Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION
This invention relates to hard surface cl~aning composi-
tions having improved soil removal capabilities. `~ore particu-
larly, this invention relates to built hard surfac~ cleaning com-
positions having low levels of surfactant in combination with low
levels of the mixture of certain primary polymeric materials with
polysaccharide salts.
Hard surface cleaning compositions are a class of deter-
gent compositions adapted to meet the variety of requirements
necessary for overall optimum performance in hard surface cleaning
usage. Examples of such hard surface cleaning compositions
- appear in U.S. Patent 3,223,646, issued December 14, 1965 to
McKenna et al, and entitled "DRY FREE-FLOWING DETERGENT COMPOSI-
TION AND METHOD OF PREPARATION" and U.S. Patent 3,591,509, issued
July 6, 1971 to Parks et al, and entitled "LIQUID HARD SURFACE
CLEANING COMPOSITIONS".
Generally, granular hard surface cleaning compositions
contain less than 5% by weight surfactant (often considerably
less) and often have very high levels of organic and inorganic
builders. Liquid hard surface cleaning compositions generally
contain from about .05% to about 15~ surfactant, by weight with
up to 25% builders. Hard surface cleaning compositions are for-
mulated in this way for a number of reasons related to the unique
performance requirements involved in hard surface cleaning.
~05901~3
For example, hard surface cleaning compositions must
possess the capability of removing highly substantive soils from
many different types of hard surfaces without damage to the sur-
face or danger to the user. Moreover, these compositions should
not leave streaks or noticeable film on the surface after the soil
is removed. Still further, the compositions must not produce
excessive foam in use since foam can be time and effort consuming
to remove. Even further such compositions must be stable over a
relatively long period of time and under a variety of conditions
including temperature and humidity changes. In short, realiza-
tion of optimum hard surface cleaning compositions has required
extensive and inventive efforts to provide maximum cleaning
efficacy within the constraints of economically suitable and con-
veniently employed, finished end products.
U.S. Patent No. 3,979,339 of Gene W. Claybaugh, issued
September 7, 1976, said patent being entitled "HARD SURFACE
CLEANING COMPOSITIONS" describes granular hard surface cleaning
compositions containing certain of the polyvinyl alcohol and poly-
vinyl pyrrolidone polymeric materials which are also useful herein.
The invention herein is directed to the further inclusion of
certain polysaccharide materials into liquid or granular hard
surface cleaning compositions.
Polymers including polysaccharides have been used for a
variety of purposes in detergents. Examples of such uses are
disclosed in British Patent Specification 994,353, issued June 2,
1965 to Domestos, and entitled "IMPROVEMENTS IN DETERGENT COMPO-
SITIONS"; U.S. Patent 2,798,047 issued July 2, 1957 to Touey et al
and entitled "DETERGENT COMPOSITIONS FOR LAUNDERING TEXTILE
FABRICS, CONTAINING A COPOLYMER OF A LOWER N-ALKYL ACRYLAMIDE AND
VINYL ALCOHOL"; U.S. Patent 3,846,324, issued November 5, 1974 to
Lohmann et al, and entitled "DETERGENTS"; U.S. Patent 3,676,352,
-- 2 --
1059003
issued July 11, 1972 to Grimm et al, and entitled "PROCESS FOR
THE MANUFACTURE OF ENZYME AND PERBORATE CONTAINING DETERGENT
COMPOSITIONS"; and U.S. Patent 3,558,499, issued January 26, 1971
to Galvin et al, and entitled "ANTI-REDEPOSITION AGENTS".
Although, as such references demonstrate, polymers have
been used in detergents for a variety of purposes, it is believed
that the beneficial use of the combination of certain primary
polymeric materials with polysaccharide salts according to the
present invention has not heretofore been recognized.
Surprisingly, it has been discovered that these materials
can provide improved soil removal when incorporated into hard sur-
face cleaning compositions and, furthermore, can be used to
encapsulate and protect unstable and/or volatile detergent adju-
vants within the hard surface cleaning composition.
Accordingly, an object of the present invention is to
provide improved hard surface cleaning compositions through the
beneficial use of certain polymeric materials with polysaccharide
salt materials.
It is a further object of the present invention to im-
prove soil removal capabilities of hard surface cleaning composi-
tions.
It is still a further object of the instant invention to
incorporate into hard surface cleaning compositions a combination
of materials which serves both to improve soil removal capabilities
of the compositions and to usefully encapsulate and preserve
detergent composition adjuvants within the hard surface cleaning
products.
These and other objects are achieved as hereinafter
disclosed.
1()59~03
SUMMARY OF THE INVENTION
_ _ _
The instant invention relates to low surfactant, built
hard surface cleaning compositions. Such compositions comprise
from about 0.05% to about 15% by weight surfactant (preferably
from about 0.5% to less than 5%), from about 0.5% to about 99%
by weight builder (preferably from about 25% to about 99% in
granular compositions and preferably from about 0.5% to 25% in
liquid compositions), and from about .03% to about 5.0% (prefer-
ably from about .04% to about 2.0%) by weight of a soil removal
improvement mixture.
