U.S. patent application number 09/180992 was filed with the patent office on 2002-03-14 for use of nitrogen-containing complexing agents for deodorization and antimicrobial treatment of the skin and textile fibre materials.
Invention is credited to BACHMANN, FRANK, EHLIS, THOMAS, OCHS, DIETMAR, UTZ, ROLAND.
Application Number | 20020031537 09/180992 |
Document ID | / |
Family ID | 7795040 |
Filed Date | 2002-03-14 |
United States Patent
Application |
20020031537 |
Kind Code |
A1 |
BACHMANN, FRANK ; et
al. |
March 14, 2002 |
USE OF NITROGEN-CONTAINING COMPLEXING AGENTS FOR DEODORIZATION AND
ANTIMICROBIAL TREATMENT OF THE SKIN AND TEXTILE FIBRE MATERIALS
Abstract
The present invention relates to the use of nitrogen-containing
complexing agents for deodorization and antimicrobial treatment of
the skin and of textile fibre materials. The complexing agents
employed according to the invention have the formula 1 in which
Q.sub.1, is Carb.sub.1; Carb.sub.2,; or a radical of the formula
--(CH.sub.2).sub.m.sub..sub.1--OH Q.sub.2 is hydrogen or
Carb.sub.2; and Q.sub.3 is Carb.sub.3; an amino acid radical; or a
radical of the formula (1a) 2 where Carb.sub.1, Carb.sub.2 and
Carb.sub.3 independently of one another are the radical of a
C.sub.1-C.sub.8-mono- or -dicarboxylic acid and m.sub.1 is 1 to 5.
The complexing agents according to the invention show a pronounced
bacteriostatic action against Corynebacterium xerosis (bacteria
which cause body odour) and are therefore suitable as the
antimicrobial active substance in body care compositions and
antimicrobial fabric finishing of textile materials.
Inventors: |
BACHMANN, FRANK; (FREIBURG,
DE) ; OCHS, DIETMAR; (SCHOPFHEIM, DE) ; UTZ,
ROLAND; (RHEINFELDEN, DE) ; EHLIS, THOMAS;
(FREIBURG, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
7795040 |
Appl. No.: |
09/180992 |
Filed: |
November 19, 1998 |
PCT Filed: |
May 9, 1997 |
PCT NO: |
PCT/EP97/02380 |
Current U.S.
Class: |
424/405 ;
424/443; 424/70.1; 424/76.1; 514/561; 514/574 |
Current CPC
Class: |
C11D 9/30 20130101; A61K
8/44 20130101; A61Q 17/005 20130101; C11D 3/48 20130101; A61K
2800/51 20130101; A61Q 19/00 20130101; A61Q 5/02 20130101; A61P
31/00 20180101; A01N 57/20 20130101; A01N 37/44 20130101; A61P
31/04 20180101; A61Q 15/00 20130101; D06M 16/00 20130101; D06M
13/342 20130101; D06M 13/005 20130101 |
Class at
Publication: |
424/405 ;
424/443; 424/70.1; 424/76.1; 514/561; 514/574 |
International
Class: |
A61K 007/06; A61K
009/70; A61K 031/195; A61K 031/19 |
Foreign Application Data
Date |
Code |
Application Number |
May 22, 1996 |
DE |
196 20 644.8 |
Claims
What is claimed is:
1. The use of a nitrogen-containing complexing agent for
antimicrobial treatment of the skin and of textile fibre
materials.
2. The use according to claim 1, wherein a compound of the formula
13in which Q.sub.1, is Carb.sub.1; Carb.sub.2,; or a radical of the
formula --(CH.sub.2).sub.m.sub..sub.1--OH; Q.sub.2 is hydrogen or
Carb.sub.2; and Q.sub.3 is Carb.sub.3; an amino acid radical; or a
radical of the formula (1a) 14where Carb.sub.1, Carb.sub.2 and
Carb.sub.3 independently of one another are the radical of a
C.sub.1-C.sub.8-mono- or dicarboxylic acid; and m.sub.1 is 1 to 5,
is used as the complexing agent.
