Patent Application
20070258912
The present invention relates to the use of fluorescent whitening agents for whitening and the antimicrobial treatment of surfaces, and preservation of cosmetics, household products, personal care products, textiles, paper and starting materials of paper, plastics and disinfectants.
The present invention concerns the use of fluorescent whitening agent for the whitening of teeth and/or antimicrobial treatment of surfaces, especially teeth.
Preferred is the use of fluorescent whitening agent for the whitening of teeth with the proviso that a fluorescent whitening agent is not covered by a crosslinked polyvinyl alcohol shell.
Further, preferred fluorescent whitening agents are bis-triazinyl-diaminostilbene, 2-(stilbene-4-yl)-naphthatriazole, 2-(4-phenylstilbene-4-yl)benzoxazole, bis(azol-2-yl)stilbene, 1,4-bis(styryl)benzene, 4,4′-bis(styryl)biphenyl, 1,3-diphenyl-2-pyrazoline, bis(benzoxazol-2-yl), bis(benzimidazol-2-yl), 2-(benzofuran-2-yl)-benzimidazole, coumarine, carbostyrile, naphthalimide, quaternized pyridotriazole, pyrene derivatives or acylamino 3,7-diamino-dibenzothiophene-2,8-disulfonic acid 5,5-dioxide.
More preferred fluorescent whitening agents are those of formulae (1) to (20): bis-triazinyl-diaminostilbene of formula (1)
wherein
R1, R2, R3 and R4 are independently from each other NR5R6, OR7 or a heterocyclic ring wherein
R5 and R6 are independently from each other hydrogen; substituted or unsubstituted C6-C10aryl, C1-C10alkyl, N,N′-diC1-C6alkylaminoC1-C10alkyl or a heterocyclic ring, and
R7 is substituted or unsubstituted C6-C10aryl, C1-C10alkyl,
preferably
R1, R2, R3 and R4 are independently from each other substituted or unsubstituted phenyl, NH(C1-C6)alkyl, N,N′-diC1-C2alkylaminoC1-C6alkyl, NH(C1-C6)alkanol, NHphenyl, O(C1-C6)alkyl, NH2, piperidine or morpholino and
R7 is substituted or unsubstituted phenyl, C1-C6alkyl;
more preferably
R1, R2, R3 and R4 are independently from each other unsubstituted aryl; or with SO3H/Na/K, COOR7, CONHR7, CON(R7) substituted aryl; substituted or unsubstituted NH(C1-C6)alkyl, N((C1-C6)alkyl)2, N,N′-diC1-C2alkylaminoC1-C3alkyl, NH(C1-C6)alkanol, N((C1-C6)alkanol)2, NHphenyl, O(C1-C6)alkyl, NH2, piperidine or morpholino and
R7 is substituted or unsubstituted phenyl, C1-C4alkyl;
most preferably
R1, R2, R3 and R4 are independently from each other unsubstituted aryl; or with SO3H/Na/K, COOR7, CONHR7, CON(R7) substituted aryl, substituted or unsubstituted NH(C1-C2)alkyl, N((C1-C2)alkyl)2, N,N′-dimethylaminopropyl, NHethanol, N(ethanol)2, NHphenyl, O(C1-C6)alkyl, NH2, or morpholino and
R7 is substituted or unsubstituted phenyl, C1-C4alkyl;
and SO3H can be the free sulfonic acid or an alkalimetal or earthalkalimetal salt
or
2-(stilbene-4-yl)-naphthatriazole of formula (2)
wherein
R8 and R9 are independently from each other hydrogen, SO3H, CN, halogen;
preferably
R8 and R9 are independently from each other hydrogen, SO3H, CN, or chloride; or
2-(4-phenylstilbene-4-yl)benzoxazole of formula (3)
or
bis(azol-2-yl)stilbene of formula (4)
or
1, 4 or 2,3′ or 2,4′-bis(styryl)benzene of formula (5)
or
4,4-bis(styryl)biphenyl of formula (6)
or
1,3-diphenyl-2-pyrazoline of formula (7)
R10 is SO3H, SO2NR11R12,
wherein
R11 and R12 are each independently from each other hydrogen, (C1-C6)alkyl-N+(C1-C6)alkyl, (C1-C6)alkyl-SO3H;
preferably
R10 is SO3H, SO2NH2, SO2NHCH2CH2CH2N+(CH3)3, SO2NHCH2CH2CH2SO3H,
or
bis-benzoxazole of formula (8)
wherein
R13 and R14 are independently from each other hydrogen; substituted or unsubstituted C6-C10aryl, C1-C10alkyl, 1,2-diphenylvinyl, COO—C1-C10alkyl or SO2—C1-C10alkyl, and
R is —C═C—, 1,2-dipenylvinylen, 1,4-naphthalen or 2,5-thiophenylene,
preferably
