CA1140831A - Abrasive-containing liquid detergent composition and non-clogging dispensing package - Google Patents
Abrasive-containing liquid detergent composition and non-clogging dispensing packageInfo
- Publication number
- CA1140831A CA1140831A CA000354964A CA354964A CA1140831A CA 1140831 A CA1140831 A CA 1140831A CA 000354964 A CA000354964 A CA 000354964A CA 354964 A CA354964 A CA 354964A CA 1140831 A CA1140831 A CA 1140831A
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- Prior art keywords
- abrasive
- clog
- liquid detergent
- containing liquid
- sealing member
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- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Closures For Containers (AREA)
Abstract
Abstract Liquid detergent compositions containing a surfactant and an abrasive are disclosed in combination with a package comprising a flexible container and a clog-resistant closure characterized by a domed shape and external sealing means.
Description
83~
Background The invention relates to the combination of a liquid detergent containing specified amounts and types of insolu-ble abrasives especially useful in the washing of tableware, kitchenware and other hard surfaces and a package which provides convenient dispensing of the detergent composition without clogging.
The use of abrasives in powdered scouring cleansers is well known. Scouring cleansers generally contain a rela-tively high level of abrasive. When such scouring cleansers are used as adjuncts in the dishwashing process such products provide abracing power to make the removal of cooked, burnt or dried-on food foods on kitchenware easier and more convenient. Recently, liquid scouring cleansers containing water-insoluble abrasives have become available. Such liquid compositions are disclosed in U.S. Patents 3,149,078;
3,210,285; 3,210,286; 3,214,380; 3,579,456; 3,623,990;
3,677,954; 3,813,349; 3,966,432; and 4,129,527; and British Patents 1,384,244 qand 1,534,680. The use of scouring cleansers, however, is normally in addition to a specific dishwashing product, one product being required for removal of non-sticking soils, especially fats and oils, and a second product being required for scouring purposes.
Canadian Patent 1,048,365 discloses granular detergent compositions suitable for dishwashing containing 20% to 35% surfactant and 5% to 20% of abrasive material having a particle diameter in the range of 200 to 850 microns.
Copending commonly assigned Canadian Patent Application Serial No. 343,185, of Mitchell et al filed January 7, 1980, discloses liquid detergent compositions suitable for dishwashing containing insoluble abrasives and detergency builders.
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)831
Background The invention relates to the combination of a liquid detergent containing specified amounts and types of insolu-ble abrasives especially useful in the washing of tableware, kitchenware and other hard surfaces and a package which provides convenient dispensing of the detergent composition without clogging.
The use of abrasives in powdered scouring cleansers is well known. Scouring cleansers generally contain a rela-tively high level of abrasive. When such scouring cleansers are used as adjuncts in the dishwashing process such products provide abracing power to make the removal of cooked, burnt or dried-on food foods on kitchenware easier and more convenient. Recently, liquid scouring cleansers containing water-insoluble abrasives have become available. Such liquid compositions are disclosed in U.S. Patents 3,149,078;
3,210,285; 3,210,286; 3,214,380; 3,579,456; 3,623,990;
3,677,954; 3,813,349; 3,966,432; and 4,129,527; and British Patents 1,384,244 qand 1,534,680. The use of scouring cleansers, however, is normally in addition to a specific dishwashing product, one product being required for removal of non-sticking soils, especially fats and oils, and a second product being required for scouring purposes.
Canadian Patent 1,048,365 discloses granular detergent compositions suitable for dishwashing containing 20% to 35% surfactant and 5% to 20% of abrasive material having a particle diameter in the range of 200 to 850 microns.
Copending commonly assigned Canadian Patent Application Serial No. 343,185, of Mitchell et al filed January 7, 1980, discloses liquid detergent compositions suitable for dishwashing containing insoluble abrasives and detergency builders.
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)831
- 2 -It is an ob;ect of the present invention to provideliquid detergent compositions containing a surfactant and an abrasive in a non-clogging dispensing package, the detergent composition being highly effective in removing food soils from kitchenware when used undiluted or in the form of a relatively concentrated water sl~rry, but which in a preferred embodiment is acceptable for hand dishwashing in_ the dilute water solutions typically used with liquid dishwashing products. It is a further object to provide 'a package suitable for such a product.
Summary of the.In~ention .
The present invention comprises as one.essential element a liquid.detergent composition containing by weight:
a) from about 0.2% to about 50~ of a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic s~rfactants and mixtures thereof;
;b) from about 1% to abou~ 20% of a water^-insoluble abrasive having a particle diameter of from about . : 20 ~ 15 to about 150 microns and a hardness on the Mohs .' scale of from about 2 to about 7; and c) from about 20g to about 80% water.
; ' The essential package characteristics are:
- a) a flexible plastic container adapated to provide i 25 . an increase in internal pressure by application of ~; . compressive forces to one or more external surface areas, and b) a clog resistant dispensing closure adapted to be mounted on said flexible plast'ic container, said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container . finish, means for attaching said skirt to said . ' container finish and a domed nozæle section with a 35 . central aperture, said aperture having an hori-zontal cross sectional area from about 0.002 square inches to about 0.025 square inches, pre-ferably from about 0.005 square inches to about .015 square inches, a minimum diameter of about S;~ r- .
~ 114~)831 0.05 inches preferably 0.08 inches, and a length of no more than about 0.25 inches, said bail-like sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in a closed position.
Detailed Descriptlon of the In~ention The detergent compositions o the present invention contain three essential components: ' a) a surfactant' b) a water-insoluble abrasive c) water.
Optional ingredients can be'added' to provide various per-! formance and aesthetic characteristics.
'Surfactant The' compositions of this invention contain from about j 20 0.2% to about 50% of a surfactant selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic ~urface actlve agents and mixtures thereof. Preferred ' composi~ions for use as a complete dishwashing product - contain from about 15% to about 40~ of surfactant by weight of the composition. Especially preferred are anionic surfactants and mixtures of anionic and-nonionic surfac-tan~ts.
Many anionic detergents can be broadly described as the water-soluble salts, particularly the alkali metal, alkaline earth metal, ammonium and amine salts, of organic sulfuric reaction products havtng in their molecular struature an alkyl radical containing from a~out 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. ~ncluded in the term alk~l is the alkyl portion of high acyl radicals.
Examples of the anionic synthetic detergents which can form .. . . , - ~ , .
114~831;
- the surfactant component of the compositions of the present invention are the sodium, ammonium or potassium alkyl sul-fates, especially those obtained by sulfatin~ the higher alcohols (C8-C18 carbon atoms) sodium or potassium alkyl benzene or toluene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain~; ~
sodium or potassium paraffin sulfonates and olefin sul-fonates in which the alkyl or alkenyl ,-oup contains from about 10 to about 20 carbon atoms; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with àbout 1 to about 30 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid and neutralized with L sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty . acid amides of a methyl tauride in which the fatty acids,.I for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
~, 2~ Specific examples of alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alXyl sulfate,: sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate and mixtures of these surfactants. Highly preferred : alkyl sulfates are sodium coconut alkyl sulfate, potassium .. . ......
. - ~ - r-l coconut alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.
Suitable alkylbenzene or alkyltoluene sulfonates include the alkali metal (lithium, sodium, potassium), alkaline earth (calcium, magnesium) and alkanolamine salts of straight-or branched-chain alkylbenzene or alkyltoluene sulfonic acids.
Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tri-decyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid. Preferred sulfonic acids as precursors of the alkyl-benzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages about 12 carbon atoms in length. Examples of commercially available alkyl benzene sulfonic acids useful in the present inven-tion include Conoc ~ SA 515 and SA 597 marketed by the Continental Oil Company and Calsoft~LAS 99 marketed by the Pilot Chemical Company.
Particularly preferred anionic surfactants useful herein are alkyl ether sulfates having the formula RO(C2H4O)XSO3M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a watersoluble cation. The alkyl ether sulfates useful in the present invention are con-densation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. Preferably, R has 12 to 18 carton atoms. The alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be synthetic. Such alcohols are reacted with 1 to 30, and especially 1 to 12, molar proportions of ethylene oxide and the resulting mixture of molecular species is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl triethylene glycol ether sulfate, magnesium tallow alkyl triethylene glycoI ether sulfate, and sodium tallow alkyl hexaoxy ethylene sulfate.
Preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture .. ..