3. The use as claimed in claim 1 or 2, wherein the amino acid
radical Q.sub.3 has the formula 15
4. The use according to claim 3, wherein Q.sub.1 is a
monocarboxylic acid; or a radical of the formula
--(CH.sub.2).sub.m.sub..sub.1--OH; Q.sub.2 is hydrogen or a
monocarboxylic acid; and Q.sub.3 is formula (ib); or a
monocarboxylic acid.
5. The use according to claim 1 or 2, wherein Carb.sub.2 and
Carb.sub.3, independently of one another are the radical of the
formula--[(CH.sub.2)].sub.n.sub..sub.1--COOH, (1c)in which n.sub.1
is 0 to 5.
6. The use according to any one of claims 1 to 4, wherein the
compound of the formula 16is employed as the complexing agent.
7. The use according to any one of claims 1 to 4, wherein the
compound of the formula 17is employed as the complexing agent.
8. The use according to claim 1, wherein nitrilotriacetic acid is
used as the complexing agent.
9. The use of a complexing agent according to any one of claims 1
to 8, wherein the complexing agent is also in the form of one of
its water-soluble salts.
10. The use according to claim 9, wherein the complexing agent is
present in the form of its lithium, sodium, potassium, ammonium or
ethanolammonium salt.
11. The use of a complexing agent according to any one of claims 1
to 10 as an antimicrobial active substance against Gram-positive
bacteria.
12. The use of a complexing agent according to any one of claims 1
to 11 in body care compositions.
13. A body care composition comprising a nitrogen-containing
complexing agent according to claim 1.
14. A body care composition according to claim 13 in the form of a
soap, a shampoo or a deodorant.
15. The use of a complexing agent according to any one of claims 1
to 10 in textile fibre materials.
Description
[0001] The present invention relates to the use of
nitrogen-containing complexing agents for deodorization and
antimicrobial treatment of the skin and of textile fibre
materials.
[0002] It is known that various nitrogen-containing complexing
agents, for example ethylene-diaminetetraacetic acid (EDTA),
nitrilotriacetic acid (NTA), .beta.-alaninediacetic acid (EDETA) or
ethylenediaminedisuccinic acid (EDDS) are widely employed in
domestic detergents because of their complexing properties.
[0003] Surprisingly, it has been found that certain
nitrogen-containing complexing agents also have an antimicrobial
action against Gram-positive bacteria and are therefore
particularly suitable for deodorization and antimicrobial treatment
of the human skin and of textile fibre materials.
[0004] The present invention therefore relates to the use of
nitrogen-containing complexing agents for antimicrobial treatment
of the skin and of textile fibre materials.
[0005] Compounds which are preferably used according to the
invention as complexing agents are those of the formula 3
[0006] in which
[0007] Q.sub.1, is Carb.sub.1; Carb.sub.2,; or a radical of the
formula --(CH.sub.2).sub.m.sub..sub.1--OH
[0008] Q.sub.2 is hydrogen or Carb.sub.2; and
[0009] Q.sub.3 is Carb.sub.3; an amino acid radical; or a radical
of the formula (1a) 4
[0010] where Carb.sub.1, Carb.sub.2 and Carb.sub.3 independently of
one another are the radical of a C.sub.1-C.sub.8-mono- or
dicarboxylic acid; and
[0011] m.sub.1 is 1 to 5.
[0012] Compounds which are particularly preferred here are those of
the formula (1) in which the amino acid radical Q.sub.3 has the
formula 5
[0013] and especially compounds of the formula (1) in which
[0014] Q.sub.1 is a monocarboxylic acid; or a radical of the
formula --(CH.sub.2).sub.m.sub..sub.1--OH;
[0015] Q.sub.2 is hydrogen or a monocarboxylic acid; and
[0016] Q.sub.3 is formula (1b); or a monocarboxylic acid.
[0017] Complexing agents which are of particular interest are those
of the formula (1) in which Carb.sub.2 and Carb.sub.3,
independently of one another are the radical of the formula
--[(CH.sub.2)].sub.n.sub..sub.1--COOH, (1c)
[0018] in which
[0019] n.sub.1 is 0 to 5.
[0020] Complexing agents which are important in practice have the
formula 6
[0021] or the formula 7
[0022] Nitrilotriacetic acid (NTA) is furthermore suitable as the
complexing agent.
