Note: Descriptions are shown in the official language in which they were submitted.
- -
:~37~
BACKGROUND OF T~IE INVENI`:[ON
This invention relates to compositions and processes
for solubilizing oils. More particularly, the invention
relates to the use of specific mixtures of long-chain alkylene
oxide surfactants and short-chain alkylene oxide co-surfactants,
said mixtures having a hydrophilic-lipophilic balance (HLB)
in the range of from about 10 to about 12.5, to remove oil
from fabrics and other surfaces.
Current laundry products and procedures exhibit
one or more deficiencies when used to clean oily stains,
particularly hydrocarbon stains, from fabrics. Fatty
triglyceride soilsl especially those arising ~rom natural
body secretions, present another type of oily stain which
is difficult to remove from modern fabrics by means of simple
aqueous laundering processes. Such deficiencies are
especially apparent when polyester or polyester fabric
blends soiled with various oily materials are laundered in
a~ueous laundry baths. The oil removal problem is so acute
that Smith, et al, Textile Chemicals, Col. 5, ~7, 138 (1973)
have concluded that detergent formulation alone is very
unlikely to solve the problem of effecting satisfactory
release of any broad spectrum of oils from today's durable
press fabrics, unless the fabrics are specially finished
with hydrophilic materials.
Heretofore, effective oil removal from modern
fabrics has largely been accomplished by means of relatively
inconvenient and expensive methods involving non-aqueous
dry cleaning processes. Accordingly, compositions and `
processes which would provide the economical and efficient
removal of oily soils and stains from fabrics employing
, .. ~ . . ...... . . . .
: .: . . .
:1~373~7
conventional household laundry equipment are desirable.
The present invention emp:Loys combinations oE
long-chain and short-chain alkoxylated nonionic materials
to effect the removal oE oily mater:ials from fabrics in an
aqueous laundering process. The use of alkoxylated nonionic
detergent materials in cleansing operations has been
described, for example, in U.S. Patents 2,133,~80 and 2,164,431.
The disclosures of these patents teach that the condensation
products of aliphatic monohydric alcohols containing from 8
to abou~ 18 carbon atoms with from 1 to 3 moles of ethylene
oxide are useful in combination with various anionic
surfactants in washing operations and for emulsifying oils.
U.S. Patent 3,679,608 discloses the use of the
ethoxylates of random secondary alcohols in low sudsing
detergent compositions.
U.S. Patent 3,008,905 teaches that the products
produced by the addition of from 1 to about 4 moles of an
- alkylene oxide with alcohols containing, at most, 12 carbon
- atoms are suitable for use in detergent compositions.
U.S. Patent 3,342,739 broadly describes the use
of condensates comprising from about 3 to about 10 moles
of ethylene oxide per mole of higher aliphatic C10-C20
hydrocarbyl alcohol in detergent compositions in combination
with various polyethyleneoxy ethers of alkyl phenols and
alkylolamides.
V.S. Patent 3,619,119 discloses spot removal
compositions containing mixed ethoxylates in combination
with sulfated ethoxylate detergents for removing oily soils
and stains from collars and cuffs of shirts and dresses.
-- 2 --
... . . . . .
~ ::,. .
~)3733'7
The Matheson and Richardson Canadian Patent No.
1,014,81~, issued April 2, 1977 teaches the use of condensa-
tion products of fatty alcohols containing from 10 to 15
carbon atoms with 3 to 10 moles of ethylene oxide, said
condensates having an ~ILB of from about 10 to about 13.5,
together with various anionic detergents in laundering
compositions.
While the use of various alkoxylated nonionic
mixtures in detergent compositions is known, the detergency
arts have not heretofore recognized that the combinations
of short-chain and long-chain alkylene oxide condensates
disclosed herein afford superior oily soil removal. For
example, British Patent 1,241,754 broadly discloses
nonionic mixtures having compositions which fall outside
the limits of those compositions now found to be particularly
advantageous for removing oil and grease from fabrics and
- other surfaces. Indeed, U.S. Patent 3,682,849 suggests
that the detergent properties of certain mixtures of ;~
alkoxylated nonionic detergents are improved when short-
chain, less highly alkoxylated materials of the type employed
herein are removed. Moreover, the article by Matson,
"Syndets with Alcohol Derivatives", Soap and Chemical
Specialities, November 1963 at page 52, 54, clearly indicates
that the heavy duty detergency of alcohol polyalkoxylates
resides in the C12 and higher ethoxylated alcohols, and
that the C8 - Cll alkoxylates such as those employed in
the instant compositions would be expected to exhibit very
low detergency performance.
In view of the conflicting information in the
- 3 -
~1~373;~7
prior art, the most that can be said .is that various
nonionic surEac tants and mixtures have been broadly
; suggested for use in detergent compositions. However,
the prior art has not recognized the advantages which can
;
;-
4 ~
_ _ .. . ..... . ... . . . ...... ..... . ... . .. ..... ...... ... ... .. .. . . ... . _ .. ... _ _ _ . ... _ _,
~L~3~337
be obtained by the proper formulation of nonionic mixtures
comprising both short-chain and long-chain alkoxylated
nonionic surface active agents oi the type disclosed
- herein.
; It has now been discovered that prop~rl~
formulated mixtures of long-chain and short~chain alkoxy-
lated nonionic surface active agents are especially useful
in aqueous solutions for solubilizing oily soils and removing
same from all manner of surfaces. Notably, the compositions
herein are characterized by the speed with which they
remove oils from fabrics, especially polyester and polyester
blends; hence, they are useful for cleansing fabrics in the
relatively limited time available in the deterging cycle
:, ~
of a home laundry operation. Moreover, the compositions
herein can be employed singly to cleanse materials such as
fabrics, or can be added to various commercial laundry
detergent compositions to enhance the oil removal properties
' thereof~
The compositions herein are useful for cleaning -~
, 20 and degreasing a variety of surfaces other than textiles and
are uselful, for example, in the metal working trades and
` as hard surface cleaners for use on floors and walls.
It is an object of -the present invention to provide
compositions for solubilizing oils and for removing oily
soils from surfaces.
SUMMARY OF THE INVENTION
The instant invention encompasses granular deter-
gent compositions especially adapted for removing oils and
oily soil from fabrics consisting essentially of:
from about 15% to about 40% by weight of an
ethoxylated nonionic surfactant mixture of which about
60-80% by weight of the mixture is a water-soluble Cg-C
-- 5 --
,. . : ~ : . : . .
~37337
primary alcohol having an average of 10 carbon atoms in the
alkyl chain condensed with an average of four ethylene
oxide groups to give an HLB of about 10.5 and about 20%
to about 40% by weight ofthe mix~ure is the condensate of
a secondary C10-C15 alcohol mixture having an average of
12-13 carbon atoms in the alcohol molecul~ with about 7-9
ethylene oxide groups to give an HLs of from 12.0 - 15.0,
said surfactant mixture having an overall HLB of from 10.5 ~
12.0; from a~out 1% to about 20% by weightof a detergent
compound selected from the group consisting of anionic,
semipolar and zwitterionic surfactants; and from about 30
to about 70~ by weight of a detergency builder selected
from the group consisting of organic and inorganic
builder saits.
The composition herein can be employed singly to
remove oils and oily soils from sur~aces by contacting
same with an aqueous solution containing from about 0.02
to about 0.50% by weight of said compositions. ~oreover,
the compositions herein can be added to both buil~ and
unbuilt commercial-type detergent compositions in the
ratios and proportions hereinafter disclosed to enhance
the oil removal properties of said commercial detergent
compositions.
DESCRIPTION OF T~IE DRAWING
The Figure herewith is a graphical illustration
of the solubilization of dodecane in water by a typical
mixture of a pure long-chain surfactant and a pure short-
chain co-surfactant of the type employed herein. The
Figure illustrates the synergistic solubilization effects
which are achieved by proper selection of surfactant: co-
surfactant ratios, and similar effects are noted for
B
1~373~7
thc other mixtu.r~s herein, Moreover, the most strik.ing visual
improvements in oily soil fabric deter~ency with both fat-ty
and hydrocarbon soils parallels the dodecane solubilization
and is optimum (for the specific mixtures of the Figure)
within the range of points A and B, as shown.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
The oil solubilization and detergent additive
compositions herein comprise two essential ingredients, a
long-chain alkoxylated nonionic surfactant and a short-
chain alkoxylated nonionic co-surfactant. While not intending
to be limited by theory, it appears that the co-surfactant :
employed herein must be selected to provide rapid transport
from the aqueous liquor into the oil which is to be removed
from the surface being treated. Once established in the oil .. :
phase, the co-surfactant and surfactant twhich remains sub-
stantially in the aqueous phase) co-act to produce a zero
interfacial tension at the water-oil interface. A positive
interfacial free energy is created and this force causes . :
the oil to disperse and dissolve in the aqueous liquor,
thereby removing said oil from the surface.
