U.S. patent application number 10/220671 was filed with the patent office on 2003-06-19 for use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances.
Invention is credited to rgen Kaschig, J?uuml, Mao, Jianwen.
Application Number | 20030110574 10/220671 |
Document ID | / |
Family ID | 8168052 |
Filed Date | 2003-06-19 |
United States Patent
Application |
20030110574 |
Kind Code |
A1 |
Kaschig, J?uuml;rgen ; et
al. |
June 19, 2003 |
Use of optical brighteners from the class of the stilbene compounds
as antimicrobially active substances
Abstract
Described is the use of a laundry detergent that includes at
least one optical brightener from the class of the stilbene
compounds for the antimicrobial finishing of textile fiber
materials, which comprises washing the fiber materials with this
laundry detergent and subsequently exposing the washed textile
material to a light source.
Inventors: |
Kaschig, J?uuml;rgen;
(US) ; Mao, Jianwen; (New Milford, CT) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8168052 |
Appl. No.: |
10/220671 |
Filed: |
September 4, 2002 |
PCT Filed: |
March 1, 2001 |
PCT NO: |
PCT/EP01/02315 |
Current U.S.
Class: |
8/137 |
Current CPC
Class: |
C11D 11/007 20130101;
D06M 10/001 20130101; C11D 3/48 20130101; D06M 16/00 20130101; D06L
4/60 20170101; C11D 3/42 20130101; D06M 13/07 20130101; D06M 13/358
20130101; D06M 13/352 20130101 |
Class at
Publication: |
8/137 |
International
Class: |
D06F 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 8, 2000 |
EP |
00104907.1 |
Claims
What is claimed is:
1. Use of a laundry detergent that includes at least one optical
brightener from the class of the stilbene compounds for the
antimicrobial finishing of textile fibre materials, which comprises
washing the fibre materials with this laundry detergent and
subsequently exposing the washed textile material to a light
source.
2. Use according to claim 1, wherein the washed textile materials
are irradiated with UV light or in daylight in the moist state.
3. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 29wherein R.sub.1 is a radical of
the formula 30R.sub.3 is substituted or unsubstituted alkyl or
aryl; R.sub.4 is M or substituted or unsubstituted alkyl or aryl;
R.sub.5 is hydrogen; substituted or unsubstituted alkyl or aryl; or
--NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 are independently
hydrogen; substituted or unsubstituted alkyl or aryl; or R.sub.7
and R.sub.8 combine with the joining nitrogen atom to form a
heterocyclic radical, especially morpholino or piperidino radical;
R.sub.6 is hydrogen or substituted or unsubstituted alkyl or aryl,
R.sub.2 is hydrogen; substituted or unsubstituted alkyl or aryl; a
radical of the formula 31 --OH; --NH.sub.2;
--N(CH.sub.2CH.sub.2OH).sub.2; --N[CH.sub.2CH(OH)CH.sub.3].su- b.2,
--NH--R.sub.4, --N(R.sub.4).sub.2 or --OR.sub.4; or R.sub.1 and
R.sub.2 are independently --OH, --Cl; --NH.sub.2, --O
--C.sub.1-C.sub.4alkyl, --O-aryl, --NH--C.sub.1-C.sub.4alkyl,
--N(C.sub.1-C.sub.4alkyl).sub.2,
--N(C.sub.1-C.sub.4alkyl)(C.sub.1-C.sub.- 4hydroxyalkyl),
--N(C.sub.1-C.sub.4hydroxyalky).sub.2, or --NH-aryl, morpholino,
S--C.sub.1-C.sub.4alkyl(aryl), M is hydrogen, Na, K, Ca, Mg,
ammonium, mono-, di-, tri- or tetra-C.sub.1-C.sub.4alkylammonium,
mono-, di- or tri-C.sub.1-C.sub.4hydroxyalkylammonium or ammonium
that is di- or trisubstituted with a mixture of
C.sub.1-C.sub.4alkyl and C.sub.1-C.sub.4hydroxyalkyl groups; and
n.sub.1 and n.sub.2, are independently 0 or 1.
4. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 32wherein R.sub.9 and R.sub.10
are independently hydrogen, C.sub.1-C.sub.4alkyl, phenyl or a
radical of the formula 33 and M is as defined in claim 3.
5. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 34wherein R.sub.11 is hydrogen,
Cl or SO.sub.3M; R.sub.12 is --CN, --SO.sub.3M,
--S(C.sub.1-C.sub.4alkyl).sub.2 or S(aryl).sub.2 and M is as
defined in claim 3.
6. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 35wherein R.sub.13 is hydrogen,
--SO.sub.3M, --O--C.sub.1-C.sub.4alkyl, --CN, --Cl,
--COO--C.sub.1-C.sub.4alkyl, or CON(C.sub.1-C.sub.4alkyl).sub.2;
and n.sub.3 is 0 or 1, and M is as defined in claim 31.
7. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 36wherein R.sub.14 is hydrogen,
C.sub.1-C.sub.4alkyl, Cl or --SO.sub.3M; R.sub.15 and R.sub.16 are
independently hydrogen, C.sub.1-C.sub.4alkyl, --SO.sub.3M, --Cl or
--O--C.sub.1-C.sub.4alkyl and M is as defined in claim 3.
8. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 37
9. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 38
10. Use according to claim 1 or 2, wherein an optical brightener
used is a compound of the formula 39wherein R.sub.17 is hydrogen or
C.sub.1-C.sub.4alkyl; R.sub.18 is hydrogen, C.sub.1-C.sub.4alkyl,
--CN, --Cl, --COO--C.sub.1-C.sub.4alkyl,
--CON(C.sub.1-C.sub.4alkyl).sub.2, aryl or --O-aryl.
11. Use according to any one of claims 1 to 10, wherein the textile
fibre materials used are natural cellulose fibres
12. Use of optical brighteners from the class of the stilbene
compounds as antimicrobially active substances against
microorganisms.
13. Use according to claim 12, wherein the microorganisms are
Gram-positive and Gram-negative bacteria.
Description
[0001] The present invention relates to the use of a laundry
detergent that comprises at least one optical brightener from the
class of the stilbene compounds for the antimicrobial finishing of
textile materials and to the use of these compounds as
antimicrobially active substances against microorganisms.
[0002] Washing with a commercially available laundry detergent
removes the soil from the textile materials and usually imparts an
improved appearance to them. However, washing and drying of
textiles does not always remove bacteria to the desired degree. Nor
does a normal wash do anything to prevent subsequent contamination
by undesirable bacteria.
[0003] Existing ways to make textile fibre materials germ free
include for example the use of bleaches, higher temperatures or
irradiation with strong sunlight during drying.
[0004] It has now been found that, surprisingly, optical
brighteners from the class of the stilbene compounds which are
customarily used in the laundry detergent and textile industries
have antimicrobial properties when the textile material is
simultaneously irradiated with a light source.
[0005] The present invention accordingly provides for the use of a
laundry detergent that comprises at least one optical brightener
from the class of the stilbene compounds for the antimicrobial
finishing of textile fibre materials, which comprises washing the
fibre materials with this laundry detergent and subsequently
exposing the washed textile material to a light source.
[0006] Useful optical brighteners for the invention preferably
conform to the formula 1
[0007] R.sub.1 is a radical of the formula 2
[0008] R.sub.3 is substituted or unsubstituted alkyl or aryl;
[0009] R.sub.4 is M or substituted or unsubstituted alkyl or
aryl;
[0010] R.sub.5 is hydrogen; substituted or unsubstituted alkyl or
aryl; or --NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 are
independently hydrogen; substituted or unsubstituted alkyl or aryl;
or R.sub.7 and R.sub.8 combine with the joining nitrogen atom to
form a heterocyclic radical, especially morpholino or piperidino
radical;
[0011] R.sub.6 is hydrogen or substituted or unsubstituted alkyl or
aryl,
[0012] R.sub.2 is hydrogen; substituted or unsubstituted alkyl or
