Note: Descriptions are shown in the official language in which they were submitted.
.283~
62301-1434
BACKGROUND OF THE INVENTION
This invention relates to laundry pre-spotting
compositions which are in the Eorm of clear, stable, micro-
emulsions, solu-tions or gels and which are suitable for the
treatment of heavily soiled areas of fabrics. More particularly,
the invention relates to single-phase pre-spotting compositions
which are especially effective for the removal of oily stains and
soils from fabrics and which are characterized by being
"infinitely dilutable" with water, as herein defined, without
concomitant phase separation. Thus, the removal of oily stains
and soils is effected by the application of the pre-spotting
composition to the generally soiled areas of the fabric which
solubilizes the oily soil, followed by rinsing with water in a
wash or rinse bath wherein the diluted pre-spotting composition
remains in a clear, sin~le-phase, avoiding the attendant problem
of redeposition of the oilv soil on the previously cleaned fabric.
The removal oE oily soils and stains from fabrics has
been the focus oE much attention in the laundry art. In
particular, emphasis has been placed on pre-treating or pre-
spotting articles of laundry which are not uniformly soiled, suchas for example, shirt collars and cuffs, as a preliminary stain-
removal treatment prior to regular washing. The detergent
compositions which have been used and disclosed for pre-spotting
have varied considerably encompassing, for example, commercial
liquid laundry detergent compositions which are applied to the
fabric as a pre~spotter prior to being added to the wash bath, as
.we~ as formulations intended specifically for oily soil removal
which contain one or more organic solvents. While the use of
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aqueous liquid laundry detergents has proven successful for
cleaning a wide variety of soils, the removal of oily soils, in
particular, is often troublesome insofar as such liquid
compositions do not generally contain a solvent especially
suited for oil solubilization, such as an organic solvent. On
the other hand, the ~nown compositions which are specifically
formulated for oily soil removal suffer from the fact that they
are either impractical to use, or they do not avoid the problem
of oily soil redeposition on the`fabric in the wash or rinse bath.
The redeposition of oily soil is a problem attributable,
in part, to phase separation of the pre-spotting composition
containing an organic solvent when such composition becomes
"infinitely" or extremely diluted with water in the wash bath. In
efect, the solubilized oily soil as well as the organic solvent
itself become soils to be removed from the fabric when phase
separation of the pre-spotting composition occurs upon dilution.
In this regard, the term "in~inite dilutability" which is used
herein to char~cterize the pre~spotting compositions of the present
inventi.on refers to the fact that the pre-spotti.ng compositions are
formulated such that when diluted with water in a ratio of at least
100 parts water to 1 part of compositi.on, they are entirely in a
clear single phase with no phase separation being present. This
degree of dilutability is significant because it corresponds
approximately to the dilution encountered by a pre-spotting
composition when applied to a fabric which is subsequently rinsed
with water, such dilution being about one hundred to one thousand-
fold.
- 3 - ~ ~835~1
62301-1434
U. S. Patent 4,180,472 to Mitchell et al is illustrative
of a pre-treatment composition for oily stain removal which
requires a multiple step operation. The patent describes a
composition comprising a solvent such as an alkane in combination
with a specified surfactant as an emulsifier. The described
composition cannot be applied directly to the soiled fabrics,
but rather, is added to the wash bath containing the items to be
laundered. After oil solubilization from the soiled fabrics is
effected, removal of the solvent must be carried out in a second
step using a specified surfactant as a solvent stripping agent.
No single-phase composition is contemplated or disclosed.
U. S. Patents 4,093,418 and 4,178,262 to Compton et al
describe laundry spot-agent compositions containing a solution of
a nonionic surfactant and an isoparaffinic solvent. No water is
present in the composition nor is there any indication that such
compositions can be readily removed from fabrics by immersion in
a wash or rinse bath without the occurrence oE phase separation.
British patent specification 1l518,786, published July
19, 1978 discloses a detergent composition comprising a nonionic
detergent, an organic solventl such as, methyl laurate, and water.
