Surfactant composition and method of making the same

The reaction product of: PA1 (a) a compound of the formula: ##STR1## wherein X is a member selected from the group consisting of N, O and S; R.sub.1 and R.sub.2 are independently a straight or branched, saturated or unsaturated non-aromatic hydrocarbon of four to eighteen carbon atoms; m is 1 or 2; and n is 0, 1 or 2; and PA1 (b) a compound selected from the group consisting of primary, secondary, tertiary and higher amines, which are liquid at room temperature. The reaction product of the present invention has excellent surfactant properties, and is suitable for use in coloring compositions to improve the fugitivity from skin and clothing. The reaction product is also useful as a cleansing agent.

FIELD OF THE INVENTION 
This invention relates in general to the field of surfactant compositions. 
BACKGROUND OF THE INVENTION 
Traditional inks and paints generally available for use by both adults and 
children exhibit several drawbacks in daily use. Spills of such coloring 
compositions lead to stained skin and clothing. Clothing is often ruined 
by such stains as they fail to wash out even after several washings. Skin 
must often be washed several times to remove such stains. 
Further, many such coloring compositions are deficient in that they bleed 
through paper, commonly known as "strike-through". Addition of traditional 
surfactants to these compositions in attempts to improve fugitivity of the 
coloring compositions from skin and clothing merely increases 
strike-through. 
Currently, some approaches to developing coloring compositions which are 
more easily washed from skin and textiles include (1) utilizing limitedly 
available dyes which have good fugitivity from fabrics and/or lowering dye 
concentrations and, (2) chemically grafting chromophores (dyes) onto a 
water soluble polymer such as poly(ethylene glycol). A major drawback to 
these methods is that they are costly. 
Surfactants are commonly used to enhance the fugitivity and cleansing 
properties of compositions by altering the surface energy of a solid or 
liquid. This ability is attributable to the dual nature of the molecules 
or ions of the surfactant compositions. Within a single molecule or ion of 
a surface-active agent, there is a group that has a tendency to repel the 
dispersing medium or solvent, and at a suitable distance within the same 
molecule or ion, there is another group that attracts the dispersing 
medium or solution. 
Typically, sulfonated surfactants are the most useful surface-active agents 
because they exhibit the most desirable fugitivity and cleansing 
properties. However, utilizing these sulfonated compounds is difficult 
because of the tendency of these compounds to remain in the solid state at 
room temperature. 
In coloring compositions, such as those used in marking instruments, the 
tendency of a sulfonated surfactant to remain in the solid state at room 
temperature translates to clogging of the capillary marking system, such 
as a bonded fiber marker nib. Therefore, the caps on these capillary 
marking systems may only be removed for very short time periods before the 
marking system becomes inoperable. 
Therefore, an object of the present invention is to provide a composition 
which imparts enhanced fugitivity when added to various coloring 
compositions. 
A further object of the present invention is to provide a surfactant 
composition which reduces the likelihood of skin irritation should the 
composition contact the skin. 
An additional object of the present invention is to provide a surfactant 
composition which remains in a liquid state at room temperature. 
Still a further object of this invention is to provide a surfactant 
composition which may be manufactured economically. 
These and other objects will become apparent to those skilled in the art to 
which the invention pertains. 
SUMMARY OF THE INVENTION 
The present invention overcomes the drawbacks associated with prior 
surfactant compositions by providing a new surfactant composition which, 
when added to coloring compositions, significantly increases the coloring 
compositions' fugitivity from fabrics and skin while largely preventing 
strike-through in paper. 
The present invention imparts the desirable cleaning characteristics of 
traditional sulfonated surfactants while avoiding the solidification 
disadvantages of those surfactants. The composition of the present 
invention therefore imparts improved and convenient cleaning properties. 
In general, the present invention is the reaction product of: 
(a) A compound of the formula: 
##STR2## 
wherein X is a member selected from the group consisting of N, O and S; 
R.sub.1 and R.sub.2 are independently a straight or branched, saturated or 
unsaturated non-aromatic hydrocarbon of four to eighteen carbon atoms; m 
is 1 or 2; and n is 0, 1 or 2; and 
(b) a compound selected from the group consisting of primary, secondary, 
tertiary and higher amines, which are liquids at room temperature 
Primary amines are characterized by the --CH.sub.2 NH.sub.2 group, while 
secondary amines contain the group (--CH.sub.2).sub.2 NH. Tertiary amines 
are tri-substituted amines characterized by the group (--CH.sub.2).sub.3 
N, for example, trimethyl amine, (CH.sub.3).sub.3 N. Higher amines are 
amines which are a combination of primary, secondary or tertiary amines. 
