Note: Descriptions are shown in the official language in which they were submitted.
' This invention applies to the field of composi-
tions for the pretreatment of heavily soiled areas of tex-
tiles prior to regular ~ashing. Many textile articles are
not uniormly soiled; examples are tablecloths, pants' knees
and collars and cufs on men's shirts. I a sultable pre-
treatment is applied to the badly stained areas, better re-
. .
sults can be obtained for the wash in general with less useof the detergent product. Especially difficult is finding a
suitable pretreatment for the removal of greasy stains from
fabrics such as polyesters.
Hydrophilic fibers, such as cotton, have a prefer-
ential affinity for water over oil. During laundering, water
displaces oily soil from the surface of the fabric, causing
the soil to "roll-up"; the soil is then more readily removed
by mechanical action. Polyester fibers, such as those made
~rom the copolymer of ethylene glycol and tereph'thalic acid,
do not have this preferential affinity for water,'but rather,
' ~ are hydrophobic. Blends of polyester and cotton also ex-
hibit hydrophobic tendencies. 'Due to this lack of affinity
bet~een fiber and ~later, ordinary laundering o~ten does not
satisfactorily remove oily soils from polyester-con~ainlng '' ~~
fibers. -
.
,, ' ',
'~ ', '
1~3~
.. . . . . .
" ' -1
The use oE certain types of materials for pre-
treàtment is known to the art. U.S. Patent 3,431,060
discloses a composition with a synthetic detergent and
an optical brightener dispensed in aerosol form using a
5 suitable propellant. The active is broadly disclosed
as being a nonionic, anionic or cationic surfactant.
U.S. Patent 3,417,023 discloses a pretreatment
stick containing a gel-forming soap, a synthetic deter- !
gent and an optical brightener. The detergent is again
broadly disclosedO
U.S. Patent 3,915,633 discloses a pre-wash com-
posltion containing an organic complexing acid and a non-
ionic or anionic surfactant. Among the sample nonionics
mentioned are the esters polyglycerol monolaurate and gly-
col dioleate. No example is given using either ester.
Certain organic es*ers are known to be cleaning
aids. U.S. Patent 2,251,691 discloses partial esters of
polyglycerol and fatty acids as being useful in dry clean-
ing. U.S. Patent 2,251,694 discloses an ester of a hydroxy-
carboxylic acid and a fatty acid as being useful in dry
cleaning. The alkyl esters of fatty acids are disclosed by
U.S~ Patent 1,875,530 as being useful ingredients of cosme--
tics. Polyethylene glycol esters of fatty acids are dis- ¦
closed as having surfactant properties by U.S. Patent
2,528,13~.
U.S. Patent 2,462,758 discloses a detergent com-
position consisting essentially of sulfate or sulfonated
anionic surfactant and an monohydric ~lcohol or glycol
ester. The ester is added to the composition in order to
improve foaming characteristics.
1~L37~60
SUMMARY OF THE INVENTION
.. ,..................................... I
It is an object of the present invention to pro-
vide a laundry pretreatment composition wllich will provide
effective stain removal on polyester contain:ing fibers.
It is also an object of this invention to provide
a laundry pretreatment composition which will effectively
remove greasy-oily soils.
Still other objects and advantages of the present
i~vention will become apparenk from the instant specifica-
tion. --
It has now been found that the above ohjects may
be accomplished by the use of a pretreating composition
comprising as an active system, about 25%~100% of an ester
of a short chain alcohol and a fatty acid, about 0-75~ of
l~ a nonionic surfactant and about 0-50% of an anionic surfac-
. ... . .
tant. In a preferred embodiment the composition is non-
aqueous and contains 50-90% ester and 10-50% of a surfac-
tant.
:
DETAILED DESCRIPTION OF THE INVENTION
2~ The instant invention provides for a method of -
treating stained fabric prior to laundering hy contacting
said~ fabric with a composition which comprises about 25%
to about 100~ of an ester of a short chain alcohol and a
fatty acid, 0 to about 75~ of a nonionic surfactant, and
2~ o to about 50~ of an anionic surfactant.