[0023] Other examples of complexing agents which can be employed
according to the invention are aminotrimethylenephosphoric acid
(ATMP) of the formula 8
[0024] serinediacetic acid (SDA) of the formula 9
[0025] asparaginediacetic acid of the formula 10
[0026] methylglycinediacetic acid (MGDA) of the formula (7) 11
[0027] The nitrogen-containing complexing agents employed according
to the invention can be employed not only as the acid but also in
the form of the water-soluble salts, preferably as lithium, sodium,
potassium, ammonium and ethanolammonium salts.
[0028] Ethylenediaminedisuccinic acid (EDDS) of the formula (2) has
two asymmetric carbon atoms. Various stereoisomeric forms of this
compound are therefore possible. The (S,S) configuration of EDDS
has the formula 12
[0029] An inexpensive chemical synthesis leads to a mixture of the
three forms S,S; R,R; and meso-EDDS. However, separation of these
stereoisomeric compounds requires a high industrial expenditure.
Optically pure (S,S)-EDDS can be prepared with the aid of an
Actinomycetes strain (T. Nishikiori et al., Production by
Actinomycetes of (S,S)-N,N'-ethylenediaminedisuccinic acid, an
inhibitor of phospholipase c; J.Antibiotics 37, 426-427
(1984)).
[0030] The purely chemical preparation of the compound of the
formula (9) is carried out in a manner known per se, such as is
described, for example, by J. A. Neal, N. Rose in Inorganic
Chemistry,7, 2405 (1985).
[0031] Racemic EDDS can be prepared in accordance with U.S. Pat.
No. 3,158,635.
[0032] The complexing agents according to the invention show a
pronounced bacteriostatic action, in particular against
Gram-positive bacteria of the skin flora, for example
Corynebacterium xerosis (bacteria which causes body odour). They
are therefore particularly suitable as the antimicrobial active
substance in body care compositions, for example soaps, shampoos,
foot care products and, in particular, deodorants, as well as an
additive in detergents.
[0033] The invention therefore also relates to a body care
composition comprising at least one nitrogen-containing complexing
agent and carriers or auxiliaries which are tolerated in
comsetics.
[0034] The body care composition according to the invention
comprises 0.01 to 15, preferably 0.5 to 10, % by weight, based on
the total weight of the composition, of a nitrogen-containing
complexing agent and auxiliaries which are tolerated in
cosmetics.
[0035] Depending on the form in which the body care composition is
present, it also comprises, in addition to the complexing agent,
other constituents, for example sequestering agents, dyes, perfume
oils, thickeners or consolidating agents (consistency regulators),
emmollients, UV absorbers, skin protection agents, antioxidants,
additives which improve the mechanical properties, such as
dicarboxylic acids and/or Al, Zn, Ca, or Mg salts of
C.sub.14-C.sub.22 fatty acids, and, if appropriate,
preservatives.
[0036] Because of their good water-solubility, the complexing
agents according to the invention can be incorporated into the
corresponding formulations without problems.
[0037] The body care compositions according to the invention can be
formulated as a water-in-oil or oil-in-water emulsion, as alcoholic
or alcohol containing formulation, as a vesicular dispersion of an
ionic or nonionic amphiphilic lipid, as a gel or solid stick or as
an aerosol formulation.
[0038] As a water-in-oil or oil-in-water emulsion, the auxiliary
which is tolerated in cosmetics preferably comprises 5 to 50% of an
oily phase, 5 to 20% of an emulsifier and 30 to 90% of water. The
oily phase can comprise any oil suitable for cosmetic formulations,
for example one or more hydrocarbon oils, a wax, a naturally
occurring oil, a silicone oil, a fatty acid ester or a fatty
alcohol. Preferred mono- or polyols are ethanol, isopropanol,
propylene glycol, hexylene glycol, glycerol and sorbitol.
[0039] An anitmicrobial soap has, for example, the following
composition:
[0040] 0.01 to 5% by weight of the compound of the formula (2)
[0041] 0.3 to 1% by weight of titanium dioxide
[0042] 1 to 10% by weight of stearic acid
[0043] to 100% of soap base, for example the sodium slats of tallow
fatty and coconut fatty acid or glycerols.
[0044] A shampoo has, for example, the following composition:
[0045] 0.01 to 5% by weight of the compound of the formula (2),
[0046] 12.0% by weight of sodium laureth-2-sulfate,
[0047] 4.0% by weight of cocamidopropylbetaine,
[0048] 3.0% by weight of NaCl and
[0049] water to 100%.
