EP1263919A1 - Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances - Google Patents

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

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Publication number
EP1263919A1
EP1263919A1 EP01917048A EP01917048A EP1263919A1 EP 1263919 A1 EP1263919 A1 EP 1263919A1 EP 01917048 A EP01917048 A EP 01917048A EP 01917048 A EP01917048 A EP 01917048A EP 1263919 A1 EP1263919 A1 EP 1263919A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
aryl
hydrogen
formula
use according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01917048A
Other languages
German (de)
French (fr)
Inventor
Jürgen Kaschig
Jianwen Mao
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP01917048A priority Critical patent/EP1263919A1/en
Publication of EP1263919A1 publication Critical patent/EP1263919A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D06M13/03—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons with unsaturated hydrocarbons, e.g. alkenes, or alkynes
    • D06M13/07—Aromatic hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • 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.
  • washing and drying of textiles does not always remove bacteria to the desired degree.
  • a normal wash do anything to prevent subsequent contamination by undesirable bacteria.
  • 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
  • Ri is a radical of the formula — NH- ⁇ V-corR, ;
  • R 3 is substituted or unsubstituted alkyl or aryl
  • R 4 is M or substituted or unsubstituted alkyl or aryl
  • R 5 is hydrogen; substituted or unsubstituted alkyl or aryl; or -NR 7 R 8 , wherein R 7 and R 8 are independently hydrogen; substituted or unsubstituted alkyl or aryl; or R 7 and R 8 combine with the joining nitrogen atom to form a heterocyclic radical, especially morpholino or piperidino radical;
  • R 6 is hydrogen or substituted or unsubstituted alkyl or aryl
  • R 2 is hydrogen; substituted or unsubstituted alkyl or aryl; a radical of the formula — N o,
  • R 1 and R ⁇ are independently -OH, -CI; -NH 2 , -O-C C 4 alkyl, -O-aryl, -NH-C ⁇ alkyl,
  • R 9 and R 10 are independently hydrogen, C C 4 alkyl, phenyl or a radical of the formula
  • R is hydrogen, CI or SO 3 M
  • R 12 is -CN, -SO 3 M, -S(C C 4 alkyl) 2 or S(aryl) 2 ;
  • R 13 is hydrogen, -SO 3 M, -O-C ⁇ alkyl, -CN, -CI, -COO-C ⁇ alkyl, or CON ⁇ -C ⁇ alkyl) ⁇
  • R 14 is hydrogen; -Chalky!, -CI or -SO 3 M;
  • R 15 and R 16 are independently hydrogen, C ⁇ alkyl, -SO3M, -CI or -O-C ⁇ alkyl;
  • R 17 is hydrogen or 0,-C ⁇ alkyl;
  • R 18 is hydrogen, C 1 -C 4 alkyl, -CN, -CI, -COO-C ⁇ alkyl, -CON(C 1 -C 4 alkyl) 2 , aryl or -O-aryl;
  • M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C C 4 alkylammonium, mono-, di- or tri-C r C hydroxyalkylammonium or ammonium that is di- or trisubstituted with a mixture of C C 4 aIkyl and C 1 -C 4 hydroxyalkyl groups; and n-i, n 2 and n 3 are independently 0 or 1.
  • Rs, Re, R7 and R a is CrC 12 alkyl, preferably C C 4 alkyl.
  • Alkyl may be branched or unbranched and may be substituted by halogen, for example fluorine, chlorine or bromine, C ⁇ -C 4 alkoxy, for example methoxy or ethoxy, phenyl or carboxyl, CrC alkoxycarbonyl, for example acetyl, mono- or di-CrC 4 alkylamino or -SO 3 M.
