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Патент USA US3070557

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Unite States Patent ()?lice
1
3,5li7h,54i7
Patented Dec. 25, 1962
2
iness or smeariness, in resistance to cracking when alter
nately wetted and dried, and in resistance to formation
3,ti7ti,547
SQAr-SYNTHE'HC BAR
of curd in hard water.
Robert H. Qhatfee, Cclcrain Township, Hamilton County,
(iiiio, assignor to The Procter & {Gamble Company,
Cincinnati, Ohio, in corporation of @illit)
No Drawing. Qontinnation of application Ser. No.
I am not certain why the detergent bar compositions
of my invention possess their improved characteristics,
but it has been observed on microscopic examination of a
portion of a bar after exposure to water, that a liquid
367,769, July 13, 1953. This application Dec. 12,
1951, §er. No. 159,431
2 Ciaims. (Qt. 252-421)
The present invention relates to detergent bars, more
particularly to bars containing substantial amounts of
synthetic detergent, and methods of making same.
crystalline phase of the active ingredients at the bar sur
face exists at least in part as middle phase or “gum”
phase, which is dif?cultly soluble in water. The forma
tion of this water resistant layer on the bar surface, in
association with other ingredients of my composition, ap
The shortcomings of sulfonated and sulfated synthetic
parently reduces Water penetration and the tendency to
form a slushy or smeary surface which ultimately de
detergents in the manufacture of bars are many. if the
attempt is made to form a straight synthetic detergent 15 velops cracks on alternate wetting and drying.
The presence of a hydrated water-insoluble alkaline
into a bar, it will not stick together in a ?rm mass like
earth metal soap in the compositions of my invention
soap does, but will become smeary, slushy, fall apart,
appears to have the functional advantage not only of
and rapidly dissolve when exposed to water in a soap
improving the lathering properties of the bar and of re
dish. Various materials have been used to add plasticity
ducing tendencies toward curd formation when the bar
and water resistance to synthetic detergents and allow
is used in hard water, but also of having binding and
the formation of a bar of satisfactory quality. These in
plasticizing properties. As more fully hereinafter ex
clude, for example, the monoglycerides of saturated fatty
plained, the alkaline earth metal soaps may be added as
acids and the monoestcrs of fatty acids of coconut oil and
such in the compounding of ingredients or may be formed
ethylene glycol. Such compositions have not produced
commercially successful bars. These esters are of no 25 in situ in this operation by reaction of a water-soluble
alkaline earth metal salt with Water-soluble alkali metal
help in reducing smeariness and slushiness and they are
soap in suitable proportions. Moreover, it is to be under
relative'y expensive for an ingredient that not only is of
stood that in the present invention the term “alkaline
no help in detergency, but actually adds to the load. By
earth metal” is intended to include magnesium as well as
“load” is meant the using up of the detergent, such as is
calcium, barium, and strontium.
,
done by oily matter in clothes or on the hands.
Soap is a good plasticizer and has the property of ab
The salting-out electrolyte in my compositions has the
sorbing a limited amount of water from a soap dish with
out disintegration, so its use with synthetics is advan
function of reducing smear or slushiness and is regulated
in amount so as to slow up the solubility of the bar with
deiergent bar will not dissolve in Water as readily as the
valent anions such as the sulfates of sodium and potas
out preventing the formation of middle phase. The salt
tageous. Moreover, when soap is added to synthetic
detergents, coherent bars may be formed from the com 35 ing-out electrolytes may be any of the chlorides, sulfates,
or carbonates of the alkali metals, but in practicing my in
position by conventional soap making methods and ma
vention it should be borne in mind that the salts of bi
chinery. However, although the mixed soap-synthetic
sium have only about half the salting-out power of the
modi?cation, get slushy in a soap dish containing a layer 40 chlorides of these alkali metals.
In the preferred method of preparing bars of the pres
of water. In addition, such mixtures have at least two
ent invention, the synthetic detergent, neutralized with
other disadvantages. During use in hard Water the
a solution of an alkali metal hydroxide or carbonate, to
soap forms a curd, especially at rinsing concentrations,
straight synthetic detergent, it does, without further
which the salting-out electrolyte has been added (if in
thus negativing part of the advantages of the synthetic
detergent, and the bars crack badly when exposed to 45 su?’icient electrolyte will be formed in situ during the
neutralization step and in other steps of the process),
conditions of alternate wetting and drying.
is introduced into a suitable mixer, such as a soap crutcher.
An object of this invention is to provide a detergent
bar in which the active detergent ingredient is mainly a
synthetic detergent, but which shows a minimum tend
ency to slush, crack, and form curd during use in medium
or hard water.
