Background
[0001] The invention relates to liquid detergent compositions containing specified amounts
and types of insoluble abrasives which are especially useful in the washing of dishes.
The compositions contain high-sudsing surfactants and may also contain detergency
builders which complement the action of the abrasive.
[0002] The invention also relates to the combination of such liquid detergents and a package
which provides convenient dispensing of the detergent composition without clogging.
[0003] The use of abrasives in powdered scouring cleansers is well known. Scouring cleansers
generally contain a relatively 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 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 and 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 micrometers.
[0004] It is an object of the present invention to provide liquid detergent compositions
containing a surfactant and an abrasive, the detergent composition being highly effective
in removing food soils from kitchenware when used undiluted or in the form of a relatively
concentrated water slurry, but which is highly acceptable for hand dishwashing in
the dilute water solutions typically used with liquid dishwashing products.
[0005] It is a further object of the present invention to provide liquid 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 slurry, 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 invention
[0006] The present invention comprises a liquid detergent composition containing by weight:
a) from 20% to 35% of an anionic surfactant;
b) from 2% to 15% of a suds stabilizing nonionic surfactant selected from amine oxides,
amides, and the ethylene oxide condensates of alcohols and alkyl phenols;
c) from 1% to 20% of a water-insoluble abrasive having a particle diameter of from
15 to 150 micrometers and a hardness on the Mohs scale of from 2 to 7; and
d) from 20% to 75% water; said composition providing an initial suds cover to a dishwashing
solution and a suds cover after the washing of eight plates when used at a concentration
of 0.07% in 7.57 litres of 46°C water containing 120 mg/I water hardness measured
as CaC03, each plate carrying 4.0 ml. of triglyceride-containing soil.
[0007] The essential package characteristics are:
a) a flexible plastic container adapted to provide 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 plastic
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 nozzle section
with a central aperture, said aperture having an horizontal cross sectional area from
1.29 mm2 to 16.13 mm2, preferably from 3.23 mmZ-9.67 mm2, a minimum diameter of 0.127 cm preferably 0.20 cm, and a length of no more than
0.635 cm, 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 description of the invention
[0008] The detergent compositions of 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 performance and aesthetic characteristics.
Surfactant
[0009] The compositions of this invention contain from 20% to 35% of an anionic surfactant
or mixtures thereof.
[0010] 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 having in their molecular structure an alkyl radical containing
from 8 to 22 carbon atoms and a radical selected from sulfonic acid and sulfuric acid
ester radicals. Included in the term alkyl is the alkyl portion of high acyl radicals.
Examples of the anionic synthetic detergents which can form the surfactant component
of the compositions of the present invention are the sodium, ammonium or potassium
alkyl sulfates, especially those obtained by sulfating the higher alcohols (C
S-C
1s carbon atoms) sodium or potassium alkyl benzene or toluene sulfonates, in which the
alkyl group contains from 9 to 15 carbon atoms, (the alkyl radical can be a straight
or branched aliphatic chain); sodium or potassium paraffin sulfonates and olefin sulfonates
in which the alkyl or alkenyl group contains from 10 to 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 1 to 30 units of ethylene oxide per molecule and in which the radicals contain
from 3 to 12 carbon atoms; the reaction products of fatty acids esterified with isethionic
acid and neutralized with 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, 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.
[0011] 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 alkyl 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
coconut alkyl sulfate, potassium lauryl alkyl sulfate and sodium lauryl alkyl sulfate.
[0012] 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, tridecyl 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 invention
include Conoco SA 515 and SA 597 marketed by the Continental Oil Company and Calsoft
LAS 99 marketed by the Pilot Chemical Company.
[0013] Particularly preferred anionic surfactants useful herein are alkyl ether sulfates
having the formula RO(C
2H
4O)
xSO
3M wherein R is alkyl or alkenyl of 10 to 20 carbon atoms, x is 1 to 30, and M is a
water-soluble cation. The alkyl ether sulfates useful in the present invention are
condensation products of ethylene oxide and monohydric alcohols having from 10 to
20 carbon atoms. Preferably, R has 12 to 18 carbon 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.
