Note: Descriptions are shown in the official language in which they were submitted.
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Field of the Invention
The present invention relates to liquid, concentrated,
homogeneous, stable, heavy duty de~ergen-t compositions.
Description of the Art
To be satisfactory for washing or pre-treating and
subsequent washing of heavily soiled abri~s, in particular
cotton fabrics, liquid detergent compositions must contain
; an adequate concentration of detergent compounds. In addition,
they must remain stable and homogeneous when subjected to
various storage conditions and be designed for use in both
horizontal ttumble drum type) and upright (vertical agitator
type) washing machines and for topical application as well as
for handwashing.
Liquid, heavy duty detergent compositions containing
a synthetic organic detergent compound, which is generally
anionic, nonionic or mixed anionic-nonionic in nature; an
inorganic builder salt; and a solvent, are disclosed, for
; example, in US patents 2,551,634; 1,908,651;2,920,045;
~ 2,947,702; 3~239~468; 3,272,753; 3,393,154; 3,554,916; 3,697,451;
3,709,838; Belgian patents 613,165; 665,532; 794,713 and
817,267; British patents 759,877; 842,813. These compositions
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frequently contain a hydrotrope or solubilizing agent to permit
the addition of sufficient quantities of surfactants and
usual builder salts to provide a reasonable volume usage/per-
formance ratio. Others are substantially anhydrous liquid
compositions containing an alkanolamine component (US patent
3,528,925). Still others contain a soap component (US pa~ents
2,875,153 and 2,543,744). -
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As can be seen from the foregoing, a substantial
effort has been expended in developing built and builder-free
detergent compositions in liquid form. Yet, there are several
problems associated with the art-disclosed compositions which
render them less optimal for wide scale use, undesirable Erom
an ecological standpoint in improperly treated sewage, objec
tionable from a performance point of view in cleaning bo~h
natural and synthetic fibers and subject to instability under
severe storage conditions.
It haslnow been found that superior detergency, in
particular with respect to bleach-sensitive stains, is obtained
if a mixture of a major amount of soluble ethoxylated nonionic
surfactant and a minor amount of a p~lyacid having at least one
pK value of at least 5~0 is combined in a liquid vehicle or
carrier, whereby the p~ of the detergent composition is in the .
range of from 6.0 to 7.5.
It has also been found that liquid, concentrated,
heavy duty detergent compositions containing a mixture of a
major amount of the soluble ethoxylated nonionic surfactant . .`
and a minor amount of the polyacids, having a pH in the range
of from 6.0 to 7.5, exhibit superior removal of bleach-sensitive
stains by topical application and through-the-wash fabric
cleaning.
In addition, it has been found that these liquid,
concentrated, heavy duty detergent compositions exhibit good
physical properties, remain homogeneous and stable under severe
storage conditions and stand the addition of màny usual adju
vantsO
It is, therefore, an object of this invention to
provide liquid, concentrated, heavy duty detergent compositions
which exhibit excellent cleaning and superior removal of
bleach-sensitive stains by topical application and through-
the-wash fabric cleaning.
It is another object herein to provide li~uid, con-
centrated, heavy duty detergent compositions which remain stable
and homogeneous under severe storage conditions.
It is still another objec~ herein to pxovide liquid,
concentrated, homogeneous, stable, heavy du-ty detergent composi-
tions acceptable from an ecological standpoint.
78
These and otller objects are obtained here:Ln, as will be seen Erom
the followin~ disclosure.
5~RY OF THE INVENTION
The present invention encompasses a liquid, concentrated, homogeneous,
stable, heavy duty detergent composition containing:
~: ~ (l) from about 20~ to about 70% by weight of a soluble ethoxylated
nonionic surfactant;
'~
(2) from 0.10% to 1.25%.by weight of a polyacid having at least one pK
value of at least 5.0;
(3~ balance: liquid carrier;
the pH of ~he detergent composition being between 6.0 and 7.5.
In a preferred composition aspect, the liquid composition comprises
a surfactant mixture containing different soluble ethoxylated nonionic
surEactants and optionally but preferably synthetic anionic surfactants
j 15 in amount up to 50% by weight cal.culated on the total nonionic sur~
: factant and synthetic anionic surEactant content.
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In another preferred embodi~.ent, the concentration of polyacid is
between 0.25% and about l.O~ by ~elght.
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In another preEerred embodiment, the pH of the composition is m the
~' 20 range between 6.0 and 7Ø
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In still another preferred en~odiment, the polyacid
has at least one pK value of at least 5.0 and preferably equal
or above x-l, wherein x represents the pH of the liquid compo-
sition.
DETAILED DESCRIPTION OF THE INVENTION
The properties of the compositions of the present
invention are the result of a combination of different compo~
nents and factors which have to be properly selected and
correlated as described in detail below.
The Ethoxylated ~onionic Surfactant
The instant compositions contain as an essential
component soluble ethoxylated nonionic surfactant.
Ethoxylated nonionic surfactants can be prepared
by a variety of methods well known in the art. In general
terms, such nonionic compounds are conventionally produced by
condensing ethylene oxide, forming the hydrophilic moiety
or ethenoxy chain, with a hydrocarbon having a reactive
hydrogen atom, e.g., a hydrox~l-, carboxyl- or amino group,
and forming the hydrophobic moiety, in the presence of acidic
or basic catalysts. Such procedures result in the production
o a product mixture comprising a number of nonionics of vary-
ing ethoxylate content. Therefore, the conventional designation
o the number of ethylene oxide units "m" present per molecule
of nonionic compound as designated~ for example, in the general
formula R-A(CEI2CEI2O)~IH, wherein R represents the hydrophobic
moiety and A the group carrying the reactive hydrogen atom,
is an indication of the average number of ethylene oxide units
; per molecule of nonionic compound according to a statistic ~ ;
distribution where the peak is situated around the "m" number.
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The properties of the ethoxylated nonionics depend
to a considerable extent on the hydr~philic moiety or average
number of ethylene oxide units present. Most commercially
available ethoxylated nonionics are viscous liquids or soft
pastes having in general from about ~ to about 20 to 24 ethylene
oxide units in average.
The soluble ethoxylated nonionic surfactants useful in
the compositions of the present invention include those compounds
which are obtained by reacting an alcohol with ethylene oxide
and which are soluble in the instant liquid compositions.
