U.S. patent application number 10/472668 was filed with the patent office on 2004-05-27 for quaternary surfactants.
Invention is credited to Bigorra Llosas, Joaquin, Bonastre Gilabert, Nuria, Pi Subirana, Rafael, Schmid, Karl Heinz.
Application Number | 20040102355 10/472668 |
Document ID | / |
Family ID | 7678119 |
Filed Date | 2004-05-27 |
United States Patent
Application |
20040102355 |
Kind Code |
A1 |
Bigorra Llosas, Joaquin ; et
al. |
May 27, 2004 |
Quaternary surfactants
Abstract
The invention relates to quaternary surfactants of formula (I)
wherein R.sup.1CO represents a linear or branched, saturated or
unsaturated acyl radical, optionally having a hydroxy function, and
having between 6 and 22 carbon atoms and 0, 1, 2 or 3 double bonds;
R.sup.2 represents a CH.sub.2COOH radical or an alkyl radical
having between 1 and 4 carbon atoms, or a CH.sub.2CH.sub.2OH or
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH.sub- .2 group; and X represents
a halide, alkylsulfate, alkylcarbonate or alkylphosphate. 1
Inventors: |
Bigorra Llosas, Joaquin;
(Sabedell, ES) ; Schmid, Karl Heinz; (Mettmann,
DE) ; Pi Subirana, Rafael; (Granollers, ES) ;
Bonastre Gilabert, Nuria; (Barbera de Vall, ES) |
Correspondence
Address: |
COGNIS CORPORATION
PATENT DEPARTMENT
300 BROOKSIDE AVENUE
AMBLER
PA
19002
US
|
Family ID: |
7678119 |
Appl. No.: |
10/472668 |
Filed: |
September 22, 2003 |
PCT Filed: |
March 9, 2002 |
PCT NO: |
PCT/EP02/02611 |
Current U.S.
Class: |
510/504 |
Current CPC
Class: |
A61K 8/442 20130101;
A61Q 15/00 20130101; C07C 233/38 20130101; A61K 8/42 20130101; A61Q
5/006 20130101; A61Q 5/00 20130101; C11D 1/62 20130101; A61Q 19/10
20130101; C07C 233/36 20130101; A61Q 5/02 20130101 |
Class at
Publication: |
510/504 |
International
Class: |
C11D 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 20, 2001 |
DE |
10113 334.0 |
Claims
1. A quaternary surfactant of the formula (I), 4in which R.sup.1CO
is a linear or branched, saturated or unsaturated, optionally
hydroxy-functionalized acyl radical having 6 to 22 carbon atoms and
0, 1, 2 or 3 double bonds, R.sup.2 is a CH.sub.2COOH radical, an
alkyl radical having 1 to 4 carbon atoms, a CH.sub.2CH.sub.2OH or
CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH group and x is halide, alkyl
sulfate, alkyl carbonate or alkyl phosphate:
2. The quaternary surfactant as claimed in claim 1, characterized
in that it has an amphoteric betaine structure or a cationic amide
quat structure.
3. A process for the preparation of quaternary surfactants of the
formula (I), 5in which R.sup.1CO is a linear or branched, saturated
or unsaturated, optionally hydroxy-functionalized acyl radical
having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R.sup.2
is a CH.sub.2COOH radical or an alkyl radical having 1 to 4 carbon
atoms, a CH.sub.2CH.sub.2OH or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH
group and X is halide, alkyl sulfate, alkyl carbonate or alkyl
phosphate, characterized in that (a) fatty acids and/or fatty acid
glycerol esters are condensed with aminopropylmethylethanolamine,
and (b) the resulting fatty acid amidoamines are then quaternized
with alkylating agents in a manner known per se.
4. The process as claimed in claim 3, characterized in that fatty
acids of the formula (II) are used, R.sup.1CO--OH (II) in which
R.sup.1CO has the meaning described above.
5. The process as claimed in claim 3, characterized in that fatty
acid glycerides of the formula (III) are used,
R.sup.1CO--CH.sub.2CH(OR.sup.3)- CH.sub.2OR.sup.4 (III) in which
R.sup.1CO has the meaning given above and R.sup.3 and R.sup.4,
independently of one another, are hydrogen or optionally
hydroxy-functionalized acyl radicals having 6 to 22 carbon atoms
and 0, 1, 2 or 3 double bonds.
6. The process as claimed in at least one of claims 3 to 5,
characterized in that mixtures of the fatty acids or fatty acid
glycerol esters with dicarboxylic acids are used.
7. The process as claimed in at least one of claims 3 to 6,
characterized in that the alkylating agent used is chloroacetic
acid and/or salts thereof.
8. The process as claimed in at least one of claims 3 to 6,
characterized in that the alkylating agents used are alkyl halides,
dialkyl sulfates, carbonates or phosphates or ethylene oxide.
9. The use of quaternary surfactants as claimed in claim 1 for the
preparation of cosmetic and/or pharmaceutical preparations.
10. The use of quaternary surfactants as claimed in claim 1 for the
preparation of laundry detergents, dishwashing detergents, cleaners
and hand modifiers.
Description
FIELD OF THE INVENTION
[0001] The invention is in the fields of cosmetics and detergents
and relates to novel surfactants with a betaine or amide quat
structure, to processes for the preparation thereof, and to their
use for the preparation of surface-active compositions.
PRIOR ART
[0002] Surface-active substances with quaternary centers are
divided roughly into amphoteric or zwitterionic surfactants on the
one hand and cationic surfactants on the other hand. For both
groups, there are countless examples in the market, such as, for
example, the reaction products of fatty acid amidopropylamine with
sodium chloroacetate (known under the INCI name Cocamidopropyl
Betaine) or the alkylation products of triethanolamine fatty acid
esters (known under the name ester quats). A common feature of
these substances is their ability to attach to solid, especially
negatively charged, surfaces, which is utilized, for example, for
hand modifiers and hair-treatment compositions. Although the known
products exhibit a performance which is in principle entirely
satisfactory, there is still a desire for improved properties for a
number of special applications. These include, in particular, the
technically simple availability of concentrates with high storage
stability.
[0003] Consequently, it was the object of the present invention to
provide novel betaines or ester quats which, even at solids
contents above 50% by weight, are flowable and pumpable, preferably
have a Brookfield viscosity (20.degree. C., spindle 1, 10 rpm) of
less than 10 000 mPas and in particular less than 6 000 mPas. At
the same time, the concentrates should neither gel nor change to a
noteworthy degree with regard to their viscosity, even after
storage at 40.degree. C. for several weeks. Finally, it was desired
to provide concentrates for various applications which are
transparent even after prolonged storage under temperature. The
demand for excellent biodegradability and dermatological
compatibility represents a permanent requirement.
DESCRIPTION OF THE INVENTION
[0004] The invention provides quaternary surfactants of the formula
(I), 2
[0005] in which R.sup.1CO is a linear or branched, saturated or
unsaturated, optionally hydroxy-functionalized acyl radical having
6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R.sup.2 is a
CH.sub.2COOH radical or an alkyl radical having 1 to 4 carbon
atoms, a CH.sub.2CH.sub.2OH or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH
group and X is halide, alkyl sulfate, alkyl carbonate or alkyl
phosphate. The quaternary surfactants can here have either a
betaine or amide quat structure, depending on the alkylating
agent.
[0006] Surprisingly, it has been found that the novel surfactants
can be adjusted to solids contents above 50% by weight without the
addition of auxiliaries, such as, for example, (hydroxy)carboxylic
acids, and nevertheless remain flowable and pumpable. In addition,
even during storage under temperature, neither gelation nor
collapse of the viscosity is observed. The concentrates are also
transparent, particularly when dicarboxylic acids have been
condensed into the molecule. The products are additionally
completely biodegradable and are tolerated by the skin to an
excellent degree.
[0007] The invention further provides a process for the preparation
of quaternary surfactants of the formula (I), 3
[0008] in which R.sup.1CO is a linear or branched, saturated or
unsaturated, optionally hydroxy-functionalized acyl radical having
6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R.sup.2 is a
CH.sub.2COOH radical or an alkyl radical having 1 to 4 carbon
atoms, a CH.sub.2CH.sub.2OH or CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OH
group and X is halide, alkyl sulfate, alkyl carbonate or alkyl
phosphate, which is characterized in that
[0009] (a) fatty acids and/or fatty acid glycerol esters are
condensed with aminopropylmethylethanolamine, and
[0010] (b) the resulting fatty acid amidoamines are then
quaternized with alkylating agents in a manner known per se.
[0011] Amidoamine Formation
[0012] Both for the betaines according to the invention and also
for the amide quats, the amidoamines represent the common
intermediates, which takes place either by amidation of the fatty
acids or transamidation of the fatty acid glycerol esters,
specifically the triglycerides, with aminopropylmethylethanolamine
(APMEA). Suitable starting materials for the amidation are fatty
acids of the formula (II)
R.sup.1CO--OH (II)
[0013] in which R.sup.1CO has the meaning described above. Typical
examples thereof are caproic acid, caprylic acid, 2-ethylhexanoic
acid, capric acid, lauric acid, isotridecanoic acid, myristic acid,
palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic
acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid,
ricinoleic acid, 12-hydroxystearic acid, elaeostearic acid,
arachidic acid, gadoleic acid, behenic acid, and erucic acid, and
technical-grade mixtures thereof which are produced, for example,
during the pressurized cleavage of natural fats and oils, during
the reduction of aldehydes from the Roelen oxo synthesis or the
dimerization of unsaturated fatty acids. Preference is given to
technical-grade fatty acids having 12 to 18 carbon atoms, such as,
for example, coconut, palm, palm kernel or tallow fatty acid. In
place of the fatty acids, it is also possible for fatty acid
glycerol esters which conform to the formula (III) to be
transamidated:
R.sup.1CO--CH.sub.2CH(OR.sup.3)CH.sub.2OR.sup.4 (III)
[0014] Here, R.sup.1CO has the meaning given above, while R.sup.3
and R.sup.4, independently of one another, are hydrogen or
optionally hydroxy-functionalized acyl radicals having 6 to 22
carbon atoms and 0, 1, 2 or 3 double bonds. Preferably, R.sup.3 and
R.sup.4 are also acyl radicals, i.e. the fatty acid glycerol esters
are natural or synthetic triglycerides, i.e. fats or oils, such as,
for example, coconut oil, palm oil, palm kernel oil, olive oil,
olive kernel oil, rapeseed oil, sunflower oil, groundnut oil,
linseed oil, beef tallow or pork lard. It is likewise possible to
carry out the condensation of the fatty acids or glycerides with
the APMEA in the presence of defined amounts of dicarboxylic acids,
such as, for example, oxalic acid, malonic acid, succinic acid,
maleic acid, fumaric acid, glutaric acid, adipic acid, sorbic acid,
pimelic acid, azelaic acid, sebacic acid and/or dodecanedioic acid.
This method results in a partially oligomeric structure of the
betaines or amide quats, which has a particularly advantageous
effect on the solubility of the products to form clear solutions,
particularly when adipic acid is co-used. Typically, the ratio of
the free carboxylic acid groups between monocarboxylic acid and
dicarboxylic acid is 90:10 to 80:20.
[0015] To prepare the fatty acid amidoamines, the fatty acids or
fatty acid glycerol esters and the APMEA can be used in the molar
ratio from 1.1:1 to 3:1. With regard to the performance properties
of the resulting betaines or amide quats, a feed ratio of from
1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1, has proven particularly
advantageous. The preferred fatty acid amidoamines are
technical-grade mixtures of mono-, di- and triamides with an
average degree of amidation of from 1.5 to 1.9. The condensation
can be carried out in a manner known per se, i.e. in the presence
of phosphorus or hypophosphorous acid as catalyst, and with removal
of the water of condensation from the reaction equilibrium.
Typically, the reaction is carried out at temperatures in the range
from 150 to 200.degree. C. over a period of from 2 to 8 h. For
performance reasons, it is, moreover, advisable to remove free
unreacted amine under reduced pressure in order that the
intermediate is odorless and subsequent irritations are
prevented.
[0016] Quaternization
[0017] The quaternization of the intermediates is an alkylation
which leads to betaines or amide quats, depending on the alkylating
agent. In the first case, suitable alkylating agents are
chloroacetic acid and/or salts thereof, specifically sodium
chloroacetate, and in the second case, suitable alkylating agents
are alkyl halides, dialkyl sulfates, carbonates or phosphates,
preferably methyl chloride, dimethyl sulfate or dimethyl carbonate.
Alternatively, the quaternization can also be carried out with
ethylene oxide. While the betainization is usually carried out in
aqueous solution, the quaternization is usually carried out in
alcoholic solution, preferably in ethanol, isopropyl alcohol or
propylene glycol. The amount of quaternizing agent will usually be
measured such that in all cases a small stoichiometric excess is
present. Particularly when dimethyl sulfate is used, a small
deficit is advisable in order to ensure that no traces of the
alkylating agent remain in the end-product. In some cases, a
thermal aftertreatment is advisable. The molar ratio of amidoamine
to alkylating agent is therefore usually 1:0.95 to 1:1.05. The
betainization or quaternization is usually carried out at
temperatures in the range from 50 to 90.degree. C. over a period of
from 2 to 10 h.
INDUSTRIAL APPLICABILITY
[0018] The novel surfactants are characterized by typical
amphoteric or cationic properties, i.e. attach to solid, especially
negatively charged, surfaces. Further subject-matters of the
invention therefore relate to their use for the preparation of
cosmetic and/or pharmaceutical preparations, and also of laundry
detergents, dishwashing detergents, cleaners and hand modifiers in
which they may be present in amounts of from 1 to 30% by weight,
preferably 5 to 25% by weight and in particular 10 to 15% by
weight.