  • R7 an R 8 is preferably a phenyl or naphthyl group which may be substituted by C C 4 alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, CrC 4 alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy or tert-butoxy, halogen, for example fluorine, chlorine or bromine, C 2 -C 5 alkanoylamino, for example acetylamino, propionylamino or butyrylamino, nitro, sulfo or di- C ⁇ C ⁇ Ikylated amino.
  • C C 4 alkyl for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, CrC
  • 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.
  • R 1 is preferably
  • C C ⁇ alkyl especially methyl or ethyl
  • R 7 and R 8 are each as defined above and are each preferably hydrogen, C C 4 alkyl, especially methyl or ethyl, a morpholino or piperidino radical, most particularly hydrogen, or a radical of the formula — NH wherein R 6 is as defined above and is preferably -SO 3 M substituted C ⁇ -C 4 alkyi, especially methyl- or ethyl-substituted -SO 3 M, wherein M is as defined above and is preferably sodium; and
  • R 2 is preferably —n ⁇ ⁇ o , -NH 2) -N(CH 2 CH 2 OH) 2 or -N[CH 2 CH(OH)CH 3 ] 2 .
  • the compounds of the formula (1) are preparable under known reaction conditions by reacting cyanuric chloride with appropriate aminostilbenesulfonic acids and with an amino compound capable of introducing an Ri group and with a compound capable of introducing an R 2 group, R, and R 2 being as defined above.
  • the stilbene compounds used in the invention have a pronounced antimicrobial action, especially against pathogenic Gram-positive and Gram-negative bacteria.
  • 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 yarn on packages, warp beams, etc.
  • optical brighteners which are useful according to the invention can be incorporated into liquid and solid laundry detergents.
  • 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.
  • 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 condensation 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.
  • 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.
  • 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.
  • Example 1 Wash test a) Formulation of laundry detergent powder used (in per cent of the total weight of the formulation):
  • 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.
  • 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.
  • Example 2 Determination of antimicrobial activitv of Tinopal CBS-X after irradiation with light The optical brightener of the formula
  • the test is used to detect antimicrobial activity by comparison with unirradiated samples.
  • a bacterial mixture of Staphylococcus aureus and Escherichia coli is plated out on the agar (final concentration cfu/ml: ⁇ 10 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.
  • Unirradiated agar plattes including 100 and 500 ppm of Tinopal CBS-X and agar plates without Tinopal are incubated as controls.
  • test germs All plates were incubated at 37°C for about 48 hours. After incubation, viable bacteria are counted (see Table 1). Examples of test germs:
  • the table reports the number of colony-forming units of bacteria after 10 minutes' and 30 minutes' irradiation.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