R13 and R14 are independently from each other hydrogen; substituted or unsubstituted phenyl, naphthyl, thiophenyl, C1-C16alkyl, 1,2-diphenylvinyl, COO—C1-C6alkyl or SO2—C1-C6alkyl;
or most preferable
or
bis(benzimidazol-2-yl) of formula (9)
wherein
R15 and R16 are independently from each other hydrogen substituted or unsubstituted C1-C16alkyl or phenyl; and
or
2-(benzofuran-2-yl)-benzimidazole of formula (10)
or
coumarines, including 3-phenyl-7-aminocoumarin, 3-phenyl-7-(azol-2-yl)coumarines, 3,7-bis(azolyl)-coumarines, and compounds of formulae (11), (12), (13) or (14)
wherein
R17 and R18 are independently from each other hydrogen or substituted or unsubstituted C1-C6alkyl
wherein
R19 and R20 are independently from each other NR21R22, OR23 or a heterocyclic ring
wherein
R21 and R22 are independently from each other hydrogen; substituted or unsubstituted C6-C10aryl, C1-C10alkyl and
R23 is substituted or unsubstituted C6-C10aryl, C1-C10alkyl;
or
carbostyrile of formula (15)
or
naphthalimide of formula (16)
wherein
R24 is hydrogen or substituted or unsubstituted C1-C16alkyl or phenyl, and
wherein
R25 is hydrogen or substituted or unsubstituted NR26R27, OR28 or a heterocyclic ring
wherein
R26, R27 and R28 have the same definition as R21, R22 and R23 as given above; or quaternized pyridotriazole;
or
pyrene of formula (17)
or
acylamino 3,7-diamino-dibenzothiophene-2,8-disulfonic acid 5,5-dioxide of formula (18)
wherein
R26 and R27 are independently from each other substituted or unsubstituted CO-alkoxybenzoyl, CO—(C1-C6)alkyl, CO-phenyl,
or
bisstyrylbenzol of formula (19)
or
bisstyrylbiphenyl of formula (20)
wherein
X and X′ independently of one another are —COO— or —CON(R31), a direct bond, oxygen, sulfur, —O—C1-C3alkylene-CON(R31)—, —SO2N(R31)—, —O—C1-C3-alkylene-COO— or —OCO—,
Y and Y′ independently of one another are a direct bond, C1-C20alkylene, a direct bond,
Z is pyridine, 2-pyridine-N-methyl, 4-pyridine-N-methyl or N(R28R29(R30)q), and
Z′ is pyridine, 2-pyridine-N-methyl, 4-pyridine-N-methyl or N(R28′R29′(R30)q′),
wherein
R28 and R28′ independently of one another are unsubstituted or substituted C1-C8-alkyl or C3-C4alkenyl, or R28 together with R29, or R28′ together with R29′, is a heterocyclic ring, R29 and R29′ independently of one another are unsubstituted or substituted C1-C8alkyl or C3-C4alkenyl, or R29 together with R28 or R29′ together with R28′, is a heterocyclic ring, or R28 and R29, or R28′ and R29′, together with R30 are a pyridine or picoline ring, R30 is hydrogen, unsubstituted or substituted C1-C4alkyl or C3-C4alkenyl, or together with R28 and R29 or with R28′ and R29′ is a pyridine or picoline ring, R30 is hydrogen or unsubstituted or substituted C1-C6-alkyl,
A− is a colourless anion, and
n and n′ independently of one another are the number 0 or 1, and
m and m′ independently of one another are the number 0 or 1, and
p and p′ independently of one another are the number 0, 1, 2 or 3, and
q and q′ independently of one another are the number 0 or 1, and
the benzene nuclei B and C can also be substituted by non-chromophoric substituents;
preferably,
bisstyrylbenzol of formula (21)
or
bisstyrylbiphenyl of formula (22)
wherein
X1 and X1′ are —COO— or —CONH—, a direct bond, oxygen, sulfur, —OC1-C3alkylene-CONH—, —SO2NH—, —O—C1-C3alkylene-COO— or —OCO—,
Y1 and Y1′ independently of one another are a direct bond, C1-C4alkylene or hydroxypropylene,
Z1 and Z1′ independently of one another are pyridine, 2-pyridine-N-methyl, 4-pyridine-N-methyl or N(R35R36(R37)q″),
wherein
R35 and R36 independently of one another are C1-C4alkyl or together are a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring, or together with R37 are a pyridine or picoline ring,