The percentage of organic solvent in such composition is severely
restricted, however, because according to the disclosure the
solvent "tends to act as a load upon the general cleaning
performance of the composition". This indicates that the solvent
does not remain in solution in the wash bath, but rather, is
separated out and acts as a soilO In example 2 of the publication,
the amount of organic solvent in the disclosed composition is
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62301-1434
3.4~. Further, the disclosed compositions which appear to be in
granular form are added directly to the wash bath, according to
the examples, rather than being conveniently applied to the
soiled fabrics as a pre-spotting composition.
Accordingly there remains a need in the art to provide
an improved composition for oily soil removal which can be applied
directly to soiled fabrics as a pre-spotter and which can be
readily removed there~rom by rinsing with water.
SUMM~RY OF THE INVENTION
_
The present invention provides a clear, single phase,
liquid microemulsion, solution, or gel laundry pre-spotting
composition comprising, by weight:
(a) from about 10 to 70% of an organic solvent compris-
ing one or more alkanes having from 10 to 18 carbon atoms;
(b) ~rom about 4 to 60% of one or more nonionic
surfactants comprising the condensation product of an aliphatic
primary or secondary alcohol having from 9 to 16 carbon atoms
with from 1 to 7 moles of ethylene oxide per mole of said alcohol;
(c) from about 0 to 50% of a supplementary nonionic
surfactant comprising an amine o~ide ox an alkyl phenol
ethoxylate, the total amount of nonionic surfactants in the pre-
spotting composition being no greater than about 60%, by weight;
(d) from about 0 to 20~ of a co-surfactant comprising
an aliphatic primary or secondary alcohol having from 10 to 18
carbon atoms;
(e) from about 0 to 10% of a polar organic co-solvent;
(f) from about 1 to 80% water, -the respective
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percentages of each component of the composition being such as to
forrn a clear, single-phase pre-spotting composition which is
further characterizecl by being lnfinitely dilutable with water
without concomitant phase separation such that the addition of
water to said pre-spotting composition in an amount of one
hundred parts wa-ter to one part of said composition results in a
diluted composition which is entirely in a clear single phase;
(g) the balance optionally comprising a minor amount of
adjuvants,
In a preferred embodimen-t of the invention the
pre-spotting composition comprises, by weight, about 45%
tridecane, about 29.2% oE a primary alcohol ethoxylate wherein the
alcohol has Erom about 9 to 11 carbon atoms and is condensed with
6 moles oE ethylene oxide per mole of alcohol. About 15.8% of a
primary alcohol ethoxylate wherein the alcohol has Erom about 14
to about 15 carbon atoms and is condensed with 2.25 moles of
ethylene oxide per moLe of alcohol and about 10% water.
In accordance with the process oE the invention, the
removal of oi:Ly soils and/or stains from fabrics with a pre-
spotting composition is effected by contactiny such stainedfabrics, generally in the immediate area of the oily soil, with an
effective amount of the above-identified liquid or gel pre-
spotting composition. This treatment can then be followed by
regular washing, if desired, or the treated fabrics can then be
simply rinsed with an aqueous liquid, preferably water, to remove
the pre-spotting composition containing the solubilized oil.
- 5a ~ 351~ ~2301-1434
In addition to their utility as laundry and pre-spotting
compositions, the compositions oE the inven-tion are also
partieularly useEul for the removal of oily or greasy soil from
hard surEaces such as plastic, vitreous and metal surfaees haviny
a shiny Einish. Oily and greasy soils presen-t on such hard
surfaces are readily solubilized in microemulsions, solutions or
gels in aceordance with the invention and hence such eompositions
may be efEectively utilized as clear single phase all purpose
cleaning compositions.
~.~
~Z~3~ 62301-1434
~ he described pre-spotting composition may be formulated
as herein described to be in the Eorm of a liquid solution,
liquid microemulsion (either water-in oil or oil-in-water type)
or a gel, depending upon the relative proportions of the three
principal components of the composition, namely, organic solvent,
surfactant and water. For each of these particular forms, the
compositions of the invention are clear at ambient room
temperature, thermodynamically stable and in a single phase.
Thus, compositions which are in the form of emulsions, or
mixtures which are not otherwise in a single-phase, clear at
ambient conditi.ons, and thermodynamically stable, are not in
accordance with the invention.