Ethoxylated nonionic compounds have a negative
temperature coefficient of solubility in water, becoming less
soluble at higher temperatures. Therefore, soluble in the
instant liquid compositions means soluble at temperatures
below about 35C.
Usually, the ethoxylated nonionic surfactants are
considered to include only those compounds which are soluble
in water. There is a large number of ethoxylated nonionic
j compounds having detersive properties but which do not have i,
enough hydrophilic character to be fully soluble in water but
are dispersible in water. They can be solubilized in water,
however, with the help of solubilizing agents such as lower
aliphatic alcohols, by admixing highly soluble ethoxylated
nonionic compounds or by hydrotropeis. Therefore, soluble
in the instant liquid compositions means soluble per se in
water or soluble in the instant liquid composition.
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i The hydrophobic moiety of the soluble ethoxylated
nonionic surfactants useful in the composition of the
present invention can be derived from primary and secondary,
straight or branched, saturated or unsaturated aliphatic
alcohols having from about 8 to about 24, preferably rom about
12 to about 20 carbon atoms. Another source is the alkylphenols
wherein the alk~l group on groups have Erom 1 to a~out 12 carbon
atoms, wherein at least one group has at least 6 carbon atoms
and the total number of carbon atoms in the alkyl groups is at
most about 15.
Primary alcohols can be derived from animal and
vegetable oils and fats by, for example, hydrogenolysis of
said oils,fats or corresponding fatty acids. They are sub-
stantially straight-chain or linear alcohols.
Primary alcohols can also be obtained from synthetic
sources by different processes. The usual raw materials are
polymers of lower alkylenes or olefins. According to the type
of polymers, olefins, processes and process conditions, alco-
hols with a different degree of linearity or branching are
obtained. The major part of the commercially available
primary synthetic alcohols are prepared by either the "oXO"
or "Ziegler" process.
Secondary alcohols are mostly obtained from synthetic
; sources, e.g., from olefins, either by direct hydration at
high temperatures and pressures or hydrolysis of thè intermediate
sulfuric acid product; by oxidation of paraffins, etc.
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Alkylphenols are obtained by reacting a phenol with
an olefin thermally preferably in the presence of a catalyst,
e.g., boron trifluoride. Xylenol and cresol can also be used
instead of phenol.
Preferred for the compositions of the present
invention are soluble ethoxylated nonionic surfactants derived
from primary and secondary aliphatic alcohols.
The hydrophilic moiety of thenonionic compounds useful in
the composition of th~ present invention is an ethenoxy chain
consisting of from 2 to about 24 e~hylene oxide units in average,
; depending upon hydrophobic character of the hydrocarbon group.
Preferred are those ethenoxy chains containing at least about
" 4 ethylene oxide units.
; Suitable examples of soluble ethoxylated nonionic
surfactants can, for example, be prepared from aliphatic primary
alcohols containing from 12 to 20 carbon atoms condensed with
from about 4 moles to about 14 moles of ethylene oxide per mole
of alcohol and mixtures thereof. Non-limiting, specific
examples of soluble ethoxylated nonionic surfactants derived from
straigh~ chain primary aliphatic alcohols are:
12 25 (C2H4O) 6 H; C16H33__ (C2H4O) 9-H; C18H35__ (C2H4O) -H;
C H -O- ~C2H40) g-Hi C14H29-- tC2H4~) 9 H; C12 25 2 4 9
12 25 (C2H4~ 4 H; C16H33-- (C2H4~) 9-EI; tallow-O-(C2H4o)ll_H;
CllH23 (C2H4)4 H; C16H33-O(C2H4O)7-H; and mixtures thereof.
~,
Non-limiting,specific examples of soluble ethoxylated nonionic
surfactants derived from secondary aliphatic alcohols are:
12 25 4 9 ( 2 4 )9 ; 8 17 (C4 9) O (C2H4) 12 H;
7 15) 2CH (C2H4) 6-H; C17H35CH (CH3)--O- (C2H40) -H;
C H gCH ( C3H7 )--O--( C2H40) 9 H; Cl4 29 3 2 4
; 30 and mixtures thereof. Non-limiting,specific examples of
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soluble ethoxylated nonionic surfactants derived from
branched primary aliphatic alcohols are: CloH21CH(CH3)CH2-0-
(C2H40)9-H; C12H25-CH(CH3)CH -0-(C H 0) H; C H CH(CH )CH -0-
(C H40)9-H; C13~27CH(CH3)CH2 CH2 C 2 2 4 9
C H CH(C2H5) CH2-0-(C2H40)9-H; (C7H15)2 2 2 4 12
9 19 8 17) 2 (C2H40)12-H; C13}I27CH(C4Hg)CH2-0-(C H 0) -~;
13 27 ( 3 7) 2 2 ~C2H40)9 H, and mixtures thereof.
Non-limiting,specific examples of soluble ethoxylated nonionic
surfactants derived from alkylphenols are CgHlgC6H4~0~(C2H40)9-H;
10 C H C6H4-O-(c2H40)l2-H; (C9Hl9)(CH3)C6 3 2 4 12
12 25 3)2 6H2 (C2H40)11-H; C12H25C6H4-0-(C H o) -H;
and mixtures thereof. Non-limiting,specific examples of
mixtures of soluble ethoxylated nonionic surfactants consisting -
of slightly water-soluble and highly water-soluble compounds
useful in the compositions of the present invention are: 1/2
mixture ~f C12H25-0-(C2H40)5-H and C12 25 2 4 12
1/1 mixture of C14H29~0-(C2H40)5-H and tallow-0-(C2H40)11-H;
2/1 miXture f C15H31-0-(C2H40)7-H an~ tall~w-o-(c2~4o)ll-H;
ClOH21 (C2H4)3-H and C13~I27CH(CH )CH -0-
(C H 0) -H; 1/1/1 mixture of C8H17CH(C6H13) (C2 4 )6
Cl2H25cH(cH3)cH2-o-(c2H4o)4 and C18 37 2 4 15
; mixture of CgHlgC~H4-O-(c2H40)g H; ClsH31 ( 2 4 5
;~ Cl8H37-o-(c2H4o)l2-H; 2/1/1 mixture of (CH3)3C(CH2)8CH2-0-
2 4 3 16 33CH~CH3)CH2-0-(C2H40~ll-H and C14H29CH(CH )~~
(C2H40)9-H (all ratios being by weight).
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A part:icularly pre~crrcd soluble ethoxylated nonion:ic surfactant ls
represented by a m:ixture o[: (1) a primary al:Lphatic alcohol ethoxylate
obtained fron~ an alcollol, the hydrocarby:L cha:in of which contains
at least 65% branched-chaln structure and is obtained by hydro-
formylation of random olefins and has from about 14 to about 22,
especially from 16 to 19 carbon atoms in the hydrocarbyl chain, and
8 to 14 ~oles of ethylene oxide; and (2) an alcohol ethoxylate derived
from a primary alcohol with preferably 40% branched-chain structure
. and havin~ from 9 to 15~ especially from 12 to 15 carbon atoms in the
10 hydrocarbyl chain, and 3 ~o 7 moles of ethylene oxide.
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Adjunct Sur~actants
The compositions herein can optionally contain various
other adjunct surfactants, which can be used to perform specific
cleaning, grease-emulsifying and suds-modifying functions.
Such optional adjunct surfac~ants include synthetic anionic
surfactants of the sulfonate and/or sulfate type, semipolar
surfactactive agents and fatty acid al~anol-a~ides known in the art.
Synthetic anionic surfactants of the sulfonate type
useful herein include paraffin sulfonic acid and olefin sulfonic
acid having from 6 to about 20 carbon atoms in the hydrocarbon
group; alkylbenzene sulfonic acids having from 8 to about 15
carbon atoms in the alkyl group; mixtures thereof; and their
water-soluble salts.
The preferred synthetic anionic surfactant component
~-~ useful in the instant detergent compositions is a water-soluble
-i salt of an alkyl-benzene sulfonic acid, preferably an alkanol
amine alkylbenzene sulfonate, having from about 12 to about
15 carbon atoms in the alkyl group. More specifically, the
most preferred synthetic anionic surfactant herein consists
of a mono-, di- or triethylamine salt of a straight chain
alkylbenzene sulfonic acid in which the alkyl group contains
in average about 12 carbon atoms. ~`
5pecific examples of alkylbenzene sulfonic acids and
of the corresponding alkanolamine salts useful in the instant
invention include decylbenzene sulfonic acid and triethanolamine
-' decylbenzene sulfonate, triethanolamine dodecyl benzene
' sulfonate, diethanolamine undecyl benzene sulfonate, ;
tridecylbenzene sulfonic acid and monoethanolamine tridecyl- ~ -
benzene sulfonate, triethanolamine tetradecylbenzene sulfonate-
and tetradecylbenzene sulfonic acid, and mixtures thereof.
` Said mixtures of acids and salts can, if necessary, be adjusted
to regulate the pH of the compositions.
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l78
A partlcularl.y pre~erred surEactant mixture for use in the composltions
of thls invention compr.ises a solub:le nonlonic surfactant whlch ls a
mixture of: (1) a primary al:iphatic alcohol ethoxyla~e wherein the
hydrocarbyl chain contains at least 65% branched chaln structure and
has from about 14 to about 22, especially from 16 to 19, carbon atoms
and containing 8 to 14 moles of ethylene oxide; and (2) an alcohol
ethoxylate derived from a primary alcohol with preferably 40% branched-
chain structure and havi.ng from 9 to 15, especiall.y from 12 to 15
carbon atoms in the hydrocarbyl chain 9 and 3 to 7 moles of ethylene
oxide; and a synthetic anionic surfactant which is an ethanolamine
alkylbenzene sulfonate having from about 9 to about 15 carbon atoms
: in the alkyl chain.
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S The concentration of the adjunct synthetic anionlc
surfactant of the sulfonate type useful in the instant compo-
sition should be below 50~ by weight, preferably below 20~ by
weight, calculated on the total amount of soluble ethoxylated
nonionic surfactant and synthetic anionic surfactant taken
to~ether.
Semi-polar surfactants useful herein include water-
soluble amine oxides containing one alkyl moiety of from about
10 to 24 carbon atoms and two moieties selected ~rom the
10 group consisting of alkyl moieties and hydroxyalkyL moieties
containing from 1 to about 3 carbon atoms. Specific examples of
semi-polar surfactants are: dodecyldimethylamine oxide;
dodecyldiethylamine oxide; tetradecyldi(hydroxyethyl)amine
. oxide; and mixtures thereof.
Alkyl sulfates useful herein are the water-soluble
salts, in particular the ethanolamine salts of sulfated higher
alcohols especially those ~btained by sulfating fatty alcohols
containing from about 10 to 18 carbon atoms. Ethoxylated
alkyl sulfates useful herein are the water-soluble salts,
20 preferably the ethanolamine salts of sulfuric acid esters
of the reaction product of one mole of a higher fatty alcohol,
e.g., tallow or coconut alcohols, most preferably lauryl,
myristyl or palmityl alcohols, and 1 to about 15, preferably
from about 1 to about 6 moles of ethylene oxide per mole of
fatty alcohol.
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The concentration of the adjunct surfactants of the
semi-polar type and the sulfate, incl~ding ethoxylated sulfate,
type in the instant compositions can be up to 50% by weight
; calculated on the total amount of soluble ethoxylated nonionic
and anionic surfactant compounds taken together. In certain
compositions it may be desirable to incorporate below 10~,
preferably below 5% by weight, calculated on the amounts of
soluble ethoxylated nonionic surfactants, of these semi-polar,
sulfate and ethoxylated sulfate types of adjunct surfactants.
10When adjunct surfactants are present in the composi-
tions of this invention, the total amount of surfactant should
not be more than 70% by weight of the total composition.
The Pol~acids
The second essential component of the compositions
of the present invention is a polyacid having at least one pK
value of 5.0 or higher.
An acid can be defined as a compound capable of
accepting a pair of electrons to form a co-ordinate bond
(G.N. Lewis definition), or as a compound furnishing a proton
(Bronsted-Lowry definition), or simply as a hydrogen-containing
substance which dissociates on solution in water producing
one or more hydrogen ions~
Acids can be classified as monobasic, dibasic, tribasic,
etc.,according to the number of hydrogen atoms contained in the
compound, replaceable by bases or dissociable in water.
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AS acids dissociate on solution in water, they
can be characterized by-~eir dissociation constant (~Jhich is to a certain
degree depelldent upon the temperature of the solution medium
or water). The practical dissociation constant, usually indi-
~t cated as and represented by the symbol pK, is e~pressed as the
negative logarlthm of the dissociation constant. Dibasic, tri-
basic acids produce 2, respectively 3 protons on solution in
water; hence, they can be characterized by their 2, respectively
3 pK values. Generally, said pK values are de-fined at ambient
temperatures, i.e., 10-30C; but, since the changes in pK
values for a given acid hardly differ if measured either at
10 or 30C, the temperature at which the pK's are measured
are of minor importance with respect to the present invention,
. .,
provided they are within said range of about 10 to about 30C.
; Thus, the second essential component of the composi- ~
tions of the present invention is a polyacid having at least ~;
one pK value of 5.0 or higher, if measured at a temperature
within the range of from about 10 to about 30C.
~ The polyacids useful in the present invention can
j; 20 be either organic, i.e~, containing carbon atoms in the
molecule and having preferably a -COOH group as proton donor,
or inorganic. Speoific non-limiting examples of
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useful polyacids having at least one pK value of 5.0 or higher
are (between braekets the temperatures at whieh the dissoeia-
tion constants are measured); see for example) Handbook of
Chemistry and Physics, published by the Chemical Rubber Publish-
ing Co., Cleveland, Ohio, 50th Edition, pp. 1753, etc.):
ascorbic acid~ pK: 4.10 and 11.79 (24, 16C);
aspar'cie aeidr pK: 3.86 and 9.82 (25C);
: eitric acid, pK: 3.08, 4.74 and 5.40 (18C);
eyelohexane-l,l-diearboxylie aeid, pK: 3.45 and 6.11 (25C);
eyelopropane~ diearboxylie aeid, pK: 1.82 and 7.43 (25C);
dimethylmalic aeid, pK: 3.17 and 6.06 (25C);
diglyeollie aeid, pK:3.4 and 5.11;
glutarie aeid, pK: 4.34 and 5.41 (25C);
o-hydroxybenzoie aeid, pK: 2.97 and 13.40 (19, 13C);
m-hydroxybenzoie aeid, pK: 4.06 and 9.92 (19C);
p-hydroxybenzoie aeid, pK: 4.48 and 9.32 (19C);
. itaeonie aeid, pK 3.85 and 5~45 (25C);
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maleic acid, pK: 1.83 and 6.07 (25C);
malic acid, pK: 3.40 and 5.11 (2~C);
methylsuccinic acid, pK: 4.13 and 5.64 (25C);
o-phthalic acid, pK: 2.89 and 5.51 (25C);
succinic acid, pK: 4.16 and 5.61 (25C);
o-phosphoric acid, pK: 2.12, 7~21 and 12.67 (25C, 25C, 18C);
pyrophosphoric acid, pK: 0.85, 1.49, 5.77 and 8.22 (25C);
Na2H2P20~, pK: 0.86, 1.96, 6.68 and 9.39 (25C);
nitrilotriacetic acid, pK: 3.03, 3.07 and 10.7 (25C);
ethylene diamine tetraacetic acid, pK: 2.0, 2.7, 6.2 and 10.3;
ethylenediaminotetramethylenephosphonic acid, pK: -, -, 3,
5.2, 6.5, 8.1, 10.2 and 12.0 (25C).
and mixtures thereaf.
Preferred are polyacids whereby at least one pK value
is at least 5.5 or, with reference to the pH of th~ compositions,
have at least one pK value which is equal to or above x-l wherein
x represents the pH of the liquid composition, thus whereby for
a composition having a pH of 6.8, has a pK value of at least
6.8 - 1 = 5.8 or hi~her.
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Most preferred polyacids are those having at least
two pK values o~ 5.0 or higher and more particularly, with
reference to the pH of the composition, have at least two pK
values of x-l or higher (x = pE~ of the composition), thus
whereby for a composition having a pH of 6.5, they have at least
two pK values of 6.5 - 1 = 5.5 or higher.
' Specific, non-limiting examples of preferred poly-
acids useful in the composition of the present invention are
diglycollic acid, ni~rilotriacetic acid and citric acid.
Specific non-limiting examples of most preferred polyacids
useful in the composition of the present invention are
s ~ Na2H2P207, pyrophosphoric acid, ort~ophosphoric acid and
ethylene.~diamine tetraacetic acid. Another class of most
, preferred polyacid species for use herein comprises organo-
phosphonic acids, particularly alkylene polyamino polyalkylene
phosphonic acids, inclusive of ethylene dianine tetramethylene phos-
phonic acid; hexamethylene diamine tetramethylene phosphonic
' acidi diethylene triamine pentamethylene phosphonic acid; and
' ~ aminotrimethylene phosphonic acid. :
The polyacids can be added as such into the composi-
tions of the present invention or in the form of their water
s~luble salts or semi-salts, e.g., as H4P207, Na2H2P207, or
Na4P207. It may be necessary, howevex, to add pH-regulating
agents, well known in the art, to adjust the pH of the com-
positions.
` Irhe pH
An essential condition of the present invention is
that the compositions have a pH within the range of from 6.0
to 7.5f preferably between about 6.0 and 7Ø
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Compositions containing the essential components of
the present invention, but having a pH below 6.0 become
difficult to process and are unstable, particularly if they
contain stilbene-type brighteners, in addition they become
less attractive because unsafe for topical application.
Compositions containing the essential components ~-
of the present invention but having a pH above 7.5 lose
their effectiveness with respect to removal of bleach-sen-
sitive stains.
Liquid Carrier
As liquid carrier, water, organic solvents, and
mixtures thereof, can be used.
Compositions containing the above-described
essential surfactants, polyacids and water will remain liquid
and stable under most circumstances, particularly if the
soluble ethoxylated nonionic surfactant has a relatively
long ethenoxy chain, i.e., wherein the number of ethoxy units
is at least equal to or higher than half the number of carbon i~
atoms of the hydrophobic moiety.
The liquid carrier used in the instant compositions
may comprise water and an organic solvent. The organic solvent
may comprise up to about 50% of the total liquid carrier usëd
I in the compositions.
The organic solvents, which should not chemically
react with any of the components of the instant compositions,
are selected from the group consisting of lower aliphatic
alcohols having from 2 to 6 carbon atoms and 1 to 3 hydroxyl
groups; ethers of diethylene glycol and lower aliphatic
mono-alcohols having from 1 to 4 carbon atoms; and mixtures
thereof.
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Elydrotropes selected from t~e water-soluble salts
of alkylbenzene sulfonic acids having up to 3 carbon atoms
in the alkyl groups are also useful in compositions of this
invention.
Suitable examples of lower aliphatic alcohols
useful in the instant compositions are ethanol, n-propanol,
isopropanol and butanol; 1,2-propanediol, 1,3-propanediol,
and n-hexanol. Useful examples of glycol ethers are monomethyl-,
-ethyl-, -propyl-, and monobutyl ethers of diethylene glycol;
and mixtures thereof. Other organic solvents having a relati-
vely high hoiling point and low vapor pressure could alsobe used, provided they do not react with any of the other
ingredients present.
Suitable examples of hydrotropes that can be used
in the instant ~positions are thewater-soluble alkylaryl sulfon-
ates having up to 3 carbon atoms in an alkyl group such as
sodium, potassium, ammonium and ethanol amine salts of xylene-,
toluene-, ethylbenzene-,and isopropylbenzene sulfonic acids.
They are preferably used in compositions containing, in addition,
a synthetic, anionic surfactant of the sulfonate type. Hydro-
tropes can conveniently be considered as part of the liquidcarrier of the composition since the hydrotrope will necessarily
dissolve therein.
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In the preferred compositions, the liquid carrier
is an aqueous mixture, wherein the amount of organic solvent,
preferably ethanol, prcpanol, isopropanol, sodium salt of
cumene sulfonic acid, and mixtures thereof, is between 2% and
,~ 15~ by weight of the total composition.
Concentration and Ratios
Heavy duty liquid detergent compositions, to be
suit~d for the washing of the heavily soiled fabrics, require
high COncentratiQnS of surfactants of powerful cleansing
; 10 effect. They must exhibit a high degree of stability upon
- ~ storage over a period of months under different temperature
conditions. They must be free-flowing from the receptacle
as manufactured and after aging. They must be homogeneous
in compositions at the time of use to ensure the addition
of the proper amount and ratio of the components.
The physical and cleaning properties of the instant
compositions are the result of mutual effect of the different
components in proper ratios. Therefore, it is the key to
stability, pourability, homogeneity and cleaning effectiveness,
. . . .
that the essential surfactants be present in specific ratios
and sufficient concentration.
The instant compositions are specifically designed
J to provide optimum cleaning benefits when used either as
pre-treatment agents, preferably applied in highly concen-
trated form directly onto the fabric stains, in particular
~ onto bleach-sensitive stains, prior to washing, or as
; detergents for conventional through-the-wash fabric
laundering operations. Hence, highly concentrated,
;,
.
6~8
liquid, stable, homogeneous detergent compositions, which can
be topically applied onto stains as such, and can be conveniently
added to the washing liquors, provide a clear formulation advan-
tage.
The instant compositions remain liquid, stable, homo-
geneous with a surfactant content variable within the range of
from about 20% to about 70~ by weight, with the balance being
primarily the minor amount of polyacids and the liquid carrier.
Preferred compositions contain at least about 25%
by weight of soluble ethoxylated nonionic surfactant in order
to ensure proper greasy stain removal performance in both
pre-treatment or topical application and through-the-wash
utilization of the instant compositions.
Most preferred are compositions containing at least
about 25% by weight of soluble ethoxylated nonionic surfactant
and up to 25% by weight of an synthetic anionic surfactant of
the sulfonat~ type and wherein the total amount of surfactants
-is below about 60% by weight~
The amount of polyacids present in the instant com- ~
20 positions is critical and must be, with reference to the acid ~`
form, within the range of from 0.10% to about 1.25~ by weight,
;calculated on the total weight of the composition. Preferably,
the amounts of polyacids vary in the range between 0.25~ and
1.0% by weight, whereby, most preferably, the concentration is
inversely related to the pK value or values that are above 5Ø
,
- 18 -
~6~
Compositions having the appropriate amount of soluble
ethoxylated nonionic surfactant and a pH between 6.0 and 7.5,
but having a c3ncentration of polyacids below 0.10~ by weight,
hardly provide any detergency effect on bleach-sensitive stains.
f By increasing the concentration of polyacids beyond 1.25% by
` weight, no additional detergency effect via topical application
' ~ will be obtained, particularly on bleach-sensitive stains,
while phase separation of the composition occurs and precipi-
tation o~ some polyacids, particularly of inorganic acids,
. 10 can take place.
Optional Components
An optional component of the instant compositions
is an alkanolamine compound. The free alkanolamine useful
hereint in particular to adjust the pH of the comp~sitions,
' is selected from the group consisting of mono-, di- and tri-
ethanolamine, and mixtures thereof; preferred is the trlethano-
lamine. The amount of alkanolamine which can be added can be
up to 5~ by weight, but is preferably below 2% by weight.
f;~ A desirable component for addition herein is a
20 suitable opacifier. An opacifier contributes to create a
` uniform appearance of the compositions of this invention.
Examples of suitable opacifiers include polystyrene commercial-
ly sold under the trade marks LYTRON 621 and LYTRON 607 manu-
factured by Monsanto Chemical Corporation. It has been found
that the LYTRON opacifiers can be incorporated in the
compositions of this invention only in presence of polyacid,
i.e., the opacifier precipitates in the compositions herein
which do not contain the polyacids.
Another optional component of the instant compositions
30 is an aliphatic carboxylic acid as suds-controlling agent,
having from 12 to 24, preferably from 16 to 22 carbon atoms.
- 19 _
~
.~ . ~. .
8~7~
Its concentrations should not exceed 2.5% by wei~ht and pref-
erably be restricted to at most 1.5~ by weight, calculated on
the total weight of the composition.
Another optional but preferred component is a sili-
cone-based suds-controlling and regulating agent. A heavy duty
liquid detergent composition desiyned for use in both horizontal
and vertical washing machines must have acceptable sudsing prop-
erties when used in either of these machines. The silicone-
based suds-controlling and regulating agents useful herein
can be alkylated polysiloxane materials of several types, in
combination with solid materials such as solid silica, silica
aerogels, xerogels and hydrophobic silicas of various types.
Suitable examples of alkylated polysiloxanes are dimethyl-
polysiloxanes having a molecular weight of from about 200 to
200,0~0. Suitable examples of mixtures of alkylated siloxanes and solid
silica have a siloxane/silica ratio of from 20:1 to 1
preferably 10:1 to 3:1. Concentrations of suds-controlling
agents useful in the instant compositions can vary between
0.01% and 2%; preferably 0O05% and 0.2~.
A preferred suds-controlling agent herein comprises
a mixture of (a) dimethylpolysiloxane and silica-aerogel in a
9:1 weight ratio emulsified in (b) a nonionic of the general
formula R'COO-(C2H40)p-H, wherein R' is an aliphatic hydrocarbon
chain having 10 to 22 carbon atoms and p is a number of 300 to
2,000, in a weight ratio of (a) to (b) of from about 1:4 to 1:1,
preferably about 1:2. Due to the pre-emulsification of the
siloxane and silica, the preferred suds-controlling agent is
easily dispersed in the instant compositions, and shows an
extraordinary storage stability and suds-controlling effective-
ness irrespective of the aging. Concentrations of the preferred
silicone-based suds-controlling agents, preferably present in the
- 20 -
6171~
instant compositions can be up to 0.5~ by weight, preferably
between 0.05% and 0.2% by weight.
Still other optional components include brighteners,
fluorescers, antimicrobial agents and enzymes. Such components
preferably comprise not more than about 3~ by weight of the
total compositions. One particular advantage of the instant
compositions is that the hardly water-soluble brighteners and
~; fluorescers can be added either directly to the compositions,
i.e., as such, or during any st~p of the formulation process.
TESTS AND EXAMPLES
,~
The Eollowing tests and examples illustrate the
liquid detergent composition~ of the present invention. The
figures mentioned in the examples refer to percentages by weight.
. ~ , .
The abbreviations for the nonionic surfactants employed, e.g.,
C12 15(EO)~, are standard for such materials and C12 15 describes
the carbon atom content of the hydrophobic moiety o~ the molecule
while (EO)4 indicates the ethylene oxide unit content of the
hydrophilic moiety of the molecule.
The effectiveness of the instant compositions, par-
ticularly with respect to bleach-sensitive stains, if compared
to practically identical or commercially available detergent
compositions, is illustrated below, whereby most tests have been
carried out by means of a "Launder-Ometer" device and some have
been duplicated under real washing conditions. The~"Launder-
Ometer" device is described, for example, in "Detergency, Theory
and Test Methods" ~y N. G. Cutler and R. C. Davis, part I,
pages 415-417 (edition 1972, Marcel Dekker, Inc., New York).
~ - 21 -
,
.,
In all tests, stalned swatches were used, prepared
as follows:
(1) cotton swatches, swatches of new but p.rewashed cotton
(5 x 5 cm) were stained with red wine and tea respectively,
by moistening them with 5 drops - Pasteur pipette - of red
wine or 5 drops oE tea obtained b~ boiling 15 gr. of tea
or 5 minutes in 200 cc. of water, and aging for at least
24 hours at ambient temperature; (2) polyester/cotton swatches
` ~( 65/35; 5 x 5 cm), swatches of new but prewashed polyester/
cotton swatches were prepared in the same manner as the
cotton swatches.
.
; ' :
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~
,~
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~ - 21a -
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,
78
TEST A
The effectiveness on removal of bleach-sensitive
stains by liquid compositions of the present invention, if
compared to pract.ically identical liquid compositions but
wlthout th2 essential polyacids,is illustrated by the follow-
ing Test A.
A series of six liquid detergent compositions Al-A6
were prepared, consi.sting of:
Components: 1 A2 A3 A4 A5 A6
-triethanolamine salt of - - - 12 16 20
: linear alkylbènzene sulfonic
acid wherein the alkyl chain
has in average 11.l9 carbon
atoms.
;. -C14_15(EO)4 15 20 25 - _ _
-tallow (EO)ll 15 20 25
~C12_15(EO)4derived from a _ _ _ 6 8 10
primary alcohol with about
60~ by weight of branched
20 chain structure
C16-19 (EO)ll derived from _ _ _ 12 16 20
a primary alcohol with about
72% by wt of branched chain
. structure
-optical brightener (stilbene 0.2 0.2 0.2 0.20.2 0.2
type)
~~thanol 15 15 15 10 10 10
-perume,dyes ~ minors
-triethanolamine ~ to adjust pH -
30 -water ~ u-balance - ~
pH of the compositions 7.0 7.0 7.0 7.0 7.0 7.0
.
Another series of six detergent compositions were ~.
. prepared identical to the ones of the previous series except ~ :
: that 0.35% by weight of ethylenediaminotetramethylenephosphonic
acid (EDTMP) was added.
- 22 -
11 ~86,~
A jar of the "Launder-Ometerl' device was filled
with 0.2 liter of water (hardness : 3.14 millimoles/liter as
CaCO3) and about 1.6 gr. o the detergent product to be tested.
Two cotton swatches stained with red wine and two cotton
swatches stained with tea were pretreated by topical applica~
tion of the product to be tested applied onto the stains
(yielding a total amount of composition to be tested per jar
of about 2.6 gr. or a concentration of about 1.3% by weight).
For each composition Al~A6, two jars were prepared as described.
The 12 jars were placed in the "Launder-Ometer" and the
temperature raised up to 60C over a period of 40 minutes.
Subsequently, the swatches were rinsed ~or about 3 minutes
under running tap water (temperature about 17C) and line-dried.
The line-dried swatches were then visually graded by two graders
working independently, using a 0-5 scale tunder Northern
standard daylight; 0 = no removal of the stain, 5 = complete
removal). Thereafter, all the results of both graders were
pooled. The results are given in Table I.
TABLE I
.;
o~poslti~, First series Second series with
wi~hout ~DTMP 0.35~ EDT~P
_. . . ~ . . . _. _ _ . _
Al 2.85 4.2
A2 2.8 4.4
A3 2.65 4.2
A~ 4.1 4.75
A5 4.0 4.7
6 4.8
' '
' ' ~ -
- 23 -
'~ :
~86~L7b~
Thus the bleach-sensitive stain removal performance
of the compositions of the present invention, i.e., containing
a small amount of a polyacid, is significally superior over
practically identical compositions but containing no polyacid~
TEST B
A series of six liquid detergentcompositions were pre-
pared consisting of:
Components 1 B2 B3 B4 B5 B6 `;
-triethanolamine salt of a 20 20 20 20 20 20
lO linear alkylbenzene sulfonic
acid wherein the alkyl chain
averages 11.9 carbon atoms
in length
-C14-15(E)7 30 30 30 30 30 30
-optical brightener (stilbene ~ -0.2 -
; type)
- -triethanolamine ~-to adjust pH - ~
-ethanol 15 15 15 15 15 15
-perfumes, dyes minors
20 -water balance
-ethylenediaminotetramethylene- - - 0.35 0.35
phosphonic acid (EDTMP) x
-citric acid - - - _ 0.5 0.5
pH 7.0 6.5 7 6.5 7.0 6.5
'
These compositions Bl-B6 were tested in exactly the
same way and under the same conditions as the compositions
Al-A6 described in Test A. Thé stained swatches were similar
; to those of Test A and they were graded in the same way too.
The pooled results are given in Table II.
~.:
., ~
- 2~ -
~: .
7~
TABLE I I
~ _ _ _ ___ . .
Compositions Bl B2 B3 B4 B5 B6
gradings 1.8 2.3 4.0 4.5 2.6 3.45
.... . _
From Table II, follows: the superiority of compositions
B3 B6 ormulated according to the present invention over
the compositions Bl and B2; the correlation between the
pH of the composition and the pK value of the acid which is
; above 5 but within one unit of the pH of the composition,
i.e. for citric acid having pK values of 3.08, 4.74 and 5.40,
the effectiveness is more pronounced with a composition having
a pH of 6.5 (B6) than with a composition having a pH of 7 (B5);
and the effectiveness of polyacids as EDTMP having more than
one pK value above 5. 0 (B3 and B4 are more effective than
B5 or B6.)
TEST C
The influence of the pK values of the polyacids
on the bleach-sensitive stain removal per~ormance in
correlation with the pH of the detergent composition is
~; illustrated by the following Test C.
A series of six liquid detergent compositions were
prepared Cl-C6, identical to the composition A6, except that
compositions C2-C6 contained in addition the following polyacids:
Cl = A6 (thus no polyacid)
C2 = A6 + 1% by weight of Na2H2P207 ~(pK:0.86; 1-96, 6-68; 9-39)
C3 - A6 + 1% " " ~I citric ~cid (pK : 3.08; 4.74; 5.40)
C4 = A6 -~ 0-5% " " " nitrilotriacetic acid (pK : 3.03; 3.07;
10.7)
5 A6 + 0 5% " ~ " glycolic acid (pK : 3.83) -~;
6 A6 + 0~5% " " " adipic acid (pK : 4.43; 4.41).
The pH of all compositions was 7Ø
- 25 -
6~7~ ,
, I ,
Each of these compositlons Cl-C6 was tested under
exactly the same conditions as the compositions Al-A6 in Test A.
The line-dried cotton swatches were grad~d by two
graders independently and the results of all stains and
all swatches were pooled. The bleach-sensitive stain removal
performance of each composition is given in Table III.
TABLE III
- - ~ . .. _ __ . .. _ ~ _ ~ _ ~
: Compositions Cl C2 C3 C~ C5 C6
.~ . _ .. __
Gradings 1.25 3.90 2.75 3 25 l.00 0.75
, _.................................. .. .. .. .
!' 10 The superiority in bleach-sehsitive stain removal
performance of compositions C2, C3 and C4, formulated according
to the present invention, over compositions C5 and C6 containing
similar amounts of a polyacid (C6) but with pK values below
x-l, or a monoacid (C5), is evident.
TEST D
The present test shows the effectiveness of removal
of bleach-sensitive stains (wine, tea) via topical application '~
by compositions of the instant invention containing no bleaching
agents versus commercially available granular detergent compo-
sitions.
A series of five detergent compositions Dl-D5 were
prepared and tested, being:
:
. .
.,
- 26 -
' .
~L~8~7E~
Dl : identical to composition A6 of Test A;
D2 : identical to Dl but containing 0O35% by weight of
ethylenediaminotetramethylenephosphonic acid (EDT~IP);
D3 : identical to Dl but containing 1~ by weight of citric
acid;
D4 and D5 : commercially available granular detergent
compositions consisting of (in % by weight)
, .
Components D4 5
-sodium salt of linear alkylbenzene 9.3 8.1
sulfonic acid wherein the alkyl
chain has 11.9 carbon atoms in
: average
-tallow (EO)ll 3.4 0.8
-hydrogenated fatty acid derived from 3.4 1.7
fish oil having 16 to 22 carbon
atoms
- sodium tripolyphosphate 35.0 67.0 ~ ::
-sodium silicate (SiO/Na20) 6.0 - : ~ .
: -brightener (stilbene type) 0.2 0.25 ,
-sodium carboxymethyl cellulose (100%) 0.8 1.5
~ -perfume 0.2 0.2
; -ethylenediaminotetraacetic acid 0.2 0.2
sodium salts
~ ''' .
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- 27 -
.
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D4 5
a2 o4 13.5 6.0
-sodium perborate 25.0
-polyethyleneglycol condensate 0.2 0.2
(average molecular ~7eight about 400)
-miscellaneous 1.0 1.0
-proteolytic enzyme * 0.2 0.2
-moisture ----- balance -~
* proteolytic enzyme: "ALCALASE" - Trade Mark - made by Novo
Industri A/S, Copenhagen, Denmark, containing about 6% by
weight of active enzyme material.
: Test D with compositions Dl-D5:is carried out in
the "Launder-Ometer" device under exactly the same conditions
as described in Test A, with the same number of wine- and
tea stained cotton swatches, except that 2.6 gr. per jar of each
granular detergent D4 respectively D5 is presolubilized in
0.2 liter of water just prior to the test tno topical application
. ~ . .
with the presolubilized granular composition)~ The rinse and
:. line-dried swatches are then graded by two graders as described
in Test A and all the results pooled. The pooled results are
given in Table IV.
~ '
~.
: . - .
- 28 -
61'7~
TABLE IV
, .. .. __ _ .
Compositions Dl D2 D3 D4 D5
Gradings 2.45 4.85 3.604.90 3.50
~,'
TEST E
: Test E shows the effectiveness of compositions of
the present invention under real washing conditions.
The following series of four detergent compositions
El-E4 were prepared and tested:
El : identical to the granular composition D4; ; :
E2 : identical to composition A6 of Test A, but
containing 0.5% by weight of citric acid and
. having a pH of 6.5;
E3 : identical to composition A6 of Test A, but containing
0.35~ by weight of EDTMP (pH = 7);
E4 : identical to E2 but containing 1% by weight of Na2H2P2o7
instead of citric acid (pH 5.65~.
-` In addition, composition= E2, E3 and E~ contained ;~
about 0.9~ by weight o~ a fatty acid having 16 to 22
carbon atoms. With each of these.compositions El-E4,
four loads of about 3 kg each of domestic soiled laundry
were washed in a horizontal drum-type washing machine .
:- tMIELE 416S). ~ . :
.
,; .
~ 29 -
~ :
.,. .. . . . ~ .
lq~B6i'78
Each load contained in addition two cotton and
two polyester/cotton swatches (10 x 10 cm), stained with
tea, coffee and red wine re~pectively (stalning~ by 5 drops
- Pasteur pipette - of red wine on cotton swatches and
5 drops on polyester/cotton swatehes; with tea: 5 drops of
a mixture obtained by boiling 15 grams of tea for 5 minutes
; in 200 cc. of water, on cotton swatehes and 5 drops on
polyester/eotton swatches; with coffee: 5 drops o a mixture
obtained by boiling 25 gr. of coffee for 5 minutes in 200 cc.
of water, on cotton swatches and 5 drops on polyester/cotton
swatehes; aging: at least 24 hours at room temperature.
Each of the stains on the swatches (12 in total
tested with compositions E2, E3 and E~) were each pretreated
with about 1 gr. of the liquid eomposition to be tested
(i,e., about 12 gr. in total per load) and about 108 gr. of
the detergent compositions E2-E4 were added into the respective
washing iiquors (resulting in a total concentration of about
0.60% by weight). The swatehes washed with test composition
El were not pretreated but the total concentration of composition
El was also 0.6% by weight.
These loads of domestie soiled laundry and swatehes
were washed at onee. In the main wash eyele of the washing
maehine in about 20 liters of water (hardness : 3.14 milli-
moles/ liter as CaCO3). The temperature of the washing
liquor was raised to about 60C over a period of 25 minutes
ancl kept at that temperature for an additional 30 minutes.
After dilution of the washing liquor, evaeuation of the diluted
liquor and rinsing of the load (five cyeles with about 10 litres
of water; hardness of water : 3.14 millimoles/liter; temperature
; 30 19-16C; and spinning) all swatehes were removed, line-dried,
and the dried swatches visually graded by two graders working
independently, using a 0-5 seale (0 = no removal of the stain;
. .
-. . . ~ :
78
5 = complete removal). Thereafter, all results of the
graders with respect to the stains on cotton and polyester/
cotton swatches were pooled. The results are given in Table
V hereafter.
The same test was repeated with the compositions
-E4, all conditions being identical, e~cept that none of the
swatches were pretreated and 120 gr. of each of the compo-
sitions E2-E4 tested were added directly into the washing
liquor. The line-dried swatches were again graded as
described previously but whereby the results with respect to
the cotton swatches and polyester/cotton swatches were
pooled separately. The results are given in Table V.
TABLE V
Washing ComposLtions
Swatches Procedure _ _
El E2 E3 E4
polyester/ with pretreatment _ 4.63 4.79 4.66
cotton
without pretreatment 4.30 3.64 4.53 3.95 ~
cotton with pretreatment _ 3.37 4.44 4.37 -
~ without pretreatment 4.36 2.73 3.66 3.00 ~
, .
From this Table V, it follows that compositions
of the present invention are - at the same concentration -
:
as good on bleach-sensitive stain removal, without pretreatment,
than a heavily built granular detergent compositions con-
taining a considerable amount of bleaching agent, and
have superlor effect on bleach-sensitive stain removal if -
using the same total concentration of the detergent compositions
- there is pretreatment by topical application.
''~ `' ''
~ - 31 -
EXAr'l.PLES
II III IV . V VI VII VIII IX X
Monoethanolamine 16.2 ~ - 20
salt of linear
alkylbenzene
sulfonic acid
having in ave-
rage 11.9 car-
bon aboms in
10 the alkyl group
Triethanolamine - 15 20 25 20 20 20 20 - 20
salt of linear
: alkylbenzène
sulfonic acid
having in ave-
rage 11.9 car-
bon atoms in
.: the alkyl group
C17-1g(E)ll - _ _ - 20
(about 25%
branched)*
16-l9(E)ll 20 15 20 25 - _ _ 20
(about 72%
: branched) }
Tallow (EO)ll - - _ _ _ 20
_15(Eo)ll _ _ _ _ _ _ 30 20
(about 50%
branched) .,
C14-15(E)4 _ _ _ - 10 10 - - - - :-
C12-15(E)4 10 5 10 15 - - - _ _ _
g-ll( )8 ~ - - 20
14-15 )7 ~ ~ ~ ~ ~ 30
12-l5(Eo~3 ~ - - - - _ _ 10
Ethanol 8.5 10 10 12 15 15 13 6 10 7
Brightener ---------------------0.2-~------------ ------------ .
' (Stilbene
type)
Perfume, ----------~~~~~~~~~~0 35---------------------------
dyes
.. .
- 32 -
7~
:[I III . IV . V . VI . .VI.I VIII. . IX X
.. . . . ~
: EDTMP ** - 0.35 - - 0.~ - 0.3 0.25 0.35 ~
Citric Acid 0.5 ~ - 0.3 0.1 - 0.75
EDTA *** - 0.5 - -0,75
Triethano- 0.75 0.78 0.51.2 1 l.S0 0.85 0.6 0.7 1.3
lamine
Water- --------- ---------balance---~
pH of the6.5 7 6.2 6.75 7.3 6.7 7 7.2 6.8 6.9
composi-
tion
* 25~ branched = about 25~ of the alkyl chains are branched.
** EDTMP = ethylenediaminotetramehylenephosphonic acid.
***EDTA - ethylenediaminotetraacetic acid.
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