The surfactant component can be any conventional anionic,
nonionic, ampholytic or zwitterionic surfactant. The builder can
be any conventional organic or inorganic builder salt or salt
mixture.
The soil removal improvement mixture comprises the com-
bination of certain water-soluble or dispersible primary polymeric
materials which are nonionizing in water with ionizing poly-
saccharide salts in a weight ratio of primary polymeric material
to polysaccharide salt of from about 4:1 to about 1:4 (preferably
from about 2:1 to about 1:2).
The primary polymeric material component of the soil
removal mixture comprises water-soluble or dispersible nonionizing
polymers such as polyvinyl alcohol (degree of hydrolysis 60% to
100%; degree of polymerization 100 to 7000), and polyvinyl
pyrrolidone (degree of polymerization 50 to 6000); or mixtures
of these polymer types.
The polysaccharide salt component comprises ionizing
polysaccharides which have recurrent acidic moieties which have
been at least in part neutralized.
The instant invention also relates to a method for re-
moving soil from hard surfaces. Such a method comprises contact-
-- 4
~059003
ing the soiled surface with an effective amount of an aqueous
solution of a composition as described above and oscillating such
a solution over the surface to remove the soil.
DETAILED DESCRIPTION OF THE INVENTION
This invention is directed to hard surface cleaning
compositions which provide improved cleaning performance by the
incorporation of a mixture of certain water-soluble or water-
dispersible primary polymeric materials with polysaccharide salts.
Essential components of such compositions are the primary poly-
meric material, polysaccharide salt, surfactant, and builder.The primary polymeric material and polysaccharide salt in certain
weight ratios comprise a soil removal improvement mixture. These
and other invention aspects are described in detail as follows.
Soil Removal Improvement Mixture
Utilization of a certain soil removal improvement mix-
ture comprising a mixture of primary polymeric material and poly-
saccharide salts in hard surface cleaning compositions unexpectedly
improves the capability of the compositions to remove soils from
hard surfaces. The soil removal mixture is added to the hard
surface cleaning composition at levels of from about .03% to about
5.0% by weight, preferably from about 0.04% to about 2.0%. The
weight ratio of the nonionizing primary polymeric material to the
ionizing polysaccharide salt within the soil removal improvement
mixture varies from about 4:1 to about 1:4, preferably from about
2:1 to about 1:2. The primary polymeric materials and poly-
saccharide salts are described below.
(a) Primary Polymeric Material
The primary or nonionizing polymeric materials include
specific types of polyvinyl alcohol and polyvinyl pyrrolidone.
Both types of polymeric materials used herein are water-soluble
or water-dispersible and are nonionizing in water.
1059003
Polyvinyl alcohol is the preferred primary polymeric
material for use in the instant composition. Polyvinyl alcohol
is a well-known polymer having the repeating monomeric unit
(-CH2CHOH-)X. Polyvinyl alcohols are normally prepared by
hydrolysis of polyvinyl acetate. The polyvinyl alcohol operable
herein includes polyvinyl acetate polymers in which at least 60%,
preferably 80% to 100~ (most preferably 97% to 100%) of the
acetate moieties are replaced by hydroxyl moieties. For simpli-
city, such polyvinyl alcohol materials are referred to herein as
polyvinyl alcohol having at least 60% degree of hydrolysis,
preferably at least about 80% to 100% degree of hydrolysis. Most
preferred polyvinyl alcohols have a degree of hydrolysis of 97%
to 100%.
Operable polyvinyl alcohols further include those which
have a degree of polymerization of from about 100 to about 7000,
preferably from about 200 to 3500.
Polyvinyl alcohols are available commercially. Examples
of such commercially available polyvinyl alcohols suitable for
use herein are Elvanols~ marketed by E.I. Dupont and Company and
Gelvatols~ marketed by Monsanto Company. These commercially
available materials are often described with a molecular weight
and a viscosity instead of in terms of degree of hydrolysis and
polymerization. Accordingly, useful commercially available poly-
vinyl alcohols include those which have a molecular weight from
about 4500 to about 300,000, preferably from about 9,000 to about
150,000, and a viscosity (of a 4% aqueous solution at 20C) of
from about 3 centipose to about 100 centipose, preferably from
about 4 centipose to about 50 centipose. Polyvinyl alcohol
materials are described in more detail at pages 72 to 81 of the
text, Handbook of Common Polymers compiled by Roff et al, Butter-
worth & Co. (Publishers), 1971 and Polyvinyl Alcohol - Properties
and Applications edited by C.A. Finch, John Wiley and Sons
(Publishers), 1973.
