Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION
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This invention concerns ah all-purpose cleaning
composition~ in the form of a liquid dispersion, that is
especially useful on carpets~and upholstery.
Many known spot-removing compositions employ a
solvent/adsorbent substrate com~ination. The solvent
mobilizes the soil and the adsorbent substrate attracts
the soil and s~lvent to itself for removal from the fabric
by, say, brushing or ~acuuming, Detergents and/or sur-
factants are sometimes employed in such cleaning composi-
tions. The surfactants are usually anionic or nonionic in
character. Examples of anionic surfactants include salts
of fatty acids, alcohol sulfates and sulfonates, polyoxy-
alkylene alkyl carboxylates and polyoxyalkylene alcohol
phosphates. Nonionic surfactants include polyethoxylated
alcohols, amines, alkyl phenols~ fatty acids and amides.
When textile products, particularly carpets and
upholstery, are cleaned with such prior art compositions
the very fine particles of adsorbent substrate tend to
adhere to the textile fibers~ This is particularly
- noticeable when the fibers and the particulates are non-
conductive. The phenomenon is believed due to static
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1~37~
attraction. The compositions of the instant invention
solve the problem by mncluding in the cleaner composition
a cationic antistatic substance which promotes the removal
of fine particulates by brushing or vacuuming the textile
material. There is nothing in the art to suggest the
particular combination of cleaning composition elements
that are disclosed herein or to suggest employing such
elements in the amounts and ratios taught herein.
SUMMARY OF THE INVENTION
This invention concerns a liquid cleaning 60m- .
position compris~ng : ?
i) 5 to 30 parts of urea-formaldehyde polymer
particles having a particle size of from lO
to 105 microns and an oil value of at least
9 0,
ii) 70 to 95 parts of halogenated solvent boiling
at from 45to 120C.,
the total of i) and ii) being 100 parts, and ;~ -
iii) 0.1 to 3.0 parts of finely divided silica
antisettling agent, ;;~ `
iv) 0.1 to 2.0 parts of cationic antistatic
agent, and
v) up to 125 parts of aerosol propellant
selected from at least one of trichloro-
fluoromethane, di~hlorodifluoromethane,
1,2-l~'dichlorotetrafluoroethane, propane,
isobutane and butane.
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A preferred cleaning composit~ons of this
invention comprises
i) 10 to 23 parts of urea-formaldehyde polymer
particles,
ii) 77 to 90 parts of halogenated solvent,
iii) 0.5 to 1 part of finely divided silica,
iv) 0.3 to 1 part of cationic antistatic agent,
and
v) up to 50 parts of aerosol propellant.
Minor amounts of additional solvents, as welll as
odorants and other additives can also be included int the
cleaning compositions of this inventi~n, as will be obvioas
to those skilled in the art.
The cleaning compositions of the invention can
be dispensed as aerosols from pressurized cans, The pro-
portion of cleaner and pressurizer can best be determined
~y experiment, but will generally be approximately a 50% -~
50~ mixture. The pressurizing agents are best used as
mixtures to obtain a favorable balance of properties, ~;
In use, the novel textile-cleaning compositions
are applied to a soiled area of a carpet or other textile
by spraying or sprinkling, or from a cloth or sponge.
applicator, and rubbed or brushed into the substrate.
After drying, which can take only seconds or a few minutes,
depending on the amount applied and on atmospheric con-
ditions, the residual particles can be vacuumed away or
brushed into a dustpan. The soil, having been loosened
by the solvent, s adsorbed on the urea-formaldehyde
polymer parti¢les and is removed therewith.
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` DETAILS`` OF` TH~`'I~7EN~I~)N
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All of the individual ingredients of the composi-
tions of this invention are available commercially and are
made by well-known methods. The cleaning compositions are
peepared by thorough mixing of the ingredients in any order.
For example, the solvent can be charged to a vessel and the
antistatic and antisettling agents can be added followed
by the addition of urea-formaldehyde polymer particulate
material. The compositions can be packaged for use at a
later date without diminution of their effectiveness.
Settling may occur on standing, but stirring or shaking be-
fore use quickly restores the homogeneity of the mixture.
Urea-formaldehyde polymer particles; of satis~
factory porosity are made by reacting urea and formaldehyde `;
in an aqueous mixture at a mole ratio of about 0.9 mole
urea to 1 mole of formaldehydeO Urea can be introduced ~-
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as a 2~% aqueous solution and formaldehyde as a 37~ aqueous
solution.