[0019] Cosmetic and/or Pharmaceutical Preparations
[0020] The surface-active preparations which comprise the novel
surfactants are preferably skin- or hair-treatment compositions
which can likewise have further auxiliaries and additives typical
for these compositions. These include, for example, mild
surfactants, oily bodies, emulsifiers, pearlescent waxes, bodying
agents, thickeners, superfatting agents, stabilizers, polymers,
silicone compounds, fats, waxes, lecithins, phospholipids, biogenic
active ingredients, UV light protection factors, antioxidants,
deodorants, antiperspirants, antidandruff agents, film formers,
swelling agents, insect repellants, self-tanning agents, tyrosine
inhibitors (depigmentation agents), hydrotropic agents,
solubilizers, preservatives, perfume oils, dyes and the like.
[0021] Surfactants
[0022] Surface-active substances which may be present are anionic,
nonionic, cationic and/or amphoteric or amphoteric surfactants, the
content of which in the compositions is usually about 1 to 70% by
weight, preferably 5 to 50% by weight and in particular 10 to 30%
by weight. Typical examples of anionic surfactants are soaps,
alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl
ether sulfonates, glycerol ether sulfonates, .alpha.-methyl ester
sulfonates, sulfo-fatty acids, alkyl sulfates, fatty alcohol ether
sulfates, glycerol ether sulfates, fatty acid ether sulfates,
hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty
acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates,
mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide
soaps, ether carboxylic acids and salts thereof, fatty acid
isethionates, fatty acid sarcosinates, fatty acid taurides,
N-acylamino acids, such as, for example, acyl lactylates, acyl
tartrates, acyl glutamates and acyl aspartates, alkyl
oligoglucoside sulfates, protein fatty acid condensates (in
particular wheat-based vegetable products) and alkyl (ether)
phosphates. If the anionic surfactants contain polyglycol ether
chains, these can have a conventional homolog distribution, but
preferably have a narrowed homolog distribution. Typical examples
of nonionic surfactants are fatty alcohol polyglycol ethers,
alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty
acid amide polyglycol ethers, fatty amine polyglycol ethers,
alkoxylated triglycerides, mixed ethers or mixed formals,
optionally partially oxidized alk(en)yl oligoglycosides or
glucoronic acid derivatives, fatty acid N-alkylglucamides, protein
hydrolysates (in particular wheat-based vegetable products), polyol
fatty acid esters, sugar esters, sorbitan esters, polysorbates and
amine oxides. If the nonionic surfactants contain polyglycol ether
chains, these can have a conventional homolog distribution, but
preferably have a narrowed homolog distribution.
[0023] Typical examples of cationic surfactants are quaternary
ammonium compounds, such as, for example, dimethyldistearylammonium
chloride, and ester quats, in particular quaternized fatty acid
trialkanolamine ester salts. Typical examples of amphoteric or
zwitterionic surfactants are alkylbetaines, alkylamidobetaines,
aminopropionates, aminoglycinates, imidazoliniumbetaines and
sulfobetaines. Said surfactants are exclusively known compounds.
With regard to structure and preparation of these substances,
reference may be made to relevant review works, for example, J.
Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag,
Berlin, 1987, pp. 54-124 or J. Falbe (ed.), "Katalysatoren, Tensid
und Mineraloladditive", Thiem Verlag, Stuttgart, 1978, pp. 123-217.
Typical examples of particularly suitable mild, i.e. particularly
skin-compatible surfactants are fatty alcohol polyglycol ether
sulfates, monoglyceride sulfates, mono- and/or dialkyl
sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates,
fatty acid taurides, fatty acid glutamates, (.alpha.-olefin
sulfonates, ether carboxylic acids, alkyl oligoglucosides, fatty
acid glucamides, alkylamidobetaines, amphoacetals and/or protein
fatty acid condensates, the latter preferably based on wheat
proteins.
[0024] Oily Bodies
[0025] Suitable oily bodies are, for example, Guerbet alcohols
based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon
atoms, esters of linear C.sub.6-C.sub.22-fatty acids with linear or
branched C.sub.6-C.sub.22-fatty alcohols and/or esters of branched
C.sub.6-C.sub.13-carboxylic acids with linear or branched
C.sub.6-C.sub.22-fatty alcohols, such as, for example, myristyl
myristate, myristyl palmitate, myristyl stearate, myristyl
isostearate, myristyl oleate, myristyl behenate, myristyl erucate,
cetyl myristate, cetyl palmitate, cetyl stearate, cetyl
isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl
myristate, stearyl palmitate, stearyl stearate, stearyl
isostearate, stearyl oleate, stearyl behenate, stearyl erucate,
isostearyl myristate, isostearyl palmitate, isostearyl stearate,
isostearyl isostearate, isostearyl oleate, isostearyl behenate,
isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl
stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl
erucate, behenyl myristate, behenyl palmitate, behenyl stearate,
behenyl isostearate, behenyl oleate, behenyl behenate, behenyl
erucate, erucyl myristate, erucyl palmitate, erucyl stearate,
erucyl isostearate, erucyl oleate, erucyl behenate and erucyl
erucate. Also suitable are esters of linear C.sub.6-C.sub.22-fatty
acids with branched alcohols, in particular 2-ethylhexanol, esters
of C.sub.18-C.sub.38-alkyl hydroxycarboxylic acids with linear or
branched C.sub.6-C.sub.22-fatty alcohols (cf. DE 19756377 A1), in
particular dioctyl malates, esters of linear and/or branched fatty
acids with polyhydric alcohols (such as, for example, propylene
glycol, dimerdiol or trimertriol) and/or Guerbet alcohols,
triglycerides based on C.sub.6-C.sub.10-fatty acids, liquid
mono-/di-/triglyceride mixtures based on C.sub.6-C.sub.18-fatty
acids, esters of C.sub.6-C.sub.22-fatty alcohols and/or Guerbet
alcohols with aromatic carboxylic acids, in particular benzoic
acid, esters of C.sub.2-C.sub.12-dicarboxylic acids with linear or
branched alcohols having 1 to 22 carbon atoms or polyols having 2
to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils,
branched primary alcohols, substituted cyclohexanes, linear and
branched C.sub.6-C.sub.22-fatty alcohol carbonates, such as, for
example, dicaprylyl carbonate (Cetiol.RTM. CC), Guerbet carbonates
based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon
atoms, esters of benzoic acid with linear and/or branched
C.sub.6-C.sub.22-alcohols (e.g. Finsolv.RTM. TN), linear or
branched, symmetrical or unsymmetrical dialkyl ethers having 6 to
22 carbon atoms per alkyl group, such as, for example, dicaprylyl
ether (Cetiol.RTM. OE), ring-opening products of epoxidized fatty
acid esters with polyols, silicone oils (cyclomethicones, silicon
methicone types, inter alia) and/or aliphatic or naphthenic
hydrocarbons, such as, for example, such as squalane, squalene or
dialkylcyclohexanes under consideration.
[0026] Emulsifiers
[0027] Suitable emulsifiers are, for example, nonionogenic
surfactants from at least one of the following groups:
[0028] addition products of from 2 to 30 mol of ethylene oxide
and/or 0 to 5 mol of propylene oxide to linear fatty alcohols
having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon
atoms, to alkylphenols having 8 to 15 carbon atoms in the alkyl
group, and alkylamines having 8 to 22 carbon atoms in the alkyl
radical;
[0029] alkyl and/or alkenyl oligoglycosides having 8 to 22 carbon
atoms in the alk(en)yl radical and the ethoxylated analogs
thereof;
[0030] addition products of from 1 to 15 mol of ethylene oxide to
castor oil and/or hydrogenated castor oil;
[0031] addition products of from 15 to 60 mol of ethylene oxide to
castor oil and/or hydrogenated castor oil;
[0032] partial esters of glycerol and/or sorbitan with unsaturated,
linear or saturated, branched fatty acids having 12 to 22 carbon
atoms and/or hydroxycarboxylic acids having 3 to 18 carbon atoms,
and the adducts thereof with 1 to 30 mol of ethylene oxide;
[0033] partial esters of polyglycerol (average degree of
self-condensation 2 to 8), polyethylene glycol (molecular weight
400 to 5 000), trimethylolpropane, pentaerythritol, sugar alcohols
(e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl
glucoside, lauryl glucoside), and polyglucosides (e.g. cellulose)
with saturated and/or unsaturated, linear or branched fatty acids
having 12 to 22 carbon atoms and/or hydroxycarboxylic acids having
3 to 18 carbon atoms, and the adducts thereof with 1 to 30 mol of
ethylene oxide;
[0034] mixed esters of pentaerythritol, fatty acids, citric acid
and fatty alcohol as in German Patent 1165574 and/or mixed esters
of fatty acids having 6 to 22 carbon atoms, methylglucose and
polyols, preferably glycerol or polyglycerol,
[0035] mono-, di- and trialkyl phosphates, and mono-, di-and/or
tri-PEG alkyl phosphates and salts thereof;
[0036] wool wax alcohols;
[0037] polysiloxane-polyalkyl-polyether copolymers and
corresponding derivatives;
[0038] block copolymers, e.g. polyethylene glycol-30
dipolyhydroxystearates;
[0039] polymer emulsifiers, e.g. Pemulen grades (TR-1, TR-2) from
Goodrich;
[0040] polyalkylene glycols, and
[0041] glycerol carbonate.
[0042] Ethylene Oxide Addition Products
[0043] The addition products of ethylene oxide and/or of propylene
oxide to fatty alcohols, fatty acids, alkylphenols or to castor oil
are known, commercially available products. These are homolog
mixtures whose average degree of alkoxylation corresponds to the
ratio of the amounts of substance of ethylene oxide and/or
propylene oxide and substrate with which the addition reaction is
carried out. C.sub.12/18-fatty acid mono- and diesters of addition
products of ethylene oxide to glycerol are known from German Patent
2024051 as refatting agents for cosmetic preparations.
[0044] Alkyl and/or Alkenyl Oligoglycosides
[0045] Alkyl and/or alkenyl oligoglycosides, their preparation and
their use are known from the prior art. They are prepared, in
particular, by reacting glucose or oligosaccharides with primary
alcohols having 8 to 18 carbon atoms. With regard to the glycoside
radical, both monoglycosides, in which a cyclic sugar radical is
glycosidically bonded to the fatty alcohol, and also oligomeric
glycosides having a degree of oligomerization of up to, preferably,
about 8, are suitable. The degree of oligomerization here is a
statistical average value which is based on a homolog distribution
customary for such technical-grade products.
[0046] Partial Glycerides
[0047] Typical examples of suitable partial glycerides are
hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride,
isostearic acid monoglyceride, isostearic acid diglyceride, oleic
acid monoglyceride, oleic acid diglyceride, ricinoleic acid
moglyceride, ricinoleic acid diglyceride, linoleic acid
monoglyceride, linoleic acid diglyceride, linolenic acid
monoglyceride, linolenic acid diglyceride, erucic acid
monoglyceride, erucic acid diglyceride, tartaric acid
monoglyceride, tartaric acid diglyceride, citric acid
monoglyceride, citric acid diglyceride, malic acid monoglyceride,
malic acid diglyceride, and the technical-grade mixtures thereof
which may also comprise small amounts of triglyceride as a minor
product of the preparation process. Likewise suitable are addition
products of 1 to 30 mol, preferably 5 to 10 mol, of ethylene oxide
to said partial glycerides.
[0048] Sorbitan Esters
[0049] [Lacuna] sorbitan esters are sorbitan monoisostearate,
sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan
triisostearate, sorbitan monooleate, sorbitan sesquioleate,
sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate,
sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate,
sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan
diricinoleate, sorbitan triricinoleate, sorbitan
monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan
dihydroxystearate, sorbitan trihydroxystearate, sorbitan
monotartrate, sorbitan sesquitartrate, sorbitan ditartrate,
sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate,
sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate,
sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate,
and technical-grade mixtures thereof. Likewise suitable are
addition products of from 1 to 30 mol, preferably 5 to 10 mol, of
ethylene oxide to said sorbitan esters.
[0050] Polyglycerol Esters
[0051] Typical examples of suitable polyglycerol esters are
polyglyceryl-2 dipolyhydroxystearate (Dehymuls.RTM. PGPH),
polyglycerol-3 diisostearate (Lameform.RTM. TGI), polyglyceryl-4
isostearate (Isolan.RTM. GI 34), polyglyceryl-3 oleate,
diisostearoyl polyglyceryl-3 diisostearate (Isolan.RTM. PDI),
polyglyceryl-3 methylglucose distearate (Tego Care.degree. 450),
polyglyceryl-3 beeswax (Cera Bellina.RTM.), polyglyceryl-4 caprate
(Polyglycerol Caprate T2010/90), polyglyceryl-3 cetyl ether
(Chimexane.RTM. NL), polyglyceryl-3 distearate (Cremophor.RTM. GS
32) and polyglyceryl polyricinoleate (Admul.RTM. WOL 1403),
polyglyceryl dimerate isostearate, and mixtures thereof. Examples
of further suitable polyol esters are the mono-, di- and triesters,
optionally reacted with 1 to 30 mol of ethylene oxide, of
trimethylolpropane or pentaerythritol with lauric acid, coconut
fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic
acid, behenic acid and the like.
[0052] Anionic Emulsifiers
[0053] Typical anionic emulsifiers are aliphatic fatty acids having
12 to 22 carbon atoms, such as, for example, palmitic acid, stearic
acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon
atoms, such as, for example, azelaic acid or sebacic acid.