While many surface active agents presumably will
migrate from a water phase into an oil phase on long standing,
they are kinetically slow, and are not useful in the relat-
ively short time ~ca. 10-15 minutes) available in the :
deterging cycle of a home laundry operation or in hard
surface cleaning. Moreover, surface active agents which do
migrate relatively quickly will not, by themselves, cause
the requisite lowering of the water-oil interfacial tension
to provide a driving force for the formation of thermo-
dynamically stable micellar solution (with the oil truly
-- 7 --
.~_ ......................... . .. ._.. ..... . . . .
~- . . , , : . ; . . , ~ . .. .
:l~D373;37
solubilized). It is only when the proper combination of
surfactant and co--surfactant is selected that rapid and
effective solubili~ation of oil occurs.
From the foregoing it is seen that both thermo-
dynamic and kinetic factors must be considered when formulating
oil-dissolving compositions for use in aqueous media. It has
been discovered that, by selecting alkoxylated nonionic
surfactants of the type disclosed herein having the proper
hydrophilic-lipophilic balance and combining them with
alkoxylated nonionic co-surfactants of the type disclosed
herein having the proper hydrophilic-lipophilic balance to
provide mixtures having the proper overall hydrophilic-
lipophilic balance, both the kinetic and thermodynamic
requirements of a through-the-wash oil solubilizing detergent
are satisfied.
MIXTURE COMPONENTS
.
The individual surface active agents employed in
the mixtures herein are well known and are commonly thought
of as constituting a hydrocarbyl chain condensed with an
alkylene oxide chain. The hydrocarbyl portion of such
materials gives rise to their lipophilic characteristics,
whereas the alkylene oxide portion determines their hydrophilic
characteristics. The overall hydrophilic-lipophilic
characteristics of a given hydrocarbyl-alkylene oxide
condensate are reflected in the balance of these two factors,
i.e., the hydrophilic-lipophilic balance (HLB). The ~LB
of alkoxylated nonionics can be experimentally determined
in well known fashion, or can be calculated as described
more fully hereinafter. Conversely, specifying the alkoxyl
content and the HLB of a hydrocarbyl alkoxylate fully
-- 8
,: . ~: .. : :
~037337
charact~riz~s such compouncls since the hydrocarbyl content
of the molecule can be approximatecl by reverse-calculation.
Alkoxylated nonionic surface active a~ents of the
type used herein can be prepared by methods well known in
the art. In general terms, a hydrocarbyl material having at
least one -0~1 group is condensed with one or more moles of
an alkylene oxide, e.g., ethylene oxide or propylene oxide.
Mixed alkoxylates can be formed by condensing the hydro-
carbyl compound with mixtures of alkylene oxides, e.g.,
mixtures of e~hylene oxide and propylene oxide. The
common terminology employed to designate the structures
of such materials usually specifies both the nature of
the hydrocarbyl group and the degree and type of alkylene
oxide substitution. For example n-ClOEO(9), a preferred
long-chain surfactant herein, is n-decanol condensed with
9 moles of ethylene oxide per mole of alcohol. Likewise,
n-ClOEO(3), a preferred short-chain co-surfactant herein,
is n-decanol condensed with 3 moles of ethylene oxide per
mole of alcohol. An example of a mixed alkoxylate is
~0 CloEO(3)PO(2), wherein "PO" is the propylene oxide moiety.
The nonionic alkoxylates used herein both as
surfactants and co-surfactants can be prepared from all
manner of hydroxylated hydrocarbyl materials such as
branched chain and straight chain alcohols and alkylphenols;
primary, secondary and tertiary alcohols; olefinic alcohols
and the like, having the requisite number of carbon atoms
disclosed herein. Glycols and poly-ols can also be used,
but monohydric alcoholic and monohydric alkyl phenolic
alkoxylates are preferred, with said alcohol alkoxylates
being most preferred. Again, the names of such compounds
g _
~ _ . . . _ . , _ . . . . _ _
. .: . .
-
103~337
often reflects the nature of bottl the hydrocarbyl group and
the nature and molecular proportions of the alkylene oxide
group. For example, Tergitol 15-S-9 is the commercial name
of a preferred long-chain surfactant herein whlch is -the
condensate of 9 moles of ethylene oxide with one mole of a
secondary monohydric alcohol averaging 13 carbon atoms in
; length. Tergitol 13-S-5, which is a preferred short-chain
co-surfactant herein, is the condensate of 5 moles of ethylene
oxide with one mole of a C12 (avg.) secondary monohydric
alcohol.
The long-chain surfactants used in the present
compositons and processes are characterized by a hydro-
philic chain of at least 5 alkylene oxide groups and an HLB
in the range of from 11.7 to about 17. The short-chain
co-surfactants herein are characterized by a hydrophilic
chain of 5 or less (preferably 2-4) alkylene oxide groups
and an HLB in the range of from 7 to about 10.5. As noted,
the carbon content of the lipophilic hydrocarbyl portion
of the alkoxylated nonionic surfactants and co-surfactants
can be approximately re~erse-calculated when the HLB and
degree o alkoxylation are as specified~
A. Surfactant Component
The term "long-chain" alkoxylated nonionic
surfactant herein encompasses the hydrocarbyl alkylene oxide
condensates of the formula:
R-O-(cyH2yo)a~(czH2zo)b Cw 2w
wherein R is selected from the group consisting of primary,
secondary and branched chain (primary and secondary) alkyl
hydrocarbyl moieties; primary, secondary and branched chain
(primary and secondary) alkenyl hydrocarbyl moieties; and
-- 10 --
~o 3~ 33!;~
primary, secondary alld branch~d chain al]cyl- and alkenyl-
substituted phenolic hydrocarbyl moieties, and having an
HLs in the range disclosed hereinabove. In the general
formula for the surfactants herein, y and z are each integers
of from 2 to 3, preferably 2, and w is an integer of from
2 to 3, preferably 2.
In the genera~ surfactant formula, the carbon
content of group R will vary somewhat, depending on whether
R represents a primary or secondary alcohol or an alkyl- or
alkenyl-phenolic group. When R is a primary alcohol, its
carbon content is in the range of C8-C15, preferably
C10-Cl3. When R is a secondary alcohol, its carbon content
is in the range of Clo-C15, preferably C10 13
an alkyl phenol group, the carbon content of the alkyl
portion is in the range of 7-9, preferably 8, carbon atoms.
Chain branching and points of unsaturation have no sub-
stantial effect on the specified carbon content of group R.
In the general surfactant formula, a and b are
each integers of o to about 11, the sum of a + b being in
the range of from 4 to about 11. The formula of the
surfactants encompasses ethylene oxide (EO) as well as mixed
EO-PO alkoxylates, all of which are useful herein. The
all-PO surfactants do not have the requisite HLB's and are
not contemplated for use herein. The EO alkoxylates are
preferred by virtue of their cost and availability.
Of course, by defining the hydrocarbyl content of
group R and the HLB, the degree of alkoxylation (i.e., the
sum of a + b) is necessarily defined. Again, however, this
will vary somewhat, depending on the nature of R. For the
preferred all-EO surfactants herein, when R is a primary
'. .
. , ,' ' ' ~ , ,
., ~ .
~37;~3'7
~lcohol moiety, the sllm of a ~ b is ~~10 (preEerably 6-9)
and the overall ethoxylate range i5 5-11, due to the presence
of the terminal group in the hydrophilic portion of the
molecule. When R is a secondary alcohol, the sum o~ a + b
is 5-11 (preferably 6-9). When R is an alkyl phenol, the
sum of a + b is 5-11 (preferably 6-9). When mixed Eo-Po
surfactants are employed, the values of a and b can be
calculated by assigning the disclosed hydrocarbyl ranges
of R, the overall I~LB values, and by using hydrophilicity
values for EO and PO groups obtainable Erom standard
tables.
Specific examples of long-chain surfactants useful
herein are as follows. The examples are only by way of
exemplification and are not intended to be limiting of
such materials.
~ i) Straight-chain, primary alcohol alkoxylates -
. . . ~
The penta-, octa-, nona-, deca-, and undeca-
alkoxylates of n-octanol, n-decanol, n-dodecanol, n-tetra-
decanol, and n-pentadecanol having an HLB within the range
recited herein are useful surfactants in the context of this
invention; the respective ethylene oxide condensates are the
most preferred alkoxylates. The n Cg_llEOn condensates
are preferred. Exemplary alkoxylated primary alcohols
- useful herein as the surfactant component of the mixtures
are: n-ClOEO(6); n-ClOEO(9); n CllEO(9);
n-cl2EO(9); n-C14EO(10); n-ClOEO(10); n-CgEO(9); n-C15EO(ll);
and n-ClOEO(6)PO(2). The most preferred pure, straight chain,
primary alcohol alkoxylates herein are n-clOEO(6) and
n-CloEO(9).