The term "microemulsions" as used herein refers to
compositions containing two immiscible li~uid phases: a dispersed
phase (i.e. micelles) and a continuous phase. The individual
droplets of the dispersed phase of the microemulsion generally
have an avera~e radius less than about lOOOA, typically between
about 50 to 1000 angstroms. In soluti.on form, the dispersed or
non-continuous phase is generally below 40A average radius. When
the dispersed phase has an average radius greater than about
lOOOA, it is no longer a microemulsion but an emulsion which is
generally turbld and thermodynamically unstable. The measurement
of average radius size of the dispersed phase can be carried out
using conventional light scattering techni~ues.
The present invention is predica~d upon the discovery
that pre-spotting compositions containing one or more organic
solvents for oily soil removal can be formulated to satisfy two
, . . ~ .
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~.~83511 62301-1434
important requirements for the efEicient application of a pre-
spotting composition to a soiled fabric and its efficient removal
therefrom while avoiding the problem of oil redeposition: (1)
the pre-spotting composition is in the form of a clear, single-
phase composition so as to allow the oily soil upon the fabric
to be rapidly solubilized by the pre-spotting composition; and
(2) the pre-spotting composition is readily removable from the
cleaned fabric by rinsing with water without phase separation
occurring in the diluted pre-spotting composition. This latter
characteristic of the composition is referred to as infinite
dilutability with water. More specifically, a composition is
considered infinitely dilutable when it can be diluted at least
one hundred-fold by weight with water to form a diluted
composition which is entirely in a clear, single-phase. Accord-
ingly, an essential characteristic of the present pre-spotting
compositions is that such compositions regardless of whether in
the form of a solution, microemulsion or gel, as well as the
infinitely dil~lted compositions derived therefrom, are formed
entirely of a clear, single-phase.
Although the applicant does not wish to be bound to
any particular theory of operation, it is believed that at a
condition of infinite dilution, the diluted pre-spottiny
compositions of the invention are in the form of an oil-in-water
microemulsion. In such microemulsion, the oil ~e.g. organic
solvent) is the dispersed phase and is suspended in water which
is the continuous phase thereby removing the organic solvent and
solubilized oil from contact with the treated fabric. This allows
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1 ~ ~ 3 5~ 1 62301-1434
-the pre-spotting composi-tions to be readily removed from the
treated fabric by rinsing with water without the accompanying
problem o~ phase separation and oily soil redeposition on the
fabric. The formation of an oil-in~water microemulsion at
infinite dilution is thus a characteristic of the presently
described pre-spotting compositions.
It can be readily determined for purposes of the
invention whether a particular pre-spotting formulation is
infinitely dilutable in accordance with the following test: tG
one part of the pre-spotting formulation there is added 100 parts
or more of water while stirring, both the water and the formula-
tion being at room temperature. The resulting diluted mixture is
then allowed to stand for at least one hour and then observed
for phase separation. I~ no phase separation is present either
as a clear phase boundary or by the appearance of cloudiness or
opacity, the composition is considered infinitely dilutable.
_ AILED DESCRIPTION OF TFIE INVENTION_ _
The pre-spotting compositions of the invention are
essentially comprised of three components: organic solvent,
nonionic surfactant and water. In addition to these components,
there may also be present, if desired, a co-solvent, a co-
surfactant, a supplementary nonionic surfactant as hereinafter
defined and adjuvants. The particular components employed and
their relative amounts in the pre-spotting composition is
determined on the basis of such composition being in a clear-
single phase and forming either a microemulsion (oil-in-water or
water-in-oil), a solution (water-in-oil type i.e. oil is the
D~ ~
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~33~
- 9 - 62301-1434
continuous phase) or gel, and such composition having the ~urther
characteristic o~ being infinitely dilutable with wa-ter. The
determination of whether a composition is in-finitely dilutable
with water is easily carried out in accordance with the test
defined above and therefore the formulation of composi-tions which
possess this characteristic is readily arrived at by a simple
trial and error t~chnique.
The amount of organic solven-t in the composition may
vary from 10 to 70%, preferably from about 45 to 50%, by weight of
the total pre-spotting composition. The organic solvent may be
comprised o~ one or more al]canes, straigh-t chain or branched,
having Erom 10 to 18 carbon atoms. Normal dodecane is a preferred
solvent for the present pre-spotting composition, with n-decane,
n-tridecane and n-hexadecane being also particularly useful.