The esters encompassed by this invention are
well known to the art. They are formed of alcohols con-
taining 1 to about 4 carbon atoms and having one or more
hydroxyl groups and fatty acids containing ahout 8 to about 22
` ~37%6(~ 1
.
C~
carbon atoms, saturated or unsaturated, branched or straight
chain. Fatty acid di-esters of t~le polyalkylene glycols, such
as polyethylene glycol and polypropylene glycol, may also
be used. These are nonionic in nature but have no surface
active properties. Among the esters contemplated are:
S (1) Esters of monohydric alcohols of the formula
R-OH, wherein R is an alkyl radical; such as
isopropyl myristate, isopropyl palmitate,
but~l stearate, butyl oleate, ethyl stearate!,
isopropyl isostearate and methyl laurate
(2) Glycerol esters such as glycerol monolaurate,
glycerol mono- and di-oleate, and glycerol
monostearake; also the corresponding esters
of polyglycerol;
(3) Glycol esters such as ethylene glycol mono- ~'
15 ~ and di-stèaràte, diethylene glycol di-
stearate, and mixtures thereof;
(4) Polyethylene glycol esters such as PEG di- ¦
- ~ stearate.
Mixtures of the above estexs may also be used,
including esters produced by the reaction of alcohols with
fatty acid groups, such as coconut oil or tallow fatty
acids~
The amount and type of surfactant to be used in
conjunction with the ester for maximum stain removal will
2~ depend on the type of stain and the type of fabric. In some
applications, 100~ ester is desirable; in cthers a 50/50
mixture gives optimal results. Active compositions compris~
ing about 25~ to about 90~ ester, along with 0 to about 60
anionic surfactant and~0 to about 75~ nonionic surfactant
'
.
37Z~O
.
are preferred for use where the range of fabrics treated
will be broad, encompassing synthetics and synthetic/cot-
ton blends.
The nonionic surface-active agents useful in
this invention include those normally used in detergent
compositions. Among these are:
(1) Polyoxyethylene condensates of alkyl phenols
containing 6-12 carbon atoms in a straight
or branched chain, and 2-25 E.O. units per
molecule. Commercial surfactants of this 1-
~!~ type are the Igepals and Tritons.
(2) Condensation products of aliphatic alcohols
containing 8-22 carbon atoms in a straight
or branched chain with ethylene oxide, 3-15
lS ~.O. units per molecule. Examples are the
- ~ Tergitols and Neodols. -
- (3) Condensation products of ethylene oxide with
the reaction products of propylene oxide and
diamine. Examples are the Tetronics.
20- (4) Condensation produc~s of ethylene oxide with
the xeaction product of propylene oxide and
propylene glycol. Examples are the Pluronics~
(5) Amine oxide surfactants having the formula
RlR2R3 N ~ O wherein Rl and R2 are Cl-C3 alkyl
groups and R3 is a C8-C22 alkyl with 0-2
hydroxyl groups.
(6) Phosphine oxide surfactants of the formula
RlR2R3 P ~ O wherein Rl, R2 and R3 arP as
defined above.
(7~ Sulfoxide surfactants of the formula
.~ t~e l~rks
--5~
37Z61~ 1
o
R3~- S R2, whexein R3 and R2 a.re as de-
fined above.
The anionic surface-active agents which may be
used are those commonly found in detergent products. In-
cluded are:
(1) The "soaps", alkali metal, ammonium and
alkyl ammonium salts of C8-C22 fatty .¦
acids; ` .¦.
t2) alkali metal and ammonium salts of organic
sulfuric reactions products containing an
alkyl radical having 8 to 22 carbon atoms.
Examples are the alkyl sulfates, the alkyl ¦ :
sulfonates, and the alkyl benzene sulfon- 1, :
1~ ates; \
- - (3) the olefin sulfonates having 8-22 carbon -
atoms;
: (4) the alkyl glyceryl ether sulfonates ha~ing
8-22 carbon atoms;
(5) alkali met.al salts of fatty acid monogly- -
ceride sulfates and sulfonates; - .
