Note: Descriptions are shown in the official language in which they were submitted.
2077398
f lELD Of THE INVENTION
This application is a continuation-in-part of copending application U.S
Serial No 7/706,54~ filed 5/24/91 which is a continuation of application U.S.
Seria/ No. 7/552,673 filed 7/16/90 which is a continuation-in-,oart of U.S. Seria
No. 7/297,807 filed 1/17/89, the disclosLlres of which are incorporated herein
by reference.
The present invention relates to the formulation of a stable, acidic
disinfectant all-purpose liquid cleaning compositions for use on hard surfaces.
The compositions are effective in removing soap scum, fatty deposits and
mineral deposits while simultaneously disinfecting the hard surfaces being
cleaned. Cleaning is provided by incorporation of a /ower a/kyl mono and/or
dicarboxylic organic acid and an acid-stable nonionic surfactant system
consisting essentially of an acid stable water-solub/e nonionic surfactant and an
acid stable wa~er-dispersible nonionic surfactant. The pH of the composition is
about 2-4 and preferably 2.5-3.O. Disinfecting properties are provided by
incorporation of an acid-stable, water soluble disinfectant compound such as a
germicida/ quaternary ammonium compound, chlorhexidine or glutaraldehyde. A
cationic or anionic soil-releasing agent which is substantive to the cteaned
surfaces is preferab/y inc/uded in the compositions of the invention to facilitate
removal of so~ls such as soap scum during svbsequent cleanings of the surface.
BACKGROUND OF THE INVENTION
Jhe prior art is replete w;th liquid all purpose hard surface cleaning
compositions which are generally comprised of two types. The first type is a
particulate aqueous suspension having water-insoluble abrasive particles
2077398
suspended therein, which particles are palpable. Some of the cleaners of this
type suffer a stability problem while others have received poor acceptance by
consumers because of their "gritty" feel which causes many people to be
reluctant to use rhem for fear of scratching the surface to be cleaned. The
second type is the fiquid detergent without suspended abrasive and this latter
type is often preferred by consumers. While the liqujd hard surface cleaner
without abrasives is generally a mixture of a surfactant and builder salt in an
aqueous medium, the product formulations in the mar*et p/ace have varied
widely in composition.
The presence of builder salts as an essential ingredient in all purpose hard
surface cleaning compositions to improve cleaning and to maintain an alkaline
pH range, is disclosed in U. S. Patents 4,576,738 and 4,597,887, and in
European Patent Applications 0165885 and 008074~ and in UK Patent
Application 2166153A.
~ lowever, these prior art all-purpose liquid detergents containing detergent
builder salts or other equivalents tend to leave films, spots or streaks on cleaned
unrinsed surfaces, particularly shiny surfaces such as glass or stainless steel.
Thus, such liquids require thorough rinsing of the cleaned surfaces which is a
time-consuming chore for the user.
In order to overcome the problem of rinsing associated with the prior art
all-purposeliquids, U.S. PatentNo. 4,017,409 teaches that paraffin sulfonate
with a reduced concentration of inorganic phosphate builder salt may be
employed. However, such compositions are often unacceptable from an
environmental point of view based upon the phosphate content. Phosphate-free
- 2077398
al/-purpose liquids have been disclosed which contain a major proportion of a
mixture of anionic and nonionic detergents with minor amounts of glyco/ ether
solvent and organic amine as shown in lJ.S. Patent No. 3,935,130. Jhis
approach has not been comp/etely satisfactory due to excessive foaming from
the high leve/s of organic detergents necessary to achieve cleaning and due tO
deposition of soap residue on the cleaned surfaces, leading to residual streaks
and spots.
In order to overcome ~he disadvantages associated with the builder salts,
Japanese Patent Kokai 52- 77111 and European Patent A pplication 0,151,517
have used organic acids to improve detergency of builder-free detergent
compositions. These compositions also contain an organic solvent as an
essential ingredient which functions to dissolve greasy soil and soa,o scum, i.e.,
to improve detergency. Japanese patent 52-77111 uses one or more organic
acids se/ected from the group consisting of glycolic acid, lactic acid, citric acid,
malic acid and malonic acid. European Patent A pplication 0,151,517 uses at
least one water-soluble dicarboxylic acid having a 5-7 carbon chain length,
which includes glutaric, adipic and pimelic acids.