[0054] Amphoteric and Cationic Emulsifiers
[0055] Furthermore, zwitterionic surfactants can be used as
emulsifiers. The term "zwitterionic surfactants" refers to those
surface-active compounds which carry at least one quaternary
ammonium group and at least one carboxylate and one sulfonate group
in the molecule. Particularly suitable zwitterionic surfactants are
the so-called betaines, such as N-alkyl-N,N-dimethylammonium
glycinates, for example cocoalkyldimethylammonium glycinate,
N-acylamino-propyl-N,N-dimethylammon- ium glycinates, for example
cocoacylaminopropyldimethylammonium glycinate, and
2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having in each
case 8 to 18 carbon atoms in the alkyl or acyl group, and
cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. Particular
preference is given to the fatty acid amide derivative known under
the CTFA name Cocamidopropyl Betaine. Likewise suitable emulsifiers
are ampholytic surfactants. The term "ampholytic surfactants" means
those surface-active compounds which, apart from a C.sub.8/18-alkyl
or -acyl group, contain at least one free amino group and at least
one --COOH or --SO.sub.3H group in the molecule and are capable of
forming internal salts. Examples of suitable ampholytic surfactants
are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric
acids, N-alkyliminodipropionic acids,
N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,
N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic
acids having in each case about 8 to 18 carbon atoms in the alkyl
group. Particularly preferred ampholytic surfactants are
N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and
C.sub.12/18-acylsarcosine. Finally, cationic surfactants are also
suitable as emulsifiers, those of the ester quat type, preferably
methyl-quaternized difatty acid triethanolamine ester salts, being
particularly preferred.
[0056] Fats and Waxes
[0057] Typical examples of fats are glycerides, i.e. solid or
liquid vegetable or animal products which consist essentially of
mixed glycerol esters of higher fatty acids, suitable waxes are
inter alia natural waxes, such as, for example, candelilla wax,
carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax,
rice germ oil wax, sugarcane wax, ouricury wax, montan wax,
beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial
grease, ceresin, ozokerite (earth wax), petrolatum, paraffin waxes,
microcrystalline waxes; chemically modified waxes (hard waxes),
such as, for example, montan ester waxes, sasol waxes, hydrogenated
jojoba waxes, and synthetic waxes, such as, for example,
polyalkylene waxes and polyethylene glycol waxes. In addition to
the fats, suitable additives are also fat-like substances, such as
lecithins and phospholipids. The term lecithins is understood by
the person skilled in the art as meaning those glycerophospholipids
which are founded from fatty acids, glycerol, phosphoric acid and
choline by esterification. Lecithins are thus also often [lacuna]
as phosphatidylcholines (PC) in the specialist world. Examples of
natural lecithins which may be mentioned are the cephalins, which
are also referred to as phosphatidic acids, and derivatives of
1,2-diacyl-sn-glycerol-3-phosphoric acids. By contrast,
phospholipids are usually understood as meaning mono--and
preferably diesters of phosphoric acid with glycerol (glycerol
phosphates), which are generally classed as fats. In addition,
sphingosines or sphingolipids are also suitable.
[0058] Pearlescent Waxes
[0059] Examples of suitable pearlescent waxes are: alkylene glycol
esters, specifically ethylene glycol distearate; fatty acid
alkanolamides, specifically coconut fatty acid diethanolamide;
partial glycerides, specifically stearic acid monoglyceride; esters
of polybasic, optionally hydroxy-substituted carboxylic acids with
fatty alcohols having 6 to 22 carbon atoms, specifically long-chain
esters of tartaric acid; fatty substances, such as, for example,
fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and
fatty carbonates, which have a total of at least 24 carbon atoms,
specifically laurone and distearyl ether; fatty acids, such as
stearic acid, hydroxystearic acid or behenic acid, ring-opening
products of olefin epoxides having 12 to 22 carbon atoms with fatty
alcohols having 12 to 22 carbon atoms and/or polyols having 2 to 15
carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.
[0060] Bodying Agents and Thickeners
[0061] Suitable bodying agents are primarily fatty alcohols or
hydroxy fatty alcohols having 12 to 22, and preferably 16 to 18,
carbon atoms, and also partial glycerides, fatty acids or hydroxy
fatty acids. Preference is given to a combination of these
substances with alkyl oligoglucosides and/or fatty acid
N-methylglucamides of identical chain length and/or polyglycerol
poly-12-hydroxystearates. Suitable thickeners are, for example,
Aerosil grades (hydrophilic silicas), polysaccharides, in
particular xanthan gum, guar guar, agar agar, alginates and
Tyloses, carboxymethylcellulose, hydroxyethylcellulose and
hydroxypropylcellulose, and also relatively high molecular weight
polyethylene glycol mono- and diesters of fatty acids,
polyacrylates (e.g. Carbopols.RTM. and Pemulen grades from
Goodrich; Synthalens.RTM. from Sigma; Keltrol grades from Kelco;
Sepigel grades from Seppic; Salcare grades from Allied Colloids),
polyacrylamides, polymers, polyvinyl alcohol and
polyvinylpyrrolidone. Bentonites, such as, for example,
Bentone.RTM. Gel VS 5PC (Rheox), which is a mixture of
cyclopentasiloxane, disteardimonium hectorite and propylene
carbonate, have also proven to be particularly effective. Also
suitable are surfactants, such as, for example, ethoxylated fatty
acid glycerides, esters of fatty acids with polyols such as, for
example, pentaerythritol or trimethylolpropane, fatty alcohol
ethoxylates having a narrowed homolog distribution or alkyl
oligoglucosides, and electrolytes such as sodium chloride and
ammonium chloride.
[0062] Superfatting Agents
[0063] Superfatting agents which can be used are substances such
as, for example, lanolin and lecithin, and polyethoxylated or
acylated lanolin and lecithin derivatives, polyol fatty acid
esters, monoglycerides and fatty acid alkanolamides, the latter
also serving as foam stabilizers.
[0064] Stabilizers
[0065] Stabilizers which can be used are metal salts of fatty
acids, such as, for example, magnesium, aluminum and/or zinc
stearate or ricinoleate.
[0066] Polymers
[0067] Suitable cationic polymers are, for example, cationic
cellulose derivatives, such as, for example, a quaternized
hydroxyethylcellulose obtainable under the name Polymer JR 400.RTM.
from Amerchol, cationic starch, copolymers of diallylammonium salts
and acrylamides, quaternized vinylpyrrolidone-vinylimidazole
polymers, such as, for example, Luviquat.RTM. (BASF), condensation
products of polyglycols and amines, quaternized collagen
polypeptides, such as, for example, lauryldimonium hydroxypropyl
hydrolyzed collagen (Lamequat.RTM. L/Grunau), quaternized wheat
polypeptides, polyethyleneimine, cationic silicone polymers, such
as, for example, amodimethicones, copolymers of adipic acid and
dimethylaminohydroxypropyldiethylenetriamine (Cartaretins.RTM.
/Sandoz), copolymers of acrylic acid with dimethyldiallylammonium
chloride (Merquat.RTM. 550/Chemviron), polyaminopolyamides, as
described, for example, in FR 2252840 A, and crosslinked
water-soluble polymers thereof, cationic chitin derivatives, such
as, for example, quaternized chitosan, optionally in
micro-crystalline dispersion, condensation products from
dihaloalkyls, such as, for example, dibromobutane with
bisdialkylamines, such as, for example,
bis-dimethylamino-1,3-propane, cationic guar gum, such as, for
example, Jaguar.RTM. CBS, Jaguar.RTM. C-17, Jaguar.RTM. C-16 from
Celanese, quaternized ammonium salt polymers, such as, for example,
Mirapol.RTM. A-15, Mirapol.RTM. AD-1, Mirapol.RTM. AZ-1 from
Miranol.
[0068] Suitable anionic, zwitterionic, amphoteric and nonionic
polymers are, for example, vinyl acetate-crotonic acid copolymers,
vinylpyrrolidone-vinyl acrylate copolymers, vinyl acetate-butyl
maleate-isobornyl acrylate copolymers, methyl vinyl ether-maleic
anhydride copolymers and esters thereof, uncrosslinked polyacrylic
acids and polyacrylic acids crosslinked with polyols,
acrylamidopropyltrimethyl- ammonium chloride-acrylate copolymers,
octylacrylamide-methyl methacrylate-tert-butylaminoethyl
methacrylate-2-hydroxypropyl methacrylate copolymers,
polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers,
vinylpyrrolidone-dimethylaminoethyl methacrylate-vinylcaprolactam
terpolymers, and optionally derivatized cellulose ethers and
silicones. Further suitable polymers and thickeners are listed in
Cosm. Toil. 108, 95 (1993).
[0069] Silicone compounds
[0070] Suitable silicone compounds are, for example,
dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones,
and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-,
glycoside- and/or alkyl-modified silicone compounds, which can
either be liquid or in resin form at room temperature. Also
suitable are simethicones, which are mixtures of dimethicones
having an average chain length of from 200 to 300 dimethylsiloxane
units and hydrogenated silicates. A detailed review of suitable
volatile silicones can additionally be found in Todd et al., Cosm.
Toil. 91, 27 (1976).
[0071] UV Light Protection Filters and Antioxidants
[0072] UV light protection factors are, for example, to be
understood as meaning organic substances (light protection filters)
which are liquid or crystalline at room temperature and which are
able to absorb ultra-violet rays and give off the absorbed energy
again in the form of longer-wavelength radiation, e.g. heat. UVB
filters can be oil-soluble or water-soluble. Examples of
oil-soluble substances are:
[0073] 3-benzylidenecamphor or 3-benzylidenenorcamphor and
derivatives thereof, e.g. 3-(4-methylbenzylidene)-camphor, as
described in EP 0693471 B1;
[0074] 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl
4-(dimethylamino)benzoate, 2-octyl 4-(dimethylamino)benzoate and
amyl 4-(dimethylamino)-benzoate;
[0075] esters of cinnamic acid, preferably 2-ethylhexyl
4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl
4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate
(octocrylene);
[0076] esters of salicylic acid, preferably 2-ethylhexyl
salicylate, 4-isopropylbenzyl salicylate, homomenthyl
salicylate;
[0077] derivatives of benzophenone, preferably
2-hydroxy-4-methoxybenzoph- enone,
2-hydroxy-4-methoxy-4'-methylbenzophenone,
2,2'-dihydroxy-4-methoxy- benzophenone;
[0078] esters of benzalmalonic acid, preferably di-2-ethyl-hexyl
4-methoxybenzmalonate;
[0079] triazine derivatives, such as, for example,
2,4,6-trianilino(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine and
octyltriazone, as described in EP 0818450 A1 or
dioctylbutamidotriazone (Uvasorb.RTM. HEB);
[0080] propane-1,3-diones, such as, for example,
1-(4-tert-butylphenyl)-3- -(4'-methoxyphenyl)propane-1,3-dione;
[0081] ketotricyclo(5.2.1.0)decane derivatives, as described in EP
0694521 B1.
[0082] Suitable water-soluble substances are:
[0083] 2-phenylbenzimidazole-5-sulfonic acid and the alkali metal,
alkaline earth metal, ammonium, alkylammonium, alkanolammonium and
glucammonium salts thereof;
[0084] sulfonic acid derivatives of benzophenones, preferably
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
[0085] sulfonic acid derivatives of 3-benzylidenecamphor, such as,
for example, 4-(2-oxo-3-bornylidenemethyl)-benzenesulfonic acid and
2-methyl-5-(2-oxo-3-bornylidene)sulfonic acid and salts
thereof.
[0086] Suitable typical UV-A filters are, in particular,
derivatives of benzoylmethane, such as, for example,
1-(4'-tert-butylphenyl)-3-(4'-metho- xyphenyl)propane-1,3-dione,
4-tert-butyl-4'-methoxydibenzoylmethane (Parsol.RTM. 1789),
1-phenyl-3-(4'-isopropylphenyl)propane-1,3-dione, and enamine
compounds, as described in DE 19712033 A1 (BASF). The UV-A and UV-B
filters can of course also be used in mixtures. Particularly
favorable compositions consist of the derivatives of
benzoyl-methane, e.g. 4-tert-butyl-4'-methoxydibenzoylmethane
(Parsol.RTM. 1789) and 2-ethylhexyl 2-cyano-3,3-phenylcinnamate
(octocrylene) in combination with esters of cinnamic acid,
preferably 2-ethylhexyl 4-methoxycinnamate and/or propyl
4-methoxycinnamate and/or isoamyl 4-methoxycinnamate.
Advantageously, such combinations are combined with water-soluble
filters such as, for example, 2-phenylbenzimidazole-5-sulfonic acid
and their alkali metal, alkaline earth metal, ammonium,
alkylammonium, alkanolammonium and glucammonium salts.
[0087] As well as said soluble substances, insoluble light
protection pigments, namely finely dispersed metal oxides or salts,
are also suitable for this purpose. Examples of suitable metal
oxides are, in particular, zinc oxide and titanium dioxide and also
oxides of iron, zirconium, silicon, manganese, aluminum and cerium,
and mixtures thereof. Salts which may be used are silicates (talc),
barium sulfate or zinc stearate. The oxides and salts are used in
the form of the pigments for skincare and skin-protective emulsions
and decorative cosmetics. The particles here should have an average
diameter of less than 100 nm, preferably between 5 and 50 nm and in
particular between 15 and 30 nm. They can have a spherical shape,
but it is also possible to use particles which have an ellipsoidal
shape or a shape deviating in some other way from the spherical
form. The pigments can also be surface-treated, i.e.
hydrophilicized or hydrophobicized. Typical examples are coated
titanium dioxides, such as, for example, titanium dioxide T 805
(Degussa) or Eusolex.RTM. T2000 (Merck). Suitable hydrophobic
coating agents are here primarily silicones and, specifically in
this case, trialkoxyoctylsilanes or simethicones. In sunscreens,
preference is given to using so-called micro- or nanopigments.
Preference is given to using micronized zinc oxide. Further
suitable UV light protection filters are given in the review by P.
