Carbonate built laundry detergent composition

Carbonate built laundry detergents having improved cleaning properties and comprising two ethoxylated fatty alcohol nonionic surfactants having different average numbers of carbon atoms in the fatty alcohol and average numbers of ethoxy groups, a sulfated ethoxylated fatty alcohol anionic surfactant, and an N-alkyl and/or unsaturated hydrocarbyl amine of an alkanoic acid or salt thereof as an amphoteric surfactant.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to novel laundry detergent compositions having a 
high water-soluble alkaline carbonate builder content, the use of which 
results in improved cleaning performance. 
2. Background Information Including Description of Related Art 
Laundry detergent compositions comprising a water-soluble alkaline 
carbonate are well-known in the art. For example, it is conventional to 
use such a carbonate as a builder in detergent compositions which 
supplement and enhance the cleaning effect of an active surfactant present 
in the composition. Such builders improve the cleaning power of the 
detergent composition, for instance, by the sequestration or precipitation 
of hardness causing metal ions such as calcium, peptization of soil 
agglomerates, reduction of the critical micelle concentration, and 
neutralization of acid soil, as well as by enhancing various properties of 
the active detergent, such as its stabilization of solid soil suspensions, 
solubilization of water-insoluble materials, emusigication of soil 
particles, and foaming and sudsing characteristics. Other mechanisms by 
which builders improve the cleaning power of detergent composition are 
probably present but are less well understood. Builders are important not 
only for their effect in improving the cleaning ability of active 
surfactants in detergent compositions, but also because they allow for a 
reduction in the amount of the surfactant used in the composition, the 
surfactant being generally much more costly than the builder. 
While laundry detergents containing a relatively large amount of carbonate 
builder are generally quite satisfactory in their cleaning ability, there 
exist situations wherein even better performance in the removal of certain 
types of soils comprising oily particulates and fatty deposits such as 
sebum, would be advantageous. Thus, any change in available carbonate 
built laundry detergent compositions which improves their ability to 
remove such soils is highly desirable. 
Possibly relevant to the invention claimed herein are U.S. Pat. No. 
4,265,790, issued May 5, 1981 to Winston et al.; U.S. Pat. No. 4,464,292, 
issued Aug. 7, 1984 to Lengyel; and U.S. Pat. No. 5,376,300 issued Dec. 
27, 1994 to Bolkan et al., each of which discloses detergent compositions 
comprising an ethoxylated long chain alcohol and a sulfate of an 
ethoxylated long chain alcohol as a combination of nonionic and anionic 
surfactants, and over 70 wt. % of anhydrous sodium carbonate (soda ash) as 
a detergent builder. 
SUMMARY OF THE INVENTION 
In accordance with this invention, a laundry detergent composition is 
provided wherein the solids content comprises at least about 60 wt. % of a 
water soluble alkaline carbonate builder; about 1.5 to about 10 wt. % of a 
first ethoxylated fatty alcohol nonionic surfactant, wherein the fatty 
alcohol is a C.sub.12 or C.sub.13 single alcohol, or a mixture of 
alcohols, a major amount, i.e., at least 50 wt. % of which contains 12 or 
13 carbon atoms, with an average of about 12.0 to about 13.0 carbon atoms, 
and the average number of ethoxy groups is about 1.0 to about 3.5; about 1 
to about 10 wt. % of a second ethoxylated fatty alcohol nonionic 
surfactant, wherein the fatty alcohol is a mixture of alcohols, a major 
amount, i.e., at least 50 wt. % of which contains 12 to 14 carbon atoms 
with an average of about 13.0 to about 13.8 carbon atoms and the average 
number of ethoxy groups is about 4 to about 7; about 1.0 to about 10.0 wt. 
% of a sulfated ethoxylated fatty alcohol anionic surfactant, wherein the 
fatty alcohol is a C.sub.12 or C.sub.13 single alcohol or a mixture of a 
alcohols, a major amount, i.e., at least 50 wt. % of which contains 12 or 
13 carbon atoms with an average of about 12 to about 13 carbon atoms, and 
the average number of ethoxy groups is about 1.0 to about 3.5; and about 
0.2 to about 30 wt. % of an amphoteric surfactant having the formula 
##STR1## 
wherein R is one or more alkyl groups each containing about 8 to about 20 
carbon atoms and/or one or more monovalent unsaturated hydrocarbyl groups 
each containing 1 to 3 ethylenic bonds and about 16 to about 18 carbon 
atoms, with a major amount, i.e., at least 50 wt. % of the R groups 
containing about 12 to about 16 carbon atoms; X is hydrogen or a 
monovalent cation; and n is zero or an interger of 1 to about 6. 
It has been found that the detergent compositions of this invention 
containing the specified second nonionic and amphoteric surfactants have 
an improved ability to remove soils caused by certain oily or fatty 
deposits, as compared with detergent compositions not containing such 
second nonionic and amphoteric surfactants. 
DETAILED DESCRIPTION OF THE INVENTION 
The water-soluble alkaline carbonate builder in the detergent composition 
of this invention may be, for example, an alkali metal carbonate, 
bicarbonate or sesquicarbonate, preferably sodium or potassium carbonate, 
bicarbonate or sesquicarbonate, and most preferably sodium carbonate. A 
combination of more than one of such compounds may be used, e.g., sodium 
carbonate and sodium bicarbonate. The total water-soluble alkaline 
carbonate may be present in an amount, for example, of at least about 60 
wt. %, preferably about 70 to about 85 wt. %. If a combination of alkali 
metal carbonate and bicarbonate is used as the water-soluble carbonate, 
then the alkali metal carbonate, e.g., sodium carbonate, is preferably 
used in an amount of about 70 to about 84 wt. % and the alkali metal 
bicarbonate, e.g., sodium bicarbonate, in an amount of about 1 to about 15 
wt. %. All the foregoing percentages are based on the weight of total 
solids in the composition. 
The fatty alcohol of the first ethoxylated fatty alcohol nonionic 
surfactant in the detergent compositions of the invention is a single 
C.sub.12 or C.sub.13 alcohol, or a mixture of alcohols, preferably linear 
(straight chain) primary or secondary monohydric alcohols, a major amount, 
i.e., at least 50 wt. % of which contains 12 or 13 carbon atoms, with an 
average which is about 12.0 to about 13.0 carbon atoms, preferably about 
12.2 to about 12.7 carbon atoms, while the average number of ethoxy groups 
in said surfactant is about 1.0 to about 3.5, preferably about 2.5 to 
about 3.3. The first ethoxylated fatty alcohol nonionic surfactant may be 
present in the detergent composition in an amount of about 1.5 to about 10 
wt. %, preferably about 2.0 to about 5.0 wt. % based on the total weight 
of solids in the composition. 
The fatty alcohol of the second ethoxylated fatty alcohol nonionic 
surfactant in the detergent composition of the invention is a mixture of 
alcohols, preferably linear (straight chain) primary or secondary 
monohydric alcohols, a major amount, i.e., at least 50 wt. % of which 
contains 12 to 14 carbon atoms, with an average which is about 13.0 to 
about 13.8 carbon atoms, preferably about 13.2 to about 13.7 carbon atoms, 
while the average number of ethoxy groups in said surfactant is about 4 to 
about 7, preferably about 4.1 to about 6. The second ethoxylated fatty 
alcohol nonionic surfactant may be present in the detergent composition in 
an amount of about 1 to about 10 wt. %, preferably about 1 to about 6.7 
wt. % based on the total weight of solids in the composition. 
The fatty alcohol of the sulfated ethoxylated fatty alcohol anionic 
surfactant in the detergent composition of the invention is a single 
C.sub.12 or C.sub.13 alcohol or mixture of alcohols, preferably linear 
(straight chain) primary or secondary monohydric alcohols, a major amount, 
i.e., at least 50 wt. % of which contains 12 to 13 carbon atoms, with an 
average which is about 12 to about 13 carbon atoms, preferably about 12.2 
to about 12.7 carbon atoms while the average number of ethoxy groups in 
the anionic surfactant is in the range of about 1.0 to about 3.5, 
preferably about 2 to about 3.3. The sulfated ethoxylated fatty alcohol 
anionic surfactant may be present in the detergent composition in an 
amount of about 1.0 to about 10.0 wt. %, preferably about 2.7 to about 7.5 
wt. % based on the total weight of solids in the composition. 
The first ethoxylated fatty alcohol nonionic surfactant and the sulfated 
ethoxylated fatty alcohol anionic surfactant present in the detergent 
compositions of this invention as described previously may be 
advantageously produced by partially sulfating a batch of said first 
nonionic surfactant to an extent such that a mixture of anionic sulfated 
and nonionic unsulfated surfactants is produced which when compounded with 
the other components of the detergent composition yields a composition 
containing percentages of first nonionic surfactant and anionic surfactant 
within the ranges described previously for each surfactant. A process for 
thus preparing a mixture of first nonionic and anionic surfactants by 
partially sulfating a batch of first nonionic surfactant is disclosed in 
previously cited U.S. Pat. No. 4,464,292 of Lengyel. 
The amphoteric surfactant in the detergent compositions of this invention 
is an N-alkyl and/or unsaturated hydrocarbyl amine of an alkanoic acid or 
a salt thereof having the following formula. 
##STR2## 
wherein R is one or more alkyl groups each containing about 8 to about 20 
carbon atoms, and/or one or more monovalent unsaturated hydrocarbyl groups 
each containing 1 to 3 ethylenic bonds and about 16 to about 18 carbon 
atoms, X is hydrogen or a monovalent cation, preferably alkali metal, and 
n is zero or an integer of 1 to about 6. Preferably, a major amount, i.e., 
at least 50 wt. % of the R groups are linear (straight chain) alkyl 
containing 12 to 16 carbon atoms and n is 1 to 3, most preferably 2. 
Specific amphoteric surfactants which may be used are 
N-coco-.beta.-aminopropionic acid wherein "coco" indicates a mixture of 
alkyl and unsaturated hydrocarbyl groups corresponding to the fatty acids 
of coconut oil; N-lauryl(70 wt. %), myristyl(30 wt. 
%)-.beta.-aminopropionic acid; N-coco-.gamma.-aminobutyric acid; 
N-lauryl(70 wt. %), myristyl(30 wt. %)-.gamma.-aminobutyric acid; 
N-coco-glycine; and N-lauryl(70 wt. %), myristyl(30 wt. %) glycine. The 
preferred amphoteric surfactant is N-coco-.beta.-aminopropionic acid or 
its sodium salt. The amphoteric surfactant may be added to the composition 
as the free acid or alkali metal salt of the acid. However, regardless of 
the form in which the surfactant is added, it will exist in the 
composition as the free acid when the pH is below the isoelectric point or 
in ionic form, e.g., as the alkali metal salt of the acid, when the pH is 
above the isoelectric point. The amphoteric surfactant may be present in 
the detergent composition in an amount of about 0.2 to about 30, 
preferably about 0.5 to about 7 wt. %, based on the total weight of solids 
in the composition. 
In addition to the necessary components described previously, the detergent 
compositions of the invention may optionally contain a 
phosphorus-containing sequestering agent which may be, for example, an 
inorganic phosphate, e.g., a soluble orthophosphate, metaphosphate, 
pyrophosphate or preferably a polyphosphate, such as an alkali metal 
phosphate of the type delineated, preferably a sodium or potassium 
tripolyphosphate. Organic phosphonates may also be employed as the 
phosphorus containing sequestering agent, particularly 
aminoethylenephosphonates (e.g., sold by Monsanto Company under the 
trademark "DEQUEST"), such as aminotri(methylenephosphonic acid) (ATMP), 
ethylenediaminetetra(methylenephosphonic acid) (EDTMP), 
hexamethylenediaminetetra(methylenephosphonic acid) (HMDTMP), and 
diethylenetriaminepenta(methylenephosphonic acid) (DETPMP). The most 
preferred phosphorus-containing sequestering agent is sodium 
tripolyphosphate (STPP). 
The phosphorus-containing sequestering agent may be present in the 
detergent composition in an amount, for example, of about 0.1 to 3.0 wt. 
%, preferably about 0.2 to 2.5 wt. % based on the total solids in the 
composition. 
The composition may also optionally contain as a soil antiredeposition 
agent a carboxylic acid-containing polymer which is a homopolymer or 
copolymer (composed of two or more co-monomers) of an alpha, 
beta-monoethylenically unsaturated carboxylic acid monomer such as acrylic 
acid, methacrylic acid, a diacid such as maleic acid, itaconic acid, 
fumaric acid, mesoconic acid, citraconic acid and the like, a monoester of 
a diacid with an alkanol, e.g., having 1-8 carbon atoms, and mixtures 
thereof. When the carboxlic acid containing polymer is a copolymer, it may 
be a copolymer of more than one of the foregoing unsaturated acid 
monomers, e.g., acrylic acid and maleic acid, or a copolymer of at least 
one of such unsaturated acid monomers with at least one non-carboxylic 
alpha, beta-monoethylenically unsaturated monomer which may be either 
non-polar such as styrene or an olefinic monomer, such as ethylene, 
propylene of butene-1, or which has a polar functional group such as vinyl 
acetate, vinyl chloride, vinyl alcohol, alkyl acrylates, vinyl pyridine, 
vinyl pyrrolidone, or an amide of one of the delineated unsaturated acid 
monomers, such as acrylamide or methacrylamide. Certain of the foregoing 
copolymers may be prepared by aftertreating a homopolymer or a different 
copolymer, e.g., a copolymer of acrylic acid and acrylamide by partially 
hydrolyzing a polyacrylamide. 
A copolymer of at least one unsaturated carboxylic acid monomer with at 
least one non-carboxylic comonomer should contain at least about 50 mol % 
of polymerized carboxylic acid monomer. 
The carboxylic acid-containing polymer should have a number average 
molecular weight of, for example about 1000 to 10,000, preferably about 
2000 to 5000. To ensure substantial water solubility, the polymeric 
polycarboxylate is completely or partially neutralized, e.g., with alkali 
metal ions, preferably sodium ions. 
The carboxylic acid-containing polymer may be present in the detergent 
composition in an amount of about 0.1 to 2 wt. %, preferably about 0.1 to 
1.5 wt. % based on the total solids in the composition. 
The detergent composition of this invention is preferably a solid 
dry-appearing powder, in which case water may be present in an amount, for 
example, of about 1-12 wt. %, preferably about 2-10 wt. %, based on the 
total weight of the composition. 
The laundry detergent compositions of this invention may also contain 
various adjuvants common to detergent formulations such as brighteners, 
enzymes, carboxymethylcellulose, perfumes, dyes and peroxide generating 
persalts.

The following examples further illustrate the invention. The soil-removing 
results shown in the table for each of the following groups of example 
were obtained as a separate unitary series . 
EXAMPLES 1 TO 5 AND COMATIVE EXAMPLE A 
In this group of examples, the soil-removing properties with respect to 
certain types of soilings were determined for various detergent 
compositions under the invention (Examples 1 to 5) as compared with a 
control composition (Comparative Example A) which was identical to the 
compositions under the invention except for the absence of a second 
ethoxylated fatty alcohol nonionic surfactant and an amphoteric surfactant 
as defined previously. 
In Comparative Example A (High Ash Test LD Base), the control base 
detergent composition consisted of about 65 grams of sodium carbonate; 
about 0.95 gram of sodium bicarbonate, an active surfactant consisting of 
about 5.7 grams of the sodium salt of sulfated predominantly C.sub.12 and 
C.sub.13 fatty alcohols with an average of 12.5 carbon atoms, ethoxylated 
with 3 moles of ethylene oxide per mole of alcohol (anionic surfactant), 
and about 3 grams of unsulfated predominantly C.sub.12 and C.sub.13 fatty 
alcohols having an average of about 12.5 carbon atoms ethoxylated with 3 
moles of ethylene oxide per mole of alcohol (nonionic surfactant); about 
1.4 gram of sodium tripolyphosphate (STPP); about 0.61 gram on a dry basis 
of the sodium salt of a polymeric blend of 50 wt. % of a polyacrylic acid 
having a number average molecular weight of about 4500, and 50 wt. % of a 
copolymer of 50:50 acrylic and methacrylic acids having a number average 
molecular weight of 3500; about 0.21 gram on a dry basis of 
carboxymethylcellulose (CMC); about 0.2 gram of an optical brightener; and 
about 7.9 grams of water. 
The compositions of Example 1 to 5 were the same as that of comparative 
Example A except that they contained varying amounts of a second 
ethoxylated fatty alcohol nonionic surfactant, wherein predominantly 
C.sub.12 and C.sub.14 fatty alcohols with an average of about 13.2 carbon 
atoms were ethoxylated with about 4.3 moles of ethylene oxide per mole of 
fatty alcohol, and an amphoteric surfactant which was 
sodium-N-coco-.beta.-aminopropionate obtained from Henkel under the 
trademark "Deriphat 151". The designation "coco" represents a distribution 
of R groups corresponding in number of carbon atoms and structure to the 
fatty acids in coconut oil, such that the R groups were made up of 3 wt. % 
octyl, 5 wt. % decyl, 50 wt. % dodecyl, 23 wt. % tetradecyl, 11 wt. % 
hexadecyl, 5 wt. % oleyl and 3 wt. % stearyl. 
Following the procedure of ASTM D-3050 utilizing full size Whirlpool 
washing machines, various swatches of cotton and poly/cotton (a blend of 
65 wt. % cotton and 35 wt. % polyester) soiled with various substances, 
were washed at 95.degree. F. with the wash water containing 100 ppm of 
calcium and magnesium hardness with a Ca/Mg molar ratio of 3:1, such 
hardness calculated as CaCO.sub.3 as described in ASTM D 1126-86 of 
October 1986. Four replicate soiled swatches were used for each 
determination, two in each of two machines. Reflectances of the clean 
unsoiled samples, the soiled samples and the washed samples were measured 
using a standard spectrophotometer, and the percent soil removal was 
calculated from the spectrophotometer measurements. The average percent 
soil removal for the various types of soiled samples are shown in Table I 
wherein "EMPA 101" indicates a soil of carbon black and olive oil on 
cotton, and "EMPA 104" indicates a soil of carbon black and olive oil on 
poly/cotton. Results obtained with these soilings and those of sebum on 
cotton and poly/cotton are an excellent indication of the cleaning power 
of a detergent composition. The acronym "EMPA" stands for "Eldgenossiche 
Materials Prufungs Anstalt", a Swiss government testing center. 
Table I shows for each example, the amounts of second nonionic surfactant 
and amphoteric surfactant added, and for each soiled sample cleaned with 
the composition of such example, the difference between the percent soil 
removal obtained and that obtained with the control composition of 
Comparative Example A, with a positive number indicating a higher 
percentage and a negative number a lower percentage of soil-removal, than 
that obtained with the contol composition. Furthermore, an asterisk (*) 
has been placed near each value of difference which has been determined to 
be statistically significant in accordance with least significant 
differences (LSD) as derived from a utilization of one way analysis of 
variance (ANOVA) per Statgraphics software package. The values of 
difference which do not have an asterisk are considered to be 
statistically equivalent to zero (no difference) in accordance with the 
described procedure for determining statistical significance 
TABLE I 
______________________________________ 
Example 
1 2 3 4 5 
______________________________________ 
Second Nonionic 
2 3 2 2 2 
Surfactant, grams 
Amphoteric 2 1 1 1 0.5 
Surfactant, grams 
Soiled Sample 
Sebum on Cotton 
+9.9* +9.6* +6.1* +6.6* 
+8.0* 
EMPA 101 +6.6* +4.4* +2.9* +2.8* 
+1 
Sebum on Poly/Cotton 
+2 +5.6* +5.4* +3.7* 
5.3* 
EMPA 104 +6.8* +6.7* +4.8* +1.8 3.8* 
______________________________________ 
EXAMPLE 6 TO 10 AND COMATIVE EXAMPLE B 
The procedure of the previous examples was followed with the control 
composition (Comparative Example B, Low Ash Test LD Base) and the 
compositions of Examples 6 to 10 being the same as the control composition 
and the compositions of Examples 1 to 5 respectively except that the 
compositions each contained 45 grams rather than 65 grams of sodium 
carbonate. The results in terms of the differences between the soil 
removal percentages of the compositions of the examples and those of the 
control composition are shown in Table II. 
TABLE II 
______________________________________ 
Example 
6 7 8 9 10 
______________________________________ 
Second Nonionic 
2 3 2 2 2 
Surfactant, grams 
Amphoteric 2 1 1 1 0.5 
Surfactant, grams 
Soiled Sample 
Sebum on Cotton 
+7.5 +1.4 -0.1 +1.4 +7.1 
EMPA 101 +7.9* +6.4* +5.1* +7.2* 
+3.8 
Sebum on Poly/Cotton 
+4.2* +3.9* +4.2* +6.7* 
+5.0* 
EMPA 104 +8.4* +7.0* +5.6* +7.0* 
+3.1* 
______________________________________ 
The results of Examples 1 to 10 show that the addition of a second 
ethoxylated fatty alcohol nonionic surfactant and an amphoteric surfactant 
under the invention to a standard control composition containing 65 or 45 
grams of sodium carbonate and constant amounts of a conventional first 
ethoxylated fatty alcohol nonionic surfactant and an anionic surfactant, 
often resulted in a statistically significant improvement in the EMPA 101 
and EMPA 104 soil-removing properties of the composition and/or an 
improvement in the sebum on cotton and/or poly/cotton soil-removing 
properties of the composition. Furthermore, there were no statistically 
significant reductions of these soil-removing properties in any of the 
examples. 
COMATIVE EXAMPLES C, C', D AND D' 
These comparative examples are for the purpose of showing that the 
improvements in the soil removing properties of the compositions of 
Examples 1 to 10 under the invention were not due merely to the added 
surfactant present in these composition as compared with the control 
compositions, but were rather due to the specific nature of the 
surfactants added in those examples. Thus, in these comparative examples, 
four additional grams of the nonionic surfactant present in the control 
compositions of the previous examples as described in comparative Example 
A, which was the same as the first nonionic surfactant present in Examples 
1 to 10 under the invention, were added to such control compositions and 
the soil-removing properties of the resulting compositions, which now 
contained the same amount (12.7 grams) or more of total surfactant as the 
inventive compositions of Examples 1 to 10, were determined as described 
in the previous examples. The composition of Comparative Examples C and 
its repetition C, and their control composition (which was the same as 
that of Comparative Example A) contained 65 grams of sodium carbonate, 
while the composition of Comparative Examples D and its repetition D' and 
their control composition (which was the same as that of Comparative 
Example B) contained 45 grams of sodium carbonate. Results in terms of the 
difference between the percentages of soil removed by the tested 
composition and the control composition, are shown in Table III. 
TABLE III 
______________________________________ 
Example 
Soiled Sample C C' D D' 
______________________________________ 
Sebum on Cotton 
+0.6 +5.0* +3.5 +6.7* 
EMPA 101 +1.2 -1.9 +3.0 +1.0 
Sebum on Poly/Cotton 
+1.7* +1.7* +1.6 +2.0* 
EMPA 104 +0.1 -2.2 +0.6 -1.3 
______________________________________ 
The results of these examples show that there were no statistically 
significant differences between the EMPA 101 and 104 soil removal 
properties of the tested compositions, which contained the same amount or 
more of total surfactant as those of examples 1 to 10 under the invention, 
and such properties of the control compositions. This proves that with 
respect to these soilings, the superior performance of the inventive 
compositions is due to the specific nature of the second nonionic and 
amphoteric surfactants present rather than to the total amount of 
surfactant present.