. .
having an average alkyl chain length of from about 12 to 16 carbon atoms and an average degree of ethoxylation of from about 1 to 12 moles of ethylene oxide.
Additional examples of anionic surfactants useful herein are the compounds which contain two anionic func- -tional groups. These are referred to as di-anionic sur-factants. Suitable dianionic surfactants are the disul-fonates, disulfates, or mixtures thereof which may be represented by thé following formula:
( 3)2M2~R(S04)2M2,R(so3) (S04)M2 where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C15 to C20 disodium 1,2-alkyldisulfates, C15 to C20 dipotassium-1,2-alkyldisulfonates or disulfates, di-sodium l,9-hexadecyl disulfates, C15 to C20 disodium 1,?-! alkyldisulfonates, disodium 1,9-stearyldisulfates and 6,10-octadecyldisulfates.
Nonionic surface active agents operable in the instant compositions can be any of three basic types -- ~he alkylene oxide condensates, the amides and the-semi-polar nonionics.
The alkylene oxide condensates are broadly defined as compounds produced by the condensation of a}kylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in -nature. The length of the hydrophilic or polyoxyalkylene radical 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.
Examplès of such alkylene oxide condensates include:
(1) The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be stra~ght or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of trideca-nol, myristyl alcohol condensed with about 10 moles of ... . ~.. .. . .. ...... ... ... .. .. . ~_, .. _, .. _ .. _ .. . .. .. _.. __ ._ _ .. _ . _. . .. ...... .. _ ._.. . .. ... .
V83~
ethylene oxide per mole of myristyl alcohol, the condensa-tion product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-desc,-ibed coconut alcohol. An example of a commercially available nonionic surfactant of this type includes Neodol~ 23-6.5 marketed by the Shell Chemical Compan~.
(2) The polyethylene oxide condensates of alkyl phenols.
The~e compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, octene, or nonen. Examples of com-pounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di-isooctylphenol con-densed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal~ CO-610 marketed by the GAF Corporation;
- and Triton~ X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
Summary of the.In~ention .
The present invention comprises as one.essential element a liquid.detergent composition containing by weight:
a) from about 0.2% to about 50~ of a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic s~rfactants and mixtures thereof;
;b) from about 1% to abou~ 20% of a water^-insoluble abrasive having a particle diameter of from about . : 20 ~ 15 to about 150 microns and a hardness on the Mohs .' scale of from about 2 to about 7; and c) from about 20g to about 80% water.
; ' The essential package characteristics are:
- a) a flexible plastic container adapated to provide i 25 . an increase in internal pressure by application of ~; . compressive forces to one or more external surface areas, and b) a clog resistant dispensing closure adapted to be mounted on said flexible plast'ic container, said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container . finish, means for attaching said skirt to said . ' container finish and a domed nozæle section with a 35 . central aperture, said aperture having an hori-zontal cross sectional area from about 0.002 square inches to about 0.025 square inches, pre-ferably from about 0.005 square inches to about .015 square inches, a minimum diameter of about S;~ r- .
~ 114~)831 0.05 inches preferably 0.08 inches, and a length of no more than about 0.25 inches, said bail-like sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in a closed position.
Detailed Descriptlon of the In~ention The detergent compositions o the present invention contain three essential components: ' a) a surfactant' b) a water-insoluble abrasive c) water.
Optional ingredients can be'added' to provide various per-! formance and aesthetic characteristics.
'Surfactant The' compositions of this invention contain from about j 20 0.2% to about 50% of a surfactant selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic ~urface actlve agents and mixtures thereof. Preferred ' composi~ions for use as a complete dishwashing product - contain from about 15% to about 40~ of surfactant by weight of the composition. Especially preferred are anionic surfactants and mixtures of anionic and-nonionic surfac-tan~ts.
Many anionic detergents can be broadly described as the water-soluble salts, particularly the alkali metal, alkaline earth metal, ammonium and amine salts, of organic sulfuric reaction products havtng in their molecular struature an alkyl radical containing from a~out 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. ~ncluded in the term alk~l is the alkyl portion of high acyl radicals.
Examples of the anionic synthetic detergents which can form .. . . , - ~ , .
114~831;
- the surfactant component of the compositions of the present invention are the sodium, ammonium or potassium alkyl sul-fates, especially those obtained by sulfatin~ the higher alcohols (C8-C18 carbon atoms) sodium or potassium alkyl benzene or toluene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain~; ~
sodium or potassium paraffin sulfonates and olefin sul-fonates in which the alkyl or alkenyl ,-oup contains from about 10 to about 20 carbon atoms; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with àbout 1 to about 30 units of ethylene oxide per molecule and in which the alkyl radicals contain from 8 to about 12 carbon atoms; the reaction products of fatty acids esterified with isethionic acid and neutralized with L sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty . acid amides of a methyl tauride in which the fatty acids,.I for example, are derived from coconut oil and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.
~, 2~ Specific examples of alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alXyl sulfate,: sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate and mixtures of these surfactants. Highly preferred : alkyl sulfates are sodium coconut alkyl sulfate, potassium .. . ......
. - ~ - r-l coconut alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.
Suitable alkylbenzene or alkyltoluene sulfonates include the alkali metal (lithium, sodium, potassium), alkaline earth (calcium, magnesium) and alkanolamine salts of straight-or branched-chain alkylbenzene or alkyltoluene sulfonic acids.
Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tri-decyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid. Preferred sulfonic acids as precursors of the alkyl-benzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages about 12 carbon atoms in length. Examples of commercially available alkyl benzene sulfonic acids useful in the present inven-tion include Conoc ~ SA 515 and SA 597 marketed by the Continental Oil Company and Calsoft~LAS 99 marketed by the Pilot Chemical Company.
Particularly preferred anionic surfactants useful herein are alkyl ether sulfates having the formula RO(C2H4O)XSO3M
wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a watersoluble cation. The alkyl ether sulfates useful in the present invention are con-densation products of ethylene oxide and monohydric alcohols having from about 10 to about 20 carbon atoms. Preferably, R has 12 to 18 carton atoms. The alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be synthetic. Such alcohols are reacted with 1 to 30, and especially 1 to 12, molar proportions of ethylene oxide and the resulting mixture of molecular species is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present invention are sodium coconut alkyl triethylene glycol ether sulfate, magnesium tallow alkyl triethylene glycoI ether sulfate, and sodium tallow alkyl hexaoxy ethylene sulfate.
Preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture .. ..
. .
having an average alkyl chain length of from about 12 to 16 carbon atoms and an average degree of ethoxylation of from about 1 to 12 moles of ethylene oxide.
Additional examples of anionic surfactants useful herein are the compounds which contain two anionic func- -tional groups. These are referred to as di-anionic sur-factants. Suitable dianionic surfactants are the disul-fonates, disulfates, or mixtures thereof which may be represented by thé following formula:
( 3)2M2~R(S04)2M2,R(so3) (S04)M2 where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C15 to C20 disodium 1,2-alkyldisulfates, C15 to C20 dipotassium-1,2-alkyldisulfonates or disulfates, di-sodium l,9-hexadecyl disulfates, C15 to C20 disodium 1,?-! alkyldisulfonates, disodium 1,9-stearyldisulfates and 6,10-octadecyldisulfates.
Nonionic surface active agents operable in the instant compositions can be any of three basic types -- ~he alkylene oxide condensates, the amides and the-semi-polar nonionics.
The alkylene oxide condensates are broadly defined as compounds produced by the condensation of a}kylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in -nature. The length of the hydrophilic or polyoxyalkylene radical 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.
Examplès of such alkylene oxide condensates include:
(1) The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be stra~ght or branched and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxide with 1 mole of trideca-nol, myristyl alcohol condensed with about 10 moles of ... . ~.. .. . .. ...... ... ... .. .. . ~_, .. _, .. _ .. _ .. . .. .. _.. __ ._ _ .. _ . _. . .. ...... .. _ ._.. . .. ... .
V83~
ethylene oxide per mole of myristyl alcohol, the condensa-tion product of ethylene oxide with coconut fatty alcohol wherein the coconut alcohol is a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensation product of about 9 moles of ethylene oxide with the above-desc,-ibed coconut alcohol. An example of a commercially available nonionic surfactant of this type includes Neodol~ 23-6.5 marketed by the Shell Chemical Compan~.
(2) The polyethylene oxide condensates of alkyl phenols.