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 fibre materials, which comprises washing the fibre materials with this laundry detergent and subsequently exposing the washed textile material to a light source.

Description

Use of optical briαhteners from the class of the stilbene compounds as antimicrobiallv active substances
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
(8) , wherein Ri is a radical of the formula — NH-Γ V-corR, ;
R3 is substituted or unsubstituted alkyl or aryl;
R4 is M or substituted or unsubstituted alkyl or aryl;
R5 . is hydrogen; substituted or unsubstituted alkyl or aryl; or -NR7R8, wherein R7 and R8 are independently hydrogen; substituted or unsubstituted alkyl or aryl; or R7 and R8 combine with the joining nitrogen atom to form a heterocyclic radical, especially morpholino or piperidino radical;
R6 is hydrogen or substituted or unsubstituted alkyl or aryl,
R2 is hydrogen; substituted or unsubstituted alkyl or aryl; a radical of the formula — N o,
-OH; -NH2; -N(CH2CH2OH)2; -N[CH2CH(OH)CH3]2l -NH-R4, -N(R4)2 or -OR4; or
R1 and R≥ are independently -OH, -CI; -NH2, -O-C C4alkyl, -O-aryl, -NH-C^alkyl,
-N C^alkyl),,, -N(C1-C4alkyl)(C1-C4hydroxyalkyl), -N(C C4hydroxyalkyl)2, or -NH-aryl, morpholino, S-C^C^alky aryl),
R9 and R10 are independently hydrogen, C C4alkyl, phenyl or a radical of the formula
R is hydrogen, CI or SO3M;
R12 is -CN, -SO3M, -S(C C4alkyl)2 or S(aryl)2;
R13 is hydrogen, -SO3M, -O-C^alkyl, -CN, -CI, -COO-C^alkyl, or CON^-C^alkyl)^
R14 is hydrogen; -Chalky!, -CI or -SO3M;
R15 and R16 are independently hydrogen, C^alkyl, -SO3M, -CI or -O-C^alkyl; R17 is hydrogen or 0,-C^alkyl;
R18 is hydrogen, C1-C4alkyl, -CN, -CI, -COO-C^alkyl, -CON(C1-C4alkyl)2, aryl or -O-aryl;
M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C C4alkylammonium, mono-, di- or tri-CrC hydroxyalkylammonium or ammonium that is di- or trisubstituted with a mixture of C C4aIkyl and C1-C4hydroxyalkyl groups; and n-i, n2 and n3 are independently 0 or 1.
(Substituted or unsubstituted) alkyl R2, R3, R . Rs, Re, R7 and Ra is CrC12alkyl, preferably C C4alkyl. Alkyl may be branched or unbranched and may be substituted by halogen, for example fluorine, chlorine or bromine, Cι-C4alkoxy, for example methoxy or ethoxy, phenyl or carboxyl, CrC alkoxycarbonyl, for example acetyl, mono- or di-CrC4alkylamino or -SO3M.
(Substituted or unsubstituted) aryl R2, R3, R4, R5. Re, R7 an R8 is preferably a phenyl or naphthyl group which may be substituted by C C4alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, CrC4alkoxy, 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- C^C^Ikylated 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), R1 is preferably
a radical of the formula — NH— (( γ— co— R3 , wherein R3 is as defined above and is
preferably C C^alkyl, especially methyl or ethyl; or
a radical of the formula — NH— < " > wherein R5 is as defined above and is
preferably d-C4alkyl, especially methyl or ethyl, or-NR7R8, wherein R7 and R8 are each as defined above and are each preferably hydrogen, C C4alkyl, especially methyl or ethyl, a morpholino or piperidino radical, most particularly hydrogen, or a radical of the formula — NH wherein R6 is as defined above and is preferably -SO3M substituted Cι-C4alkyi, especially methyl- or ethyl-substituted -SO3M, wherein M is as defined above and is preferably sodium; and
R2 is preferably —n ~^o , -NH2) -N(CH2CH2OH)2 or -N[CH2CH(OH)CH3]2.
The compounds of the formula (1) are preparable under known reaction conditions by reacting cyanuric chloride with appropriate aminostilbenesulfonic acids and with an amino compound capable of introducing an Ri group and with a compound capable of introducing an R2 group, R, and R2 being as defined above.
Optical brighteners that are advantageously useful in the present invention are recited below in Table 1 by way of example:
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 yarn 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 condensation 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 per cent of the total weight of the formulation):
8% of alkylbenzenesulfonate
5% of alcohol ether sulfate
2% of alcohol ethoxylate (nonionic)
30% of sodium tripolyphosphate
20% of sodium carbonate
8% of sodium silicate
18.9% of sodium sulfate
1% of enzymes
1 % of polycarboxylates
0.1% of perfume oil
6% of water
b) Preparation of laundry detergent powder which includes Tinopal CBS-X:
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.
c) Wash with the laundry detergent obtained according to b):
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. Example 2: Determination of antimicrobial activitv of Tinopal CBS-X after irradiation with light The optical brightener of the formula
is incorporated in agar plates and subsequently inoculated with bacteria and irradiated with xenon light for 10 minutes or 30 minutes.
The test is used to detect antimicrobial activity by comparison with unirradiated samples.
To this end, a 1.5% stock solution in DMSO is prepared.
0.5 and 0.1 ml of this solution are added to 15 ml of liquid agar (final concentration: 500 and 100 ppm).
After solidification and drying, a bacterial mixture of 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.
All plates were incubated at 37°C for about 48 hours. After incubation, viable bacteria are counted (see Table 1). Examples of test germs:
Bacteria: Staphylococcus aureus ATCC 9144
Escherichia coli NCTC 8196
Cultures 18 to 24 hours in casein soymeal peptone broth diluted 1:5000 (Staph.) and 1:10,000 (E. coli) and mixed together
The results are summarized in Table 1.
The table reports the number of colony-forming units of bacteria after 10 minutes' and 30 minutes' irradiation.
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.

