EP0513240B1 - 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 PDFInfo
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- EP0513240B1 EP0513240B1 EP91905371A EP91905371A EP0513240B1 EP 0513240 B1 EP0513240 B1 EP 0513240B1 EP 91905371 A EP91905371 A EP 91905371A EP 91905371 A EP91905371 A EP 91905371A EP 0513240 B1 EP0513240 B1 EP 0513240B1
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/92—Sulfobetaines ; Sulfitobetaines
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
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- 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
- C11D17/0043—For use with aerosol devices
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- 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
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 oily soil removal over-powdered cleaning compositions.
- 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.
- EP-A-337 576 discloses a heavy duty hard surface composition
- a surfactant selected from the group consisting of nonionic surfactant, amphoteric surfactant and mixtures thereof, about 2 % by weight of a builder, about 2 % by weight of alkanolamine selected from the group consisting of monoethanolamine, di- and tri- ethanolamine and from 2% to 8% by weight of a polar organic solvent.
- No hydrocarbylamidoalkylene sulfobetaines are disclosed.
- US 3 876 563 discloses a concentrated heavy-duty liquid detergent composition
- a concentrated heavy-duty liquid detergent composition comprising ethanolamine compound, from 25% to 80% by weight of a nonionic surfactant, and a zwitterionic surfactant in a weight ratio of the nonionic surfactant to the zwitterionic surfactant of from 1:1 to 8:1.
- No hydrocarbylamidoalkylene sulfobetaines are disclosed.
- US 4 690 779 discloses aqueous liquid surface cleaning compositions with surfactants selected from the group of anionic, nonionic, cationic and/or zwitterionic surfactants, a polymer and an aqueous solvent. No monoethanolamine and no beta-aminoalkanol are disclosed.
- US 4 158 644 discloses hard surface detergent compositions comprising an aqueous composition of a nonionic surfactant, a quaternary ammonium salt and a betaine. No monoethanolamine and no beta-aminoalkanol are disclosed.
- US 4 257 907 discloses an aqueous composition useful as disinfectant comprising ortho-benzyl-para-chlorophenol, naphthalene sulfonic acid, a sulfobetaine surfactant, an acrylic copolymer and an anionic surfactant. No monoethanolamine and no beta-aminoalkanol are disclosed.
- US 4 414 128 discloses liquid compositions comprising surfactants like anionic, nonionic and/or zwitterionic surfactants at a level of 1% to 20% by weight, monsesquiterpenes, polar solvents and up to 10% by weight of hydrotrope like monoethanolamine. No hydrocarbylamidoalkylene sulfobetaines are disclosed.
- GB 2 114 996 discloses detergent mixtures comprising anionic surfactants, zwitterionic surfactants and alkylalkanolamide. No monoethanolamine and no beta-aminoalkanol are disclosed.
- the present invention relates to an aqueous liquid hard surface detergent composition, particularly suitable for the cleaning of glass, comprising : (a) from 0.05% to 0.5% by weight of the total composition of a zwitterionic detergent surfactant, which has the formula : R 3 -[C(O)-N(R 4 )-(CR 5 2 ) n -] m N(R 6 ) 2 (+) -(CR 5 2 ) p -Y (-) wherein each R 3 is an alkyl, or alkylene group containing from 8 to 20 carbon atoms, each (R 4 ) and (R 6 ) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R 5 ) is selected from the group consisting of hydrogen and hydroxy groups, with no more than one hydroxy group in any (CR 5 2 ) moiety; m is 0 or 1, and each n and p is
- the present invention further relates to an aqueous liquid hard surface detergent composition, particularly suitable for the cleaning of glass, comprising : (a) from 0.001% to 15% by weight of the total composition of a zwitterionic detergent surfactant, which has the formula : R 3 -[C(O)-N(R 4 )-(CR 5 2 ) n -] m N(R 6 ) 2 (+) -(CR 5 2 ) p -Y (-) wherein each R 3 is an alkyl, or alkylene group containing from 8 to 20 carbon atoms, each (R 4 ) and (R 6 ) is selected from the group consisting of hydrogen, methyl, ethyl, propyl, hydroxy substituted ethyl or propyl and mixtures thereof, each (R 5 ) is selected from the group consisting of hydrogen and hydroxy groups, with no more than one hydroxy group in any (CR 5 2 ) moiety; m is 1, and each n and p is a number from
- compositions preferably do 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 surfacrs 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-aminoalkanol 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.