Some water may then be added to improve ?uidIty, and
a sodium or potassium soap, preferably as kettle soap con
taining about 30% Water, is added. These ingredients
are mixed and then an appropriate amount of water-solu
Another object of the invention is to
produce a composition which, when formed into a bar
in the equipment employed to form soap into bars-such
as mils, plodders and stamps-has a soap-like rather
than a sticky, smeary or greasy feel as used.
I have discovered that detergent bars, made from a
suitably proportioned mixture of a water-soluble syn
thetic detergent, a water-soluble alkali metal soap, a hy
drated water-insoluble alkaline earth metal soap, and a
salting-out electrolyte, are desirably plastic and have
many advantages over synthetic detergent-soap bars pre
viously prepared, especially in resistance to excessive
penetration of water and resulting development of slush
ble aTkaTine earth metal salt, such as magrzesfurn su'fate
or chloride, or calcium chloride, is added to convert a
portion of the water-soluble soap to water-insoluble soap,
55
sodium or potassium salting-out electrolyte being formed
as by-product. Mixing is then continued to insure the
equilibrium in the formation of the alkaline earth metal
soap is attained. Desirable adjustments in water-soluble
soap content may, of course, be made after the water
insoluble soap has been formed.
The resulting mix is then dried either by drum drying,
screen drying, or spray drying, to a Water content of
1/2 to 12 percent, and the dried product is transferred to
an amalgamator where perfume, coloring matter or other
3,070,547
‘2
uct basis) was held at 75 but the ratio was varied. The
other ingredients on a ?nished product basis were:
minor ingredients may be added and mixed to achieve
uniformity. From the amalgamator, the material is
milled, plodded and stamped, in accordance with proce
dures well known in the art of soapmaking.
It is not essential that the calcium and magnesium
soaps be formed in the crutcher; they may be produced
separately and then added to the other ingredients. If
so added, they should contain enough water to be plas
tic or they should be mixed with the other ingredients
Moisture _________________ __ 8 parts.
Sodium chloride ___________ __ 5.4 parts.
Magnesium sulfate _________ _._ 5 parts per 30 parts soap.
Miscellaneous (unsulfated fatty
alcohol, whitener, preserva
tive, perfume) ___________ .._ 7 parts.
in the presence of water so that they may absorb water 10
su?iciently to become plastic and enable thorough incor
poration and homogeneous distribution throughout the
entire mass, thereby assisting in binding together the
constituents of the ?nished bar. If this is not done,
the binding power of the alkaline earth metal soaps is
lost and it becomes necessary to add a binder or gum
to stick the mass together.
The following examples illustrate the present inven
tion, but it is understood that details relating to ingredi
ents, proportions, and methods of processing are given
merely for exempli?cation purposes and are not to be
construed as limiting the scope of the appended claims.
In all instances, the proportions are expressed as parts by
weight.
Example 1.—50 parts of a mixture consisting essen
tially of lauryl and myristyl alcohols derived from coco
nut oil by sodium reduction and subsequent fractional
distillation (sometimes referred to as “middle cut” alco
hols) were sulfated with chlorosulfonic acid to a com
pleteness of 96%.
The monosulfuric acid ester thus
produced was neutralized with a 45% aqueous solution
of potassium hydroxide. The resulting preparation was
a paste containing 78 parts of the potassium salt of the
sulfuric acid esters of the alcohols described above.
62.5 parts of this neutralized mix, containing 54 parts
of the potassium alkyl sulfates of the middle cut alcohols
and about 0.4 part potassium chloride, were mixed with
5 parts of sodium chloride and 51 parts of kettle sodium
soaps (containing about 15 parts of water) derived from
Relative amounts of synthetic detergent, water-soluble
soap, and water-insoluble soap were as follows:
A
Alkyl su1fate—-as potassium salt .................. ._
B
C
45
37. 5
._
0
7. 5
Emir-as magnesium soap ________________________ _.
24
30
36
Saliugout electrolyte (sodium chloride equivalent).
Percent saliingbut electrolyte based on synthetic
7. 2
7. 7
S. 1
detergent plus sodium soap _____________________ __ l4. 3
17. 3
21.0
Soap-as sodium soap __________ __
30
‘J
All three samples were satisfactory with respect to
cracking and smear and were not substantially affected
by the change in ratio of potassium alkyl sulfate to total
soap from 1.5:1 to .6621, the ratio of magnesium soap
to alkali metal soap remaining constant at 4: 1.