- 12 -
' - , ,', .: ~ . :
1q~3'~'~3~7
(ii~ str.~glt-cha_n,_ econdary alcohol _lkoxylates -
The hexa-, hepta-, oc~a-, nona-, cleca-, and undeca-
alkoxylates of 2-decanol, 2-undecanol, 3-dodecanol, 2-dodecanol,
4-tridecanol ancl 2-pentadecanol haviny an HLs within the
range recited herein are useful surfactants in the context
of this invention; the respective ethylene oxide condensates
are the most preferred alkoxylates. Exemplary alkoxylated
secondary alcohols useful herein as the surfactant component
of the mixtures are: 2-CloEO(9); 2-C12EO(9); 2-C14EO(10);
2-C15EO(11); 4-CloEO(9); 2-C15EO(12); and 2-CloEO(9)PO(3).
Preferred straight chain, secondary alcohol alkoxylates
herein are the materials marketed under the trademark
Tergitol 15-S-9 and Tergitol 15-S-7, which comprise a mixture
of secondary alcohols having an average hydrocarbyl chain
length of 13 carbon atoms condensed with an average of 9 ~ .
and 7 moles of ethylene oxide per mole equivalent of
alcohol, respectively.
(iii) Alkyl phenolic alkoxylates -_
As in the case of the secondary alcohol alkoxylates,
the hexa-through undeca-alkoxylates of alkylated phenols, ~
particularly monohydric alkylphenols, having an HLB within ~ -
the range recited herein are useful as the surfactant compo-
nent of the instant mixtures. The respective ethylene oxide
condensates are the most preferred alkoxylates. The hexa-
through undeca-alkoxylates of p-hexaphenol, m~octylphenol,
p-octylphenol, p-nonylphenol and the like are useful herein;
most preferred are the ethoxylates of p-octylphenol and p-
nonylphenol, inasmuch as these materials are readily
available. Exemplary alkoxylated alkyl phenols useful as
the surfactant component of the mixtures herein are: -
- 13 -
~1~373~7
p-octylphenol EO(9); p-nonylphenol EO(9); p-dccylphenol EO(9);
p-dodecylphenol EO(10); and p-octylphenol Eot9)P0(2). The
most preferred alkylphenol alkoxylates herein are p-octyl-
phenol (nonoxyethylene) and p-nonylphenol (nonoxyethylene).
(iv) Olefinic alkoxylates -
The alkenyl alcohols, both primary and secondary,
and alkenyl phenols corresponding to those disclosed immed-
iately hereinabove can be alkoxylated to an EILB within the
range recited herein and used as the surfactant component
of the instant mixtures. Typical alkenyl alkoxylates herein
are 2-n-dodecenol EO(9); 3 n-tetradecenol EO(9); p-(2-
nonenyl)-phenol EO(9)PO(2); and 2-tetradecen-4-ol EO~9).
(v) Branched chain alkoxylates -
sranched chain primary and secondary alcohols which
are available by the well known "OXO" process can be alkoxy-
lated and èmployed as the surfactant component of mixtures
herein. Exemplary branched-chain alkoxylates are as follows:
2-methyl-1-dodecanol EO(9); 3-ethyl-2-tetradecanol EO(9);
2-methyl-1-tetradecanol EO(9)PO(2) and the like. The ethylene
oxide condensates of branched-chain alcohols having HLB's
within the range specified for the surfactant component of
the instant mixtures are preferred herein. Most preferred
branched chain alkoxylates are commercial mixtures known
as Dobanol 91-5, 91-6 and 91-8.
B. Co-Surfactant Component
The term "short chain" alkoxylated nonionic co-
surfactant herein encompasses the hydrocarbyl alkylene oxide
condensates of the formula:
R -o-(CyH2yo)~(czH2zo)~-cwH2woH
- 14 -
.
3Lal37;~
herein ~ ls selected from th~ group consisting of primary,
secondary and branched chain (primary and secondary) alkyl
hydrocarbyl moieties; primary, secolldary and branched chain
(primary and secondary) alkenyl hydrocarbyl moieties; and
primary, secondary and branched chain alkyl- and alkenyl-
substituted phenolic hydrocarbyl moieties, and having an HLs
in the range disclosed hereinabove. In the general formula
for the co-surfactants herein, y and z are each integers of
from 2 to 3, preferably 2, and w is an integer of from 2 to
3, preferably 2.
In the general co-surfactant formula, the carbon
content of group Rl will vary somewhat, depending on whether
R represents a primary or secondary alcohol or an alkyl- or
alkenyl-phenolic group. When Rl is a primary alcohol, its
carbon content is in the range of C8-Cll, preferably Cg-Cll,
most preferably C10. When Rl is a secondary alcohol, its
carbon content is in the range of C10-Cl5, preferably C10-Cl3.
When R is an alkyl phenol group, the carbon content of the
alkyl portion is in the range of 7-8, preferably 7, carbon
atoms. Chain branching and points of unsaturation have no
substantial effect on the specified carbon content of group
Rl : .
In the general co-surfactant formula ~ and ~ are
each integers of 0 to about 4, the sum of ~ + ~ being in the
range of from 1 to about 4. The formula of the co-surfactants
encompasses ethylene oxide (EO) as well as mixed EO-PO
alkoxylates, all of which are useful herein. The all-PO
surfactants do not have the requisite HLB's and are not
contemplated for use herein. The EO alkoxylates are pre-
ferred by virtue of their cost and availability.
~ 15 -
.
~37337
Of course, by defining the hydrocarbyl content o~
group Rl and the ~ILB, the degree o~ alkoxylation (i.e., the
sum of ~ + ~) is necessarily defined. Again, however, this
will vary somewhat, depending on the nature of Rl. For the
preferred all-EO surfactants herein, when Rl is a primary
alcohol moietv, the sum of ~ + ~ is 1-3 (preEerably 2) and
the overall ethoxylate range is 2-4, due to the presence of
the terminal group in the hydrophilic portion of the molecule.
When Rl is a secondary alcohol, the sum of ~ + ~ is 1-4
(preferably 2-4). When R is an alkyl phenol, the sum of
+ ~ is 2-4 (preferably 3-4). When mixed EO-PO co-sur~actants
are employed, the values of ~ and ~ can be calculated by
assigning the disclosed hydrocarbyl ranges of Rl, the
overall HLB values, and by using hydrophilicity values for
EO and PO groups obtainable from standard tables.
Specific examples of short-chain co-surfactants
useful herein are as follows. ~he examples are only by way
of exemplification and are not intended to be limiting of
such materials.
(i) Straight-chain, primary alcohol alkoxylates -
----
The di-, tri-, tetra-, and penta-alkoxylates of
n-octanol, n-nonanol, n-decanol, and n-undecanol having an
HLB within the range recited herein are useful co-surfactants
in the context of this invention; -the respective ethylene
oxide condensates are the most preferred alkoxylates.
Exemplary alkoxylated primary alcohols useful herein as
the co-surfactant component of the mixtures are: n-C8EO(2);
n-C8EO(3); n-CgEO(3); n-ClOEO(3); n-CllEO(3); n-ClOEO(4);
n-ClOEO(3)PO(l); and n-ClOEO(2)PO(2). The most preEerred
straight chain, primary alcohol alkoxylate co-surfactant
- 16 -
r ~
. ~03~d~3;~7
herein is n-Cl oEO ( 3 ) .
tii) Straight-chain, secondary alcohol alkoxylates -
, ~
The di-, tri-, tetra- and penta-alkoxylates of
2-nonanol, 3-decanol, 2-decanol, 3-tetradecanol, and S-penta-
decanol having an HLB within the rarlge recited herein are
useful co-surfactants in the context: of this invention:
the respective ethylene oxide condensates are the most
preferred alkoxylates. Exemplary alkoxylated secondary alco-
hols useful herein as the co-surfac-tant component o~ the
10 mixtures are: 2-CloEO(3); 2-C12Eo(5j; 2-CgEO(2); 2-CloEO(2)-
PO(2); and 2-C12EO(3)PO(l). A highly preferred straight-
chain, secondary alcohol alkoxylate herein is the material
marketed under the tradename Tergitol 13-S-5, whi.ch comprises
a mixture of secondary alcohols having an average hydrocarbyl
chain length of 12 carbon atoms condensed with an average of
5 moles of ethylene oxide per mole equivalent of alcohol.