A polar organic co-solvent may optionally be added to
the composition in an amount oE up to about 10~, by weight. Among
the useful polar co-soLvents are the Eollowing: low molecular
weight alcohols, such as isopropanol and hexanol; benzyl alcohol;
oxoalcohol esters, such as the TM Exxates* (sold by Exxon); Butyl
Carbitol* (sold by Union Carbide Corporation); ketones, such as
benzophenone; diglyme; dialkyl ph-thalate esters, such as dibutyl
phthalate, esters of monohydric alcohols and fatty acids; esters
of glycols and fatty acids; es-ters of glycerol and fatty acids;
and esters of polyglycols and fatty acids.
*Trade-mark
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~Z8~51~ 62301-1434
The nonionic surfactant is preferably comprised of one
or a mixture of primary alcohol ethoxylates or secondary alcohol
ethoxylates. The primary alcohols ethoxylates are represented by
the general formula:
R~O-(cH2-cH2-O) -H
wherein R is an alkyl radical having from 9 to 16 carbon atoms
and the number of ethoxylate groups, n, is from 1 to 7.
Commercially available nonionic surfactants of this type are sold
by Shell Chemical Company under the trade~mark Neodol and by Union
Carbide Corporation under the trade mark Tergitol. Especially
preferred for use herein are the following: Tergitol 24-L-5,
Neodol 91-6, Neodol ~5-2.25, and Neodol 45-1, the latter, for
example, being a C14-C15 alcohol condensed with 1 mole of ethylene
oxide per mole of alcohol.
The secondary alcohol ethoxylates are represented by the
general formula:
CH3 - (CH2)X - IH (C~I2)y 3
( l2 CH2 )n - H
wherein X~Y is from 6 to 13 and the number of ethoxylate groups,
n, is from 1 to 7. Commercially available surfactants of this
type are sold by Union Carbide Corporation under the trade-mark
Tergitol S series surfactants.
The nonionic surfactants or mixture of surfactants
which are useful for the present compositions ha~e an HLB
(hydrophilic-lypophilic balance) of from about 9 to 13, preferably
" .
133~
62301-1434
from about 9 to 11, and most preferably from about 9.5 to 10.5.
Generally, if the surfactant or surfactant mixture in the
composition has an HLB higher than about 12, an oil-soluble fatty
alcohol co-surfactant (e.g. a C14~C15 alcohol) or a water and oil
miscible polar organic co-solvent is re~uired in the composition
such as, isopropanol, hexanol or Butyl Carbitol.
In suitable circumstances, other nonionic surfactants
can be present in partial replacement or supplementary to the
above-defined alcohol ethoxylated surfactants. These supplementary
surfactants are comprised principally of two types of nonionic
surfactants: amine oxides and alkyl phenol ethoxylates.
The useful amine oxides are represented by the general
formula:
1 2
Rl--N--~0
R3
wherein Rl is an al]cyl radical containing from 12 to 18 carbon
atoms, and R2 and R3 are methyl, ethyl or hydroxyethyl.
Commercially availabe surfactants of this type are sold by Armak
under the trade-mark Aromox surfactant, such as, for example,
Aromox DMMC-W the trade-mark for dimethyl cocoamine oxide.
The alkyl phenol ethoxylates which may be used in the
present compositions include the condensation products of alkyl-
phenol having an alkyl group containing from about 8 to 10 carbon
atoms in either a straight chain or branched chain configuration
with ethylene oxide, said ethylene oxide being present in an amount
of 4 to 15 moles of ethylene oxide per mole of alkyl phenol.
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623~1-1434
Commercially available nonionic surfactant~ of this type'include
*
Tergitol NP surfactant sold by Unlon Carbide Corporation and
Igepal surfactants sold by G~F Corporation. Particularly useful
is Igepal C0-630 comprised of a C9 alkyl phenol ~thoxylate with
9 moles oE ethylene oxide per mole of phenol,
In general, a supplementary nonionic surfactant may be
advantageously used dependlng upon product economics, surfactant
availability or to adjust the HLB of the nonionic surfactant
mixture to a desired value.
