US20030110574A1

US20030110574A1 - Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances

Info

Publication number: US20030110574A1
Application number: US10/220,671
Authority: US
Inventors: J?uuml;rgen Kaschig; Jianwen Mao
Original assignee: Individual
Current assignee: BASF Corp
Priority date: 2000-03-08
Filing date: 2001-03-01
Publication date: 2003-06-19
Also published as: EP1263919A1; MXPA02008709A; BR0109039A; AU2001244177A1; WO2001066681A1

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.

Description

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.

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.

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.

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.

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.

Useful optical brighteners for the invention preferably conform to the formula

R ₁is a radical of the formula

R ₃is substituted or unsubstituted alkyl or aryl;

R ₄is M or substituted or unsubstituted alkyl or aryl;

R ₅is hydrogen; substituted or unsubstituted alkyl or aryl; or —NR₇R₈, wherein R₇and R₈are independently hydrogen; substituted or unsubstituted alkyl or aryl; or R₇and R₈combine with the joining nitrogen atom to form a heterocyclic radical, especially morpholino or piperidino radical;

R ₆is hydrogen or substituted or unsubstituted alkyl or aryl,

R ₂is hydrogen; substituted or unsubstituted alkyl or aryl; a radical of the formula

—OH; —NH ₂; —N(CH₂CH₂OH)₂; —N[CH₂CH(OH)CH₃]₂, —NH-R₄, —N(R₄)₂or —OR₄; or

R ₁and R₂are independently —OH, —Cl; —NH₂, —O—C₁-C₄alkyl, —O-aryl, —NH—C₁-C₄alkyl, —N(C₁-C₄alkyl)₂, —N(C₁-C₄alkyl)(C₁-C₄hydroxyalkyl), —N(C₁-C₄hydroxyalkyl)₂, or —NH-aryl, morpholino, S—C₁-C₄alkyl(aryl),

R ₉and R₁₀are independently hydrogen, C₁-C₄alkyl, phenyl or a radical of the formula

R ₁₁is hydrogen, Cl or SO₃M;

R ₁₂is —CN, —SO₃M, —S(C₁-C₄alkyl)₂or S(aryl)₂;

R ₁₃is hydrogen, —SO₃M, —O—C₁-C₄alkyl, —CN, —Cl, —COO—C₁-C₄alkyl, or CON(C₁-C₄alkyl)₂;

R ₁₄is hydrogen; —C₁-C₄alkyl, —Cl or —SO₃M;

R ₁₅and R₁₆are independently hydrogen, C₁-C₄alkyl, —SO₃M, —Cl or —O—C₁C₄alkyl;

R ₁₇is hydrogen or C₁-C₄alkyl;

R ₁₈is hydrogen, C₁-C₄alkyl, —CN, —Cl, —COO—C₁-C₄alkyl, —CON(C₁-C₄alkyl)₂, aryl or —O-aryl;

M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C ₁-C₄alkylammonium, mono-, di- or tri-C₁-C₄hydroxyalkylammonium or ammonium that is di- or trisubstituted with a mixture of C₁-C₄alkyl and C₁-C₄hydroxyalkyl groups; and

n ₁, n₂and n₃are independently 0 or 1.

(Substituted or unsubstituted) alkyl R ₂, R₃, R₄, R₅, R₆, R₇and R₈is C₁-C₁₂alky, preferably C₁-C₄alkyl. Alkyl may be branched or unbranched and may be substituted by halogen, for example fluorine, chlorine or bromine, C₁-C₄alkoxy, for example methoxy or ethoxy, phenyl or carboxyl, Cl-C₄alkoxycarbonyl, for example acetyl, mono- or di-C₁-C₄alkylamino or —SO₃M.

(Substituted or unsubstituted) aryl R ₂, R₃, R₄, R₅, R₆, R₇and R₈is preferably a phenyl or naphthyl group which may be substituted by C₁-C₄alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, C₁-C₄alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy, halogen, for example fluorine, chlorine or bromine, C₂-C₅alkanoylamino, for example acetylamino, propionylamino or butyrylamino, nitro, sulfo or di- C₁-C₄alkylated amino.

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 ₁is preferably a radical of the formula

wherein R ₃is as defined above and is preferably C₁-C₄alkyl, especially methyl or ethyl; or a radical of the formula

wherein R ₅is as defined above and is preferably C₁-C₄alkyl, especially methyl or ethyl, or —NR₇R₈, wherein R₇and R₈are each as defined above and are each preferably hydrogen, C₁-C₄alkyl, especially methyl or ethyl, a morpholino or piperidino radical, most particularly hydrogen, or a radical of the formula

wherein R ₆is as defined above and is preferably —SO₃M substituted C₁-C₄alkyl, especially methyl- or ethyl-substituted —SO₃M, wherein M is as defined above and is preferably sodium; and R₂is preferably

—NH ₂, —N(CH₂CH₂OH)₂or —N[CH₂CH(OH)CH₃]₂.

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 ₁group and with a compound capable of introducing an R₂group, R₁and R₂being as defined above.

Optical brighteners that are advantageously useful in the present invention are recited below in Table 1 by way of example:

TABLE 1


Compounds
of the
formula


(9)

(10)

(11)

(12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

The stilbene compounds used in the invention have a pronounced antimicrobial action, especially against pathogenic Gram-positive and Gram-negative bacteria.

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.

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.

To provide an antimicrobial finish, the optical brighteners which are useful according to the invention can be incorporated into liquid and solid laundry detergents.

For this they are generally diluted with further auxiliaries or water to the optimum concentration for the particular use.

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.

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.

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.

Useful stabilizing assistants include for example ethylene glycol, propylene glycol and further dispersants.

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.

The examples which follow illustrate the invention.

EXAMPLE 1

Wash Test

a) Formulation of Laundry Detergent Powder Used (In Percent of the Total Weight of the Formulation): [0045]
8% of alkylbenzenesulfonate [0046]
5% of alcohol ether sulfate [0047]
2% of alcohol ethoxylate (nonionic) [0048]
30% of sodium tripolyphosphate [0049]
20% of sodium carbonate [0050]
8% of sodium silicate [0051]
18.9% of sodium sulfate [0052]
1% of enzymes [0053]
1% of polycarboxylates [0054]
0.1% of perfume oil [0055]
6% of water [0056]
b) Preparation of Laundry Detergent Powder which Includes Tinopal CBS-X: [0057]
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° 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. [0058]
c) Wash with the Laundry Detergent Obtained According to b): [0059]
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° 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. [0060]

EXAMPLE 2

Determination of Antimicrobial Activity of Tinopal CBS-X after Irradiation with Light [0061]
The optical brightener of the formula [0062]
is incorporated in agar plates and subsequently inoculated with bacteria and irradiated with xenon light for 10 minutes or 30 minutes. [0063]
The test is used to detect antimicrobial activity by comparison with unirradiated samples. [0064]
To this end, a 1.5% stock solution in DMSO is prepared. [0065]
0.5 and 0.1 ml of this solution are added to 15 ml of liquid agar (final concentration: 500 and 100 ppm). [0066]
After solidification and drying, a bacterial mixture of [0067] Staphylococcus aureus and Escherichia coli is plated out on the agar (final concentration cfu/ml:˜10⁵). 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.
Unirradiated agar plattes including 100 and 500 ppm of Tinopal CBS-X and agar plates without Tinopal are incubated as controls. [0068]
All plates were incubated at 37° C. for about 48 hours. After incubation, viable bacteria are counted (see Table 1). [0069]

Examples of Test Germs

Bacteria: [0070]
[0071] Staphylococcus aureus ATCC 9144
[0072] Escherichia coli NCTC 8196
Cultures 18 to 24 hours in casein soymeal peptone broth diluted 1:5000 (Staph.) and 1:10,000 ([0073] E. coli) and mixed together

The results are summarized in Table 1.

TABLE 1


	Staphylococcus aureus ATCC 9144/
Test organisms →	Escherichia coli NCTC 8196

Sample	10 minutes	30 minutes

Tinopal CBS-X 500 ppm	3.0 × 10⁴	1.5 × 10²
(irradiated with xenon light)
Tinopal CBS-X 500 ppm control	4.3 × 10⁴(t: 0′)	—
substance (not irradiated with
xenon light)
Tinopal CBS-X 100 ppm	2.3 × 10⁴	5.1 × 10²
(irradiated with xenon light)
Tinopal CBS-X 100 ppm control	4.4 × 10⁴(t: 0′)	—
substance (not irradiated with
xenon light)
DMSO control substance	5.7 × 10⁴	4.5 × 10⁴
(irradiated with xenon light)
DMSO control substance (not	8.9 × 10⁴(t: 0′)	—
irradiated with xenon light)
Agar control substance	4.1 × 10⁴	3.3 × 10⁴
(irradiated with xenon light)
Agar control substance (not	2.7 × 10⁵(t: 0′)	—
irradiated with xenon light)

The table reports the number of colony-forming units of bacteria after 10 minutes' and 30 minutes' irradiation. [0075]
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 [0076] 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.

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

wherein

R₁is a radical of the formula

R₃is substituted or unsubstituted alkyl or aryl;

R₄is M or substituted or unsubstituted alkyl or aryl;

R₅is hydrogen; substituted or unsubstituted alkyl or aryl; or —NR₇R₈, wherein R₇and R₈are independently hydrogen; substituted or unsubstituted alkyl or aryl; or R₇and R₈combine with the joining nitrogen atom to form a heterocyclic radical, especially morpholino or piperidino radical;

R₆is hydrogen or substituted or unsubstituted alkyl or aryl,

R₂is hydrogen; substituted or unsubstituted alkyl or aryl; a radical of the formula

—OH; —NH₂; —N(CH₂CH₂OH)₂; —N[CH₂CH(OH)CH₃]₂, —NH—R₄, —N(R₄)₂or —OR₄; or

R₁and R₂are independently —OH, —Cl; —NH₂, —O —C₁-C₄alkyl, —O-aryl, —NH—C₁-C₄alkyl, —N(C₁-C₄alkyl)₂, —N(C₁-C₄alkyl)(C₁-C₄hydroxyalkyl), —N(C₁-C₄hydroxyalky)₂, or —NH-aryl, morpholino, S—C₁-C₄alkyl(aryl),

M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C₁-C₄alkylammonium, mono-, di- or tri-C₁-C₄hydroxyalkylammonium or ammonium that is di- or trisubstituted with a mixture of C₁-C₄alkyl and C₁-C₄hydroxyalkyl groups; and

n₁and n₂, are independently 0 or 1.

4. Use according to claim 1 or 2, wherein an optical brightener used is a compound of the formula

wherein

R₉and R₁₀are independently hydrogen, C₁-C₄alkyl, phenyl or a radical of the formula

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

wherein

R₁₁is hydrogen, Cl or SO₃M;

R₁₂is —CN, —SO₃M, —S(C₁-C₄alkyl)₂or S(aryl)₂and

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

wherein

R₁₃is hydrogen, —SO₃M, —O—C₁-C₄alkyl, —CN, —Cl, —COO—C₁-C₄alkyl, or CON(C₁-C₄alkyl)₂; and

n₃is 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

wherein

R₁₄is hydrogen, C₁-C₄alkyl, Cl or —SO₃M;

R₁₅and R₁₆are independently hydrogen, C₁-C₄alkyl, —SO₃M, —Cl or —O—C₁-C₄alkyl 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

9. Use according to claim 1 or 2, wherein an optical brightener used is a compound of the formula

10. Use according to claim 1 or 2, wherein an optical brightener used is a compound of the formula

wherein

R₁₇is hydrogen or C₁-C₄alkyl;

R₁₈is hydrogen, C₁-C₄alkyl, —CN, —Cl, —COO—C₁-C₄alkyl, —CON(C₁-C₄alkyl)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.