(iii) Alkyl phenolic alkoxylates -
As in the case of the alcohol alkoxylates, the di-
through penta-alkoxylates of alkylated phenols, particularly
monohydric alkylphenols, having HLs's within the ranges
recited herein are useful as the co-surfactant component of
the mixtures herein. The respective ethylene oxide conden~
sates are the more preferred alkoxylates. The di- through
penta-alkoxylates of p-heptylphenol, m-octylphenol, p-
octylphenol, and the like are useful herein;
most preferred are the alkoxylates of p-octylphenol,
inasmuch as this material is readily available. Exemplary ~ ~ ;
alkoxylates of alkyl phenols useful as the co-surfactant
component of the mixtures herein include: p-octylphenol EOt3);
p-heptylphenol EO(3); p-octylphenol EO(5); p-octylphenol EO(4);
- 17 -
__.... . . .
.,. .~ : . . ~ . , ~ : . .
~037337
and p-octyluhel)ol ~0(5)PO(2). The most preferred alkyl
phenol alkoxylat~ co-surf~ctant herein is p-octylphenol EO(5) .
tiv) Olefinic alkoxylates -
. .
The alkenyl alcohols, both primary and secondary,and alkenyl phenols corresponding to those disclosed immed-
iately hereinabove can be alkoxylated to an HLs within the
range recited herein and used as the co-surfactant component
of the instant oil solubilizing mix-tures. Typical alkenyl
alkoxylates useful herein are 2-n-decanol EO(3); 2-penta-
decen-4-ol EO~5); and p~(2-octenyl)phenol EO(3).
(v) Branched-chain alkoxylates -
Branched-chain primary and secondary alcohols which
are available by the well-known "OXO" process can be alkoxy-
lated to an HLB within the co-surfactant range noted herein
and employed in -the instant mixtures. Exemplary branched-
chain alkoxylated co-surfactants are as follows: 2-methyl-1-
dodecanol EO(3); 3-ethyl-2-decanol EO(3); 2-methyl-1-decanol
EO(3)PO(l) and the like. The ethylene oxide condensates of
branched-chain alcohols are preferred herein.
The foregoing alkoxylates can be employed herein ~ -
as the pure compounds or as mixtures. When prepared on a
commercial scale, the alkoxylates are usually not the
individual pure compounds listed, but rather comprise
mixtures having an average degree of alkoxylation and
average lipophilic hydrocarbon chain length corresponding
to the ranges disclosed herein for the surfactants and co-
surfactants. Moreover, fractional average values for the
- alkoxylates occur in such mixtures, i.e., mixtures such as
n-C10 5(EO)3 5. Such mixtures are fully contemplated for
use herein.
- 18 -
.
. . .
~373~7
Commerclal mixtures oE the co-surfactants herein
often contain portions of the non-alkoxylated parent alcohols
or phenols, together with varying amounts of the mono-
alkoxylated alcohols or phenols. It is preferred herein to
"strip" the co-surfactants of these non-alkoxylated and
mono-alkoxylated materials, inasmuch as they do not contribute
to detergency performance in a significant way and have odor
problems associated wi-th them. The stripping can be achieved
by standard distillation procedures to provide preferred
stripped co-surfactant mixtures containing less than about 3
by weight of the non- and mono-alkoxylated nonionics.
The compositions herein comprise mixtures of the
aforesaid surfactants and co-surfactants. Such mixtures are
characterized as having an HLB in the range of from 9 to 13.
The HLB' s of the surfactants, co-surfactants and mixtures
herein can be calculated in the manner set forth in Becker, ;
"Emulsions Theory and Practice" Reinhold 1965 pp. 233 and
248. For example, the equation:
. ~ :
HLB = E/ 5
20 wherein E is the weight percentage of oxyethylene content, ~.
can be used to calculate the ~LB of the normal fatty alcohol ;~
ethyoxylates employed herein. -~
For mixtures of surfactant (A) and co-surfactant
(B), the composite HLB is calculated as follows:
HLB (mi~) = wt. fraction A x HLBA +
wt. fraction B x HLBB.
Alternatively, the weight fraction of the co-
surfactant which must be used with a given surfactant to
provide a mixture having an EILB within the range recited
herein can be calculated as follows:
-- 19 --
. .
.
:. . - .. . . , . . . : . .
~u~
wt. fraction EILB surf. HLB mixt.
co-surfactant HLB surf. HLB co-surf.
On the basis of the foregoing, i-t is po~sible to
calculate the weight of short chain co-surfactant of the
type disclosed herein which must be combined with the long
chain surfactant of the type disclosed herein to provide a
mixture having a mixture HLs within the required range.
Moreover, such mixtures will provide an interfacial tension
at a hydrocarbon/water interface of essentially zero. Accord-
ingly, such compositions effect the solubilization of oilin aqueous media with rapid kinetics.
~ Oil solubili7ing mixtures of surfactant and co-
- surfactant can be determined experimentally by measuring
: .
the ability of test mixtures to provide a clear, aqueous ~-
solution or clear dispersion of n-dodecane in water. In a
typical procedure, n-dodecane is added to a 0.36 (wt.)
aqueous solution of the surfactant/co-surfactant mixture
at a ratio of said mixture:n-dodecane of about 1:0.5 to 1:1,
` with stirring. Stirring is continued for 30 minutes and
the results observed visually. Under these test conditions,
the mixtures herein result in a micellar solution (or clear
stable dispersion) of the n-dodecane in water (sometimes
- referred to as a "microemulsion") whereas other detergent
systems result in a- cloudy emulsion, or unstable dispersion
j of n-dodecane in water.
An alternate procedure for determining surfactant/
co-surfactant mixtures of the type disclosed herein comprises
evaluating their ability to remove dirty motor oil (auto-
mobile crankcase oil) from cloth swatches. In a typical
test, 0.01 ml. of dirty motor oll is placed on a fabric,
- 20 -
-
.
~L03~3~7
which can be cotton, polyester or b:Lends. The swatch is
then laundered in water at 100F to 140F containing 0.02
to 0.05~ of the mixtures herein. The oil removal is then
evaluated visually, or by means of a Gardner meter. Typical
mixtures herein remove up to 98~ of the dirty motor oil,
whereas other detergent systems result in little, or no,
oil removal.
Non limiting examples of preferred nonionic mix-
tures herein appear in Table I.
: ~ '
.
.~
: :
- 21 -
:'.
-
~373;3~7
T Lr. I
Mixture Components (wt.~) ~IL~ Mixture
,
65% n-ClO(EO)3, 35~ n C10( 9 10.9
50% n-Clo(EO) 3, 50~ n-C'lO(EO)6 10.8
55~ n-ClO(Eo)3, 45~ TergitOl* 15-S-9 11.0
35% n-ClO(Eo)3, 65~ Dobanol** 91-5 10.8
50~ n-ClO(EO)3, 50% Dobanol 91-6 10.8
60~ n-ClO(EO)4, 40~ Tergitol 15-S 7
80~ stripped n-ClO(EO)3, 20% Tergitol 15-S-9+ 11.0
10 80% stripped Dobanol 91-3, 20% Tergitol 15-S-9 11.0
80% stripped Dobanol 91-3, 20~ Dobanol 91-6 10.9
65~ stripped n-C10(EO)2, 35% Tergitol 15-S-g+ 10.9
55% Tergitol 15-S-5, 45% Tergitol 15-S-9 11. 7
30% Tergitol 15-S-3, 70% Tergitol 15-S-9 11.7
25~ Tergitol 15-S-5, 75% Tergitol 15-S-7 11.7
30~ Tergitol 13-S-3, 70% Tergitol 15-S-9 11.8
55% Tergitol 13-S-5, 45% Tergitol 15-S-9 11.9
55% Tergitol 13-S-5, 45% Tergitol 13-S-9 11.8
* Tergitol is the trademark for alkoxylates of secondary
alcohol mixtures. Tergitol 13 is based on a C -C 3
alcohol with an average hydrocarbon chain leng~h o~ 12; ~-
Tergitol 15 is based on a Cl -C15 alcohol mixture with
an average of 13 carbon atom~ in the chain. The S-3,
S-5, S-7 and S-9 designations indicate an average degree
of ethoxylation of 3, 5, 7 and 9, respectively.
** Dobanol is the trademar]c for alkoxylates of primary "oxo"
alcohol having an average alcohol molecular weight of 160.
The alcohols used to prepare the Dobanol alkoxylates
are primarily Cg-Cll, with the major proportion being C10.
The final integers 3, 5 and 6 with the Dobanols indicates
average degrees of ethoxylation of 3, 5 and 6, respectively.
+ Highly preferred based on performance and availability.
- 22 -
~L03~
Tlle ~orec~oing optimized mixtures can be used singly
to clean and degrease fabrics, metals and other hard surfaces.
Alternatively, the mixtures can be employed as oil solubiliza-
tion systems which can optionally be combined with adjuvant
materials, as disclosed hereinafter.