The total amount o non:lonic surfactant in the composi-
tion is from about 8 to 60%, preferably from about 15 to 50~, and
most preferably from about 30 to 50~, by weight of the
composition. The percentage of primary or secondary alcohol
ethoxyl.ate m~y vary from about 4 to 60~ of the composltion. Hence,
if the level of the defined alcohol ethoxylates ln the composition
is below about,8'~, hy welght, a supplementary nonionic surfactant
as herein ~efi.n~cl mu~ ordlna~lly be present ln conjunction
therewith. The supplementary nonlonlc ~urfactant may be present
ln a ratio of up to 5:1 relative to the alcohol ethoxylates, a
20 ratio of from about 0.5:1 to 3:1 belng preferred.
A co-surfactant may optionally bs used ln the pre-
spotting compositons ln an amount of up to about 20~, by weight,
for purposes of lowering the HI,~ value of the nonionic surfactant
or mixture of nonionic surfactants to the desired value, The
: co-surfactant is preferably comprised of a prlmary or secondary
fatty alcohol having from 10 to 18 carbon atoms. Commercially
available alcohols of this type are sold under the trade-mark
*Trade-mark
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62301-1434
Neodol by Shell Chemical Company. Neodol 45, a C14-C15 alcohol,
is particularly useful as a co-surfactant in the present
compositions.
The amount of water in the pre-spotting compositions
may vary from about 1 to 80%, by weight, depending upon the
desired form of the composition. Water-in-oil microemulsions or
water-in-oil soLutions are generally favoured when water is
present at levels of from about 1 to 15%, of the composition.
Gels which are typically liquid crystalline or isotropic micro-
emulsion gels, are generally formed when the amount of water isfrom about 25~ to 50%, by weight. Oil-in-water microemulsions
are generally favoured when the water lS present at levels of
about 50% or higher o the total composition. When the water
content is between about 15 to 25~, the resulting compositions
will generally ~eine a range of water-solvent-surfactant
mixtures which are not in a single phase and hence are outside
the scope of the present invention.
Various adjuvants may be present in the pre-spotting
compositions, such as 1uorescent brighteners, bleaches, enzymes,
perfumes and colourants. The perfumes that are employed usually
include essential oils, esters, aldehydes and/or alcohols, all
of which are known in the perfumery art. The colourants may
include dyes and watex dispersible pigments of various types. The
bleach is preferably hydrogen peroxide in an amount of from 0 to
3%, by weight. The enzymes may be protease or amylase enzymes or
mixtures thereof. A]so present may be builders, such as sodium
sesquicarbonate; antiredeposition agents, such as sodium
~3~ 62301-1434
carboxymethyl-cellulose; dispersing agents, such as sodium
polyacry]ate; bactericides; funyicides; anti-foam agents, such
as silicones; anti-soiling agents, such as copolyesters;
preservatives such as formalin; and foam stabilizers.
The individual proportion of the aforementioned
adjuvants will be less than 3~, by weight, often less than 1~,
except for builders for which the proportion may sometimes be
about 5% or higher. The total percentage of adjuvants will
normally be no more than 10%, by weight, of the pre-spotting
composition and desirably less than 5% thereof. It is, of course,
understood that the adjuvants employed are selected so as not to
interfere with the essential physical characteristics of the pre-
spotting composition as well as the oily soil removal effected by
such pre-spotting composition.
The pre-spotting compositions may be prepared by simply
mixing the components, the amount of agitation and the order of
addition of components not being critical process parameters.
However, to reduce the mixing time and energy required in the
manufacturing process the following orders of addition are
preferred.
To form water-in-oil solutions, water-in-oil micro-
amulsions or gels, the organic solvent and surfactant are
combined followed by the addition of water. When two or more
surfactants are used, the more oil soluble (i.e. hydrophobic)
surfactant is combined with the solvent prior to adding the more
water soluble (i.e. hydrophilic) surfactant, with water then being
added to the resulting mixture.
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- 15 ~ 35~1
62301-1434
To form oil-in-water microemulsions, the order of
addition is reversed. Thus, the surfactant or surfactant mixture
is first added to water followed by addition of the organic
solvent. If a polar organic co-solvent is employed, it should be
combined with the organic solvent prior to being added to the
water-surfactant mixture. Where two or more surfactants are to
be used, the more hydrophilic surfactant is first added to the
water followed by addition of the more hydrophobic surfactant.
If water-soluble adjuvants are to be used, they are the first
components dissolved in the water before addition of the other
components.