Finkel in SFW-Journal 122, 543 (1996) and Parf. Kosm. 3, 11
(1999).
[0088] As well as the two abovementioned groups of primary light
protection substances, it is also possible to use secondary light
protection agents of the antioxidant type; these interrupt the
photochemical reaction chain which is triggered when UV radiation
penetrates the skin. Typical examples thereof are amino acids (e.g.
glycine, histidine, tyrosine, tryptophan) and derivatives thereof,
imidazoles (e.g. urocanic acid) and derivatives thereof, peptides,
such as D,L-carnosine, D-carnosine, L-carnosine and derivatives
thereof (e.g. anserine), carotenoids, carotenes (e.g.
.alpha.-carotene, .beta.-carotene, lycopene) and derivatives
thereof, chlorogenic acid and derivatives thereof, lipoic acid and
derivatives thereof (e.g. dihydrolipoic acid), aurothioglucose,
propylthiouracil and other thiols (e.g. thioredoxin, glutathione,
cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl,
ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl,
.gamma.-linoleyl, cholesteryl and glyceryl esters thereof) and
salts thereof, dilauryl thiodipropionate, distearyl
thiodipropionate, thiodipropionic acid and derivatives thereof
(esters, ethers, peptides, lipids, nucleotides, nucleosides and
salts), and sulfoximine compounds (e.g. buthionine sulfoximines,
homocysteine sulfoximine, buthionine sulfones, penta-, hexa-,
heptathionine sulfoximine) in very low tolerated doses (e.g. pmol
to .mu.mol/kg), and also (metal) chelating agents (e.g.
.alpha.-hydroxy fatty acids, palmitic acid, phytic acid,
lactoferrin), .alpha.-hydroxy acids (e.g. citric acid, lactic acid,
malic acid), humic acid, bile acid, bile extracts, bilirubin,
biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty
acids and derivatives thereof (e.g. .gamma.-linolenic acid,
linoleic acid, oleic acid), folic acid and derivatives thereof,
ubiquinone and ubiquinol and derivatives thereof, vitamin C and
derivatives (e.g. ascorbyl palmitate, Mg ascorbyl phosphate,
ascorbyl acetate), tocopherols and derivatives (e.g. vitamin E
acetate), vitamin A and derivatives (vitamin A palmitate), and
coniferyl benzoate of gum benzoin, rutic acid and derivatives
thereof, .alpha.-glycosylrutin, ferulic acid,
furfurylideneglucitol, carnosine, butylhydroxytoluene,
butylhydroxyanisole, nordihydroguaiacic acid, nordihydroguaiaretic
acid, trihydroxybutyrophenone, uric acid and derivatives thereof,
mannose and derivatives thereof, superoxide dismutase, zinc and
derivatives thereof (e.g. ZnO, ZnSO.sub.4) selenium and derivatives
thereof (e.g. selenomethionine), stilbenes and derivatives thereof
(e.g. stilbene oxide, trans-stilbene oxide) and the derivatives
(salts, esters, ethers, sugars, nucleotides, nucleosides, peptides
and lipids) of said active ingredients which are suitable according
to the invention.
[0089] Biogenic Active Ingredients
[0090] Biogenic active ingredients are understood as meaning, for
example, tocopherol, tocopherol acetate, tocopherol palmitate,
ascorbic acid, (deoxy)ribonucleic acid and fragmentation products
thereof, .beta.-glucans, retinol, bisabolol, allantoin,
phytantriol, panthenol, AHA acids, amino acids, ceramides,
pseudoceramides, essential oils, plant extracts, such as, for
example, prunus extract, bambara nut extract and vitamin
complexes.
[0091] Deodorants and Antimicrobial Agents
[0092] Cosmetic deodorants counteract, mask or remove body odors.
Body odors arise as a result of the effect of skin bacteria on
apocrine perspiration, with the formation of degradation products
which have an unpleasant odor. Accordingly, deodorants comprise
active ingredients which act as antimicrobial agents, enzyme
inhibitors, odor absorbers or odor masking agents.
[0093] Antimicrobial Agents
[0094] Suitable antimicrobial agents are, in principle, all
substances effective against gram-positive bacteria, such as, for
example, 4-hydroxybenzoic acid and its salts and esters,
N-(4-chlorophenyl)-N'-(3,- 4-dichlorophenyl)urea,
2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan),
4-chloro-3,5-dimethylphenol, 2,2'-methylenebis(6-bromo-4-chl-
orophenol), 3-methyl-4-(1-methylethyl)phenol,
2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1,2-propanediol,
3-iodo-2-propynyl butylcarbamate, chlorhexidine,
3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrances,
thymol, thyme oil, eugenol, oil of cloves, menthol, mint oil,
farnesol, phenoxyethanol, glycerol monocaprate, glycerol
monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate
(DMC), salicylic acid N-alkylamides, such as, for example,
n-octylsalicylamide or n-decylsalicylamide.
[0095] Enzyme Inhibitors
[0096] Suitable enzyme inhibitors are, for example, esterase
inhibitors. These are preferably trialkyl citrates, such as
trimethyl citrate, tripropyl citrate, triisopropyl citrate,
tributyl citrate and, in particular, triethyl citrate (Hydagen
.RTM. CAT). The substances inhibit enzyme activity, thereby
reducing the formation of odor. Other substances which are suitable
esterase inhibitors are sterol sulfates or phosphates, such as, for
example, lanosterol, cholesterol, campesterol, stigmasterol and
sitosterol sulfate or phosphate, dicarboxylic acids and esters
thereof, such as, for example, glutaric acid, monoethyl glutarate,
diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate,
malonic acid and diethyl malonate, hydroxycarboxylic acids and
esters thereof, such as, for example, citric acid, malic acid,
tartaric acid or diethyl tartrate, and zinc glycinate.
[0097] Odor Absorbers
[0098] Suitable odor absorbers are substances which are able to
absorb and largely retain odor-forming compounds. They lower the
partial pressure of the individual components, thus also reducing
their rate of diffusion. It is important that in this process
perfumes must remain unimpaired. Odor absorbers are not effective
against bacteria. They comprise, for example, as main constituent,
a complex zinc salt of ricinoleic acid or specific, largely
odor-neutral fragrances which are known to the person skilled in
the art as "fixatives", such as, for example, extracts of labdanum
or styrax or certain abietic acid derivatives. The odor masking
agents are fragrances or perfume oils, which, in addition to their
function as odor masking agents, give the deodorants their
respective fragrance note. Perfume oils which may be mentioned are,
for example, mixtures of natural and synthetic fragrances. Natural
fragrances are extracts from flowers, stems and leaves, fruits,
fruit peels, roots, woods, herbs and grasses, needles and branches,
and resins and balsams. Also suitable are animal raw materials,
such as, for example, civet and castoreum. Typical synthetic
fragrance compounds are products of the ester, ether, aldehyde,
ketone, alcohol and hydrocarbon type. Fragrance compounds of the
ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl
acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate,
benzyl formate, allyl cyclohexylpropionate, styrallyl propionate
and benzyl salicylate. The ethers include, for example, benzyl
ethyl ether, and the aldehydes include, for example, the linear
alkanals having 8 to 18 carbon atoms, citral, citronellal,
citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,
lilial and bourgeonal, the ketones include, for example, the
ionones and methyl cedryl ketone, the alcohols include anethole,
citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl
alcohol and terpineol, and the hydrocarbons include mainly the
terpenes and balsams. Preference is, however, given to using
mixtures of different fragrances which together produce a pleasing
fragrance note. Essential oils of relatively low volatility, which
are mostly used as aroma components, are also suitable as perfume
oils, e.g. sage oil, camomile oil, oil of cloves, melissa oil, mint
oil, cinnamon leaf oil, linden blossom oil, juniper berry oil,
vetiver oil, olibanum oil, galbanum oil, labdanum oil and lavandin
oil. Preference is given to using bergamot oil, dihydromyrcenol,
lilial, lyral, citronellol, phenylethyl alcohol,
.alpha.-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen
aldehyde, linalool, boisambrene forte, ambroxan, indole, hedione,
sandelice, lemon oil, mandarin oil, orange oil, allyl amyl
glycolate, cyclovertal, lavandin oil, clary sage oil,
.beta.-damascone, geranium oil bourbon, cyclohexyl salicylate,
Vertofix coeur, iso-E-super, Fixolide NP, evernyl, iraldein gamma,
phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide,
romilat, irotyl and floramat alone or in mixtures.
[0099] Antiperspirants
[0100] Antiperspirants reduce the formation of perspiration by
influencing the activity of the eccrine sweat glands, thus
counteracting underarm wetness and body odor. Aqueous or anhydrous
formulations of antiperspirants typically comprise the following
ingredients:
[0101] astringent active ingredients,
[0102] oil components,
[0103] nonionic emulsifiers,
[0104] coemulsifiers,
[0105] bodying agents,
[0106] auxiliaries, such as, for example, thickeners or complexing
agents and/or
[0107] nonaqueous solvents, such as, for example, ethanol,
propylene glycol and/or glycerol.
[0108] Suitable astringent antiperspirant active ingredients are
primarily salts of aluminum, zirconium or of zinc. Such suitable
antihydrotic active ingredients are, for example, aluminum
chloride, aluminum chlorohydrate, aluminum dichlorohydrate,
aluminum sesquichlorohydrate and complex compounds thereof, e.g.
with 1,2-propylene glycol, aluminum hydroxyallantoinate, aluminum
chloride tartrate, aluminum zirconium trichlorohydrate, aluminum
zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate
and complex compounds thereof, e.g. with amino acids, such as
glycine. In addition, customary oil-soluble and water-soluble
auxiliaries may be present in antiperspirants in relatively small
amounts. Such oil-soluble auxiliaries may, for example, be:
[0109] anti-inflammatory, skin-protective or perfumed essential
oils,
[0110] synthetic skin-protective active ingredients and/or
[0111] oil-soluble perfume oils.
[0112] Customary water-soluble additives are, for example,
preservatives, water-soluble fragrances, pH regulators, e.g. buffer
mixtures, water-soluble thickeners, e.g. water-soluble natural or
synthetic polymers, such as, for example, xanthan gum,
hydroxyethylcellulose, polyvinylpyrrolidone or high molecular
weight polyethylene oxides.
[0113] Film Formers
[0114] Customary film formers are, for example, chitosan,
microcrystalline chitosan, quaternized chitosan,
polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers,
polymers of the acrylic acid series, quaternary cellulose
derivatives, collagen, hyaluronic acid and salts thereof, and
similar compounds.
[0115] Antidandruff Active Ingredients
[0116] Suitable antidandruff active ingredients are pirocton olamin
(1-hydroxy-4-methyl-6-(2,4,4-trimythylpentyl)-2-(1H)-pyridinone
monoethanolamine salt), Baypival.RTM. (climbazole),
Ketoconazole.RTM., (4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)
r-2-(1H-imidazol-1-ylmethyl)-1,3--
dioxylan-c-4-ylmethoxyphenyl}piperazine, ketoconazole, elubiol,
selenium disulfide, sulfur colloidal, sulfur polyethylene glycol
sorbitan monooleate, sulfur ricinole polyethoxylate, sulfur tar
distillates, salicylic acid (or in combination with
hexachlorophene), undexylenic acid monoethanolamide sulfosuccinate
Na salt, Lamepon.RTM. UD (protein undecylenic acid condensate),
zinc pyrithione, aluminum pyrithione and magnesium
pyrithione/dipyrithione magnesium sulfate.
[0117] Swelling Agents
[0118] The swelling agents for aqueous phases may be
montmorillonites, clay mineral substances, Pemulen, and
alkyl-modified Carbopol grades (Goodrich). Other suitable polymers
and swelling agents are given in the review by R. Lochhead in Cosm.
Toil. 108, 95 (1993).
[0119] Insect Repellents
[0120] Suitable insect repellents are N,N-diethyl-m-toluamide,
1,2-pentanediol or ethyl butylacetylaminopropionate.
[0121] Self-Tanning Agents and Depigmentation Agents
[0122] A suitable self-tanning agent is dihydroxyacetone. Suitable
tyrosine inhibitors, which prevent the formation of melanin and are
used in depigmentation agents, are, for example, arbutin, ferulic
acid, kojic acid, coumaric acid and ascorbic acid (vitamin C).
[0123] Hydrotropic Agents
[0124] To improve the flow behavior, it is also possible to use
hydrotropic agents, such as, for example, ethanol, isopropyl
alcohol, or polyols. Polyols which are suitable here preferably
have 2 to 15 carbon atoms and at least two hydroxyl groups. The
polyols can also contain further functional groups, in particular
amino groups, or be modified with nitrogen. Typical examples
are
[0125] glycerol;
[0126] alkylene glycols, such as, for example, ethylene glycol,
diethylene glycol, propylene glycol, butylene glycol, hexylene
glycol, and polyethylene glycols with an average molecular weight
of from 100 to 1 000 daltons;
[0127] technical-grade oligoglycerol mixtures with a degree of
self-condensation of from 1.5 to 10, such as, for example,
technical-grade diglycerol mixtures with a diglycerol content of
from 40 to 50% by weight;
[0128] methyol compounds, such as, in particular,
trimethylolethane, trimethylolpropane, trimethylolbutane,
pentaerythritol and dipentaerythritol;
[0129] lower alkyl glucosides, in particular those having 1 to 8
carbon atoms in the alkyl radical, such as, for example, methyl and
butyl glucoside;
[0130] sugar alcohols having 5 to 12 carbon atoms, such as, for
example, sorbitol or mannitol,
[0131] sugars having 5 to 12 carbon atoms, such as, for example
glucose or sucrose;
[0132] amino sugars, such as, for example, glucamine;
[0133] dialcohol amines, such as diethanolamine or
2-amino-1,3-propanediol.