The~e compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, octene, or nonen. Examples of com-pounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol, di-isooctylphenol con-densed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal~ CO-610 marketed by the GAF Corporation;
- and Triton~ X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company.
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and of course exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water-solubility of the molecule as a A
. . . ~
~, ~
)831 whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the tota' weight of the condensation product.
Examples of compounds of this type include certain of the commercially available Pluronic~ surfactants marketed by the Wyandotte Chemicals Corporation.
. . . ~
~, ~
)831 whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the tota' weight of the condensation product.
Examples of compounds of this type include certain of the commercially available Pluronic~ surfactants marketed by the Wyandotte Chemicals Corporation.
(4) The condensation products of ethylene oxide with the product resulting form the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products consists of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of from about 2500 to about 3000. This base is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about
5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic~ compounds marketed by the Wyandotte Chemicals Corporation.
Examples of the amide type of nonionic surface active agent include the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
Examples of the semi-polar type of nonionic surface active agents are the amine oxides, phosphine oxides and sulfoxides. These materials are described more fully in Berry, U.S. Patent 3,819,528, issued June 25, 1974.
Particularly preferred are amine oxides of the formula:
..~
~ ,.--.. .~.... . . ~
.: .
1)831 `~ g _ .
i Rl - N i_ O
herein R1 is a Cl0-l8 alkyl and R2 and R3 are methyl or ethyl.
Ampholytic synthetic detergents can be broadly des-cribed as deri~ati~es of aliphatic amir.es which contain a long chain of about 8 to 18 carbon atoms and an anionic water-solubilizing group, e.g. carboxyr ~ulfo or sulfato~
E~amples of compounds falling within this definition are sodium 3-dodecylamino-propionate, sodium-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
Zwitterionic surface active agents operable in the instant composition are broadly described as internally-neutralized derivatives of aliphatic quaternary ammonium andphosphonium and tertiary sulfonium compounds in which ~he aliphatic radical c~n be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phos-phato, or phosphono.
I In a preferred embodiment o~ the invention in which the t,, detergent composition can be used as a complete dishwashing product, the level and type of surfactant used in the compositions of this invention provide an initial suds cover to a dishwashing solution and a suds co~er after ~he washing of 8 plates when used at a concentration o~ 0.07% in 2 gallons of 115~. water containing 7 grains/ gallon water hardness measured as CaCO3, each plate carrying 4.0 ml of a triglyceride containing soil. Suds are generated by mech-anical agitation and the suds cover and height measured. A
dinner plate carrying the soil is washed successively with the introduction of 4.0 ml of soil each time. An essen-tially complete suds cover of the washing solution is more important than suds height, but, preferably, the suds cover after the washing of 8 plates is at least about 1/2 inch in height.
.. _ ., .... ~.. , . .. .. , .. .............. .. __ _. __~
~1~0~331 ' The sudsing characteristic of the preferred high-sudsing compositions of the invention is that necessary to . . provide the user of the product with an indication of ; cleaning potential in a dishwashing solution~ Soils en-countered in dishwashing act as suds depressants and the presence or absence of suds fxom the surface of a dish-washing solution is a convenient guide to product usage.
Mixtures of anionic surfactants and nonionic surfactants, ~
especially amides and amine oxide nonionic surfactants, are particularly p~eferred in the compositions of the invention because of their high sudsing chaxacteristics,..their suds stability in the presence of food soils-and their. ability to indicate accurately an adequate level of product-usage in thé presence of-soil. A preferred ratio o~ anionic sur-factants to nonionic suractants is from abo~t 2:-1 to about ~ lO:l;by weight. ~
Cationic surfactants such as quaternary ammonium i compounds can find optional use.in.the;p~actice of the .
, invention, particularly in compositions containing nonionic .. . . . .
.~ 20 surfactants~ ............. .... .... -ABRASIVE
The abrasive agent can be any of the water-insoluble abrasive materials known.in the art which have a particle ~ ~ diameter of from about 15 to about 150, preferably from .~ 25 about 35 to about 125, microns and a hardness on the Mohs . . , scale of from about 2 to about 7. Included are materials such as agate, mica, calcite, garnet, quartz, kieselguhr, silica, marble, tripoli, flint, ~eldspar, emexy, pumice, alumina, perlite, expanded perlite, volcanlc ashj diato-maceous earth, bentonite, amorphous silica from dehydrated silica gels, precipitated silica, plastics such as poly-styrene and polyacrylates, and natural and synthetlc alumi-nosilicates and mixtures thereof.
The amount of abrasive included in the compositions is in the range of from about 1% to about 20% o~ the total composition by weight. Preferred compositions contain from about 5~ to about 10% by weight of abrasive.
?i . r .
OPTIONAL DETEROENCY BUILDER
The compositions of this in~ention can contain up to about 20~, preferably from about 5% to about 15~, by weight of detergency builders either of the organic or inorganic types. Examples of water-soluble inorganic builders which can be used, alone or in admixture wilh themselves ana organic alkaline sequestrant builder sal_s ! are alkali metal carbonates, polyphosphates, and silica~es. Specific ex-amples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate. Examples of organic builder salts which can be used alone, or in admixture with each other or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, e.g., watér-soluble citrates such as sodi~m and potassium citrate, sodilim and potassium tartrate, sodium and potasslum ethylenediaminetetraa~etate, ~- sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodlum and potassium N-(2-hydroxyethyl)-nitrilo diace-tates. Other organic builder salts include the alkali metalsalts of phytic acid, e.g., sodium phytate (see U.S. Patent 2,739,942). Water-soluble salts of ethane-l-hydroxy-l,l-diphosphonate (EHDP) are also suitable. Mixtures of any of the preceding water-soluble organic or inorganic builder salts can be used.
The compositions of this inVention can contain insolu-ble builder salts selected from certain zeolites or alumi-nosilicates. One such aluminosilicate which is useful in the compositions of the invention is water-insoluble cry-stalline aluminosilicate ion exchange material of theformula:
Naz~(AlO2)z^tSiO2)y] xH2O
;, - wherein Z and y are at least 6, the molar ratio of Z to y is from 1.0 to 0.5 and x is from 10 to 264, said material , 114Q83~
having a particle size diameter of from about 0.1 micron to about 10 microns, a calcium ion exchange capacity of at least about 200 mg. CaCO3eq./gram and a calcium ion exchange rate of at least about 2 grains Ca++/gallon/ minute/gram.
This ion exchange builder is more fully described in Belgian Patent 814,874 issued on November 12, 1974 to Corkill et al.
A preferred aluminosilicate of this type is Zeolite~ A.
A second water insoluble aluminosilicate ion exchange material useful herein is water-insoluble amorphous hydrated aluminosilicate material of the emperical formula:
MZ(ZA102-YSiO2) wherein M is sodium, potassium, ammonium, or substituted ammonium, Z is from about 0.5 to about 2, y is 1 and said material having a particle size diameter of less than 100, preferably less than 10, microns, a magnesium ion exchange capacity of at least about 50 milligrams equivalent of CaCO3 hardness per gram of anhydrous aluminosilicate and a mg+ exchange rate of at least about 1 grain/gallon/minute/
gram/gallon; and mixtures thereof. This ion exchange builder is more fully described in Gedge et al's French Patent 2,237,839 published February 14, 1975.
Water The compositions of this invention contain from about 20%
to about 85%, preferably from about 40~ to about 75%, water.
Optional Ingredients Alcohols, such as ethyl alcohol, and hydrotropes, such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related com-pounds (as disclosed in U.S. Patent 3,915,903), and urea, can be utilized in the interests of achieving a desired product phase stability, viscosity, and yield value. Also useful in the ;
114~:)831;
compositions of this invention are suspending or thickening agents such as those disclosed in U.S. Patent 3,393,153 including colloidal silica having a mean particle diameter ranging from about 0.01 micron to about 0.05 micron colloidal clays such as bentonites or chemically treated bentonites, isomorphous silicates, especially those with a high magnesium content, and particulate polymers such as polystyrene, oxidized polystyrene having an acid number of from 20 to about 40, sulfonate polystyrene having an acid number of from about 10 to about 30, polyethylene, oxidized polyethylene having an acid number of from about 10 to about 30; sulfonated polyethylene having an acid number of from about 5 to about 25; polypropylene, oxidized polypropylene having an acid number of from about 10 to about 30 and sulfonatee polypropylene having an acid number of from about 5 to about 25, all of said particulate polymers having mean particle diameters ranging from about 0.01 micron to about 30 microns. Other examples of suspending and thickening agents include copolymers of styrene with monomers such as maleic anhydride, nitrilonitrile, methacrylic acid and lower alkyl esters of methacrylic acid, copolymers of styrene with methyl or ethyl acrylate, methyl or ethyl maleate, vinyl acetate, acrylic, maleic or fumaric acids and mixtures thereof. The mole ratio of ester and/or acid to styrene is preferably in the range from about 4 to about 40 styrene units per ester and/or acid unit. Such materials preferably have a mean particle diameter range of from about 0.05 micron to about 1 micron and molecular weights ranging from about 500,000 to about 2,000,000. Cellulosic polymers such as carboxymethyl cellulose and hydroxpropyl cellulose and gums such as guar gum and gum tragacanth are also suitable suspending and thickening agents.