The inclusion of a grease-removing organic solvent in an all purpose liquid
cleaner composition for the degreasing of hard surfaces, is also disclosed in the
above cited patents as well as others. Cleaning compositions containing a high
boiling water-miscible organic solvent such as propylene glycol or ethyJene
glycol-monobutyl ether are disclosed in GB Patent 2166153A; a binary solvent
system of Pinane and an ethylene glycol - or propylene glycol - monoethyl or
monobutyl etheris disclosed in U.S. Patents 4,576,738 and 4,597,887; a dual
2~77398
so/vent system of dipropy/ene g/yco/ methy/ ether and mineral spirits is
disclosed in (J.S. Patent 4,673,524; and a propylene g/ycol monomethy/ ether
and/or dipropy/ene g/yco/ monomethyl ether as a penetrant to penetrate road
film is disc/osed in U. S. Patent 4, 670, 171.
The prior art a/so discloses acidic /iquid cleaning corrtpositions containing
organic so/vents. A microemulsion-based acid composition containing
phosphoric ester surfactants, hydrocarbon solvents and phosphoric acid for use
as an all-purpose meta/ surface cleaner is disclosed in U.S. Patent 4,540,448.
U.S. Patent 4,501,680 discloses an acidic liquid detergent for cleaning ceramic
tiles without eroding the grout between the ti/es. This composition contains
two acids
~i.e., glvtaric acid and phosphoric acid~, a nonionic surfactant, and an organic
solvent.
I /owever, none of the above-cited prior art, including the acidic all
purpose cleaners, provides cleaning compositions which simu/tane- ous/y
disinfect the hard surfaces being c/eaned.
I/owever, non-acidic disinfectant compositions containing the combination
of a quaternary ammonium germicida/ compound and a nony/pheno/-ethy/ene
oxide condensate in an aqueous solution are disclosed in U. S. Patent No.
3,017,278 for use in sterilizing medical and dental instruments and in U.S.
Patent No. 3,052,604 for direct application to human and anima/ tissue
surfaces to promote wound hea/ing.
A/so, U.S. Patent No. 3,223,643 discloses a /iqvid acid detergent-sanitizer
composition of pH 2.5 - 3.5 containing phosphoric acid, a C0-C~O a/kyl dimethyl
2~7739~
benzyl ammonium chloride sanitizer, and an alkylaryl polyether alcohol having
about 5 to 7.5 ethylene oxide units. The nonionic detergent ~nd the quaternary
ammonium compound are in a 1: 1 ratio in the disclosed compositions.
U.S. Patent No. 4,661,523 disc/oses a concentrated acidic disinfectant
composition having a pH of 3.5-4 which contains a synergistic bactericidal
mixture of a/dehydes and a quaternary ammonium compound,
phosphonocarboxy/ic acid, and an amino-po/ycarboxy/ic acid sa/t, in an aqueous
or aqueous-organic solvent vehicle.
German Patent Appln. 344590? disc/oses a disinfectant agent concentrate
in an aqueous or aqueous-organic solvent medium containing a synergistic
mixture of hydrogen peroxide, a quaternary ammonium compound, a biguanide
as the antimicrobial disinfectant agent, a complexing agent such as alkane poly-
phosphonic acids and salts thereof to stabi/ize the hydrogen peroxide, an acid
such as boric acid or phosphoric acid in an amount to provide a plf of 3-7 and
optional/y a nonionic and/or amphoteric surfactant.
U.S. Patent No. 3,223,643, U.S. Patent No. 4,661,523 and German
Patent Appln. 3445901 are all acidic disinfecting cleaners. However, all of
these prior art compositions incorporate phosphate acids and consequently have
associated problems concerning environmental safety.
None of the above-mentioned disinfectant cleaning compositions provide a
stable acidic disinfectant ali-purpose liquid cleaning composition with improved
removal of soap scum in the absence of detergent builders, organic solvents and
phosphate compounds. In addition, unlike the cleaning compositions of the
present invention, the prior art compositions are unable to provide a cleaned
2077398
surface such that the remova/ of soi/ during subsequent cleanings is significantly
enhanced.