[0134] Preservatives
[0135] Suitable preservatives are, for example, phenoxy ethanol,
formaldehyde solution, parabenes, pentanediol or sorbic acid, and
the silver complexes known under the name Surfacins.RTM., and also
the other classes of substance listed in Annex 6, Part A and B of
the Cosmetics Directive.
[0136] Perfume Oils and Aromas
[0137] Perfume oils which may be mentioned are mixtures of natural
and synthetic fragrances. Natural fragrances are extracts from
flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems
and leaves (geranium, patchouli, petitgrain), fruits (aniseed,
coriander, cumin, juniper), fruit peels (bergamot, lemon, orange),
roots (mace, angelica, celery, cardamon, costus, iris, calmus),
woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood),
herbs and grasses (tarragon, lemongrass, sage, thyme), needles and
branches (spruce, fir, pine, dwarf-pine), resins and balsams
(galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Also
suitable are animal raw materials, such as, for example, civet and
castoreum. Typical synthetic fragrance compounds are products of
the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
Fragrance compounds of the ester type are, for example, benzyl
acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate,
linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl
acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl
glycinate, allyl cyclohexylpropionate, styrallyl propionate and
benzyl salicylate. The ethers include, for example, benzyl ethyl
ether, the aldehydes include, for example, the linear alkanals
having 8 to 18 carbon atoms, citral, citronellal,
citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal,
lilial and bourgeonal, and the ketones include, for example, the
ionones, .alpha.-isomethylionone and methyl cedryl ketone, the
alcohols include anethole, citronellol, eugenol, isoeugenol,
geraniol, linalool, phenylethyl alcohol and terpineol, and the
hydrocarbons include mainly the terpenes and balsams. Preference
is, however, given to using mixtures of different fragrances which
together produce a pleasing fragrance note. Essential oils of
relatively low volatility, which are mostly used as aroma
components, are also suitable as perfume oils, e.g. sage oil,
camomile oil, oil of cloves, melissa oil, mint oil, cinnamon leaf
oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum
oil, galbanum oil, labolanum oil and lavandin oil. Preference is
given to using bergamot oil, dihydromyrcenol, lilial, lyral,
citronellol, phenylethyl alcohol, .alpha.-hexylcinnamaldehyde,
geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene
forte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin
oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil,
clary sage oil, .beta.-damascone, geranium oil bourbon, cyclohexyl
salicylate, Vertofix coeur, iso-E-super, Fixolide NP, evernyl,
iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate,
rose oxide, romilat, irotyl and floramat alone or in mixtures.
[0138] Suitable aromas are, for example, peppermint oil, spearmint
oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel
oil, lemon oil, wintergreen oil, oil of cloves, menthol and the
like.
[0139] Dyes
[0140] Dyes which can be used are the substances which are approved
and suitable for cosmetic purposes, as are summarized, for example,
in the publication "Kosmetische Farbemittel" [Cosmetic Colorants]
from the Farbstoffkommission der Deutschen Forschungsgemein-schaft
[Dyes Commission of the German Research Council], Verlag Chemie,
Weinheim, 1984, pp. 81-106. Examples are cochineal red A
(C.I.16255), patent blue V (C.I.42051), indigotin (C.I.73015),
chlorophyllin (C.I.75810), quinoline yellow (C.I.47005), titanium
dioxide (C.I.77891), indanthrene blue RS (C.I.69800) and madder
lake (C.I.58000). As a luminescent dye, it is also possible for
luminol to be present. These dyes are customarily used in
concentrations of from 0.001 to 0.1% by weight, based on the total
mixture.
[0141] The total amount of auxiliaries and additives can be 1 to
50% by weight, preferably 5 to 40% by weight, based on the
compositions. The compositions can be prepared by customary cold or
hot processes; preference is given to using the phase-inversion
temperature method.
[0142] Laundry Detergents, Dishwashing Detergents, Cleaners and
Hand Modifiers
[0143] The surface-active compositions can, for example, also
represent laundry detergents, dishwashing detergents, cleaners or
hand modifiers which can further comprise auxiliaries and additives
typical of these preparations. These include, for example, anionic,
nonionic, cationic, amphoteric or zwitterionic surfactants,
builders, cobuilders, oil- and grease-dissolving substances,
bleaches, bleach activators, antiredeposition agents, enzymes,
enzyme stabilizers, optical brighteners, polymers, defoamers,
disintegrants, fragrances, inorganic salts and the like, as are
explained in more detail below.
[0144] Anionic Surfactants
[0145] Typical examples of anionic surfactants are soaps,
alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl
ether sulfonates, glycerol ether sulfonates, .alpha.-methyl ester
sulfonates, sulfo-fatty acids, alkyl sulfates, fatty alcohol ether
sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates,
monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates,
mono- and dialkyl sulfosuccinates, mono- and dialkyl
sulfosuccinamates, sulfotriglycerides, amide soaps, ether
carboxylic acids and salts thereof, fatty acid isethionates, fatty
acid sarcosinates, fatty acid taurides, N-acylamino acids, such as,
for example, acyl lactylates, acyl tartrates, acyl glutamates and
acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid
condensates (in particular wheat-based vegetable products) and
alkyl (ether) phosphates. If the anionic surfactants contain
polyglycol ether chains, these can have a conventional homolog
distribution, but preferably have a narrowed homolog distribution.
Preference is given to using alkylbenzenesulfonates, alkyl
sulfates, soaps, alkanesulfonates, olefinsulfonates, methyl ester
sulfonates, and mixtures thereof. Typical examples of nonionic
surfactants are fatty alcohol polyglycol ethers, alkylphenol
polyglycol ethers, fatty acid polyglycol esters, fatty acid amide
polyglycol ethers, fatty amine polyglycol ethers, alkoxylated
triglycerides, mixed ethers or mixed formals, alk(en)yl
oligoglycosides, fatty acid N-alkylglucamides, protein hydrolysates
(in particular wheat-based vegetable products), polyol fatty acid
esters, sugar esters, sorbitan esters, polysorbates and amine
oxides. If the nonionic surfactants contain polyglycol ether
chains, these can have a conventional homolog distribution, but
preferably have a narrowed homolog distribution. Preference is
given to using fatty alcohol polyglycol ethers, alkoxylated fatty
acid lower alkyl esters or alkyl oligoglucosides.
[0146] Builders
[0147] The laundry detergents, dishwashing detergents, cleaners and
hand modifiers according to the invention can further comprise
additional inorganic and organic builder substances, for example in
amounts of from 10 to 50% by weight and preferably 15 to 35% by
weight, based on the compositions, where the inorganic builder
substances used are primarily zeolites, crystalline
phyllosilicates, amorphous silicates and, where permissible, also
phosphates, such as, for example, tripolyphosphate. The amount of
cobuilder here is to be included in the preferred amounts of
phosphates. The finely crystalline, synthetic and bonded
water-containing zeolite often used as detergent builder is
preferably zeolite A and/or P. As zeolite P, particular preference
is given, for example, to zeolite MAP.RTM. (commercial product from
Crosfield). Also suitable, however, are zeolite X and mixtures of
A, X and/or P and also Y. Of particular interest is also a
cocrystallized sodium/potassium-aluminum silicate of zeolite A and
zeolite X, which is available commercially as VEGOBOND AX.RTM.
(commercial product from Condea Augusta S.p.A.). The zeolite can be
used as a spray-dried powder or else as an undried stabilized
suspension still moist from its preparation. In cases where the
zeolite is used as suspension, the latter can comprise small
additions of nonionic surfactants as stabilizers, for example 1 to
3% by weight, based on zeolite, of ethoxylated
C.sub.12-C.sub.18-fatty alcohols having 2 to 5 ethylene oxide
groups, C.sub.12-C.sub.14-fatty alcohols having 4 to 5 ethylene
oxide groups or ethoxylated isotridecanols. Suitable zeolites have
an average particle size of less than 10 .mu.m (volume
distribution; measurement method: Coulter counter) and preferably
comprise 18 to 22% by weight, in particular 20 to 22% by weight, of
bonded water.
[0148] Suitable substitutes or partial substitutes for phosphates
and zeolites are crystalline, layered sodium silicates of the
general formula NaMSi.sub.xO.sub.2x+1.yH.sub.2O, where M is sodium
or hydrogen, x is a number from 1.9 to 4 and y is a number from 0
to 20 and preferred values for x are 2, 3 or 4. Such crystalline
phyllosilicates are described, for example, in European patent
application EP 0164514 A1. Preferred crystalline phyllosilicates of
the given formula are those in which M is sodium and x assumes the
values 2 or 3. Particular preference is given to both .beta.- and
also .delta.-sodium disilicates Na.sub.2Si.sub.2O.sub.5.-
yH.sub.2O, where .beta.-sodium disilicate can be obtained, for
example, by the process described in international patent
application WO 91/08171. Further suitable phyllosilicates are
known, for example, from the patent applications DE 2334899 A1, EP
0026529 A1 and DE 3526405 A1. Their usability is not limited to a
specific composition or structural formula. Preference is given
here, however, to smectites, in particular bentonites. Suitable
phyllosilicates which belong to the group of water-swellable
smectites are, for example, those of the general formulae
(OH).sub.4Si.sub.8-yAl.sub.y(Mg.sub.xAl.sub.4-x)O.sub.20
montmorillonite
(OH).sub.4Si.sub.8-yAl.sub.y(Mg.sub.6-zLi.sub.z)O.sub.20
hectorite
(OH).sub.4Si.sub.8-yAl.sub.y(Mg.sub.6-zAl.sub.z)O.sub.20
saponite
[0149] where x=0 to 4, y=0 to 2, z=0 to 6. In addition, small
amounts of iron can be incorporated into the crystal lattice of the
phyllosilicates according to the above formulae. In addition, the
phyllosilicates can comprise hydrogen, alkali metal and alkaline
earth metal ions, in particular Na.sup.+ and Ca.sup.2+, because of
their ion-exchanging properties. The amount of water of hydration
is in most cases in the range from 8 to 20% by weight and is
dependent on the swelling state or on the type of processing.
Phyllosilicates which can be used are, for example, known from U.S.
Pat. No. 3,966,629, U.S. Pat. No. 4,062,647, EP 0026529 A1 and EP
0028432 A1. Preference is given to using phyllosilicates which,
because of an alkali metal treatment, are largely free from calcium
ions and strongly coloring iron ions.
[0150] Preferred builder substances also include amorphous sodium
silicates with an Na.sub.2O:SiO.sub.2 modulus of from 1:2 to 1:3.3,
preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6,
which have delayed dissolution and secondary detergency properties.
The delayed dissolution compared with conventional amorphous sodium
silicates can be brought about in a variety of ways, for example by
surface treatment, compounding, compaction/compression or by
overdrying. For the purposes of this invention, the term
"amorphous" is also to be understood as meaning "X-ray-amorphous".
This means that, in X-ray diffraction experiments, the silicates do
not produce sharp X-ray reflections typical of crystalline
substances, but, at best, one or more maxima of the scattered X-ray
radiation having a breadth of several degree units of the
diffraction angle. However, particularly good builder properties
may very likely result if the silicate particles produce poorly
defined or even sharp diffraction maxima in electron diffraction
experiments. This is to be interpreted to the effect that the
products have microcrystalline regions with a size from 10 to a few
hundred nm, preference being given to values up to a maximum of 50
nm and in particular up to a maximum of 20 nm. Such so-called
X-ray-amorphous silicates, which likewise have delayed dissolution
compared with traditional waterglasses, are described, for example,
in the German patent application DE 4400024 A1. Particular
preference is given to compressed/compacted amorphous silicates,
compounded amorphous silicates and overdried X-ray-amorphous
silicates.
[0151] It is of course also possible to use the generally known
phosphates as builder substances if such a use is not to be avoided
for ecological reasons. Suitable are, in particular, the sodium
salts of the orthophosphates, the pyrophosphates and, in
particular, the tripolyphosphates. Their content is generally not
more than 25% by weight, preferably not more than 20% by weight, in
each case based on the finished composition. In some cases, it has
been found that, in particular, tripolyphosphates, even in small
amounts up to at most 10% by weight, based on the finished
composition, in combination with other builder substances lead to a
synergistic improvement in the secondary detergency.
[0152] Cobuilders
[0153] Organic framework substances which can be used and are
suitable as cobuilders are, for example, the polycarboxylic acids
which can be used in the form of their sodium salts, such as citric
acid, adipic acid, succinic acid, glutaric acid, tartaric acid,
sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA),
provided such a use is not objectionable for ecological reasons,
and mixtures thereof. Preferred salts are the salts of the
polycarboxylic acids, such as citric acid, adipic acid, succinic
acid, glutaric acid, tartaric acid, sugar acids and mixtures
thereof. The acids per se can also be used. In addition to their
builder action, the acids typically also have the property of an
acidifying component and thus also serve for setting a relatively
low and relatively mild pH of laundry detergents or cleaners. In
this connection, particular mention may be made of citric acid,
succinic acid, glutaric acid, adipic acid, gluconic acid and any
mixtures thereof.
[0154] Further suitable organic builder substances are dextrins,
for example oligomers or polymers of carbohydrates which can be
obtained by partial hydrolysis of starches. The hydrolysis can be
carried out in accordance with customary, for example
acid-catalyzed or enzyme-catalyzed, processes. The hydrolysis
products preferably have average molar masses in the range from 400
to 500 000. Here, a polysaccharide with a dextrose equivalent (DE)
in the range from 0.5 to 40, in particular from 2 to 30, is
preferred, where DE is a usual measure of the reducing action of a
polysaccharide compared with dextrose, which has a DE of 100. It is
possible to use either maltodextrins with a DE between 3 and 20 and
dry glucose syrups with a DE between 20 and 37, and also so-called
yellow dextrins and white dextrins with relatively high molar
masses in the range from 2 000 to 30 000. A preferred dextrin is
described in British patent application GB 9419091 A1. The oxidized
derivatives of such dextrins are their reaction products with
oxidizing agents which are able to oxidize at least one alcohol
function of the saccharide ring to give the carboxylic acid
function. Such oxidized dextrins and processes for their
preparation are known, for example, from European patent
applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP
0542496 A1, and the international patent applications WO 92/18542,
WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and
WO 95/20608. Also suitable is an oxidized oligosaccharide according
to German patent application DE 19600018 A1. A product oxidized on
C.sub.6 of the saccharide ring may be particularly
advantageous.
