Note: Descriptions are shown in the official language in which they were submitted.
2 ~ 1 7 ~ S
IR-4874 ¦ HARD SURF~CE LIQUID CLEANINÇ: COMPOSITION
WIT13 ANTI SOILING POLYHeR
¦ This application is a continuation-in-part of our
commonly a~signed, copending application Serial No. 07/297,807,
filed January 17, 1989.
BACKGROUN~ OF THE INVEN~ION
The present invention relates to an aqueous formulation
¦of an anti-soiling recleaning agent for use on common household
¦hard surface~ to impart soil release propertlee thereto to
¦facilitate subsequent cleaning. The composltions may also
¦include various surface active ingredient~ and/or disinEecting
¦agents to provide effective cleaning and/or disinfecting of the
¦hard surface being treated. More particul~rly, certain cationic,
¦anionic or nonlonic polymeric soil-releaslng agent which is
¦substantive to the treated hard surface iB deposited from an
¦aqueou6 solution, preferably together with various cleaning
¦and/or disinfecting agents or present aleaning/disinfecting, to
¦facilitatè removal of subse~uently deposited soils, such as soap
scum, during cleaning or recleaning of the solled surEace.
In our prior application, Ser~al No. 297,807, Eiled
January 17, 1989, it was reported that aquecus cleaning
compositions with certain nonionic surfactants, characterized by
their water solubilities and HLB values gave good performance in
preventing the adhesion o soap ~cum on hard household surfaces,
such as ceramic tile~, when the tiles are soaked in a 1~ aqueous
solution. It was hypothesized that the nonionic surfactant
system treatment increased the degree of hydration or water
content on the hard surface resulting in preventing tenacious
adhesion of the ~oap scum to the tile surface. The prior
application al~o disclo~ed that addition of up to 2~ of an acid
~ ~ ,
,~"~,.S.7(J8~. ~
¦stable cationic or anionic ~oil release agent enhanced this
¦effect. Example 4 of the prlor appl~cation demonstrated that
¦incorporation of 2.3~ of a 15-2~ solution of poly-[beta~methyl
l diethylammonium) ethylmethacrylate] (poly(MDAEM)) in the mixed
¦ nonionic surfactant system aqueou~ ac~dlc d~s~nfectant
composition results in significant improvement of ea~e of
recleaning soiled tiles. The disclosure of our prior
application, Serial No. 297,807, i8 incorporated herein in its
¦entirety by xeference thereto.
¦ However, the efficacy of the soil relea~e polymers,
¦such a~ poly(MDAEM), as a hard surface recleaning or anti-soiling
¦agent, is not limited to the acidic aqueous dlsinfecting cleaning
¦composition of our prior application, or to poly(MD~EM), but
¦appears to a broader range of anionic, catlonlc and nonionic
¦polymers having certain characteristics, and have utility when
¦used alone, or in the presence of other surfactant systems.
¦ SUMMARY OF THE INVENTION
¦ In one aspect of the inventi.on, therefore, there is
provided a hard surface treating composit~on for lmproving the
soil removal or anti-soLling cllaracteristlc~ of the treated
surface, the composition compri~ing an aqueou~ liquld solution or
di~per~ion of a water-soluble cationic, anionic or nonionic
polymer which is capable of being adsorbed to the hard surface,
and which when applied to the hard surface, leaves a residual
anti-soiling polymer layer thereon wlllah lncrea~e~ the
hydrophilicity thereof, whereby the `nydration of the hard surface
from the ambient atmospheric water vapor facilitates removal of
soils subsequently deposited thereon, i.e. less work. is required
to remove the soil than in the absence of the re~idua]. layer.
: ;' :
~Jf~
n another a~pect, the inventlon provide~ a hard
surface treating compo~ition for cleaning the ~urface and for
improving tlle ~oil removal characteristics thereof, the
l composition comprising an aqueous liquld contalnlng at least one
¦ non-soap synthetic ~urfactant and a aoll release promoting water-
soluble cationic, anionic or nonionic polymer which i5 capable
of being adsorbed to the hard surface, and which, when ab60rbed
to the hard surface, leaves a residual ant~-~oiling polymer layer
l thereon which increases the hydrophilicity thereof, whereby the ;-
¦ hydration of ~aid hard surface witll ambient atmospheric water
vapor facilitates removal of solls subsequently deposlted
thereon. .
In still another a~pect of the invention, there i8
l provided a method for improving the soil remo~al property of
¦household hard surfaces which comprises applying to the hard
¦6urface an aqueou~ solution of a ~oil release promoting water-
¦~oluble cationic, anionic or nonionic polymer which will bs
¦adsorbed by the ha:rd surface and drying the hard surEace whereby
said ad~orbed poly!mer form~ a re~ldual nnt~-eoJling hydrophlllc
layer of said soil release promotlng polymer on said surEace,
whereby removal of aoils subsequently deposited thereorl requlres
les~ work than in the absence of said re~idual layer.
~ ccording to still another aspect of the inverltion,
there 18 provided a method for increasing gloss of worn tiles
which comprise6 treating the worn tile with an aqueous solution
of a cationic quaternized polymer having a molecular weight in
the range of from about 4,000 to 100,000, the polymer being
adsorbable to the surface of said tlle and, when ad~orbed to said
tile, increase6 the hydrophiliclty thereof.
;,, . ' ' .
DETAILED DESCRIPTION OF THE INVENTION
Although not wishing to be bound by any apecific theory
of operation, it is presently believed that the anti-soiling or
soil release polymers which are effective hereln have in common
the property of adsorbing to the hard surface being -treated, for
example, by associating to tKe sllica groups of ceramic type
materials, in such manner that the hydrophilic groups of the
polymer are oriented away from the surface whereby the
hydrophilic groups are available to attract and trap water
molecules. The re~ulting hydrophilic surface can attract and
trap ambient atmo~pheric water vapor (e.g. the moisture in a
humid room) to more effectively reduce adhee~on of solid (or as
referred to by the inventors, to promote "abhesion") by any or
all of the followlng mechanisms:
(1) form a barrler (water film) which prevents or
reduces the contact of Yoil with the surface
(2) form a slip layer that facilitates wiping away of
the soil;
(3) for soils, such as soap ~cum, whiall rely on drying
out as part of their mechani~m of tenaaious adherence, by
preventing the 80il from drying out.