(6) alkali metal salts of alkylphenol ethylene
oxide ether sulfates, containing 1 12 E.O.
units per molecule and 8-22 carbon atoms
~ - in the`alkyl chain;
- (7) the.fa~ty acid isethionates;
(8) the alkyl ether sulfates having 1-30 E.O.
units per molecule and an alkyl or al.kenyl
unit of 8-22 carbon atoms;
3~ (9) salts of.a fatty acid amide of a methyl
tauride.
37~
.
Nonionic surfactants are preferred for the compo-
sitions of this invention and may be used at levels up to
about 75%~ Anionic surfactants are less effective in these
compositions, but can still be used at levels up to about 60%.
In addition, the combinations of anionics and esters showed
a tendency to separate in many cases, and were therefore
less suitable for commercial application.
Mixtures of the various surfactants herein
described may also be used. I
In addition to the surfactant/ester system, the
pretreatment composition may contain other adjuvants known
to the detergent art such as builders, bleaches, and opti- i
cal brighteners. Other materials to ease dispensing may
also be added. If the product is to be used in stick form,
~irming agents such as clays may be used; if it is to be
dispensed as an aerosol, a propellant may be added.
In its most preferred form, the composition com-
prises about 50-90% ester, 0 to about 50~ nonionic surface-
active agent and 0 to about 50~ anionic surface-active agent,
the total surfactant being a~out 10% to about 50~. The pre-
ferred compositions contain little or no water, since added
water can hasten hydrolysis of the ester, or separation of
th~ surfactant and ester.
The preferred esters for use in the compositions are
esters formed of alcohols of the formula R-OH wherein R is an
alkyl radical, with fatty acids; isopropyl myristate and
butyl stearate particularly preferred. The preferred sur-
factants are nonionics with ethylene oxide condensates of
primary and secondary alcohols having 11-15 carbon atoms
30- and 3-5 ~.O. units per molecule particularly preferred.
~3~;~6~
. . ,
The following examples serve to illustrate the
invention. All proportions are by weight.
In the following e~amples, the procedure for
determining stain removal is as follows:
, ~ 65/35 Dacron/cotton (D/C) and single knit poLy-
ester swatches are s~ained with 3 and 5 drops of dirty
mo~or oil, xespectively/ and the oil is allowed to be
- absorbed into the,cloth for one hour. The result of the
staining procedure is swatches with stains of approximately
equal si~e. The reflectance of each swatch is then mea- ',
sured with a Gardner Reflectance Spectrophotometer, Model
No. XL-lO, CDM.' The stained swatches are treated by drop-
ping a specified amount of a pretreatment composition on ',
each stain, and adding two swatches to a pot containing l
L5 , literof a standard detergent solution. The detergents, de-
scribed belo~, and made up with 180 ppm (unless otherwise
specified) hardness water (Ca~+:Mg+~ = 2:l~. The swatches
are agitated in this detergent solution at 120F for 10 '
minutes, rinsed or one minute'in fresh 180 ppm, 120F 1
water, and dried in a commercial clothes dryer. A final
reflectance value is then measured. Detergency is calcu-
lated by subtracting the initial average reflectance of
the soiled cloth before pretreatment from the reflectance
of the cloth after'treating and drying. The ~ detergency
'is determined by dividing this detergency number by a num-
ber representing the average difference in reflectance
between a soiled cloth and a clean cloth. Thus,
Ref (after washing) -_Re~ (after soiling) x lO0
, ~ detergency Ref ~-fore soiling) - Ref (after soillng)
A difference in % detergency between two samples run together
of about 5 percentage points should be considered a signifi-
- 'cant difference~
- Two laundry detergents were used to wash the cloths.