[0050] A deodorant has, for example, the following composition:
[0051] 0.01 to 5% by weight of the compound of the formula (2),
[0052] 60% by weight of ethanol,
[0053] 0.3% by weight of perfume oil and
[0054] water to 100%.
[0055] The complexing agents according to the invention are
furthermore suitable for the treatment of textile fibre materials.
The fibre materials are non-dyed and dyed or printed fibre
materials, for example of silk, leather, wool, polyamide or
polyurethanes, and in particular all types of cellulosic fibre
materials. Such fibre materials are, for example, naturally
occurring cellulosic fibres, such as cotton, linen, jute and hemp,
and cellulose and regenerated cellulose. Textile fibre materials
which are preferably suitable are those of cotton.
[0056] The following examples serve to illustrate the
invention.
EXAMPLE 1
[0057] Determination of the Antimicrobial Activities of S,S-EDDS,
R,R-EDDS, Racemate of EDDS and EDETA, EDTA and NTA
[0058] Test method: An agar diffusion test is carried out with the
following modifications:
[0059] Medium: casein-soya flour peptone agar (caso-agar)
[0060] Test organisms: Corynebacterium xerosis ATCC 373
[0061] Corynebacterium xerosis ATCC 7711
[0062] Corynebacterium minutissimum ATCC 23358
[0063] Procedure: 500 ml of caso-agar are innoculated with 3.5 ml
of an overnight culture of the bacteria, diluted 1:100, and caso
plates (18 ml) are covered with a layer of about 5 ml of the
bacteria-containing agar. After the plates have cooled, holes of
diameter 1 cm are stamped out with a cork borer. Each stamped-out
hole is filled with in each case 100 .mu.l of a test substance
dilution and the plates are incubated at 37.degree. C. for 2 days.
Double-distilled water is employed as the solvent for all the
substances. In the case of EDETA GS, the pH is adjusted to 3.3 by
addition of 1 N NaOH. Chemically prepared S,S-EDDS is adjusted to
the pH of 5.6 by addition of 1 N NaOH.
[0064] Controls: Double-distilled water
[0065] The test results are listed in Table 1:
1 TABLE 1 Concen- Inhibitory aureola diameter tration Cory. xerosis
Cory. xerosis Substance [ppm] AUG 7711 ATTC 373 EDETA 10000
5/5.sup.1 1/1.sup.1 S,S-EDDS 10000 15/15.sup.1 10/10.sup.1
(prepared chemically) S,S-EDDS 10000 15/15.sup.1 10/10.sup.1
(prepared by fermentation EDTA 10000 2/2.sup. 5/5.sup. R,S-EDDS
10000 n.d. 12/13.sup. R,R-EDDS 10000 n.d. 15/15.sup. .sup.1Slight
growth on inhibitory aureolas
[0066] The test results show that both EDETA, EDTA and the EDDS
prepared by fermentation and chemically (.dbd.R,R; S,S; R,S) show a
pronounced bacteriostatic action against Corynebacterium
xerosis.
[0067] Examples of formulations having a bacteriostatic action
EXAMPLE 2
[0068] Preparation of a Washing Powder
2 Laurylammonium sulfate 8.0% Nonionic surfactants 2.9% Soaps 3.5%
Sodium tripolyphosphate 43.8% Sodium silicate 7.5% Magnesium
silicate 1.9% Carboxymethylcellulose 1.2% EDTA 0.2% Sodium sulfate
21.2% EDDS 1% Water to 100%
[0069] The formulation is prepared as follows:
[0070] The solid components are mixed and homogenized in a mortar
and stirred with deionized water until a uniform pourable and
pumpable paste (slurry) is obtained, which is finally
spray-dried.
EXAMPLE 3
[0071] Preparation of a Cleansing Tonic
3 Ethanol 20% Glycerol 5% PEG-40 hydrogenated castor oil 1%
(hydrogenated ethoxylated castor oil) EDDS 0.5% Perfume ad libidum
Water to 100%
[0072] The formulation is prepared as follows:
[0073] EDDS is dissolved in ethanol. Under stirring at room
temperature PEG-40, glycerol and perfume are added. Finally, the
water is added.