- Suitable zwitterionic detergent surfactants for use herein contain a cationic group, preferably a quaternary ammonium group, and an anionic group, preferably carboxylate, and sulfonate group, more preferably sulfonate.
- 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 the pH range of interest for cleaning hard surfaces.
- the sulfonate group is the preferred anionic group.
- Preferred zwitterionic detergent surfactants have the generic formula: R 3 -[C(O)-N(R 4 )-(CR 5 2 ) n ] m N(R 6 ) 2 (+) -(CR 5 2 ) p -Y (-) wherein 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 8 to 20, preferably from 10 to 18, more preferably from 12 to 16 carbon atoms; wherein each (R 4 ) is either hydrogen, or a short chain alkyl, or substituted alkyl, containing from one to 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
- 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 exellent 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 -C 14 fatty acylamidopropylene (hydroxypropylene) sulfobetaine, e.g., the detergent surfactant available from the Sherex company as a 40% active product under the trade name "Varion CAS® Sulfobetaine".
- the composition particularly suitable for the cleaning of glass when used full strength, or wash solution containing the composition, should contain from 0.02% to 0.5% by weight of the zwitterionic detergent surfactant as described herein before, preferably from 0.05% to 0.5%, more preferably from 0.1 % to 0.25%.
- the zwitterionic surfactant is a hydrocarbylamidoalkylene sulfobetaine (i.e. wherein m is 1 and Y is sulfonate group)
- the level of said hydrocarbylamidoalkylene sulfobetaine surfactant is from 0.001% to 15%, preferably from 0.02% to 10%, more preferably from 0.05% to 10%, even more preferably from 0.1% to 5%, and more preferably from 0.2% to 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 0.02% to 1%, preferably from 0.05% to 0.5%, more preferably from 0.1% to 0.25%, of said detergent surfactant.
- the level can, and should be, higher, typically from 0.1% to 10%, preferably from 0.25% to 2%.
- Concentrated products will typically contain from 0.2% to 10%, preferably from 0.3% to 5%. It is an advantage of such 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.
- Such zwitterionic detergents are also extremely effective at very low levels, e.g., below 1%.
- zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat. No. 4,287,080, Siklosi. 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. Commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1984, McCutcheon Division, MC Publishing Company.
- 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 detergency 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 9 to 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 herein contain 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 5 to 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 8 carbons to 16 carbon atoms and having an average carbon chain length of from 10 to 12 carbon atoms with from 4 to 8 moles of ethylene oxide per mole
- 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 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. Other similar materials that are solvents do not provide the same benefit and the effect can be different depending upon the other materials present. When perfumes that have a high percentage of terpenes are incorporated, the benefit is greater for the beta-alkanolamines, and they are often preferred, whereas the monoethanolamine is usually preferred.
- Monoethanolamine and/or beta-alkanolamine are used at a level of from 0.05% to 10%, preferably from 0.2% to 5%.
- dilute compositions they are typically present at a level of from 0.05% to 2%, preferably from 0.1% to 1.0%, more preferably from 0.2% to 0.7%.
- concentrated compositions they are typically present at a level of from 0.5% to 10%, preferably from 1% to 5%.
- Preferred beta-aminoalkanols have a primary hydroxy group.
- Suitable beta-aminoalkanols have the formula: wherein 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 beta-aminoalkanols preferably have boiling points below about 175°C. Preferably, the boiling point is within 5°C of 165°C.
- 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.
- a useful definition of such solvents can be derived from the solubility parameters as set forth in "The Hoy,” a publication of Union Carbide.