-- 6 --
59CJ103
Another type of primary polymeric material operable in
the soil removal improvement mixture of the instant compositions
is polyvinyl pyrrolidone. Chemically, polyvinyl pyrrolidones are
homopolymers of N-vinylpyrrolidone. The repeating monomer is of
the following structure:
r 7 -
f_ CH2
/ N \
H2 l C=O .
l 2C - CH2
Polyvinyl pyrrolidones having a degree of polymerization
of from about 50 to about 6000, preferably about 90 to 3500 are
useful in the soil removal improvement mixture of the hard sur-
face cleaning compositions of the present invention.
Examples of commercially available polyvinyl pyrrolidones
include Plasdone~ marketed by GAF Corp. and Albigen A~ marketed
by BASF Corp. These commercially available materials are also
often described in terms of polymer molecular weights. Accord-
ingly, commercially useful polyvinyl pyrrolidones include those
having molecular weights of from about 10,000 to about 360,000.
Either of the two above-described types of nonionizing
polymeric materials can be used alone in the soil removal improve-
ment mixture of the present invention. As noted polyvinyl alco-
hols are the preferred materials. Mixtures of the two types of
primary polymeric materials can also be employed in the soil
removal improvement mixture.
10~9C303
(b) Polysaccharide Salt
The second essential component of the soil removal im-
provement mixture comprises a polysaccharide salt material having
a molecular weight of at least about 4,000 up to as much as
5,000,000 or more and a propensity to ionize in aqueous solution.
Such polysaccharide salts can either be naturally occurring or
derived and are either fully or partially neutralized acidic
polysaccharides.
Preferred polysaccharide salts useful herein can be in
the alkali metal, alkaline earth metal or ammonium form. Thus,
sodium, potassium, calcium, magnesium and ammonion polysaccharides
are preferred in the soil removal improvement mixture.
Useful naturally occurring acidic polysaccharides and
their salts include those obtained, for example, from seaweed
extracts (e.g. algin); plant exudates (e.g. gum arabic); seed gurns
(e.g. guar gum); plant extracts (e.g. pectin) or animal extracts.
Preferred naturally occurring polysaccharides are sub-
stantially linear polymers and have recurrent carboxylate func-
tional groups which are at least in part neutralized. Algin, a
seaweed extract, is an especially preferred polysaccharide salt.
Biosynthetic polysaccharides in salt form are also use-
ful herein. Xanthan gum is an example of such a biosynthetic
polysaccharide.
Polysaccharides (including starches and celluloses) which
have been chemically modified to forrn ionizing polysaccharide
salts are also useful herein. Examples of such modified poly-
saccharides include those disclosed in U.S. Patent 3,784,475
issued January 8, 1974 to Diehl and U.S. Patent 3,629,121 issued
December 21, 1971 to Eldib. These two patents disclose carboxy-
lated polysaccharides. Other useful polysaccharide salts includesuch modified cellulose compounds as sodium carboxymethylcellu-
loses, generally known as CMC.
~9003
As can be seen, a wide variety of polysaccharide salts
are readily available and can be usefully employed in the soil
removal improvement mixture herein. Further examples of useful
polysaccharide salts can be found in well-known texts such as
_ndustrial Gums - Polysaccharides and Their Derivatives, 2nd
Edition, edited by Whistler et al (Academic Press, 1973).
It should be noted that the polysaccharide salts useful
herein need not be water-soluble or dispersible per se but should
be convertible to a water-soluble or dispersible form when added
to water along with other components of the hard surface cleaning
compositions herein. Thus the alkaline earth metal alginate
materials, for example, are not water-soluble but when added to
water with a detergent builder are converted to a water-soluble
alginate form as the builder acts to sequester the alkaline earth
metal and remove it from the alginate molecule.
Preferred polysaccharide salts include alkali metal and
alkaline earth metal alginates, gum arabics, xanthan gums and
carrageenans with alginates and xanthan gums most preferred. Low
viscosity grades of sodium and calcium alginates are particularly
preferred.
Organic Surfactants
The organic surfactant compounds which can be utilized in
the present invention include anionic, nonionic, ampholytic, and
zwitterionic surfactants. These surfactants are included at
levels which inhibit undesirable foaming and surface streaking
yet which provide advantageous removal of soils, particularly
soils of lipophilic and particulate character. Surfactant is
incorporated at from about 0.05% to about 15%, preferably from
about 0.5% to less than 5% by weight of the instant compositions.
_ g _
1059~03
A. Anionic Soap and Non-Soap Synthetic Surfactants
This class of surfactants includes ordinary alkali metal
soaps such as the sodium, potassium, ammonium and alkanol-
ammonium salts of higher fatty acids containing from about 8 to
about 24 carbon atoms and preferably from about 10 to about 20
carbon atoms. Suitable fatty acids can be obtained from natural
sources such as, for instance, plant or animal esters (e.g., palm
oil, coconut oil, babassu oil, soybean oil, castor oil, tallow,
whale and fish oils, grease, lard, and mixtures thereof). The
fatty acids also can be synthetically prepared (e.g., by the
oxidation of petroleum, or by the Fischer-Tropsch process). Resin
acids are suitable such as rosin and those resin acids in tall oil.