aryl; a radical of the formula 3
[0013] --OH; --NH.sub.2; --N(CH.sub.2CH.sub.2OH).sub.2;
--N[CH.sub.2CH(OH)CH.sub.3].sub.2, --NH-R.sub.4, --N(R.sub.4).sub.2
or --OR.sub.4; or
[0014] R.sub.1 and R.sub.2 are independently --OH, --Cl;
--NH.sub.2, --O--C.sub.1-C.sub.4alkyl, --O-aryl,
--NH--C.sub.1-C.sub.4alkyl, --N(C.sub.1-C.sub.4alkyl).sub.2,
--N(C.sub.1-C.sub.4alkyl)(C.sub.1-C.sub.- 4hydroxyalkyl),
--N(C.sub.1-C.sub.4hydroxyalkyl).sub.2, or --NH-aryl, morpholino,
S--C.sub.1-C.sub.4alkyl(aryl),
[0015] R.sub.9 and R.sub.10 are independently hydrogen,
C.sub.1-C.sub.4alkyl, phenyl or a radical of the formula 4
[0016] R.sub.11 is hydrogen, Cl or SO.sub.3M;
[0017] R.sub.12 is --CN, --SO.sub.3M,
--S(C.sub.1-C.sub.4alkyl).sub.2 or S(aryl).sub.2;
[0018] R.sub.13 is hydrogen, --SO.sub.3M,
--O--C.sub.1-C.sub.4alkyl, --CN, --Cl, --COO--C.sub.1-C.sub.4alkyl,
or CON(C.sub.1-C.sub.4alkyl).sub.2;
[0019] R.sub.14 is hydrogen; --C.sub.1-C.sub.4alkyl, --Cl or
--SO.sub.3M;
[0020] R.sub.15 and R.sub.16 are independently hydrogen,
C.sub.1-C.sub.4alkyl, --SO.sub.3M, --Cl or
--O--C.sub.1C.sub.4alkyl;
[0021] R.sub.17 is hydrogen or C.sub.1-C.sub.4alkyl;
[0022] R.sub.18 is hydrogen, C.sub.1-C.sub.4alkyl, --CN, --Cl,
--COO--C.sub.1-C.sub.4alkyl, --CON(C.sub.1-C.sub.4alkyl).sub.2,
aryl or --O-aryl;
[0023] M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or
tetra-C.sub.1-C.sub.4alkylammonium, mono-, di- or
tri-C.sub.1-C.sub.4hydr- oxyalkylammonium or ammonium that is di-
or trisubstituted with a mixture of C.sub.1-C.sub.4alkyl and
C.sub.1-C.sub.4hydroxyalkyl groups; and
[0024] n.sub.1, n.sub.2 and n.sub.3 are independently 0 or 1.
[0025] (Substituted or unsubstituted) alkyl R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 is
C.sub.1-C.sub.12alky, preferably C.sub.1-C.sub.4alkyl. Alkyl may be
branched or unbranched and may be substituted by halogen, for
example fluorine, chlorine or bromine, C.sub.1-C.sub.4alkoxy, for
example methoxy or ethoxy, phenyl or carboxyl,
Cl-C.sub.4alkoxycarbonyl, for example acetyl, mono- or
di-C.sub.1-C.sub.4alkylamino or --SO.sub.3M.
[0026] (Substituted or unsubstituted) aryl R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 is preferably a
phenyl or naphthyl group which may be substituted by
C.sub.1-C.sub.4alkyl, for example methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, sec-butyl or tert-butyl, C.sub.1-C.sub.4alkoxy,
for example methoxy, ethoxy, propoxy, isopropoxy, butoxy,
isobutoxy, sec-butoxy or tert-butoxy, halogen, for example
fluorine, chlorine or bromine, C.sub.2-C.sub.5alkanoylamino, for
example acetylamino, propionylamino or butyrylamino, nitro, sulfo
or di- C.sub.1-C.sub.4alkylated amino.
[0027] The compounds of the formula (1) are preferably used in
neutralized form, i.e. M is preferably a cation of an alkali metal,
especially sodium, or an amine. In the compounds of formula (1),
R.sub.1 is preferably a radical of the formula 5
[0028] wherein R.sub.3 is as defined above and is preferably
C.sub.1-C.sub.4alkyl, especially methyl or ethyl; or a radical of
the formula 6
[0029] wherein R.sub.5 is as defined above and is preferably
C.sub.1-C.sub.4alkyl, especially methyl or ethyl, or
--NR.sub.7R.sub.8, wherein R.sub.7 and R.sub.8 are each as defined
above and are each preferably hydrogen, C.sub.1-C.sub.4alkyl,
especially methyl or ethyl, a morpholino or piperidino radical,
most particularly hydrogen, or a radical of the formula 7
[0030] wherein R.sub.6 is as defined above and is preferably
--SO.sub.3M substituted C.sub.1-C.sub.4alkyl, especially methyl- or
ethyl-substituted --SO.sub.3M, wherein M is as defined above and is
preferably sodium; and R.sub.2 is preferably 8
[0031] --NH.sub.2, --N(CH.sub.2CH.sub.2OH).sub.2 or
--N[CH.sub.2CH(OH)CH.sub.3].sub.2.