SUMMARY OF THE /NVENTION
/t has been found that a stab/e homogenous, acidic disinfectant a/ipurpose
/iquid c/eaning composition having improved c/eaning and disinfecting properties
with minima/ damage to hard surfaces can be prepared in accordance with the
present invention in the absence of a bui/der sa/t and an organic so/vent. The
compositions comprise ~a) from about 0.~-4% by weight of a nonionic
surfactant system containing a mixture of an acid stab/e water so/ub/e nonionic
surfactant and an acid stable water dispersible nonionic surfactant in
approximately a 4:1 to 4:3 ratio by weight of soluble to dispersible surfactant;
IbJ at least 0. 1% by weight of an acid stable disinfectant compound; /cJ about
3-7% by weight of an organic acid selected from the group consisting of a
lower aliphatic monocarboxy/ic acid, dicarboxy/ic acid and m/xtures thereof,
and; /dJ optiona//y 0-2% of an acid stab/e cationic or anionic soi/ re/easing
agent, in an aqueous medium. The /iquid c/eaning compositions have a pil of
approximately 2-4 and may be in the form of dilute solu-ions or dilute
microemulsions. These acidic cleaning compositions are particu/arly suitable for
cleaning hard surfaces svch as plastic, vitreous and meta/ surfaces, and more
specifically grout, stainless steel, glass and ceramic tile. The instant novel liquid
cleaner penetrates soil efficiently, spreads quickly and disinfects with little or no
damage to the hard surfaces being cleaned. The present compositions exhibit
.
:
- 2~73~8
improved efficacy in removing soap scum and mineral deposits and, therefore,
have particular utility in the c/eamng of bathrooms and kitchens.
Accordingly, the primary object of the present invention is to provide an
acidic disinfectant liqùid cleaning composition which effective/y disinfects and
removes soils, particularly soap scum and mineral de,oosits, from hard surfaces
without damaging the cleaned svrface. An additional object of the invention is
to provide said acidic disinfectant liquid cleaning composition also containing a
surface soil releasing agent functional at acid pH to facilitate remova/ of soil
during subsequent cleanings of the previously cleaned surface.
In a preferred embodiment of the invention, the liquid all purpose
disinfectant cleaning compositions comprise, by weight, about 2-4% of a
nonionic detergent system wherein the ratio of acid-stable water soluble
nonionic surfactant to acid-stable water dispersib/e nonionic surfactant is about
3:1 to 3:2, at /east 0. 1% of a water soluble, acid stable germicidal or
antimicrobial compound, about 3-5% of a /ower aliphatic dicarboxylic acid
mixture, about 0.25-1% of an acid stab/e cationic or anionic soi/ re/ease
treatment agent in an aqueous medium, said liquid cleaning composition having
a pH of about 2.5-3.
DETAILED DESCRIP~ION OF THE INVENTION
The acidic disinfectant /iquid detergent compositions of the present
invention are in the form of stable aqueous solutions or microemulsions. The
compositions comprise water, an organic acid or a mixture of organic acids, a
mixture of acid-stable water-soluble and water-dispersible nonionic surfactants
and a water soluble, acid-stable germicidal or disinfectant compound.
207~39~
Optionally, a cationic or anionic soil releasing compound which is substantive to
the surface being c/eaned may be included in the composition in order to reduce
subsequent adhesion of soil and provide easier recleaning of the treated surface.
Additional minor ingredients commonly used in the preparation of cosmetically
and commercially acceptable liquid detergent compositions may also be present
in the composition of the present invention and will be obvious to those skil/ed
in the art upon practicing the invention. These minor ingredients include, but
are not /imited to, acid stabte perfumes and fragrances, compatible coloring
agenrs, viscosifiers and the like.
The active detergent ingredient of the present all-purpose liquid detergent
composition consists essentially of a mixture of acid-stable water soluble and
water dispersible nonionic surfactants. The mixture of surfactants acts
synergistically to provide rapid and efficient spreading of the detergent
composition over the surface to be cleaned. The synergistic mixture of nonionic
surfactants provides improved detergency against soils such as soap scum and
mineral deposits when compared to commercially available acidic liquid hard
surface cleaning products but with /ess damage to surfaces as compared with
with the most acidic of such commercial products.
The nonionic surfactants useful in the present inventive compositions must
be stable at the acid pH of the liquid detergent composition. They are generally
the condensation product of an organic aliphatic or alkyl aromatic hydrophobic
compound and hydrophilic ethylene oxide or propylene oxide groups.
Hydrophobic compounds having a carboxy, hydroxy, or an amido group or an
amino group with a free hydrogen can be condensed with ethylene oxide,
207739~
po/yerhylene glycol or propylene oxide to form a nonionic detergent. The /ength
of the polyetheneoxy or po/ypropeneoxy chain can be adjusted during the
condensation reaction to achieve a desired ratio of hydrophobic and hydrophilic
e/ements. The length of the hydrophi/ic ~po/arJ chain re/ative to the length of
the hydrophobic /nonpolarJ component also determines the degree of solubility
of the nonionic detergent in water, i.e the degree of polarity.