Their compositions were as follows: ~
e m~rk ~ ~ -
~L37260 J
- . Detergent A - _ -
... , . - , -
~lei~ht %
Sodium Linear Alkylbenzene Sulfonate (C14-C18 7.4
Sodium Plcohol Sulfate (Cl~-C18 chaln) 5.2
Sodium Fatty Alcohol E.O. Sulfate (C12-C1~ 4.2
chain, 4.7 E.O. Avera~e)
Polyethylene Glycol (M.W. = 6000-7500) 1.6
Sodium Sulfate 36.6
Sodium Phosphates 23.2
Sodium Silicate (SiO2:Na2O = 2.4) . 10.4
Sodium Carbonate . 3.9
Water -- 6.8
Miscellaneous to 100
'
Detergent B
Weight
oxylated Primary Alcohol - C14-ls Chain
. Length,13 E.O. Average , . 8.9
, Sodium Soap . 1.0
: 20 Sodium Tripolyphosphate - 30,0
dium Silicate (SiO2:Na2O = 2.4) 4.5
Sodium Perborate 2.5
Sodium Sulfate 43.Q
Water 9 3
25 Miscellaneous to 100
- ~3~6~) 1
EXAMPLES 1-5
Test formulations were made up as follcws:
~ster - isopropyl myristate
urEactant - C~ 5 secondary alcohol, 3 E.O. (sold
by Union Carbide as Tergitol 15-S-3).
EsterNonionic Surfactant
1 - 100%
2 25% 75~ i
3 50% 50~ ,i
' 4 '75% 25%
100~
The detergent solution used in the testing was
made from Detergent A. 0.5 grams pretreatment witli a~ove ,
mixture per swatch was used.
5 ~ .,. .. ~. Q Detergency
' Det. A conc. ,
Sample ~ /C Polyester
.. - . ~ _
Control (no pretreatment) ' 2.0 16.2 4.2
1 - 1.4 28.9 2~.~
~0 2 ' - ' 1.4 35~8 39.2
3 1.4 39.2 40.8
4 ' 1.4 37.7 33.9 ' 1,
~ 40.8 21.6 I ,
The data show that it is more difficult to remove
the stain from polyester than from blends with cotton,,prob-
ably due to the aforementioned hydrophobic nature of poly-
ester. On polyester, mixtures of nonionic and ester clearly
' show the greatest detergency. On Dacron~cotton, the ester
alon~ is comparable to the mixtures.
--10--
~L~3726~) -
... .~ .~ . ,
E~AMPLES 6-10
Test formulations were made up as follows:
Iso~ro~yl myristate Cll-15 sec- alcohol 5 E.O.
(Tergitol 15-S-5)
6 - 100%
7 25% 75%
8 50% 50%
9 75~ 25%
'100~ -
The detergent solution was Detergent A. Pre-
treat~ent = 0.5 g/swatch.
~ Deterqenc~
Det. A
Sample q/l D/C Polyester
~Control (no pretreatment) 2.0 28.4 , 1.5
6 1.4 20.3 13.8
7 1.4 37.3 32.3
- 8 - 1.4 55.4 46.1
- 9 1.~ 49.2 46.5
~ 10 1.4 51.3 31.
,
With this formulation peak detergency on poly-
ester cloths appears to be somewhere in the range of 50-
75~ ester; on Dacron/cotton comparable detergency was
- found in the 50-100% ester range.
~11--
~. ~
~3~
EX~MPLES 11-15
Test formulations:
Isopropyl m~ristate C11-15 sec- alcohol 7 E.O,
(Tergitol 15-S-7)
11 - 100%
12 25% 75%
13 50% 50
14 75~ 25%
1~ 100%
Detergent solution: Detergent A. Pretrea-t-
ment: 0.5 g/swatch.
~ Detergency
Det. A
~ q~lD/C Pol!yester \
Control (no pretreatment) 2.0 28.5 3.4 ~`
' ~ .
11 1.4 15.9 8.1
12 1.~ 21.1 12.7
13 1.4 31.0 32.2
lg 1.4 36.8 33.1
2~ 15 1.4 49.4 43.0
This surfactant gives poorer detergency than
- those with less E.O. per molecule. Improvements are ~ound
with greater ester concentrations.
