CN1036073C (zh) 1997-10-08
EP0513240A1 (en) 1992-11-19
KR927003772A (ko) 1992-12-18
AU7342691A (en) 1991-08-21
CN1054265A (zh) 1991-09-04
EP0513240B1 (en) 1998-08-12
AU659994B2 (en) 1995-06-08
ES2119773T3 (es) 1998-10-16
NZ236922A (en) 1994-06-27
CA2074823A1 (en) 1991-07-30
MX173001B (es) 1994-01-27
BR9105962A (pt) 1992-10-20
AR245202A1 (es) 1993-12-30
MY107342A (en) 1995-11-30
EP0513240A4 (en) 1993-10-20
JPH05503547A (ja) 1993-06-10
DE69129981D1 (de) 1998-09-17

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