Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1 3 ~ 9
;¦ BACKG~ O~
The present invention relates to the formulation of a stable, h~rd
:1 il :
surface detergent composition in the form of a non-pourable viscous cleaning
. ~ I
composition, subs~antlally ree of ~ater, i.e~, ha~ng a max~um water
i content:of 6~ by we1ght, compris~ng a gelled mixtu~e of an org2nic liquid
: ; li vshicle conslstin~ essentially of organic solvont~ and nonlonic surfac~an~s
includlng an ethoxylated fatty acid 8S the essential component in the in
~i situ gelation of said liquid vehicle, upon the addition of a s~all a ~nt of
¦: ~ about 0.7-1.5% by weight sodium hydroxide. The addition of gel-insoluble
ingrPdients, particularly a water-soluble inor~anic builder-absasive, to the
; ~ ~ gel mixtu~re forms a viscous paste product containing a stabIe suspension ~f
thP relatively large pa~tlcles of said sbrasive.
: The abrasiYe~is in~olub1e In the gel product, but solub1e ln water.
t ~ Thus, after using thls pa ta produ&t to clean a hard surface, the water
applied to rin~e off the clean~ng product-dissolves both the gel and the
abrasivPs, and leaves no gritty resldue on or a~ound the cleanad ~urfaces.
,
~,
.,.
' ~'`` '`'`''`~`.`
. ~
,.
~ ~31~7~ ~3
The prior art is replete with hard surface cleansers containing
abrasives both in the form of scouring powders and in liquid form. Water
insoluble abrasives as the major and primary c:Leaning compo~ent in scouring
powder cleansers is ~ell known, as disclosed in U.S. Patent No. 3J850~833.
However, the use of said water-insoluble abrasives in hard surface scouring
powder cleansers has been found to lea~e an unpleasant gritty residue on the
cleaned surface. This problem has been addressed in the prior art by
substituting a water soluble abrasive for all or part of the insoluble
abrasive, resulting in a composition wherein the water soluble components
rinse away with the wash water, leaving substantially no residue on the
I cleaned surface, as disclosed in U.S. Patent No. 3,577,347. Another method
oE addressing the abrasive residue problem is the use of a powdered or
particulate water-insoluble abrasive having a maxi = particle size under
" 0.15 mm., and about 8~ by weight of the abrasive particle having a diameter
of about 0.03/ mm or larger for eifective cleaning, and a small amount of an
organic hydrotrope ~i.e. 9 sodium cumene sulfonzte~ to improve greas~
removal, as disclosed in U.S. Patent No. 4,2~9,640.
; Likewise, hard surface liquid detergent composition containing water-
nsoluble abrasives suspended in an aqueous medium encounter th~ problems of
stability as well as the difficulty of complete re~oval of the insoluble
abrasive particles from the cleaned surface. These problems have beeD
addressed in the prior art by preparing a~heavy duty liquid detergent
composition containing a ~ater soluble builder salt ha~ing colloidal-size
I partlcles (below 1 mioron and usually below 0.1 ~icron), dispersed in an
- aqueous medium containing a fat~y acid amide emulsifying agent as disclosed
I in V.S. Patent No. 4,057~506. Other means of addressing the stability
problem is disclosed in U.S. Patent No. 3,522,186 ~herein is disclosed a
water-insoluble abrasi~e dispersed in an aqueous medium containing
te~rapo~assium pyrophospha~, sodium soap, dietha~olamide and about 0.25-
I.S~ meth}~o r ethanol to prevent the separation oE th; equeoos liqold
Il ~
~ 31~7 ~ (~
'~
'I into two layers. Another means of addressing the stability problem is
disclosed in U.S. Patent No. 4,051,055 wherein an aqueous hard surface
cleaning ~omposition ~ontaining water insoluble abrasive is suspended in a
thickened aqueous medium with at least 17~ clay as the thickening agent, said
thickened system preventing separation of the abrasive from the liquid
medil~. The presence of fluoride salts enhances the ability of the clay-
i, thickened systQm to hold the abrasive pirticles in suspension.