[0014] Specific examples of alkyl ether sulfates of the present invention are sodium coconut
alkyl triethylene glycol ether sulfate, magnesium tallow alkyl triethylene glycol
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 12 to 16 carbon atoms and an average degree
of ethoxylation of from 1 to 12 moles of ethylene oxide.
[0015] Additional examples of anionic surfactants useful herein are the compounds which
contain two anionic functional groups. These are referred to as di-anionic surfactants.
Suitable dianionic surfactants are the disulfonates, disulfates, or mixtures thereof
which may be represented by the following formula:
where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and
M is a water-solubilizing cation, for example, the C
15 to C
20 disodium 1,2-alkyldisulfates, C
15 to C
20 dipotassium-1,2-alkyldisulfonates or disulfates, di-sodium 1,9-hexadecyl disulfates,
C
15 to C
20 disodium 1,2-alkyl- disulfonates, disodium 1 ,9-stearyldisulfates and 6,10-octadecyldisulfates.
Nonionic surfactant
[0016] The compositions of this invention contain from 2% to 15%, preferably from 3% to
8%, most preferably 4%, of a suds stabilizing nonionic surfactant or mixtures thereof.
The presence of this component is essential to satisfactory performance and acceptance
as a complete dishwashing product. In preferred embodiments the nonionic surfactant
will be in a weight ratio to the anionic surfactants of from 1:10 to 1:2, most preferably
from 1:7 to 1:3.
[0017] Nonionic surface active agents operable in the instant compositions can be any of
three basic types―the alkylene oxide condensates, the amides and the semi-polar nonionics.
[0018] The alkylene oxide condensates are broadly defined as compounds produced by the condensation
of alkylene 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.
[0019] Examples 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 straight or branched and generally contains
from 8 to 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation
product of 6 moles of ethylene oxide with 1 mole of tridecanol, myristyl alcohol condensed
with 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation 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 6 moles of ethylene oxide per mole of alcohol, and the condensation
product of 9 moles of ethylene oxide with the above-described coconut alcohol. An
example of a commercially available non-ionic surfactant of this type includes Neodol
(23-6.5 marketed by the Shell Chemical Company.
(2) The polyethylene oxide condensates of alkyl phenols. These compounds include the
condensation products of alkyl phenols having an alkyl group containing from 6 to
12 carbon atoms in either a straight chain or branched chain configuration, 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 nonene.
Examples of compounds of this type include nonyl phenol condensed with 9.5 moles of
ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with 12 moles of
ethylene oxide per mole of phenol, dinonyl phenol condensed with 15 moles of ethylene
oxide per mole of phenol, di-isooctylphenol condensed with 15 moles of ethylene oxide
per mole of phenol. Commercially available nonionic surfactants of this type include
Igepal CO-61 0 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 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 moiecule as a whole, and the liquid
character of the product is retained up to the point where the polyoxyethylene content
is about 50% of the total 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 2500 to 3000. This base is condensed with ethylene
oxide to the extent that the condensation product contains from 40% to 80% by weight
of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of
this type of nonionic surfactant include certain of the commercially available Tetronic
compounds marketed by the Wyandotte Chemicals Corporation.
[0020] 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 8 to
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.
[0021] 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. Particularly preferred are amine oxides of the formula:
wherein R, is a C,
o-,a alkyl and R
2 and R
3 are methyl or ethyl.
[0022] 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 cover after the washing
of 8 plates when used at a concentration of 0.07% in 7.57 litres of 46°C water containing
120 mg/I water hardness measured as CaC0
3, each plate carrying 4.0 ml of a triglyceride containing soil. Suds are generated
by mechanical 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 essentially 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
1.27 cm in height.
[0023] 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 encountered in dishwashing act as suds
depressants and the presence or absence of suds from the surface of a dishwashing
solution is a convenient guide to product usage. Mixtures of anionic surfactants and
nonionic surfactants, especially amides and amine oxide nonionic surfactants, are
utilized in the compositions of the invention because of their high sudsing characteristics,
their suds stability in the presence of food soils and their ability to indicate accurately
an adequate level of product usage in the presence of soil.
Optional surfactants
[0024] The compositions of the invention may contain optional surfactants other than anionic
and nonionic surfactants such as ampholytic, zwitterionic and cationic surfactants.