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
Ri is a radical of the formula
R3 is substituted or unsubstituted alkyl or aryl;
R4 is M or substituted or unsubstituted alkyl or aryl;
Rs is hydrogen; substituted or unsubstituted alkyl or aryl; or -NR7R8, wherein R7 and R8 are independently hydrogen; substituted or unsubstituted alkyl or aryl; or R7 and R8 combine with the joining nitrogen atom to form a heterocyclic radical, especially morpholino or piperidino radical;
R6 is hydrogen or substituted or unsubstituted alkyl or aryl, R2 is hydrogen; substituted or unsubstituted alkyl or aryl; a radical of the formula
- ~ > -0h|; _NH2; -N(CH2CH2OH)2; -N[CH2CH(OH)CH3]2, -NH-R4, -N(R4)2 or -OR4;
or R1 and R2 are independently -OH, -CI; -NH2, -O-C^alkyl, -O-aryl, -NH-C^alkyl,
-N(C1-C4alkyl)2, -N(C C4alkyl)(C C4hydroxyalkyl), -N(C C4hydroxyalkyl)2, or -NH-aryl, morpholino, S-C^C^alkyKaryl),
M is hydrogen, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-CrC^lkylammonium, mono-, di- or tri-CrC4hydroxyalkylammonium or ammonium that is di- or trisubstituted with a mixture of d-C4alkyl and C C4hydroxyalkyl groups; and n1 and 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
R9 and R 0 are independently hydrogen, C C alkyl, phenyl or a radical of the formula
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
R., is hydrogen, CI or SO3M;
R12 is -CN, -S03M, -S^-C^alkyl)., or S(aryl)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
wherein
R13 is hydrogen, -SO3M, -O-C C4alkyl, -CN, -CI, -COO-C^alkyl, or
CON(C C4alkyl)2; and n3 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
wherein
R14 is hydrogen, C C4alkyl, CI or -SO3M;
R15 and R are independently hydrogen, 0,-C^alkyl, -SO3M, -CI or -O-C^C^alkyl 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
R17 is hydrogen or C -C4alkyl;
R18 is hydrogen, C C^al yl, -CN, -CI, -COO-C^alkyl, -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.
EP01917048A 2000-03-08 2001-03-01 Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances Withdrawn EP1263919A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01917048A EP1263919A1 (en) 2000-03-08 2001-03-01 Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00104907 2000-03-08
EP00104907 2000-03-08
PCT/EP2001/002315 WO2001066681A1 (en) 2000-03-08 2001-03-01 Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances
EP01917048A EP1263919A1 (en) 2000-03-08 2001-03-01 Use of optical brighteners from the class of the stilbene compounds as antimicrobially active substances

Publications (1)

Publication Number Publication Date
EP1263919A1 true EP1263919A1 (en) 2002-12-11

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US (1) US20030110574A1 (en)
EP (1) EP1263919A1 (en)
AU (1) AU2001244177A1 (en)
BR (1) BR0109039A (en)
MX (1) MXPA02008709A (en)
WO (1) WO2001066681A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003020862A1 (en) * 2001-09-04 2003-03-13 Ciba Specialty Chemicals Holding Inc. Process for inhibiting the dye transfer
EP2993222A1 (en) 2014-09-03 2016-03-09 Tim Bast Detergent composition comprising rare earth metal and a stilbene brightening agent

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
DE2157209A1 (en) * 1971-11-18 1973-05-24 Henkel & Cie Gmbh Antimicrobial treatment of textiles - with synergistic compsn free of halogenated diphenyl urea
IN153407B (en) * 1979-09-28 1984-07-14 Ciba Geigy Ag
DE3100470A1 (en) * 1981-01-09 1982-09-02 Bayer Ag, 5090 Leverkusen "METHOD FOR ANTIMICROBIAL EQUIPMENT OF TEXTILES"
CH657864A5 (en) * 1984-02-17 1986-09-30 Ciba Geigy Ag WATER-SOLUBLE PHTHALOCYANINE COMPOUNDS AND THE USE THEREOF AS PHOTOACTIVATORS.
US4978475A (en) * 1988-02-26 1990-12-18 The Procter & Gamble Company Stable liquid detergents containing anionic surfactant and monosulfonated brightener
DE58903875D1 (en) * 1988-10-13 1993-04-29 Ciba Geigy Ag DISTYRYLBIPHENYL COMPOUNDS.
US5830526A (en) * 1994-12-28 1998-11-03 Fibermark, Inc. Light-activated antimicrobial and antiviral materials
GB9726365D0 (en) * 1997-12-13 1998-02-11 Ciba Sc Holding Ag Compounds

Non-Patent Citations (1)

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Title
See references of WO0166681A1 *

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US20030110574A1 (en) 2003-06-19
BR0109039A (en) 2003-06-03
MXPA02008709A (en) 2003-02-24
WO2001066681A1 (en) 2001-09-13

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