The preferred polymers for providing soil release
(abhesion) properties to hard surfaces are the cationic and
anionic polymers, and especially the cationic quaternized
polymetl)acrylates, such as the beta(tr~Alkyl ammonium)
ethylmethacrylate~ described in our prior application, Serial
No. 297,807, and having repeating units of the formula
.. :. .,. "
`f~
l CE13
S I -CH2~C Rl
C00-C2H4-N~2X-
l ~3
1 where Rl, R2 and R3, which may bo the ~ame or
10 ¦ different, are each lower alkyl groups of 1 to 4 carbon
atoms, preferably methyl or ethyl.
¦ The corresponding acrylates can al~o be used. More
¦generally, the cationic polymers useful herein include
¦homopolymers of unsaturated amines which are at least partially
¦and preferably wholly ~e.g. at least 9S~) quaternized with an
¦appropriate counterion. The preferred unsaturated amines are
¦aminoalkyl esters of acrylic or methacryllc acid, in which the
¦amino group may be ~ubstituted by one or two alkyl, alkenyl,
¦aryl, aralkyl or other suitable group~, or by substituent~ which
¦together with the nitrogen atom form a heterocyclic ring.
¦ The repeating units derived from the aminoalkyl ester
¦is preferably of the formula (I):
R,3
25-CH2 C- / R1
C00-R4-N (I)
R2
wherein R1 and R2, wh~ch may be the same or different,
are hydrogen or alkyl, or together with the nitrogen
atom to which they are attached, form a heterocyclic
ring; R4 is an alkylene group containing 1 to 8 carbon
atom~; and R3 ls methyl or hydrogen.
: ' ~' '',":
~ 3
Preferably both Rl and R2 are alkyl~ of 1 to 4 carbon
atoms, especially methyl or ethyl. When Rl and R2 together with
the nitrogen atom form a heterocycllc r~ng, the ring may have
from 5 to 7 atoms and may include 1 or 2 addltional hetero atoms,
5 such as N, 5 or O in addition to the amine nitrogen atom to which
Rl and R2 are bonded. R3 isrpreferably methyl and R4 preferably
has 2 to 4 carbon atoms~ and e~pecially preferably is ethylene.
The units of formula (I) ln the homopolymer are at
least partially quaternized by reaction with a suitable alkyl
~alt of an acid, such as, for example, methyl or ethyl chloride,
methyl or ethyl sulfate, dlmethyl or diethyl ~ulfate, methyl or
ethyl bromide, and the like. The quatern~zed cationic repeating
unit in the resulting homopolymer will then have the following
formula (II):
R3
-C~2-C- Rl
Coo-R4-N+-R2-x- (II)
R5
where Rl, R2, R3 and R4 are as defined above, Rs iB a
lower alkyl group of from 1 to 4 carbons, preferably
methyl or ethyl, e~pecially methyl, and X~ is a
monovalent anion or l/m of an m-valent anion.
It is most preferred that at lea~t 50~, preferably at
least 80%, more preferably essentially all, i.e. from 95 to 100~,
especially preferably 98 to 100% of the repeatlng units of the
polymer have the quaternized form of formula (II).
The molecular weight of the polymer is not e~pecially
¦critical so long as the polymer 1) is water-soluble, 2) has some
surfaae activity, a~d 3) i~ ad~orbed to th~ hard ~urface from its
aqueous solution in such manner as to increase the hydrophilicity
of the surface. In general, however, good re~ults will be
obtained with the quaternized cationic polymer~ having molecular
weight~ in the range of from about 4,000 to 100,000 or higher,
preferably from about 5,000 to 50,000, more preferably from about
6,000 to 30,000 and e~peclal~y preferably from about 12,000 to
26,000. At molecular weights below 4,000, the polymers tend to
be too water-soluble to adhere to the hard surface while at
molecular weight above about 100,000, especially above 50,000,
the polymers tend to be in~ufficiently watsr-soluble or are more
difficult to process and formulate into stable, pourable
formulations.
While the preferred cationic quaternized polymers are
the homopolymers as described abo~e, it ~ also within the scope
of the invention to use copolymers of the above amines and
quaternized salts thereof with, for example, an acrylamide or
acrylonitrile, so long as the copolymer retain~ the required
surface active propertie~ to adhere to the substrate while
xhlblting the appropriate aonformatlon to expo~e the hydrophilic
ortion of the polymer to be able to at-traat water and hydrate
he surface of the ~ub~trate. Thu~, up to about 25 mol~,
specially up to about 20%, for example, up to 5% or 10%, of the
nti.re repeating units of the cationic polymer may be comprised
f acrylamide unit~ of formula (III):
-CH2~CR6- (III)
CONH2
wllere R6 is hydrogen or methyl;
or acryl.onitrile units of formula IV:
. ,
. ' ':
2~'17~'? j
-CH2 -C~6-
~ (IV)
CCN3
where ~6 Ls a~ deflned above.
Other ethylenically un~aturated aopolymerizable
comonomers, in amount6 up to about 20 mol%, preferably up to 10
mol~, can also be included in the anionic polymer if they will
not adversely impact on the solubility, adhesion and soil release
properties of the polymer. A~ examples of such copolymerizable
comonomers, mention may be made, for example, to unsaturated
monocarboxylic acids, ~uch as acrylic aaid~ methacrylic acid,
propionic acid, and the like, un~aturated olefin~, such as
ethylene, propylene and butene, alkyl esters of the un6aturated
carboxylic acids, such as methylacrylate, ethyl acrylate, methyl
methacrylate, hydroxy derivatives of the~e esters, ~uch as, for
example, 2-hydroxyethyl metllacrylate, unsaturated aromatic
compounds, such as styrene, methyl styrene, vinyl styrene, and
heterocyclic compounds, such as vinyl pyrrolidone, and others.
Of these, hydrophilic comonomer~, ~uch as acryllc acid,
methacrylic acid, vinyl pyrrolidone, etc., ar~a preEerred.