R37 is hydrogen, C1-C4alkyl, C3-C4alkenyl, C1-C3alkoxycarbonylmethyl, benzyl, C2-C4-hydroxyalkyl or C2-C4cyanoalkyl, or together with R35 and R36 is a pyridine or picoline ring,
R32 is hydrogen, chlorine, C1-C4alkyl, C3-C4alkenyl, C1-C3alkoxy, or (X1)m—Y1—N(R35R36(R37)q—), or together with R33 is a trimethylene or tetramethylene group,
R33 is hydrogen, chlorine, C1-C4alkyl or C1-C3alkoxy, or together with R32 is a trimethylene or tetramethylene group,
R34 is hydrogen, chlorine or methyl,
n1 and n1′ independently of one another are the number 0 or 1,
m1 and m1′ independently of one another are the number 0 or 1, and
p1 and p1′ independently of one another are the number 0, 1, 2 or 3, and
q″ is the number 0 or 1, and
A- is a colourless anion;
and
more preferred are bisstyrylbenzol of formula (40)
or
bisstyrylbiphenyl of formula (41)
bisstyrylbenzol of formula (42)
or
bisstyrylbiphenyl of formula (43)
wherein
X4 is oxygen, sulfur,
Y4 is a direct bond C1-C4alkylene,
Z4 is N(R40R41(R42)q4),
wherein
R40 and R41 independently of one another are C1-C4alkyl or together are a pyrrolidine, piperidine, hexamethyleneimine or morpholine ring, or together with R42 are a pyridine or picoline ring,
R42 is hydrogen or C1-C4alkyl,
R33 is hydrogen, chlorine, C1-C4alkyl or C1-C3alkoxy,
R34 is hydrogen, chlorine or methyl,
q4 is the number 0 or 1.
Further,
more preferred fluorescent whitening agents are those of formulae (1) to (4) and (7) to (10), (15), (17) to (20), within the above given definitions and preferences.
Most preferred fluorescent whitening agents are compounds of formulae (23) to (34)
Especially preferred fluorescent whitening agents are compounds of formulae (26) and (28).
In the present invention one or more of the same or different substitutent chosen from the following group of substituents are for example suitable C1-C16alkyl, C1-C20alkylene, arylene or aryl-C1-C10alkylene, hydroxyl, C1-C8alkoxy, cyanide, halide, aryl, aralkyl, alkylaryl and NR40R41, wherein
R40 and R41 are each independently of the other hydrogen, unsubstituted or substituted aryl radical or C1-C6alkyl; or C1-C8alkyl, C1-C8alkoxy, cyanide and/or halide.
Preferred are R40 and R42 hydrogen or unsubstituted C1-C6alkyl.
Heterocyclic ring are an unsubstituted or substituted aromatic or non aromatic ring, such as for example thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, picoline, pyrazolyl, benzimidazolyl, benzopyrazolyl, morpholino, pyrrolidine, piperidine, hexamethyleneimine, 2-pyridine-N-methyl, 4-pyridine-N-methyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether or azobenzenyl.
Aryl is, for example, unsubstituted or substituted phenyl or naphthyl,
The substituted or unsubstituted alkylene or alkyl residues may be straight-chain, branched, or, from C5alkyl upwards, monocyclic or polycyclic, and may be uninterrupted or interrupted by hetero atoms, such as such as O, S, CO, N, NH, NR40; for example C1-C10alkylene may be a residue such as:
—CH2CH2—O—CH2CH2—O—CH2CH2—, or —CH2CH2—O—CH2CH2—, or —CH2CH2—O—CH2—, or
—CH2—O—CH2—, or —CH2CH2—CH2CH2—O—CH2—CH2—, or —CH2CH2—CH(N(CH3)2)—CH2—CH2—, or
CH2—NH2—CH2—CH2.
C1-C16alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tredecyl, tetradecyl, pentadecyl, hexadecyl.
C1-C10alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl, nonyl, decyl.
C1-C8alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1,1′,3,3′-tetramethylbutyl or 2-ethylhexyl.
C1-C6alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2′-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl.
C1-C4alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl.
NH(C1-C6)alkyl is, for example, NH-methyl, NH-ethyl, NH-propyl, NH-isopropyl, NH-n-butyl, NH-sec-butyl, NH-tert-butyl, NH-n-pentyl, NH-2-pentyl, NH-3-pentyl, NH-2,2′-dimethylpropyl, NH-cyclopentyl, NH-cyclohexyl, NH-n-hexyl.