The detergent compositions of this invention can contain, if desired, any of the usual adjuvants, diluents and addi-tives, for example, perfumes, enzymes, dyes, antitarnishingagents, antimicrobial agents, and the like, without detract-ing from the advantageous properties of the compositions.
Alkalinity sources and pH buffering agents ,.....
ll~Q83~
such as alkali metal carbonates and bicarbonates, mono-ethanolamine, triethanolamine, alkali metal hydroxides, etc., can also be utilized. A preferred pH range for a 1 solution in water is from about 6 to about 11.
Physical Characteristics of the Detergent Composition The liquid detergent compositions of the invention contain abrasives as suspended solids and may contain other solid or liquid ingredients that provide desired product stability charac~eristics and that affect product viscosit~.
In general, the products of the invention are thixotropic or pseudoplastic and resistant to settling out of the abrasive or other solids yet sufficientl~ fluid for dispensing with the package of the invention. In general, the compositions have a Brookfield viscosity of from about 400 cps to about 2500 cps when measured at 50 rpm and a yield value of from about 5 to about 600 dynes per square centimeter.
The important physical property consideration of the compositions of the invention is their yield value. The ~ consistency of simple (or Newtonian) liquids is a function 1 20 of the nature of the material, temperature, and pressure only. This consistency is known as the "fluid viscosity coefficient," "absolute viscosity," or merely 'iviscosity,"
ana is usually measured in-centipoises (1 centipoise = 0.01 gram/centimeter-second). With a Newtonian liquid, any ¦ 25 force applied to the-system produces some defomation, according to the formula du/dr=F/~ where du/dr = the rate of shear; F = the shear stress, or shearing force per unit area; and ~ = the viscosity coeeficient, In the case of non-Newtonian liquids, on the other hand, the consistency is a function of the material, pressure, temperature, and also the shear stress applied to the system.
Those non-Newtonian liquids which are classified as Bingham plastics, or real plastics, are not always deformed when a force is applied to the system. Deformation, if any, takes place according to the formula du/dr=(Fr)/~a where ~a= the apparent viscosity, or plastic viscosity, at the shear stress F;J=a characteristic of the liquid called the ., -!
114V8~1 -yield stress, or yield value, measured in units of pressure;
and du/dr and F are as defined above.
If the shear stress applied to the system is less than the yield value, the system will not be deformed at all. Hence a Bingham plastic system is capable of suppor-ting inde~initely insoluble particulate material which has ~
a density greater than that of the supporting medium, so long as the material has such a particle size and density that the shear stress which each particle places 10 on the supporting medium does not exceed the yield value.
This is to be contrasted with suspension of heavy insoluble particulate material in Newtonian liquids with high viscosities. In highly viscous Newtonian liquids, ! insoluble particulate material is suspended only because the ~ 15 rate of flow is slow. In Bingham plastics, insoluble par-; ticulate material is suspended because the stress imposed by the particles does not exceed the yield value of the liquid, t and therefore, there is no flow at all. Of course, if the yield value of the supporting medium should sufficiently 20 decrease for any reason, the particles would not longer be suspended. This could be caused, for example, by a physical or chemical change in the supporting medium. If one of the componennts of the supporting medium is an émulsion which settles into layers upon standing, the yield value can be 25 lost temporarily, but in such a case, the original compo-sition can be reconstituted by mixing. If a chemical reaction either consumes a vital component or produces a damaging one, the loss of yield value can be permanent.
Because it is usually not known whether a system 30 behaves in a truly plastic manner at low shear rate~, the measurement of exact yield values is estimated, in dynes per square centimeter, by the followin~ relationship:
Yield Value =
Viscosity at 0.5 r.p.m. - Viscosity at 1 r.p.m.
` 100 .... ~ , .
.
This relationship represents an ex~rapolation of the sheer i curve to 0 r.p.m. since an absolute shear stress cannot be measured at 0 r.p.m.
¦ The yield value of the liquid detergent compositions of this invention ranges from about S to about 60~ dynes per square centimeter. If the yield value is too low, the insolu~le, particulate material will not be suspended, because the weight of the individual particles, distri-buted over the area which supports the particles, will exceed the yield value. However, if the yield value is too great, the composition will become thick and unmanageable because as the yield value increases, so will the apparent viscosity. -A preferred range of yield values to support the insoluble particulate material used in the liquid detergentcompositions of this invention is from about 100 to about 40~ dyn.s per square cen.imeter.
The physical characteristics of the compositions can present a dispensing problem because of a slow "drain bacX"
characteristic that leads to product retention and sub-i sequent clogging in various parts of a dispensing closure.
~¦ This difficulty is greatly intensified when the closure is l not sealed after use and water and other s~lvents evaporate -from the product retained in the closure.
The Clog Resistant Package As discussed hereinbefore the essential package ele-ments are: 1) a flexible package container to provide the squeeze dispensing characteristics typical of a variety of consumer products including dishwashing liquids and liquid abrasive cleansers; and 2) a clog resistant closure.
Typical dishwashing liquid detergents ha~e a viscosity within the range of fro~ 30 cps to 300 cps, contain no suspended solids other than low levels of opacifiers and are not thixotropic or psuedoplastic to any great extent.
Closure clogging is not a serious problem and directional control of dispensed product is of no particular concern.
As disclosed, for example, in U.S. Patents 3,981,421 t 114~8~I
and 4,065,037, the design of closures for abrasive liquid cleaning preparations involve consideration of the thixo-tropic nature of such products because of product retention in the closure aperture.
In the package of the present invention, the closure design is distinguished by elements particularly suited to the dispensing of the product of the invention.
The design elements of particular importance are:
1) the absence of internal mechanisms or other obstructions to product flow in the closure up to the aperture;
2) a domed nozzle portion with a horizontal inner diameter of at least about 0.2 inches;
3) an aperture through the domed nozzle portion with a horizontal cross sectional area of from about 0.002 in2 to about 0.025 in2 a minimum diameter of about 0.05 in and a length through the dome wall of no more than about 0.25 in.
The domed or hemispherical nozzle design with its absence of acute angles, i.e. "corners" does not allow any appreci-able product buildup and has the beneficial effect of concen-trating and focusing any compressive force applied to the flexible container in a manner to keep the nozzle region and aperture clear of product buildup. The release of pressure from the container after dispensing clears the aperture.
Brief Description of the Drawings Figure 1 is a top plan view of an example of the closure of the invention.
Figure 2 is a cross sectional view taken along the line 2-2 of Figure 1.
Figure 3 is a partial section, taken along the line 3-3 of Figure 1.
Description of Preferred Package ~mbodimens An example of the dispensing closure of the present invention is illustrated in Figures 1 through 3 wherein like ., ~ ?~ , ~ .. . ..
parts are identified by the same number. The closure is generally indicated at 1 having a body portion 2 and a bail-like sealing member 3. The body portion 2 has a downwardly depending annular portion or skirt 4. The inside surface o~
S the annular portion 4 is provided with threads 5 adapted to ' mate and engage corresponding threads on the neck or finish I of a container ~not shown). Means other than threading as are well kr.owr. in the art may be employed to engage the closure 1 with the neck or finish of a container within the scope of the present invention. The outside surface of the annular portion 4 can, if desired, be provided with grooves, ridges or the like both for decorative purposes and to facilitate grasplng o~ the shell for threading it onto the container finish. The interior surface of the top portion of the body portion 2 can have a downwardly depending annual rib 6 to abut and form a seal with the top surface of the container finish.