The degree of so/ubility in water of nonionic surfactants is characterized
and predicted in the art by the hydrophi/e//ipophi/e balance ~HLBJ of the
surfactant mo/ecu/e. Nonionic detergents which are more /ipophi/ic, that is oil
soluble, have low HLB numbers. These form dispersions when agitated in
water. High HLB numbers correspond to increased water solubility of the
nonionic detergent. For nonionic detergents, the HLB number is directly related
to the relative molar ratio of ethy/ene oxide and/or propylene oxide to the alkyl
chain of the molecule.
The most useful mixtures of nonionic surfactants for purposes of the
invention are the acid stable condensation products of higher alcohols
containing 8 to 20 carbon atoms in straight or branched chain configuration,
preferably containing 8 to 14 carbon atoms.
Jhe water soluble nonionic surfactant companent of the surfactant mixture
has a minimum HLB number of approximately 11 and forms a translucent to
c/ear dispersion or a c/ear solution when mixed with water. Examp/es of water
soluble nonionic surfactants usefu/ in the present invention include, but are not
limited to, Cg-,, alcohols condensed with 8 ethoxyethylene radicals ~for example
Neodol 91-8 avai/able from Shell Oil CoJ which have an HLB number of
- 207739~
approximately 13.9 and C9 11 a/cohols condensed with 6 ethoxyethylene radicals
~for example Neodol 91-6 availab/e from Shell Oil Co. J with an HLB number of
approximate/y 12.5. Other water soluble nonionic surfactants having HLB
numbers of 11 or greater which are useful in the present invention are well
known in the art, such as those nonionic surfactants which are the
condensation products of an alkyl phenol with ethylene oxide ~the nonyl
phenolsJ or higher alcohols condensed with a combination of ethylene oxide and
propylene oxide Ithe Pluronics) having a terminal ethoxylate group.
The water-dispersible nonionic surfactant component of the surfactant
mixture of the present invention is characterized by an HL~ number of about 7-
10. These surfactants, being more lipophilic, form a milky dispersion when
agitated in water. Examples of water-dispersible nonionic surfactants useful in
the present invention include Cg-C,, alkanol ethoxylates having 2.5 moles of
ethylene oxide per mole of alcohol ~for example Neodol 91-2. 5 available from
Shell Oil Co. having HLB = 8.5). Additional examples of suitable water-
dispersible nonionic surfactants and may be selected from such surfactant
groups as the nonylphenols and the Pluronics as described above.
Nonionic surfactant mixtures are assayed for their synergistic properties in
two assay systems. Spreading properties of the surfactant mixture are
assessed on clean glass surfaces. Approximately 20 microliters of a surfactant
mixture containing a total concentration of surfactant of less than 5% is placed
a3 a droplet on a clean glass surface and allowed to sit undisturbed for
approximately two minutes. At that time, the diameter of the surfactant drop is
measured. A diameter of at least about 20 mm indicates a synergistic effect on
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surface spreading for the surfactant mixture. Under simil~r test conditions, a
deionked water drop spreads to approximately 8 mm in diameter and surfactant
so/utions which do not exhibit enhanced spreading reach a maximum diameter
of about 15 mm.
The soil c/eaning or detergency properties of the nonionic surfactant
mixtures are determined using the Roll-up test, in which
9 ml of the surfactant mixture to be tested is added to a vial containing
approximately 10 microliters of oleic acid ~/aced in the vial as a droplet. The
amount of time required for the oleic acid droplet to rise to the surface of the
liquid is measured. A colored dye may be added to the oleic acid for improved
visibility. Decreasing roll-up time is indicative of increasing detergent efficacy,
and effective detergents generally exhibit a roll-up time of 60 seconds or less.
Effective acid-stab/e nonionic surfactant mixtures in accordance with the
Invention provide ro/l-up times of about 60 seconds or less when tested in this
system. Within nonionic surfactant ratios of 3:1 to 3:2 by weight, ro//-up times
of about 30 seconds or less were obtained using Neodol 91-8 Iwater solubleJ in
combination with Neodol 91-2.5 Iwater dispersib/e) in an acidic aqueous
medium. Samples consisting of Neodol 91-8 in combination wi~h Neodol 91-2.
a/so showed ro//-up times of less than 60 seconds within the range of weight
ratios of 4:1 to 4:3. These synergistic surfactant mixtrJres e/iminate the need
for grease-removing organic solvents such as are conventionally used in liquid
hard surface cleaning compositions. The mixtures remain stable over a wide
range of temperatures.