Other water-aoluble cat~onic polymers such as, Eor
example, quaternary nitrogen eub~tituted cellulose ethers, for
example Polymer JR-30M, can also impart anti-soiling properties.
The anionic soil release polymers which can be used i.Jl
this invention include, for example, the soluble polymeric 6alts
disclosed in U.S. Patent 3,696,043 to Labarge, et al., the
disclosure of which is incorporated herein by reference thereto.
In particular, soluble polymeric salts may be obta;ned by
neutralizing copolymers of 1 to 2 moles of a monovinyl aromatic
monomer per mole of an unsaturated dicarboxylic acid or anhydride
, .
~ r~
there of to form solubilizing ~alt groups. Preferably the
copolymer is an equal molar copolymer.
Solubllizlng ~alt groups include half-amide ~alts
formed from the neutralization (interaction) of the anhydride
group with ammonia or with a monoamine ha~ing at least one
hydrogen attached to the amine nitrogen and having no other
groups reactive with an anhydride. Neutralization of the
unsaturated dicarboxylic acid copolymers with an alkali metal,
ammonia or an amine produces carboxylate ~olubilizing groups
O
II-ox
by a simple acid-ba~e reaction where X i~ a positively charged
ion which may be an alkali metal ion such as sodium or potassium,
an ammonium ion or a substituted ammonium ion.
The neutralization of the anhydride group may be
illustrated by the reaction of ammonia with a maleic anhydride
copolymer (showlng only the anhydride un~t of the copolymer~.
-~ CH3 1H2 ~ .~NH3 ~ CH fll }
0-- - C C _ 0 0 = C~ 0
\0 H21 1H
(half-amide)
Tlle half-amide may be further neutralized by further
reaction with ammonia or another base to form A half-amide salt,
~f 3 T 2 ~
=f T--
112N OX
. .: ..
. . .
~ 7 ~
where X iB the same as above. An N-substituted half-amide salt
is formed when said amine is used in place of the ammonia.
By a soluble polymeric salt lt ~ meant to include any
of the unsaturated dlcarboxylic acid or anhydrlde copolymer
neutralization products which contain a sufflcient number of salt
group~ to render said copoly~er soluble ~n the concentrations
employed. It is to be understood that complete neutralization
of all the acid groups or anhydride groups may not be required to
obtain the desired solubility, however, complete or
substantially complete, e.g. at least 95%~ neutralization is
preferred.
Any primary or secondary monoamlne may be employed to
neutralize the anhydride copolymers provided the amine has no
other group reactive with an anhydride and providing it forms a
salt group capable of solubilizing the ~opolymer. While a
variety of aliphatic, cycloaliphatic, heterocyclic and like
¦amines may be employed certain amine~ are preferred from the
¦human toxicity and handling standpoint, since the products are
principally intended for use by humans, and from the availability
and cost standpoint. The lower alkyl amine~ ~uch as
¦diethylamine, dimethylamine and the like are frequently used.
¦ Alkali metal base~ include hydroxides of sodium,
¦potassium, lithlum or the corresponding carbonates, bicarbonates,
¦etc. are the most preferred neutrallzing agents, especially the
¦sodium salts. Ammonium hydroxide is the u~ual form of ammonia
employed. ~ny amine may be used provlded it forms a carboxylate
salt group capable of solubillzing tlle polymer. Certain amines
are prefèrred for the previously stated reasons. Typical amines
for forming substituted ammonium ion-carboxylate salt groups
include the mono-, dl- and tri-alkyl amines (trimethyl amine,
; ` .' : . ' ". "., " . :
~ ~ ~i r~
diethylamine, i60propylamine, etc.); mono-, di- and tri-alkanol
amines (triethanolamine, diiaopropanolamine, monoethanolamine,
~tc.); cycloaliphatic amines such a~ cyclohexylam~ne;
heterocyclic amine~ suah as morpholine; and like amlnes.
For complete neutraliæation of the copolymers at least
about 2 moles of base per mole unit of dicarboxylic acid or
anhydride iB required. As indicated complete neutrallzation i~
not always needed and in many caaes excess base i~ beneficial.
The copolymers themselves and thelr methods of
preparation are well known to the art and need no detailed
de~cription herein. Briefly one widely uaed method is to prepare
the polymers by ~olution polymerization employing a solvent which
is a solvent for both the monomer~ and the polymer. Suitable
free radical catalysts such as benzoyl peroxide may be used to
initiate the polymerization which can be run over a wide
temperature range. The monomers tend to polymerLze readily in
equal molar proportions. U.S. 3,336,267 d~scloses how to make
non-equal molar copolymera. A variety of other patent~
disclose methods of polymerization by batch or continuoua
techniques or to produce low molecular weight or high moleaulax
weight copolymers. It i~ also taught to employ solvents for the
monomer only. Other patents which may be consulted include Re.
23,514; U.S. 2,606,891; V.S. 2,675,370; V.S. 2,838,475; U.S.
2,971,939; U.S. 3,178,395 and U.S 3,418,292.
The molecular weight of the copolymers may vary quite
widely from about four thousand up to as high aa 500,000 or more,
80 long as the criteria a~ described above for the cationic
polymer~ are satisfied.
Monomers which may be uaed to prepare the copolymers
include unaaturated dicaxboxylic acid~ such as maleic acid,
. ,, ,',
chloromaleic acid, fumaric acid, itaconic acid, citraconic acid,
phenylmaleic acid, aconitic acid and tha like. Any of the
anhydrides of the unsaturated acids may be employed. Aromatic
monomer3 include styrene, alpha-methyl styrene, vinyl toluene, t-
butyl styrene and similar well known monomer~. Preferredcopolymers are sodium salt of ~-tyrene-maleic anhydride or
styrene-maleic acid.
While the cationic and anionic polymers are preferred,
nonionic polymer~ which adsorb to the hard surface and increase
the hydration thereof aan also be used. For example, polyvinyl
pyrrolidone (PVP), poly(vinyl pyrrolidone-C0-dlmethylaminoetllyl
methacrylate) (also known as polyquatern~um II), polyethylene
glycols, ethylene oxide polymers, and the llke provide anti-
soiling benefits to hard surface treated therewith.