Example 3.--30 parts (dry basis) of potassium alkyl
sulfate made from middle cut alcohol as described in
Example 1 were mixed with 19 parts of a commercial
synthetic detergent containing 15 parts of sodium coconut
fatty acid monoglyceride sulfonate (sodium salt of coco
nut fatty acid monoester of 1,2-dihydroxy-propane-3-su1
fonic acid) and about 3 parts of sodium chloride and
about 1 part of sodium sulfate. To this mixture were
added 43 parts of kettle sodium soap of 20 coconut-80
tallow mix containing 13 parts water. An amount of
epsom salts equivalent to 2.1 parts of magnesium sulfate
and sufficient to convert one-third of the soap to the mag
nesium form and 4.3 parts of NaCl were added. In the
reaction of the magnesium sulfate with the soap about
a mixture of 20% coconut oil and 80% tallow. To this 4:0 2.5 parts of sodium sulfate, equivalent to about 1.3 parts
were added 10.6 parts of epsom salts, the latter being
equivalent to 5 parts of magnesium sulfate. This amount
of magnesium sulfate was sufficient to convert 24 of the
36 parts of sodium soap (dry basis) to magnesium soap,
forming also 5.9 parts sodium sulfate which has the salt
ing-out effect of about 2.9 parts sodium chloride. The
sodium chloride, were formed, the total sodium chloride
salting-out electrolyte equivalent being about 14% of the
synthetic plus alkali metal soap. After thorough crutch
ing, drum drying, and mixing in an amalgamator with
perfume, whitener, etc., the product was milled, plodded
and stamped into bars. The bars were satisfactory from
the
standpoint of smear and wet crack and also formed
ingredients were thoroughly mixed in a crutcher to enable
no
visible
curd when used in hard water, although the
reaction to equilibrium, and the mixture was thereafter
sodium soap content was greater than in Examples 1
dried on an atmospheric drum drier. The dried product
was transferred to an amalgamator where 1% of per 50 and 2. We believe this is due to the good curd dispers
ing effect of this monoglyceride sulfonate used. The
fume and sui?cient water to bring the total water con
ratio of synthetic to soluble soap was 2.25:1.
tent to about 8% were thoroughly incorporated. The
amalgamator charge was milled, plodded and stamped.
Example 4.—As another example coming within the
By comparison, a product prepared similarly from a
mixture of 54 parts of the same potassium alkyl sulfate
ing about 30 parts of potassium soap and about 13 parts
scope of my invention, 60.0 parts of Santomerse #3 paste,
The bars were satisfactory with respect to cracking and
55 containing 45 parts of sodium alkyl benzene sulfonate
development of smear.
(having predominantly 12-15 C. in the alkyl radical),
In this example the ratio of synthetic detergent to total
substantially all of the remaining 15 parts being water,
soap was 1.5 to 1, the ratio of magnesium soap to sodium
are put into the crutcher. 5 parts of sodium chloride is
soap was 2:1, and the sodium chloride salting-out elec
added.
Then add 43 parts of kettle potassium soap de
trolyte equivalent was about 12.5% of the sum of the
60 rived from a 20 coconut-80 tallow fat mix and contain
synthetic detergent and alkali metal soap.
and 36 parts of same soda soap as used in Example 1,
but Without addition of sodium chloride or magnesium
sulfate, was de?nitely inferior.
-
The potassium salt of the coconut oil fatty acid mono
ester of 1,2-dihydroxy-propane-3-sulfuric acid may be
water.
Crutch the mixture, and to it add an amount of
epsom salts equivalent to 5 parts of magnesium sulfate
and suf?cient to convert 24 parts of sodium soap to mag
65 nesium soap.
After further adequate crutching, the mix
is dried on a drum drier.
In the reaction, salting-out
electrolyte equivalent to about 2.9 parts sodium chloride
is formed, making the total sodium chloride salting-out
substituted for the alkyl sulfate in this example with sat
electrolyte equivalent equal to about 15.5% of the sum
isfactory results.
70 of the synthetic and alkali metal soap. The dried mix
Example 2.--In this example three products were pre
is mixed with perfume, color, and antioxidant in an amal
pared, the potassium alkyl sulfate and the sodium soap
gamator, and then milled, plodded and stamped into bars.
being identical with those of Example 1 and the proce
An equivalent amount of calcium chloride can be sub
stituted for the magnesium sulfate in this Example 4 with
dure for making the bars being substantially the same.
out material change in the characteristics of the bar.