The surfactants and co-surfactants employed herein
can be prepared, for example, in the manner disclosed in
U.S. Patent 2,164,431. Mixe~ materials, e.g., EO-PO surfac-
tants and co-surfactants, can be prepared as described in
10 U.S. Patent 3,650,965. The Tergitol 13-S-5 and Tergitol
15-S-9 materials are available from the Union Carbide ` -
Corporation. The Dobanols are available from the Shell
Chemicals U.K. Ltd. U.S. Patent 2,355,823, teaches the
preparation of secondary alcohol alkoxylates. U.S. Patent
2,508,035, teaches the preparation of branched chain
secondary alkoxylates. U.S. Patent 2,508,036 teaches the
preparation of branched chain primary alkoxylates. The
a1koxylated phenolic alkoxylates are available from various
commercial sources.
OPTIONAL DETERGENTS AND ADJUVANTS
As noted, the nonionic mixtures of the instant
invention can be employed in a variety of compositions and
processes where solubiiization of oil or grease is desired.
The most common situation calling for oil and grease solub-
ilization is in the area of stain removal from fabrics
during aqueous laundering operations. The instant nonionic
oil solubilization systems can be utilized alone for fabric
stain laundering, but are more commonly employed in combina-
tion with other conventional detergent formulation materials.
Such optional materials include, for example, conventional
- 23 -
., ,; . ; , . . : :. :
~373~
surfactants and builders. The Eollowing list of suchdetergent adjuvants which can be used in combination with
the alkoxylated nonionic long chain surfactant-plus-short
- chain co-surfac-tant mixtures is typical of such adjuvant
- materials, but is not intended to be limiting.
Detergents
_ _
Optional detergents useful in the embodiments of
the present invention include all manner of anionic, semi-
polar, zwitterionic and amphoteric organic, water-soluble
detergent compounds, inasmuch as the nonionic mixtures
herein are compatible with all such materials. A typical
listing of the classes and species of detergent compounds
useful herein appears in ~.S. Patent 3,664,961. Compositions
comprising from about 1% to about 99% (preferably 15~ to 40~) -
by weight of the alkoxylated surfactant mixtures herein and
from about 1% to about 60% (preferably 1-~ to 20~) of one or ~ -
more optional detergent components are especially useful as
heavy duty cleaning compositions. The following list of
detergent compounds and mixtures which can be used in the
instant compositions and processes is representative of such
materials, but is not intended to be limiting.
-
Water-soluble salts of the higher fatty acids,
i.e., "soaps" àre useful as an optional detergent component
herein. This class of detergents includes ordinary alkali
metal soaps such as the sodium, potassium, ammonium and
alkylolammonium salts of higher fatty acids containing Erom
about 8 to about 24 carbon atoms and preferably from about
10 to about 20 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutralization of
free fatty acids. Particularly useful are the sodium and
- 2~ -
~03733'~
potassium salts of thc mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and
coconut soap.
Another class of deteryents includes water-soluble
salts, particularly the alkali metal, ammonium and alkylol-
' a~nonium salts, of organic sulfuric reaction products having '
in their molecular structure an alkyl group containing from ~
about 8 to about 22 carbon atoms and a sulfonic acid or ~ 5
sulfuric acid ester ~roup. ~Included in the term "alkyl"
` 10 is the alkyl portion of acyl groups.) Examples of thisgroup of synthetic detergents which can be used in the
~' present invention are the sodium and potassium alkyl sulfates,
especially those obtained by sulfating the higher alcohols
(C8 ~ C18 carbon atoms) produced by reducing the glycerides
of tallow or coconut oil; and sodium and potassium alkyl
benzene sulfonates, in which the alkyl group contains from
about 9 to about 15 carbon atoms, in straight chain or ~ '
branched chain configuration, e.g., those of the type
described in U.S. Patents, 2,220,099 and 2,477,383. Especially
valuable are linear straight chain alkyl benzene sulfonates
in which the average of the alkyl groups is about 13 carbon
atoms, abbreviated as C13LAS.
Other anionic detergent'compounds herein include
the sodium alkyl glyceryl ether sulfonates, especially those
ethers of higher alcohols derived from tallow and coconut
oil; sodium coconut oil fatty acid monoglyceride sulfonates
and sulfates; and sodium or potassium salts of alkyl phenol
ethylene oxide ether sulfate containing about 1 to about 10
units of ethylene oxide per molecule and wherein the
alkyl groups contain about 8 to about 12 carbon atoms.
- 25 -
~, ~
~IV3~3~7
Seml-E~olar deterc3ents useful h~rei,n include water-
soluble amine oxid~s con-taining one alkyl moiety of from
about 10 to 28 carbon atoms and 2 moieties selected from
the group consisting of alkyl groups and hydrox~alk~l groups
containing ~rom 1 to about 3 carbon atoms; water-soluble
phosphine oxide detergents containing one alkyl moiety of
about 10 to 28 carbon atoms and 2 moieties selected from
the group consisting of alkyl groups and hydroxyalkyl groups
containing from about l to 3 carbon atoms; and water-soluble
sulfoxide detergents containing one alkyl moiety of from
about 10 to 28 carbon atoms and a moiety selected ~ro~ the
group consisting of alkyl and hydroxyalkyl moieties of from
l to 3 carbon atoms.
Ampholytic detergents include derivatives of ;~
aliphatic or aliphatic derivatives of heterocyclic secondary
and tertiary amines in which the aliphatic moiety can be
straight chain or branched and wherein one of the a,liphatic
substituents contains from about 8 to l~ carbon atoms and
at least one aliphatic substituent contains an anionic water-
solubilizing group.
Zwitterionic detergents include derivatives of
aliphatic quaternary ammonium, phosphonium and sulfonium
compounds in which the aliphatic moieties can be straight ~ '
chain or branched, and wherein one of the aliphatic sub- ~ '
stituents contains from about 8 to 18 carbon atoms and one
contains an anionic water solubillzing group.
Other useful detergent compounds herein include the ' '
water-sol'uble salts of esters of ~-sulfonated fatty acids
containing from about 6 to 20 carbon atoms in the fatty ,
acid group and from about l to 10 carbon atoms in the ester
- 26 -
.- . . . . . . .
. : :;: . . . :. . .
,:: -. . ~ . .- . ~ . .
~L~373~Y7
group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic
acids containing from about 2 to 9 carbon atoms in the acyl
group and from about ~ to about 23 carbon atoms in the -
alkane moiety; alkyl ether sulfates containing from about
10 to 20 carbon atoms in the alkyl group and from about
1 to 30 moles of ethylene oxide; water-soluble salts of
olefin sulfonates containing from about 12 to 24 carbon
atoms; and ~-alkyloxy alkane sulfonates containing from about
1 to 3 carbon atoms in the alkyl group and from about 8 to
20 carbon atoms in the alkane moiety.
Preferred water-soluble organic detergent compounds
- herein include linear alkyl benzene sulfonates containing
from about 11 to 14 carbon atoms in the alkyl group, the
tallow range alkyl sulfates, the coconut range alkyl glyceryl
sulfonates; alkyl ether sulfates wherein the alkyl moiety :
contains from about 14 to 18 carbon atoms and wherein the
average degree of ethoxylation varies between 1 and 6; the
sulfated condensation products of tallow alcohol with from
about 3 to 10 moles of ethylene oxide; olefin sulfonates
containing from about 14 to 16 carbon atoms; alkyl dimethyl
amine oxides wherein the alkyl group contains from about 11
to 16 carbon atoms; alkyldimethyl-ammonio-propane-sulfonates
and alkyl-dimethyI-ammonio-hydroxy-propane-sulfonates wherein
the alkyl group in both types contains from about 14 to 18
carbon atoms; and soaps, as hereinabove defined.
Specific preferred detergents for use herein include:
sodium linear C10 - C18 alkyl ben2ene sulfonate; triethano-
lamine C10 - Cl~ alkyl benæene sulfonate; sodium tallow alkyl
sulfate, sodium coconut alkyl glyceryl ether sulfonate; the
sodium salt of a sulfated condensation product of a tallow
- 27 -
-: - ,
~ . . .
1~3Y~33'7
alcohol with from about 3 to about 10 moles of ethylene oxide;
- 3-tN,N-dimethyl-N-coconutalkyl-ammonio)-2-hydroxypropane-1-
sulfonate; 3-(N,N-dimethyl-N-coconut-alkylammonio)-propane-
l-sulfonate; 6-(N-dodecyl-benzyl-N,N-dimethylammonio)hexanoate;
dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine
oxide; and the water-soluble sodium and potassium salts of
higher fatty acids containing 8 to 24 carbon atoms.
It is to be recognized that any of the foregoing
detergents can be used separately herein or as mixtures.
Examples of preferred detergent mixtures herein are as
follows.