In one form, the present invention is a reaction product of: (a) a mono- or 
di- substituted diphenyl ether disulfonic acid ("DEDA") and (b) a member 
of the group consisting of primary, secondary, tertiary and higher amines 
In one preferred form, the amine is N-aminoethylpiperazine ("N-AEP"). 
When the composition of the invention is a reaction product of a mono- or 
di- substituted DEDA and N-AEP, the reaction product would appear to be of 
the formula: 
##STR3## 
wherein R.sub.1 is a branched or unbranched, saturated or unsaturated 
non-aromatic hydrocarbon of four to eighteen carbon atoms and wherein any 
two of the three nitrogen atoms in the amine moiety are protonated. 
The composition of the present invention is useful as a surfactant. The 
composition is chemically compatible with a variety of acid and basic dyes 
as well as inks, paints and other marking compositions. 
Further, the composition of the present invention is useful as a cleaning 
agent for such articles as plastics and vinyl. 
DETAILED DESCRIPTION OF THE INVENTION 
Reactions involving primary, secondary, tertiary and higher amines with 
various acids are well documented throughout the chemical literature. This 
invention involves reactions of substituted diphenyl ether disulfonic 
acids ("DEDA") with a member of the group consisting of primary, 
secondary, tertiary and higher amines. 
Reacting these two reagents produces a resultant product with surfactant 
properties. Also, this product can be employed in amounts of about 10% to 
about 40% by weight in inks, paints and the like to increase fugitivity 
from fabrics and skin while largely preventing strike-through in paper. 
In general, the present invention is the reaction product of: 
(a) a compound of the formula: 
##STR4## 
wherein X is a member selected from the group consisting of N, O and S; 
R.sub.1 and R.sub.2 are independently a straight or branched, saturated or 
unsaturated non-aromatic hydrocarbon of four to eighteen carbon atoms; m 
is 1 or 2; and n is 0, 1 or 2; and 
(b) a compound selected from the group consisting of primary, secondary, 
tertiary and higher amines, which are liquid at room temperature. 
In one preferred form, the invention is a reaction product of: (a) a mono- 
or di-substituted diphenyl ether disulfonic acid ("DEDA") of the formula: 
##STR5## 
wherein R.sub.1 is a straight or branched, saturated or unsaturated 
non-aromatic hydrocarbon of four to eighteen carbon atoms; and (b) a 
member of the group consisting of primary, secondary, tertiary and higher 
amines, which are liquid at room temperature. 
Amines are organic compounds derived from ammonia by replacing one or more 
of the hydrogen atoms with organic radicals. Primary amines are 
characterized by the --CH.sub.2 NH.sub.2 group, while secondary amines 
contain the group (--CH.sub.2).sub.2 NH. Tertiary amines are 
tri-substituted amines characterized by the group (--CH.sub.2).sub.3 N, 
for example, trimethyl amine, (CH.sub.3).sub.3 N. Higher amines are amines 
which are a combination of primary, secondary or tertiary amines. 
Unexpectedly, N-aminoethylpiperazine ("N-AEP"), a higher amine which 
contains a primary, a secondary and a tertiary amine, is particularly 
appropriate for use. As a large molecule with a high molecular weight, 
N-AEP exhibits low mobility in solution, an attribute which is passed on 
to the reaction product of the invention. Low mobility is important in 
that it translates to less strike-through. 
In addition to N-AEP, other suitable amines include primary amines such as 
N-butylamine; secondary amines such as ethylamino ethanol, butyl 
monoethanolamine, and diethylamine; tertiary amines such as diethylamino 
ethanol, ethyldiethanol amine, triethylamine, n-butyl diethanolamine, 
N-methyl morpholine, N-ethyl morpholine, and triethylene diamine; and 
higher amines such as dimethylaminopropylamine, which contains both a 
primary and a tertiary amine 
Like N-AEP, the above-mentioned compounds have high molecular weights, have 
boiling points greater than room temperature and are sufficiently basic to 
form the appropriate reaction products. 
A preferred embodiment of the invention is the reaction product of dodecyl 
substituted DEDA and a member of the group consisting of primary, 
secondary, tertiary and higher amines, which are liquid at room 
temperature. 