-12~
- ~37;~6C~ 1
EXAMPLES 16-24
The following formulations were made with primary
alcohol ethoxylates and isopropyl m~ristate.
Isopropyl m~ristate Nonionic
-- !
: 5 16 - 100% C12_15, 3 E-O-
17 25~ 75~ C12-15' 3 E.O.
18 75% 25~o cl2-l5~ 3 E-O-
19 100%
. 100% C12_1s~ 9 E-O- ;
21 25% -75% C12-15' 9 E.O. .
22 50% 50~ C12-15~
23 75~ 25% C12-15' 9
24 100~ - C12 15~ 9 E.O. .
The C12 15~ 3 E.O. surfactant is sold by Shell as Neodol .
C12 15, 9 E.O, surfactant is Neodol 25-9 ~
The detergent solution is Detergent A.
% Deter~enc~ _
Pretreatment Det. A . .
Sampleg/swatch ~ D/C Polyester
16 ~75 1~36 32~0 . 37~9 .
17 ~50 1~36 34~2 36~3
18 ~50 1~36 39~9 49~2
19 ~75 1.36 50~5 35.2
_ . . . _ .
Control (no pretreatment~ 2~0 22~8 3~4
- 20 ~50 1~4 10~1 16~7
21 50 104 18~2 14~2
22 ~ 50 1.4 32.4 42.2
23 .50 1.~ 48~9 S0~5
24 O50 1~4 46~1 37~
. ' I
--13-- !
~ ~372~
.. ` ` ` .~ .: . ` ~ . , .
The higher E.O. material again provides poorer
detergency, with less ester. ~t higher ester concentra-
tion, the differences between surfactants are small.
EXAMPLES 25-34
The following formulations were made with vari-
ous esters as indicated, and Cll 15 secondary alcohol with
: 5 EØ
ster Type Ester_% Nonionic
Isopropyl myristate/ - 100% i
palmitate blend
26 " 25% 75%
27 " 50% 50
- 28 " ; 75~ 25%
29 " . 100~ , -
Butyl Stearate - 100~
31 . " 25~ 75% .
32 " 50% ~ 50%
33 " 75% 25
34 " 100~ -
Detergent solution: Detergent A. Pretreatment:
0.5.g/swatch.
-14-
.
1372BO
% Detergency
Det. A
_g/l D/C Polyester
Control (no pretreat- 2.0 29.9 4.5
ment)
1.~ 20.~ 17.3
26 . 1.4 30.8 33.5
27 1.4 60.2 52.0
28 1.4 53.4 55.9
29 1.4 49.3 40~5
Control (no pretreat- 2.0 31.0 4.9
ment)
1.4 19.9 16.4
31 1.4 34.5 29.0
32 1.~ S8.5 ~9.9
33 1.~ 41.9 36~3
34 1.4 ~6.0 22.1
1.
Both esters provide good results and,.for a
variety of abrics are best used in proportions of 50-
75% with 25-50~ noni.onic.
EXAMPLES 35-38
- Pretreatment was done using butyl stearate as ,'
the ester and as surfactant, a condensate of ethylene -
oxide with hydrophobic bases formed by condensing propy-
lene oxide with pxopylene glycol, and having an aver.age
molecular weight of about 2000 was used. This surfac-
tant is known commercially as BASF-Wyandotte Pluronic
L-61t and contains about 10~ ethylene oxide.
~ tra~ k
- - 113 oJZ60
~, ... . ~ . .
Sample EsterSurfactant
- 100%
.` 36 25~ 75%
37 75~d 25%
. 38 100%
Detergent solution: Detergent A, 1.36 g/l.
. % Detergency
Pretreatment
Sample g/swatch D/C Polyester
~ 35 .75 12.1 1.8
. 36 .50 ~ 2~.0 18.3
37 .50 36.0 35~3 .
3~ .75 48.9 42.7 ` I
'`' . .
. EXAMPLES 39-42
\
,., , .., . _ ,,
,
Pretreatment wàs done with combinatio,ns of poly- ~
ethylene glycol (M.W. = 400) dioleate and dimethyl dihydro-
gena~ed tallow amine oxide.