U.S. Patent No. 4,657,692 also discloses a thickened a~ueous scouring
cleanser, free of syneresis (separation of solids from liquid), containing a
Il uater insoluble abrasive suspended in an aqueous medium containing a
¦1I colloidal aluminu~ oxide thickener, water soluble al~ali metal inorganic
¦ll salts such as the phosphates, polyphosphates, carbonates, etc., and about
~0.5-3% of a surfactant and a halogen bleach. European Patent Application
¦¦¦ No. 0,193,375 resorts to the use of a water soluble salt, which functions
,I both as an abrasive and detergency builder, such as sodium bicarbonate,
tripolyphosphate, and ~he like, in a pourable, homogenous abrasi~e-
~containing aqueous detergent composition for cleaning hard surfaces3 and
;`i¦ also containing a mixture of anionic and nonionic surfactants in the weight~¦ratio of 1:1 to 9:1 anionic to nonionic surfactant.
~¦A hard surface, water-based cleanser in paste form comprising 50-65%
sodium bicarbonate and 50-35% by weight water con~aining sodium chloride and
a fatty acid (Clz-C~) diethanolamide is disclosed in U.S. Patent No.
1 4,179,414.
;~Water-based gels containing at least 40% nonionic surfactant and 2-10%
water soluble builder salts is disclosed in U.S. Patent 4,107 9 067 as a
flowable gel laundry deterg = t composition.
U.S. Patent Mo. 4,257,908 also discloses a laundry deterBent
composition in a stable flowable form, containing 25-55Z of a phosphate
builder sal~J 5-40% of an anionic surfact~lt in 30-50% of an aqueous medium
containing alcohol in the weight ratio of 5:1 to 20:1 water to alcohol.
`~ ~ 3 ~ ~ ~ 7 o~3
,
Also, non-aqueous liquid pasty or gelatinous detergent compositions
having scouring properties is disclosed in U.S. Patent No. 3,981,826,
comprising a dispersion of a normally solid water soluble anionic surfactant
and a solid particulate water soluble inorganic salt la builder salt) and a
suspending ~gent such as highly-voluminous oxides (silica, magnesia,
all~ina or clay) in about 19-79% of a water-miscible organic liquid solvent
such as a polyhydric alcohol (glycerol, ethylene glycol, and the like), and
optionally a lower monohydric alcohol (ethanol, methanol, etc.). Another
organic solvent-based gelled or thickened hard s~rface cleaning composition
~, which is flowable and pour~ble is disclosed in U.S. Patent 3,~65,756
,l comprising a gelling agent which functions as an abrasive such as colloidal
silica, an alkaline builder salt such as water soluble phosphates and
silicates, a surfactant, a wa~er insoluble abrasive, i.e., calcium silicate,
and about 55-9~% of an organic cleaning solvent such as a major amount of an
aliphatic hydrocarbon mineral spirit mixed with 4-7~ ethylene glycol
monobutyl ether. U.S. Patent No. ~,8649770 also discloses a pourable non-
aqueous water-soluble organic solvent-based thixotropic liquid detergent
composition containing glycols and glycerol as the organic solvent, an
¦ anionic surfactant, and a phosphate builder i= suspension.