[0155] Further suitable co-builders are oxydisuccinates and other
derivatives of disuccinates, preferably ethylene-diamine
disuccinate. Particular preference is also given in this connection
to glycerol disuccinates and glycerol trisuccinates, as are
described, for example, in US-American patent specifications U.S.
Pat. No. 4,524,009, U.S. Pat. No. 4,639,325, in the European patent
application EP 0150930 A1 and the Japanese patent application JP
93/339896. Suitable use amounts in zeolite-containing and/or
silicate-containing formulations are 3 to 15% by weight. Further
organic co-builders which can be used are, for example, acetylated
hydroxycarboxylic acids or salts thereof, which may optionally also
be in lactone form and which contain at least 4 carbon atoms and at
least one hydroxyl group and a maximum of two acid groups. Such
co-builders are described, for example, in international patent
application WO 95/20029.
[0156] Suitable polymeric polycarboxylates are, for example, the
sodium salts of polyacrylic acid or of polymethacrylic acid, for
example those with a relative molecular mass of from 800 to 150 000
(based on acid and in each case measured against
polystyrenesulfonic acid). Suitable copolymeric polycarboxylates
are, in particular, those of acrylic acid with methacrylic acid and
of acrylic acid or methacrylic acid with maleic acid. Copolymers of
acrylic acid with maleic acid which contain 50 to 90% by weight of
acrylic acid and 50 to 10% by weight of maleic acid have proven
particularly suitable. Their relative molecular mass, based on free
acids, is generally 5 000 to 200 000, preferably 10 000 to 120 000
and in particular 50 000 to 100 000 (in each case measured against
polystyrenesulfonic acid) . The (co)polymeric polycarboxylates can
either be used as powder or as aqueous solution, preference being
given to 20 to 55% by weight strength aqueous solutions. Granular
polymers are in most cases added subsequently to one or more base
granulates. Particular preference is also given to biodegradable
polymers of more than two different monomer units, for example
those which, according to DE 4300772 A1, contain salts of acrylic
acid and of maleic acid and vinyl alcohol or vinyl alcohol
derivatives as monomers, or, according to DE 4221381 C2, salts of
acrylic acid and of 2-alkylallylsulfonic acid and sugar derivatives
as monomers. Further preferred copolymers are those which are
described in German patent applications DE 4303320 A1 and DE
4417734 A1 and have, as monomers, preferably acrolein and acrylic
acid/acrylic acid salts or acrolein and vinyl acetate. Further
preferred builder substances are also polymeric aminodicarboxylic
acids, salts thereof or precursor substances thereof. Particular
preference is given to polyaspartic acids or salts and derivatives
thereof.
[0157] Further suitable builder substances are polyacetals, which
can be obtained by reacting dialdehydes with polyolcarboxylic acids
which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for
example as described in European patent application EP 0280223 A1.
Preferred polyacetals are obtained from dialdehydes such as
glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof
and from polyolcarboxylic acids such as gluconic acid and/or
glucoheptonic acid.
[0158] Oil- and Grease-Dissolving Substances
[0159] In addition, the compositions can also comprise components
which have a positive effect on the ability to wash oil and grease
out of textiles. Preferred oil- and grease-dissolving components
include, for example, nonionic cellulose ethers, such as
methylcellulose and methylhydroxypropylcellulose having a
proportion of methoxy groups of from 15 to 30% by weight and of
hydroxypropoxy groups of from 1 to 15% by weight, in each case
based on the nonionic cellulose ethers, and the polymers, known
from the prior art, of phthalic acid and/or of terephthalic acid,
or of derivatives thereof, in particular polymers of ethylene
terephthalates and/or polyethylene glycol terephthalates or
anionically and/or nonionically modified derivatives thereof. Of
these, particular preference is given to the sulfonated derivatives
of phthalic acid polymers and of terephthalic acid polymers.
[0160] Bleaches and Bleach Activators
[0161] Among the compounds which supply H.sub.2O.sub.2 in water and
which serve as bleaches, sodium perborate tetrahydrate and sodium
perborate monohydrate are of particular importance. Further
bleaches which can be used are, for example, sodium percarbonate,
peroxypyrophosphates, citrate perhydrates, and
H.sub.2O.sub.2-supplying peracidic salts or peracids, such as
perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino
peracid or diperdodecanedioic acid. The content of bleaches in the
compositions is preferably 5 to 35% by weight and in particular up
to 30% by weight, where perborate monohydrate or percarbonate is
used advantageously. Bleach activators which can be used are
compounds which, under perhydrolysis conditions, produce aliphatic
peroxocarboxylic acids having, preferably, 1 to 10 carbon atoms, in
particular 2 to 4 carbon atoms, and/or optionally substituted
perbenzoic acid. Substances which carry O- and/or N-acyl groups of
said number of carbon atoms and/or optionally substituted benzoyl
groups are suitable. Preference is given to polyacylated
alkylenediamines, in particular tetraacetylethylenediamin- e
(TAED), acylated triazine derivatives, in particular
1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated
glycolurils, in particular tetraacetylglycoluril (TAGU),
N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated
phenolsulfonates, in particular n-nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic
anhydrides, in particular phthalic anhydride, acylated polyhydric
alcohols, in particular triacetin, ethylene glycol diacetate,
2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from
German patent applications DE 19616693 A1 and DE 19616767 A1, and
acetylated sorbitol and mannitol or mixtures thereof described in
European patent application EP 0525239 A1 (SORMAN), acylated sugar
derivatives, in particular pentaacetylglucose (PAG),
pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and
acetylated, optionally N-alkylated glucamine and gluconolactone,
and/or N-acylated lactams, for example N-benzoylcaprolactam, which
are known from international patent applications WO 94/27970, WO
94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498.
The hydrophilically substituted acylacetals known from German
patent application DE 19616769 A1, and the acyllactams described in
German patent application DE 196 16 770 and international patent
application WO 95/14075 are likewise used with preference. The
combinations of conventional bleach activators known from German
patent application DE 4443177 A1 can also be used. Such bleach
activators are present in the customary quantitative range,
preferably in amounts of from 1% by weight to 10% by weight, in
particular 2% by weight to 8% by weight, based on the overall
composition. In addition to the above-listed conventional bleach
activators, or instead of them, the sulfonimines known from
European patent specifications EP 0446982 B1 and EP 0453 003 B1
and/or bleach-boosting transition metal salts or transition metal
complexes may also be present as so-called bleach catalysts.
Suitable transition metal compounds include, in particular, the
manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen
complexes known from German patent application DE 19529905 A1, and
their N-analogous compounds known from German patent application DE
19620267 A1, the manganese-, iron-, cobalt-, ruthenium- or
molybdenum-carbonyl complexes known from German patent application
DE 19536082 A1, the manganese, iron, cobalt, ruthenium, molybdenum,
titanium, vanadium and copper complexes having nitrogen-containing
tripod ligands described in German patent application DE 19605688
A1, the cobalt-, iron-, copper- and ruthenium-amine complexes known
from German patent application DE 19620411 A1, the manganese,
copper and cobalt complexes described in German patent application
DE 4416438 A1, the cobalt complexes described in European patent
application EP 0272030 A1, the manganese complexes known from
European patent application EP 0693550 A1, the manganese, iron,
cobalt and copper complexes known from European patent
specification EP 0392592 A1, and/or the manganese complexes
described in European patent specification EP 0443651 B1 or
European patent applications EP 0458397 A1, EP 0458398 A1, EP
0549271 A1, EP 0549272 A1, EP 0544490 A1 and EP 0544519 A1.
Combinations of bleach activators and transition metal bleach
catalysts are known, for example, from German patent application DE
19613103 A1 and international patent application WO 95/27775.
Bleach-boosting transition metal complexes, in particular with the
central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, are used in
customary amounts, preferably in an amount up to 1% by weight, in
particular from 0.0025% by weight to 0.25% by weight and
particularly preferably from 0.01% by weight to 0.1% by weight, in
each case based on the overall composition.
[0162] Enzymes and Enzyme Stabilizers
[0163] Suitable enzymes are, in particular, those from the class of
hydrolases, such as proteases, esterases, lipases or lipolytic
enzymes, amylases, cellulases or other glycosylhydrolases and
mixtures of said enzymes. All of these hydrolases contribute during
washing to the removal of stains, such as protein, grease or
starchy stains, and redeposition. Cellulases and other glycosyl
hydrolases may, by removing pilling and microfibrils, contribute to
color retention and to an increase in the softness of the textile.
For bleaching or for inhibiting color transfer, it is also possible
to use oxidoreductases. Particularly suitable enzymatic active
ingredients are those obtained from bacterial strains or fungi,
such as Bacillus subtilis, Bacillus licheniformis, Streptomyces
griseus and Humicola insolens. Preference is given to using
proteases of the subtilisin type and, in particular, proteases
obtained from Bacillus lentus. Of particular interest in this
connection are enzyme mixtures, for example mixtures of protease
and amylase or protease and lipase or lipolytic enzymes, or
protease and cellulase or of cellulase and lipase or lipolytic
enzymes or of protease, amylase and lipase or lipolytic enzymes or
protease, lipase or lipolytic enzymes and cellulase, in particular,
however, protease- and/or lipase-containing mixtures or mixtures
containing lipolytic enzymes. Examples of such lipolytic enzymes
are the known cutinases. Peroxidases or oxidases have also proven
suitable in some cases. Suitable amylases include, in particular,
.alpha.-amylases, isoamylases, pullulanases and pectinases. The
cellulases used are preferably cellobiohydrolases, endoglucanases
and .beta.-glucosidases, which are also called cellobiases, or
mixtures thereof. Since the various cellulase types differ in their
CMCase and avicelase activities, it is possible to adjust the
desired activities through targeted mixing of the cellulases.
[0164] The enzymes for their part can also be adsorbed on carrier
substances and/or embedded in coating substances in order to
protect them against premature decomposition. The proportion of
enzymes, enzyme mixtures or enzyme granulates can, for example, be
from about 0.1 to 5% by weight, preferably 0.1 to about 2% by
weight.
[0165] In addition to the mono- and polyfunctional alcohols, the
compositions can comprise further enzyme stabilizers. For example,
0.5 to 1% by weight of sodium formate can be used. The use of
proteases which have been stabilized with soluble calcium salts and
a calcium content of, preferably, about 1.2% by weight, based on
the enzyme, is also possible. Apart from calcium salts, magnesium
salts also serve as stabilizers. However, the use of boron
compounds, for example of boric acid, boron oxide, borax and other
alkali metal borates, such as the salts of orthoboric acid
(H.sub.3BO.sub.3), of metaboric acid (HBO.sub.2) and of pyroboric
acid (tetraboric acid H.sub.2B.sub.4O.sub.7) is particularly
advantageous.
[0166] Antiredeposition Agents
[0167] Antiredeposition agents have the task of keeping the soil
detached from the fiber in suspended form in the liquor, and thus
preventing reattachment of the soil. For this purpose,
water-soluble colloids of a mostly organic nature are suitable, for
example the water-soluble salts of polymeric carboxylic acids,
glue, gelatin, salts of ether carboxylic acids or ether sulfonic
acids of starch or of cellulose or salts of acidic sulfuric esters
of cellulose or of starch. Water-soluble polyamides which contain
acidic groups are also suitable for this purpose. In addition, it
is also possible to use soluble starch preparations, and starch
products other than those mentioned above, e.g. degraded starch,
aldehyde starches etc. Polyvinylpyrrolidone can also be used.
Preference is, however, given to using cellulose ethers, such as
carboxymethylcellulose (Na salt), methylcellulose,
hydroxyalkylcellulose and mixed ethers, such as
methylhydroxyethylcellulose, methylhydroxypropylcellulose,
methylcarboxymethylcellulose and mixtures thereof, and
polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by
weight, based on the compositions.
[0168] Optical Brighteners
[0169] The compositions can comprise derivatives of
diaminostilbenedisulfonic acid, or alkali metal salts thereof, as
optical brighteners. For example, salts of
4,4'-bis(2-anilino-4-morpholino-1,3,5--
triazinyl-6-amino)stilbene-2,2'-disulfonic acid or compounds
constructed in a similar way which carry a diethanolamino group, a
methylamino group, an anilino group or a 2-methoxyethylamino group
instead of the morpholino group are suitable. Brighteners of the
substituted diphenylstyryl type may also be present, e.g. the
alkali metal salts of 4,4'-bis(2-sulfo-styryl)diphenyl,
4,4'-bis(4-chloro-3-sulfostyryl)-diphen- yl, or
4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the
abovementioned brighteners may also be used. Uniformly white
granulates are obtained if the compositions comprise, in addition
to the customary brighteners in customary amounts, for example
between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by
weight, also small amounts, for example 10.sup.-6 to 10.sup.-3% by
weight, preferably around 10.sup.-5% by weight, of a blue dye. A
particularly preferred dye is Tinolux.degree. (commercial product
from Ciba-Geigy).