A chimney 7 is located centrally of the top portion of ¦ the hody portion 2. The-chimney is generally cylindrical in configuration and is pro~ided with an axial bore 8, open at its lower end to communicate with the interior of the container and is surmounted at its upper end with a domed or hemispherical portion 9 terminating in an aperture 10 for , dispensing the product from the container and closure. The :J 25 diameter of the axial bore 8 also defines the interior horizontal diameter of the domed portion which preferably is at least about 0.2 inches. The bail-like sealing member 3 has an arcuate conformation and rotatab~e joints 11, 12 with the top portion of the closure body portion 2. In other embodiments, the-joint is located on the outside wall of the chimney by means, for example, of protllberant posts from the chimney engaging sockets on the sealing member. The sealing mem~er 3 has a gripping portion 13 centrally located and a downwardly-projecting protrusion 14 adapted to plug the aperture 10 when the sealing member 3 is in an closed position.
, .. ... . ~ .. _ ._._.. _ . . . _ .. _ . ... .
..... ... .. .... .
?~
114~J831 The sealing member may be adapted to provide a more positive seal of the protrusion 14 with the aperture 10 during shipment than is desirable during the period of consumer use. By way of example, ~he posts 15, 16 can be engaged into sockets 17, 18 for shipment and sale r Although the materials used for the dispensing package portion of the invention can be any materials that meet the ~, stated qualifications, conventional plastic material are generally satisfactory. The ~ontainer may be made of such materials as,polyethylene, polypropylene or polyvinyl chloride. Particularly suitable are materials capable of formation into containers by blow molding. ~he parts of the closure can be made from plastic materials such as poly-ethylene, polystyrene, polycarbonates or polypropylene that can be formed into desired shapes by injection molding.
, Materials resistent to cold flow such as the polycarbonates ! are particularly su ~ble for the sealing member.
'I The following examples are given to illustrate the !- detergent compositions of the invention. All amounts and ,, 20 percentages ar,e by we,ight unless otherwise indicated.
,, ' .... .. - ' EXAMPLE I
~, Liquid detergent compositions were prepared containing the ingredients listed below:
A B C D E
,~ 25 Sodium C12_13 alkyl sulfate 11.5% 11;5% 11.5% 13.8~ 0.2'5%
Sodium C ethoxy~3) 12.512.5 12:5 16.2 ,-alkyl s~fa~e C alkyl dimethyl 4.0 4.0 4.0 - -i~e oxide Trisodium sulfosuccinate 2.0 2.0 2.0 - _ ' Calcite (avg. - 10.0 diameter = 125 microns) Diatomaceous earth ~avg. 5.0 - ~ - ~ ~
diameter = 60 microns) Silica ~43-105 micron - - '5~0 diameter) ;:
.. ... -- .. _,., _." . ,~ . .... _ . _. _ _ .. , , _ _ _. __ _~_,, _._,_ ____ . _ .. _ . ...... _.. _.. .~ ., ._ ___ _.
..... . ~ , - ` ~14Q831 ~ 20 - !
. . I
Perlite - - - 8.0 8.0 Bentonite clay (sus- 2.5 2.5 pending agent) Fumed silica (CAb-0-Sil) - - 2.0 Gelwhite clay - - - 3.0 2.8 MgC12 _ _ 7.6 ¦ Ethanol 10.0 10.0 10.0 6.0 Soaium xylene sulfonate - - - 10.6 Water and miscellaneous Baidn~e _ - ~
Viscosity (Brookfield- 1200- 1200- 1200- 400- 1700-50 rpm) 1800~ps 1800cps 1800cps 500cps l900cps Yield Value (dynes/cm2) 250 250 250 5-15 230 ; Compositions A and B were stored in packages o~ the invention with a closure having a circular cross-section aperture with a diameter of 0.12 inches. Product was ! dispensed from 22 fl. oz. containers as packed and after storage of 3, 8, 10, 17 and 30 days. When the aperture was covered between uses, there was essentially no evidence of clogging to restrict or misdirect product flow when the container was subjected to a pressure of 6 lbs. applied 4 inches from the base of the container. When the aperture was left open between uses, performance was impaired but generally satisfactory. Control samples utilizing the "push-pull" liquid detergent closure of U.S. Patents 2S 3,227,332 and 3,201,013 and the liquid abrasive cleanser closures of U.S. Patents 3,981,421 and 4,065,037 did not ; provide dispensing characteristics as satisfa$tory.
Equivalent results are obtained when sodium C12 13 alkyl benzene sulfonate is substituted for the sodium C12 13 alkyl sulfate of compositions A, B, C and D.
W~AT IS CLAIMED I5: ¦
i .
, .. .. , . ~ ~ _ .. _ .... _ . ..... .... . .. _ . .... _ _._ .,__ _ .__ _, ._ .. _ _, . _. . . ... . _,_, _ _ _ ,, , . I
t
Examples of the amide type of nonionic surface active agent include the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
Examples of the semi-polar type of nonionic surface active agents are the amine oxides, phosphine oxides and sulfoxides. These materials are described more fully in Berry, U.S. Patent 3,819,528, issued June 25, 1974.
Particularly preferred are amine oxides of the formula:
..~
~ ,.--.. .~.... . . ~
.: .
1)831 `~ g _ .
i Rl - N i_ O
herein R1 is a Cl0-l8 alkyl and R2 and R3 are methyl or ethyl.
Ampholytic synthetic detergents can be broadly des-cribed as deri~ati~es of aliphatic amir.es which contain a long chain of about 8 to 18 carbon atoms and an anionic water-solubilizing group, e.g. carboxyr ~ulfo or sulfato~
E~amples of compounds falling within this definition are sodium 3-dodecylamino-propionate, sodium-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
Zwitterionic surface active agents operable in the instant composition are broadly described as internally-neutralized derivatives of aliphatic quaternary ammonium andphosphonium and tertiary sulfonium compounds in which ~he aliphatic radical c~n be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phos-phato, or phosphono.
I In a preferred embodiment o~ the invention in which the t,, detergent composition can be used as a complete dishwashing product, the level and type of surfactant used in the compositions of this invention provide an initial suds cover to a dishwashing solution and a suds co~er after ~he washing of 8 plates when used at a concentration o~ 0.07% in 2 gallons of 115~. water containing 7 grains/ gallon water hardness measured as CaCO3, each plate carrying 4.0 ml of a triglyceride containing soil. Suds are generated by mech-anical agitation and the suds cover and height measured. A
dinner plate carrying the soil is washed successively with the introduction of 4.0 ml of soil each time. An essen-tially complete suds cover of the washing solution is more important than suds height, but, preferably, the suds cover after the washing of 8 plates is at least about 1/2 inch in height.
.. _ ., .... ~.. , . .. .. , .. .............. .. __ _. __~
~1~0~331 ' The sudsing characteristic of the preferred high-sudsing compositions of the invention is that necessary to . . provide the user of the product with an indication of ; cleaning potential in a dishwashing solution~ Soils en-countered in dishwashing act as suds depressants and the presence or absence of suds fxom the surface of a dish-washing solution is a convenient guide to product usage.
Mixtures of anionic surfactants and nonionic surfactants, ~
especially amides and amine oxide nonionic surfactants, are particularly p~eferred in the compositions of the invention because of their high sudsing chaxacteristics,..their suds stability in the presence of food soils-and their. ability to indicate accurately an adequate level of product-usage in thé presence of-soil. A preferred ratio o~ anionic sur-factants to nonionic suractants is from abo~t 2:-1 to about ~ lO:l;by weight. ~
Cationic surfactants such as quaternary ammonium i compounds can find optional use.in.the;p~actice of the .
, invention, particularly in compositions containing nonionic .. . . . .
.~ 20 surfactants~ ............. .... .... -ABRASIVE
The abrasive agent can be any of the water-insoluble abrasive materials known.in the art which have a particle ~ ~ diameter of from about 15 to about 150, preferably from .~ 25 about 35 to about 125, microns and a hardness on the Mohs . . , scale of from about 2 to about 7. Included are materials such as agate, mica, calcite, garnet, quartz, kieselguhr, silica, marble, tripoli, flint, ~eldspar, emexy, pumice, alumina, perlite, expanded perlite, volcanlc ashj diato-maceous earth, bentonite, amorphous silica from dehydrated silica gels, precipitated silica, plastics such as poly-styrene and polyacrylates, and natural and synthetlc alumi-nosilicates and mixtures thereof.