[0032] The compounds of the formula (1) are preparable under known
reaction conditions by reacting cyanuric chloride with appropriate
aminosfilbenesulfonic acids and with an amino compound capable of
introducing an R.sub.1 group and with a compound capable of
introducing an R.sub.2 group, R.sub.1 and R.sub.2 being as defined
above.
[0033] Optical brighteners that are advantageously useful in the
present invention are recited below in Table 1 by way of
example:
1TABLE 1 Compounds of the formula (9) 9 (10) 10 (11) 11 (12) 12
(13) 13 (14) 14 (15) 15 (16) 16 (17) 17 (18) 18 (19) 19 (20) 20
(21) 21 (22) 22 (23) 23 (24) 24 (25) 25 (26) 26 (27) 27
[0034] The stilbene compounds used in the invention have a
pronounced antimicrobial action, especially against pathogenic
Gram-positive and Gram-negative bacteria.
[0035] They are therefore useful for the treatment, especially
decontamination and also antimicrobial finishing of textile fibre
materials. Useful textile fibre materials include undyed and dyed
or printed fibre materials, for example in silk, wool, polyamide or
polyurethanes, and especially cellulosic fibre materials of any
kind. Such fibre materials include for example natural cellulose
fibres, such as cotton, linen, jute and hemp, and also pulp and
regenerated cellulose. Preferred suitable textile fibre materials
are composed of cotton.
[0036] The textile materials may be present in various forms.
Preference is given to piece goods, such as formed-loop knits or
wovens, or else yam on packages, warp beams, etc.
[0037] To provide an antimicrobial finish, the optical brighteners
which are useful according to the invention can be incorporated
into liquid and solid laundry detergents.
[0038] For this they are generally diluted with further auxiliaries
or water to the optimum concentration for the particular use.
[0039] The formulations thus obtained may additionally include the
customary formulation auxiliaries such as dispersants, builders,
protective colloids, stabilizers, preservatives, scents, pigments,
enzymes and also sequestrants.
[0040] Preferred dispersants are nonionic dispersants, for example
fatty alcohols, ethoxylation products of fatty alcohols or fatty
acids, or anionic dispersants, such as the condensations products
of aromatic sulfonic acids with formaldehyde, for example those
based on oxyditolylsulfonic acid or naphthalenesulfonates, or
ligninsulfonates.
[0041] Useful builders or protective colloids include for example
modified polysaccharides which are derived from cellulose or
heteropolysaccharides such as xanthan, carboxymethylcellulose and
also aluminium silicate or magnesium silicate.
[0042] Useful stabilizing assistants include for example ethylene
glycol, propylene glycol and further dispersants.
[0043] For the process of the invention, the textile fibre
materials are subjected for example to a customary wash cycle in a
wash liquor that includes the corresponding optical brightener. The
irradiation with UV light or in daylight preferably takes place
after the textiles have been removed from the wash liquor, in the
moist state, and the preferred light source is sunlight.
Illumination can in this case conveniently take place during the
drying of the textiles. When the textiles are not line dried, but
are dried for example in a tumble dryer, illumination may also be
effected during this drying process, for example by means of a
suitable artificial light source attached to or in the tumble
dryer.
[0044] The examples which follow illustrate the invention.
EXAMPLE 1
Wash Test
[0045] a) Formulation of Laundry Detergent Powder Used (In Percent
of the Total Weight of the Formulation):
[0046] 8% of alkylbenzenesulfonate
[0047] 5% of alcohol ether sulfate
[0048] 2% of alcohol ethoxylate (nonionic)
[0049] 30% of sodium tripolyphosphate
[0050] 20% of sodium carbonate
[0051] 8% of sodium silicate
[0052] 18.9% of sodium sulfate
[0053] 1% of enzymes
[0054] 1% of polycarboxylates
[0055] 0.1% of perfume oil
[0056] 6% of water
[0057] b) Preparation of Laundry Detergent Powder which Includes
Tinopal CBS-X:
[0058] 0.06 part of the brightener of the formula (101) reported in
Example 2 is placed in a mortar together with a small amount of
deionized water and then pestled with a further 15 parts of
deionized water. 20 parts of the laundry detergent powder specified
above under a) are then added within a short time, and the pestling
continues to form a homogeneous mass. The mass obtained is placed
in a crucible and air dried at 60.degree. C. for about 12 hours.