,
Sam~le Ester Nonionic
~ ,_
39 - 100%
.40 25% 75%
` 20 ~1 75% ` 25%
42 100% - .
oetergent solution: Detergent ~, 1.36 g/l.
-16~
~9~37~60
- - - . . ?
~ Deteraencv
Pretreatment ~~
Sample g/swatch D/C Polyester
39 .75 13.3 6.5
.50 19.6 g.8
541 .50 35.3 31.1
42 .75 31.3 31.5
.
E~AMPL,ES 43-52
A series of dirty motor oil stains were pre- i
treated with compositions consisting of 25% nonionic, 75%
isopropyl myristate, with washes in Detergent A, 120 ppm
water. Pretreatment: 0.5 g~swatch. Results were as fol-
.
lows:
.
~ Detergencv
Det. A
lSSample Nonionic g/l D/CPolyester
__ .
Control no pretreatment 2~033.0 2~3
43 Tergitol 15-S-3 1.4 53.646.3
44 Tergitol 15-S-5 1.4 57.852~8
Tergitol 15-S-7 1.4 40.631.1
20 46 Tergitol 15-S-9 1.4 43.848.4
47 ~eodol 25-9 1.4 46.748.0
Another series o dirty motor oil stalns were
pretreated with compositions consisting of 75% nonionic
and Z5% isopropyl myristate, with washes in Detergent A,
120 ppm water. Pretreatment: 0.5 g/swatch. Results are
as follo~s:
-
.
-17-
L3~
~ ~0 Dete~ency
.
Sample Nonionic ~/1D/C Polyester
Control no pretreatment 2.0 26.6 6.0
48 Tergitol 15-S-3 1.4 4~.2 46.0
49 Tergitol 15~S-5 1.4 35.1 36.3
Tergitol 15-S-7 1.4 20.6 15.3
Sl Tergitol 15-S-9 1.4 22.1 15.2
52 Neodol 25-9 1.4 25.7 21.1
With compositions high in nonionic, peak stain
removal is obtained with Tergitol 15-S-3, with 15-S-5
also acceptable. With the low-nonionic compositions, Tergi-
tol 15-S-5 is the best performer, although the others were
~3 acceptable. Overall stain removal is better with the low-
nonionic composition.
,
- \ I
EXAMPLES 53-57
,
Test formulations were made up as follows:
.
Isopropyl -
Sam~le Myristate Anionic
- 53 25% 75% sodium C14-C16 alpha olefin sulfonate
54 75% 25% sodium secondary alkane sulfonate
25~ 75% sodium secondary alkane sulfonate
56 75~ 25% sodium lauryl hydroxy ether sulfonate
57 75% 25~ sodium C10 linear alcohol sulfate
,
Det~rgent solution: Detergent B, 1.99 g/l.
2~ Pretreatment = 0.5 g/swatch.
.
,
1137261~ ~
., ., ~ . . . .
.
% Detergency
Sample D/CPolyester
Control (no pretreatment) 35.3 7.4
53 27,69~9
54 50.630.7
29.38.7
56 51.427.4
57 53.026.6
Sample 55 was a translucent-opaque gel-like vis-
- 10 cous paste. ~11 other samples showed some separation, but
were readily dispersed upon shaking.
~.- ., , . ,
EXAMPLES 58-59
Test formulations were made up as follows: )
Isopro ~ Myrlstate Surfactant
58 ~ 50% 50% Na C10 Alcohol Sulfate
59 25% 50% Na C10 Linear Alcohol
Sulfate
3 - 25% Cll-cl5 Sec AlcO
5 E.O.
20Detergent solution: Detergent B, 1.99 g/l.
Pretreatment: 0.5 g/swatch.
% Detergency
D/C Polyester
Control lno pretreatment) 36.4 2.6
S8 - 51.6 24.5
~9 42.2 23.2
Compositions containing 75% anionic and 25~ ester
were generally ineffective. Compositions with 50% anionic
were accepta~le.
19