- hydrogen bonding parameters are preferably less than about 7.7, more preferably from 2 to 7, and even more preferably from 3 to 6. Solvents with lower numbers become increasingly difficult to solubilize in the compositions and have a greater tendency to cause a haze on glass. Higher numbers require more solvent to provide good greasy/oily soil cleaning.
- Cosolvents are typically used at a level of from 1% to 30%, preferably from 2% to 15%, more preferably from 4% to 8%.
- Dilute compositions typically have cosolvents at a level of from 1% to 10%, preferably from 3% to 6%.
- Concentrated compositions contain from 10% to 30%, preferably from 10% to 20% of cosolvent.
- 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 20°C.
- 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 3 to 8 carbon atoms, each R 7 is either ethylene or propylene, and m is a number from 1 to 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 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 20°C.
- 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 9.5 to 13, preferably from 9.7 to 12, more preferably from 9.7 to 11.5. pH is usually measured on the product.
- the buffering system comprises monoethanolamine and/or beta-aminoalkanol 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 5%, preferably from 0% to 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 0.5% to 40%, preferably from 1% to 10% and the level of water is from 50% to 99%, preferably from 75% to 95%.
- 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:
- 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 30%, preferably from 1% to 15%, more preferably from 1% to 12%, of detergent builder.
- a level of builder of from 0.1% to 0.5%, preferably from 0.1% to 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-diphosphonate, the nonphosphorous chelating agents described in the copending U.S. Pat. Application of Culshaw and Vos, Ser. No. 285,337, filed Dec.
- 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 ethylenediaminetetraacetate, 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. 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.
- Relati-vely 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 250°C 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 250°C to 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.
- 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, para-cymene, decanal, dihydrolinalool, 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 acetaldehy
- 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 are
- 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-cyclopenta-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 propellant and spray valve, etc.
- EXAMPLE I Formula No. (Wt.%) Ingredient 1 2 3 4 Propylene Glycol Monobutylether 2.0 2.0 2.0 2.0 Isopropanol 5.0 5.0 5.0 5.0 Cocoamidopropyl (Hydroxypropyl)sulfobetaine 0.15 0.15 0.15 0.15 Monoethanolamine 1.0 - - - 1-amino-2-propanol - 1.0 - - 2-amino-1-butanol - - 1.0 - 2-amino-2-methyl-1-butanol - - - 1.0 Perfume 0.20 0.20 0.20 0.20 0.20 0.20 Deionized Water q.s. q.s. q.s. q.s.
- the following example shows the Filming/Streaking performance for various formulations including the preferred zwitterionic/alkanolamine combinations.
- 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.
Landscapes
- 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)
Applications Claiming Priority (15)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US471908 | 1983-03-03 | ||
US628067 | 1984-07-05 | ||
US47190990A | 1990-01-29 | 1990-01-29 | |
US47190890A | 1990-01-29 | 1990-01-29 | |
US49985890A | 1990-03-27 | 1990-03-27 | |
US499858 | 1990-03-27 | ||
US62806590A | 1990-12-21 | 1990-12-21 | |
US62806790A | 1990-12-21 | 1990-12-21 | |
US62806690A | 1990-12-21 | 1990-12-21 | |
US07/628,064 US5108660A (en) | 1990-01-29 | 1990-12-21 | Hard surface liquid detergent compositions containing hydrocarbyl amidoalkylenesulfobetaine |
US628065 | 1990-12-21 | ||
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 |
US628064 | 1996-04-04 | ||
US471909 | 1999-12-23 | ||
US628066 | 2000-07-28 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0513240A1 EP0513240A1 (en) | 1992-11-19 |