The total parts of soap and alkyl sulfate (?nished prod
3,070,547
6
5
It will be observed that in selecting the ingredients for
of the present invention, those versed in the art will ap
compounding the products in the above examples, soaps
and synthetic detergents in the form of sodium and/or
preciate that normally solid synthetic detergents are used.
Synthetic detergents of the following types can be used
potassium salts were employed in the admixture. It is
substantially as set forth in the above examples, suitable
choice of alkali metal hydroxides, and adjustment of
ratios of synthetic detergent, soluble and insoluble soaps
and electrolytes being made as those versed in the art will
well known that the ?rmness and solubilities of these ma
terials vary depending on the alkali metal salt, and the
relative proportion of each may be adjusted so that the
desired ?rmness and solubility of the ultimate‘ mixture
recognize.
Synthetic detergents of special interest are the normally
clusively or other proportions than those speci?cally used 10 solid alkali metal salts of sulfuric acid esters of normal
primary aliphatic alcohols having 10 to 18 carbon atoms.
in the examples may, of course, be employed, especially
Thus the sodium and potassium salts of alkyl sulfuric
with change in type of synthetic or soap, without departing
acids obtained from the mixed higher alcohols derived
from the spirit of the invention. Those versed in the art
by the reduction of tallow or by the reduction of coconut
will also recognize that by virtue of ionization during proc
essing, the alkali metal ions may become redistributed in 15 oil, palm kernel oil, babassu oil or other oils of the coco
nut‘ group which are characterized by a content of more‘
establishing chemical equilibrium in the mix.
than 50 percent combined lauric ‘and myristic acids, may
The water-soluble soap which is used in the practice of
be used.
the invention may be of any form-retaining type suitable
Other aliphatic sulfuric acid esters which may be em
for preparing soap bars. These will ordinarily be sodium
and/ or potassium soaps of tallow, grease, palm oil, palm 20 ployed in the preparation of detergent bars of the present
invention include appropriate water-soluble salts of sul
kernel oil, coconut oil, hydrogenated vegetable oils, hy
furic acid esters of polyhydric alcohols incompletely ester
drogenated marine oils, and mixtures thereof, as is well
known in the art of bar soap making.
i?ed with high molecular weight soap forming carboxylic
A wide range of ratios of synthetic detergent to total
acids. Such synthetic detergents include the water-soluble
soap is permissible in the practice of my invention, ratios 25 alkali metal salts of sulfuric acid esters of higher molecu
from 6:1 to 0.3 :1 giving satisfactory bars, ratios from 4:1
lar weight fatty acid monoglycerides such as the sodium
to .5 :1 being preferred. Likewise the ratio of alkaline
and potassium salts of the coconut oil fatty acid monoester
earth metal soap to alkali metal soap can vary from 6:1 to
of l,2-hydroxy-propane-3-sulfuric acid ester, sodium
0.l76:1, those of 4:1 to .4:1 being preferred. In the
and potassium monomyristoyl ethylene glycol sulfate, and
choice of ratios as outlined, it is preferable to select those 30 sodium and potassium monolauroyl diglycerol sulfate.
that maintain the ratio of synthetic detergent to alkali
There may be employed also the synthetic detergents
metal soap between 15:1 and 1.521; similarly the ratio of
having a true sulfonate group, such as water-soluble salts
synthetic detergent to alkaline earth metal soap should be
of higher molecular weight monofatty acid esters of lower
maintained between 5:1 and 11/2:1. As more fully ex
molecular weight hydroxy alkyl sulfonic acids, for ex
plained below, the salting-out electrolyte calculated as 35 ample the sodium salt of the coconut oil fatty acid mono
sodium chloride equivalent can vary from 5% to 30%
ester of 1,2-dihydroxy-propane-3~sulfonic acid, and the
of the sum of synthetic detergent and soluble soap, 7 to
coconut fatty acid ester of the potassium salt of isethionic
25% usually being su?‘icient in mixtures of preferred
acid. Included also are the water-soluble salts of the
formulation. Percentagewise the compositions normally
higher molecular weight alcohol esters of sulfocarboxylic
comprise 20 to 60% synthetic detergent, 10 to 50% of 4.0 acids, for example the sodium salt of the lauryl alcohol
may be achieved.
Potassium salts or sodium salts ex
total soap, said soap being about
earth metal soap, the remainder of
metal soap, and the sodium chloride
equivalent being 5 to 30% of the
15 to 85% alkaline
the soap being alkali
salting-out electrolyte
sum of the synthetic
ester of sulfo acetic acid, as well as the alkylated aryl
sulfonic acid, including the sodium and potassium salts
of the sulfonic acid derived from the condensation prod
ucts of benzene and either a chlorinated kerosene frac
detergent and the alkali metal soap in the ?nished bar.