An especially preferred alkyl ether sulfate deter-
gent component useful in the instant compositions and
processes is a mixture of alkyl ether sulfates, said mixture
having an average (arithmetic mean) carbon chain length
within the range of from about 12 to 16 carbon atoms,
preferably from about 14 to 15 carbon atoms, and an average
(arithmetic mean) degree of ethoxylation of from about 1 to
4 moles of ethylene oxide, preferably from about 2 to 3
moles of ethylene oxide.
Specifically, such preferred mixtures comprise
from about 0.05% to 5% by weight of mixture of C12 13 com-
pounds, from about 55% to 70~ by weight of mixture of
C14 15 compounds, from about 25% to 40~ by weight of mixture
of C16 17 compounds and from about 0.1~ to 5~ by weight of
mixture of C18 19 compounds. Further, such preferred alkyl
ether sulfate mixtures comprise from about 15% to 25% by
weight of mixture of compounds having a degree of ethoxylation
of 0, from about 50% to 65% by weiyht of mixture of compounds
having a degree of ethoxylation from 1 to 4, from about 12%
- 28 -
; ~3~337
to 22~ by weight of mixture of compounds having a degree ofethoxylation from 5 to 8 and from about 0.5~ to 10~ by
weight of mixture of compounds having a degree of ethoxy-
lation greater than 8.
Examples of alkyl ether sulfate mixtures falling
within the above-specified ranges are set for-th in Table II.
- 29 -
.. . . .
'' ' ~' ' `
`~ -
~3~3;~7
. .
_ _ - . _ _ ~ _ _n_
,`
.
~; CO o\ o\Oo\O o\o O o\ A o\O o\O
E~ ~ ~ ~ I` o;) ~I . a~ . ~
H H In ~ ~) ~1 11'1 ~ iZ
_ ....... _ ____ __ __ _
E~ ~ u~ o\
~¢H 00 o~ o`~o\rA ~I a~ A Ao O~o
~H ' ~1 11~~)r-l . . U~ ~ ~1 (a
t l H ~r ~D ~ ~1 (~I ~ ~-1 Z
U~ .
H _ __ _ _ ~ -
H
p:; 00 U~ ~ ' :
I L~~1 ~ o\ r,\o o\ O\o ~ o\O o\ 0\ ~A /1~
1~1 p H ~1Ul t~ ~1 , ~I cn 1~ ~ Z ~7
~ E~ H ~ ~ 7 t~ N 1~1 r l
_ _ ., ~_ _ _....... _ . ~ ,
1~1 ~D ~0
C~ o\O o\O o~O 0\o ~ o\ o\O o\O 0\0
H ~ 10 ~ Ll') . 11~ ~ ~I r~l ~;
.' ~ ~ Il') ~ ~1 r~ . ~:,
__ _ .. __ . .,
0~o 0~o0~o 0~o ~ a~ a) . : ~
O ~) ~ ~ ~ X . ~ ~ .
H 3 3 3 3~ ^ r~ X X '~
E-l ~ ^ ~ _ _ _ ~ O ~1 0 0 X .
~n ~ a~ x o
H (11 ~ U~ O a) a)
p:; ~ O E~ 13 ~ ~ a
~ u ~ o .o o o o ~ ~
E~ ~ ~ ~ ~ ~ ~ ~ . ':
0 (d 111 (a ~u o o
o c~ a) ~ ,~
s~
S~.- O O O O ~ ~ ~ ~ Q)
~C 0 0 ,4 R ,LI R a) O
c~ c~ æ ~ ~ æ au u~
_. ~ ~ 0 ~ _ a) a) u~
r~ ~ v t~ a~ u~
P; ~ ~ ~: a) ~ o _ o~ ~ _
~ ~ ~) ~ Il') t~ ~ 0 0 ~1 oA ~3 D\O ~ 0\0 0 0~0
E~ ~ ~ ~ h r l ~ ~
:~c ~ ~ l l l l a~ o ~ ~-1
H ~ o ~ ~ ~D co ~ a 3 1 3 1 3 + 3 ~
~ ~ 1-1 . __ _ O-- r~ ~ V~
,................. . . .
:~03~33~7
Preferred "olefin sulfonat:e" detergent mixtures
utilizable hereln comprise olefin sulfonates containin~ from
about 10 to about 24 carbon atoms. Such materials can be
produced by sulfonation of ~-olefins by means of uncomplexed
sulfur dioxide followed by neutraliz:ation under conditions
such that any sultones present are hydrolyzed to the corres-
ponding hydroxy-alkane sulfonates. The ~-olefin starting
materials preferably have from 14 to 16 carbon atoms. Said
preferred a-olefin sulfonates are described in U.S. Patent
3,332,880.
Preferred a-olefin sulfonate mixtures herein consist
essentially of from about 30% to about 70% by weight of a
Component A, from about 20% to about 70% by weight of a
Component B, and from about 2% to about 15% of a Component
C, wherein
(a) said Component A is a mixture of double-bond
positional isomers of water-soluble salts of
alkene-l-sulfonic acids containing from about
10 to about 24 carbon atoms, said mixture of
positional isomers including about 10% to
about 25% of an alpha-beta unsaturated isomer,
about 30% to about 70% of a beta-gamma unsat-
urated isomer, about 5% to about 25% of a
gamma-delta unsaturated isomer, and abou-t 5%
to about 10% of a delta-epsilon unsaturated
isomer;
(b) said Component B is a mixture of water-soluble
salts of bifunctionally-substituted sulfur-
containing saturated aliphatic compounds
containing from about 10 to about 24 carbon
- 31 -
. .
103~33'7
atoms, the functional units being hydroxy
and sulfonate groups wi-th the sulfonate
groups always being on the terminal carbon
and the hydroxyl group being attached to a
carbon atom at least two carbon atoms
removed from the termi.nal carbon atoms at
least 90~ of the hydroxy group substitutions
being in 3, 4, and 5 positions; and
(c) said Component C is a mixture comprising from
about 30%-95~ water-soluble salts of alkene
disulfonates containing from about 10 to about
24 carbon atoms, and from about 5% to about
70~ water-soluble salts of hydroxy disulfonates
containing from about 10 to about 24 carbon
atoms, said alkene disulfonates containing a
sulfonate group attached to a terminal carbon
atom and a second sulfonate group attached , - ~ ;to an internal carbon atom not more than about .::-six carbon atoms removed from said terminal -~ ~.
carbon atom, the alkene double bond being dis-
tributed between the terminal carbon atom and
about the seventh carbon atom, said hydroxy
disulfonates being saturated aliphatic compounds ~
having a sulfonate group attached to a terminal --:
carbon, a second sulfonate group attached to
an internal carbon atom not more than about
six carbon atoms removed from said terminal
carbon atom, and a hydroxy group attached
to a carbon atom ~hich is not more than about
four carbon atoms removed from the site of
- 32 -
~3~3;~7
attachment o~ said second sulfonate group.
Adjuvan~ ~laterials
The herein-disclosed compositions can contain, in
addition to the nonionic mixtures and optional organic
detergent compounds, all manner of detergency ~uilders
commonly taught for use in detergent compositions. Such
builders can be optionally employed in the present compositions
at concentrations of from about 0% to about 90% by weight,
preferably from about 30% to about 70~ by weight, of said
optional builders. Useful builders herein include any of
the conventional inorganic and organic water-soluble builder
salts.
Such detergency builders can be, for example,
water-soluble salts of phosphates, pyrophosphates, ortho-
phosphates, polyphosphates, phosphonates, carbonates,
polyhydroxysulfonates, silicates, polyacetates, carboxylates,
polycarboxylates and succinates. Specific examples of
- inorganic phosphate builders include sodium and potassium
tripolyphosphates, phosphates and hexamethaphosphates. The
polyphosphonates specifically include, for example, the
sodium and potassium salts of ethylene diphosphonic acid,
the sodium and potassium salts of ethane l-hydroxy-l,
l-diphosphonic acid and the sodium and potassium salts of
ethane-1,1,2-triphosphonic acid. Es~amples of these and
other phosphorous builder compounds are disclosed in U.S.
Patents 3,159,581; 3,Z13,030; 3,422,021; 3,422/137; 3,400,176
and 3,400,148.
Non-phosphorus containing sequestrants can also
be selected for use herein as detergency builders.
Specific examples of non-phosphorus, inorganic
- 33 -
. :,
~0373;3 7
builder ingredients include water-~oluble inorganic carbonate,
bicarbonate, and silicate salts. The alkali metal, e.~.,
sodium and potassium, carbonates, bicar~onates, and silicates
are particularly useful herein.
Water-soluble, organic builders are also useful
herein. For example, the alkali metal, ammonium and sub-
stituted ammonium polyacetates, carboxylates, polycarboxylates
and polyhydroxysulfonates are useful builders in the present
compositions and processes. Specific examples of the
polyacetate and polycarboxylate builder salts include
sodium, potassium, lithium, ammonium and substituted
ammonium salts of ethylene diamine tetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, mellitic acid,
benzene polycarboxylic acids, and citric acid.
Highly preferred non-phosphorus builder materials
herein include sodium carbonate, sodium bicarbonate, sodium
silicate, sodium citrate, sodlum oxydisuccinate, sodium
mellitate, sodium nitrilotriacetate, and sodium ethylene-
diaminetetraacetate, and mixtures thereof.
Other highly preferred builders herein are the
polycarboxylate builders set forth in U.S. Patent 3,308,067,
Diehl. Examples of such materials include the water-soluble
salts of homo- and co-polymers of aliphatic carboxylic acids
such as maleic acid, itaconic acid, mesaconic acid, ~umaric
acid, aconitic acidr citraconic acid and me-thylenemalonic
acid.
Additional, preferred builders herein include the
water-soluble salts, especially the sodium and potassiu~
salts, of carboxymethyloxymalonate, carboxymethyloxysuccinate,
cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxy--
- 34 -
: '. : . ~ ,
~3733~
late and phloro~lucinol trisulfonate.
Another type of ~etergency builder material usefulin the present composltions and processes comprises a water-
soluble material c~pable oE forming a water-insoluble
reaction product with water hardness cations in combination
with a crystallization seed which is capable of providing
growth sites for said reaction product. Such "seeded
builder" compositions are fully disclosed in the ~enjamin
Canadian Patent 991,942.
More particularly, the seeded builders useful
herein comprise a crystallization seed having a maximum
particle dimension of less than 20 microns, preferably a
particle diameter of fram about 0.01 micron to about 1
micron, in combination with a material capable of forming
a water-insoluble reaction product with free metal ions.
Many builder materials, e.g, the water-soluble
carbonate salts, precipitate water hardness cations,
thereby performing a builder function. Unfortunately,
many of the precipitating builders used in detergent
compositions do not reduce the free metal ion content of
laundry baths quickly, and such builders only compete with
the organic detergent and the soil for the free metal ions.
The result is that while some of the free metal ions are
removed from the solution, some ions do react with the
organic detergent and the soil, thereby decreasing the deter-
sive action. The use of the crystallization seed quickens
the rate of precipitation of the metal hardness, thereby
removing the hardness ions before they can adversely affect
the detergency performance.
- 35 -
.;; . . - . .:; . ............ . . .
- .:. .
~3~ 7
By using a material capable of formin~ a water-
insoluble product with free metal ions in combination with
a crystallization seed, the combined free metal ion con-
centration of an aqueous laundering liquor can be reduced
to less tllan 0.5 grains of hardness within about 120 seconds.
In fact, the preferred seeded builders can reduce the free
metal hardness to less than 0.1 grains/gallon within about
30 seconds.
Preferred seeded builders consist of: a water-
soluble material capable of forming a reaction product having
a solubility in water of less than about 1.4 x 10 wt.%
~at 25C) with divalent and polyvalent metal ions such as
calcium, magnesium and iron; and a crystallization seed
(0.001 20 micron diameter) which comprises a material
which will not completely dissolve in water within 120
seconds at 25C.
Specific examples of materials capable of forming
the water-insoluble reaction product include the water-
soluble salts of carbonates, bicarbonates, sesquicarbonates,
silicates, aluminates and oxalates. The alkali metal,
especially sodium, salts of the foregoing materials are
preferred for convenience and economy.
The crystallization seed employed in such seeded
builders is preferably selected from the group consisting
of calcium carbonate; calcium and magnesium oxalates;
barium sulfate; calcium, magnesium and aluminum silicates;
calcium and magnesium oxides; calcium and magnesium salts
of fatty acids having 12 to 22 carbon atoms; calcium and
magnesium hydroxides; calcium fluoride; and barium carbonate.
Specific examples of such seeded builder mixtures comprise:
- 36 -
.,
1~3733~7
3:1 wt. mixtures of sodium car~onate and calcium carbonatehaving a 5 micron particle diameter; 2.7:1 wt. mixtures of
sodium sesquicarbonate and calcium carbonate having ~
particle diameter of 0.5 microns; 20:1 wk. mixtures of
sodium sesquicarbonate and calcium hydroxide having a
particle diameter of 0.01 micron; and a 3:3:1 wt. mixture
o~ sodium carbonate, sodium aluminate and calcium oxide
having a particle diameter of 5 microns.
The compositions herein can optionally contain
all manner of additional materials commonly found in
laundering and cleaning compositions. For example, thick-
eners and soil suspending agents such as carboxymethyl-
cellulose and the like can be included in the compositions.
Enzymes, especially the thermally stable~proteolytic and
lipolytic enzymes commonly used in high temperature laundry
detergent compositions, can also be present herein.
Various perfumes, optical bleaches, fillers, anti-caking
agents, fabric softeners and the like can be present to
provide the usual benefits occasioned by the use of such
materials in detergent compositions. Perborate bleaches
commonly employed in European detergent compositions can
also be present as a component of the compositions herein.
It is to be recognized that all such adjuvant materials are
useful, inasmuch as they are compatible and stable in the
-compositions herein.
The alkoxylated nonionic mixtures herein can be
- used separately as detergent compositions, but are most
often employed at a concentration of from about 5% to about
95% (preferably 8%-45%) by weight in combination with 0~ to
95% (preferably 55~-95%) by weight of a carrier. Liquid
- 37 --
: :-......... . ............. .
~ , ' ~ , . . . ' ' '
~C13 ~337
carriers include water and water-alcohol mixtures, e~g.,
90:10 (wt.) water-ethanol; 80:20 (wt.) water:n-propanol;
70:30 (wt.) water-isopropanol; 95:5 (wt.) water-n-butanol,,
and the like. Water-ethanol mixtures at weight ratios of
water:ethanol o~ 95:5 to 1:1 are especially preferred
liquid carriers herein.
Solid, sorbent carriers for the present nonionic
mixtures include any o~ the hereinabove disclosed water-
soluble solid builder materials, as well as water-insoluble
lO solids such as the microfine silicas, clays, kieselguhr, ' ~`
vermiculites and the like. The nonionic mixtures are
sorbed on such solid carriers at a weight ratio of nonionic:
carrier from about 1:20 to 20:1 for use in dry detergent
compositions. The appropriate ratio will, of course, depend
on the sorbency of the carrier, and can be readily determined
experimentally.
The Wise British Patent 1,460,646, sealed rlay 4,
1977, discloses the use of kaolinite clay to provide a
crutcher-stable nonionic surfactant/clay mixture suitable
for use in the preparation of spray-dried detergent granules.
Kaolinite clay employed in this manner is a preferred water-
insoluble carrier for preparing spray-dried detergent
granules containing the nonionic mixtures of the present
invention.
The followin~ examples illustrate various compo-
sitions employing the nonionic oil solubilization systems of
this invention. The materials employed in the formulation
of said compositions are commercially available, or can
be prepared by methods well-known in the art.
- 38 -
~0373~
EX ~lPLE I
A liquid oil dissolving composition is as follows:
Component Wt.~
., _
n-C10(EO)3 (stripped)* 80
Tergitol 15-S-9 20
*Stripping the unalkoxylated alcohols raises the
average degree of alkoxylation to ca. 4.
The above composition is dissolved in water at
a concentration of 0.11% by weight. Oily metal surfaces
and oil-stained rags are cleansed by agitating same with
the solution for periods of from about 1 minute to about
10 minutes, depending on the amount of oil to be removed.
In the above composition the nonionic mixture
is replaced by the following mixtures: Tergitol 15-S-5/
p-octylphenol EO(9) 50:50 wt. ratio; n-C10EO(3)/n-C12EO(9)
60:40 wt. ratio; n-C8EO(2)~n-C10EO(9) 55:45 wt. ratio;
2-C10EO(3)/n-C10EO(9) 55:45 wt. ratio: p-hexylphenol EO(3)/
p-nonylphenol EO(9) 60:40 wt. ratio; and 3-ethyl-2-decanol
(3)/3-ethyl-2-dodecanol(9) 55:45 wt. ratio, respectively, and
oil solubili~ing compositions are thereby secured.
- 39 -
, . . . .
~03733 7
EXl~MPLE I I
,
A granular detergent composition is formulated
having the following composition.
Component Wt.%
Sodium silicate 86.0
(Na2O:SiO2 ratio 1:1.8;
Britesil (CA)
n-ClOEO(3) 8.0
10 0(9) 6.0
The above composition is used in an aqueous sol-
ution at a concentration of 0.12% wt. to launder fabrics.
The pH of the laundering liquor is 10.1. Improved hydro-
carbon removal is secured; additionally, superior removal
of lipid soils is noted.