[0170] Polymers
[0171] Suitable soil-repellent polymers are those which preferably
contain ethylene terephthalate and/or polyethylene glycol
terephthalate groups, where the molar ratio of ethylene
terephthalate to polyethylene glycol terephthalate may be in the
range from 50:50 to 90:10. The molecular weight of the linking
polyethylene glycol units is, in particular, in the range from 750
to 5000, i.e. the degree of ethoxylation of the polyethylene glycol
group-containing polymers may be about 15 to 100. The polymers are
characterized by an average molecular weight of about 5000 to 200
000 and can have a block structure, but preferably have a random
structure. Preferred polymers are those with ethylene
terephthalate/polyethylene glycol terephthalate molar ratios of
from about 65:35 to about 90:10, preferably from about 70:30 to
80:20. Also preferred are those polymers which have linking
polyethylene glycol units with a molecular weight of from 750 to 5
000, preferably from 1 000 to about 3 000 and a molecular weight of
the polymer from about 10 000 to about 50 000. Examples of
commercially available polymers are the products Milease T (ICI) or
Repelotex.RTM. SRP 3 (Rhne-Poulenc).
[0172] Defoamers
[0173] Defoamers which can be used are wax-like compounds.
"Wax-like" is to be understood as meaning those compounds which
have a melting point at atmospheric pressure above 25.degree. C.
(room temperature), preferably above 50.degree. C. and in
particular above 70.degree. C. The wax-like defoamer substances are
virtually insoluble in water, i.e. at 20.degree. C. they have a
solubility below 0.1% by weight in 100 g of water. In principle,
all wax-like defoamer substances known from the prior art may be
present. Suitable wax-like compounds are, for example, bisamides,
fatty alcohols, fatty acids, carboxylic esters of mono- and
polyhydric alcohols, and paraffin waxes or mixtures thereof.
Alternatively, the silicone compounds known for this purpose can of
course also be used.
[0174] Suitable paraffin waxes are generally a complex mixture of
substances without a sharp melting point. For characterization, its
melting range is usually determined by differential thermoanalysis
(DTA), as described in "The Analyst" 87 (1962), 420, and/or its
solidification point. This is to be understood as meaning the
temperature at which the paraffin converts from the liquid state to
the solid state by slow cooling. Here, paraffins which are entirely
liquid at room temperature, i.e. those with a solidification point
below 25.degree. C., cannot be used according to the invention. The
soft waxes, which have a melting point in the range from 35 to
50.degree. C., preferably include the group of petrolatums and
hydrogenation products thereof. They are composed of
microcrystalline paraffins and up to 70% by weight of oil, have an
ointment-like to plastically solid consistency and represent
bitumen-free residues from petroleum refining. Particular
preference is given to distillation residues (petrolatum stock) of
certain paraffin-base and mixed-base crude oils which are further
processed to give vaseline. Preferably, they are also bitumen-free,
oil-like to solid hydrocarbons deposited from distillation residues
of paraffin-base and mixed-base crude oils and cylinder oil
distillates by means of solvents. They are of semisolid, viscous,
tacky or plastically solid consistency and have melting points
between 50 and 70.degree. C. These petrolatums represent the most
important starting base for the preparation of microcrystalline
waxes. Also suitable are the solid hydrocarbons having melting
points between 63 and 79.degree. C. deposited from high-viscosity,
paraffin-containing lubricating oil distillates during
deparaffinization. These petrolatums are mixtures of
microcrystalline waxes and high-melting n-paraffins. It is possible
to use, for example, the paraffin wax mixtures known from EP
0309931 A1 which are composed of, for example, 26% by weight to 49%
by weight of microcrystalline paraffin wax with a solidification
point of 62.degree. C. to 90.degree. C., 20% by weight to 49% by
weight of hard paraffin with a solidification point of 42.degree.
C. to 56.degree. C. and 2% by weight to 25% by weight of soft
paraffin with a solidification point of from 35.degree. C. to
40.degree. C. Preference is given to using paraffins or paraffin
mixtures which solidify in the range from 30.degree. C. to
90.degree. C. In this connection, it is to be taken into
consideration that even paraffin wax mixtures which appear to be
solid at room temperature may also comprise varying proportions of
liquid paraffin. In the case of the paraffin waxes which can be
used according to the invention, this liquid proportion is as low
as possible and is preferably not present at all. Thus,
particularly preferred paraffin wax mixtures have at 30.degree. C.
a liquid content of less than 10% by weight, in particular of from
2% by weight to 5% by weight, at 40.degree. C. a liquid content of
less than 30% by weight, preferably of from 5% by weight to 25% by
weight and in particular from 5% by weight to 15% by weight, at
60.degree. C. a liquid content of from 30% by weight to 60% by
weight, in particular from 40% by weight to 55% by weight, at
80.degree. C. a liquid content of from 80% by weight to 100% by
weight and at 90.degree. C. a liquid content of 100% by weight. The
temperature at which a liquid content of 100% by weight of the
paraffin wax is achieved is, in the case of particularly preferred
paraffin wax mixtures, still below 85.degree. C., in particular
75.degree. C. to 82.degree. C. The paraffin waxes may be
petrolatum, microcrystalline waxes or hydrogenated or partially
hydrogenated paraffin waxes.
[0175] Suitable bisamides as defoamers are those which are derived
from saturated fatty acids having 12 to 22, preferably 14 to 18,
carbon atoms, and from alkylenediamines having 2 to 7 carbon atoms.
Suitable fatty acids are lauric acid, myristic acid, stearic acid,
arachidic acid and behenic acid, and mixtures thereof, as are
obtainable from natural fats or hydrogenated oils, such as tallow
or hydrogenated palm oil. Suitable diamines are, for example,
ethylenediamine, 1,3-propylenediamine, tetramethylenediamine,
pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and
tolylenediamine. Preferred diamines are ethylenediamine and
hexamethylenediamine. Particularly preferred bisamides are
bismyristoylethylenediamine, bispalmitoylethylenediamine,
bisstearoylethylenediamine and mixtures thereof, and the
corresponding derivatives of hexamethylenediamine.
[0176] Suitable carboxylic esters as defoamers are derived from
carboxylic acids having 12 to 28 carbon atoms. In particular, these
are esters of behenic acid, stearic acid, hydroxystearic acid,
oleic acid, palmitic acid, myristic acid and/or lauric acid. The
alcohol moiety of the carboxylic ester comprises a mono- or
polyhydric alcohol having from 1 to 28 carbon atoms in the
hydrocarbon chain. Examples of suitable alcohols are behenyl
alcohol, arachidyl alcohol, cocoyl alcohol, 12-hydroxysteryl
alcohol, oleyl alcohol and lauryl alcohol, and also ethylene
glycol, glycerol, polyvinyl alcohol, sucrose, erythritol,
pentaerythritol, sorbitan and/or sorbitol. Preferred esters are
those of ethylene glycol, glycerol and sorbitan, where the acid
moiety of the ester is, in particular, chosen from behenic acid,
stearic acid, oleic acid, palmitic acid or myristic acid. Suitable
esters of polyhydric alcohols are, for example, xylitol
monopalmitate, pentaerythritol monostearate, glycerol monostearate,
ethylene glycol monostearate and sorbitan monostearate, sorbitan
palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan
distearate, sorbitan dibehenate, sorbitan dioleate, and mixed
tallow alkyl sorbitan monoesters and diesters. Glycerol esters
which can be used are the mono-, di- or triesters of glycerol and
said carboxylic acids, preference being given to the mono- or
diesters. Glycerol monostearate, glycerol monooleate, glycerol
monopalmitate, glycerol monobehenate and glycerol distearate are
examples thereof. Examples of suitable natural esters as defoamers
are beeswax, which consists primarily of the esters
CH.sub.3(CH.sub.2).sub.24COO(CH.sub.2).sub.27CH.sub.3 and
CH.sub.3(CH.sub.2).sub.26COO(CH.sub.2).sub.25CH.sub.3, and carnauba
wax, which is a mixture of carnaubic acid alkyl esters, often in
combination with small amounts of free carnaubic acid, further
long-chain acids, high molecular weight alcohols and
hydrocarbons.
[0177] Suitable carboxylic acids as further defoamer compound are,
in particular, behenic acid, stearic acid, oleic acid, palmitic
acid, myristic acid and lauric acid, and mixtures thereof as are
obtainable from natural fats or optionally hydrogenated oils, such
as tallow or hydrogenated palm oil. Preference is given to
saturated fatty acids having 12 to 22, in particular 18 to 22,
carbon atoms. The corresponding fatty alcohols of the same carbon
chain length may likewise be used.
[0178] In addition, dialkyl ethers may additionally be present as
defoamers. The ethers may have an asymmetrical or symmetrical
structure, i.e. contain two identical or different alkyl chains,
preferably having 8 to 18 carbon atoms. Typical examples are
di-n-octyl ether, di-isooctyl ether and di-n-stearyl ether. Dialkyl
ethers which have a melting point above 25.degree. C., in
particular above 40.degree. C. are particularly suitable.
[0179] Further suitable defoamer compounds are fatty ketones, which
can be obtained in accordance with the relevant methods of
preparative organic chemistry. They are prepared, for example,
starting from carboxylic acid magnesium salts, which are pyrolyzed
at temperatures above 300.degree. C. with elimination of carbon
dioxide and water, for example in accordance with German laid-open
specification DE 2553900 A. Suitable fatty ketones are those which
are prepared by pyrolysis of the magnesium salts of lauric acid,
myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic
acid, elaidic acid, petroselic acid, arachidic acid, gadoleic acid,
behenic acid or erucic acid.
[0180] Further suitable defoamers are fatty acid polyethylene
glycol esters, which are preferably obtained by homogeneous
base-catalyzed addition reaction of ethylene oxide with fatty
acids. In particular, the addition reaction of ethylene oxide with
the fatty acids is carried out in the presence of alkanolamines as
catalysts. The use of alkanolamines, specifically triethanolamine,
leads to an extremely selective ethoxylation of the fatty acids,
particularly when the aim is to prepare compounds which have a low
degree of ethoxylation. Within the group of fatty acid polyethylene
glycol esters, preference is given to those which have a melting
point above 25.degree. C., in particular above 40.degree. C.
[0181] Within the group of wax-like defoamers, particular
preference is given to the paraffin waxes described used alone as
wax-like defoamers, or in a mixture with one of the other wax-like
defoamers, where the proportion of paraffin waxes in the mixture
preferably constitutes more than 50% by weight, based on wax-like
defoamer mixture. The paraffin waxes can be applied to supports as
required. Suitable carrier materials are all known inorganic and/or
organic carrier materials. Examples of typical inorganic carrier
materials are alkali metal carbonates, alumosilicates,
water-soluble phyllosilicates, alkali metal silicates, alkali metal
sulfates, for example sodium sulfate, and alkali metal phosphates.
The alkali metal silicates are preferably a compound with an alkali
metal oxide to SiO.sub.2 molar ratio of from 1:1.5 to 1:3.5. The
use of such silicates results in particularly good particle
properties, in particular high abrasion stability and nevertheless
a high dissolution rate in water. The aluminosilicates referred to
as carrier material include, in particular, the zeolites, for
example zeolite NaA and NaX. The compounds referred to as
water-soluble phyllosilicates include, for example, amorphous or
crystalline water glass. In addition, it is possible to use
silicates which are available commercially under the name
Aerosil.RTM. or Sipernat.RTM.. Suitable organic carrier materials
are, for example, film-forming polymers, for example polyvinyl
alcohols, polyvinylpyrrolidones, poly(meth)acrylates,
polycarboxylates, cellulose derivatives and starch. Cellulose
ethers which can be used are, in particular, alkali metal
carboxymethylcellulose, methylcellulose, ethylcellulose,
hydroxyethylcellulose and so-called cellulose mixed ethers, such
as, for example, methylhydroxyethylcellulose and
methylhydroxypropylcellulose, and mixtures thereof. Particularly
suitable mixtures are composed of sodium carboxymethylcellulose and
methyl-cellulose, where the carboxymethylcellulose usually has a
degree of substitution of from 0.5 to 0.8 carboxymethyl groups per
anhydroglucose unit and the methylcellulose has a degree of
substitution of from 1.2 to 2 methyl groups per anhydroglucose
unit. The mixtures preferably comprise alkali metal
carboxymethylcellulose and nonionic cellulose ethers in weight
ratios of from 80:20 to 40:60, in particular from 75:25 to 50:50. A
suitable carrier is also natural starch which is composed of
amylose and amylopectin. Natural starch is the term used to
describe starch such as is available as an extract from natural
sources, for example from rice, potatoes, corn and wheat. Natural
starch is a commercially available product and thus readily
available. As carrier materials it is possible to use one or more
of the compounds mentioned above, in particular chosen from the
group of alkali metal carbonates, alkali metal sulfates, alkali
metal phosphates, zeolites, water-soluble phyllosilicates, alkali
metal silicates, polycarboxylates, cellulose ethers,
polyacrylate/polymethacrylate and starch. Particularly suitable
mixtures are those of alkali metal carbonates, in particular sodium
carbonate, alkali metal silicates, in particular sodium silicate,
alkali metal sulfates, in particular sodium sulfate, and
zeolites.
[0182] Suitable silicones are customary organopolysiloxanes which
may have a content of finely divided silica, which in turn may also
be silanized. Such organopolysiloxanes are described, for example,
in European patent application EP 0496510 A1. Particular preference
is given to polydiorganosiloxanes and, in particular,
polydimethylsiloxanes which are known from the prior art. Suitable
polydiorganosiloxanes have a virtually linear chain and have a
degree of oligomerization of from 40 to 1 500. Examples of suitable
substituents are methyl, ethyl, propyl, isobutyl, tert-butyl and
phenyl. Also suitable are amino-, fatty acid-, alcohol-,
polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified
silicone compounds, which may either be liquid or in resin form at
room temperature. Also suitable are simethicones, which are
mixtures of dimethicones having an average chain length of from 200
to 300 dimethylsiloxane units and hydrogenated silicates. As a
rule, the silicones generally, and the polydiorganosiloxanes in
particular, contain finely divided silica, which may also be
silanized. For the purposes of the present invention,
silica-containing dimethylpolysiloxanes are particularly suitable.