Following two successive sieving operations (0.8 mm mesh and then
0.315 mm mesh) the granules obtained range in size from 0.315 to
0.8 mm.
[0059] c) Wash with the Laundry Detergent Obtained According to
b):
[0060] A Linitest laboratory washing machine is used to wash 10
parts of bleached cotton fabric with 100 parts of tap water and 0.4
part of the laundry detergent obtained as per b) at 25.degree. C.
for 15 minutes. After the wash, the fabric is rinsed three times
under running tap water and then dried in sunlight. The fabric thus
washed possesses antimicrobial activity.
EXAMPLE 2
[0061] Determination of Antimicrobial Activity of Tinopal CBS-X
after Irradiation with Light
[0062] The optical brightener of the formula 28
[0063] is incorporated in agar plates and subsequently inoculated
with bacteria and irradiated with xenon light for 10 minutes or 30
minutes.
[0064] The test is used to detect antimicrobial activity by
comparison with unirradiated samples.
[0065] To this end, a 1.5% stock solution in DMSO is prepared.
[0066] 0.5 and 0.1 ml of this solution are added to 15 ml of liquid
agar (final concentration: 500 and 100 ppm).
[0067] After solidification and drying, a bacterial mixture of
Staphylococcus aureus and Escherichia coli is plated out on the
agar (final concentration cfu/ml:.about.10.sup.5). The plates are
fixed on cotton by means of double sided Scotch tape and are
irradiated with a xenon lamp for 10 or 30 minutes.
[0068] Unirradiated agar plattes including 100 and 500 ppm of
Tinopal CBS-X and agar plates without Tinopal are incubated as
controls.
[0069] All plates were incubated at 37.degree. C. for about 48
hours. After incubation, viable bacteria are counted (see Table
1).
Examples of Test Germs
[0070] Bacteria:
[0071] Staphylococcus aureus ATCC 9144
[0072] Escherichia coli NCTC 8196
[0073] Cultures 18 to 24 hours in casein soymeal peptone broth
diluted 1:5000 (Staph.) and 1:10,000 (E. coli) and mixed
together
[0074] The results are summarized in Table 1.
2TABLE 1 Staphylococcus aureus ATCC 9144/ Test organisms .fwdarw.
Escherichia coli NCTC 8196 Sample 10 minutes 30 minutes Tinopal
CBS-X 500 ppm 3.0 .times. 10.sup.4 1.5 .times. 10.sup.2 (irradiated
with xenon light) Tinopal CBS-X 500 ppm control 4.3 .times.
10.sup.4 (t: 0') -- substance (not irradiated with xenon light)
Tinopal CBS-X 100 ppm 2.3 .times. 10.sup.4 5.1 .times. 10.sup.2
(irradiated with xenon light) Tinopal CBS-X 100 ppm control 4.4
.times. 10.sup.4 (t: 0') -- substance (not irradiated with xenon
light) DMSO control substance 5.7 .times. 10.sup.4 4.5 .times.
10.sup.4 (irradiated with xenon light) DMSO control substance (not
8.9 .times. 10.sup.4 (t: 0') -- irradiated with xenon light) Agar
control substance 4.1 .times. 10.sup.4 3.3 .times. 10.sup.4
(irradiated with xenon light) Agar control substance (not 2.7
.times. 10.sup.5 (t: 0') -- irradiated with xenon light)
[0075] The table reports the number of colony-forming units of
bacteria after 10 minutes' and 30 minutes' irradiation.
[0076] The results of Table 1 show that 100 ppm or 500 ppm Tinopal
CBS-X incorporated into agar nutrient medium is effective to
substantially reduce the microorganisms (mixture of Staphylococcus
aureus and Escherichia coli) after 30 minutes' irradiation with a
xenon lamp compared with the agar plates containing unirradiated
Tinopal CBS-X and agar plates containing no Tinopal CBS-X.
* * * * *