,
2~77398
The liquid cleaner of the present invention cleans soap scum soil and
removes mineral deposits through the action of both the nonionic surfactant
system and, additionally, at least one organic acid selected from the group
consisting of /ower aliphatic monocarboxylic acids and dicarboxylic acids in an
amount of about 3-7% by weight of the composition. Representative members
of the aliphatic acids include C,-C6 alkyl and alkenyl monobasic acids and
dibasic acids such as glutaric acid, succjnic acid, propionic acid, adipic acid,
hydroxyacetic acid and mixtures thereof. Glutaric acid is preferred, however, a
mixture of the dibasic acids, adipic, glutaric and succinic acids is easily available
commercially and is useful in the inventive compositions. The ratio of the acids
in the foregoing mixture is adjusted to maximize water solubility of the mixture
by employing g/utaric acid, the most water-soluble of these three saturated
aliphatic dibasic acids, as the major component. Generally, the weight ratio of
adipic acid:glutaric acid: succinic acid is selected to be within the range of 1-
3: t-8: 1-5, and preferably within the range of 1-2:1-6:1-3. The organic acids
provide moderate acidity to the cleaning compositions of present invention and
thereby enhance cleaning performance, particvlarly removal of soap scum from
tiles and other hard surfaces, with very little damage to the grout between the
tiles and with reduced irritation to the skin of the user.
A third essential ingredient present in the liquid cleaning composition of
the present invention is an acid-stable antimicrobial, germicidal or disinfectant
compound comprising at least about 0. 1% by weight of the composition.
Suitable antimicrobial germicidal and disinfectant compounds are well known in
the art and include chlorhexidine, acid stable germicidal quaternary ammonium
207739~
compounds /e.g. Variquat 50 Mc mari~eted by Sherex or BTC 2125 M marketed
by Onyx~ glutaraldehyde, forrnaldehyde, and betaines. Minor amounts, up to
about 2%, of isopropyl alcohol may also be included in the composition to
enhance the antimicrobial effect, particularly against Pseudomonas. It will be
obvious to those skilled in the art that useful antimicrobials may be cationic,
nonionic or anionic as long as the compound se/ected is acid stable and does
not interact with other components of the composition, maintaining germicida/
activity without adversely affecting the cleaning properties of the composition.
The pH of the acidic liquid detergent composftion is adjusted to maximke
the antimicrobial effect of the disinfecting agent whi/e maintaining effective
cleaning of soap scum and oily soils. Generally, the pH is from about 2-4,
preferably about 2. 5-3. tn addition to providing efficient c/eaning, this pH range
is less damaging to the cleaned surface and /ess ir~itating to the skin than the
commercia/ly available acidic cleaners.
Optionally, an acid-stable cationic or anionic soil releasing agent may be
included in the composition in an amount of about 0.25% to 2% by weight,
preferably 0.25-1% weight. The soil releasing agent must be substantive to the
surface being cleaned at the pH of the liquid cleaning composition and acts to
inhibit subsequent redeposition and/or adhesion of soils, particularly soap scum
and mineral deposits, on the cleaned surface. Although the applicants do not
wish to be bound by any theory of operation, it is believed that the cleaned
surface is modified by the deposition of the soil releasing agent, which provides
for easier remova/ of soils during subsequent cleanings. Compounds which
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promore surface hydration are believed to be rhe most efficient soil relæasing
agents for the present cleaning compositions.
The soil releasing agent may be cationic or anionic, se/ected to be acid-
stable and compatible with the other components of the composition, especially
the disinfectant Compounds useful for their soil releasing properties include
antistatic polymers consisting of recurring monomers of beta ~trialkyl
ammoniuml ethyl methacrylate twherein the alkyl group attached to the
ammonium moiety may be ethyl or methyl~ and styrene maleic anhydride
polymers with antifogging properties.
The antistatic polymers useful as soil releasing agents in the present
invention have the following basic structure:
1l
These antistatic compounds are poly beta-trialkyl ammonium ethyl
methacry/ates ~herein abbreviated as AAEMJ wherein the alkyl groups ~RJ may
be methyl or ethyl or a mixture thereaf, and X is an anion which may be a halide
such as chloride, an alkyl sulfate such as methyl sulfate or lauryl sulfate or an
ethoxylated alkyl sulfate or mixtures thereof.
A preferred antistatic polymer for use as a soil releasing agent in the
present invention is poly beta [methyl diethyl ammoniuml ethyl methacrylate
methyl sulfate ~herein abbreviated as MDAEMJ. MDAEM has the following basic
structure:
207739~
"~ , ' \ N+ --- Et X
o \// \Me
wherein Me is methyl, Et is ethyl and X is methyl sulfate. The molecular weight
of the polymer is about 2, 000-500, 000.
MDAEM is avai/able commercia/ly as an opaque, moderately viscous
emulsion having a pH of 6-8 and a specific gr~vity of 1. It is complete/y
miscib/e in w~ter. The active antistatic ingredients constitute approximate/y 15-
20% by weight and the volatile ingredients constitute approximately 80-8~% by
weight of the commercia/ product, which is stable, will not decompose or
polymerize, and is incompatible with oxidizing or reducing agents. i3ecause
sodium lauryl su/fate is present in the commercial preparation, the polymer is
present as a 3:1 mixture of the methyl sulfate and lauryl sulfate forms. The
inc/usion of the soi/-release agent MDAEM in the present novel acid disinfectant
all-purpose liquid c/eaning composition provides significant/y enhanced soi/
removal on subsequent cleaning of pretreated surfaces. Thus, during rec/eaning
of a previously c/eaned surface, soil removal of soap scum from a hard surface
such as bathroom tlle or the like can be effected with significantly /ess effort as
compared to the use of commercia//y available products.
The balance of the novel acidic disinfectant liquid cleaning composition is
water, preferably distilled water, reduced by any optiona/ ingredients which may
be present. Genera/ly, the proportion of water in the compositions is about
88% to 94% by weight of the composition. Those skilled in the art wil/ readi/y
16
2077398
appreciate that minor amounts of additiona/ ingredients may be optiona//y
present to provide cosmetical/y appea/ing products and increase consvmer
acceptabi/ity Examp/es of such adjuvants inc/ude acid-stab/e co/oring agents,
fragr~nces, perfumes, viscosifiers, and plt adjusting agents such as 50%
sodium hydroxide.
/n final form, the a/l-purpose /iquid detergents are homogeneous aqueous
compositions which exhibit stabi/ity at both reduced and increased
temperatures. More specifica//y, such compositions remain stab/e in the range
of 5C to 40C. The /iquids are readi/y pourab/e and free f/owing from any
suitab/e container or may be sprayed from a pump-type sprayer.
The compositions are direct/y ready for use. On/y minima/ rinsing is needed
and substantia/ly no residue or streaks are left behind on the cleaned surface.
Because the compositions are free of detergent builders such as alkali metal
polyphosphates they are environmentally acceptable and provide a better
"shine" on cleaned hard surfaces.
Typically, the inventive compositions are prepared simply by combining a/l
of the ingredients in a suitab/e mixing vesse/ or container. Genera//y, ~he
various ingredients can be added sequentia//y, or a// at once, to form an aqueous
solution of each or al/ of the essential ingredients. Preferably, when a fragrance
is present, the fragrance is first disso/ved in the water dispersible nonionic
surfactant which is then added to the other ingredients in aqueous acid solution.
When the surfactant/fragrance mixture is added to the aqueous acid solution
containing the remaining ingredients, the solution may become s/ightly hazy. If
a cationic disinfectant compound is added to the aqueous mixture, the fragrance
20773g8
becomes completely solubilized and the final mixture is clear as well as stable.
The compositions may be prepared at room temperature.
In use, the compositions of this invention are applied to the surfaces to be
cleaned with a cloth or sponge or by sprayjng onto ceramic or other surfaces
which have been soiled by accumulations of insoluble soaps, mineral deposits,
and oi/y soi/s. The c/eaning compositions, without added thickeners, are of
about the viscosity of water but may be thinner than water. The material wi//
usua//y be a/lowed to remain on the surface to be cleaned for a period from 10
seconds to 5 or 10 minutes, but preferably such contact time will be from about
30 seconds to five minures or from 1 to 3 minutes. The liquid cleaner
composition may then be removed either by wiping or rinsing with water.
These compositions leave substantially no spots or streaks whether or not they
are rinsed from the cleaned surface.
The compositions of the invention provide enhanced cleaning with /ess
acidity as compared to commercial/y available cleaners and, therefore, are less
damaging to the cleaned surface. Microscopic examinations of the grout
between tiles shows no erosion or other deterioration after cleaning as
compared to commonly available cleaning compositions.
The following examples illustrate the acidic liquid disinfectant cleaning
compositions of the described invention. Unless otherwise specified, a/l
percentages are by weight. The exemplified compositions are illustrative on/y
and do not /imit the scope of the invention.
18
2~77398
EXAMPLE 1
/NGREDIENT WE GHT %
DAGS' 5.0
Neodol 9 l ~2 1 5
Neodol 91-2.53 O. 7
BTC 2125M4 ~30% solution) 0.4
Water QS
p~ 2.5
1. Dlcarboxylic acids mixture of 1 1. 6% adipic, 57. 5% glutaric and 27%
succinic acids in the form of water soluble white flakes having the
formula HOOC-~CH2J2 4-COOH marketed by Dupont.
æ c9-c" alcohol E08: 1 marketed by Shell Oi/ Co.
3. C9-C" alcohol E02.5:1 marketed by She/l Oi/ Co.
4. 3enzalkonium chtoride lC6H6CH2N~CH3J2C8 ,0 alkylmixturel ~ C~ marketed
by Onyx.
This composition is prepared by adding DAGS to the formula amount of
water to form an acidic aqueous solution, to which is added either
simultaneously or sequentially the Neodo/s and the B JC. If necessary, 50%
sodium hydroxide is added to adjust the pH to 2. 5. A c/ear stable aqueous
composition is formed having improved cleaning and disinfecting properties.
The acidic disinfectant cleaning composition of Example 1 was tested
comparatively against commercial/y available cleaning compositions for cleaning
performance in a soap scum remova/ test. Four comparative tests were
conducted, each consisting of the composition of Example 1 against a single
commercia/ cleaner. Etched white ceramic tiles ~4.25 in. x 4.25 in.~ were
sprayed with a 250 9/1 solution of CaC12 2H20 followed by a red dyed 5%
sodium oleate solution. After permitting the tiles to dry for one hour at 30C,
the soiling procedure was repeated. The soil so produced was uniform and
19
~07739~
reproducible within acceptable limits. A fter the second soi/ layer was dried, the
tiles were mounted in a Gardner Abrasion Tester ~Pacific Scientific Gardner--
Neotec Instrument Div.~ equipped with two cellulose sponges measuring 5cm x
5cm x 5cm. Three grams of the liquid cleaning composition being tested were
pipetted onto the sponge holding 5gms water, and the soiled tiles were
subjected to 20 back and forth strokes of the sponge ~abrader cyc/esJ. A
reflectometer was used to measure the reflectance before and after the 20
abrader cycles and the % soil removal was determined. The results obtained
are set forth in Table 1 below:
TABLE 1
PERCENT SOAP SCUM REMO VAL OF COMPOSIT!ON OF THE INVENTION VERSUS
COMMERCIAL CLEANING COMPQSITIONS
Test Example 1 Dow Disinfectant Lysol Disinfectant Lime ScrubQ~ oH 2.5 Bathroom Basin, Tub & Away3 Free4
C/e~ner' pH 12 rie2 C/eaner oH 12 oH 0. 5 ~H 1. 0
52 % 1 5 %
2 49 % ----- 1 1 % ----- ----
3 4 7 % --- --- 65 /0 ---
4 69% --- --- --- 80%
IDow Consumer Products, Inc.
Lehn & Fink Products, Division of Sterling Drug, Inc.
3Benckiser Consumer Products, Inc.
4Benckiser Consumer Products, Inc.
The Standard Deviation of the above resu/ts is plus or minus 5 soil remova/
percent units.
The above results demonstrate that the acidic cleaning composition of the
present invention is markedly superior to commercially available alkaline
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compositions in cleaning efficacy. As compared to commercia/ acidic cleaners,
the present composition provides s/ightly mferior cleaning of soap scum but is
considerably less acidic than these commercial formulas and therefore less
irritating to the skin of the user. Moreover, the composition of the invention
has disinfectant properties.
EXAMPLE 2
Formulas A and B were prepafed as shown below:
FORMULA A:
INGREDIENT WEIGHT /0
DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2. 5 O. 7
B JC 2125M /50% solution) 0.4
Perfume 0. 2
Water QS
FORM~LA B:
DAGS 5.0
Neodol 91-8 1.5
Neodo/ 91-2.5 O. 7
BTC 2125M ~50% solution~ 0.4
Perfume 0. 2
MDAEM' ~15-20% solution~ 1.4
Water QS
'Commercially available preparation consisting of 15-20% polymer, 5-10%;sopropanol, 3-5% N-octanol, 3-5% sodium acetate, 1-3% terpene
hydrocarbons and 3-5% sodium lauryl sulfate.