¦ However, none of the above mentioned patents disclose a hard surface
non-pourable viscous cleaning composition, substantially free of water,
comprising a gelled mixture of an organic liquid vehicle consisting
! I ~ essen~ially of water-soluble organic solvents and nonionic surfactants
incl~ding an ethoxylated fatty acid as o=e vf the surfsctants, and a small
I amount of sodium hydroxlde which reacts in situ with the etho~y}ated fatty
; ¦ aoid to form a clear organic, non-flowable gel, and about 10-25% of a water
1~ soluble builder-abrasive suspended in said gelled vehicle.
lu~ 0~ 111- W~W
It has now been found that the formulation of present novel organic
cltaning compo i ion i9 bas~d o= the abillty of etho~ylatecl iatty ~cid,
J 1 ~ 7
!
i.e., ethoxylated lauric acid, to react with sodium hydroxide iQ organic
media and form a gel with the media. Another feature of present novel
formulation is the incorporation of a water-soluble abrasive material into
the organic gelling mixture. This enables the preparation of viscous
products containing inorganic solids suspended in a gelled organic vehicle.
, While this ab~asive is insoluble in the gelled vehicle, it becomes soluble
ll upon dilution of the product with water. Cleaning with the undiluted
1~ product is aided by the mild abrasive action of the abrasive, i.e., sodium
pyrophosphate. The entire product dissolves in water leaving no gritty
residue on or around the cleaned surfsces. Furthermore, this abrasive
becomes a "surfactant builder" when the product is used diluted. Household
¦¦ surfaces such as ceramic and formlca surfaces can be cleaned with present
novel products in the absence or presence of water without scratching the
l surface. This product, both undiluted and diluted, has significantly
¦ improved cleaning efficie~cy providad by the triple action oE the organic
solvent, the nonionic detergent and the abrasive. In the diluted product,
the abrasive dissolves in the water and becomes a detergency builder. The
hard surface organic viscous product in accordance with this invention can
function as a spray cleaner, a scouring cream and a floor a~d wall all
purpose cleanser. Simulated floor cleaning tests show that at 3 g/l of
1~ i ~ present novel cleaning product pçrformed better than "Mr. Clean" at 15 g/l. /
this translates to 5 bottles of Mr. Clean being equal to 1 bottle of
present cleaning product.
;~ hccordingly, ~he primary object of this invention is ~o provide a novel
hard surface viscous organic cleaning product comprising an ethoxylated
fatty acid and sodium hydroxide dissol~ed in an organic ~ehicle which react
in situ to form a gelled vehicle.
; Another ob~ect of this invention is to provide a novel viscous organic
cleaning co~position containing lnorganic water-soluble particulat~ abrasive
suspen~ed in the gelled organic vehicle.
~ P~ R~ S
'
131 087~
Still another object of ~his invention is to provide an abrasive-
containing organic gel which dissolves in water leaving no gritty residue on
or around the cleaned surfaces.
Still another object of this invention is to provide an all purpose
organic cleanser having threefold cleansin~ action.
Additional objects, advantages and novel features of the invention ~ill
be set forth in part in the description which follows, and in part will
become apparent upon examination of the following specification or may be
learned by practice of this invention.
To a~hieve the foregoing and other objects in accordance with the
present invention as embodied and broadly described herein, the novel,
stable, hard surface non-pourable organic cleaning gel composition of this
invention comprises about 65-80Z by weight of an organic liquid vehicle
coosistin~ essentially of about 15-35Z by weight of a water ~iscible organic
solvent, about 35-70~ of a non~onic surfactant mixture containing an
ethoxylated fatty acid as one of the surfactants, and a small amount of
about 0.7-l.SZ by weight of sodium hydroxide, which reacts in situ with the
ethoxylated fatty acid to form a clear5 nonflowable gelled vehicle,
substantially free of water, capable of suspending water-soluble inorganic
particulate abrasive.
More speci~ically7 the organic gel compositlon of present invention
comprises about 65-80~ by wPight of a substantially water-free organic
vehicle con~isting essentially of about 15-35X by wight of a water soluble
organic solvent and about 35-70% by weight of a nonionic surfact3nt mi~tur~
containing an etho~ylated fatty acld as one oE the surfactants, about 0.7-
1.5Z by ~eight of sodium hydroxide, gelled by the in situ reaction of the
ethoxylated fa~ty acid with the sodium hydro~ide; and about 10-25% by ~eight
of an inorganic water soluble particulate abrasive (builder salt~ uniformly
suspended in the gelled veh~cle.
3L3~87~
62301-1501
The water miscible organic solvent is selected from
the group consistiny of lower alkyl glycol ethers, lower alkyl
monohydric alcohols, lower alkyl dihydric alcohols, and
mixtures thereof.
The described hard surface cleaning products of
present invention are stable, nsn-pourable, clear, thick
~viscous) pastes, having a minimum viscosity of about 14,000-
15,000 cps units m~asured on Brookfield HATD viscometer. The
viscosity of the gel product provides a stable suspension of
relatively large particles of water-soluble abrasives i.e.,
larger than colloidal sized particles. The product of present
invention has many applications as an all purpose cleaner.
Undiluted with water, the product can be used as a scouring
cleaner for sinks and tubs, and as a spot cleaner for soiled
hard surfaces, providing triple cleaning action due to the
coaction of the organic solvent, the nonionic detergent and the
abrasive, without leaving a gritty residue conventional with
abrasive cleansers. Present novel organi~ pastes diluted with
; water can be used as a floor and wall cleaner. Present novel
organic cleaning pastes can also be used as a waterless hand
cleaner, particularl~ for mechanics and gardeners; for cleaning
industrial and institutional cooking vessels, urns, etc.
~ p~TAIL~D D~SCRIPTION OF T~E INVENTION
: The major essential component of present nonpourable
~ viscous cleaning composition is the nonionic surfactant system
; ~ which constitutes about 35-70% by weight of a mixture of
nonionic surfactants containing about 6-38% of an ethoxylated
fatty acid, and about 10-64% of the other ethoxylated nonionic
surfactants which may be a fatty alcohol, an alkyl phenol, a
propylene oxide-propylene glycol condensation product or a
mixture thereof. More speclfically, the additional ethoxylated
.,
~ 7
~3~7~
62301-1501
nonionic surfactant may be selected from the group consisting
of a polyethylene oxide condensate of an alkyl phenol having an
allcyl group containing about 6 to 22 carbon atoms, a
polyethylene oxide condensate of an aliphatic a].cohol
containing about 8 to 22 carbon atoms, a polyethylene oxide
condensate of the condensation
v~ 7a
- 1 3 ~
i product of propylene oxide with propylene glycol having a molecular weight
of about 1500 to 1800, and mixturPs thereof. Typical exampls of
polyethylene oxide condensates of alkyl phenol are nonyl phenol condensed
il with about 9.5 moles ethylene o~ide per mole nonyl phenol, dode~yl phenol
condensed with about 12 moles of ethylene oxide per mole of phenol. Typical
examples of ethoxylated alcohols include about 6 moles ethylene oxide
condensed with one mole of tridecanol, myristyl alcohol condensed with about
,l 10 moles ethylene oxide, Cl~-C,4 fatty alcohol condensed with about 6 moles
;~l ethylene oxide) C~O_C,~ alcohol condensed with 5 moles ethylene oxide per
il mole alcohol (Alfonic 1012-60). Examples of the polyethylene oxide
condensates of the condensation product of propylene oxide with propylene
¦ glycol are com~ercially available as Pluronic surfactants marketed by the
l~ Wyandotte Chemicals Corporation. The liquid character of this product is
,I retained up to the point where the polyoxyethylene content is about 50Z of
the total weight of ~he condensation product. ~xamples of ethoxylated fatty
acids include lauric, palmitic, stearic acid, etc., ethoxylated with about 5
to 10 ethylene oxides per mole fatty acid. A preferred fatty cid
ethoxylate is laur~c acid having 9 ethylene oxides (Alkasurf-L-9). The
presence of the ethoxylated fatty acid in the organic vehicle is essential
in the formation of the gel, for ~he in situ reaction in the organic solvent
with the sodium hydroxide to form a small amount of a soap which thickens
and gels the organic liquid media. A small amount of sodium hydroxide
svokes time-delayed hydrolysis followed by gela~ion of the ~ehicle holding
the ethoxylated fatty acld.
