U.S. patent number 3,862,965 [Application Number 05/306,014] was granted by the patent office on 1975-01-28 for shaped washing agents based on synthetic tensides.
This patent grant is currently assigned to Henkel & Cie GmbH. Invention is credited to Werner Schneider, Lothar Werner.
United States Patent |
3,862,965 |
Werner , et al. |
January 28, 1975 |
SHAPED WASHING AGENTS BASED ON SYNTHETIC TENSIDES
Abstract
Shaped washing agents based on synthetic detergents having a
composition consisting essentially of (A) from 50% to 85% by weight
of a tenside mixture consisting essentially of (1) from 70% to 100%
by weight of the tenside mixture of a sulfonate mixture consisting
essentially of (a) from 10% to 80% by weight of the sulfonate
mixture of a water-soluble salt of a monoester of a
sulfodicarboxylic acid selected from the group consisting of
sulfoalkanedioic acids having 3 to 8 carbon atoms and
sulfobenzenedicarboxylic acids, monoesterified with aliphatic
alcohols having 8 to 18 carbon atoms and (b) from 20% to 90% by
weight of the sulfonate mixture of a water-soluble salt of an
olefin sulfonate having 10 to 18 carbon atoms, and (2) from 0 to
30% by weight of the tenside mixture of other tensides selected
from the group consisting of anionic surface-active compounds,
non-ionic surface-active compounds and amphoteric surface-active
compounds, (B) from 12% to 47% by weight of non-tenside
water-insoluble builders customarily utilized in shaped washing
agents, and (C) from 3% to 15% by weight of water.
Inventors: |
Werner; Lothar (Krefeld,
DT), Schneider; Werner (Krefeld-Bockum,
DT) |
Assignee: |
Henkel & Cie GmbH
(Dusseldorf-Holthausen, DT)
|
Family
ID: |
27182170 |
Appl.
No.: |
05/306,014 |
Filed: |
November 13, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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76203 |
Sep 28, 1970 |
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Foreign Application Priority Data
Current U.S.
Class: |
510/155; 510/150;
510/506; 510/477; 510/489; 510/505; 510/498; 510/491 |
Current CPC
Class: |
C11D
17/006 (20130101); C11D 3/2079 (20130101); C11D
1/667 (20130101); C11D 3/2093 (20130101); C11D
3/2013 (20130101); C11D 1/37 (20130101); C11D
1/123 (20130101); C11D 1/28 (20130101); C11D
1/14 (20130101); C11D 1/16 (20130101) |
Current International
Class: |
C11D
1/02 (20060101); C11D 1/12 (20060101); C11D
1/37 (20060101); C11D 1/28 (20060101); C11D
3/20 (20060101); C11D 1/14 (20060101); C11D
1/16 (20060101); C11d 003/066 () |
Field of
Search: |
;252/121,535,538,555,557 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Attorney, Agent or Firm: Hammond & Littell
Parent Case Text
This is a continuation of Ser. No. 76,203, filed Sept. 28, 1970,
now abandoned.
Claims
1. Shaped washing agents based on synthetic detergents having a
composition consisting essentially of (A) from 55% to 80% by weight
of a tenside mixture consisting essentially of (1) from 70% to 100%
by weight of said tenside mixture of a sulfonate mixture consisting
essentially of (a) from 20% to 70% by weight of said sulfonate
mixture of a water-soluble salt of a monoester of a
sulfodicarboxylic acid selected from the group consisting of
sulfoalkanedioic acids having 3 to 8 carbon atoms and
sulfobenzenedicarboxylic acids, monoesterified with fatty alcohols
having 8 to 18 carbon atoms, at least 50% of said fatty alcohols
having 10 to 16 carbon atoms and (b) from 30% to 80% by weight of
said sulfonate mixture of a water-soluble salt of a mixture of
hydroxyalkane sulfonates, alkene sulfonates and alkane
disulfonates, the individual components of said water-soluble salt
of a mixture of sulfonates having 10 to 18 carbon atoms, said
water-soluble salts being selected from the group consisting of
alkali metal salts and alkylolamine salts, and (2) from 0 to 30% by
weight of said tenside mixture of tensides excepting said (a) and
(b) selected from the group consisting of anionic surface-active
compounds, non-ionic surface-active compounds and amphoteric
surface-active compounds, (B) from 18% to 40% by weight of
non-tenside water-insoluble superfatting agents melting at from
30.degree.C to 80.degree.C selected from the group consisting of
fatty acids, fatty alcohols, monoglycerides of fatty acids,
diglycerides of fatty acids, triglycerides of fatty acids, fatty
acid esters of fatty alcohols, lanolin, vaseline, esters of 1 mol
of a citric acid difatty alcohol ester and 1 mol of pentaerythritol
difatty acid ester and non-ionic alkylene oxide derivatives having
an alkoxylation degree which is incomplete for water solubility,
and (C) from 5% to 10% by
2. The shaped washing agent of claim 1 wherein said
sulfodicarboxylic acid
3. The shaped washing agent of claim 2 wherein said monoester of
sulfosuccinic acid is with a primary alkanol having 12 to 14 carbon
atoms.