EP0513240A4 EP0513240A4 (en) | 1993-10-20 |
EP0513240B1 true EP0513240B1 (en) | 1998-08-12 |
Family
ID=27569798
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91905371A Expired - Lifetime EP0513240B1 (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) |
Families Citing this family (17)
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 |
AU3473093A (en) * | 1992-01-23 | 1993-09-01 | Procter & Gamble Company, The | 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 |
US5468423A (en) * | 1992-02-07 | 1995-11-21 | The Clorox Company | Reduced residue hard surface cleaner |
US5817615A (en) * | 1992-02-07 | 1998-10-06 | The Clorox Company | Reduced residue hard surface cleaner |
US5585342A (en) * | 1995-03-24 | 1996-12-17 | The Clorox Company | Reduced residue hard surface cleaner |
US5523024A (en) * | 1992-02-07 | 1996-06-04 | The Clorox Company | Reduced residue hard surface cleaner |
ES2100444T3 (es) * | 1992-10-26 | 1997-06-16 | Procter & Gamble | Composiciones detergentes liquidas para superficies duras que contienen tensioactivo detergente de anfocarboxilato de cadena corta. |
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 |
US5531933A (en) * | 1993-12-30 | 1996-07-02 | The Procter & Gamble Company | Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders |
ES2229226T3 (es) | 1994-07-07 | 2005-04-16 | The Clorox Company | Producto de limpieza antimicrobiano para superficies duras. |
KR19980702442A (ko) * | 1995-02-23 | 1998-07-15 | 에스 제이 에드워즈 | 표면 세정 방법 및 조성물 |
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 |
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 |
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 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA751361A (en) * | 1962-03-15 | 1967-01-24 | Wathne Sigvard | Preparation for internal cleaning ovens |
US3876563A (en) * | 1972-09-22 | 1975-04-08 | Procter & Gamble | Liquid detergent compositions |
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 |
US4158644A (en) * | 1978-03-17 | 1979-06-19 | Kewanee Industries, Inc. | Cleaner and grease emulsifier |
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 |
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 |
GB8522413D0 (en) * | 1985-09-10 | 1985-10-16 | Amphoterics International Ltd | Surfactants |
GB8608148D0 (en) * | 1986-04-03 | 1986-05-08 | Procter & Gamble | Liquid cleaner |
US4698181A (en) * | 1986-06-30 | 1987-10-06 | The Procter & Gamble Company | Detergent compositions containing triethylenetetraminehexaacetic acid |
US4921629A (en) * | 1988-04-13 | 1990-05-01 | Colgate-Palmolive Company | Heavy duty hard surface liquid detergent |
US4948531A (en) * | 1988-11-22 | 1990-08-14 | Sterling Drug Incorporated | Liquid one-step hard surface cleaning/protector compositions |
-
1991
- 1991-01-22 EP EP91905371A patent/EP0513240B1/en not_active Expired - Lifetime
- 1991-01-22 WO PCT/US1991/000337 patent/WO1991011505A1/en active IP Right Grant
- 1991-01-22 JP JP3505042A patent/JPH05503547A/ja active Pending
- 1991-01-22 BR BR919105962A patent/BR9105962A/pt not_active Application Discontinuation
- 1991-01-22 DE DE69129981T patent/DE69129981T2/de not_active Expired - Fee Related
- 1991-01-22 KR KR1019920701779A patent/KR927003772A/ko not_active Application Discontinuation
- 1991-01-22 CA CA002074823A patent/CA2074823C/en not_active Expired - Fee Related
- 1991-01-22 ES ES91905371T patent/ES2119773T3/es not_active Expired - Lifetime
- 1991-01-22 AU AU73426/91A patent/AU659994B2/en not_active Ceased
- 1991-01-25 MY MYPI91000124A patent/MY107342A/en unknown
- 1991-01-28 AR AR91318928A patent/AR245202A1/es active
- 1991-01-28 NZ NZ236922A patent/NZ236922A/en unknown
- 1991-01-28 MX MX024313A patent/MX173001B/es unknown
- 1991-01-29 CN CN91100662A patent/CN1036073C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CA2074823C (en) | 1998-01-20 |
DE69129981T2 (de) | 1999-04-15 |
WO1991011505A1 (en) | 1991-08-08 |
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 |
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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