The amount of abrasive included in the compositions is in the range of from about 1% to about 20% o~ the total composition by weight. Preferred compositions contain from about 5~ to about 10% by weight of abrasive.
?i . r .
OPTIONAL DETEROENCY BUILDER
The compositions of this in~ention can contain up to about 20~, preferably from about 5% to about 15~, by weight of detergency builders either of the organic or inorganic types. Examples of water-soluble inorganic builders which can be used, alone or in admixture wilh themselves ana organic alkaline sequestrant builder sal_s ! are alkali metal carbonates, polyphosphates, and silica~es. Specific ex-amples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate. Examples of organic builder salts which can be used alone, or in admixture with each other or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, e.g., watér-soluble citrates such as sodi~m and potassium citrate, sodilim and potassium tartrate, sodium and potasslum ethylenediaminetetraa~etate, ~- sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodlum and potassium N-(2-hydroxyethyl)-nitrilo diace-tates. Other organic builder salts include the alkali metalsalts of phytic acid, e.g., sodium phytate (see U.S. Patent 2,739,942). Water-soluble salts of ethane-l-hydroxy-l,l-diphosphonate (EHDP) are also suitable. Mixtures of any of the preceding water-soluble organic or inorganic builder salts can be used.
The compositions of this inVention can contain insolu-ble builder salts selected from certain zeolites or alumi-nosilicates. One such aluminosilicate which is useful in the compositions of the invention is water-insoluble cry-stalline aluminosilicate ion exchange material of theformula:
Naz~(AlO2)z^tSiO2)y] xH2O
;, - wherein Z and y are at least 6, the molar ratio of Z to y is from 1.0 to 0.5 and x is from 10 to 264, said material , 114Q83~
having a particle size diameter of from about 0.1 micron to about 10 microns, a calcium ion exchange capacity of at least about 200 mg. CaCO3eq./gram and a calcium ion exchange rate of at least about 2 grains Ca++/gallon/ minute/gram.
This ion exchange builder is more fully described in Belgian Patent 814,874 issued on November 12, 1974 to Corkill et al.
A preferred aluminosilicate of this type is Zeolite~ A.
A second water insoluble aluminosilicate ion exchange material useful herein is water-insoluble amorphous hydrated aluminosilicate material of the emperical formula:
MZ(ZA102-YSiO2) wherein M is sodium, potassium, ammonium, or substituted ammonium, Z is from about 0.5 to about 2, y is 1 and said material having a particle size diameter of less than 100, preferably less than 10, microns, a magnesium ion exchange capacity of at least about 50 milligrams equivalent of CaCO3 hardness per gram of anhydrous aluminosilicate and a mg+ exchange rate of at least about 1 grain/gallon/minute/
gram/gallon; and mixtures thereof. This ion exchange builder is more fully described in Gedge et al's French Patent 2,237,839 published February 14, 1975.
Water The compositions of this invention contain from about 20%
to about 85%, preferably from about 40~ to about 75%, water.
Optional Ingredients Alcohols, such as ethyl alcohol, and hydrotropes, such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related com-pounds (as disclosed in U.S. Patent 3,915,903), and urea, can be utilized in the interests of achieving a desired product phase stability, viscosity, and yield value. Also useful in the ;
114~:)831;
compositions of this invention are suspending or thickening agents such as those disclosed in U.S. Patent 3,393,153 including colloidal silica having a mean particle diameter ranging from about 0.01 micron to about 0.05 micron colloidal clays such as bentonites or chemically treated bentonites, isomorphous silicates, especially those with a high magnesium content, and particulate polymers such as polystyrene, oxidized polystyrene having an acid number of from 20 to about 40, sulfonate polystyrene having an acid number of from about 10 to about 30, polyethylene, oxidized polyethylene having an acid number of from about 10 to about 30; sulfonated polyethylene having an acid number of from about 5 to about 25; polypropylene, oxidized polypropylene having an acid number of from about 10 to about 30 and sulfonatee polypropylene having an acid number of from about 5 to about 25, all of said particulate polymers having mean particle diameters ranging from about 0.01 micron to about 30 microns. Other examples of suspending and thickening agents include copolymers of styrene with monomers such as maleic anhydride, nitrilonitrile, methacrylic acid and lower alkyl esters of methacrylic acid, copolymers of styrene with methyl or ethyl acrylate, methyl or ethyl maleate, vinyl acetate, acrylic, maleic or fumaric acids and mixtures thereof. The mole ratio of ester and/or acid to styrene is preferably in the range from about 4 to about 40 styrene units per ester and/or acid unit. Such materials preferably have a mean particle diameter range of from about 0.05 micron to about 1 micron and molecular weights ranging from about 500,000 to about 2,000,000. Cellulosic polymers such as carboxymethyl cellulose and hydroxpropyl cellulose and gums such as guar gum and gum tragacanth are also suitable suspending and thickening agents.
The detergent compositions of this invention can contain, if desired, any of the usual adjuvants, diluents and addi-tives, for example, perfumes, enzymes, dyes, antitarnishingagents, antimicrobial agents, and the like, without detract-ing from the advantageous properties of the compositions.
Alkalinity sources and pH buffering agents ,.....
ll~Q83~
such as alkali metal carbonates and bicarbonates, mono-ethanolamine, triethanolamine, alkali metal hydroxides, etc., can also be utilized. A preferred pH range for a 1 solution in water is from about 6 to about 11.
Physical Characteristics of the Detergent Composition The liquid detergent compositions of the invention contain abrasives as suspended solids and may contain other solid or liquid ingredients that provide desired product stability charac~eristics and that affect product viscosit~.
In general, the products of the invention are thixotropic or pseudoplastic and resistant to settling out of the abrasive or other solids yet sufficientl~ fluid for dispensing with the package of the invention. In general, the compositions have a Brookfield viscosity of from about 400 cps to about 2500 cps when measured at 50 rpm and a yield value of from about 5 to about 600 dynes per square centimeter.
The important physical property consideration of the compositions of the invention is their yield value. The ~ consistency of simple (or Newtonian) liquids is a function 1 20 of the nature of the material, temperature, and pressure only. This consistency is known as the "fluid viscosity coefficient," "absolute viscosity," or merely 'iviscosity,"
ana is usually measured in-centipoises (1 centipoise = 0.01 gram/centimeter-second). With a Newtonian liquid, any ¦ 25 force applied to the-system produces some defomation, according to the formula du/dr=F/~ where du/dr = the rate of shear; F = the shear stress, or shearing force per unit area; and ~ = the viscosity coeeficient, In the case of non-Newtonian liquids, on the other hand, the consistency is a function of the material, pressure, temperature, and also the shear stress applied to the system.
Those non-Newtonian liquids which are classified as Bingham plastics, or real plastics, are not always deformed when a force is applied to the system. Deformation, if any, takes place according to the formula du/dr=(Fr)/~a where ~a= the apparent viscosity, or plastic viscosity, at the shear stress F;J=a characteristic of the liquid called the ., -!
114V8~1 -yield stress, or yield value, measured in units of pressure;
and du/dr and F are as defined above.
If the shear stress applied to the system is less than the yield value, the system will not be deformed at all. Hence a Bingham plastic system is capable of suppor-ting inde~initely insoluble particulate material which has ~
a density greater than that of the supporting medium, so long as the material has such a particle size and density that the shear stress which each particle places 10 on the supporting medium does not exceed the yield value.
This is to be contrasted with suspension of heavy insoluble particulate material in Newtonian liquids with high viscosities. In highly viscous Newtonian liquids, ! insoluble particulate material is suspended only because the ~ 15 rate of flow is slow. In Bingham plastics, insoluble par-; ticulate material is suspended because the stress imposed by the particles does not exceed the yield value of the liquid, t and therefore, there is no flow at all. Of course, if the yield value of the supporting medium should sufficiently 20 decrease for any reason, the particles would not longer be suspended. This could be caused, for example, by a physical or chemical change in the supporting medium. If one of the componennts of the supporting medium is an émulsion which settles into layers upon standing, the yield value can be 25 lost temporarily, but in such a case, the original compo-sition can be reconstituted by mixing. If a chemical reaction either consumes a vital component or produces a damaging one, the loss of yield value can be permanent.
Because it is usually not known whether a system 30 behaves in a truly plastic manner at low shear rate~, the measurement of exact yield values is estimated, in dynes per square centimeter, by the followin~ relationship:
Yield Value =
Viscosity at 0.5 r.p.m. - Viscosity at 1 r.p.m.