Conversely, not all water-~oluble ~nd adherent or
surface-active polymers can provide the des~red anti-~oiling
propertiea to harcl ~urfaces. For example, ~ilicone-based
polymers, fluorocarbon polymere, polyvinyl alcohol, copolymer~ of
methyl vinyl ether and maleic anhydride ~i.e. Gantrez ~N) and
polyacrylates wers tested as descrlbed below a~ neat 0.5~ wt.
aqueous solutions on ceramic tiles but dld not confer any anti-
soiling benefits or facilitate recleaning. A1BO, a copolymer
inyl pyrrolldone and vinyl acetate (60/40) did not coner
recleaning beneflts, thereby showing that whereas PVP homopolymer
provides a residual anti-soiling hydrophillc layer, the amount of
hydropllobic comonomer is limited to no more than about 25 mol~.
~ 8 described above, many different types of cationic,
anionic and nonionic polymer~ can be u~ed ae the anti-soiling,
abhesion promoting agents in this inventlon. However, the best
results have been obtained with the cationic quaternized polymers
f~ . J
of formula (II) and e~pea~ally wlth poly(MDAEM). Furthermore, a~
de~cribed below, even better performance can be obtained when. the
cationi.c polymer is present a~ it~ complex with an anionic
surface active agent, the amount of the anionic surfactant being
~ufficiently low such that the complex ~s Also water-soluble and
a significant proportion of..~he quaternized ammonium groups are
not complexed.
The amount of the soil-releasing agent to promote
abheSiOtl i8 not particularly crltical ~o long as thin residual
anti-soiling layer of the polymer remains adhered to the hard
surface after the aqueous solution thereof 1~ dried or wiped off.
Generally, however, at lea~t, and usually no more than, a
monomolecular layer of the polymer i8 sufflcient to exhibit the
full anti-soiling effect of the polymer since a monomolecular
layer of the polymer ~hould be adequate to form a hydrated water .
layer on the treated surface. Such monomolecular residual film
or coating layer can be achieved with aqueou~ solutions
containing as llttle a~ 0.02 weight percent of the ~oil release
polymer, especial].y for new or unsoiled hard ~urfaces. ~
referred concentr.ation range ls from about 0.04 to ~, more
referably 0.08 to 1%, by weight of the composltlon, of the soil
elease polymer.
As u~ed herein and in the appended claims, the
expression "less work" in reference to the anti-soiling or
recleaning property of the treated hard surfAce having a re~idual
layer of polymer thereon mean~ that deposlted 80il can be
removed from the treated ~urface with les~ scrubbing or wiping
when using the same cleanlng composition or with a milder
. cleaning compo~ition and le~s chemical action than for the same
. , . : . .
,' ,. ~' .',' ,' ,' ,''' ','.:
20 r~7oB~
similarly solled hard surface which ha~ not been treated with a
soil-relea~e polymer according to the Lnvention.
While the 80il relea~e polymer~ can be u~ed as such to
provide easier "next time" cleaning performance, it ~8 generally
5 preferable for the consumer to formula-te the soil relea~e polymer
recleaning agents together with one or more compatible surface
active cleaning agents and/or germiclde~, a~ in conventional all-
purpose cleaning products or a bathroom or kitchen or general
hard surface cleaning compositions, as are well known in this
10 art, including, for example, the germiaidal acldic hard ~urface
cleaning compositions of our prior application Serial No.
297,807.
Such cleaning compositions have ln common the presence
of one or more ~urface active detergent compound~, u6ually
15 ~ynthetic anionic (non-~oap), ca-tionic, nonionic, amphoteric or
zwitterionic ~urfactant~. Other common ingredlent~ often present
in ~uch type6 of aqueous cleaning composition~ include, for
example, detergent builder ~alts; solvents; acids, bases and pH
buffer~; germiclde~, bactericides, and preservatives; th:ickeners;
20 coloring agents and perfume~; and the 11ke. Any of these
ingredients whlch do not interfere with the solubility and
adherence of the anti-soiling polymer may be pre~ent: in the hard
~urface cleaning and anti-solllng compo~.itlons of thi.s invention
although it i~ often preferred to exclude detergent builder salt~
25 which are often associated with ~potting or streaking of hard
~urface~.
Organic 601vents are often a preferred additive where
needed to llelp solubilize the anti-~oilinq polymer or any other
ingredient pre~ent in the composition. For instance, tlle
30 poly(MDAEM) anti-soiling polymer may often form a ~lightly haæy
. : ., : , - :
~ 2 0 ~
a~ueous composition and the lncorporation of a ~mall amount of
isopropanol, for example, or other low molecular weight alcohol,
can clarify the composition. Generally, amount~ of solvent, wllen
present, will be in the range of from about 0.5 to 5~ by weight,
preferably about 2~ by weight.
The polymeric anti'so11ing agent~ w~ll, by themselves,
provide a small contrlbution toward~ inc~easing the visco~lty of
the aqueous composition~ however, in view of the low "~olids"
concentrations in the typical hard ~urface treating or combined
hard surface treating and cleaning compo~itlon~, the viscos~ties,
even with the polymeric additive tend to be as low a~ about 7 cps
or less. Without the polymer or added thickener viscosities of
the aqueou`s composition tend to be less than 5 Cp8, or example,
about 3 cps. For many types of applicat~ons, for instance, for
treating/cleaning vertical surface, for r~pray dispensers, and the
like, product viscosities in exces~ o~ about 10 centipoises, for
instance, from about 10 to 100 Cp5 for wlpe-on products and from
about 10 to 20 cps for spray-on product~, are de~irable. The
increase in viscosity can be accomplished by addition of
conventional polymeric thicken~ng agent~ ~uch as polyacrylntes,
guar gum, Irish Moss, carrageenan, polycarboxy vinyl ethers and
the like.
In selecting the polymeric thickening agent, as well as
other additives, the ionic nature of the additive must be taken
into con~ideration. Thus, when the anti-soiling polymer is
anionic in nature, then cationic additives ~hould be avoided.
Similarly, fox a cationic anti-soiling polymer, anionic polymeric
thickeners, coloring agents, suractant (except a~ discusised
~ below in connection with cationic polymer/anionic complexes),
~hould be avoided.