An even more preferred embodiment of the invention is the reaction product 
of mono- or di-dodecyl DEDA with N-AEP, the resulting reaction product 
appearing to be: 
##STR6## 
wherein any two of the three nitrogen atoms in the amine moiety are 
protonated to form ammonium ions. In other words, the hydrogen atoms can 
readily migrate from one site to another in the amine moiety. 
Dodecyl DEDA is commercially available as an acid sold under the trademark 
"Poly-Tergent 2EP Acid" from Olin Chemical. This commercial preparation 
contains approximately 45% by weight of dodecyl DEDA and approximately 55% 
by weight of water. The reagent N-AEP is commercially available as a 100% 
liquid under the trademark "5379 N-Aminoethylpiperazine" sold by Texaco 
Chemical Company. 
In general, the procedure for producing the reaction product of the present 
invention is the combination, usually by titration, of (a) a compound of 
formula I; and (b) a member of the group consisting of primary, secondary, 
tertiary and higher amines which are liquid at room temperature until a pH 
of about 7 to about 10, preferably from about 7 to about 8, and more 
preferably about 7.0, is achieved. 
Specifically, the reaction of dodecyl DEDA with N-AEP is preferably carried 
out by adding from about 5% to about 15% by weight, preferably about 10% 
by weight of N-AEP, to from about 95% to about 85% by weight, preferably 
about 90% by weight of a commercial preparation containing approximately 
45% by weight of dodecyl DEDA and approximately 55% by weight of water, 
and allowing the reaction to continue until a pH of about 7.0 to about 
10.0, preferably until a pH of about 7.0 to 8.0, and most preferably until 
a pH of about 7.0 is achieved. This equates to Ph from about 10% to about 
30% N-AEP by weight, preferably 20% by weight N-AEP to from about 90% to 
about 70% by weight, preferably about 80% by weight of active dodecyl 
DEDA. The pH of the reaction may be checked by any conventional method. A 
suitable method for determining the pH is a pH meter. Heat is evolved in 
the neutralization reaction to the extent that the reactant temperature 
increases from 25.degree. C. to about 50.degree. C. 
Typically, DEDA contains an excess of 2-3% sulfuric acid, which leads to 
the formation of piperazine sulfate when the N-AEP is added. The 
piperazine sulfate will eventually precipitate out of solution. Although 
piperazine sulfate is inert, the precipitate particle size is capable of 
plugging a capillary marking system such as a bonded fiber marker nib 
should the reaction product of the invention be used in a marking 
composition of such a system. Therefore, the piperazine sulfate 
precipitate should be removed from the reaction product. A suitable method 
for removing the precipitate is to filter the composition, as through a 
30.mu. filter. 
The resultant reaction product composition of the invention is useful in 
many applications. The composition improves skin and fabric fugitivity 
when used in coloring compositions such as dyes, inks and paints, and may 
also function as a cleansing agent. 
The instant invention will be better understood by referring to the 
following examples.

TEST DATA AND EXAMPLES 
The composition of the present invention is chemically compatible with a 
variety of acid and basic dyes and inks formed using those coloring 
agents. Coloring compositions, such as an ink utilizing the present 
invention comprise from about 10% to about 40% by weight, preferably from 
about 20% to about 30% by weight, of the reaction product of the present 
invention; from about 40% to about 60% by weight, preferably about 43%, by 
weight, of deionized water ("DI"); and from about 0.5% to about 10.0% by 
weight, preferably about 4.0%, by weight, of a colorant. 
The colorant may be an acid or basic dye. Typical dyes employed in the 
marking compositions of the present invention include acid red 1, acid red 
388, acid yellow 23, acid yellow 17, acid blue 9 and acid violet 12. 
Optionally, the coloring composition may further comprise a humectant and 
preservatives such as biocides and fungicides. 
Addition of humectant ensures that coloring compositions when in the form 
of an ink do not prematurely dry while in a capillary marking system, such 
as a bonded fiber marking nib. Typical humectants which may be employed in 
the coloring compositions of the present invention include polyhydric 
alcohols such as ethylene glycol, propylene glycol, hexylene glycol and 
poly(ethylene glycol), and hydroxylated starches. The humectant is 
preferably glycerin. The humectant is generally present from about 0% to 
about 30%, preferably about 22% by weight of the coloring composition. 