[0025] Ampholytic surfactants can be broadly described as derivatives of aliphatic amines
which contain a long chain of 8 to 18 carbon atoms and an anionic water-solubilizing
group, e.g. carboxy, sulfo or sulfate. Examples of compounds falling within this definition
are sodium-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
[0026] Zwitterionic surface active agents operable in the instant composition are broadly
described as internally-neutralized derivatives of aliphatic quaternary ammonium and
phosphonium and tertiary sulfonium compounds in which the aliphatic radical can be
straight chain or branched, and wherein one of the aliphatic substituents contains
from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g.,
carboxy, sulfo, sulfato, phosphato, or phosphono.
[0027] Cationic surfactants such as quaternary ammonium compounds can find optional use
in the practice of the invention to the extent they are compatible with the other
surfactants in the particular composition.
Abrasive
[0028] The abrasive agent can be any of the water-insoluble abrasive materials known in
the art which have a particle diameter of from 15 to 150, preferably from 35 to 125,
microns and a hardness on the Mohs scale of from 2 to 7. Included are materials such
as a gate, mica, calcite, garnet, quartz, kieselguhr, silica, marble, tripoli, flint,
feldspar, emery, pumice, alumina, perlite, expanded perlite, volcanic ash, diatomaceous
earth, bentonite, amorphous silica from dehydrated silica gels, precipitated silica,
plastics such as polystyrene and polyacrylates, and natural and synthetic aluminosilicates
and mixtures thereof.
[0029] The amount of abrasive included in the compositions is in the range of from 1% to
20% of the total composition by weight. Preferred compositions contain from 5% to
10% by weight of abrasive.
Optional detergency builder
[0030] The compositions of this invention can contain up to 20%, preferably from 5% to 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 with
themselves and organic alkaline sequestrant builder salts, are alkali metal carbonates,
polyphosphates, and silicates. Specific examples 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., water-soluble
citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium
and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene
diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodium and
potassium N-(2-hydroxyethyl)-nitrilo diacetates. Other organic builder salts include
the alkali metal salts of phytic acid, e.g., sodium phytate (see U.S. Patent 2,739,942).
Water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate (EHDP) are also suitable.
Mixtures of any of the preceding water-soluble organic or inorganic builder salts
can be used.
[0031] The compositions of this invention can contain insoluble builder salts selected from
certain zeolites or aluminosilicates. One such aluminosilicate which is useful in
the compositions of the invention is water-insoluble crystalline aluminosilicate ion
exchange material of the formula:
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 having a particle size diameter of from 0.1 micrometer
to 10 micrometers, a calcium ion exchange capacity of at least 200 mg. CaC0
3 eq./gram and a calcium ion exchange rate of at least 34.1 mg Ca
++/litre/minute/gram. This ion exchange builder is more fully described in Belgian Patent
814,874. A preferred aluminosilicate of this type is Zeolite A.
[0032] A second water-insoluble aluminosilicate ion exchange material useful herein is water-insoluble
amorphous hydrated aluminosilicate material of the emperical formula:
wherein M is sodium, potassium, ammonium, or substituted ammonium, Z is from 0.5 to
2, y is 1 and said material having a particle size diameter of less than 100, preferably
less than 10 micrometers, a magnesium ion exchange capacity of at least 50 milligrams
equivalent of CaCO hardness per gram of anhydrous aluminosilicate and a Mg
++ exchange rate of at least 17.1 mg/liter/minute/gram/liter; and mixtures thereof.
This ion exchange builder is more fully described in Gedge et al's French Patent 2,237,839.
Water
[0033] The compositions of this invention contain from 20% to 75% water.
Optional ingredients
[0034] Alcohols, such as ethyl alcohol, and hydrotropes, such as sodium and potassium toluene
sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related
compounds (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 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 0.01 micrometers to 0.05 micrometers 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 40, sulfonate polystyrene
having an acid number of from 10 to 30, polyethylene, oxidized polyethylene having
an acid number of from 10 to 30; sulfonated polyethylene having an acid number of
from 5 to 25; polypropylene, oxidized polypropylene having an acid number of from
10 to 30 and sulfonated polypropylene having an acid number of from 5 to 25, all of
said particulate polymers having mean particle diameters ranging from 0.01 micrometers
to 30 micrometers. 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 4 to 40 styrene units per ester and/or acid unit. Such materials
preferably have a mean particle diameter range of from 0.05 micrometers to 1 micrometer
and molecular weights ranging from 500,000 to 2,000,000. Cellulosic polymers such
as carboxymethyl cellulose and hydroxypropyl cellulose and gums such as guar gum and
gum tragacanth are also suitable suspending and thickening agents.