~ .. I
With these caveat~ ln mind, any of the surface active
detergent cleaning compound~ usually used ln hard surface, all
purpo~e or bathroom/kitchen cleaning product~, can be used in the
present invention. Cation~c, amphoteric or zwitterionic
surfactant may also be used (except that cationic surfactant
should be avoided in combina~ion with anionic soil release
polymers) although they are less preferred.
Suitable nonionic surfactant detergent cleaning
compounds include, but are not limited to those disclosed in our
prior applLcation Serial No. 297,807. More generally, mention
can be made, for example, of polyethylene oxide and polypropylene
oxide etl)ers of fatty alcohols, fatty acids, fatty amide~, alkyl
phenols and the like. For instance, the conden~ation products of
fatty alcohols or fatty acids whereLn the alkyl group thereof has
from 8 to 22 carbon atom~, preferably from 10 to 18 carbons, with
from about 1 to 50, preferably from about 3 to 15 moles of
ethylene oxide or propylene oxide or mixturos thereof;
olyoxyethylene oxide ethers of alkyl phenols, wherein the alkyl
has Erom 6 to 16, preferably 8 to 14 carbon, and the number of
repeating ethylene oxide unitB 1B from about 6 to 25, preferably
from 8 to 15; and the condensat.ion reaction product of ethylene
oxide and/or propylene oxide with a C8 to C22 alkyl or C6 to Cg
aryl (lncluding alkaryl) amine or amide or (Cl-C6) alkanolamide,
can be used as the nonionic surfactant.
Suitable surface active anionic detergent cleaning
compounds include, for example, the water-~oluble salts,
e~pecially the alkali metal salts, of sulfate~ and sulfonates of
fatty acids and alcohols and the water-soluble alkali metal salts
. of the alkyl aryl sulfonate~. More specifically, the anionic
3Q includes, in the sale form, alkyl sulfate~ of 8 to 22 carbons,
:' ' : ' , ,
` ~ i`7~
preferably 12 to 18 carbons; alkoxy (polyalkoxy) sulfa-te6 wherein
the alkyl portion has between 12 and 18 carbon atom~ and the
alkoxy portion has from 1 to about 10 repeating un~ts, the alkoxy
portion most preferably being ethoxy of from 1 to 5 repeating
units; alkyl phenoxypolyalkoxy sulfates wherein the alkyl portion
has from about 8 to about 16rcarbon atoms and the alkoxy portion
is selected from the group of ethoxy and propoxy, the number of
repeating units thereof being between 1 and 10, the alkoxy
portion preferably belng ethoxy of 1 to 5 repeating unit6;
~ulfonate alkyl and alkylaryl alkoxylate~ wherein the alkyl
portion and the alkoxy portlons are a~ previously aet forth for
the alkoxy (polyalkoxy) sulfate~ and alkyl phenoxypolyalkoxy
sulfate~, respectively; hydroxy alkane sulfonatea wherein tlle
alkane is from 12 to 18 carbon atoms; alpha-olefln sulfonates and
alkyl benzene sulfonates, espeaially linear alkyl benzene
sulfonates, the alkyl of which has from 10 to 18 carbon atoms;
sulfated monoglycerides, and ~ulfosuccinates, for example, the
reaction product oE malic acid esters with sodium bi~ulfate.
Most preferably, the anlonia surfaatant 18 aodium lauryl sulfate
or dodecylbenzene sulfonate.
Mixtures of anionic and nonionic surfactants can also
be used with anionic anti-soiling polymers and mixtures of
cationic and nonionia ~urfactants can eimilarly be used with
cationic anti-60iling polymers. ~mphoterlc or zwitterionic
aurfactants can alao be used along or with the anionic, cationic
or nonionic surfactants. Of course, for the nonionic anti~
soiling polymers any of the type~ of surfactants may be used.
The amount of surfactant which will be included in the
composition for cleaning purposes may vary widely depending on
the intended use, type of surfactant, other ingredients in the
:..... , . . , - . `, '. . :
7 ~ ~ ~
composition, and other factors known in the art. However, for
many types of hard surface, all purpose, and bathroom or kltchen
cleaning compositions, the total amount of surface active
detergent cleaning compounds will usually be in the range of from
about 0.1 to 10% by weight, preferably 0.2 to 4% by weight.
As noted above, an~onic ~urfaatant~ ln combination with
cationic 80il release polymer~ form complexe~ whLch modLfy the
solubility of the polymer and, dependlng on the amount, as well
as type of the anionic surfactant, these complexes can adversely
or beneficially impact on either or both of the adsorption of the
polymer to the hard surface and the abheslon performance of the
polymer. For any particular cationic 80il release polymer, the
positive, negative, or neutral lmpact on adheslon and/or abhesion
characteristics can be determined by routine experimentation.
The preferred anionic surfactant~ for complexing with
the cationic polymers for improving adhesion and facilitating
recleaning are the alkali metal C10 to Clg alkyl sulfates or
carboxylates, preferably C12 to C14 alkyl, ~uch as ~odium lauryl
sulfate, the ethoxylated (2 to 10 moles ethylene oxide) C14 to
C20 fatty acld ~OapB~ and the ethoxylated (2 to 10 mole~ etllylene
oxide) C10 to Clg fatty alcohol sulfates~ ~uch as sodlum stearate
condensed with 2 to 10 moles ethylene oxlde, and sodium C14 to
C16 alkyl ether (2 to 10 moles ethoxylatlon) ~ulfate.
However, the anlon~cs are not l~m~ted to these but also
include, for example, the mono and divalent alcohol sulfates and
sulfonates, anionic carboxylates, olefln sulfonates, aryl
sulfonates and the corre~ponding ethoxylated anlonic surfactants.
In general, any of the anionic ~urfactant~ mentioned above for
the anionic detergent cleaning compound when used in amounts
,: .-; ~ , , , : . . -. .. ~ ~ . :
which will not cau~e the cationic polymer complex to precipitate
can be u3ed.