Addition of preservatives inhibits the growth of bacteria and fungi in 
water-based products. A preferred biocide, "Nuosept 95", is a bicyclic 
oxazolidines solution and is commercially available from Hulls America, 
Inc. Nuosept 95 is a preferred biocide due to its chemical stability in 
coloring compositions. The biocide is generally present from about 0% to 
about 0.5%, preferably from about 0.06% to about 0.5%, and most preferably 
about 0.5% by weight of the composition. A preferred fungicide is 
"Polyphase P100" which is commercially available from Troy Chemical. 
Polyphase P100, principally containing 3-iodo 2-propynyl butyl carbamate, 
and generally represented by the formula, C.sub.8 H.sub.12 INO.sub.2. 
Polyphase P100 is a preferred fungicide because it displays an 
exceptionally low order of toxicity. The fungicide is typically present 
from about 0% to about 2.5%, preferably about 0.08% to about 0.6%, and 
most preferably about 0.6% by weight of the composition. 
Washable coloring compositions utilizing the present invention are 
preferably produced by blending together the deionized water, the 
humectant and other optional ingredients, if used, the reaction product of 
the present invention and the colorant. 
Examples of washable coloring compositions utilizing the composition of the 
invention are as follows. Quantities are in percent by weight. 
______________________________________ 
WASHABLE COLORING COMPOSITIONS 
Component BLUE GREEN 
______________________________________ 
Deionized Water 47.88 50.90 
Glycerin 16.00 19.80 
Composition of 32.00 25.20 
Invention* 
Acid Red 388 2.08 -- 
Acid Yellow 17 -- 3.00 
Acid Blue 9 1.54 0.60 
Nuosept 95 0.50 0.50 
______________________________________ 
*Reaction product of dodecyl DEDA and NAEP 
Generally, from about 10% to about 40% by weight, and preferably from about 
20% to about 30% by weight of the reaction product of the invention in an 
coloring composition provides an improved fugitivity from the skin, fabric 
or surfaces, by presumably blocking colorants from binding thereon. The 
fugitivity from skin of the coloring compositions combined with the 
reaction product of mono-dodecyl DEDA and N-AEP was measured by the 
following test: 
1. Wash hands with soap and warm water. This pre-stain cleaning removes 
excess oil and dirt from the skin and provides a more consistent skin 
surface for testing. Allow the skin to dry for 30 seconds. 
2. In the case of a marker containing the coloring composition, draw a 
stripe on the palm of the hand with the flat side of the nib. In the usual 
case, a 1/4 inch wide by 1 inch long stripe works well. Apply enough 
pressure and/or multiple passes to make a comparison among two or more 
compositions. More than one stripe may be drawn. Let the stripes dry for 
15 minutes. 
3. Briefly rinse off the excess coloring composition from the marked hand 
with warm water. 
4. Wash hands using a minimum amount of soap, rubbing hands together 
briskly with modest pressure for 30 seconds, then rinse away the soap. 
5. Wipe hands dry with paper towels, and complete the drying with a 
relatively dry towel A dry towel will help remove any residual traces of 
colorant. 
6. Evaluate the removability of the coloring composition from skin by 
assigning a score using the following visual rating system: 
5=no stain 
4=barely visible 
3=slight 
2=moderate 
1=severe 
If removal of the marks was incomplete, repeat steps 4 through 6. 
Skin wash testing was performed with coloring compositions comprising about 
4.0% by weight of colorant; about 43% by weight of deionized water; about 
22% by weight of glycerin; 0.5% by weight of biocide; 2.5% by weight of 
fungicide; and 28% by weight of the reaction product formed as a result of 
the reaction of the below listed amines with monododecyl substituted DEDA 
The results were as follows: 
______________________________________ 
Compound Skin Wash Rating 
______________________________________ 
N-methyl morpholine 
3.0 
N-ethyl morpholine 
2.5 
N-AEP 4.5 
ethylamino ethanol 
4.5 
ethyldiethanol amine 
4.5 
diethylamino ethanol 
4.0 
butyl monoethanolamine 
3.0 
n-butyl diethanolamine 
3.0 
diethylamine 3.5 
triethylamine 4.5 
N-butylamine 4.0 
dimethylaminopropylamine 
3.5 
triethylene diamine 
3.5 
______________________________________ 
The fugitivity from fabric of a coloring composition containing the 
composition of the present invention was tested by a standard wash test 
conducted on both 100 percent cotton fabric ("Fabric 419") and 50 percent 
cotton/50 percent polyester fabric ("Fabric 9406 WRL"). Children's 
clothing is constructed primarily from Fabric 9406 WRL. In the test, a 
washability value or "Delta E" was given to each surfactant tested. The 
higher the value of Delta E, the worse the stain remaining on the fabric 
Generally, stains at 3.0 or under are considered acceptable by consumer 
standards. 
