U.S. patent number 3,910,848 [Application Number 05/452,339] was granted by the patent office on 1975-10-07 for liquid cleaning composition.
This patent grant is currently assigned to E. I. Du Pont de Nemours and Company. Invention is credited to Helmut H. Froehlich, William Jacob Lautenberger.
United States Patent |
3,910,848 |
Froehlich , et al. |
October 7, 1975 |
Liquid cleaning composition
Abstract
A liquid cleaning dispersion comprising a halogenated solvent
and urea-formaldehyde polymer particles as the major components,
also with small amounts of an antistatic agent and an antisettling
agent and, optionally, chlorofluorinated propellant for aerosol
application; useful for cleaning textiles.
Inventors: |
Froehlich; Helmut H.
(Wilmington, DE), Lautenberger; William Jacob (Wilmington,
DE) |
Assignee: |
E. I. Du Pont de Nemours and
Company (Wilmington, DE)
|
Family
ID: |
23796093 |
Appl.
No.: |
05/452,339 |
Filed: |
March 18, 1974 |
Current U.S.
Class: |
510/329; 510/279;
510/418; 510/281; 510/475 |
Current CPC
Class: |
C11D
3/43 (20130101); C11D 3/0031 (20130101); C11D
17/0043 (20130101); C11D 1/62 (20130101); C11D
3/3703 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C11D 3/43 (20060101); C11D
1/38 (20060101); C11D 1/62 (20060101); C11D
3/37 (20060101); C11D 17/00 (20060101); C11D
003/26 () |
Field of
Search: |
;252/90,DIG.2,88,DIG.13 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Schulz; William E.
Attorney, Agent or Firm: Costello; James A.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A liquid cleaning composition dispensible from a container under
pressure comprising
i. 5 to 30 parts of urea-formaldehyde polymer particles having a
particle size of from 10 to 105 microns and an oil value of at
least 90,
ii. 70 to 95 parts of halogenated solvent boiling at from
45.degree. to 120.degree.C.,
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 trichlorofluoromethane, dichlorodifluoromethane,
1,2-dichlorotetrafluoroethane, propane, isobutane and butane.
2. A composition according to claim 1 comprising
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.
3. A composition according to calim 2 comprising
i. 10 parts of urea-formaldehyde polymer particles,
ii. 90 parts of 1,1,1-trichloroethane,
iii. 1.0 part of fumed silica, and
iv. 1.0 part of stearyl trimethylammonium chloride.
Description
BACKGROUND OF THE INVENTION
This invention concerns an 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 sulvent/absorbent
substrate combination. The solvent mobilizes the soil and the
adsorbent substrate attracts the soil and solvent to itself for
removal from the fabric by, say, brushing or vacuuming. Detergents
and/or surfactants are sometimes employed in such cleaning
compositions. The surfactants are usually anionic or nonionic in
character. Examples of anionic surfactants include salts of fatty
acids, alcohol sulfates and sulfonates, polyoxyalkylene alkyl
carboxylates and polyoxyalkylene alcohol phosphates. Noionic
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
attraction. The compositions of the instant invention solve the
problem by including 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 composition
comprising
I. 5 to 30 parts of urea-formaldehyde polymer particles having a
particle size of from 10 to 105 microns and an oil value of at
least 90,
Ii. 70 to 95 parts of halogenated solvent boiling at from
45.degree. to 120.degree.C.,
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 trichlorofluoromethane, dichlorodifluoromethane,
1,2-dichlorotetrafluoroethane, propane, isobutane and butane.
A preferred cleaning composition 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 well as odorante and other
additives can also be included in the cleaning compositions of this
invention, as will be obvious to those skilled in the art.
The cleaning compositions of the invention can be dispensed as
aerosols from pressurized cans. The proportion of cleaner and
pressurizer can best be determined by 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
conditions, the residual particles can be vacuumed away or brushed
into a dustpan. The soil, having been loosened by the solvent, is
adsorbed on the urea-formaldehyde polymer particles and is removed
therewith.
DETAILS OF THE INVENTION
All of the individual ingredients of the compositions of this
invention are available commercially and are made by well-known
methods. The cleaning compositions are prepared 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 before use quickly
restores the homogeneity of the mixture.
Urea-formaldehyde polymer particles of satisfactory 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 formaldehyde. Urea
can be introduced as a 20% 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 in a lowering of pH
to about 3.9. Sulfuric acid is immediately added as catalyst, to
bring the pH to 1.6-2.0. Polymerization starts at once, with
evolution of heat. The charge is then heated at 55.degree. to
60.degree.C. for 2 hours, and the pH is adjusted 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 70.degree.C. After
grading to eliminate particles larger and smaller than desired, the
particles are ready to use.
In order to function satisfactorily 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. If
too large they 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 Society 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 follows, with typical values
for the specific gravity being around 1.4 g/cc: ##EQU1##
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 they do not
prevent removal of the dried soil-particulate combination. These
properties are provided by solvents having boiling points from
about 45.degree. to 120.degree.C. Preferred solvents are methyl
chloroform, perchloroethylene, trichloroethylene and
1,1,2-trichloro-1,2,2-trifluoroethane. Solvent freezing points
must, of course, be low enough so that the solvent does not freeze
at use temperatures. The most preferred solvent is
1,1,1-trichloroethane, commonly called methyl chloroform.
Contemplated chlorinated hydrocarbons are subject to decomposition
upon contact with metal surfaces. It is therefore customary to add
to these solvents small amounts of stabilizing agents. Effective
stabilizers that can be used with the solvents described herein
include 1,4-dioxane, secondary butylene alcohol, and 1,2-butylene
oxide.