Although not wishing to be bound by any particular
theory as to why the complexes can often provlde further
improvements in anti-soiling properties, it i~ believed that the
complex become~ slightly moré hydrophobic and can, therefore,
more readily deposit on and adhere to the hard surface without
changing the orientation of the hydrophillc portion of the
polymer with re~pect to the hard surface.
In general, however, ba~ed on the experiment~ conducted
by the inventor~ for poly[MDAEM] (mol.26. approximately 20,000)
at a molar ratlo of at lea~t 3, and preferably 4 or more,
cationic group~ in the polymersl anionia ~urfactant head group
the best performance for both promoting adhe~on and increasing
abhesion of soap ~cum are achieved with the Clo to Cl4 alkyl
sulfate salts, especially ~odium lauryl sulfate and moderately
ethoxylated (5 to lO moles ethylene oxide) Cl2 to Cl6, especially
Cl4, alkyl sulfate or alkyl carboxylate.
The balance of the novel liquld hard surface anti-
soiling/treating or anti-~oillng/aleaning composLtion is water,
preferably dLstLlled water, reduced by any optlonal ingredient6
which may be pre~ent. Generally, the proportion of water in the
compositions i~ about 80~ to 94~ by weight~ preferably 85 to 92
by weight of the composit1On. Those ~kllled ~n the art will
readily appreciate that minor amounts of addltional ingredient3
may be optionally pre~ent to prov~de cosmetically appealing
products and increa~e con~umer acceptability. Examples of 8uch
adjuvants include coloring agent~, fragrances, perfumes,
. viscosifier3, germicides, bactericides, dis1nfectants, and p~l
adju~ting agent~.
:. .
' . - '-, ' ~
~ 5 the acidic compound~ for modifying pH~eTtt~i~n- ~an be
made of the organic acid~, ~uch as lower aliphatic monocarboxylic
acids, hydroxycarboxylic acids and dicarboxylic acids. Examples
of the aliphatic monocarboxylic and dicarboxylic acids include
Cl-C6 alkyl and alkenyl monobasic and dlbasic acids, such a~
glutaric acid, succinic acid, propionic acld, adipic acid, acetic
acid and the like. Examples of the hydroxy carboxylic acids
include hydroxyacetic acid and citric acid. Mixtures of
saturated aliphatic dicarboxylic acids, and e~pecially mlxtures
oE adipic, glutaric and succinic aclds are ~ommercially available
and are conveniently used. These mixtures are described in
greater detail in our prior application Serial No. 297,807.
Of course, inorganLc acids, such as HCl, HN03, H2S04,
can also be used, but usually in comblnatlon with organic acids,
or appropriately diluted.
Similarly, organic and inorgan~c bases, ~uch as
ammonia, ammonium hydroxide and various amlnes, amides and
alkanolamines and alkanolamides, can also bo added to raise the
H were necessary or desired to formulate less acidia or more
alkaline formulations.
In this regard, it is well understood by the
practitioner that product pH not only affects cleaniny
performance against specific soil types~ but that the pH will
also have an affect on the form and stability of the cationic or
anionic soil abhesion promoting polymers. It i8 also well
understood that the choice and selection of the surfactant
component and other optional additives, such as, coloring ager-ts,
thickening agents (viscosifiers) and the l~ke will be made in
consideration of the ionic nature of the ant~-soiling polymer.
It should also be apparent to tho~e of ordinary ~kill
in the art that when, for example, a aationic germicidal or
surfactant compound 1B to be included ln the composition, the
complex of the catlonic antl-soiling polymer with the anionic
surface active agent ~hould be ~ormed out of the presence of the
cationic compound since, othérwise, the cationic compound and
anionic compound may form a complex rather than the desired
anionic surfactant-cationic polymer complex.
For example, for the preferred catlonic polymers,
anionic surfactants, except as descrlbed above, and anionic
coloring agents or thickening agents, and other anionic
additives should be avolded ~ince they tend to form insoluble
complexes with the cationic polymer. Anionic surfactant
concentrations in cationic polymer embodiments should, in any
case, be limited to about 0.25~ by weight, while anionic polymer
thickening agents or other anionic polymers ahould be altogether
avoided.
In addition to the improvement in facilitating
recleaning of surfaces treated with the aomposltions of this
invention, it ha~ been surprisingly di~covered that the
appearance (gloss) o damaged ceramic ti~e~ or similar household
hard surfaces, e.g. porcelains, to which the compositions of this
invention are applied can be improved (e.g. gloss readings are
increased) as compared to tiles treated with the same
compositions, excluding the cationic polymer. For example, an
acidic (pH=2.5) aqueous composition containing 0.4 weight percent
of poly[MD~EM~ of 20,000 molecular weight complexed with C14
alkyl sulfate condensed with 7 moles ethylene oxide when applied
1 in a laboratory test to a ceramic tile etched for 15 minutes by
¦immersion in a 1.3~ }3F bath (BUCh that the g10BB iB reduced from
. . ~ . ,:
?~ ~7' 3 ;
an initial value of 90 to a value between 30 and 50 - ~imulating
¦older tile~ washed with abrasive cleaners for sevexal year~)
lmproves the gloss of the surface by 1 glo~s unit when measured
l with a Gardner 20 glo~ meter.
¦ Even more signLficant, however, iB that ln consumer
¦panel te~ts, almost all of t~e panelists ~ndicated that they
¦attribute higher shine to the tiles treated with the invention
compositions. The appearance of higher shine is most pronounced
1 with acidic treating composit~ons, presumably because the acid
¦treatment itself provides better soap scum removal and cleaning.
¦However, even at p~ values of about 6 or more, the paneli~t~
¦still report a higher shine for -tiles treated with the
¦compositions of the invention.
1 In comparison, when the same tlle~ are treated with a
¦similar composition but without the poly[MDAEM], no differences
¦in gloss are measured. This effect on ~urface appearance i~ on]y
¦observed for worn tile~, that is, glo~ difference~ are not
measured after treating a new tile surface. However, recleaning
performance is obtained on both new and old tlles and other hard
surfaces.
