Note: Descriptions are shown in the official language in which they were submitted.
~ 1332137
LIQUID DETERCiENTS CONTAINING ANlONlC SURFACTANT,
âUCCINATE BUILDER AND FATTY ACID
Stanton L. Boyer
` Technical Field
The present invention relates to liquid detergent compo-
sitions, preferably heavy-duty liquid detergents, containing an
anionic synthetic surfactant and a builder system comprising a
C12-C14 alkyl or alkenyl succinic acid or salt thereof (hereinafter
referred to as a "succinate") and a C12-C14 fatty acid or salt
thereof (hereinafter referred to as a "fatty acid") in a molar ratio
(calculated on an acid basis) of succinate to fatty acid of from
about 0.8 to about 2.4. Within this range, the succinate and
fatty acid mixture surprisingly provides a minimum of sudsing in
otherwise high sudsing detergents containing a significant amount
of anionic synthetic surfactant.
Background Art
British Patent 1,293,753, Fvans et al, published October 25,
1972, discloses dicarboxylate builders, including alkyl and alkenyl
succinates . Example 10 is a low-sudsing detergent containing 2%
dodecyl benzene- sulfonate, 6% of an 80:20 mixture of
; ~ tallow:coconut soap, and 6% disodium hexadecane-1,2-dicarbox~
ylate. This results in a molar ratio of dicarboxylate to C12-C14
fatty acid of about 2.7.
European Patent Application 28,850, van der Griend, pub-
lished May 20, 1981, discloses liquid detergents containing
nonionic surfactant, a small amount of C10-C15 alkylbenzene
sulfonate, builder and C7-C12 alkyl or alkenyl succinate as a
hydrotrope. Examples D-M contain 0-1% LAS, 5 ~ 5-6% nonenyl
succinic anhydride and 1.2-3% coconut fatty acid . The lowest
j , 30 ~ lratio of suçcinate to fatty ac;d present is about 1.7.U.S. Patent 3,776,851, Cheng, issued December 4, 1973,
discloses detergents containing 5-70% tetrahydroxysuccinic acid
builders. Example 4 contains 20~ tetrahydroxysuccinic acid and
1.89~ 80:20 tallow:coconut soap as a suds suppressor.
. ,~
U.S. Patent 3,707,511, Lamberti et al, issued December 26,
1972, discloses that C10-C16 alkyl or alkenyl succinates are useful ; '
as suds boosters and stabilizers for detergents, particularly those
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~ 1332137
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containing alkylaryl sulfonates. There are no examples of compo-
sitions containing succinate and fatty acid.
Summary of the Invention
The present invention relates to a liquid detergent
composition comprising, by weight:
(a) from about 10% to about 50% of an anionic synthetic
surfactant;
(b) from about 2% to about 25% of a C12-C14 alkyl or
alkenyl succinic acid, or salt thereof; and
(c) from about 196 to about 15% of a C12-C~4 fatty acid, or
salt thereof;
the molar ratio of (b) to (c), on an acid basis, being from about
0.8 to about 2.4.
Detailed Description of the Invention
The detergent c:ompositions of the present invention contain
anionic synthetic surfactant and succinate and fatty acid builder~
in a molar ratio (calculated on an acid basis) of succinate to fatty
- acid of from about 0.8 to about 2.4, preferably from about 0.9 to
about 1.8, more preferably from about 1.0 to about 1.4. Within
these ratios, the succinate and fatty acid provide a minimum of
~,
suds in otherwisa high sudsing detergents containing a significant
amount (e.g., greater than 10% by weight) of anionic synthetic
surfactant. This is particularly surprising given that one would
have expected that sudsing would gradually increase with
increasing levels of succinate and decrease with increasing levels
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of fatty acid.
Anionic Synthetic Surfactant
The detergent compositions herein contain from about
1096 to about ~5096, preferably from about 13% to about 40%, more
~ 30 preferably from about 16% to about 30%, by weight, on an acid
.~ basis, of an anionic synthetic surfactant. Anionic synthetic
¦~ surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al,
issued August 25, t981, and in U.S. Patent 3,919,678, Laughlin
et al, issued Decen~ber 30, 1975 .
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Useful anionic surfactants include the water-soluble salts,
particularly the alkali metal, ammonium and alkylolammonium
(e.g., monoethanolammonium or triethanolammonium) salts, of
organic sulfuric reaction products having in their molecular
structure an alkyl group containing from about 8 to about 20
carbon atoms and a sulfonic acid or sulfuric acid ester group.
(Included in the term "alkyl" is the alkyl portion of aryl groups.~
Examples of this group of synthetic surfactants are the alkyl
sulfates, especially those obtained by sulfating the higher alcohols
(C8-C1 8 carbon atoms) such as those produced by reducing the
glycerides of tallow or coconut oil; and the alkylbenzene sulfo-
nates 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 United States Patents
2 ,220,099 and 2 ,477 ,383.
Other anionic surfactants herein are the water-soluble salts
of: paraffin sulfonates containing from- about 8 to about 24
- (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether
sulfonates, especiaily those ethers of C8 18 alcohols (e.g., those
20 derived from tallow and coconut oil); alkyl phenol ethylene oxide
ether sulfates containing from about 1 to about 4 units of
ethylene oxide per molecule and from about 8 to about 12 carbon
atoms in the alkyl group: and alkyl ethylene oxide ether sulfates
containing about 1 to about 4 units of ethylene oxide per molecule
25 and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water~
soluble salts of esters of alpha sulfonated fatty acids containing
from about 6 to 20 carbon atoms in the ~tty acid group and from
about 1 to 1û carbon atoms in the ester group water-soluble! salts
30 of 2-acyloxy-alkane- 1-sulfonic acids containing from about 2 to 9
carbon atoms in the acyl group and from about 9 to about 23
carbon atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing from about 12 to 24 carbon atoms; and
beta-alkyloxy alkane sulfonates containing from about 1 to 3
.,:.. ': . .~.'
:
4 _ ~ 3 3 ~ 1 3 7
carbon atoms in the alkyl group and from about 8 to 20 carbon
atoms in the alkane moiety.
Preferred anionic surfactants herein are the alkyl sulfates of
the formula
R0 ( C2 H40 ) X503M
wherein R is an alkyl chain having from about 12 to about 18
carbon atoms, saturated or unsaturated, M is a cation which
makes the compound water-soluble, especially an alkali metal,
ammonium or substituted ammonium cation, and x is from 0 to
about 4 . Preferably, R is a C1 2-C1 6 alkyl or hydroxyalkyl
group, especially a C12-C15 alkyl, and x is from about 0 to about
3.
Highly preferred anionic surfactants are the linear straight
chain alkylbenzene sulfonates in which the average number of
carbon atoms in the alkyl group is from about 12 to about 13, and
~; the C12 15 alcohol sulfates containing from 0 to about 3 ethytene
` ~ oxide units, as described above. Also preferred are mixtures of
these surfactants in a weight ratio of from about 3 :1 to about
1:3, preferably from about 2:1 to about 1:2. These anionics form
hardness, preferably magnesium, surfactants that are particularly
~; effective at lowering interfacial tension and removing greasy/oily
~ soils.
`~ Succinate Builder
~; The detergent compositions herein also contain from about 2%
to about 25~6, preferably from about 3% to about 20%, more pref-
erably from about 596 to about 15%, by weight of a succinate
`~ ~ builder of the general formula R-CH(COOH)CH2(COOH), wherein
R is C12-C14 alkyl or alkenyl group.
! ~ 1 Thesei succinate builders are preferably used in the form of
their water-soluble salts, including the sodium, potassium,
ammonium and alkanolammonium salts (e.g., mono-, di-, or
tri-ethanolammonium).
Specific examples of succinate builders include: lauryl
succinate, myristyl succinate, 2-dodecenyl succinate (preferred)
and 2-tetradecenyl succinate.
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~ 33~13~ ~
Fatty Acid
The compositions of the present invention further contain
from about 196 to about 15%, preferably from 2% to about 1096, more
preferably from about 3% to about 696, by weight of a C12-C14
fatty acid, or salt thereof.
Suitable fatty acids can be obtained from natural sources
such as plant or animal esters (e.g., palm kernel oil, palm oil
and coconut oil) or synthetically prepared (e.g., via the oxida-
tion of petroleum or by hydrogenation of carbon monoxide via the
10 Fisher-Tropsch process). Examples of suitable fatty acids for
use in the compositions of this invention include lauric, myristic,
coconut and palm kernel fatty acid. Preferred are saturated
coconut fatty acids, from about 5:1 to 1:1 (preferably about 3:11
weight ratio n~ixtures of lauric and myristic acid, and palm kernel
15 fatty acid.
- The succinate and fatty acid builders herein are calci-
um-selective builders, which means they preferentially control
~- calcium ion in the wash solution, rather than magnesium or other
hardness ions. It is believed that these calcium-selective builders
20 adequately control wash water hardness, preventing excessive
ihteractions with the anionic surfactant herein and with soils,
while allowing sufficient free hardness to cornplex some of the
anionic surfactant to produce a hardness surfactant (such as
magnesium linear alkylbenzene sulfonate) that is highly effective
25 at removing greasy and oily soils. Such hardness-surfactants
; -~ pack at the oil/water interface where they lower interfacial
tension and enhance removal of greasy/oily soils.
The liquid detergent compositions herein can optionally
contain any of the auxiliary ingredients known for use in
30 detergent cornpositions. These include cosurfactants, cobuilders,
neutralizing agents, buffering agents, phase regulants, solvents,
hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds
regulants, opacifiers, antioxidants, bactericides, dyes, perfumes,
and brighteners, such as those described in U . S.
~S
~.................................................................... .. ~ ,.. , . :, . - :
6 ~ 1 3 3 2 137
Patent 4,285,841, Barrat et al, issued August 25, 1981.
Preferred compositions herein include those
described in U.S. Patent 4,561,998, Wertz et al, issued
December 31, 1985, and U.S. Patent 4,507,219, Hughes,
issued March 26, 1985.
The compositions herein preferably contain from about 1% to
about 20%, more preferably from about 3% to about 15%, most
3 preferably from about 5% to about 10%, by weight of an
ethoxylated nonionic surfactant of the formula R1 (OC2H4)nOH,
wherein R is a C10-cl6 alkyl group (preferred) or a C8-C12
3 alkyl phenyl group, n is from about 3 to about 9, and said
nonionic surfactants has an HLB lhydrophile-lipophile balance) of
from about 9 to about 13, preferably from about 10 to about 13.
HLB is defined in detail in Nonionic Surfactants, by M.J. Schick,
Marcel Dekker, Inc., 1966, pages 607-613. These
ethoxylated nonionic surfactants suspend
hardness-surfactants in the wash water solution.- They are used
at a level high enough to prevent~ excessive precipitation of
hardness-surfactants at the oil/water interface lwhich makes soil
removal more difficult), but low enough to allow for the desired
~ adsorption and packing at the interface.
1~ ~ The compositions herein can be formulated to have a pH of
from about 7 . 5 to about 12, more preferably from about 8 to
about 11. Certain preferred compositions herein are alkaline
2 5 compositions that are particularly useful in combination with
,
peroxyacid bleach compositions, which generally have a pH of
from about 2 to about 5 for best bleach stability. Such alkaline
compositions have a pH of from about 9 to about 12, preferably
from about 9 . 5 to about 11 . 5, more preferably from about 10 to
about 11. They preferably contain from about 296 to about 1596,
more preferably from about 4% to about 10~, by weight of
monoethanolamine. The combination of such an alkaline
composition and peroxyacid bleach preferably delivers a wash
~; water pH of from about 7.8 to about 9, preferably from about 7.9
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to about 8.5, which is desired for good bleaching performance, a
minimum of fabric yellowing, and a minimum of bleach
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decomposition by the monoethanolamine.
The following examples illustrate the compositions of the
present invention.
All parts, percentages and ratios used herein are by weight ~ ~
unless otherwise specified. ~; -
EXAMPLE I ` ~-`
The following composition was prepared by adding the ` `
components to a mixing tank in the order listed with continuous
mixing .
% Wt. % Wt. %
Components Assay Product Stock -~ -
Sodium C14_15 alkyl poly-
ethoxylate (2.25) sulfate 48 . 811 . 3 23 21 ,
C13 linear alkylbenzene
sulfonic acid 96.0 8.0 8.33 ~;
Sodium diethylenetriamine
pentaacetate -41.0 0.35 0,7
Propylene glycol 1 00 . 0 10.5 10.5 `~ ;~
Aonoethanolamine 100 . 0 5 . 0 3 . 0 ; i~Brightener mix 100.0 - 6.212
C12 13 alcohol polyethoxy~
- late ( 6 . 5 ~ * 1 00 . 0 9 . 0 7.0
: ~ 25 Ethanol 92.0 10.48 7.3
Potassium hydroxide 45.0 2.48 5.51
Sodium hydroxide 50.0 2.94 5.88
Boric acid 100.0 1.25 1~25
Water ' - - 5.65 ;
Sodium 2-dodecenyl succinate 80.0 5.53 6.9 ;~
C12 14 fatty acid 100.0 3.5 3.5
Citric acid 50.0 4.0 8.0
Calcium formate 10 . 0 0.12 1.2
TEPA-El ~,-18 80 . 0 3 . 0 3 . 75
pH trim to 10.5
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- 8 _~ 332 ~ 3'~
Protease enzyme (2.0 AU/g) 100.0 1.16 1.16
Amylase enzyme (375 AM. Utg) 100.0 0.16 0.16
Perfume 100.0 0.25 0.25
Dye 100 . 00 . 08 0 . 08
Water - to 100% 3 . 25
Pasl:e also contains 16.296 ethanol and 35% water
2Contains 32.2% monoethanolamine, 32.2% water, 32.2% C12 13
alcohol polyethoxylate (6.5), and 3.36% of brightener.
* Alcohol and monoethoxylated alcohol removed.
** Tetraethylene pentaimine ethoylated with 15-18 moles (avg.
of ethylene oxide at each hydrogen site.
The above composition is preferably used in combination with
the following liquid diperoxyacid bleach composition. The liquid
bleach composition was prepared by high shear mixing of the
components in an Eppenbach mixer while in an ice bath. The
DPDA and water were added to the mixer before turning the
mixer on. The suds suppressor was added to minimize foaming
while mixing and to minimize air entrapment in the finished
composition. The other components were added in the order
listed at the indicated times after turning on the mixer.
Grams Wt.% Time
; 1 ,1 2-Diperoxydodecanedioic -
acid tDPDA( (26.68%
active slurry ) 10,821.6 18.0 0 ;
Water (additional~ 1896 11.8 0 -~
Suds suppressor 12.8 0.08 l min.
C13 linear alkylbenze *
sulfonic acid (96% active ) 417.8 2.5 3 min.
Sodium cumene sulfonate I I
(50% active ) 463.4 1.45 3 min.
Dipicolinic acid 1.6 0.01 3 min.
Sodium sulfate 641.6 4.0 1 hr.25 min.
Magnesium sulfate 1684.2 10.5 2 hr.10 min.
Sodium hydroxide (5096
active ) 104 0.32 3 hr.10 min.
Balance primarily water.
:; - g - ::
;i ~ 3 3 2 1 .'~ 7 :`
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After 3 hr. 30 min., the ptl of the composition was
!~ determined to be 3 . 20 at 20C . After 4 hr . 10 min ., the pH was
again determined to be 3 . 20 at 20C and the mixer was turned
off~ The composition was a stable suspension of the ingredients
and had a viscosity of about 350 cps at about 20C. The DPDA
had an average particle size of about 2~5 microns.
The above describes the preferred process for making the
composition since high shear mixing of the components in an ice
bath, their order of addition and the approximate times of
addition have all been found to be important to obtain the desired
physical stability.
The compositions are preferably used in a volume ratio of
detergent composition to liquid bleach of about 5 . 5 :1 . The
detergent composition is designed for a usage level of about 0 . 55
cups in a typical U.S. Iaundering process. This delivers a
concentration of product in the wash water of aboùt 0 . 22% by
weight. Usage of about 0.1 cups (i.e., about 25 ml) of the
- liquid bleach delivers about 10 ppm of available oxygen to the
wash water. The detergent composition and liquid bleach are
preferably simultaneously codispersed from a dual compartment
bottle at a volume ratio of detergent to bleach of about 5.5:1.
¦~ The mixture of the succinate and fatty acid builders in the
above detergent composition is preferred because it causes less
fabric yellowing and measuring cup residue than an all fatty acid
formula when used with the above liquid bleach.
EXAMPLE I I
Other compositions of the invention, which can be prepared
: , .
by adding the components to a mixing tank in the order listed
with continuous mixing, are as follows.
Components A B ;~
Sodium C14_15 alkyl poly-
ethoxylate (2.25) sulfate 12.7 8.1 ~
Sodium C13 linear alkylbenzene - ~ -
sulfonate 8.5 3.9
3 5
,,-" ;",~ ", ,, "~
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i, - 10 -
1 33~3~
Sodium diethylenetriamine
pentaacetate 0 . 3
Propy lene glycol 8 . 5
Monoethanolamine 2 . 0 5 . 4
C12-13 alcohol polyethoxy-
late ~6.5)* 5.0
C12-C16 alkyldimethylamine oxide 6.6
Ethanol 4. 0
Sodium toluene sulfonate 8 . 0
Sodium 2-dodecenyl succinate 11 . 0 15 . 0
C12-14 fatty acid 7.0 7.0
Citric acid 4.0 2.0
Calcium formate 0.12
Sodium formate 0. 87 - :
TEPA E15-18 2.0 2.0
Protease enzyme (2.0-AU/g) ~ 0.75
Amylase enzyme ~375 AM. U/g) 0.16 -
~: Water and minors - Balance to 100%
WHAT IS CLAIMED IS~
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