4. The shaped washing agent of claim 1 wherein the individual
components of said water-soluble salt of a mixture of sulfonates
has from 12 to 16
5. The shaped washing agent of claim 1 wherein said other tensides
include up to 15% by weight of non-ionic surface-active compounds
having a melting
6. Shaped washing agents based on synthetic detergents having a
composition consisting essentially of (A) from 55% to 80% by weight
of a tenside mixture consisting essentially of (1) from 70% to 100%
by weight of said tenside mixture of a sulfonate mixture consisting
essentially of (a) from 20% to 70% by weight of said sulfonate
mixture of an alkali metal salt of a monoester of sulfosuccinic
acid monoesterified with a primary alkanol having 12 to 14 carbon
atoms and (b) from 30% to 80% by weight of said sulfonate mixture
of an alkali metal salt of a mixture of hydroxyalkane sulfonates,
alkene sulfonates and alkane disulfonates, the individual
components of said alkali metal salt of a mixture of sulfonates
having from 12 to 16 carbon atoms, and (2) from 0 to 30% by weight
of said tenside mixture of tensides excepting said (a) and (b)
selected from the group consisting of anionic surface-active
compounds, non-ionic surface-active compounds and amphoteric
surface-active compounds, (B) from 18% to 40% by weight of
superfatting agents melting at temperatures from 40.degree. to
70.degree.C selected from the group consisting of fatty acids
having from 10 to 20 carbon atoms and an iodine number below 10,
monoglycerides of said fatty acids, diglycerides of said fatty
acids, triglycerides of said fatty acids, fatty alcohols having
from 10 to 20 carbon atoms and an iodine number below 10, esters of
said fatty alcohols with said fatty acids, lanolin, vaseline, the
esterification product from equimolar amounts of a diester of
citric acid with a fatty alcohol having 10 to 20 carbon atoms and a
diester of pentaerythritol with a fatty acid having 10 to 20 carbon
atoms, and mixtures thereof, and (C) from 5% to 10%
7. The shaped washing agents of claim 6 having a further content of
from 0.01% to 0.2% by weight of fabric brighteners selected from
the group consisting of derivatives of diaminostilbene slfonic
acids, derivatives of diarylpyrazoline, derivatives of
aminocoumarins,
9-cyanoanthracene,1-(benzimidazolyl-2')-2-(N-hydroxyethyl-benzimidazolyl-2
')-ethylene, 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril,
2,5-di-(benzoxazolyl-2')-thiophene and
1,2-di-(5'-methyl-benzoxazolyl-2')-ethylene and from 0.1% to 1% by
weight of organic complexing agents selected from the group
consisting of nitrilotriacetic acid, ethylenediaminetetraacetic
acid, N-hydroxyethyl-ethylenediaminetriacetic acid,
polyalkylenepolyamine-N-polycarboxylic acids, diphosphonic acids
and polyphosphonic acids, and their alkali metal salts.
Description
THE PRIOR ART
Since the emergence of synthetic tensides, soap has more and more
been replaced by the synthetic tensides, above all in the
production of powdered detergents. There has been no lack of
attempts to use the synthetic tensides, particularly of the sulfate
or sulfonate type, also for the production of piece-shaped washing
agents, and there are a great number of respective proposals in the
literature. In spite of this, on the market, washing agent pieces
based on synthetic tensides play only a small role compared to
washing agent pieces based on soap. There are substantially two
reasons for this. The first reason is in the different physical
properties and the second in the different physiological properties
of soap, on the one hand, and synthetic tensides, particularly
those of the sulfate and sulfonate type, on the other hand.
Cakes of soap have the ability to absorb large amounts of water in
contact with it, and, thereby, first form a still solid gel. If one
washes with such a soap, swollen on a part of the surface, the soap
substance rubs off quicker at the swollen areas than at the
non-swollen ones, so that the desired foam formation occurs quicker
than usual. No loss of soap occurs in this. Washing agent cakes
based on the named synthetic tensides behave completely
differently. In them the area in which the swollen material adheres
solidly to the residual piece is much smaller. In most cases, on
the surface of the pieces a smeary mass is formed, which rubs off
immediately in washing with such a cake and produces a much higher
tenside concentration than would be required for the desired foam
formation. For this reason greater material losses occur.
But also in drying of the partly swollen cakes a remarkable
difference appears. The classical soap cakes lose their moisture
with a reversal of the swelling and a close union between the
non-swollen material and the initially swollen surface is
maintained. In cakes from synthetic tensides, the mechanical union
between the two parts is so far broken that also in drying of the
surface the initially solid structure of the cake is no longer
maintained.
A further disadvantage of the known washing agent cakes based on
synthetic tensides lies in the strong degreasing of the skin. After
washing with them, the disagreeable sensation of a dried-out skin
remains.
The mechanical and physiological properties of washing agent cakes
based on synthetic tensides can indeed be improved by incorporation
of water-insoluble soap cake builders, but even these improved
cakes do not satisfy the requirements for a satisfactory washing
agent cake.
OBJECTS OF THE INVENTION
An object of the present invention is the development of a shaped
washing agent composition based on synthetic tensides which
overcomes the drawbacks mentioned above and can be utilized in
place of hand soap cakes.
Another object of the invention is the development of shaped
washing agents based on synthetic detergents having a composition
consisting essentially of (A) from 50percent to 85percent by weight
of a tenside mixture consisting essentially of (1) from 70% to 100%
by weight of the tenside mixture of a sulfonate mixture consisting
essentially of (a) from 10% to 80% by weight of the sulfonate
mixture of a water-soluble salt of a monoester of a
sulfodicarboxylic acid selected from the group consisting of
sulfoalkanedioic acids having 3 to 8 carbon atoms and
sulfobenzenedicarboxylic acids, monoesterified with aliphatic
alcohols having 8 to 18 carbon atoms and (b) from 20% to 90% by
weight of the sulfonate mixture of a water-soluble salt of an
olefin sulfonate having 10 to 18 carbon atoms, and (2) from 0 to
30% by weight of the tenside mixture of the other tensides selected
from the group consisting of anionic surface-active compounds,
non-ionic surface-active compounds and amphoteric surface-active
compounds, (B) from 12% to 47% by weight of non-tenside
water-insoluble builders customarily utilized in shaped washing
agents, and (C) from 3% to 15% by weight of water.
These and other objects of the invention will become more apparent
as the description therof proceeds.
DESCRIPTION OF THE INVENTION
The invention relates to shaped washing agents based on synthetic
tensides, which do not have the above described disadvantages. The
shaped washing agents of the invention are characterized by the
following composition:
50% to 85% preferably 55% to 80% by weight of a tenside mixture
composed of:
70% to 100% preferably 80% to 95% by weight of a sulfonate mixture
of:
10% to 80% preferably 20% to 70% by weight of a water-soluble salt
of a monoester of a sulfodicarboxylic acid, containing 3 to 8
carbon atoms, with aliphatic alcohols having 10 to 18 carbon
atoms,
20% to 90% preferably 30% to 80% by weight of a water-soluble salt
of an olefin sulfonate with 10 to 18 carbon atoms in the
molecule,
0 to 30% by weight of other tensides;
at least 12%, preferably at least 15% by weight of other
non-tenside-like water-insoluble builders which, in themselves, are
customary in shaped washing agents; and
3% to 15%, preferably 5% to 10% by weight of water.
The other tensides, optionally present in the tenside mixture, can
be anionic, amphoteric, or nonionic. The shaped washing agents of
the invention, in addition to containing ingredients customary in
such products, such as superfatting agents, can contain impurities,
originating from the tensides, etc. Insofar as the below more
extensively described water-insoluble superfatting agents
(particularly fatty acids and fatty alcohols) are present as solids
at temperatures of 30.degree.C, and preferably of 40.degree.C, they
act as builders and belong to the other customary builder materials
in the frame of the above recipe.
The above-defined surface-active sulfodicarboxylic acid monoesters
are known and are accessible by various ways. Monoesters of
aliphatic sulfodicarboxylic acids with 4 to 8 carbon atoms, such as
sulfoalkanedioic acids having 4 to 8 carbon atoms, such as
sulfoalkanedioic acids having 4 to 8 carbon atoms, are, for
example, obtained by bisulfite addition to the corresponding
monoesters of unsaturated dicarboxylic acids. Sulfodicarboxylic
acid monoesters can, however, be also prepared by the introduction
of the sulfonate group into the dicarboxylic acid radical and
subsequent conversion of the sulfodicarboxylic acid or its salts to
the monoester. Thus, the monoester of the sulfophthalic acid is
obtained by treating of phthalic acid monoesters with saturated
alcohols with appropriate sulfonating agents. For this preparation
of the shaped detergents, according to the invention, the
monoesters of sulfosuccinic acid are preferentially used.
The alcohol radicals present in the named compounds are derived
from preferably saturated, straight-chain, primary aliphatic
alcohols such as alkanols with 10 to 18, preferably 12 to 14 carbon
atoms. The alcohols can be of synthetic origin or be formed by
reduction of synthetic or natural fatty acids. Preferably, the
alcohol mixture obtained from coconut or palm kernel fatty acids,
and particularly lauryl alcohol or the mixture of lauryl and
myristyl alcohol separated from these fatty alcohol mixtures, are
used. Such mixtures can contain fatty alcohols with more than 18
and less than 10, preferably those with 8 carbon atoms, however at
least 50, and preferably 70% of the fatty alcohols or fatty alcohol
radicals should contain 10 to 16, and particularly 12 to 14, carbon
atoms.
Of particular practical importance are sulfosuccinic acid
monoesters of fatty alcohols derived from coconut or palm kernel
fatty acids or the respective C.sub.12 to C.sub.14 fractions.
The olefin sulfonates utilized in the shaped washing agents of the
invention are accessible by sulfonation of straight or
branched-chain olefins having a terminal or non-terminal double
bond by known procedures. For the shaped washing agents, according
to the invention, preferably products are used which consist
preponderantly of at least 70%, and preferably to more than 85%, of
straight-chain olefin sulfonates and of these the sulfonates from
straight-chain .alpha.-olefins are preferred.
Various processes for the preparation of olefin sulfonates are
known. Of particular practical importance is a procedure in which
the olefins are first reacted with gaseous sulfur trioxide in the
presence of inert gases. 1 to 2, preferably 1 to 1.5 mols of
SO.sub.3 are used per mol of olefin. An intermediate is formed
which gives, after acidic or alkaline hydrolysis at elevated
temperatures, the desired sulfonate.
The thus obtained sulfonates are chemically non-homogenous. They
consist essentially of a mixture of hydroxyalkane sulfonates,
alkene sulfonates and disulfonates. The latter can also possess
hydroxyl groups. All the named substances, in regard to the
position of the sulfonate group or groups, the hydroxyl group, and
the double bond, can be present as mixtures of isomers. The
quantitative ratio of hydroxyalkane sulfonates, alkene sulfonates
and disulfonates depends to a certain extent upon the conditions of
sulfonation and hydrolysis. Above all, the working conditions
during hydrolysis influence the quantitative proportion of
hydroxyalkane sulfonates and alkene sulfonates. With an increasing
excess of sodium hydroxide solution in the hydrolysis and with
rising hydrolysis temperature (50.degree. to 200.degree.C,
preferably 90.degree. to 160.degree.C) the amount of hydroxyalkane
sulfonates is reduced in favor/of the alkene sulfonates.
Both the sulfodicarboxylic acid monoesters and the olefin
sulfonates are obtained, depending upon the selected preparation
procedure, in a more or less colored state. Above all, the products
obtained by sulfonation with gaseous sulfur trioxide are sometimes
colored yellowish or brownish, and it may be desirable to bleach
these sulfonates. For bleaching, oxidizing bleaching agents such as
H.sub.2 O.sub.2 or sodium hypochlorite, are usable. With the use of
sodium hypochlorite, slight amounts of sodium chloride remain in
the sulfonation product. In addition, the sulfonates contain often
slight amounts of sodium sulfate. The amount of these neutral salts
should, however, be not greater than 15percent and preferably not
greater than 15percent with reference to the anhydrous tenside. In
many cases, the amount of neutral salts is much less and is for
instance 1% to 5%.
The favorable properties of the washing agent cakes, according to
the invention, are still preserved if limited amounts, up to 30% by
weight of the tensides, of other tensides are also present. These
tensides can be anionic, nonionic or amphoteric. Most of them
contain a preferably straight-chain alkyl radical of 8 to 18,
preferably 12 to 16 carbon atoms.
Within the scope of the anionic tensides, the sulfonates and the
sulfates are of particular practical importance. To them belong,
for example, the alkylbenzene sulfonates, fatty alcohol sulfates,
sulfated adducts of 0.5 to 5 mols of ethylene and/or propylene
oxide to fatty alcohols, sulfated fatty acid-monoglycerides,
mono-fatty acid esters or mono-fatty alcohol ethers of
dihydroxypropane-sulfonic acid, fatty acid esters of
hydroxyethane-sulfonic acid, fatty acid amides of taurine or methyl
taurine, sulfated adducts of 1 to 5, preferably of 1.5 to 4 mols of
ethylene-and/or propylene oxide to alkylphenols, etc.
To the anionic tensides also belong synthetic carboxylates, such as
amides of fatty acids and aminocarboxylic acids, particularly the
corresponding derivatives of alanine or of sarcosine.
In the washing agent cakes, according to the invention, soaps also
can be present as anionic tensides, although their presence is not
compellingly necessary for the improvement of the properties of the
cake, particularly of the swelling properties toward water. If
olefin sulfonates are used for the preparation of the cakes,
according to the invention, in the hydrolysis of intermediaries,
first formed during the sulfonation, which has been carried out
with the use of excess alkali, soaps are necessarily formed if free
fatty acids are added to the washing agent compositions as
superfatting agents.
The shaped washing agents, according to the invention, can also
contain nonionic tensides, but it is recommended, in view of the
compactness properties of the shaped washing agents, not to
increase their amount above 15percent, preferably 10percent by
weight of the tenside mixture in the shaped washing agent,
particularly if these nonionic tensides are present in an oily or
pasty consistency at temperatures below 30.degree.C. If one wants
to incorporate larger amounts of nonionic tensides, appropriate
products should be selected which melt in the range of
40.degree.-90.degree.C.
As nonionic tensides, adducts of ethylene oxide to alkylphenols,
fatty alcohols, fatty acids, or fatty acid amides are suitable,
which, for example, can contain in the molecule 5 to 80, preferably
8 to 60 ethyleneoxide units. The melting points of these products
rise on the one hand with the melting point of the starting
material, and on the other hand with the amount of added ethylene
oxide. In place of the derivatives prepared with the use of
ethylene oxide, or together with them, mixed adducts of ethylene
oxide, on the one hand, and propylene and/or butylene oxide, on the
other hand, can be used where the named alkylene oxides can be
added in any sequence one after the other, or as a mixture.
The products known by their commercial names "Pluronics" or
"Tetronics" are also usable as nonionic tensides. These products
occupy a special place within the scope of the tensides insofar as
they do not have to contain an alkyl radical of 8 to 18, preferably
12 to 16 carbon atoms. These alkyl radicals are replaced by
polypropylene glycol, or polybutyleneglycol radicals. Such nonionic
tensides are obtained from water-insoluble polypropyleneglycols or
from water-insoluble propoxylated lower aliphatic alcohols with 1
to 8, preferably 3 to 6 carbon atoms and/or from water-insoluble
propoxylated alkylene diamines. These water-insoluble propylene
oxide derivatives are ethoxylated with ethylene oxide until water
soluble and coverted to the named nonionic tensides. Also, these
types of nonionics are liquid or solid products at normal
temperatures, and melt partly above 40.degree.C. Here, there is the
possibility to select the suitable substance for the desired
purpose.
Mono- or dialkylolamides of fatty acids, particularly fatty acid
mono- or diethanolamides belong further to the nonionic
tensides.
In each of the above numerated types of nonionics there are
substances which are solid at normal temperatures and melt above
30.degree.C. The following list of such nonionics gives only
examples, it does not claim to be complete.
Nonionics, solid at normal temperatures, of the type of ethoxylated
fatty alcohols, fatty acids, or alkylphenols with straight-chain
C.sub.8 to C.sub.10 alkyl radicals are, for instance, the adducts
of 45 mols of ethylene oxide to 1 mol of coconut fatty alcohol; of
20, 25 or 50 mols of ethylene oxide to 1 mol of tallow alcohol; and
of 40 mols of ethylene oxide to 1 mol of oleyl alcohol; reaction
products of 1 mol of palmitic acid with 40 mols of ethylene oxide
or of 1 mol of stearic acid with 30 mols of ethylene oxide as well
as of 1 mol of an alkylphenol especially nonylphenol, with 25 to 50
mols of ethylene oxide.
Finally, the following commercial products are also solid nonionics
which belong to the type of "Pluronics" or "Tetronics" (the first
of the two figures in parentheses gives in the "Pluronics", the
molecular weight of the polypropyleneglycol radical and, in the
"Tetronics", the molecular weight of the ethylenediamine-propylene
oxide adducts, while the second number gives the amount of the
ethyleneoxide units in the product in percent by weight): Pluronic
F 38 (950/80), Pluronic F 68 (1750/80), Pluronic F 77 (2050/70),
Pluronic F 87 (2250/70), Pluronic F 88 (2250/80), Pluronic F 98
(2750/80), and Pluronic F 108 (3250/80); Tetronic 707 (2750/75),
and Tetronic 908 (4000/85).
The washing agent cakes, according to the invention, may also
contain amphoteric tensides of which some, particularly the below
named compounds with carboxyl groups, possess anti-microbial
properties.
To the amphoteric tensides, useable, according to the invention,
belong, for instance, compounds of the following general
formula:
R.sub.1 -- NH -- (R.sub.2 -- NH --).sub.x -- R.sub.3 -- COOH,
wherein R.sub.1 is a higher-molecular-weight alkyl, alkylphenyl,
alkylphenoxyalkyl or alkyloxyalkyl radical, particularly a
corresponding hydrocarbon radical with 6 to 18, preferably 8 to 14
aliphatic carbon atoms; R.sub.2 is ethylene or propylene; x is a
whole number from 1 to 6; and R.sub.3 is an aliphatic,
aliphatic-aromatic or aromatic link with 1 to 8 carbon atoms,
preferably R.sub.3 is alkylene, alkylphenylene, phenylalkylene and
phenylene. As examples, the following compounds can be named;
dodecylaminopropyl-glycine, tetradecyl-aminoethyl-.beta.-alanine,
dodecyl-di-(aminoethyl)-glycine,
dodecyl-aminoiso-propyl-ammino-methylsalicylic acid,
hexadecyl-tri-(aminoethyl)-.beta.-aminobutyric acid,
dodecyl-benzylaminopropyl-.beta.-alanine,
octyl-phenoxy-ethyl-di-(aminoethyl)-glycine,
dodecylaminoethyl-phenylalanine, dodecyl-aminoethyl-aminobenzoic
acid.
The radical R.sub.1 can also be interrupted by an ether oxygen
atom, such is, e.g., the case in the following compounds;
dodecyl-oxypropyl-aminopropionic acid,
1-lauryloxy-3-hydroxypropyl-.beta.-aminobutyric acid, C.sub.12-14
-alkyl-oxyethyl-aminoacetic acid,
1-dodecyloxy-2-hydroxypropyl-aminomethyl-salicylic acid,
octyl-phenoxyethyl-aminobenzoic acid.
To the amphoteric tensides, according to the invention, belong
further carboxybetaines of the general formula ##SPC1##
In this formula R.sub.1 has the same meaning as in the preceding
formula, R.sub.2 represents an ethylene- or propylene group,
R.sub.3 and R.sub.4 are lower alkyl radicals, R.sub.5 is a lower
molecular weight aliphatic link such as lower alkylene, and X is an
ether oxygen atoms, or the --CONH-- group. Examples for such
compounds are lauryl-1,3-amidopropyl-dimethyl-aminoacetic acid,
lauryl-oxyethyl-di-(hydroxyethyl)-aminopropionic acid,
octyl-phenoxy-ethyl-di-(hydroxyethyl)-aminoacetic acid, and
others.
To the amphoteric tensides useable, according to the invention,
belong also sulfobetaines, which are, for example, obtained by
reacting of dialkyl fatty amines (alkyl radical C.sub.1 to C.sub.4,
fatty radical C.sub.10 to C.sub.16, preferably C.sub.12 to C.sub.14
with sultones, particularly with propane sultone and 1,3- or
1,4-butane sultone.
The anionic tensides contained in the shaped detergents, according
to the invention, are preferably present in the form of their
alkali metal salts, particularly as sodium salts. If needed, there
is also the possibility to incorporate them in the form of their
water-soluble salts with amines, particularly with alkylolamines,
such as mono-, di-, or triethanolamines. The amphoteric compounds
can be incorporated as inner salts, as salts with the above named
alkaline reacting compounds, or as salts with acids.
The detergent cakes, according to the invention, contain other
non-tenside ingredients, customary in shaped detergents, such as
super fatting agents, complexing compounds, disinfectants,
microbicidal substances, brighteners, buffers for a slightly acidic
pH, perfumes, dyes, etc.
As superfatting agents, water-insoluble fatty acids, fatty
alcohols, mono-, di-, or triglycerides, fatty acid esters,
particularly fatty acid esters with fatty alcohols, lanolin,
vaseline, etc. are suitable, preferably melting at temperatures
from 30.degree. to 80.degree.C, and particularly 40.degree. to
70.degree.C. Further are useable as superfatting agents are the
esterification products, described in German Pat. No. 1,165,574,
from equimolecular amounts of a diester of 1 mol of citric acid and
two mols of a fatty alcohol with 10 to 20, preferably 12 to 18
carbon atoms and a pentaerythritol-diester of one mol of
pentaerythritol and two mols of a fatty acid with 10 to 20,
preferably 12 to 18 carbon atoms.
Preferably, the washing agent cakes of the invention contain from
about 12% to 47% preferably from 18% to 40% by weight of
superfatting agents melting at temperatures of from 30.degree. to
80.degree.C, preferably from 40.degree. to 70.degree.C. These are
preferably fatty acids having from 10 to 20 carbon atoms and an
iodine number below 10, fatty alcohols having from 10 to 20 carbon
atoms and an iodine number below 10, mono-, di- or triglycerides of
the above fatty acids, esters of the above fatty acids with the
above fatty alcohols, lanolin, vaseline, the citric acid-difatty
alcohol pentaerythritol difatty acid esterification product and
mixtures of the above.
Many of the above described nonionic ethylene derivatives, fatty
acid alkylolamides, and amphoteric tensides possess skin-pleasing
properties. If such tensides are incorporated into the shaped
washing agents, according to the invention, they can at the same
time partially take the role of a superfatting agent. Also suitable
as superfatting agents are products which differ from the above
described nonionic alkylene oxide derivatives only in those that
have an alkoxylation degree which is incomplete for water
solubility. These are water-insoluble propylene oxide derivatives
or ethoxylation products, optionally containing propylene and/or
butyleneglycol radicals, in which the amount of the added ethylene
oxide is insufficient for the water insolubility. Such
water-insoluble nonionic compounds are, for instance, commercially
available under the name "Ucon Fluid."
In the shaped washing agents, according to the invention,
water-soluble or water-insoluble dyes may be present. The
water-insoluble dyes include here also the color pigments
frequently used for the brightening of washing agent cakes. Besides
such washing agent cakes may contain brighteners, particularly in
case of white washing agent cakes. Finally, as stabilizers organic
complexing agents can be added, and in addition frequently the
incorporation of dirt carriers has proven useful.
The usable brighteners are mostly, if not exclusively, derivatives
of the diaminostilbene sulfonic acid of the diarylpyrazolines, and
of aminocoumarin.
Examples for brighteners from the class of the
diaminostilbenesulfonic acid are compounds according to formula I:
##SPC2##
In this formula R.sub.1 and R.sub.2 may be halogen atoms, alkoxyl
groups, the amino group or radicals of aliphatic, aromatic or
heterocyclic primary or secondary amines, as well as radicals of
aminosulfonic acids, whereby the aliphatic radicals present in the
above groups contain preferably 1 to 4, and particularly 2 to 4
carbon atoms, while the heterocyclic ring systems are mainly 5- or
6-membered rings. As aromatic amines preferably radicals of
aniline, anthranilic acid or aniline sulfonic acid are used.
Brighteners derived from diaminostilbene sulfonic acid are used
mainly for cotton. The following products deriving from formula I
are commercially available whereby R.sub.1 is the radical
--NH--C.sub.6 H.sub.5 and R.sub.2 can be the following radicals:
--NH.sub.2 --NH--CH.sub.3,--NH--CH.sub.2 --CH.sub.2 OH,--
NH--CH.sub.2 --CH.sub.2 --OCH.sub.3,--NH--CH.sub.2 --CH.sub.2
--CH.sub.2 --O--CH.sub.3 ##SPC3## --N=(CH.sub.2 -CH.sub. 2
OH).sub.2, morpholino-, --NH--C.sub.6 H.sub.5, --NH--C.sub.6
H.sub.4 --SO.sub.3 H and --OCH.sub.3. In respect to their fiber
affinity some of these brighteners are to be regarded as transition
types to the polyamide brighteners, for example, the brightener
with R.sub.2 being --NH--C.sub.6 H.sub.5. To the cotton brighteners
of the diaminostilbene sulfonic acid type belong also the compound
4,4'-bis-(4-phenyl-vicinal-triazolyl-2)-stilbene disulfonic
acid-2,2' .
To the polyamide brighteners, of which again some have a certain
affinity for cotton fibers belong diarylpyrazolines of the formulas
II and III: ##SPC4##
In the formula II, R.sub.3 and R.sub.5 are hydrogen atoms, possibly
alkyl or aryl radicals substituted by carboxyl-, carbamide-, or
ester groups, R.sub.4 and R.sub.6 are hydrogen or short chain alkyl
radicals, Ar.sub.1 and Ar.sub.2 are aryl radicals, such as, phenyl,
diphenyl, or naphthyl and may have other substituents, such as,
hydroxy-, alkoxy-, hydroxyalkyl-, amino-, alkylamino-, acylamino-,
carboxyl-, carboxylic ester-, sulfonic acid-, sulfonamide-, and
sulfonic groups, or halogen atoms. Commercially available
brighteners of this type are derived from formula III whereby the
radical R.sub.7 is the groups C1,--SO.sub.2 --NH.sub.2 --SO.sub.2
--CH=CH.sub.2, and --COO--CH.sub.2 --CH.sub.2 --O--CH.sub.3, while
the radical R.sub.8 is in all cases a chlorine atom. Also
9-cyanoanthracene is a polyamide brightener commercially
available.
To the polyamide brighteners belong also aliphatic or aromatic
substituted aminocoumarins, for example, the
4-methyl-7-dimethylamino-, or the 4-methyl-7-diethylaminocoumarin.
Further usable as polyamide brighteners are the compounds
1-(benzimidazolyl-2')-2-(N-hydroxyethyl-benzimidazolyl-2')-ethylene
and 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril. Suitable
brighteners for polyester and polyamide fibers are the compounds
2,5-di-(benzoxazolyl-2')-thiophene and
1,2-di-(5'-methyl-benzoxazolyl-2')-ethylene.
Insofar the brighteners, together with other ingredients of the
invention products, are present as aqueous solutions or as pastes,
and are converted into solids by heat drying, it is recommended to
add organic complexing agents as stabilizers for the brighteners in
amounts of at least 0.1% preferably 0.2 to 1% by weight of the
solid products.
To the organic complexing agents belong, for instance,
nitrilotriacetic acid, ethylenediaminetetraacetic acid,
N-hydroxyethyl-ethylenediaminetriacetic acid,
polyalkylene-polyamine-N-polycarboxylic acid, and other known
organic complexing agents. Also combinations of different
complexing agents can be used. To the other known complexing agents
belong also di- and polyphosphonic acids of the following
constitutions: ##SPC5##
wherein R is alkyl and R' is alkylene, both with 1 to 8, preferably
1 to 4 carbon atoms, X and Y are hydrogen or alkyl with 1 to 4
carbon atoms and Z is the groups --OH,NH.sub.2 or --NXR.
For a practical use above all the following compounds are of
interest: methylenediphosphonic acid,
1-hydroxyethane-1,1-diphosphonic acid,
1-aminoethane-1,1-diphosphonic acid, amino-tri-(methylenephosphonic
acid) methylamino or ethylamino-di-(methylenephosphonic acid) as
well as ethylene diamine-tetra-(methylenephosphonic acid). All
these complexing agents can be present as free acids, preferably as
alkali metal salts.
Into the washing agent cakes, according to the invention, such dirt
carriers or soil suspending agents can be incorporated which have
also been proposed as additions for powdery washing agents. For
this water-soluble colloids, mostly organic, are suitable, such as
the water-soluble salts of polymeric carboxylic acids, glue,
gelatine, salts of ether-carboxylic acids or ether-sulfonic acids
of starch or cellulose or salts of acidic sulfuric acid esters of
cellulose or starch. Also water-soluble polyamides, containing
acidic groups, are suitable for this purpose. Furthermore, soluble
starch preparations and other than the above named starch products
can be used, such as degraded starch, aldehyde starch, gelatinized
starch, etc. Also polyvinylpyrrolidone is usable.
The above named non-tenside addition products are preferably
charged by weight of the total composition.
0.01% to 0.2%, preferably 0.015% to 0.1% by weight of
brighteners
0.1% to 1%, preferably 0.2% to 0.5% by weight of organic complexing
agents.
The shaped washing agents, according to the invention, are prepared
in a conventional manner. The power necessary for the processing of
the mass on rolls, in extruding presses, and in converting of the
crude shaped pieces to the desired form can be changed by the water
content of the mass. If, for the processing of a special mixture, a
too large power expenditure should be required, the latter can be
decreased by increasing the water content. In this event, the
claimed upper limit of the water content can be surpassed however
on storing the pieces dry and thus attain after some time the
claimed water content.
The following specific examples are illustrative of the shaped
washing agents and compositions of the invention without being
limitative in any manner.
EXAMPLES
For the preparation of the below described detergent cakes a
sulfosuccinic acid-mono alcohol ester (Na-salt) was used which had
been prepared from the C.sub.12 to C.sub.18 fraction of coconut oil
alcohols. The olefin sulfonate was derived from a mixture of
straight-chain .alpha.-olefins with 15 to 18 carbon atoms. This
olefin mixture had been prepared by sulfonation of 1 mol of olefin
with about 1.2 mols of gaseous sulfur trioxide, diluted with inert
gas, hydrolysis of the crude sulfonation product with the
calculated amount of aqueous sodium hydroxide at temperatures of
about 100.degree.C and bleaching of the sulfonate with the aid of
hypochlorite. The mixture of the two sulfonates contained about 5%
by weight of neutral salts (Na.sub.2 SO.sub.4 and NaCl), based on
the anhydrous sulfonate mixture.
The "mixed citric acid ester" mentioned in the examples was an
esterification product of one mol of citric acid tallow fatty
alcohol-diester and one mol of pentaerythritol-coconut fatty acid
diester.
For the preparation of the shaped detergent pieces, the ingredients
in the given amounts were mixed in a kneader at temperatures of
60.degree. to 70.degree.C, brought to the requried water content,
homogenized on rolls and then extruded from vacuum extruders in a
strand of the cross-section of the customary commercial toilet-soap
cakes. By cutting and pressing of these strands, products of the
desired shape and size were obtained.
The detergent cakes were prepared from the composition given in the
examples, whereby the quantitative data for the olefin sulfonate
and the sulfosuccinic acid ester refer to the anhydrous technical
product, i.e., they include neutral salts and unsulfonated olefin
as well as unreacted fatty alcohol (about 1%).
EXAMPLE 1
65% by weight of a tenside mixture consisting of
57% by weight of olefin sulfonate
43% by weight of sulfosuccinic acid ester
16% by weight of a hardened tallow alcohol (Iodine No. <1)
5% by weight of a coconut fatty acid (C.sub.12-18 fraction)
5% by weight of stearin (Iodine No.=2)
1% by weight of lanolin
1% by weight of lecithin
6% by weight of water
1% by water of perfume
EXAMPLE 2
55% by weight of a tenside mixture consisting of
33.3% by weight of olefin sulfonate
66.6% by weight of sulfosuccinic acid ester
20% by weight of stearin (Iodine No.=2)
14% by weight of tallow fatty alcohol (Iodine No. <1)
2% by weight of lanolin
2% by weight of mixed citric acid ester
6% by weight of water
1% by weight of perfume
EXAMPLE 3
60% by weight of a tenside mixture consisting of
30% by weight of olefin sulfonate
60% by weight of sulfosuccinic acid ester
10% by weight of coconut fatty acid diethanolamide
19 % by weight of hardened tallow fatty acid (Iodine No.=2)
10 % by weight of tallow fatty alcohol (Iodine No. <1)
2 % by weight of lanolin
2 % by weight of mixed citric acid ester
1 % by weight of perfume
0.03% by weight of brightener
0.1 % by weight of TiO.sub.2
0.3 % by weight of hydroxyethanediphosphonate (sodium salt) residue
water (5.57% by weight)
EXAMPLE 4
70% by weight of a tenside mixture consisting of
50% by weight of sulfosuccinic acid ester
20% by weight of olefin sulfonate
20% by weight of coconut fatty alcohol sulfate
10% by weight of soap
9 % by weight of stearin (Iodine No.=2)
9 % by weight of tallow fatty alcohol (Iodine No.<1)
1 % by weight of mixed citric acid ester
2 % by weight of lanolin
0.1 % by weight of TiO.sub.2
0.003% by weight of dye
residue water (8.897% by weight)
The properties in use of the shaped detergents, according to the
invention, show a remarkable similarity with soap. They differ,
therefore, advantageously from the until now known shaped
detergents on the basis of synthetic tensides even if those contain
water-insoluble builders. Above all, their swelling behavior is
largely identical to that of soap. On longer lying on a moist
substrate, such as a soap dish of a wash basin, they indeed absorb
water. This can be recognized by the bright discoloration, but they
lose this water in dry surroundings without a noteworthy decrease
in the compactness of the dried materials. The foam formed during
washing is similar to that of soap both in its structure and in its
behavior. The foam present in the wash basin collapses quickly on
rinsing. The abrading observed in washing is largely identical to
that of good toilet soap. People who wash or bathe with these cakes
did not observe a disagreeable degreasing of the skin.
It should be kept in mind that the term "builders" is also used in
the field of the detergent powders, where it means certain water
soluble substances enhancing the washing action of detergents. In
this case, however, the term "builders" designates a certain kind
of water insoluble substances, usualy incorporated into soap pieces
to improve their body properties when in contact with water.
The preceding specific embodiments are illustrative of the practice
of the invention. It is to be understood, however, that other
expedients known to those skilled in the art may be utilized
without departing from the spirit of the invention or the scope of
the appended claims.
* * * * *