ExamPle 1
An anti-soiling polymer according to the invention is
~ed in the fo110wiDg bathroom o1e~ning oompo~ition:
22
,~ ,n ~ ,
Amount
Inqredient (Wt.~ L
Acid mixturel) 5.0
Neodol 91-82) 1.5
Neodol 91-2.53) 0 7
Cationic disinfectant4) 0 2
Poly(MDAEM)5) 0.4
I~opropanol 2.0
Perfume and color 0.21
10 Water r Q S
(ph = 2.5)
1) Mixture of 57.5~ glutaric, 11.6~ adlpia and 27~ succinic acids
in the form of water so]uble white flakea, a product of E.I. Du
Pont de Nemour~ & Co.
2) A nonionic surfactant from Shell Chemlcal Co. which is tlle
conden6ation product of Cg-Cll fatty alaohol with 8 moles, on
average, of ethylene oxide.
3) A nonionic aurfactant from Shell Chemical Co. which iB the
condensation product of Cg-Cll fatty alcohol with 2.5 mole~, on
average, of ethylene oxide.
4) Variquat 50hC disinfectant, from Sherex Chemical Co.
5) A commercially available preparation containing 15-20~
polymer, average mol.wt of 20,000, 5-10% i~opropanol, 3-5% N-
octanol, 3-5% sodium acetate, 1-3% terpene hydrocarbons and 3-5
of either sodium lauryl sulfate or AEOS (7 mole~ ethoxylated C14
alkyl sulfate).
The anti-soiling performance of the composition is
tested on each of a new white ceramic tlle and of a ~oap scum
soiled new or etched white aeramic tile. One-half of the new
tile i8 immersed and the other half 18 ~mmer~ed ln the same
formulation but without the poly(MDAEM). After removal from the
bath, the tile i~ gently wiped dry with a soft paper towel.
The soap scum soiled tiles are prepared by spraying
the tiles with a 250 g/l solutlon of CaC12-H20 followed by a red
dyed 5~ 60dium oleate ~olutlon. The tlle~ are allowed to dry for
one hour at 30C and the 60iling procedure i8 repeated. The
gO11 90 PrOd.]Ced 1B uniform and reproducible within accepted
limits.
One-half of each 60ap ~cum solled tllff is cleaned witl
iO Ithe ven-ion ~ompoaition deacribed above a d the other half ia
~ r~ 3 j ~
cleaned with the ~ame compo~ition excluding the poly(MDAEM). The
tiles are cleaned by hand until all the ~oap scum is removed. ,1
After the treatment of the new or soiled tiles with the
cleaning composition w~th or without the anti-~olling polymer the
tile~ are rinsed and a~r-dr~ed and the entlre tlle surface i~ re-
soilsd with soap scum by ther~ame procedure as described above.
The re-soiled tile is then washed with a m~ld cleaning consisting
of a 1~ aqueous Eolution of a 1:1 w/w mlxt~re of Neodol 91-
6/Neodol 91-2.5. This mild cleaning solutton wlll provide a
minimum amount of chemical cleaning action. The tiles are
cleaned according to 5tandard Practice In~truction 8173 u~ing the
mild cleaner and 10 cycles on a Gardner Abras~on Tester. In thls
test, the tiles are mounted in the Tester equipped ~ith two
cellulose sponge~ measuring 5 cm x 5 cm x 5 cm. Three grams of
the mild cleaner are pipetted onto the ~ponges wetted with 5 gm
water. A xeflectometer is u~ed to mea~ure the reflectance before
and after the 10 abrader cycle~ and the percent 80il removal is
determined. The results are shown in the following table.
New Tile Percent Soil ~emoval
Treated halfa) 90-100
Untreated half 0-30
Soap Scum Soiled New Tile
Treated halfa) 90-100
Untreated half 15
Soap Scum Soiled Etched Tile
Treated halfb) 55
Untreated half 15~
a) poly~MDAEM) with sodium lauryl sulfate
b) poly( MDAEM) with AEOS
Wllen the above test iB repeated by treating the tiles
with a similar composition according to the lnvention except that
. .
~ l' ;` ~s) ~
the pH is increased to 6 by addition of sodlum hydroxide, the
tile-half treated with the poly(MDAEM)-AEOS containing
composition, gave l00~ soil removal after 5 cycles on the Gardner
Abrasion tester using the same mild cleanlng ~olution whereas the
untreated tile gave 55% soil removal.
Example 2 r
The procedure of Example 1 i~ repeated on soap scum
~oiled new tiles prepared as described ln Example 1 using the
following composition:
Amount
Inqredient
Acid Mixtur2e1) 3.0
Neodol 91-8 ) 1.5
Neodol 91-2.53) 0.7
Isopropyl Alcohol 3.0
Cationic disi~fectant4) 0.2
Poly(MDAEM)5)6) 0 4
Perfume and color 0.21
Water Q.S.
1), 2), 3), 4), 5) - ~ee footnote~ in Example 1
6) _ Complexed to sodlum lauryl ~ulfate.
After recleaning with the same mild cleaning
composition as in Bxample 1, the untreated side showed
essentially no clean~ng (<10~ floil removal) wherea~ ~he
poly(MD~EM) treated side showed an average of 90~ soil removal.
Example 3
Tlli~ example demonstrates that the treating
composition~ of this Lnvention can be applled to various types of
ard surfaces commonly found in the home.
~5
,.
2~ ''3 . ~
The following formulation i8 prepared:
~mount
Inqredient (Wt.%)
Mixed Acidl) 3.5
Neodol 91-82) 1 5
Neodol 91-2.53) 0 7
Isopropyl alcohol 3.0
Poly(MDAEM)5)7) 0.4
Perfume and color 0.21
Water Q.S.
11, 2J, 3), S) _ see footnotes in Example 1
7) - Complexed with ~EOS
The ~ame test as described in ExRmplra 1 i8 carried out
on unsoiled polymethacrylate test plates, except that only 5
cycles are applied on the Gardner ~brasion tester using 'che same
mild cle~ner as used Ln Example 1. The average 80il removal on
the poly(MDAEM) treated side 18 66% and on the untreated side is
45%. No significant difference in the shine or glos~ of the
surface is observed.