The urea solution can be made up in a reactor
and the pH of the solution adjusted to 5.6-5.8 by adding
sulfuric acid. The formaldehyde is best added at once,
resulting ~n a lowering of pH to about 3.9. Sulfuric
acid is immediately addad as catalyst~ to bring the pH
to 1.6 2Ø Polymerization starts at once, with evolution "
of heat. The charge is then heated at 55 to 60C. for two
hours, and the pH is ad~usted to 7 0 to 7.5 by adding
caustic soda solution. The solid particles can be
removed by filtration, washed with water and dried at ~ `
about 70C After grading to eliminate particles larger
and smaller than desired~ the particles are ready to use.
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In order to ~unction satisfactoril~ the polymer
particles must have a particle size between 10 and 105
microns. If too small, the particles will be difficult
to remove from the textile fibers. I~ too large tbey
will not have the desired cleaning capacity.
The oil value of the particles a function of
their porosity, must be at least 90. Oil value can be
determined according to Method D281 of the American
Socaety for Testing Materials. In this procedure, raw
linseed oil is gradually added to a weighed amount of
dry, particulate material until there is obtained a
stiff, putty-like paste that does not come apart easily.
Oil value for cleaning particles is calculated as ~ollows,
with typical values for the specific gravity being around
1.4 g/cc:
. Grams of Oi~
01l value = G~elb~b~~lr~Rer~Cr~EaC x Sp. Gr.of particulate
material x 100
The halogen-containing solvents that are useful
herein are those that readily dissolve oily and greasy
materials and that have satisfactory volatility. They
are not so volatile as to evaporate before exerting their
solvent property on the soil, but should volatilize in no ~ -
more than a few minutes so that theycldonn~trp~eve~t
removal of the dried soil-particulate com~ination. These
properties are provided by solvents having boiling points
from about 45 to 120C. Preferred solvents are ~ethyl
chloroform, perchloroethylene, trichlorethylene and
1,1,2-trichloro-1,2,2~trifluoroethane. Solvent freezing ~;
points must, of course, be low enough so that the solvent
doesnnot freeze at use temperatures. The most preferred
solvent is l,l,1-trichloroethane, commonly called methyl
chloroform.
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Contemplated chlorinated hydrocarbons are
subject to decomposition upon con1act with metal surfaces. -- ?
It is therefore customary to add to these solvents small
amounts of stabilizing agents. Effective stabllizers
that can be used with the solvents described herein
include l,4-dioxane, secondary butylene alcohol, and
l,2-butylene oxide~
Cationic antistatic agents have a benefical
effect on particulate recovery in the compositions of
the invention. Nonionic surfactants such as trialkyl-
phosphates and ethoxylated alcohols have little or no
effect. Likewise, anionic surfactants such as the amine
salts of alcohol phosphates and alcohol sulfates do not
improve particulate recovery performance.
The preferred cationic antistatic agents that ~
are useful in the cleaning composi~ions of this i~vention - ,
are those that incorporate at least one Cl2 to C
aliphatic group in a quaternary salt configuration. The ~-
aliphatic group can be a hydrocarbyl group or can
include a linking oxygen or nitrogen atom in the chain.
The most preferred agent is stearyltrimethylammonium
chloride, Good resul~s are obtained with similar com-
. . ~ . ~.
pounds derived from ClO to C24 aliphatic straight chainamines.
Another series of effec~ive~ antistatic agents
has the general formula ~ ~f~
~-C112J ~, ;
.
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.,: . : . ..... , : . . . :
~C~37,3;~1~
where Rl and R2 are Cl to C4 alkyl and R~ 1~ a C10 to C24
alkyl group. An example of this group i8 the commerclal
product "Quaternary" O of the Ciba-Geigy Corporation.
Another useful anti~tatic agent has the formula ~N~lR2R3X
where R i~ C12 to C22 alkyl; Rl-R2 CH3, CH2 2
CH2CH(CH~)OH; R~ is C~ , C2H5 or C6H5C ~ ; and X is Cl~ Br
or CH3S04. An example is "Arquad" 18 sold by Armour
Indu6trial Chemical Company. Still another useful compound
is
C12H250CH2-cH~o~-cH2-N(c~c ~ OH)2 CH~S04.
OH CH~
Satisfactory quaternary antistatlc agents can employ as
anions halides, CH3S04, C2H5S04, ~ P04 and others.
The relative effectivenëss`of the antistatlc
agents can be determined by preparing duplicate cleaning
compositions distingulshed only by the difference in anti- -
static agent employed, followed by application to a dark-
colored textile article (preferably a test piece of nylon
carpet) and removal by vacuuming9 each operation being
performed in the same manner for each cleaning compositionO
Rubbing the toe end of the sole of a black shoe over the
cleaned spot for about 10 strokes will cause the deposit
of more or less polymer particles on the toe of the shoe
depending on the efficiency of the antistatic agent.