Formula A was prepared by separately dissolving the fragrance jn
Neodol 91 -æ 5 and adding Neodol 91-8 to form a Neodol-fragrance mixture. An
acid water solution was made by dissolving DAGS in the formula amount of
21
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water to which was added the perfume-Neodol mixture. A slightly hazy
so/ution was formed. The benzalkonium chloride was added to the acid water
solution which clarified the haziness, and the pH was adjusted to a pH of 2.5,
as needed, by the addition of a 50% sodium hydroxide solution.
Formula B was prepared in the same way as Formula A except that
MDAEM was added to the acidic aqueous solution containing perfume, BTC and
the Neodols Optionally, 2.0% isopropanol may be included in formv/a B for
cosmetic purposes, to clarify the slightly hazy composition which results when
MDAEM is added to the formulation. Isopropanol does not interfere with the
cleaning performance of the composition and other low molecular weight
alcohols may be substituted for isopropanol for purposes of producing a clear
composition containing MDAEM. Inclusion of about 2.0% of a low molecular
weight alcohol, particularly isopropanol, provides the additional advantage to the
composition of enhancing the antimicrobial properties of the disinfectant
cleaner.
Formula A and Formula B above were compared for cleaning
performance in the soap scum removal test set forth in Example 1, using 20
abrader cycles. The results are presented in Table 2:
TABLE 2
PERCENTSOAP SCUM F~EMOVAL
FORMULA
A Q
67% 65%
20773~8
These results demonstrate that inc/usion of the soil-releasing agent
MDAEM does not interfere with the first-time cleaning performance of the acidic
liquid disinfectant detergent composition of the present invention.
EXAMPLE 3
Formulas C and D were prepared as shown below:
FORMULA C:
INGREDIENT WE/GHT ~O
DAGS 5.0
Neodol 91-8 1.5
Neodol 91-2. 5 O. 7
Chlorhexidine 0. 2
Water QS
FQRMULA D
DAGS 5.0
Neodol 91-8 1 5
Neodol 91-2. 5 o, 7
Chlorhexidine 0. 2
MDAEM ~15-20% solution~ 2. 3
Water QS
Formulas C and D were prepared as described in Example 2 for the
corresponding compositions. The resu/ts of the soap scum removal tests for
Formulas C and D are given in Jable 3 below:
TABLE 3
PERCENT SOAP SCUM REMOVAL
FOP~MULA
C D
Test#1 49% 60%
Test #2 52% 65%
: 207739~
EXA MPLE 4
Formulas E and F were prepared as shown be/ow~
FORMULA E:
INGREDIENJ WEIQHT %
DAGS 5.0
Neodol 91-8 1-5
Neodol 91-2. 5 7
Variquat 50 MC (50% solution) 0.4
Water QS
FO~MULA F:
DAGS 5.0
Neodol 91-8 1 5
Neodol 91-2. 5 O. 7
Variquat 50 MC ~50% solutionJ 0.4
MDAEM ~15-20% solutionJ 2. 3
Water QS
To test for ease of recleaning, ceramic tiles were cleaned with Formulas
E and F under normal ambient conditions of temperature and humidity, rinsed
with distilled water and patted dry. Jhe tiles were then soiled as described in
the soap scum remova/ test of Example 1 and recleaned, a/so under normal
- ambient conditions of temperature and humidity, using a non-acidic
conventional cleaning composition comprised of an aqueous solvtion of 1:1 by
weight Neodol 91-6 and Neodol 91-2. 5. Ten abrader cyc/es were used for the
recleaning step, which represents one-half the number of abrader cyc/es used
in the first-cleaning tests described in Examples 1-3. The resu/ts of this
recleaning test are given in Table 4 below:
24
2~773g8
TABLE 4
PERCENT SOAP SCUM REMOVAL ON RECLEANING
PRETREA TMENT
FORMULA
E E
24% 95%
As shown in Table 4, pretreatment of the test tjles with the inventive
composition F containing a soil releasjng agent provided 95% soil removal with
10 abrader cycles. Pretreatment with formula E withovt the soil releasing agent
provided only 24% soi/ removal with an equiva/ent amount of scrubbing in the
recleaning test. These results demonstrate that ease of recleaning is
siqnlficantly enhanced by inclusion of the soil releasing agent in the inventive
composition.
Ease of recleaning was found to improve as humidity levels were
increased above about 35% humidity.