Example 4
The test procedure of Example 1 ~ repeated orl new
white ceramic tiles treated with neat 0.5~ aqueous ~olu~.ion~ oE
either poly(MD~EM) or the following polymerss polyvinyl
pyrrolidone (avg. mol. 26. 360,000); Gafquat 755N (vinyl
pyrrolidone/dimethylam~noethylmethacrylate copolymer,
polyquaternium II), Polymer J~-30M (a quaternary nitrogen
substituted cellulose ether, where 30M is the designation of
viscosity at 1~ concentration, sodium salt of styrene-maleic
anhydride copolymer, Sokalan (CP7) (sodium salt of copolymer of
methacrylic acid and maleic anhydride), polyethylene
. ¦terephthalate/polyethylene oxide terephthalate copolymer, and
polyethylelle oxide (mol. wt. 4,000,000). The best recleaning
- . . : ~: .
~ ,
, ~ ...
~J~ P~ 'J
performance (least amount of work required for given 50il removal
or most soil removal for a given amount of work) was provided by
the poly(MDA~M) treated surface, with le~er improvements in the
order given (from good to adequate) for the remaining polymers.
Accordingly, it can be appreciated that the present
invention provides a compo~i~ion and method for treatlng hard
surfaces, ~uch aa ceramic tiles, porcelaln, enamel, Formica,
polymethacrylate~, and the like, ~uch as found in bathrooms
(sinks, tubs, shower stall~, walls, ~loor~, vanities, etc.),
whereby the treated ~urface i~ modified to lncrease its
hydrophilicity, with or without simultaneou~ aleaning of exi~ting
80il. As a result of thls treatment any further ~oiling becomes
easier to clean during ~ubsequent cleaning (wi~h the same or
different cleaning solution) because the built-up ~oil will not
adhere as tenaclou~ly to the treated surfaae as it would to the
same surface which has not been treated with an anti-soiling
polymer according to the invention.
Lt should be noted that the performance of the 9011
release polymer containlng compo~i~ione of thi~ lnverltion is
dependent on the prevailing humidlty of the ambient Atmosphere:
lf there is little moisture in the air the degree of llydration of
the treated surface becomes insufficient to adequately prevent
soll adhe~lon by whichever of the above proposed theories or
other mechani~m is in operation. Generally, humidity level~ of
at least about 35~ RH at 70F will provlde the best re6ult~ upon
subsequent recleanlng. For most area~ of application, such as
bathrooms and kitchens, the prevailing atmospherlc moisture
levels will be equivalent to at lea~t 35~ RH.
It ~hould al~o be understood that the treating
compo~itions of this invention are not llmited to hou~ehold hard
~urfaces but can al~o be used to facil~tate recleaning for other
types of hard surfacea, such a~ automobiles (e.g. vinyls, metals,
painted ~urfaces, etc.), window ca~ement~ and the like.
In final form, the aqueou~ llqu~d hard surface
modifying compos~tLon~, including the treatlng and cleaning
compositions are typically hormogeneous compositions which exhibit
stability at both reduced and increased temperatures. More
specifically, such compo~itions remaln st~ble in the range of 5C
to 40C. The liquids are readlly pourable and free flowing from
any suitable container or may be sprayed from a pump-type
sprayer. Another advantage of the composlt~on~ of this invention
is that by virtue of the increase in viscoslty from the polymer
anti-soiling agent, especially the cationlc polymer-anionic
surfactant complex, the products can be formulated with
viscositieis between about 10 to 20 cp~ which allows the products
to be sprayed with most conventional pump ~pray no~zles with
substantially less misting than for lower vi~co~itie~ but without
logging the spray nozzle aa would tend to occur with hlgher
viscosities.
The compositions are directly ready for use. Only
minimal rinslng 1B needed and substantially no reaidue or streaks
re left bèhind on the cleaned surface. Becau~e the preferred
ompo~itlon~ are free of detergent bullder~, such as alkali metal
olyp}-osphates they provide a better "~hine", i.e. less
streaklng, on cleaned hard surfacea.
Typically, the inventive compositions are prepared
~imply by combining all of the ingredient~ in a suitable mixing
vessel or container. Generally, the various ingredient~ can be
added sequent~ally, or all at once, to form an aqueous solutlon
of each or all of the essential ingredient~, care being taken -to
;: :
~ ! S ~
avoid mixing together any anionic and cationic components as
described previou~ly. Preferably, when a fragrance i8 preSerlt,
the fragrance ls flrst dlssolved Ln a water disperslble nonionic
surfactant which ls then added to the other ingredlents in
aqueous acid solution. When the ~urfactant/fragrance mixture is
added to the aqueous acld sorution contain~ng the remaining
ingredients, the solution may become slightly hazy. If a
cationic disinfectant compound 18 added to the aqueous mixture,
the fragrance becomes completely ~olubil~zed and the final
mixture is clear as well as stable. Additional base may then be
added, if de~ired, to lncrease product pH. The compositions may
be prepared at room temperature.
In use, the composltions of this invention are applied
to the surfaces to be modlfied/cleaned w~th a cloth or sponge or
by spraying onto ceramic or other surfaces which may have been
soiled by accumulations of insoluble soaps~ mlneral deposits, and
oily soil~. The compositlons, without added th~akeners, other
than the soil-releasing polymer, are of somewhat higher viscosity
than water, generally up to about 3-10 cps or higher, the polymer
complexes providing higher viscoslty in general. ~he material
will usually be allowed to remain on the surface to be modified
~or a period from 10 seconds to 5 or 10 minutes, but preferably
such contQct time will be from about 30 seconds to five minutes
or from 1 to 3 mioutes. The liquid composit~on may then be
removed either by wlping or rln~ing wlth water. Depending on the
degree of soiling of a hard surface not prev~ously treated with
the invention composition more or less strenuous wiping and
rinsing may be required. However, in all cases subsequent
. recleaning requires substantially less work to remove any
3~ subsequently deposited soils. These compositions leave
~ '6~
substantially no ~pots or streaks whether or not ttley are rinsed
from the cleaned surface.
Tlle foregoing description and specific examples are
intended merely as illustrations of speclflc and preferred
embodiments for the practice of tlle inventlon. It is to be
understood, however, that ot~er expedient~ known to those skilled
in the art or disclosed herein may be employed without departing
from the spirit of the invention or ~cope of the appended claims.
, . ,
.:
