Note: Descriptions are shown in the official language in which they were submitted.
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Background of the Invention
This invention relates to storage-stable, alkaline
laundry detergent compositions, preferred embodiments of
which exhibit excellent particulate and greasy/oily soil
removal performance, as well as fabric softening, static
control and dye transfer inhibition benefits, to fabrics
laundered therewith.
It is taught in Canadian Patent Application Serial
No. 306,456, Cockrell, filed June 29, 1978, and Canadian
Patent Application Serial No. 306,474, Murphy, filed
June 29, 1978, that by selection and combination of
specific types of nonionic and cationic surfactants,
excellent particulate and greasy/oily soil removal
laundering performance can be obtained. In preferred
embodiments of those compositions, by choosing specific
types of cationic surface-active agents, biodegradable
laundry detergent c~mpositions can be formulated which
exhibit particulate and grease/oil removal benefits as
well as fabric softening, static control, and dye transfer
inhibition benefits. Detergent compositions containing
these specific biodegradable surfactants are described in
Canadian Patent Application Serial No. 306,513, Letton,
filed June 29, 1978, and Canadian Patent Application
Serial No. 306,517, Letton, filed June 29, 1978.
It is further taught in the above applications that it
is desirable that the detergent compositions form alkaline
laundry solutions in order to improve the removal of oily
body soils. However,because these preferred cationic sur-
factants contain a biodegradable linkage, such as an ester
or amide linkage, they tend to hydrolyze upon storage and
use, when included in such alkaline detergent compositions,
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thereby reducing their effectiveness during the launder-
ing operation. It has now been found that by using the
specific types of alkalinity sources defined herein,
alkaline detergent compositions may be formulated which - ;
minimize the hydrolysis of hydrolyzable linkage-containing
cationic surfactants, and particularly the preferred bio-
degradable cationic surfactants discussed above, during
storage and use.
It is, therefore, an object of the present invention
to provide alkaline laundry detergent compositions,
containing cationic surfactants including hydrolyzable
linkages, which are storage-stable.
9~S3
It is a further object of the present invention to
provide laundry detergent compositions which yield excellent
removal of particulate and greasy~oily soils, as well as
fabric softening, static control, and dye transfer inhibition,
to fabrics laundered therewith.
lt is a still further object of the present invention
to provide laundry detergent compositions, yielding the
above cleaning and fabric care benefits, which are biodegradable.
It is yet another.object of the present invention to - -
provide a process for laundering fabrics, yielding excellent
removal of oily body soils, clay and g~easy/oily soils,
utilizing detergent compositions which contain selected
cationic and nonionic surfactants.
Summary of the I-nvention
The present invention relates to storage and wash
solution-stable laundry detergent compositions comprising:
(a) from about 2% to about 95% of a cationic surfactant
which contains at least one hydrolyzable linkage
selected from the group consisting of:
O O O O O H
-C-, -C-O-, -O-C-, -O-, -O-C-O-, -~-N-,
H O O H H O
1 11 11 ~ I 11
-~-C-, -O-C-N-, -N-C-O-, and mixtures
thereof; and
(b) from about l~ to about 25~ of an inorganic alkaline
component which is insoluble in said cationic
surfactant, and which is present in an amount such
that the detergent composition forms a solution
having a pH of from about 8 to about lO within 3
9753
.
minutes after it is placed in 100F water at a
concentration of about 0.15~.
A preferred aspect of the present invention en~ompasses
alkaline, laundry detergent compositions, which provide
excellent cleaning of particulate and greasy/oily soils,
together with a range of fabric care benefits, comprising:
(a) from about 2~ to about 95% of a surfactant mixture
consisting essentially of:
(1) a nonionic surfactant having an HLR of from
about 5 to about 17; and
(2) a cationic surfactant selected from the group
consisting of:
(i) R2-(Zl)a~(R3)n-Z2-(CH2)m-N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxy-
alkyl; R2 is C5 to C30 straigh~ or branched
chain alkyl, alkenyl, alky].benzyl, or alkyl
phenyl group or
X Rl- N-(CH2)s-, wherein s is from 0 to S;
Rl
R3 is Cl to C20 alkylene or alkenylene, a is
0 or 1, n is 0 or 1, and a is 1 only when n
is l; m is f~om 1 to 5; zl and z2 are each
selected from the group consisting of:
~ ~J9753
O O O ~ H
It 11 11 11 l
-C -O -, -O -C -, -O-, -O-C -O -, -C -N-,
H O O H H O
--N--C--, --O--C--N--, --N--C-O--
and wherein at least one of said groups is
selected from the group consisting of ester,
reverse ester, amide and reverse amide; and X
is an anion which makes the surfactant at
least water-dispersible;
R2 Rl
(ii) R3-ot(c~)noly-(zl)a-lR4)~-z2-(cH2)m N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxyalkyl;
each R2 is either hydrogen or Cl to C3
alkyl; R3 is C4 to C3~ straight or branched
chain alkyl~ alkenyl or alkylbenzyl; R4 is Cl
to C10 alkylene or alkenylene; n is rom 2 to
4; y is from 1 to 2Q; a is O or 1, t is O o~
1, and a can be 1 only when t is 1; m is from
1 to 5; z2 is selected from the group consisting
of
O O O O H
-C-O-, -C-, -O-, -O-C-O-, -C-N -,
H O O H H O
1 11 11 1 ( 11
-N-~-, -O-C-N-, -N-C-O-
-
97~;3
r-
~
Z is selected from the group consisting of
O O O H H O H O
Il 11 11 1 1 il I 11
-C-O-, -C-, -C-N-, -N-C-, -N-C-O-,
and wherein at least one of said zl and z2
groups is selected from the group consisting
of ester, reverse ester, amide, and reverse
amide; and X is an anion which makes the
surfactant at least water-dispersible; and
(iii) mixtures thereof;
wherein the ratio of said nonionic surfactant
to said cationic surfactant is in the range
of from about 1:1 to about 100:1; and
(b) from about 1% to about 25% of an inorganic alkaline
component which is insoluble in said cationic/
nonionic surfactant mixture, and which is present
in an amount such that the detergent composition
forms a solution having a pH of from about 8 to
about 10 within about 3 minutes after addition to
100F water at a concentration of about 0.15% by
weight.
Preferred nonionic surfactants are biodegradable and
have the formula R(OC2H4)nOH wherein R is a primary or
secondary alkyl chain of from about 8 to about 22 carbon
atoms and n is an average of from about 2 to about 12.
Preferred alkalinity sources for use in the compositions
of the present invention include borax pentahydrate, borax
decahydrate, sodium carbonate and mixtures of these components.
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11~)9753
The compositions herein may also contain various optional
adjunct materials commonly employed in laundry detergent
compositions.
A method of laundering fabrics, yielding the cleaning
and fabric care benefits described herein, utilizing the
detergent compositions of the present invention, is also
taught.
Detailed Description of the Invention
The compositions of the present invention contain a
hydrolyzable cationic surfactant, or preferably a mixture
of selected nonionic and cationic surfactants, together
with specific types of inorganic alkalinity-producing
components. The compositions contain from about 2% to
about 95%, preferably from about 10% to about 90%, and
most preferably from about 15% to about 85%, of the
cationic or nonlonic/cationic surfactant components.
The preferred mixtures are disclosed in detail
and claimed in Canadian Patent Applications Serial Nos~
306,513 and 306,517, Letton, filed June 29, 1978, and
provides excellent cleaning of particulate and greasy/oily
soils, together with a range of fabric care benefits.
The specific nonionic and cationic surfactants disclosed
therein, and which are also described below, may be
combined in ratios of nonionic surfactant to cationic
surfactant by weight of from about 1:1 to about 100:1,
preferablv from about 5:3 to about 50:1, most preferably
from about 5:3 to about 20:1. Particularly preferred
ratios are from about 5:3 to about 10:1, preferably from
about 5:3 to about 5:1, particularly about 5:2. The
specific components useful in the compositions of the
present invention are described below.
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Preferred compositions of the present invention are
formulated based on their cloud points and/or reduced
cationic monomer concentrations; these concepts are
described in detail in Canadian Patent Application Serial
No. 306,456, Cockrell, filed June 29, 1978 and Canadian
Patent Application Serial No. 306,474, Murphy, filed
June 29, 1978. In optimizing greasy/oily soil removal,
the compositions should be formulated to have a cloud
point of from about 0 to about 95 C, preferably from about
10 to about 70 C, most preferably from about 20 to about
70 C, and a reduced cationic monomer concentration of from
about 0.002 to about 0.2, especially from about 0.002 to
about 0.15, particularly from about 0.002 to about 0.08.
In optimizing particulate soil removal, the compositions
should be formulated to have a reduced cationic monomer
concentration of from about 0.005 to about 0.2, preferably
from about 0.008 to about 0.15, and particularly from
about 0.01 to about 0.1.
_nionic Surfactant
Nonionic surfactants, having an HLB of from about 5
to about 17, well-known in the detergency arts, may be
included in the compositions of the present invention
together with the cationic surfactants defined herein-
after. They may be used singly or in combination with
one or more of the preferred alcohol ethoxylate nonionic
surfactants, described below, to form nonionic surfactant
mixtures useful in combination with the cationic surfac-
tants. Examples of such surfactants are listed in U.S.
Patent 3,717,630, Booth, issued February 20, 1973, and
U.S. Patent 3,332,880, Kessler et al, issued July 25,
1967. Nonlimiting examples of suitable nonionic
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1~)9753
surfactants which may be used in the present invention are
as follows:
(1) The polyethylene oxide condensates of alkyl phenols.
These compounds include the condensation products of
alkyl phenols having an alkyl group containing from about
6 to 12 carbon atoms in either a straight chain or
branched chain configuration with ethylene oxide, said
ethylene oxide being present in an amount equal to 5 to
25 moles of ethylene oxide per mole of alkyl phenol. The
alkyl substituent in such compounds can be derived, for
example, from polymerized propylene, di-isobutylene, and
the like. Examples of compounds of this type include
nonyl phenol condensed with about 9.5 moles of ethylene
oxide per mole of nonyl phenol; dodecylphenol condensed
with about 12 moles of ethylene oxide per mole of phenol;
dinonyl phenol condensed with about 15 moles of ethylene
oxide per mole of phenol; and di-isooctyl phenol condensed
with about 15 moles of ethylene oxide per mole of phenol.
Commercially available nonionic surfactants of this type
include Igepal* C0-630, marketed by the GAF Corporation,
and Triton* X-45, X-114, X-100, and X-102, all marketed by
the Rohm & Haas Company.
(2) The condensation products of aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide. The
alkyl chain of the aliphatic alcohol can either be
straight or branched, primary or secondary, and generally
contains from about 8 to about 22 carbon atoms. Examples
of such ethoxylated alcohols include the condensation
product of myristyl alcohol condensed with about 10 moles
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of ethylene oxide per mole of alcohol; and the conden-
sation product of about 9 moles of ethylene oxide with
coconut alcohol (a mixture of fatty alcohols with alkyl
chains varying in length from 10 to 14 carbon atoms).
Examples of commercially available nonionic surfactants
of this type include Tergitol* 15-S-9, marketed by Union
Carbide Corporation, Neodol* 45-9, marketed by Shell
Chemical Company, and Kyro* EOB, marketed by The Procter
& Gamble Company.
(3) The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol. The hydrophobic portion of
these compounds has a molecular weight of from about 1500
to 1800 and exhibits water insolubility. The addition of
polyoxyethylene moieties to this hydrophobic portion tends
to increase the water solubility of the molecule as a
whole, and the liquid character of the product is retained
up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product, which
corresponds to condensation with up to about 40 moles of
ethylene oxide. Examples of compounds of this type
include certain of the commercially available Pluronic*
surfactants, marketed by Wyandotte Chemical Corporation.
(4) The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide
and ethylene diamine. The hydrophobic moiety of these
products consists of the reaction product of ethylene
diamine ands excess propylene oxide, said moiety having a
molecular weight of from about 2500 to about 3000. This
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hydrophobic moiety is condensed with ethylene oxide to
the extent that the condensation product contains from
about 40~ to about 80% by weight of polyoxyethylene and
has a molecular weight of from about 5,000 to about
11,000. Examples of this type of nonionic surfactant
include certain of the commercially available Tetronic*
compounds, marketed by Wyandotte Chemical Corporation.
A preferred group of nonionic surfactants useful
herein comprises a mixture of "surfactant" and "cosur-
factant", containing at least one nonionic surfactantfalling within the definition of nonionic surfactants
useful in the present invention, as described in Canadian
Patent No. 1,059,8~5, Collins, issued on August 7, 1979.
Preferred alcohol ethoxylate nonionic surfactants for
use in the compositions of the present invention are bio-
degradable and have the formula R(OC2H4)nOH, wherein
R is a primary or secondary alkyl chain of from about 8
to about 22, preferably from about 10 to about 20, carbon
atoms and n is an average of from about 2 to about 12,
particularly from about 2 to about 9. The nonionics
have an HLB (hydrophilic-lipophilic balance) of from
about 5 to about 17, preferably from about 6 to about
15. HLB is defined in detail in Nonionic Surfactants, by
M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.
In preferred nonionic surfactants, n is from 4 to 7.
Primary linear alcohol ethoxylates (e.g., alcohol ethoxy-
lates produced from organic alcohols which contain about
20~ 2-methyl branched isomers, commercially available from
Shell Chemical Company under the trademark Neodol) are
Ipreferred from a performance standpoint.
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Particularly preferred nonionic surfactants for use in
the compositions of the present invention include the
condensation product of C10 alcohol with 3 moles of ethylene
oxide; the condensation product of tallow alcohol with 9
moles of ethylene oxide; the condensation product of coconut
alcohol with 5 moles of ethylene oxide; the condensation
product of coconut alcohol with 6 moles of ethylene oxide;
the condensation product of C12 alcohol with 5 moles of
ethylene oxide; the condensation product of C12 13 alcohol -
with 6.5 moles of et~lylene oxi.de, and the same condensatinnproduct which is stripped so as to r~move substantially all
lower ethoxylate and nonethoxylated fractions; the condensation
product of C12 13 alcohol with 3 moles of ethylene oxide,
and the same condensation product which i5 stripped so as to
remove substantially all lower ethoxylate.and nonethoxylated
fractions; the condensation product of C12 ]3 alcohol with 9
moles of ethylene oxide; the condensation product of Cl~ 15
alcohol with 2.25 moles of ethylene oxide; the condensati.on
product of Cl~ 15 alcohol with 4 moles of ethylene oxide;
the condensation product of C14 15 alcohol with 7 moles of
ethylene oxide; and the condensation product of Cl~ 15
alcohol with 9 moles of ethylene oxide.
The compositions of the present invention may contain
mixtures of the preferred alcohol ethoxylate nonionic
surfactants together with other types of nonionic surfactants.
Preferred nonionic surfactant mixtures contain at least one
of the preferred alcohol ethoxylate nonionics, and have a
ratio of the preferred alcohol ethoxylate surfactant (or
surfactants) to the other nonionic surfactant ~or surfactants)
of from about 1:1 to about 5:1. Specific examples of surfactant
mixtures useful in the present invention include a mixture
1 1~9753
of the condensation product of C14 15 alcohol with 3 moles
of ethylene oxide (Neodol* 45-3) and the condensation
product of C14 15 alcOhol with 9 moles of ethylene oxide
(Neodol* 45-9), in a ratio of lower ethoxylate nonionic to
higher ethoxylate nonionic of from about 1:1 to about 3:1;
a mixture of the condensation product of C10 alcohol with
3 moles of ethylene oxide together with the condensation
product of a secondary C15 alcohol with 9 moles of ethylene
oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate
nonionic to higher ethoxylate nonionic of from about 1:1
to about 4:1; a mixture of Neodol* 45-3 and Tergitol* 15-S-9,
in a ratio of lower ethoxylate nonionic to higher ethoxylate
nonionic of from about 1:1 to about 3:1; and a mixture of
Neodo~* 45-3 with the condensation product of myristyl
alcohol with 10 moles of ethylene oxide, in a ratio of
lower ethoxylate to higher ethoxylate of from about 1:1 to
about 3:1.
Preferred nonionic surfactant mixtures may also contain
alkyl glyceryl ether compounds together with the preferred
alcohol ethoxylate surfactants. Particularly preferred are
glyceryl ethers having the formula
R-O(CH2CH2O)nCH2CHCH2OH
OH
wherein R is an alkyl or alkenyl group of from about 8 to
about 18, preferably about 8 to 12, carbon atoms or an
alkaryl group having from about 5 to 14 carbons in the alkyl
chain, and n is from 0 to about 6, together with the pre-
ferred alcohol ethoxylates, described above, in a ratio of
alcohol ethoxylate to glyceryl ether of from about 1:1 to
about 4:1, particularly about 7:3. Glyceryl ethers of the
type useful in the present invention are disclosed in
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, ~ ~
Canadian Patent Application Serial No. 266,629, Jones,
filed November 26, 1976; and U.S. Patent 4,098,713, Jones,
issued July 4, 1978.
Cationic Component
The compositions of the present invention contain a
cationic surfactant, or a mixture of such surfactants, which
undergo degradation, through hydrolysis, when they are placed
in an alkaline, aqueous environment. Such surfactants con-
tain one or more linkages which are subject to attack by
hydroxide ions in solution. Examples of such linkages include
O O O O O H H O
ll 11 11 11 . Ii I I i1
-C-, -C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C -,
O H H O
Il l l 11
-O-C-N-, and -N-C-O-
Preferred surfactants are those containing ester,reverse ester, amide, or reverse amide linkages.
Preferred compositions include the cationic surfactants
which are described in Canadian Patent Application Serial
Nos. 306,513 and 306,517, Letton, both filed June 29, 1978.
These surfactants exhibit excellent biodegradability char-
acteristics, as long as they do not contain highly-branched
substituents. One type of surfactant useful in the present
invention has the formula
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9753
)a (R )n Z ~(CH2)m-1 -R X
Rl
wherein R1 is Cl to C4 alkyl or hydroxyalkyl; R is C5 to
C30 straight or branched chain alkyl or alkenyl/ alkyl
phenyl, or
X Rl- N-(CH2)-S ; wherein s is from 0 to 5;
Rl
R is Cl to C20 alkyl or alkenyl; a is 0 or 1, n is 0 or 1,
and a is 1 only when n is 1; m is from 1 to 5; zl and z2 are
each selected from the group consisting of
O O O O H H O o H H o
I o, o c, o, o ll o, c w, 1 11, _o_l~ l;! o,
and wherein at least one of said groups is an ester, reverse
ester, amide or reverse amide; and X is an anion which
makes the compound at least water-dispersible, preferably
selected from the group consisting of halide, methyl sulfate,
sulfate, and nitrate, preferably methyl sulfate, chloride,
bromide or iodide.
Particularly preferred cationic surfactants of this
type are the choline ester derivatives having the following
formula:
- 15 -
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:11)97S3
O CH
R -C-O-CH2CH2-~ -CH3 X
as well as those wherein the ester linkage in the above
formula is replaced with a reverse ester, amide or reverse
amide linkage.
Particularly preferred examples of this type of cat-
ionic surfactant include stearoyl choline ester quaternary
ammonium halides (R2 = C17 alkyl), palmitoyl choline ester
quaternary ammonium halides (R2 = C15 alkyl), myristoyl
choline ester quaternary ammonium halides (R2 = C13 alkyl),
lauroyl choline ester ammonium halides (R = Cll alkyl), and
tallowyl choline ester quaternary ammonium halides
(R = C15-C17 alkyl).
Additional preferred cationic components of the
choline ester variety are given by the structural formulas
below, wherein p may be from O to 20
O O CH
R -O-C-(CH2)P~-O-CH2CH2- -CH3 X
H3
X CH3- F_CH2_CH2-O-C-(CH2)P-C-O-CH2-CH2-F -CH3 X
CH3 CH3
16
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11~9753
The preferred choline-derivative cationic substances,
discussed above, may be prepared by the direct esterification
of a fatty acid of the desired chain length with dimethyl-
aminoethanol, in the presence of an acid catalyst. The
reaction product is then ~uaternized with a methyl halide,
forming the desired cationic material. The choline-derived
cationic materials may also be prepared by the direct
esterification of a long chain fatty acid of the desired
chain length together with 2-haloethanol, in the presence of
an acid catalyst material. The reaction product is then
used to quaternize trimethylamine, forming the desired
cationic component.
Another type of cationic surfactant, useful
in the compositions of the present invention, has the formula
R Rl
R -O[(CH)nO]y~(Z )a~(R )t-Z -(CH2)m-N -R X
Rl
In the above formula, each Rl is a Cl to C4 alkyl or hydroxy-
alkyl group, preferably a methyl ~roup. Each R2 is either
hydrogen or Cl to C3 alkyl, preferably hydrogen. R3 is a
C4 to C30 straight or branched chain alkyl, alkenylene, alkyl
phenyl, or alkyl benzyl group, preferably a C8 to C18 alkyl
group, most preferably a C12 alkyl group. R4 is a Cl to
C10 alkylene or alkenylene group. n is from 2 to 4,
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preferably 2; y is from l to 20, preferably from about 1 to
lO, most preferably about 7; a may be 0 or l, t may be 0 or
l, and a can ~e l only when t is l; and m is from l to 5,
preferably 2. z2 is selected from the group consisting of:
O O O O H ~I O O H ~I O
Il 11 il 1~ 1 1 11 11 1 1 ~1
-C-O-, -C-, -O-, -O-C-O-,-C-N~ C~ O-C~ -N-C--O- ,
zl is selected from the group consisting of
,
O O O H H O H O
Il 11 11 1 1 11 1 11
-C~O-, -C-, -C-N-, -N-C-, -N-C-o-r
and wherein at least one of said zl and z2 groups is
selected from the group consisting of ester, revers~ ester, ~mide
and reverse amide. X is an anion which w.ill make the compound
at least water-dispersible, and is selected from the group
consisting of halides, methyl sulfa~e, sulfate, and nitrate,
particularly methyl sulfate, chloride, bromide and iodide.