,
'
4 0 - :
, . '
-
1al3~933~7
EXArlPLE II.L
A spray-dried, granular detergent composition is
as follows:
Crutcher Mix
Ingredient Grams
Sulfated tallow alcohol 2.0
Linear alkylbenzene sulfonate
(alkyl = Cll 8 avg.) 2.0
Calcium carbonate (1.0 micron) 9.0
Sodi~ carbonate 30.0
Sodium sulfate 9.7
Sodium sulfosuccinate 2.0
Sodium toluene sulfonate 2.0
Sodium silicate (SiO2:Na2O = 2.0) 10.0
Water 45.0
Pre-Slurry
Ingredient Grams
Tergitol 15-S-9 9.0
Tergitol 13-S-5 11.0
Xaolinite clay (1.0 micron) 6.5
- 41 -
. .
: , . ,;,. . .
33~ .
~ l~he kaolinite~ clay ~nd the nonionic surfactants
are admixed separately from the crut:cher mix as a pre-slurry
at a temperature of 150F and blended thoroughly at this
temperature for about 5 minutes until a smooth slurry is
obtained. The crutcher mix ingredients are separately mixed
and raised to a temperature of 150~. The hot kaolinite-
nonionic slurry is then admixed witll the hot crutcher mix
and blended. The resulting homogeneous crutcher mix is
spray-dried at 200C to provide a granular detergent
composition.
The foregoing composition is employed as a 0.1
aqueous solution and provides superior oil removal from
polyester fabrics when laundered at 100F-110F.
In the foregoing composition the mixture of
Tergitol 15-S-9 and Tergitol 13-S-5 is replaced by an
equivalent amount of the other nonionic mixtures set forth
herein in Table I, respectively, and equivalent results are
secured.
In the foregoing composition, the anionic surfac-
tant component of the crutcher mix comprising the sulfated
tallow alcohol and the linear alkylbenzene sulfonate is
replaced by an equivalent amount of sodium linear C10-Cl8
alkylbenzene sulfonate; triethanolamine C10-Cl8 alkylbenzene
sulfonate; sodium tallow alkyl sulfate, sodium coconut alkyl
glycerylether sulfona-te; the sodium salt of a sulfated
condensation product of a tallow alcohol containing from
about 3 to about 10 moles of ethylene oxide; 3-(N,N-dimethyl-
N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-
dimethyl-N-coconutalkylammonio)-propane-l-sulfonate; 6-(N-
dodecylbenzyl-N,N-dimethylammonio)-hexanoate; dodecyl
- 42 -
.,. . ~ ~, . . .
13~33~
dimethyl amine oxi~e; coconutalkyldimethyl amine oxide; andthe water-soluble sodium and potass:Lum salts of higher fatty
acids containing 8 to 24 carbon atorns, respectively, and
equivalent results are secured.
In the foregoing compositlon, the seeded builder
comprising the mixture of sodium carbonate and calcium
carbonate is replaced by a total of 40 grams of the following
builders, respectively: sodium tripolyphosphate, sodium
nitrilotriacetate; sodium citrate; sodium oxydisuccinate;
sodium mellitate; sodium ethylenediaminetetraacetate;
sodium carboxymethyloxymalonate; sodium carboxymethyloxy-
succinate; sodium cis-cyclohexanehexacarboxylate; sodium
cis-cyclopentanetetracarboxylate; and the sodium salt of
phloroglucinol trisulfonate, respectively, and equivalent
results are secured.
The foregoing compositions exhibit excellent
removal of oll and clay soil from fabrics when employed
in aqueous laundry baths at concentrations of 0.04~ (wt.),
and greater. The compositions also provide excellent hard
surface cleaners useful for scrubbing walls, floors and
dishes.
- 43 -
~03~337
EXAMPLE IV
A spray-dried granular detergent composition prepared in
the manner of this invention is as follows:
Ingredient Wt.%
Branch-chain alkylbenzene sulfonate
(alkyl = C12 avg.) 20.0
Nonionic component consisting of
1:1 (wt.) mixture of
n-ClO(Eo)3 and n C10( )6
Sodium tripolyphosphate 33.0
Sodium toluene sulfonate 2.0 ~ "
Carboxymethylcellulose 0.6 -
Sodium sulfate 21.9
Kaolinite clay (0.5 micron diam.) 2.5
Sodium silicate (SiO2:Na20 = 2.0) 5.4
Colorants 0.1
Water 9~5
i ~; ,':
- 44 -
.. .. .. . .. . . .. . . . .
:-.~ ,. . ... ::, , .: ~. , ., . :
, ~ , . . : . :
~3~3~7
The foregoing composition is prepared by pre-
slurrying the kaolinite clay and the nonlonics at 150F
and admixing the pre-slurry with a crutcher mix comprising
the remaining components set for-th, also at 150F. The
resulting mix is spray-dried in a tower with an inlet air
stream of 600F at about 300F to provide the detergent
granules.
- 45 - :
. - . . . . . .
~CI 3733'~
E~~MPLE V
An unbuilt, heavy duty liquid detergent is formulated having
the following composition:
Component Wt.%
~onionic oil solu~ilization system 33.0
comprising 80 wt.~ stripped
n-Cl oEO ( 3) and 20 wt.% Tergitol
15-S-9
Triethanolamine salt of linear 16.1 .
alkyl benzene sulfonic acid
wherein the alkyl chain averages
12 carbon atoms in length
,
Triethanolamine (free form) 5.3
Ethanol 5.5 ~: -
Potassium Chloride 2.5
Brighteners, Perfumes, Dye 1.2
Water Balance .
. :
.
- 46 -
;
... . .. . . . . . . .
::: ., , :: .
. . .
- ~.
~L~3~33~
The a~ove composition provides cxcellent removal
of a wide variety of oily soils from cotton, polyester and
polyester/cotton fabrics.
Substantially equivalent cleter~ency performance
is realized when in the above-described composition the
nonionic oil solubilization system i.s replaced by an
equivalent amount of the other mixtures set forth herein in
Table I, respectively.
In the foregoing composition the oil solubilization
system is replaced by an equivalent amount of a mixture
comprising 70 wt.% Tergitol 15-S-5 and 30 wt.% of a hepta-
ethoxylate of a mixture of C14 15 primary alcohols, marketed
as Dobanol 45-7 (total mixture EILB ca. 11), and equivalent
results are secured.
,
- ~7 -
~037337
EXAMPLE VI
An automatic dishwashing detergent compos.ition prepared in
the manner o~ this invention is as .Eollows:
Ingredient Grams
Nonionic component* 25.0
Kaolinite clay (0.5 microns)15.0 .
Coconutalkyl EO(3) PO(6)** 2.0
Sodium tripolyphosphate 100.0
Sodium silicate 25.0
lO Potassium dichlorocyanurate 2.0
Water g.o ~ ~
* Comprising stripped n-ClO(EO)3 and Tergitol 15-S-9, ~ :-
4:1 wt. ratio.
** Suds suppressing agent
- 48 -
.
~03733~
~ e foregoiny composition is ~repared by admixing
the nonionic component and kaolinite clay at a temperature
of 150F and blending therewith the ethylene oxide-propylene
oxide suds suppressing agent. The resulting mixture, at
150F, is admixed with the remaining components, also
maintained at a temperature of 150F, -to provide a homo-
geneous crutcher mix. The mix is sprayed through a drying
tower to provide a homogeneous detergent composition
especially adapted for use in automatic dishwashers.
As can be seen from the foregoing, detergent
compositions in the manner oE the present invention com-
prising from about 5% to about 100% (preferably about 8% to
about 45%) by weight of thP surfactant/co-surfactant mixtures
herein and from about 0% to about 95~ (preferably about 55%
to about 95%) by weight of a solid or liquid water-dispersible
carrier, provide superior oil-dissolving detergent composi-
tions for use in aqueous laundering baths. The mixtures
herein can be added to commercial detergent formulations
to impart improved oil removal properties thereto. Such
compositions most preferably comprise from about 15% to
about 40% by weight of the oil-dissolving mixtures herein,
from about 1% to about 20% by weight of a detergent compound
to optimize sudsing and to provide broad spectrum cleaning
with a variety of fabrics and soil types, and, for heavy
duty cleaning use, from about 30% to about 70% of detergency
builders.
Fabric softener compositions comprising a major
proportion of a quaternary ammonium surface active agent
and minor amounts (ca. 1~) of alkoxylate mixtures are
known in the art. When employed in such compositions, the
.. : . . .~ - :
~373~7
alkoxylate mixtures act as emulsion stabilizers, rather than
oil solubilizing agents. In contrast, the present composi-
tions are characterized as being free from quaternary compounds.
,' '
:
- 50 -
.