Cationic antistatic agents have a beneficial effect on particulate
recovery in the compositions of the invention. Nonionic surfactants
such as trialkylphosphates 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 compositions of this invention are those that incorporate
at least one C.sub.12 to C.sub.24 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
results are obtained with similar compounds derived from C.sub.10
to C.sub.24 aliphatic straight chain amines.
Another series of effective antistatic agents has the general
formula ##EQU2## where R.sub.1 and R.sub.2 are C.sub.1 to C.sub.4
alkyl and R.sub.3 is a C.sub.10 to C.sub.24 alkyl group. An example
of this group is the commercial product "Quaternary" 0 of the
Ciba-Geigy Corporation. Another useful antistatic agent has the
formula RN.sup.+R.sub.1 R.sub.2 R.sub.3 X.sup.- where R is C.sub.12
to C.sub.22 alkyl; R.sub.1 =R.sub.2 =CH.sub.3,CH.sub.2 CH.sub.2 OH,
or CH.sub.2 CH(CH.sub.3) OH; R.sub.3 is CH.sub.3, C.sub.2 H.sub.5
or C.sub.6 H.sub.5 CH.sub.2 ; and X is Cl, Br or CH.sub.3 SO.sub.4.
An example is "Arquad" 18 sold by Armour Industrial Chemical
Company. Still another useful compound is ##EQU3## Satisfactory
quaternary antistatic agents can employ as anions halides, CH.sub.3
SO.sub.4 .sup.-, C.sub.2 H.sub.5 SO.sub.4 .sup.-, H.sub.2 PO.sub.4
.sup.- and others.
The relative effectiveness of the antistatic agents can be
determined by preparing duplicate cleaning compositions
distinguished only by the difference in antistatic agent employed,
followed by application to a darkcolored textile article
(preferably a test piece of nylon carpet) and removal by vacuuming,
each operation being performed in the same manner for each cleaning
composition. 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
compositions, the particulate material does not adhere as
tenaciously to the textile fibers as it would in the absence of the
antistatic agent. Essentially all of the particles, even those
extremely fine residual fragments which may have been deposited due
to break-up during the rubbing or brushing, are readily removed by
a vacuum cleaner or a brush. Where the antistatic agent is not
included, these small particles adhere to the textile fibers and,
if in sufficient amount, confer an undesirable change in
appearance, a "frosty" look, to the substrate.
As an antisettling agent a very fine insoluble inorganic material
is employed, exemplified by fumed silica which has a particle size
of from about 0.01 to 0.007 micron. Such antisettling agent
promotes the dispersion of the cleaning particulates in the solvent
and aids in providing a uniform composition. As an additional
antisettling aid there can, optionally, be included a small amount
of ethylene glycol or a polyethylene glycol of up to about 1,000
molecular weight.
The following Examples illustrate the invention. They do not limit
the invention.
EXAMPLE 1
Into a suitable vessel were charged 81.13 parts of
1,1,1-trichloroethane, with agitation. There was successively added
3.35 parts of 1,4-dioxane, 0.042 parts of secondary butyl alcohol,
0.042 parts of 1,2-butylene oxide, 0.626 parts of a 50% aqueous
solution of stearyltrimethylammonium chloride, and 0.511 parts of
fumed silica of particle size 0.01 to 0.007 microns, and the
ingredients were thoroughly mixed. There was then added slowly,
allowing each addition to wet out thoroughly, 18.87 parts of
urea-formaldehyde particulates having an Oil Value above 90 and
particle size between 10 and 105 microns. After thorough blending,
the product was transferred to small containers for eventual
use.
Several nylon carpets that were badly soiled were cleaned with the
composition of this Example, in this manner:
The cleaner was applied to the spots by shaking through a 1/32 inch
opening in a bottle top to cover the area of the spots. The cleaner
was gently worked in with a nylon bristle brush. The application
was repeated a second time, and 30 minutes allowed for the solvent
to evaporate. The residual particulate material was removed by a
conventional beater type vacuum cleaner, 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 liquid.
EXAMPLE 2
A composition of 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 chloroform (95.9% 1,1,1-trichloroethane,
4.0% 1,4-dioxane, 0.05% 1,2-butyleneoxide and 0.25% 2-butanol) and
0.64 part of a 50% aqueous solution of stearyltrimethylammonium
chloride, 1.02 part of fumed silica (particle size 0.01 to 0.007
micron) and 20.3 parts of urea-formaldehyde polymer particles were
added. After thorough mixing, the product was charged into a spray
can cooled in a bath of frozen carbon dioxide and 25.4 parts of
dichlorodifluoromethane was added. The can was then fitted with a
spray head. The polymer particles were prepared in 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
described in Example 1. Stained areas were cleaned so well that no
trace of stain remained.
EXAMPLE 3
A composition was prepared as in Example 2 with the exception of
certain proportions of materials that varied as follows:
89.8 parts of inhibited methyl chloroform, 0.64 part of 50%
stearyltrimethylammonium chloride in isopropanol, 1.02 part of
fumed silica and 10.2 parts of urea-formaldehyde polymer particles
with 25.4 parts of dichlorodifluoromethane. This composition
performed equally well when sprayed on textile stains and used as
described in Example 1.
EXAMPLE 4
By the general procedure of Example 1, a preferred cleaning
composition can be made containing 10 parts of urea-formaldehyde
polymeric particles having a particle size between 10 and 105
microns, 90 parts of 1,1,1-trichloroethane, 1.0 part of
stearyltrimethylammonium chloride cationic antistatic agent, and
1.0 part of fumed silica antisettling agent.
* * * * *