` 100 .... ~ , .
.
This relationship represents an ex~rapolation of the sheer i curve to 0 r.p.m. since an absolute shear stress cannot be measured at 0 r.p.m.
¦ The yield value of the liquid detergent compositions of this invention ranges from about S to about 60~ dynes per square centimeter. If the yield value is too low, the insolu~le, particulate material will not be suspended, because the weight of the individual particles, distri-buted over the area which supports the particles, will exceed the yield value. However, if the yield value is too great, the composition will become thick and unmanageable because as the yield value increases, so will the apparent viscosity. -A preferred range of yield values to support the insoluble particulate material used in the liquid detergentcompositions of this invention is from about 100 to about 40~ dyn.s per square cen.imeter.
The physical characteristics of the compositions can present a dispensing problem because of a slow "drain bacX"
characteristic that leads to product retention and sub-i sequent clogging in various parts of a dispensing closure.
~¦ This difficulty is greatly intensified when the closure is l not sealed after use and water and other s~lvents evaporate -from the product retained in the closure.
The Clog Resistant Package As discussed hereinbefore the essential package ele-ments are: 1) a flexible package container to provide the squeeze dispensing characteristics typical of a variety of consumer products including dishwashing liquids and liquid abrasive cleansers; and 2) a clog resistant closure.
Typical dishwashing liquid detergents ha~e a viscosity within the range of fro~ 30 cps to 300 cps, contain no suspended solids other than low levels of opacifiers and are not thixotropic or psuedoplastic to any great extent.
Closure clogging is not a serious problem and directional control of dispensed product is of no particular concern.
As disclosed, for example, in U.S. Patents 3,981,421 t 114~8~I
and 4,065,037, the design of closures for abrasive liquid cleaning preparations involve consideration of the thixo-tropic nature of such products because of product retention in the closure aperture.
In the package of the present invention, the closure design is distinguished by elements particularly suited to the dispensing of the product of the invention.
The design elements of particular importance are:
1) the absence of internal mechanisms or other obstructions to product flow in the closure up to the aperture;
2) a domed nozzle portion with a horizontal inner diameter of at least about 0.2 inches;
3) an aperture through the domed nozzle portion with a horizontal cross sectional area of from about 0.002 in2 to about 0.025 in2 a minimum diameter of about 0.05 in and a length through the dome wall of no more than about 0.25 in.
The domed or hemispherical nozzle design with its absence of acute angles, i.e. "corners" does not allow any appreci-able product buildup and has the beneficial effect of concen-trating and focusing any compressive force applied to the flexible container in a manner to keep the nozzle region and aperture clear of product buildup. The release of pressure from the container after dispensing clears the aperture.
Brief Description of the Drawings Figure 1 is a top plan view of an example of the closure of the invention.
Figure 2 is a cross sectional view taken along the line 2-2 of Figure 1.
Figure 3 is a partial section, taken along the line 3-3 of Figure 1.
Description of Preferred Package ~mbodimens An example of the dispensing closure of the present invention is illustrated in Figures 1 through 3 wherein like ., ~ ?~ , ~ .. . ..
parts are identified by the same number. The closure is generally indicated at 1 having a body portion 2 and a bail-like sealing member 3. The body portion 2 has a downwardly depending annular portion or skirt 4. The inside surface o~
S the annular portion 4 is provided with threads 5 adapted to ' mate and engage corresponding threads on the neck or finish I of a container ~not shown). Means other than threading as are well kr.owr. in the art may be employed to engage the closure 1 with the neck or finish of a container within the scope of the present invention. The outside surface of the annular portion 4 can, if desired, be provided with grooves, ridges or the like both for decorative purposes and to facilitate grasplng o~ the shell for threading it onto the container finish. The interior surface of the top portion of the body portion 2 can have a downwardly depending annual rib 6 to abut and form a seal with the top surface of the container finish.
A chimney 7 is located centrally of the top portion of ¦ the hody portion 2. The-chimney is generally cylindrical in configuration and is pro~ided with an axial bore 8, open at its lower end to communicate with the interior of the container and is surmounted at its upper end with a domed or hemispherical portion 9 terminating in an aperture 10 for , dispensing the product from the container and closure. The :J 25 diameter of the axial bore 8 also defines the interior horizontal diameter of the domed portion which preferably is at least about 0.2 inches. The bail-like sealing member 3 has an arcuate conformation and rotatab~e joints 11, 12 with the top portion of the closure body portion 2. In other embodiments, the-joint is located on the outside wall of the chimney by means, for example, of protllberant posts from the chimney engaging sockets on the sealing member. The sealing mem~er 3 has a gripping portion 13 centrally located and a downwardly-projecting protrusion 14 adapted to plug the aperture 10 when the sealing member 3 is in an closed position.
, .. ... . ~ .. _ ._._.. _ . . . _ .. _ . ... .
..... ... .. .... .
?~
114~J831 The sealing member may be adapted to provide a more positive seal of the protrusion 14 with the aperture 10 during shipment than is desirable during the period of consumer use. By way of example, ~he posts 15, 16 can be engaged into sockets 17, 18 for shipment and sale r Although the materials used for the dispensing package portion of the invention can be any materials that meet the ~, stated qualifications, conventional plastic material are generally satisfactory. The ~ontainer may be made of such materials as,polyethylene, polypropylene or polyvinyl chloride. Particularly suitable are materials capable of formation into containers by blow molding. ~he parts of the closure can be made from plastic materials such as poly-ethylene, polystyrene, polycarbonates or polypropylene that can be formed into desired shapes by injection molding.
, Materials resistent to cold flow such as the polycarbonates ! are particularly su ~ble for the sealing member.
'I The following examples are given to illustrate the !- detergent compositions of the invention. All amounts and ,, 20 percentages ar,e by we,ight unless otherwise indicated.
,, ' .... .. - ' EXAMPLE I
~, Liquid detergent compositions were prepared containing the ingredients listed below:
A B C D E
,~ 25 Sodium C12_13 alkyl sulfate 11.5% 11;5% 11.5% 13.8~ 0.2'5%
Sodium C ethoxy~3) 12.512.5 12:5 16.2 ,-alkyl s~fa~e C alkyl dimethyl 4.0 4.0 4.0 - -i~e oxide Trisodium sulfosuccinate 2.0 2.0 2.0 - _ ' Calcite (avg. - 10.0 diameter = 125 microns) Diatomaceous earth ~avg. 5.0 - ~ - ~ ~
diameter = 60 microns) Silica ~43-105 micron - - '5~0 diameter) ;:
.. ... -- .. _,., _." . ,~ . .... _ . _. _ _ .. , , _ _ _. __ _~_,, _._,_ ____ . _ .. _ . ...... _.. _.. .~ ., ._ ___ _.
..... . ~ , - ` ~14Q831 ~ 20 - !
. . I
Perlite - - - 8.0 8.0 Bentonite clay (sus- 2.5 2.5 pending agent) Fumed silica (CAb-0-Sil) - - 2.0 Gelwhite clay - - - 3.0 2.8 MgC12 _ _ 7.6 ¦ Ethanol 10.0 10.0 10.0 6.0 Soaium xylene sulfonate - - - 10.6 Water and miscellaneous Baidn~e _ - ~
Viscosity (Brookfield- 1200- 1200- 1200- 400- 1700-50 rpm) 1800~ps 1800cps 1800cps 500cps l900cps Yield Value (dynes/cm2) 250 250 250 5-15 230 ; Compositions A and B were stored in packages o~ the invention with a closure having a circular cross-section aperture with a diameter of 0.12 inches. Product was ! dispensed from 22 fl. oz. containers as packed and after storage of 3, 8, 10, 17 and 30 days. When the aperture was covered between uses, there was essentially no evidence of clogging to restrict or misdirect product flow when the container was subjected to a pressure of 6 lbs. applied 4 inches from the base of the container. When the aperture was left open between uses, performance was impaired but generally satisfactory. Control samples utilizing the "push-pull" liquid detergent closure of U.S. Patents 2S 3,227,332 and 3,201,013 and the liquid abrasive cleanser closures of U.S. Patents 3,981,421 and 4,065,037 did not ; provide dispensing characteristics as satisfa$tory.
Equivalent results are obtained when sodium C12 13 alkyl benzene sulfonate is substituted for the sodium C12 13 alkyl sulfate of compositions A, B, C and D.