EXAMPLE 1
Illustrative of the pre-spotting compositions of the
invention, Compositions 1 through 21 were prepared in accordance
with the above-described method of preparation. The particular
form of the pre-spotting composition is indicated for each
composition described.
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~Z83~ 62301-1434
WT. PERCENT
1- n-Dodecane 42.0
Alcohol (Cg-Cll) 42.0 (Neodol 91-6)
ethoxylate (EO 6)
Alcohol (C14 C15) 11.2 (Neodol 45-1)
ethoxylate (EO 1)
Water 4.8
Form: water-in-oil solution 100.0
(a) The names in par~ntheses represent the commercial trade-
marks of the alcohol ethoxylates marketed by Shell Chemical
Company used in the composition. Neodol 91-6, for example, is
an ethoxylated alcohol having from 9 to 11 carbon atoms with 6
moles of ethylene oxide per mole of alcohol.
WT. PERCENT
2- n-Dodecane 30%
ohol (C12-C14 )
ethoxylate (EO 5)
Water 40
-
Form: gel 100%
n-Hexadecane 15.4%
Alcohol (Cg-Cll) 9 5
ethoxylate (EO 6)
Alcohol (C14-C15) 4-~
ethoxylate (EO 1)
Water 70.3
Form: oil-in-water (o/w)
microemulsion 100.0
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- 17 - ~ ~3S~
62301-1434
WT. PERCE~T
4- n-Dodecane 35.3%
( 9 11
ethoxylate (EO 6)
Alcohol (Cg-Cll) 4.3
ethoxylate (EO 2.25)
Benzyl alcohol 6.9
Water 15 6
Form: water-in-oil (w/o) 100.0
microemulsion
5- n-Dodecane 15.0%
Secondary alcohol (C15) 15.0 (Tergitol 15-S-7)
ethoxylate (EO 7)
Alcohol (C14 C15) 2.0
ethoxylate ~EO 1)
Benzyl alcohol 3.0
Water 65.0
Form: o/w microemulsion 100.0%
6- n-Dodecane 10.0%
Secondary alcohol (C15) 10.0
ethoxylate (EO 5)
Alcohol (C12 C15) 2.0
ethoxylate (EO 3)
; Benzyl alcohol 2.0
Water 76.0
Form: o/w microemulsion 100.0
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1283~ 62301-1434
WT. PERCENT
7- n-Dodecane 24.0%
Butyl Carbitol (Union Carbide T~) 6.0
Alcohol (C14 C15 8.0
ethoxylate (E0 2.25)
Dimethyl cocoamine oxide10.0
Water 52.0
Form: o/w microemulsion100.0
8- PEG 400 Distearate 5.6%
n-Dodecane 22.2
Alcohol (C14 C15)
ethoxylate (E0 2.25)
Dimethyl cocoamine oxide 7.4
Butyl carbitol 7.4
Water 50.0
Form: o/w microemulsion100.0
9- n-Dodecane 48.0%
Alkyl (Cg) phenol 30.0 (Igepal C0-630)
ethoxylate (E0 9)
Alcohol (C14 C15) 21.0
ethoxylate (E0 2.25)
Water 1.0
Form: w/o solution 100.0
, -
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:
~83~ 62301-1434
WT. PERCENT
10- n-Dodecane 10.0%
Alkyl (Cg) phenol 5.0
ethoxylate (EO 9)
Alcohol (C14 C15)
ethoxylate (EO 2.25)
Butyl carbitol 5.7
Water 74.3
Form: o/w microemulsion100.0
11- n-Dodecane 54.0%
Alkyl (Cg) phenol 30.0
ethoxylate (EO 9)
Alcohol (C14 C15) 14.0
ethoxylate (EO 2.25)
Water _ 2.0
Form: w/o microemulsion100.0
12- n Dodecane 17.0%
Alcohol (Cg-Cll) 9-7
ethoxylate (EO 6)
Alcohol (C14 15)
ethoxylate (EO 1)
Water 68.8
Form: o/w microemulsion 100.0
,
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~Z835~ ~
62301-1434
WT. PERCENT
13- n-Tridecane 15.4%
( 9 11) 9.5
ethoxylate (EO 6)
Alcohol (C14 C15 4.8
ethoxylate (EO 1)
Water 70.3
_
Form: o/w microemulsion100.0
14- n-Hexadecane 48.0
Alcohol (Cg-Cll) 31.8
ethoxylate (EO 6)
Alcohol (C14 C15) 16.9
ethoxylate (EO 1)
Water 3.3
Form: w/o solution 100.0
15- n-Dodecane 35.1
Alcohol (Cg-Cll) 51.3
ethoxylate (EO 6)
Alcohl (C14 C15) 9.1
Water 4.5
-
Form: w/o solution 100.0
` ' '. ` ' ' ' .