Naphthenic acids are also suitable. Sodium and potassium soaps
can be made by direct saponification of the fats and oils or by
the neutralization of the free fatty acids which are prepared in
a separate manufacturing process. Particularly useful are the
sodium and potassium salts of the mixtures of fatty acids derived
from coconut oil and tallow, i.e., sodium or potassium tallow and
coconut soap.
This class of anionic surfactants also includes water-
soluble salts, particularly the alkali metal salts, of organic
sulfuric reaction products having in their molecular structure an
alkyl group containing from about 8 to about 22 carbon atoms and
a sulfonic acid or sulfuric acid ester radical. (Included in
the term alkyl is the alkyl portion of higher acyl groups.)
Examples of this group of synthetic detergents which form a part
of the built detergent compositions of the present invention are
the sodium or potassium alkyl sulfates, especially those obtained
by sulfating the higher alcohols (C8-C18 carbon atoms) produced
~0 by reducing the glycerides of tallow or coconut oil; sodium or
potassium alkyl benzene sulfonates, in which the alkyl group
-- 10 --
1059~03
contains from about 8 to about 16 carbon atoms in straight chain
or branched chain configuration, e.g. those of the type described
in U.S. Patents Numbers 2,220,099 and 2,477,383 (especially
valuable are linear straight chain alkyl benzene sulfonates in
which the average of the alkyl groups is about 11-12 carbon atoms
and commonly abbreviated as Cll 8LAS); sodium alkyl glyceryl ether
sulfonates, especially those ethers of higher alcohols derived
from tallow and coconut oil; sodium coconut oil fatty acid mono-
glyceride sulfonates and sulfates.
Other synthetic anionic surfactants useful herein are
alkyl ether sulfates. These materials have 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 water-soluble cation
as defined hereinbefore. The alkyl ether sulfates useful in the
present invention are condensation products of ethylene oxide and
monohydric alcohols having about 10 to about 20 carbon atoms.
Preferably, R has 12 to 18 carbon atoms. The alcohols can be
derived from fats, e.g., coconut oil or tallow, or can be syn-
thetic. Lauryl alcohol and straight chain alcohols derived from
tallow are preferred herein. Such alcohols are reacted with 1 to
30, and especially 3 and 6, molar proportions of ethylene oxide
and the resulting mixture of molecular species, having, for
example, an average of 3 or 6 moles of ethylene oxide per mole of
alcohol, is sulfated and neutralized.
Specific examples of alkyl ether sulfates of the present
invention are sodium coconut alkyl ethylene glycol ether sulfate;
lithium tallow alkyl triethylene glycol ether sulfate; sodium
tallow alkyl hexaoxyethylene sulfate; and sodium tallow alkyl
trioxyethylene sulfate. The alkyl ether sulfates are known com-
pounds and are described in U.S. Patent 3,332,876 to Walker.(July 25, 1967).
-- 11 --
1~59~03
Generally then, a wide variety of preferred anionic sur-
factants are useful in the instant compositions as providing the
necessary detergency for hard surface cleaning. Most preferred
anionic surfactants include C8 to C16 alkyl benzene sulfonates,
C12 to C18 alkyl sulfates, and C12 to C18 ethoxylated alkyl sul-
fates having from 1 to 10 ethoxy moieties. For reasons of
cleaning efficacy, economics and environmental compatibility,
sodium linear alkyl benzene sulfonates having from 11 to 12 car-
bon atoms (Cll 8 avg.) in the alkyl portion are most particularly
preferred, especially in combination with ethoxylated rosin acids
such as tall oil which can be used as a spray-on antidusting agent
in granular products.
B. Nonionic Synthetic Surfactants
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.
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.
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
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 tridecanol, myristyl alcohol
- 12 -
lOS9~03
condensed with about 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 about 6 moles of ethy-
lene oxide per mole of alcohol, and the condensation product of
about 9 moles of ethylene oxide with the above-described coconut
alcohol. Examples of commercially available nonionic surfactants
of this type include "Tergitol 15-S-9"* marketed by the Union
Carbide Corporation, "Neodol 23-7"** marketed by the Shell
Chemical Company and "Kyro EOB"*** marketed by The Procter &
Gamble Company.
(2) The polyethylene oxide condensates of alkyl phenols.
These 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
nonene. Examples of compounds 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-isooctyl-
phenol condensed 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.
* Trademark
** Trademark
*** Trademark
**** Trademark
***** Trademark
- 13 -
1059C~03
(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 whole, and the liquid character
of the product is retained up to the point where the polyoxy-
ethylene content is about 50% of the total weight of the condensa-
tion product. Examples of compounds of this type include certainof the commercially available "Pluronic" surfactants marketed by
the Wyandotte Chemicals Corporation.
(4) The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethyl-
ene 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 the Fischer-Tropsch process.