The polydiorganosiloxanes advantageously have a Brookfield
viscosity at 25.degree. C. (spindle 1, 10 rpm) in the range from 5
000 mPas to 30 000 mPas, in particular from 15 000 to 25 000 mPas.
The silicones are preferably used in the form of their aqueous
emulsions. The silicone is generally added to an initial charge of
water with stirring. If desired, in order to increase the viscosity
of the aqueous silicone emulsions, it is possible to add
thickeners, as are known from the prior art. These may be inorganic
and/or organic in nature, and particular preference is given to
nonionic cellulose ethers, such as methylcellulose, ethylcellulose
and mixed ethers, such as methylhydroxyethylcellulose,
methylhydroxypropylcellulose, methylhydroxybutylcellulose, and
anionic carboxycellulose grades, such as carboxymethylcellulose
sodium salt (abbreviation CMC). Particularly suitable thickeners
are mixtures of CMC to nonionic cellulose ethers in the weight
ratio 80:20 to 40:60, in particular 75:25 to 60:40. Usually, and
particularly in the case of the addition of the described thickener
mixtures, recommended use concentrations are from about 0.5 to 10%
by weight, in particular from 2.0 to 6% by weight, calculated as
thickener mixture and based on aqueous silicone emulsion. The
content of silicones of the type described in the aqueous emulsions
is advantageously in the range from 5 to 50% by weight, in
particular from 20 to 40% by weight, calculated as silicones and
based on aqueous silicone emulsion. According to a further
advantageous embodiment, the aqueous silicone solutions receive, as
thickener, starch accessible from natural sources, for example from
rice, potatoes, corn and wheat. The starch is advantageously
present in amounts of from 0.1 up to 50% by weight, based on
silicone emulsion and, in particular, in a mixture with the already
described thickener mixtures of sodium carboxymethylcellulose and a
nonionic cellulose ether in the amounts already given. To prepare
the aqueous silicone emulsions, the procedure expediently involves
allowing the optionally present thickeners to preswell in water
before adding the silicones. The silicones are expediently
incorporated using effective stirring and mixing devices.
[0183] Disintegrants
[0184] The solid preparations can further comprise disintegrants.
This term is to be understood as meaning substances which are added
to the shaped bodies in order to accelerate their disintegration
upon contact with water. Overviews on this subject can be found,
for example, in J. Pharm. Sci. 61 (1972), Rompp Chemilexikon, 9th
Edition, Volume 6, p. 4440 and Voigt "Lehrbuch der pharmazeutischen
Technologie" [Textbook of Pharmaceutical Technology] (6th Edition,
1987, pp. 182-184). These substances increase in volume upon
ingress of water, with on the one hand an increase in the intrinsic
volume (swelling) and on the other hand, by way of release of gases
as well, the possibility of generating a pressure which causes the
tablet to disintegrate into smaller particles. Examples of
established disintegration auxiliaries are carbonate/citric acid
systems, with the use of other organic acids also being possible.
Examples of swelling disintegration auxiliaries are synthetic
polymers such as optionally crosslinked polyvinylpyrrolidone (PVP)
or natural polymers and/or modified natural substances such as
cellulose and starch and their derivatives, alginates or casein
derivatives. Preferred disintegrants used for the purposes of the
present invention are disintegrants based on cellulose. Pure
cellulose has the formal gross composition
(C.sub.6H.sub.10O.sub.5).sub.n, and, considered formally, is a
.beta.-1,4-polyacetal of cellobiose, which itself is constructed
from two molecules of glucose. Suitable celluloses consist of about
500 to 5 000 glucose units and, accordingly, have average molar
masses of from 50 000 to 500 000. Cellulose-based disintegrants
which can be used for the purposes of the present invention are
also cellulose derivatives obtainable by polymer-analogous
reactions from cellulose. Such chemically modified celluloses
include, for example, products of esterifications and
etherifications in which hydroxyl hydrogen atoms have been
substituted. However, celluloses in which the hydroxyl groups have
been replaced by functional groups not attached via an oxygen atom
may also be used as cellulose derivatives. The group of cellulose
derivatives includes, for example, alkali metal celluloses,
carboxymethylcellulose (CMC), cellulose esters and ethers and also
aminocelluloses. Said cellulose derivatives are preferably not used
alone as cellulose-based disintegrants, but instead are used in a
mixture with cellulose. The cellulose derivative content of these
mixtures is preferably less than 50% by weight, particularly
preferably less than 20% by weight, based on the cellulose-based
disintegrant. A particularly preferred cellulose-based disintegrant
used is pure cellulose which is free from cellulose derivatives. A
further cellulose-based disintegrant, or constituent of this
component, which may be used is microcrystalline cellulose. This
microcrystalline cellulose is obtained by partial hydrolysis of
celluloses under conditions which attack only the amorphous regions
(approximately 30% of the total cellulose mass) of the celluloses
and break them up completely, but leave the crystalline regions
(about 70%) intact. Subsequent deaggregation of the microfine
celluloses resulting from the hydrolysis yields the
microcrystalline celluloses, which have primary particle sizes of
approximately 5 .mu.m and can be compacted, for example, to give
granulates having an average particle size of 200 .mu.m. The
disintegrants can, viewed macroscopically, be homogeneously
distributed within the shaped body, but, viewed microscopically,
form zones of increased concentration as a result of the
preparation. Disintegrants which may be present for the purposes of
the invention, such as, for example, kollidon, alginic acid and
alkali metal salts thereof, amorphous and also partially
crystalline phyllosilicates (bentonites), polyacrylates,
polyethylene glycols are given, for example, in the printed
specifications WO 98/40462 (Rettenmaier), WO 98/55583 and WO
98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 A1
(Henkel). Reference is expressly made to the teaching of these
specifications. The shaped bodies can comprise the disintegrants in
amounts of from 0.1 to 25% by weight, preferably 1 to 20% by weight
and in particular 5 to 15% by weight, based on the shaped
bodies.
[0185] Fragrances
[0186] Perfume oils or fragrances which can be used are individual
fragrance compounds, e.g. the synthetic products of the ester,
ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance
compounds of the ester type are, for example, benzyl acetate,
phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl
acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate,
linalyl benzoate, benzyl formate, ethyl methylphenylglycinate,
allyl cyclohexylpropionate, styrallyl propionate and benzyl
salicylate. The ethers include, for example, benzyl ethyl ether;
the aldehydes include, for example, the linear alkanals having 8-18
carbon atoms, citral, citronellal, citronellyloxyacetaldehyde,
cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal; the
ketones include, for example, the ionones, .alpha.-isomethylionone
and methyl cedryl ketone; the alcohols include anethole,
citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and
terpineol; the hydrocarbons include mainly the terpenes, such as
limonene and pinene. Preference is, however, given to using
mixtures of different fragrances which together produce a pleasing
fragrance note. Such perfume oils can also comprise natural
fragrance mixtures, such as are obtainable from vegetable sources,
e.g. pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or
ylang-ylang oil. Likewise suitable are muscatel, sage oil, camomile
oil, oil of cloves, melissa oil, mint oil, cinnamon leaf oil,
linden blossom oil, juniper berry oil, vetiver oil, olibanum oil,
galbanum oil and labdanum oil, and orange blossom oil, neroli oil,
orange peel oil and sandalwood oil.
[0187] The fragrances can be incorporated directly into the
compositions according to the invention, although it may also be
advantageous to apply the fragrances to carriers which enhance the
adhesion of the perfume to the laundry and, as a result of a slower
release of fragrance, ensure long-lasting fragrance of the
textiles. Cyclodextrins have, for example, proven successful as
such carrier materials, where the cyclodextrin-perfume complexes
can also additionally be coated with further auxiliaries.
[0188] Inorganic Salts
[0189] Further suitable ingredients of the compositions are
water-soluble inorganic salts, such as bicarbonates, carbonates,
amorphous silicates, normal waterglasses, which do not have
outstanding builder properties, or mixtures thereof; in particular,
alkali metal carbonate and/or amorphous alkali metal silicate,
primarily sodium silicate with a molar ratio of Na.sub.2O:SiO.sub.2
of 1:1 to 1:4.5, preferably from 1:2 to 1:3.5, are used. The
content of sodium carbonate in the end preparations is here
preferably up to 40% by weight, advantageously between 2 and 35% by
weight. The content in the compositions of sodium silicate (without
particular builder properties) is generally up to 10% by weight and
preferably between 1 and 8% by weight. Fillers and extenders which
may be present are also, for example, sodium sulfate in amounts of
from 0 to 10% by weight, in particular 1 to 5% by weight, based on
the compositions.
EXAMPLES
Example P1
[0190] In a 3-1 three-neck flask fitted with stirrer, distillation
attachment and vacuum connection, 1 000 g (1.52 mol) of
hydrogenated coconut oil, 720 g (4.45 mol) of
aminopropylmethylethanolamine (APMMEA) and 7 g of hypophosphoric
acid were mixed at 85.degree. C. The mixture was heated to
180.degree. C. and stirred at this temperature for 5 h, during
which the water of condensation was continuously distilled off.
Finally, the pressure was reduced to 10 mbar in order to remove
unreacted amine. Then, in a second reaction vessel, 230 g (1.97
mol) of sodium chloroacetate were dissolved in 670 ml of water at
85.degree. C. To this solution were added, in portions, 550 g (1.78
mol) of the amidoamine prepared previously, the pH being maintained
between 6 and 9. The mixture was then heated to 90.degree. C. and
stirred at this temperature for 5 h, where, toward the end of the
reaction, sodium hydroxide was added in order to keep the pH
constant. The betaine was obtained as a yellowish-transparent
liquid which had a dry residue of 51.3% by weight. The active
substance content was 44.0% by weight, the content of NaCl was 7.7%
by weight.
Example P2
[0191] Analogously to Example P1, 632 g (2.05 mol) of the
amidoamine obtained as intermediate were dissolved in 98 g of
isopropyl alcohol at 60.degree. C. Then, 245 g (1.94 mol) of
dimethyl sulfate were added to the mixture in portions with
stirring, during which the temperature was maintained between 60
and 70.degree. C. over 4 h. The amide quat was obtained as a
viscous liquid with an active substance content of 90% by
weight.
[0192] The table below gives a number of formulation examples.
1TABLE 1 C smetic preparations (water, preservatives ad 100% by
weight) Composition (INCI) 1 2 3 4 5 6 7 8 9 10 Texapon .RTM. NSO
-- -- -- -- -- -- 38.0 38.0 25.0 -- Sodium Laureth Sulfate Texapon
.RTM. SB 3 -- -- -- -- -- -- -- -- 10.0 -- Disodium Laureth
Sulfosuccinate Plantacare .RTM. 818 -- -- -- -- -- -- 7.0 7.0 6.0
-- Coco Glucosides Plantacare .RTM. PS 10 -- -- -- -- -- -- -- --
-- 10.0 Sodium Laureth Sulfate (and) Coco Glucosides Betaine as in
Ex. P1 -- -- -- -- -- -- 5.0 5.0 10.0 4.0 Amide quat as in Example
P2 2.0 2.0 2.0 2.0 4.0 4.0 -- -- -- -- Eumulgin .RTM. B2 0.8 0.8 --
0.8 -- 1.0 -- -- -- -- Ceteareth-20 Eumulgin .RTM. VL 75 -- -- 0.8
-- 0.8 -- -- -- -- -- Lauryl Glucoside (and) Polyglyceryl-2
Polyhydroxystearate (and) Glycerin Lanette .RTM. OB 2.5 2.5 2.5 2.5
3.0 2.5 -- -- -- -- Cetearyl Alcohol Cutina .RTM. GMS 0.5 0.5 0.5
0.5 0.5 1.0 -- -- -- -- Glyceryl Stearate Cetiol .RTM. HE 1.0 -- --
-- -- -- -- -- 1.0 -- PEG 7 Glyceryl Cocoate Cetiol .RTM. PGL --
1.0 -- -- 1.0 -- -- -- -- -- Hexyldecanol (and) Hexyldecyl Laurate
Cetiol .RTM. V -- -- -- 1.0 -- -- -- -- -- -- Decyl Oleate Eutanol
.RTM. G -- -- 1.0 -- -- 1.0 -- -- -- -- Octyldodecanol Nutrilan
.RTM. Keratin W -- -- -- 2.0 -- -- -- -- -- -- Hydrolyzed Keratin
Lamesoft .RTM. LMG -- -- -- -- -- -- 3.0 2.0 4.0 -- Glyceryl
Laurate (and) Potassium Cocoyl Hydrolyzed Collagen Euperlan .RTM.
PK 3000 AM -- -- -- -- -- -- -- 3.0 5.0 5.0 Glycol Distearate (and)
Laureth-4 (and) Cocamidopropyl Betaine Generol .RTM. 122 N -- -- --
-- 1.0 1.0 -- -- -- -- Soya sterol Highcareen .RTM. GS 1.0 1.0 1.0
1.0 1.0 1.0 1.0 1.0 1.0 1.0 Betaglucan Hydagen .RTM. CMF 1.0 1.0
1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Chitosan Copherol .RTM. 12250 -- --
0.1 0.1 -- -- -- -- -- -- Tocopherol Acetate Arlypon .RTM. F -- --
-- -- -- -- 3.0 3.0 1.0 -- Laureth-2 Sodium Chloride -- -- -- -- --
-- -- 1.5 -- 1.5 (1-4) hair rinse, (5-6) hair treatment, (7-8)
shower preparation, (9) shower gel, (10) washing lotion
* * * * *