Mixtures of the above structures can also be used
Preferred embodiments of th~s type of ca~ionic component
are the choline ester derivatives ~Rl is a methyl group and
z2 is an ester or reverse ester group), particular ormulas
of which are given below, in which t is 0 or l, y is from l
to 20 and R3 and X are defined a~ove.
O CIl
~3-o~c~2cH~o)y-~cEl2)t-c-o-cE~2-cEI~-N -Ci~3 X
CEl~
.
975;~
O CH
R -O(CH2CH20)y~C~CH2~N -CH3 X
C 3
R3 O(IHCH O) _II_CH2_~1+_CH3 X
CH3
CH3 O CH
R3-o(CHCH20)y~(CH2)t~C~~CH2~CH2~~ -CH3 X
CH3
2 2 y ( 2)t ~--C~l2cH2-N -CH3 X-
O H H a CH
R -O(CH2CH20)y~C~C=C~C~O~CH2CH2~N -CH3 X
H3
R -o(cH2cH2cH2cH2o)y-c-cH2-~ -CH3 X
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9753
o CH
R3-o(cH2cH2cH2cH2o)y-(cH2~t 1 2 2 1 3
Mixtures of any of the above cationic surfactants
may also be used in the compositions of the present invention.
The preferred choline derivatives, described above,
may be prepared by the reaction of a lony chain alkyl poly-
alkoxy (preferably polyethoxy) carboxylate, having an alkyl
chain of desired length, with oxalyl chloride, to form the
corresponding acid chloride. The acid chloride is then
reacted with dimethylaminoethanol to form the appropriate
amine ester, which is then quaternized with a methyl halide
to form the desired choline ester compound. Another way of
preparing these compounds is by the direct esterification of
the appropriate long chain ethoxylated carboxylic acid
together with 2-haloethanol or dimethyl aminoethanol, in the
presence of heat and an acid catalyst. The reaction product
formed is then quaternized with methylhalide or used to
quaternize trimethylamine to form the desired choline ester
compound.
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Alkaline Component
The compositions of the present invention also
contain from about 1% to about 25%, preferably from about
5% to about 20%, and most preferably from about 8% to about
16%, of an inorganic alkalinity-producing component, pre-
ferably as the compositions' sole alkalinity-producing
component. These components must be chosen such that they
are relatively insoluble in the cationic or nonionic/cationic
surfactant component included in the composition. Thus,
alkalinity sources such as monoethanolamine and triethanolamine,
which are often used as alkalinity sources in detergent
compositions, are not useful in the compositions of the
present invention, since they tend to be too soluble in
cationic/nonionic surfactant mixtures. The particular alkaline
component used must also be selected and included in an amount
such that the detergent composition forms a solution having
a pH of from about 8 to about lO, preferably from about 8.5
to about 9.5, within about 3 minutes, preferably within about
2 minutes, most preferably within about 1 minute, after it
is placed in 100F water at a concentration of about 0.15% by
weight. Thus, anhydrous borax is not useful in the compos-
itions of the present invention since it dissolves too
slowly to give the desired pH within the required time period.
Preferred alkaline com~onents for use in the compos-
itions of the present invention include sodium tetraborate
decahydrate (Na2B4O7'10H2O; borax decahydrate), sodium
tetraborate pentahydrate (Na2B4O7'5H2O; borax pentahydrate),
sodium carbonate, and mixtures of these components.
Particularly preferred alkalinity-producing components are
borax pentahydrate
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and borax decahydrate and mixtures thereof.
Preferred embodiments of the present invention add-
itionally contain from about 2 to about 25%, preferably
from about 2 to about 16~, and most preferably from about
3 to about 10~, of a fatty amide surfactant. The ratio
of the total cationic and nonionic surfactant components
contained in the composition to the amide component is
from about 5:1 to about 50:1, preferably from about 8:1 to
about 25:1. These preferred embodiments yield excellent
particulate soil removal performance, as well as improved
soil anti-redeposition characteristics, and the develop-
ment is described in Canadian Patent Application, Serial
No. 306,559, Cambre, filed June 29, 1978.
The compositions of the present invention may also
contain additional ingredients generally found in laundry
detergent compositions, at their conventional art-
established levels, as long as these ingredients are
compatible with the nonionic and cationic components.
For example the compositions may contain up to about 15%,
preferably up to about 5%, and most preferably from about
0.1% to about 2% of a suds suppressor component. Typical
suds suppressors include long chain fatty acids, such as
those described in U.S. Patent 2,954,347, issued September
27, 1960, St. John, and combinations of certain nonionics
therewith as disclosed in U.S. Patent 2,954,348, issued
September 27, 1960, Schwoeppe. Other suds suppressor
components useful in the compositions of the present
invention include, but are not limited to, those described
below.
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11097S3
Preferred suds suppressing additives are described
in U.S. Patent 3,933,672, issued January 20, 1976,
Bartolotta et al., relative to a silicone suds controll-
ing agent. The silicone material can be represented by
alkylated polysiloxane materials such as silica aerogels
and xerogels and hydrophobic silicas of various types.