-~ Trademark
~* Trademark
- 14 -
1~59~03
Examples of the semi-polar type of nonionic surface
active agents are the amine oxides, phosphine oxides and sulfox-
ides. These materials are described more fully in serry, U. S.
Patent 3,819,528, issued June 25, 1974.
C. Ampholytic Synthetic Surfactants
Ampholytic synthetic detergents can be broadly described
as derivatives of aliphatic amines which contain a long chain of
about 8 to 18 carbon atoms and an anionic water-solubilizing
group, e.g. carboxy, sulfo or sulfato. Examples of compounds
falling within this definition are sodium 3-dodecylamino-propio-
nate, sodium -3-dodecylamino propane sulfonate, and dodecyl
dimethylammonium hexanoate.
D. Zwitterionic Synthetic Surfactants
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 about 8 to 18 carbon atoms and one
contains an anionic water solubilizing group, e.g., carboxy,
sulfo, sulfato, phosphato, or phosphono. Some of these zwitter-
ionic surfactants are described in the following U.S. Patents:
2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.
The ammoniopropane sulfonates containing about 8 to about 21
carbon atoms are one class of surfactant compounds preferred here-
in by virtue of their relatively low calcium ion (hardness)
sensitivity.
Of all the above described surfactants, anionic sur-
factants are the most preferred. An especially preferred anionic
surfactant component comprises a mixture of sodium linear Cll 12
alkyl benzene sulfonate (LAS) and ethoxylated tall oil. Such a
- 15 -
~059~03
mixture is generally present in the instant composition in amounts
such that the LAS comprises from about 0.05% to 3% by weight of
the composition and the ethoxylated tall oil comprises from about
0.05% to about 0.5% by weight of the composition.
Builder Salts
Builder salts are essential to the compositions herein
and comprise from about .5% to about 99% by weight of the hard
surface cleaning composition, preferably from 25% to about 99% by
weight in granular compositions and from about 0.5% to 25% by
weight in liquid compositions.
Suitable builders are water-soluble or water-dispersible
in nature and comprise organic and inorganic salts. Mixtures of
organic and inorganic builders can be employed.
Suitable inorganic alkaline builder salts which can be
used in this invention alone or in admixture include alkali metal
carbonates, borates, phosphates, polyphosphates, bicarbonates,
and silicates. Ammonium or substituted ammonium e.g., triethanol
ammonium, salts of these materials can also be used. Specific
examples of suitable salts are sodium tripolyphosphate, sodium
carbonate, sodium tetraborate, sodium and potassium pyrophosphate,
sodium and ammonium bicarbonates, potassium tripolyphosphate,
sodium hexaphosphate, sodium sesquicarbonate, sodium orthophos-
phate, potassium bicarbonate. The preferred inorganic alkaline
builders according to this invention are the alkali metal phos-
phates, carbonates, silicates, polyphosphates and sesquicarbonates.
Examples of suitable organic alkaline builder salts used
in this invention alone or in admixture are alkali metal, ammonium
or substituted ammonium aminocarboxylates, e.g.,sodium and potas-
sium ethylenediaminetetraacetate, sodium and potassium N-(2-
hydroxyethyl)-ethylenediaminetriacetates, sodium and potassium
nitrilotriacetates and sodium, potassium and triethanolammonium
- 16 -
lOS9~)03
N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these poly-
carboxylates are also suitable. The alkali metal, ammonium and
alkanol ammonium salts of citric acid can be suitably employed.
The alkali metal salts of phytic acid, e.g. sodium phytate are
also suitable as organic alkaline sequestrant builder salts.
Polyphosphonates are also valuable builders in terms of
the present invention including specifically sodium and potassium
salts of ethane-l-hydroxy-l,l-diphosphonic acid, sodium and
potassium salts of methylene diphosphonic acid, and sodium and
potassium salts of ethane-1,1,2-triphosphonic acid. Other ex-
amples include the alkali metal salts of ethane-2-carboxy-1,1-
diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldi-
phosphonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid,
ethane-l-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tetra-
phosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and
propane-1,2,2,3-tetraphosphonic acid.
Useful builders can be formulated to provide either
phosphate-containing or phosphate-free cleaning compositions,
although phosphate-containing compositions are preferred from the
standpoint of soil removal and economics.
Preferred granular phosphate-containing hard surface
cleaning compositions comprise by weight percent from about 5% to
65~ alkali metal phosphate mixtures. These phosphate mixtures
comprise from about 5% to 50% alkali metal polyphosphates and
from about 0% to 30% alkali metal orthophosphates. The phosphate-
containing hard surface cleaning compositions can further contain
from about 25% to about 90% alkali metal carbonates (including
sesquicarbonate) and from about 0% to 5% alkali metal silicates.
Preferred granular phosphate-free hard surface cleaning
compositions contain on a weight basis from about 0.5% to about
25% organic builder salts, such as citrates, ethylenediamine-
- 17 -
lOS9a:~03
acetates and nitriloacetates; from about 40% to about 95% alkali
metal carbonates (including preferably 25% to about 90% sesqui-
carbonate), and from about 0% to 5% alkali metal silicates.
Optional Ingredients
In addition to the above-described essential components
the compositions of the instant invention can optionally contain
such conventional detergent composition components as moisture
(free or bound), fillers (neutral salts such as sodium sulfate),
bleaches, hydrotropes, processing aids, enzymes, germicides,
abrasives, perfumes and coloring agents. If present such com-
ponents generally comprise from 0.5% up to 50% by weight of the
composition especially if high levels of fillers are employed.
Preferably, the compositions herein contain no bleach or enzyme
which could be potentially deleterious to the surface being
cleaned.
Composition Preparation
The compositions herein can be liquid or granular.
Granular compositions can be prepared as follows.
(a) Granular Compositions
The granular compositions of the instant invention can
be prepared simply by admixing the essential and optional com-
ponents together in granular form. Alternatively the surfactant,
builder, and appropriate optional components including soil
removal improvement mixture can be admixed with water in a
crutcher and spray dried to granular form. Further amounts of
soil removal improvement mixture (i.e., primary polymeric
materials, polysaccharide salts) and other optionals also can be
admixed into the spray-dried composition, if desired.
The soil removal improvement mixture of the present
invention can be incorporated into hard surface cleaning composi-
tions in a variety of forms. However, it is particularly
- 18 -
1059003
desirable that the mixture be in a form which can readily dis-
solve or disperse upon dilution of the hard surface cleaner with
water. Consequently, preferred hard surface cleaning compositions
contain the soil removal improvement mixture mixed throughout the
composition in readily dispersible or dissolvable form.
One such dispersible or dissolvable form is provided
simply by admixing the surfactant and builder granules with the
soil removal improvement mixture in the form of small particles
or aggregates ranging from about 10 to about 300 microns in
diameter. Particles having average diameter below about 40 mi-
crons are preferred.
Alternatively, the soil removal improvement mixture can
be melted or dissolved in a solvent such as water and sprayed
onto one or more of the hard surface cleaning composition granu-
lar components. For example, a molten or aqueous slurry of the
soil removal improvement mixture can be sprayed onto an agitated
dry mixture of builder and, optionally, surfactant. It is
desirable that compositions prepared in this manner exhibit no
substantial delay in solubility. Consequently, the layer of the
soil removal improvement mixture as a film on the composition
granules should be relatively thin and highly water-soluble or
dispersible at normal usage temperatures. Usually such a polymer
layer is less than about 100 microns in average thickness.
The soil removal improvement mixture can also be used to
wholly encapsulate certain hard surface cleaning composition
adjuvants such as, for example, perfume. Encapsulation tech-
niques using polymeric materials, including polyvinyl alcohol,
are known. (See, for instance, U.S. Patent 3,015,128, issued
January 2, 1962 to Somerville, relating to encapsulation of
liquids with a mixture of polyvinyl alcohol and alginates.
-- 19 --
~(~S9003
Again, however, it is desirable that the soil removal improvement
mixture be in a form which readily dissolves or disperses upon
dilution of the cleaning composition. Encapsulation of liquids
(perfumes) as disclosed in U.S. Patent 3,015,128 above is par-
ticularly desirable for use in granular compositions inasmuch as
the built granular hard surface cleaning composition advantageously
interacts with the capsule wall promoting dissolution of calcium
alginate formed on the surface of the capsules according to the
capsule hardening method in the Sommerville patent.
A granular composition herein can, of course, contain
the soil removal improvement mixture in several different forms.
Thus a composition can contain some of the total soil removal
improvement mixture, say 5% to about 50% by weight, in the form
of encapsulation material and some, say from about 50% to about
95% by weight, of the material in granular form.
In granular hard surface cleaning compositions it is
particularly desirable that the surfactant concentration be below
5% by weight.
(b) Liquid Compositions
Liquid compositions can be prepared in aqueous form by
simply admixing the soil removal improvement mixture, preferably
in dispersed or dissolved aqueous form, with shearing agitation
into a conventional liquid hard surface cleaning composition.
Liquid compositions preferably contain from about .5%
to less than 5% surfactant.
Hard Surface Cleaning
Cleaning of hard surfaces using the compositions of the
present invention can be accomplished in conventional manner.
Generally the composition is diluted with water to form an aqueous
cleaning solution. This cleaning solution is then contacted with
the surface to be cleaned. A substrate such as a mop, sponge,
cloth, brush, etc., is used to oscillate the cleaning composition
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1059003
across the hard surface thereby loosening, dissolving and removingsoil.
Cleaning solutions formed from the compositions of the
instant invention generally contain from about 50 ppm to 2000 ppm
surfactant, from about 50 ppm to 20,000 ppm builder and from about
2 ppm to 1500 ppm of the soil removal improvement mixture.
It is highly preferred that the cleaning solution formed
from the compositions herein have a non-acid pH. Thus preferably
the instant compositions when dissolved should provide aqueous
solutions having a pH within the range of from about 7 to 12,
more preferably 9 to ll.
The following exemplifies the hard surface cleaning com-
positions of this invention and the soil removal benefits achieved
by incorporation of the polymeric materials herein into such com-
positions. These examples are illustrative of the present inven-
tion and are not considered as limiting thereof.
EXAMPLE I
The granular hard surface cleaning compositions of the
following formulation is prepared in conventional manner.
1059~03
Component Weight Percent
Surfactant
Sodium Cll 8 linear alkyl benzene
sulfonate (LAS) 0.9% "Sterox CD*t
ethoxylated tall oil) 0.1%
Sodium tripolyphosphate 20
Trisodium phosphate 20
Sodium sesquicarbonate 57
Polyvinyl alcohol
("Elvanol" 90/50**, 99-100% 0.025
hydrolyzed)
("Elvanol" is a Trademark)
Sodium alginate*** 0.025
Moisture and miscellaneous Balance
100
*Marketed by Monsanto Company
**Marketed by E.I. Dupont (viscosity of 12-14 cp. at 20 C,
4% by weight aqueous solution and a molecular weight
within the range of the herein claimed invention)
***Marketed by Edward Mendell Company as "Cecalgine TBV"
(trademark)
t Trademark
Such a composition can be dissolved in water to the
extent of about 1.3% by weight to provide a cleaning solution
suitable for effectively removing a variety of soil types from a
variety of hard surfaces. Use of such a cleaning solution in con-
ventional manner produces little undesirable solution foaming.
Cleaning solutions prepared in this manner from such a composi-
tion leave little insightly filming or streaking on hard surfaces
cleaned therewith.
Compositions of substantially similar performance
characteristics are realized when in the Example I composition
the PVA material is replaced with an equivalent amount of a
commercially available polyvinyl pyrrolidone, such as K-60
- 22 -
lOS9~03
marketed by GAF Corp., having a degree of polymerization of about
1500. Substantially similar results are obtained when the sodium
alginate is replaced with an equivalent amount of xanthan gum
("Biopolymer X-23"* marketed by Melle-Bezons Co.) in the above
Example I compositions.
Soil Removal Evaluation Method
The ability of the compositions of the instant invention
to remove soil from hard surfaces is evaluated by means of the
following procedure. Surfaces consisting of individual linoleum
and vinyl asbestos tiles are treated with various types of soil
formulated to simulate naturally occurring home cleaning situa-
tions. Linoleum (L) and vinyl asbestos (VA) are common flooring
materials representative of the types of surfaces encountered by
persons cleaning in home and industry. Rectangular tiles of
25.4 cm long and 6.2 cm wide are used in the evaluation.
Standard soil types approximating normal household soils
are used in determining cleaning efficacy. One soil is called
"particulate soil" (PS) and simulates a street-like soil which
contains a mixture of soot, clay, rust, sand, cement and humus
combined with a small proportion of greasy/fatty materials. This
particulate soil is brushed on the tiles and left to age at room
temperature for varying times, usually at least about one week.
A second soil employed in evaluation is called "kitchen
type soil" (KTS) and comprises a mixture of fatty materials, pre-
dominately unsaturated oils, combined with a minor amount of a
particulate type soil. This KTS soil is sprayed onto the tiles
and then aged at room temperature for relatively long periods,
usually at least about 1-2 months. Alternatively, higher tempera-
ture aging is used to shorten the time necessary to prepare the
soiled tiles.
* Trademark
- 23 -
1059003
A third soil used herein is called waxy soil (WS) and
has a waxy component consisting of floor wax. This soil further
has particulate soil and fatty materials mixed in and is placed
on a clean tile with a roller. The tile is usually aged for about
one week or more at room temperature before testing.
A modified Gardner Washability Machine is employed to
simulate normal hard surface washing conditions. sasically, this
Washability Machine is a device which holds a sponge having
cleaning solution soaked therein onto a tile surface which is to
be cleaned. This sponge is then mechanically drawn at constant
rate and pressure across the tile to be cleaned, each completed
pass being called a stroke. After a predetermined number of
passes or strokes, the tile surface is evaluated for cleanliness.
Utilization of the modified Gardner Washability Machine allows
for each individual soiled tile to be washed with five different
cleaning solutions.
Grading experts visually evaluate soil removal performance
by comparing soil removal achieved with a standard cleaning com-
position (Basis) and soil removal achieved with the compositions
such as those of the instant invention which further contain the
soil removal improvement mixture. Replicate testing is carried
out making paired comparisons between individual treatments on a
single tile.
The following scale is utilized to quantify the differ-
ences between the pairs of cleaned surfaces seen by the visual
graders.