~;~ ;Another essential component of present cleaning composition is the
water miscible organic solvent in an amount of about 15-35% by weight of the
total formulation. The organic solvent provides an organic medla for the in
situ reaction between the ethoxyla~ed fatty acid and ~he sodium hydroxide in
~,the gelling of the organic ~edia. Suitable organic water mlscible solvents
incl~de the lower alkyl monohydric alcohol, lower alkyl dihydric slcohols
l ~ 7'R ~
; ~3~7~
. ~ .
(glycols), the ;ver alkyl glycol ethers, and mixtures thereof. ~xamples of
water soluble lowe~ monohydric alcohols are ethanol, iso-propanol, and
butanol. Examples of s~i~ahle glyols are ethylene glycol, diethylene
glycol (Carbitol~, and propylene glycol. Exa~ples of lower alkyl glycol
ethers are the diethylene glycol monobutyl etlher having the formula:
C~H~OCH~CHzocH~cH2o~ also known as Butyl Carbitol ~Union Carbide), ethylene
glycol monobutyl ether having the formula: C~H90C~ZCH20~ and the like. It
is preferred to use a mixture o-f ~onohydric and dihydric alcohols, and most
preferably a mixture of a monohydric alcohol, a dihydric alcohol and a
glycol ether as the solven~ for the nonionic surfactant mixture.
Another esse~tial ingredient in present viscous cleaning composition is
a water-soluble inorganic particulate abrasive, suspended in the gelled
vehicle, in an amount of about 10-25Z by weight of the total composition.
The abrasive is insoluble in the gel, but soluble in water. The water
soluble abrasive particles are relatively large particles of about 1/2 m~ in
diameter. The viscosity of the gelled vehicle which is a mini~um of l4,000
to 15,000 cps units, is capable of ~aintaining the large particles in
suspension. Suitable water soluble abrasives are selected from the group
consîsting of alkali metal phosphates, polyphosphates and carbonates.
Examples of suitable water soluble abrasives include pyrophosphates such as
tetrasodium or tetrapotas5iu~ pyrophosphates, tripolyphosphates,
tetrapolyphosphates~ carbonates, etc. This abrasiv~ beco~es a surfactant-
builder when the product is used diluted and ie readily removed rom the
cleaned surface, leaving no gritty residue. The preferred abras~ves include
tetrasodium pyrophosphate, and sodium carbonate.
The hard surface cleaning composition of this invention also ~ay
contain minor amounts of conventional additional component~ to impart any
desired characteristic, which are compatible with the gel and do not
adver9ely aEfect the ~el structure. Suitable additives in~lude coloring
~ ~3~7~; )
agents, pe~fl~es, preservatives, antiseptic agents and the like. These
I additives constitute a maximum of 15% by weight of the composition.
The cleaning eo~positions of present invention are generally p~epared
by mixing the orgænic water misci~le solvent componen~s with an ethoxylated
fatty acid and at least one additional nonionic surfactant component to form
a clear, low viscosity liquid vehicle; adding a sodium hydroxide solution to
i
I' the clear liquid vehicle and mixing until the liquid gels, which may vary
'I from a few minutes to several hours, depending on the amounts of the
i1 components; and lastly admixing the water soluble abrasive, color, perfume
and any other additional conventional ingredient with the gelled vehicle,
~1 until the abrasive is uniformly dispersed throu~hout the gelled vehicle and
'~ a paste is formed. The cleaning composition is packaged in any suitable
il container, both Elexible or rigid. The paste can also be e~truded from a
I collapsible container.
,i The final cleaning gel product is a stable thick (viscou~) creamy, hard
surface cleaner, substantially free of water, and has an alkaline p~ within
il the range of about 8-11. It can be applied to ~he surface to be cleaned in
any suitable manner, i.e., with a sponge or a cloth, followed by rinsing the
¦¦ surface with water,l leaving no gritty residue.
The -Eollowing examples merely illustrate the invention, but it is
¦ understood that the invet1tion is not limited thereto. All amounts of
I various ingredients in the examples and elsewhere in the specification are
by weight unless otherwlse specified.
~ ~ .
1~ I
''~, .
~ 1310873~
; Example 1
~j Ingredients
¦¦ Lauric Acid Ethoxylate (9~0) 28.30
I¦ Tetrasodium Pyrophospha~e 20.00
! j Diethylene Glycol Monobutyl Ether 14.00
Ethanol 14.00
Cl~-Cl4 Alcohol EO 5:1 10.00
Propylene Glycol 6.00
ll Deioniæed Water 4.00
iI Caustic Soda ~50%) , 3.00
¦1 1% Graphtol Blue 0.40
Perfume 0.30
¦ pH (1~) = 10.9
¦ The vehicle ingredients, namely ethoxylated lauric acid, ethoxylated
¦ alcohol, butyl carbitol, ethanol and propylene glycol and the perfume are
mixed to form a clear mobile liquid. The NaO~ is mixed with the clear
liquid until the vehicle is gelled and forms a solid gel. After 5 minutes
of gel ripening the tetrasodium-pyrophosphate is mixed with the ripened gel
to form a cream (paste). The blue pigment dispersion is admixed with the
cream.
This formulation produces a creamy b~ue cleaning product possessing
superior cleaning propertles, leaving no gritty residue on the cleaned
surSac-.
~ ~ : '
11
13111~37~3 o
!1 ~2ample 2
~ In~redients %
! Lauric Acid ~th~xylate ~9~O~ 28.00
Sodium Carbonate 23.00
C1O_C1~ Alcohol EO 5:1 21.00
Ethanol 12.50
Diethylene Glycol Monobutyl ~ther 7.00
i~ Propylene Glycol 5.00
'i 38~ Caustic Soda 3.00 .
¦! Perfume 0.30
: I LPmon/l,ime Color Solution 0.20
, This product is prepared in accordance with the process of Exa~ple 1.
This product is a viscous colored paste also havlng superior cleaning
properties.
xa~e~es 3-5
3 4 5
lfonic 1012-601 48.0 10.0 14.0
¦¦ Alkasurf L-9Z 6 . 0 28 . 3 21. O
- 1 Plurafac RA40' - ~ 7.0
Pluronic L-644 15.5 - -
- Butyl Carbitol 8.0 14.0 7.0
. Propylene Glycol - 6.0 6.0
I Ethanol ~.0 14.0 14.0
Water & Color .9 5.9 5.9
~, NaO~ . .7 1.5 1.5
; ¦I Tetrasodium pyrophospha~e 12.0 20.0 23.0
; ~ Pragrance .5 .3 .3
12
. .:
'~'~' ' '
.-
l~lB87$~
.1 .
l! 1. c~o~c~ alcohol ~0 5:1
2. Lauric acid EO 9:1
3. Low forming polyol :
! pr~pylene oxide and ethylene oxide poly-condensates
I, of propylene glycol
4. High foaming polyol:
These compositions are prep~red in accorda~ce with the process of
Example 1.
The final products are viscous hard surface cleaning compositions,
i easily removed by rinsing with water without having a gritty residue.
1 All of the above undiluted cleaning pastes can be dilu~ed with water
il for equally effective cleanling of hard su R aces~ The entire paste product
¦ dissolves in water leaving no gritty residue, i.e., abrasive particles, on
Il or around the cleaned surfaces.
il It is understood that the foregoing detailed description is given
merely by way of illustration and that variations may be ~ade therein
~ithout departlng i o: the spirl~ of the invent,on.
:~ ;
~ ~ I
.