[0035] The detergent compositions of this invention can contain, if desired, any of the
usual adjuvants, diluents and additives, for example, perfumes, enzymes, dyes, antitarnishing
agents, antimicrobial agents, and the like, without detracting from the advantageous
properties of the compositions. Alkalinity sources and pH buffering agents such as
alkali metal carbonates and bicarbonates, monoethanolamine, triethanolamine, alkali
metal hydroxides, etc., can also be utilized. A preferred pH range for a 196 solution
in water is from 6 to 11.
Physical characteristics of the detergent composition
[0036] 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 characteristics and that affect product viscosity. In general, the products
of the invention are thixotropic or pseudoplastic and resistant to settling out of
the abrasive or other solids yet sufficiently fluid for dispensing with the package
of the invention. In general, the compositions have a Brookfield viscosity of from
400 mPas. to 2500 mPas. when measured at 50 rpm and a yield value of from 5 to 600×10
-5M per square centimeter at 25°C.
[0037] 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
of the nature of the material, temperature, and pressure only. This consistency is
known as the "fluid viscosity coefficient", "absolute viscosity," or merely "viscosity",
and is usually measured in centipoises (1 centipoise=0.01 gram/centi- meter-second).
With a Newtonian liquid, any force applied to the system produces some deformation,
according to the formula du/dr=F/,u where du/dr=the rate of shear; F=the shear stress,
or shearing force per unit area; and ,u=the viscosity coefficient.
[0038] 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=(F∫)µ
α where β
α=the apparent viscosity, or plastic viscosity, at the shear stress F;J=a characteristic
of the liquid called the yield stress, or yield value, measured in units of pressure;
and du/dr and F are as defined above.
[0039] 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 supporting
indefinitely 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 on the supporting medium does not
exceed the yield value.
[0040] 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 rate of flow is slow. In Bingham
plastics, insoluble particulate material is suspended because the stress imposed by
the particles does not exceed the yield value of the liquid, and therefore, there
is no flow at all. Of course, if the yield value of the supporting medium should sufficiently
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 components of the supporting medium is an emulsion which settles into layers
upon standing, the yield value can be lost temporarily, but in such a case, the original
composition 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.
[0041] Because it is usually not known whether a system behaves in a truly plastic manner
at low shear rates, the measurement of exact yield values is estimated, in Newtons
x 10-
5 per square centimeter, by the following relationship:
This relationship represents an extrapolation of the sheer curve to 0 r.p.m. since
an absolute shear stress cannot be measured at 0 r.p.m.
[0042] The yield value of the liquid detergent compositions of this invention ranges from
5x10-
5 to 600x 0-5 N per square centimeter. If the yield value is too low, the insoluble,
particulate material will not be suspended, because the weight of the individual particles,
distributed 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.
[0043] A preferred range of yield values to support the insoluble particulate material used
in the liquid detergent compositions of this invention is from 100×10
-5 to 400x 10-
5 Newtons per square centimeter.
[0044] The physical characteristics of the compositions can present a dispensing problem
because of a slow "drain back" characteristic that leads to product retention and
subsequent clogging in various parts of a dispensing closure. This difficulty is greatly
intensified when the closure is not sealed after use and water and other solvents
evaporate from the product retained in the closure.
The clog resistant package
[0045] As discussed hereinbefore the essential package elements 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.
[0046] Typical dishwashing liquid detergents have a viscosity within the range of from 30
mPas to 300 mPas, contain no suspended solids other than low levels of opacifiers
and are not thixotropic or pseudoplastic to any great extent. Closure clogging is
not a serious problem and directional control of dispensed product is of no particular
concern.