Visual Scoring Scale
0 - equal
+l - I think there is a difference
+2 - I know there is a difference
~3 - I know there is a large difference
+4 - I know there is a very large difference
1059~03
Numerical data obtained from this visual scoring scale
are treated statistically by analysis of variance. Positive values
indicate greater soil removal from the test tile than from tiles
treated with the standard or basis cleaning composition.
Evaluation Results
Several cleaning solutions are prepared by dissolving
compositions substantially similar to those of Example I to the
extent of about 1.3% by weight in water of 5 to 7 grains/gallon
hardness at 46C.
Five separate sets of evaluations are made. Soil removal
grading results in Grading Scale Units (GSU) are provided in
Tables I-V below. The cleaning performance of a solution of a
composition similar to that of Example I (except that no primary
polymeric material or polysaccharide is added) is used as a
standard or basis for comparison by the visual grading experts.
Thus, the cleaning performance of this Example I composition
(without primary polymeric materials or polysaccharides) is com-
pared to the cleaning performance of aqueous solutions of compo-
sitions (similar to Example I compositions) further containing
(1) primary polymeric material, (2) polysaccharide salt, (3)
primary polymeric material and polysaccharide salt at different
levels. The level of the primary polymeric material and/or poly-
saccharide salt appears in each table as a granular product weight
percent. All cleaning comparison results in the Tables are
statistically significant from basis (95% confidence) unless so
noted as non-significant (NS).
Table I shows evaluations of polyvinyl alcohol ("Elvanol"
70-05, 99-100% hydrolyzed; a viscosity of 4-6 cp. at 20C, 4% by
weight aqueous solution, and a molecular weight within the scope
of the invention herein) and a low viscosity sodium algin
("Cecalgine TBV" having a molecular weight within the range
lOS9003
claimed herein marketed by E. Mendell Company) in hard surface
cleaning compositions as compared to a composition without such
materials. As can be seen in this table algin provides no signi-
ficant soil removal benefit while the combination of polyvinyl
alcohol and alginate gives a greater soil removal benefit than
polyvinyl alcohols alone.
Table II similarly shows evaluation of polyvinyl alcohol
("Elvanol" 51-05, 88-89% hydrolyzed; viscosity of 4-6 cp. at 20C,
4% aqueous solution, and a molecular weight within the scope of
the invention herein) and high viscosity xanthan gums ("Biopolymer
XB-23" having a molecular weight within the range claimed herein
marketed by Melle-Bezons Co.) in hard surface cleaning compositions.
Table III shows the evaluation of polyvinyl pyrrolidone
(K-15 having a Mol. Weight 10,000 and marketed by GAF Corp.) along
with algin ("Cecalgine TBV" marketed by Edward Mendell Co.) in hard
surface cleaning compositions. While this polyvinyl pyrrolidone
at this particular level does not provide a significant benefit
alone, the combination of polyvinyl pyrrolidone and alginate does.
Tables IV and V show an evaluation of polyvinyl pyrroli-
dones of different molecular weights in hard surface cleaningcompositions. Table IV shows evaluation of polyvinyl pyrrolidone
(K-60 having a Mol. Wt. 160,000, markete~ by GAF Corp.) and algin
("Cecalgine TBV" marketed by Edward Mendell Co.).
Table V shows evaluation of the soil removal performance
of polyvinyl pyrrolidone (K-90 having a Mol. Wt. 360,000 marketed
by GAF Corp.) and alginate ("Cecalgine TBV" marketed by Edward
Mendell Co.).
As can be seen by examination of these tables soil
removal improvement mixtures generally provide improved soil re-
moval when added to the hard surface cleaning compositions herein.
- 26 -
1~59003
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~OS9~03
EXAMPLE II
The following granular phosphate-free composition is
prepared.
Component Weight Percent
Sodium citrate 12
Sodium carbonate 20
Sodium sesquicarbonate 40
Sodium sulfate 26
Surfactant
Sodium C12 linear alkyl benzene
sulfonate 0.9% "Sterox CD" (polyoxy-
ethylene ester of tall oil)* 0.1%
Perfume capsule shell materials
Polyvinyl alcohol ("Elvanol" 51-05)** 0.5
Sodium/calcium alginate*** 0.5
Water, perfume and miscellaneous Balance
to 100%
*Marketed by Monsanto Corp.
**Marketed by E.I. Dupont (as previously described)
***Marketed by Edward Mendell Co. as "Cecalgine TBV"
The polyvinyl alcohol and sodium/calcium alginate of
this composition comprise shell materials encapsulating liquid
perfume. The encapsulated perfume is prepared in a manner similar
to that disclosed in U.S. Patent 3,310,612 issued March 21, 1967
to Sommerville. These capsules are hardened as in this Sommerville
patent with a CaC12 hardening bath.
This Example II composition is found to remove soil
more effectively from hard surfaces than a corresponding composi-
tion that does not contain the soil removal improvement mixture
when such compositions are used in a conventional manner.