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- 21 - ~ ~3~
62301-1434
WT. PERCENT
16- n-Dodecane 14.8%
Oxohexyl acetate 0.2
Alcohol (Cg-Cll) 22.0
ethoxylate (EO 6)
(C14 C15) 3.0
Water 60.0
Form: o/w microemulsion 100.0
17- n-Dodecane 30.0
Alcohol (Cl2 C14) 20.0
ethoxylate (EO 5)
Water 50,0
Form: gel 100.0
18- n-Dodecane 25.0
(Cg Cll) 37-3
ethoxylate (EO 6)
Alcohol (C14 C15) 5~1 (Neodol 45)
Oxyhexyl acetate 0.4
Water 32.2
Form: gel 100.0
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WT. PERCENT
19- n-Decane 40.9%
Alcohol (Cg-Cll) 23.6
ethoxylate (EO 6)
Alcohol (C14 C15) 11.0
ethoxylate (EO 1)
Water 24.5
Form: gel 100.0
20- n-Dodecane 10.0%
Alcohol (C12 C14 ) 10 . O
ethoxylate (EO 5)
Water 80.0
Form: oil-in-water 100.0
microemulsion
21- n-Dodecane 45.0%
Alcohol (C12 C14) 45.0
ethoxylate (EO 5)
Water 10.0
Form: water-in-oil
microemulsion 100.0
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EXAMPLE 2
Compositions 22-24 described below are illustrative of
formulations which were all in the form of clear single-phase
solutions yet were not infinitely dilutable as herein defined,
and hence are not in accordance with the invention.
WT. PERCENT
22- n-Dodecane 58.8%
Alcohol (C12 C14) 39.2
ethoxyla-te (EO 5)
Water 2.0
Form: w/o solution 100.0
,
23 n-Tridecane (Norpar 13) 50.0
Alcohol (Cg-Cll) 22.2
ethoxylate (EO 6)
Alcohol (C14 C15) 17.8
: ethoxylate (EO 2.25)
Water 10.0
Form: w/o solution 100.0
24- n-Tridecane 40.0
Alcohol (Cg-Cll) 27.8
ethoxylate (EO 6)
Alcohol ~Cg-Cll) 22.2
ethoxylate (EO 1)
Water 10.0
Form: w/o solution 100.0
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EXAMPLE 3
Shown below is Composition 25, similar to Compostions 23
and 24 but significantly different insofar as it is formulated
to be infinitely dilutable and hence in accord with the invention.
WT. PERCENT
25- n-Tridecane 45.0%
Alcohol (Cg-Cll) 25.0
ethoxylate (EO 6)
Alcohol (C14 C15) 20.0
ethoxylate (EO 2.25)
Water 10.0
Form: w/o solution 100.0
EXAMPLE 4
The following procedure was followed in evaluating the
eficacy of pre spotting compositions in accordance with the
invention relative to the performance of commercial liquid
compositions intended for oily soil removal.
The stained swatches to be cleaned were 3" x 4" and consisted
of the following:
1- Dirty motor oil on Dacron doubleknit (DMO);
2- Barbecue sauce on Dacron doubleknit (BB~);
3- Carbon black in olive oil on cotton percale (EMPA ); and
4- Artificial sebum/particulate on a blend of 65% Dacron/35%
cotton (SEBUM).