EXAMPLE 3
[0074] Preparation of a Deodorant Stick
4 Ethanol 20% Glycerol 30% Propylene glycol 20% Ceteareth-25 3% (=
ethoxylated cetyl/stearyl alcohol) Sodium stearate 7% EDDS 0,5%
Perfume ad libidum Water to 100%
[0075] The formulation is prepared as follows:
[0076] Sodium stearate is melted at 60.degree. C. Propylene glycol,
Cetearath-25 and glycerol are added to the melting until a
homogeneous clear suspension is obtained. Finally, the suspension
is stirred with a EDDS-solution in an alcohol/water mixture at
50.degree. C. and cooled slowly.
EXAMPLE 4
[0077] Preparation of Soluble EDDS Salts and Deodorant
Formulations
[0078] S,S-EDDS is obtained by means of microbiological (WO
96/36725) or chemical synthesis (J. A. Neal et al., Inorg.Chem. 7,
2405 (1968)). Racemic EDDS is prepared from maleic anhydride and
ethylenediamine (U.S. Pat. No. 3,158,635).
[0079] A 1% suspension of racemic EDDS or S,S-EDDS is prepared in
water/ethanol (about 7:3) with vigorous stirring. An aqueous
solution of NaOH is metered in with an autoamtic titration device
until the pH of 7 remains constant for 30 minutes. Any slight milky
clouding which occurs is removed by filtering through paper.
[0080] By addition of a thickener like hydroxy ethyl cellulose a
clear deodorant formulation which is stable at room temperature,
comprises about 1% of active substance (based on the tetra-acid)
and has a skin-friendly pH is obtained.
[0081] If NaOH is replaced by KOH, ammonia or ethanolamine, the
corresponding potassium, ammonium and ethanolammonium salts are
obtained. Lithium hydroxide, sodium carbonate, sodium bicarbonate
or laurylamine can also be employed as the base.
EXAMPLE 5
[0082] Detection of the Substantial Antimicrobial Activity of
R,S-EDDS Salts on the Skin
5 Formulations 1% of R,S-EDDS/sodium salt (Solutions in 30%
ethanol): 1% of R,S-EDDS/amine salt (for the preparation, cf.
Example 4) Medium: Casein-soya flour peptone agar (caso-agar) Test
organism: Corynebacterium xerosis ATCC 373
[0083] Test method:
[0084] Before application of the test solutions, the underarms are
washed with a non-antimicrobial soap twice for 1 minute each time.
A total of 6 ml of test product is then applied to the washed, dry
skin of the underarm. Immediately and 2 hours after application of
the test products, the EDDS on the skin is extracted by means of
discs of filter paper (2 cm diameter) moistened in 0.9% NaCl
solution (pH: 8.2). For this, the moist filter disc is placed on
the treated skin without airbubbles for 4 minutes. The filter discs
are subsequently dried at room temperature and then placed on solid
agar media with test bacteria.
[0085] To prepare the solid agar media, 500 ml of liquid agar are
innoculated with 3.5 ml of a 12-16-hour culture, diluted 1:100, of
the test bacteria at 47.degree. C. and caso plates (18 ml) are
covered with a layer of about 5 ml of the bacteria-containing
agar.
[0086] After the filter discs have been placed on top, the agar
media are incubated for 2 days at 37.degree. C. and the inhibition
under the filter disc or the inhibitory aureolas of the filter
discs is/are then determined.
[0087] The test results are listed in Table 2:
6 TABLE 2 Substance Inhibitory aureola dia- meter (mm)/inhibition
under the filter disc* Coryneb. xerosis ATCC 373 Placebo 0/0
R,S-EDDS (sodium salt) immed- 5/4 iately 2 hours 3/4 after
application R,S-EDDS (Amine salt) immed- 2,5/4 iately 2 hours 2/4
after application *Inhibition under the filter disc:
[0088] Explanation:
[0089] 0=good growth (no inhibition)
[0090] 2=inhibited but clear growth (weak inhibition)
[0091] 4=no growth (potent inhibition)
[0092] The test results show that a pronounced inhibition of
Corynebacterium xerosis is achieved with both test substances.
[0093] The test shows that sufficiently high concentrations of EDDS
to achieve inhibition of Corynebacterium xerosis are also still
present on the skin 2 hours after the last application.
* * * * *