The silicone material can be described as a siloxane
having the formula:
~ 5 ~,
t R~
wherein x is from about 20 to about 2,000, and R and R'
are each alkyl or aryl groups, especially methyl, ethyl,
propyl, butyl and phenyl. The polydimethylsiloxanes (R
and R' are methyl) having a molecular weight within the
range of from about 200 to about 200,000, and higher,
are all useful as suds controlling agents. Additional
suitable silicone materials wherein the side chain
groups R and R' are alkyl, aryl, or mixed alkyl and
aryl hydrocarbyl groups exhibit useful suds controlling
properties. Examples of such ingredients include
diethyl-, dipropyl-, dibutyl-, methyl- ethyl-, phenyl-
methyl-polysiloxanes and the like. Additional useful
silicone suds controlling agents can be represented
7~3
by a mixture of an alkylated siloxane, as referred to
hereinbefore, and solid silica. Such mixtures are pre-
pared by affixing the silicone to the surface of the
solid sil ca. A preferred silicone suds controlling
agent is represented by a hydrophobic silanated (most
preferably trimethylsilanated) silica having a particle
size in the range from about 10 millimicrons to 20
millimicrons and a specific surface area above about
50 m2/gm~ intimately admixed with dimethyl silicone
fluid having a molecular weight in the range from about
500 to about 200,000 at a weight ratio of silicone to
silanated silica of from about 19:1 to about 1:2. The
silicone suds suppressing agent is advantageously
releasably incorporated in a water-soluble or water-
dispersible, substantially non-surface-active detergent-
impermeable carrier.
Particularly useful suds suppressors are the self-
emulsifying silicone suds suppressors, described in U.S.
Patent No. 4,136,045, Gault et al, issued January 23,
1979. An example of such a compound is DB-544*, commer-
cially available from Dow Corning, which contains a
siloxane/glycol copolymer together with solid silica
and a siloxane resin.
Microcrystalline waxes having a melting point in
the range from 35C-115C and a saponification value
of less than 100 represent additional examples of a
preferred suds regulating component for use in the
subject compositions, and are described in detail, in
U.S. Patent 4,056,481, Tate, issued November 1, 1977.
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The microcrystalline waxes are substantially water-insoluble,
but are water-dispersible in the presence of organic surfact-
ants. Preferred microcrystalline waxes have a melting point
from about 65C to 100C, a molecular weight in the range
from 400-1,000; and a penetration value of at least 6,
measured at 77F by ASTM-D1321. Suitable examples of the
above waxes include: microcrystalline and oxidized micro-
crystalline petrolatum waxes; Fischer-Tropsch and oxidized
Fischer-Tropsch waxes; ozokerite; ceresin; montan wax;
beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional
preferred suds suppressant for use herein. These preferred
phosphate esters are predominantly monostearyl phosphate
which, in addition thereto, can contain di- and tristearyl
phosphates and monooleyl phosphates, which can contain di-
and trioleyl phosphates.
The alkyl phosphate esters frequently contain
some trialkyl phosphate. Accordingly, a preferred phosphate
ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 mole percent of di-
alkyl phosphate and up to about 5 mole percent of trialkyl
phosphate.
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Other adjunct components which may be included in
the compositions of the present invention, in their
conventional art-established levels for use (i.e.,
from O to about 40%), include anionic, zwitterionic
and ampholytic cosurfactants, detergency builders,
bleaching agents, bleach activators, soil-suspending
agents, corrosion inhibitors, dyes, fillers, optical
brighteners, germicides, pH adjusting agents, enzymes,
enzyme-stabilizing agents, perfumes, fabric soEtening
components, static control agents, and the like. How-
ever, because of the numerous and diverse performance
advantages of the preferred compositions of the present
invention, certain types of adjunct components, such
as detergency builders, static control agents, fabric
softening agents and germicides, will not usually be
necessary.
Examples of cosurfactants and detergency builders,
which may be used in the compositions of the present
invention, are found in U.S. Patent 3,717,630, Booth,
Ca "O~
issued February 20, 1973, and U.S. Patent Application
306, 't7'f 19 7"
Serial No. 311,~ O, Murphy, filed June 29, ~g~.
The compositions of the present invention may be
manufactured and used in a variety of forms, such as
solids, powders, granules, pastes, or liquids. The
compositions are particularly well suited for incorp-
oration into substrate articles for use in the home
laundering process. Examples of such articles are
described in U.S. Patent No. 4,170,565, Flesher et al.,
issued October 9, 1979; U.S. Patent 4,095,946,
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~1~9753
Jones et al., issued June 20, 1978; U.S. Patent
4,118,525, Jones,issued October 3, 1978; and U.S.
Patent 4,113,630, Hagner et al, issued September 12,
1978. These articles consist of a water-insoluble
substrate which releasably incorporates an effective
amount, preferably from about 3 to 120 grams, particu-
larly from about 20 to 80 grams, of the detergent
compositions of the present invention. When the
compositions of the present invention are used in
substrate articles it may be advantageous to include
the solubilization aids, described in U.S. Patent No.
4,199,464, Cambre, issued April 22, 1980, and the anti-
bleeding components, described in U.S. Patent No.
4,199,465, Rodriguez, issued April 22, 1980.
The compositions of the present invention are used
in the laundering process by forming an aqueous solution
containing from about 0.01 (100 parts per million) to
0.3~ (3,000 parts per million), preferably from about
0.02 to 0.2%, and most preferably from about 0.03 to
about 0.15%, of the compositions of the present inven-
tion, and agitating the soiled fabrics in that solution.
The fabrics are then rinsed and dried. When used in
this manner, the preferred compositions of the present
invention yield exceptionally good particulate soil,
oily body soil and greasy/oily soil removal performance,
as well as fabric softening, static control, and dye
transfer inhibition benefits to the fabrics
A
9753
.
laundered therewith. Further, the compositions are stable
upon storage, and exhibit a minimum of hydrolysis of the
- cationic component when placed in laundry solution.
All percentages, parts, and ratios used herein are by
S weight unless o~herwise specified.
The following nonlimiting examples illustrate the
compositions and method of the present invention.
'
. '.
....
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97S3
,
EXAMPLE I
The storage and wash solution stability of detergent
compositions containing various types of alkalinity-producing
components were tested in the following manner.
The detergent compositions tested contained the cationic
surfactant having the formula:
- O CH3
Il +l
H35 C O CH2CH2- ~-CH3 Cl
CH3
present in an amount yielding a concentration of 143 ppm in
the test wash solution, together with the condensation
product of coconut alcohol with 5 moles of ethylene oxide~
present in an amount yielding a concentratioll o~ 357 ppm in
the test wash solution. The compositions additionally
contained the alkalinity-producing components, given in ~he
table below, in the amounts specified. Each composition was
added to a four liter beaker, containing abou~ three liters
o water at 100F (i grains per gallon of mixed calciurn and
magnesium hardness). The solutions were s~irred for ~bout
ten minutes and samples were taken at the end o~ tha~ ~ime_
For each solution, the pH and the percent loss o~ the cationic
component was determined. The percent los~ of the cationic
component in the wash solution was determined by mixed
indicator titration.
In the mixed indicator titration, a wash solution
sample, containing the cationic surfactant (some of which
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9~53
had been hydrolyzed), was combined with a mixed indica-
tor of cationic- and anionic-complexing dyes, in a
water-chloroform system. A known amount of 0.00400N
Cll 8 linear alkylbenzene sulfonate was added to
provide an excess of anionic surfactant. A complex of
anionic surfactant, hydrolysis ragment and cationic
dye was formed; this complex was soluble in the chloro-
form layer, giving it a red-pink color. The solution
was then titrated with an approximately 0.00400N
lQ solution of Hyamine* 1622 (di-isobutyl phenoxy ethoxy
ethyl dimethylbenzyl ammonium chloride, available from
Rohm and Haas), destroying the dye/surfactant complex
and the pink color. A color change to grey in the
chloroform layer indicated the end point, and the
amount of the hydrolysis fragment present was calcula-
ted, based on the amount of Hyamine* used in the
titration.
The percent loss of the cationic component during
storage was determined by taking a sample (approximately
6 grams) of each detergent composition, placing the
sample in a closed Petri dish, and storing the dishes,
for a four week period, under conditions of 80F/60%
relative humidity; 80F/80% relative humidity; and
120F/60% relative humidity. The percent loss of the
cationic component was determined at various stages dur-
ing storage by the mixed indicator titration technique,
described above. The data obtained are summarized in
the table belo~:
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11~9753
o
a~
,
~ r
h
O
0 Ul _
I,!C O I I ~
0 3 o 'I ~ I t
_I I V V V V V
er U') o _
dP--t`
q~ In o
--~ ~
0 ~,1
0~ ~n ~ c~
O ~ ~D ~ r~ I ~ I ~n co ' ~D ~ t` r`
~r
h ~: _ u) n I
w ~-,~ ~ n o~ ~ r~
rl O
Q~ E3 0
u7 r~ ~~ .
o n ~ o o ~ ~n o L-~ ~D O n
, ~ ~r ~D O ~ ~` ~r cn ,1 ~ ~r
o
O
0 C~
Ei ~ 0
,1 ~ ~ m Q
O ~1 m o ~,
O
S ~ . .
a) ~ ~ x x
o a~
O S~ O O O O
m m u~
U~
-- 31 --
.. ..
.... ,.~ , ..... .
39'7~3
The above data demonstrate that acceptable wash and
storage stability of the cationic component is obtained when
the alkalinity-producing components defined herein are,
included in'the detergent compo~itions in the,required
amounts~
Similar results are obtained where the nonionic component.
used above is replaced by the condensation product of C10
alcohol with three moles of ethylene oxide, the condensation
product of coconut alcohol with six mole~ of ethylene oxid~,
the condensation product of coconut alcohol with 7 moles o~
ethylene oxide, the condensation product o C12 13 alcohol
with 6.5 moles of ethylene oxide, the condensation p~oduc~
of C14 15 alcohol with 7 moles of ethylene oxide, or th~
condensation product of C12 13 alcohol with three moles of
ethylene oxide stripped so as to remove the lower ethoxylate
and unethox~lated fractions.
Excellent stability results are also obtained where th2
detergent composition includes nonionic to cationic surfactant
weight ratios of about 100:1, 50:1, 35:1, 25:1, 15:1, 10:1,
7:1, 5:1, 4:1, 10:3, 20:7, 20:9, 2:1, or 5:3.
Excellent results are also obtained where the nonionic
component, used above, is replaced by a mixture of ~he
condensation product of C14 15 alcohol with three moles o~
ethylene oxide together with the condensation product of
C14 15 alcohol with 7 moles of ethylene oxi.de, in a ratio o
lower ethoxylate nonionic to higher etlloxylate nonionic o~
about 2:1; a mixture of the condensation product of C14 15
alcohol with 3 moles of ethylene oxide together with the
condensation product o~ myristyl alcohol with 10 moles of
9753
of ethylene oxide, in a ratio or lower ethoxylate nonionic
to higher ethoxylate nonionic of about 1:1; or a mixture o~
the condensation product of coconut alcohol with 5 moles of
ethylene oxide together with an alkyl glyceryl ether havi.ng
the formula
C12EI25-0CH2- 1CH-CH2
OH
in a ratio o~ alcohol ethoxylate to gl~ceryl ether o abou~
7:3.
Substantially similar stability results are also ob~ained
where the cationic component is replaced by those havinc3 the
formulae given below, or mixtures of those surfac~ants:
O CH
Il 1 3
C16H33 C O-CH2CH2- N-CH3 Br
CH3
O o CH3
i2 25 C CH2CH2_c_o_cH2cH2-N~-C~3 Cl-
CH3
CH Ol CH3
. Br CH3- I_cH2cH2_0 C (C 2)12 2 2 j 3
CEI3 CH3
- 33 -
97S3
o fH3
10 21 (CH2cx2o)lo-c~cH2-N -CH3 Cl
C 3
CIH3 IC 3
S C13H27--(CHCH2)11-C CH2 ll CH3 B
EX~MPLE II
A heavy-duty liquid laundry detergen~ composition,
having the formula given below, is produced by mixing together
the following components in the stated proportions.
Component Weight %
0 CH
Il 1 3
17H35 C -CH2cH2- N-CH3 Cl 26.1
C 3
Condensation product of coconut
alcohOl with 5 moles of
ethylene oxide 51,5
Borax 10 H2O 11~5
Ethanol ~,o
Minors (suds suppressor, perfume,
brighteners, etc.) balance ~o 100
This composition provides excellent removal of both
clay and greasy/oily soils, as well as stora~e and wash
solution stability o the cationic component.
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EX~LE III
A paste-form laundry detergent composition, having the
formula given below, is prepared by mixing together the
following components in the stated proportions~
Component ~eight %
O CH
ll 1 3
C17E135-C-O-CH2CH2-+N-CH3 Cl 26.0
CH3
Csndensation product of coconut
lo alcohol with 5 moles of
ethylene oxide 5~5
C12_16 fatty acid ammonia amide 7~0
Borax 5 H20 13.0
Minors tsuds suppressor, perfume,
brightener, etc.) balance to .lOO
This composition, when used as a paste or in a substrate
article, as described hereinafter, prov.i.des excel:Len~ remova~
of both clay and greasy/oily soils, as well as storage and
wash solution stability of the cationic component~
..... .. .
11~)9~53
EXAMPLE IV
A substrate article, for use in the automatic
machine laundering of fabrics, is made by coating one
side of an 8" x ll" sheet of a Scott 8050* Industrial
Towel, having an air permeability o, about 130 cu. ft./
min./sq. ft., a basis weight of about 77.5 grams per
square yard, and a thickness of 44 mils, with about 50
grams of the detergent composition having the formula-
tion given below. The composition is made by intimately
mixing the nonionic and cationic surfactants together,
at a temperature of about 80 C, to form a thick paste,
and then mixing in the remaining components.
Component Weight %
o CH3
C17H35-C-O-CH2CH2- N~CH3 Cl 21.4
Condensation product of coconut
alcohol with 5 moles of ethylene
oxide 42.2
C12-16 fatty acid ammonia amide 5.9
Borax 5 H2O 10.8
Choline chloride 10.6
Zeosyl* 200 (a silica material having
an average particle size of about
2 microns, commercially available
from J. M. Huber Corp.) 9.1
An identical sheet of the paper towel is placed
over the coated side of the original sheet, and the
edges of the two sheets are sewn together so as to
enclose the composition. This article provides a
convenient method for introducing the compositions
of the present invention into the laundering
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9753
solution, as well as providing excellen~ cleaning performance,
and wash solution and storage stability of the cationic
component.
A substrate article may also be made by coating
one side of an 11" x 11" sheet of melt-blown polypropylene,
having a thickness of about 29 mils, a basis weight of about
58.5 grams per square yard, and an air permeability of
about 66 cubic ft./min./sq. ft., with about 60 grams of the
detergent composition described above, placing an identical
substrate sheet over the coated sheet, and heat sealing
together the edges of the two substrates, enclosing the
detergent composition within the article.
EXAMPLE V
A heavy-duty liquid laundry detergent composition,
having the formula given below, is prepared by mixing to-
gether the following components in the stated proportions.
Component Wt. %
O CH
Il ~ I _
CH3
Condensation product of C14 15
alcohol with 7 moles of ethylene oxide 47.7
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97S3
Borax-5 H20 12.0
Lauramide 7.0
Ethanol 10.0
Minors (suds suppressor,
perfume, brightener, etc.) balance to 100
This product, when used in an automatic laundering
operation, at a concentration of about 0.05%, provides excellent
removal of both particulate and greasy/oily soils, while exhibit-
ing stability of the cationic component in the wash solution
and during storage.
EXAMPLE VI
A substrate article, for use in the automatic launder-
ing operation, having the composition given below, is made
using the procedure outlined in Example IV, above, with Scott
8050* Industrial Towels as the substrate material.
Component Weight ~
o CH3
Il I
C17H3s-C-0 CH2CH2 1 3 24.6
CH3
Condensation product of coconut
alcohol with 5 moles of ethylene
oxide 61.6
C12_16 fatty acid ammonia amide 7.8
Borax 10 H20 4.2
Minors (suds suppressor, perfume,
brightener, etc.) balance to 100
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- - . ~
This article provides a convenient method for
introducing the compositions of the present invention
into the laundering solution, and, in addition, exhibits
excellent storage and wash solution stability for the
S cationic component.
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