An initial reflectance reading (Rd initial) of the
stained swatches was recorded. A duplicate of each stained
swatch was used in the test. To each swatch there was applied
0.2 gram of the particular pre-spotting fluid which was then
allowed to soak for four (4) minutes. The 'reated swatches were
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then added to a Tergotometer vessel with each bucket thereof
containing the stained swatches to be tested in duplicate (a
total of 8 stained swatches) for a particular pre-spotting
composition. Each bucket of the Tergotometer contained one liter
of water having dissolved therein 1.3 grams of a commercial
powder laundry detergent composition, the water hardness being
150 ppm of artificial hardness as calcium carbonate. After adding
the treated stained swatches to the wash li~uor, the swatches were
washed for 12 minutes at 100F while agitated at 100 rpm. The
wash liquor was then discarded and replaced with one liter of
water at 100F containing 150 ppm of artificial hardness. The
swatches were then rinsed for 5 minutes at 100 rpm, removed from
the rinse water and allowed to air dry. The reflectance reading
of each of the washed swatches (Rd final) was then recorded.
The percent soil removal (% SR) was calculated using
the ollowing e~uation:
Rd final - Rd initial
% SR = x 100
92 - Rd initial
An oil-in-water microemulsion (Composition A) and a
water-in-oil solution (Composition B), compositions in accordance
with the invention, were formulated as shown below:
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COMPOSITION A
WT. PERCENT
n-Dodecane 15.0%
Alcohol (Cg-Cll) 15.0
ethoxylate ( EO 6)
(C14 C15) 4.0
ethoxylate (EO 1)
Water 66.0
Form: o/w micxoemulsion 100.0
COMPOSITION B
n-Dodecane 44.0%
( 9 11) 44.0
ethoxylate (EO 6)
Alcohol (C14 C15)11.0
ethoxylate (EO 1)
Water 1.0
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Form: w/o solution 100.0
Compositions A and B were evaluated for soil removal in
accordance with the procedure described above as were the follow-
ing four commercial formulations: a pre-spotter; a liquid
laundry deterg~nt composition; a pine oil-based liquid cleaner
containing about 30% pine oil; and a petroleum-based all purpose
cleaner containing about 40% petroleum distillates. The results
of the soil removal tests are shown below indicating the % SR
achieved for each composition. A difference of about 5% SR uni-ts
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is considered to be -the minimum that can be visually detected
in a side-by-side comparison of two fabrics.
% SR
Pre-spotter D BBQ EMPA SEBUM_
Composition A
(o/w microemulsion) 8.2 55.9 30.1 73.4
Composition B
(w/o solution3 42.2 57.5 50.2 68.1
Pre-spotter 7.~ 39.6 49.0 63.5
Liquid laundry detergent 5.1 49.7 37.6 72.3
Pine oil-based cleaner9.8 63.6 55.3 66.5
Petroleum-based cleaner 15.9 61.3 52.9 67.1
As shown in the Table, the solution form of the present
pre-spotting compositions (Composition B) was markedly superior
in perEormance relative to all four of the commercial pre-spotting
and cleaning compositions. This was most evident with regard to
removal of the DMO stain. The o/w microemulsion composition
(Composition A) was essentially equivalent in performance to the
commercial pre-spotter and liquid laundr~ detergent but slightly
inferior ove,rall to the pine oil-based cleaner and the petroleum-
based cleaner. The latter cleaners however are more susceptible
to problems of redeposition of the organic solvent, particularly
at higher temperatures, such as above 100F.
EXAMPLE 5
The procedure of Example 4 was followed to evaluate
Composition C, a water-in-oil solution in accordance with the
invention, relative to a commercial liquid pre-spotting composition
and a commercial liquid laundry deteryent. Tap water at 114F was
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used in place of 100F water containing 150 ppm hardness. The
stains tested were ~MO, BBQ and EMPA as previously described.
Composition C was comprised of the following:
COMPOSITION C
WT. PERCEMT
n-Dodecane 48.2%
Oxohexyl alcohol 0.8
Alcohol (C~-Cll~ 34.2
ethoxylate (EO 6)
Alcohol (C14 C15) 14.8
ethoxylate (EO 1)
Water _ 2.0
Form: w/o solution 100.0
The results of the cleaning tests are shown below:
% S.R
Pre-S~_tter DMO BBQ EMPA
Composition C 30.166.1 42.1
Commercial pre-spotter 6.441.5 37.5
Liquid laundry detergent 3.2 47.0 35.6
As shown in the Table above, Composition C was markedly
superior as a pre-spotting composition relative to the commercial
compositions.
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