As a result of the cationic antistatic component
of the composltions, the particulate material does not
adhere as tenaciously to the textile fibers as it would
in the absence of the antistatlc agent. Essentially all
of the particle~, eve~ those extxemely fine residual
~ragments which may h~ve been deposited due to break-up
during the rubbing or brushing3 are readily removed by
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a vacuum cleaner or a brush. Where the antlstatic agent
i~ not included, these small partlcles adhere to the
textile fibers and, if in sufficien~ amount, conf'er an
unde~lrable change in appearance, ~ "fro~ty" look9 to the
- substrate O
As an antisettling agent a very fine insoluble
inorganic material is employed~ exempllfied by ~umed silica
which has a particle size o~ from about 0.01 to 0.007
micron. Such antisettling agent promotes the dispersion
of the cleaning particulates ln the solvent and aids in
providing a ~miform composition. A~ a~ additional anti-
settling ald there can~ optionally, be included a small
amount of ethylene gl~col or a polyethylene glycol of up
to about 1,000 molecular weight.
The ~ollowing Examples illustrate the invention.
They do not limit the invention.
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EXAMPLE 1
Into a suitable vessel were charged 81.13 parts
, s'
of l,l,l-trichloroethane, with agitation~ There was 8UC- :
cesQively added 3.35 parts o~ 1,4-dioxane, 0.042 parts of
secondary butyl alcohol, 0.042 par~s of 1,2-butylene oxide,
o.626 parts of a 50~ aqueous ~olution of stearyltrimethyl-
amm~nium chloride, and 0~511 parts o~ fumed silica o~
particle size 0.01 to 0~007 microns~ and the ingredlents
were thoroughly mixed. There WaQ then added slcwly,
allowing oach addition to wet out thoroughly~ 18~87 parts
of urea-formaldehyde particulates having an 011 Value
a~ove 90 and particle size b0tween 10 and 105 microns.
After thorough blending, the product was trans~erred to
small containers for eventual use.
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Several n~lon carpeks that were badly solled
were cleaned with the composit-Lon of thlq E:xample, in thi~
manner:
The cleaner was applied to the spots by shaking
through a 1/32" opening in a bottle top to cover the area
of the spots. The cleaner w~ ~ently worked ln with a
nylon bristle brush. The applicatlon wa~ repeated a
second time, and 30 minutes allowed ~or the solvent to
evapora~e~ The residual particulate material was removed
by a conventional beater type vacuum cleaner3 leaving no
trace of the original spots~ Addition of 0.12 parts of
ethylene glycol to the composition was found to help
keep the particulate material suspended in the liquidO
EXAMPLE 2
A composition o~ the invention was prepared in
the following manner for dispensing as an aerosol spray~
Into a vessel was placed 79.7 parts of inhibited methyl
chloro~orm (95.9% l,l~l-trichloroethane, 4.0% 1,4-dioxane,
0.05~ 1~2-butyleneoxide and 0 25% 2-butanol) and ~.64
part o~ a 50% aqueous solution o~ stearyltrimeth~lammonium
chloride~1002 part of fumed silica (particle size 0.01 to
0.007 micron) and 2Q.3 parts of urea-~ormaldehyde polymer
particles were addedO A~ter thorou~h mixin~ the product was
charged into a spray can cooled in a bath of rro~en carbon
dioxide and 2504 parts of dichlorodifluoromethane was added.
The can was then ~itted with a spray head~ The polymer
particles were prepared ln the same manner as described
in Example 1. This composition was sprayed from the can
on stained spots on carpets and chair upholstery and
used as de~cribed in Exampl~ 1. Stained areas were
cleaned so well that no trace o~ stain remained.
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EXAMPLE 3
A composition wa~ prepared as in Example 2 with
the exception of certain proportions of materials that
varled as follow~:
89.~ parts of inhiblted methyl chloroform, 0.~4
part of 50~ ~tearyltrimethyl~nonium chloride in i~o-
propanol, 1.02 part of fumed ~ilica and 10.2 part3 of urea
~ormaldehyde polymer Particles with 25.~ part~ of dichloro~
difluorom~thane. This composition performed equally well
when sprayed on textile stains and used as described in
Ex~mple 1.
EXAMPLE 4 ~
By the g~neral procedure of Example 1, a pre- .
~erred cleaning composition can be made conta~nlng 10
part~ o~ urea-~ormaldehyde polymaric particles having a
particle size between 10 and 105 mlcrons, 90 parts o~
1,131-trichloroethane, 1.0 part o~ stearyltrimethyl~mmoni~m ~ .
chloride catlonic antistatic agent9 and 1.0 part o~ ~umed
~ilica antisettling aæent.
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