[0047] As disclosed, for example, in U.S. Patents 3,981,421 and 4,065,037, the design of
closures for abrasive liquid cleaning preparations involve consideration of the thixotropic
nature of such products because of product retention in the closure aperture.
[0048] 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.
[0049] 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 0.51 cm;
3) an aperture through the domed nozzle portion with a horizontal cross sectional
area of from 1.29 mm2 to 16.13 mm2 a minimum diameter of 0.127 cm and a length through the dome wall of no more than
0.635 cm.
[0050] The domed or hemispherical nozzle design with its absence of actue angles, i.e. "corners"
does not allow any appreciable product buildup and has the beneficial effect of concentrating
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
[0051]
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 embodiments
[0052] 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
of the annular portion 4 is provided with threads 5 adapted to mate and engage corresponding
threads on the neck or finish of a container (not shown). Means other than threading
as are well known 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 grasping of 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.
[0053] A chimney 7 is located centrally of the top portion of the body portion 2. The chimney
is generally cylindrical in configuration and is provided 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 diameter of the
axial bore 8 also defines the interior horizontal diameter of the domed portion which
preferably is at least 0.51 cm. The bail-like sealing member 3 has an arcuate conformation
and rotatable 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 protuberant posts from the chimney engaging sockets on the sealing
member. The sealing member 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.
[0054] 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, the posts 15, 16 can be engaged into sockets 17, 18 for shipment
and sale.
[0055] 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 container may be made of such materials as polyethylene,
polypropylene or polyvinyl chloride. Particularly suitable are materials capable of
formation into containers by blow molding. The parts of the closure can be made from
plastic materials such as polyethylene, 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 suitable for the sealing member.
[0056] The following examples are given to illustrate the detergent compositions of the
invention. All amounts and percentages are by weight unless otherwise indicated.
Example I
[0057] Liquid detergent compositions were prepared containing the ingredients listed below:
[0058] All compositions listed above contain approximately 45 to 55% water and have a pH
value in the range of 8.0 to 10.0.
[0059] The compositions are entirely satisfactory when used in dilute solutions as a dishwashing
detergent compositions and are substantially superior to typical liquid dishwashing
detergent compositions when used undiluted or in concentrated solution for removal
of tightly attached soils.
[0060] Equivalent results are obtained when C
12 alkyldiethanolamide and the reaction product of a C
12-15 alcohol and 8 moles of ethylene oxide are substituted for the C
12 alkylmonoethanolamide of Composition E.
[0061] Equivalent results are obtained when sodium C
12-13 alkylbenzene sulfonate and C
12-15 paraffin sulfonate are substituted for the sodium C
12-13 alkyl sulfate of compositions A, B, C, D and E.
[0062] Compositions A and B were stored in packages of the invention with a closure having
a circular cross-section aperture with a diameter of 0.305 cm. Product was dispensed
from 624 ml 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 26.65 N applied 10.2 cm 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 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 satisfactory.
[0063] Equivalent results are obtained when sodium C,
2-13 alkyl benzene sulfonate is substituted for the sodium C
12-13 alkyl sulfate of compositions A, B, C, D and E.
1. Composition détergente liquide contenant un abrasif, comprenant en poids:
(a) de 20 à 35% d'un agent de surface anionique;
(b) de 2 à 15% d'un agent de surface non-ionique stabilisateur de mousse choisi dans
le groupe comprenant les oxydes d'amine, les amides, et les condensats de l'oxyde
d'éthylène et d'alcools et d'alkylphénols;
(c) de 1 à 20% d'un abrasif insoluble dans l'eau ayant une granulométrie de 15 à 150
micromètres et une duretés ur l'échelle de Mohs de 2 à 7; et
(d) de 20 à 75% d'eau;
cette composition créant une couverture initiale de mousse sur une solution détersive
pour la vaisselle et une couverture de mousse après le lavage de huit assiettes quand
elle est utilisée à une concentration de 0,07% dans 7,57 litres d'eau à 46°C contenant
120 mg/I d'eau de dureté mesurée en tant que CaC0
3, chaque assiette portant 4,0 ml d'une salissure contenant des triglycérides.