W~AT IS CLAIMED I5: ¦
i .
, .. .. , . ~ ~ _ .. _ .... _ . ..... .... . .. _ . .... _ _._ .,__ _ .__ _, ._ .. _ _, . _. . . ... . _,_, _ _ _ ,, , . I
t
Claims (12)
1. An abrasive-containing liquid detergent in a clog-resistant dispensing package comprising:
(a) a liquid detergent composition comprising by weight from about 0.2% to about 50% of a sur-factant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof, from about 1% to about 20% of a water-insoluble abrasive having a particle diameter of from about 15 to about 150 microns and a hardness on the Mohs scale of from about 2 to about 7 and from about 20% to about 85%
water, said composition having from about 20% to about 85% water and (b) a clog-resistant package containing said liquid detergent composition comprising:
(i) a flexible plastic container adapted to provide an increase in internal pressure by application of a compressive force to one or more external surface areas, and (ii) a clog-resistant dispensing closure adapted to be mounted on said flexible plastic con-tainer said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container finish, means for attaching said skirt to said container finish and a domed nozzle section with a central aperture, said aperture having an horizontal cross sectional area from about 0.002 in2 to about 0.025 in2, a minimum diameter of about 0.05 in, and a length of not more than about 0.25 in, said bail-like sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in closed position.
(a) a liquid detergent composition comprising by weight from about 0.2% to about 50% of a sur-factant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof, from about 1% to about 20% of a water-insoluble abrasive having a particle diameter of from about 15 to about 150 microns and a hardness on the Mohs scale of from about 2 to about 7 and from about 20% to about 85%
water, said composition having from about 20% to about 85% water and (b) a clog-resistant package containing said liquid detergent composition comprising:
(i) a flexible plastic container adapted to provide an increase in internal pressure by application of a compressive force to one or more external surface areas, and (ii) a clog-resistant dispensing closure adapted to be mounted on said flexible plastic con-tainer said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container finish, means for attaching said skirt to said container finish and a domed nozzle section with a central aperture, said aperture having an horizontal cross sectional area from about 0.002 in2 to about 0.025 in2, a minimum diameter of about 0.05 in, and a length of not more than about 0.25 in, said bail-like sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in closed position.
2. The abrasive-containing liquid detergent in a clog-resistant package of Claim 1 wherein the surfactant comprises an anionic surfactant.
3. The abrasive-containing liquid detergent in a clog-resistant package of Claim 2 wherein the amount of sur-factant is from about 15% to about 40% by weight.
4. The abrasive-containing liquid detergent in a clog-resistant package of Claim 3 wherein the anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl ether sulfates, alkylbenzene sulfonates paraffin sulfonates, olefin sulfonates and mixtures thereof.
5. The abrasive-containing liquid detergent in a clog-resistant package of Claim 4 which comprises a nonionic surfactant selected from the group consisting of ethanol-amides and amine oxides.
6. The abrasive-containing liquid detergent in a clog-resistant package of Claim 1, 2, or 3 which comprises a detergency builder selected from the group consisting of alkali metal polyphosphates, water soluble polycarboxy-lates, sodium aluminosilicates and mixtures thereof.
7. The abrasive-containing liquid detergent in a clog-resistant package of Claim 3 wherein the particle diameter of said water-insoluble abrasive is from about 40 to about 125 microns.
8. The abrasive-containing liquid detergent in a clog-resistant package of Claim 1, 2 or 3, wherein the abrasive comprises a material selected from the group consisting of quartz, silica, feldspar, perlite, calcite and mixtures thereof.
9. The abrasive-containing liquid detergent in a clog-resistant package of Claim 1, 2, or 3 wherein the amount of water is from about 40% to about 75% by weight.
10. The abrasive-containing liquid detergent in a clog-resistant package of Claim 1 wherein the domed portion of the body portion of the closure has an interior horizontal diameter of at least about 0.2 inches.
11. The abrasive-containing liquid detergent in a clog-resistant package of Claim 10 wherein the aperture is circular and has a diameter of at least 0.08 inches.
12. A clog resistant package comprising:
(i) a flexible plastic container adapted to provide an increase in internal pressure by application of a compressive force to one or more external surface areas, and a clog-resistant dispensing closure adapted to be mounted on said flexible plastic con-tainer said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container finish, means for attaching said skirt to said container finish and a domed nozzle section with a central aperture, said aperture having an horizontal cross sectional area from about 0.002 in2 to about 0.025 in2, a minimum diameter of about 0.05 in, and a length of not more than about 0.25 in, said bailike sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in closed position.
(i) a flexible plastic container adapted to provide an increase in internal pressure by application of a compressive force to one or more external surface areas, and a clog-resistant dispensing closure adapted to be mounted on said flexible plastic con-tainer said closure consisting of a body portion and a bail-like sealing member, the body portion consisting of an annular skirt for surrounding said container finish, means for attaching said skirt to said container finish and a domed nozzle section with a central aperture, said aperture having an horizontal cross sectional area from about 0.002 in2 to about 0.025 in2, a minimum diameter of about 0.05 in, and a length of not more than about 0.25 in, said bailike sealing member having an arcuate conformation and a rotatable joint to said body section at each end, said sealing member having a gripping portion centrally located and a downwardly-projecting protrusion on its underside adapted to plug the outside of said aperture when the sealing member is in closed position.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5316279A | 1979-06-29 | 1979-06-29 | |
| US53,162 | 1979-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1140831A true CA1140831A (en) | 1983-02-08 |
Family
ID=21982330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000354964A Expired CA1140831A (en) | 1979-06-29 | 1980-06-27 | Abrasive-containing liquid detergent composition and non-clogging dispensing package |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5638397A (en) |
| CA (1) | CA1140831A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797231A (en) * | 1985-04-18 | 1989-01-10 | Henkel Kommanditgesellschaft Auf Aktien | Multipurpose cleaning preparations for hard surfaces |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5912997A (en) * | 1982-07-15 | 1984-01-23 | ライオン株式会社 | Liquid detergent composition |
| JPS59193997A (en) * | 1983-04-19 | 1984-11-02 | ライオン株式会社 | Liquid detergent in container |
| JPS606797A (en) * | 1983-06-27 | 1985-01-14 | ライオン株式会社 | Abrasive-containing liquid detergent composition |
| JPS6013357U (en) * | 1983-07-05 | 1985-01-29 | ライオン株式会社 | cap |
| JPS6021449U (en) * | 1983-07-19 | 1985-02-14 | 株式会社資生堂 | Cream pouring container |
| JPS6092964U (en) * | 1983-12-02 | 1985-06-25 | 株式会社吉野工業所 | Pour cap with pot |
| JPS6096253U (en) * | 1983-12-06 | 1985-07-01 | 株式会社吉野工業所 | Pour cap with spout |
| JPS60129363U (en) * | 1984-02-06 | 1985-08-30 | 株式会社吉野工業所 | Cap with spout |
| JPS60188496A (en) * | 1984-03-09 | 1985-09-25 | ライオン株式会社 | Cleaning abrasive base material |
| JPS618550U (en) * | 1984-06-20 | 1986-01-18 | 東京ライト工業株式会社 | Spout for dispenser container |
| JPS6157695A (en) * | 1984-08-30 | 1986-03-24 | ライオン株式会社 | Liquid detergent composition |
| JPS62273297A (en) * | 1986-05-20 | 1987-11-27 | 栗島 良江 | Detergent |
| JPH01242697A (en) * | 1988-03-23 | 1989-09-27 | Kao Corp | Liquid cleanser composition |
| JPH0251598A (en) * | 1988-08-12 | 1990-02-21 | Mimasu Clean Kea Kk | Polishing detergent |
| WO2016112984A1 (en) | 2015-01-15 | 2016-07-21 | Ecolab Inc. | Long lasting cleaning foam |
| JP7199992B2 (en) * | 2019-02-14 | 2023-01-06 | 花王株式会社 | Containerized liquid softener article |
-
1980
- 1980-06-27 CA CA000354964A patent/CA1140831A/en not_active Expired
- 1980-06-30 JP JP8907080A patent/JPS5638397A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797231A (en) * | 1985-04-18 | 1989-01-10 | Henkel Kommanditgesellschaft Auf Aktien | Multipurpose cleaning preparations for hard surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5638397A (en) | 1981-04-13 |
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