The composition of the invention was tested in comparison to several 
commercially available cleaning agents. The cleaning agents included 
sodium dioctyl sulfosuccinate which is commercially available under the 
trademark "AEROSOL OT 75%" by American Cyanamid Company; sodium lauryl 
sulfate which is commercially available under the trademark "POLYSTEP-B5" 
by Stepan Co.; and propylene benzene sulfonic acid which is commercially 
available under the trademark "WITCO 1298HA" by Witco Organic Division. 
About 28% by weight of each of the cleaning agents to be tested in the 
standard wash test were added to the coloring composition comprising about 
43% of deionized water; about 4% of Acid Blue dye; about 28% by weight of 
glycerin; about 0.5% of a biocide; and about 2.5% by weight of fungicide. 
______________________________________ 
Fabric 9406 WRL 
Fabric 419 
Cleaning Additive 
Delta E Delta E 
______________________________________ 
Composition of Invention* 
0.40 0.24 
Sodium dioctyl 1.83 1.07 
sulfosuccinate 
Sodium lauryl sulfate 
2.09 0.56 
Propylene benzene 
3.79 4.75 
sulfonic acid 
______________________________________ 
*Reaction product of dodecyl DEDA and NAEP 
The reaction product of the subject invention in coloring compositions 
containing dyes also permits a decrease in dye loading in the wash water 
during washing of fabric by holding and suspending the coloring 
composition on top of the wash water. Thus, the reaction product in the 
resultant coloring composition enhances the detergency of the composition 
as it is easily washable from fabrics. 
In addition, coloring compositions containing from about 10% to about 40% 
by weight of the surfactant of the present invention have not been 
observed to cause skin irritation upon contact with the skin. 
Generally, from about 10% to about 40%, preferably from about 20% to about 
30% by weight of the reaction product of the subject invention in coloring 
compositions also improves the lightfastness and increases the brightness 
of said coloring compositions. 
Addition of from about 10% to about 40%, preferably from about 20% to about 
30%, by weight, of the reaction product of the invention to coloring 
compositions also inhibits the migration of the compositions through paper 
and other materials. As a result, strike-through of inks and paints 
containing the composition of the invention is decreased. These 
characteristics are believed to be attributable to the reaction product 
having large molecules with a high molecular weight. These large molecules 
have a low mobility. When added to coloring composition formulations, the 
resultant formulations have a low surface tension, a lower viscosity and a 
low mobility through paper, as well as on skin or other surfaces. 
Adding an effective amount of the composition of the invention to coloring 
compositions does not alter the color of the composition. The color is not 
altered because the reaction product is chemically compatible with almost 
all conventional water-based coloring compositions. 
When the reaction product is used in coloring compositions on paper, the 
colors are more uniform when dried than compositions without the reaction 
product. The reaction product allows the water borne composition to evenly 
wet papers fibers and results in the paper fibers being obscured. In 
systems without the reaction product, the dyes tend to settle in the 
depressions on either side of the fiber, thus highlighting the fiber. 
Addition of from about 10% to about 40% by weight, preferably from about 
20% to about 30% by weight of the reaction product of the invention to a 
paint composition comprising a water-based paint composition, effectively 
increases the fugitivity of the paint composition from fabric and skin. A 
preferred water-based liquid paint composition is tempera paint. Tempera 
paint is typically applied with a paint brush or similar instrument. 
When the composition of the present invention is used in an ink 
composition, the solvent system may be an aqueous or non-aqueous system. 
Conventional non-aqueous solvents such as toluene, ketones, and oxygenated 
solvents are suitable. 
The reaction product of the present invention also possesses desirable 
cleansing characteristics, and may be used as a cleansing agent for such 
products as vinyl and plastics. When used as a cleansing agent the 
reaction product of the invention is most suitably combined with a 
carrier. A preferred carrier is water. The reaction product is generally 
present in an amount from about 1.0% to about 50% by weight of the 
cleaning composition. 
Those skilled in the art will understand that said invention is not limited 
by these examples which are offered merely as illustrations. Also those 
skilled in the art will understand that modifications can be made without 
departing from the spirit and scope of the invention.