2. Composition détergente liquide contenant un abrasif, dans un récipient distributeur
ne se bouchant pas, comprenant:
(a) une composition détergente liquide contenant un abrasif selon la revendication
1; et
(b) un récipient imbouchable contenant cette composition détergente liquide, et comprenant:
(i) un conteneur plastique souple adapté pour créer une augmentation de la pression
interne par l'application d'une force de compression sur une ou plusieurs zones de
sa surface extérieur, et
(ii) une fermeture distributrice imbouchable, adaptée pour être montée sur le conteneur
plastique souple, cette fermeture consistant en une partie corps et en un élément
d'obturation du type anse, la partie corps consistant en une jupe annulaire destinée
à entourer la bague du conteneur, en un moyen pour fixer cette jupe à la bague du
conteneur et en une section verseuse en dôme avec une ouverture centrale, cette ouverture
ayant une aire horizontale en section transversale de 1,29 à 16,13 mm2, un diamètre minimum de 0,127 cm et une longueur non-supérieure à 0,635 cm, l'élément
d'obturation du type anse ayant une conformation incurvée et un joint rotatif le reliant
à la partie corps en chaque extrémité, l'élément d'obturation ayant une partie de
saisie située centralement et une saillie dépassant vers le bas sur son côté inférieur
adaptée pour pénétrer dans la partie extérieure de cette ouverture quand l'élément
d'obturation est en position fermée.
3. Détergent liquide contenant un abrasif selon l'une des revendications 1 ou 2, dans
lequel l'agent de surface anionique comprend une matière choisie dans le groupe comprenant
les alkyl- sulfates, les alkyléthersulfates, les alkylbenzènesulfonates, les paraffinesulfonates,
les oléfine- sulfonates et leurs mélanges.
4. Composition détergente liquid contenant un abrasif selon la revendication 3, dans
laquelle l'agent de surface non-ionique stabilisateur de mousse comprend une matière
choisie dans le groupe consistant en les éthanolamides, les oxydes d'amine et leurs
mélanges.
5. Composition détergent liquid contenant un abrasif selon la revendication 4, dans
laquelle l'abrasif comprend une matière choisie dans le groupe comprenant le quartz,
la silice, le terre de diatomées, le feldspath, la perlite haute densité, la calcite
et leurs mélanges.
6. Composition détergent liquid contenant un abrasif selon la revendication 5, dans
laquelle la granulométrie de l'abrasif insoluble dans l'eau est comprise entre 40
et 125 micromètres.
7. Composition détergente liquide contenant un abrasif selon la revendication 6, dans
laquelle l'abrasif comprend une matière choisie dans le groupe comprenant le quartz,
la silice, le feldspath, la perlite, la calcite et leurs mélanges.
8. Composition détergente liquide contenant un abrasif selon l'une quelconque des
revendications 1 ou 2, comprenant en outre un adjuvant de détergence choisie dans
le groupe comprenant les polyphosphates de métaux alcalins, les polycarboxylates solubles
dans l'eau, les aluminosilicates de sodium et leurs mélanges.
9. Composition détergente liquide contenant un abrasif selon l'une quelconque des
revendications 1 ou 2, dans laquelle la quantité d'eau est comprise entre 40 et 70%
en poids.
10. Composition détergente liquide contenant un abrasif selon la revendication 2,
dans laquelle la partie en dôme de la partie corps de la fermeture a un diamètre horizontal
intérieur d'au moins 0,51 cm.
11. Composition détergente liquide contenant un abrasif selon la revendication 10,
caractérisée en ce que l'ouverture est circulaire et a un diamètre d'au moins 0,20
cm.
1. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung, enthaltend,
bezogen auf das Gewicht:
(a) 20% bis 35% eines anionischen oberflächenaktiven Mittels;
(b) 2% bis 15% eines schaumstabilisierenden, nichtionischen oberflächenaktiven Mittels
ausgewählt aus der Gruppe bestehend aus Aminoxiden, Amiden und den Ethylenoxid-kondensaten
von Alkoholen und Alkylphenolen;
(c) 1 % bis 20% eines wasserunlöslichen Scheuermittels mit einem Teilchendurchmesser
von 15 bis 150 jUm und einer Härte auf der Mohs-Skala von 2 bis 7; und
(d) 20% bis 75% Wasser;
wobei diese Zusammensetzung einer Geschirrspüllösung eine anfängliche Schaumdecke
und nach dem Waschen von 8 Tellern bei Anwendung in einer Konzentration von 0,07%
in 7,57 1 Wasser von 46°C, das eine Wasserhärte, gemessen als CaC0
3, von 120 mg/I enthält, wobei jeder Teller 4,0 ml an triglyceridhaltigem Schmutz trägt,
eine Schaumdecke liefert.
2. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung in einem
Verstopfungen widerstehenden Ausgabebehälter, enthaltend:
(a) eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß
Anspruch 1 und
(b) einen Verstopfungen widerstehenden Behälter, der diese flüssige Reinigungsmittelzusammensetzung
enthält, enthaltend;
(i) einen biegsamen Kunststoffbehälter, der so adaptiert ist, daß er einen Ansteig
des Innendruckes durch Anwendung einer Druckkraft auf eine oder mehrere äußere Oberflächenbereiche
liefert, und
(ii) einen Verstopfungen widerstehenden Spenderverschluß, der so adaptiert ist, daß
er auf diesem biegsamen Kunststoffbehälter montiert wird, wobei dieser Verschluß aus
einem Körperteil und einem bügelartigen Verschlußglied besteht, wobei der Körperteil
aus einem ringförmigen Mantel, der das Behälterende umgibt, Einrichtungen zur Befestigung
dieses Mantels an diesem Behälterende und einem gewölbten Düsenabschnitt mit einer
zentralen Öffnung besteht, wobei diese Öffnung eine waagerechte Querschnittsfläche
von 0,0051 cm2 bis 0,06 35 cm2, einen Mindestdurchmesser von 0,127 cm und eine Länge von nicht mehr als 0,635 cm
aufweist, wobei dieses bügelartige Verschlußglied eine bogenförmige Gestalt aufweist
und an jedem Ende eine drehbare Verbindung zu dem Körperteil hat, wobei dieses Verschlußglied
einen zentral angeordneten Griffteil und an seiner Unterseite einen sich nach unten
erstreckenden, vorstehenden Teil aufweist, der so adaptiert ist, daß er die Außenseite
der Öffnung verschließt, wenn sich das Verschlußglied in geschlossener Stellung befindet.
3. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den
Ansprüchen 1 oder 2, worin das anionische oberflächenaktive Mittel ein Material ausgewählt
aus der Gruppe bestehend aus Alkylsulfaten, Alkylethersulfaten, Alkylbenzolsulfonaten,
Paraffinsulfonaten, Olefinsulfonaten und Gemischen daraus umfaßt.
4. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch
3, worin das schaumstabilisierende nichtionische oberflächenaktive Mittel ein Material
ausgewählt aus der Gruppe bestehend aus Ethanolamiden, Aminoxiden und Gemischen daraus
umfaßt.
5. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch
4, worin das Scheuermittel ein Material ausgewählt aus der Gruppe bestehend aus Quarz,
Kieselerde, Diatomeenerde, Feldspat, Perlit hoher Dichte, Calcit und Gemischen daraus
umfaßt.
6. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch
5, worin der Teilchendurchmesser des wasserunlöslichen Scheuermittels 40 bis 125 Mikrometer
beträgt.
7. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch
6, worin das Scheuermittel ein Material ausgewählt aus der Gruppe bestehend aus Quarz,
Kieselerde, Feldspat, Perlit, Calcit und Gemischen daraus, umfaßt.
8. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den
Ansprüchen 1 oder 2, welche weiterhin einen Detergensgerüststoff ausgewählt aus der
Gruppe bestehend aus Alkalimetallpolyphosphaten, wasserlöslichen Polycarboxylate,
Natriumaluminosilikate und Gemischen daraus enthält.
9. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den
Ansprüchen 1 oder 2, worin die Menge an Wasser 40 Gew.-% bis 75 Gew.-% beträgt.
10. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß
Anspruch 2, worin der gewölbte Teil des Körperteils des Verschlusses einen inneren,
waagerechten Durchmesser von mindestens 0,51 cm aufweist.
11. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß
Anspruch 10, worin die Öffnung rund ist und einen Durchmesser von mindestens 0,20
cm aufweist.