45 tion containing predominantly 10 to 14 carbon atoms
Variations in the salting-out electrolyte can, of course,
per molecule, or a polypropylene having 12 to 15 carbons,
be made, depending on the primary ingredients of the
composition. The minimum amount is that required to
repress the rate of solubility of the synthetic detergent
both of such compositions being represented by the
formula
'
and the maximum amount is that which will change the
middle phase of active ingredients at the surface of the
bar to the curd phase. The actual amounts used vary
with the character of the components. If the water-solu
where R is the alkyl group.
ble soap is coconut soap more salting-out electrolyte will
The materials which may be added in the am-algamator,
be required than in the case of the 80 tallow-20 coconut 55 in addition to coloring matter, perfume, and antioxidants,
soap of the examples. If a straight tallow soap is used,
may include water or other liquids to improve the plasticity
less electrolyte will be required than in the case of the 80
of the mix.
tallow-20 coconut Soap of the examples.
In a like man
ner, the choice of synthetic detergent will affect the amount
of salting-out electrolyte, since it is known that synthetic
detergents exhibit phases similar to those exhibited by
soap. However, in any case the amount of such elec
trolyte is such as to slow up the rate of solution of the
synthetic and to allow the formation of middle phase on
the surface when the bar is placed in contact with water.
The synthetic detergent constituent of the present de
In some cases it is helpful to add 2 to 5 percent of a
non-ionic or anionic liquid synthetic detergent.
The non
ionics are practically all liquid, so any one with the
desired plasticizing qualities may be used. Among the
anionic detergents, the substituted amine salts, made liquid
with a small amount of water, for instance triethanolamine
alkyl sulfate with 10 percent of water, are satisfactory
plasticizing detergents.
As is well known in the art, cold creams and similar
emollients may be added in the amalgamator.
This application is a continuation of application Serial
organic sulfonic acids and of aliphatic sulfuric acid esters,
No. 367,769, now abandoned.
that is, water-soluble salts of organic sulfuric reaction 70 Having thus described my invention, what I claim and
products having in the molecular structure an alkyl radi
desire to secure by Letters Patent is:
cal of 10 to 22 carbon atoms and a radical selected from
' 1. A milled detergent bar characterized by good lather
the group consisting of sulfonic acid and sulfuric acid
ing performance and a reduced tendency to crack and
ester radicals. As indicated above in the designation of
smear during use, consisting essentially of a homogeneous
the soaps which may be used in compounding the bars 75 mixture of
tergent bar composition may be broadly designated as a
detergent of the class consisting of water-soluble salts of
3,070,647
7
8
(l) a water-soluble, normally solid synthetic detergent
2. The detergent composition of claim 1 in which the
that is a potassium salt of an alkyl sulfuric acid conpotassium salt of the alkyl sulfuric acid is a mixture of
taining an alkyl radical of from 10 to 22 carbon
alkyl sulfates of lauryl and myristyl alcohols.
atoms,
(2) a water-soluble, normally solid alkali metal soap, 5
References Cited in the ?le of this patent
(3) a. hydrated magnesium soap, and
UNITED STATES PATENTS
(4) an alkali metal salting-out electrolyte selected from
the group consisting of chloride, sulfate and carbonate salts’
,
_
_
10
1,906,484
2,390,295
,
Nuesslem ------------- —- May 2’ 1933
Flett _________________ __ Dec. 4, 1945
2,438,169
Hoyt ________________ __ Mar. 23, 1948
the who of synthetic detergent to total soap being about
2,673,921
Tm-ck ________________ __ May 18’ 1954
6:1 to 0.321, the magneslum soap constitutmg from 15%
to 85% of the total soap, the remainder of the soap being
alkali metal soap, and the amount of salting-out elec-
2,781,320
2,731,321
jelinek at al ___________ __ F611 12, 1957
Maybe“, et a1 __________ __ pct, 12 1957
’
689,569
Great Britain _________ __ Apr, 1, 1953
trolyte, calculated as sodium chloride, being from about
5% to 30% of the sum of synthetic detergent plus alkali 15
metal soap, and such that a water resistant phase is formed
at the surface of the bar when said bar is contacted with
Water, the moisture content of the ?nished bar immediately
after milling being about 8%.
FOREIGN PATENTS
OTHER REFERENCES
“Surface Active Agents,” Schwartz et al., Interscience
Publ. Inc, 1949, pp. 236 and 335.
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