NH(C1-C6)alkanol is, for example, NH-methanol, NH-ethanol, NH-propanol, NH-isopropanol, NH-n-butanol, NH-sec-butanol, NH-tert-butanol, NH-n-pentanol, NH-2-pentanol, NH-3-pentanol, NH-2,2′-dimethylpropanoyl, NH-cyclopentanol, NH-cyclohexanol, NH-n-hexanol.
N,N′-diC1-C6alkylaminoC1-C10alkyl is for example N,N′-dimethylaminomethyl, N,N′-diethylaminomethyl, N,N′-dimethylaminoethyl, N,N′-dipropylaminomethyl, N,N′-dipropylaminomethyl, N,N′-dipropylaminopropyl, N,N′-diisopropylaminomethyl, N,N′-diisopropylaminoetyl, N,N′-diisopropylaminopropyl or N,N′-dihexylaminomethyl, N,N′-dioctylaminoetyl, N,N′-dinonylaminopropyl.
N,N′-diC1-C2alkylaminoC1-C6alkyl is for example N,N′-dimethylaminomethyl, N,N′-diethylaminomethyl, N,N′-dimethylaminoethyl, N,N′-dimethylaminomethyl, N,N′-dimethylaminoisopropyl, N,N′-dimethylaminobutyl, N,N′-dimethylaminopentyl, N,N′-dimethylaminohexyl.
O-alkyl is the same as alkoxy and stands preferably for O(C1-C8)alkyl, O(C1-C6)alkyl, O(C1-C3)alkyl.
O(C1-C8)alkyl is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2′-dimethylpropoxy, cyclopentoxy, cyclohexoxy, n-hexoxy, n-heptoxy or n-octoxy.
O(C1-C6)alkyl is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2′-dimethylpropoxy, cyclopentoxy, cyclohexoxy, n-hexoxy.
O(C1-C3)alkyl is, for example, methoxy, ethoxy, propoxy, isopropoxy.
C1-C6alkanol is, for example, methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, 2-pentanol, 3-pentanol, 2,2′-dimethylpropanol, cyclopentanol, cyclohexanol, n-hexanol.
C1-C20alkylene is, for example, methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 2-pentylene, 3-pentylene, 2,2′-dimethylpropylene, cyclopentylene, cyclohexylene, n-hexylene, n-octylene, 1,1′,3,3′-tetramethylbutylene or 2-ethylhexylene, nonylene, decylene, undecylene, dodecylene, tredecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, ocatdecylene, nonadecylene.
C1-C4alkylene is, for example, methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, tert-butylene.
C1-C3alkylene is, for example, methylene, ethylene, propylene, isopropylene.
C3-C4alkenyl is, for example, propenyl, isopropenyl, n-butenyl, sec-butenyl, tert-butenyl.
Halogen is, for example, fluoride, chloride, bromide or iodide, especially chloride and fluoride.
A− is a colourless anion such as for example an organic or inorganic anion, such as halide, preferably chloride and fluoride, sulfate, hydrogen sulfate, phosphate, boron tetrafluoride, carbonate, bicarbonate, oxalate or C1-C8alkyl sulfate, especially methyl sulfate or ethyl sulfate; anion also denotes lactate, formate, acetate, propionate or a complex anion, such as the zinc chloride double salt.
The anion is especially a halide, preferably chloride or fluoride, sulfate, hydrogen sulfate, methylsulfate, phosphate, formate, acetate or lactate.
The anion is more especially fluoride, chloride, methyl sulfate, formate or acetate.
Teeth stand in the context of the present invention for natural or imitated teeth.
Teeth has the meaning of tooth and teeth.
In the context of the present invention fluorescent whitening agents encompass all fluorescent whitening agents known in the prior art. The definitions and preferences of fluorescent whitening agents given in the present invention are identical for the compositions comprising fluorescent whitening agents, and their uses.
The fluorescent whitening agents used according to the invention exhibit a marked antimicrobial effect, in particular against pathogenic Gram-positive and Gram-negative bacteria and also against skin flora bacteria. They are therefore suitable, in particular, for the disinfection, deodorization, and also the general and antimicrobial treatment of the skin and mucosae, and skin appendages (hair), very particularly for hand and wound disinfection. They are therefore suitable as antimicrobial active substances and preservatives in bodycare compositions, such as, for example, shampoos, tooth past, bath products, haircare compositions, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist cleansing wipes, oils or powders.
The invention therefore further provides a bodycare composition comprising at least one compound of the formula (1) and cosmetically acceptable carriers or auxiliaries.
The bodycare composition according to the invention comprises 0.01 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the composition, of fluorescent whitening agents and cosmetically acceptable auxiliaries.
Tooth paste according to the invention comprises 0.01 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the composition, of fluorescent whitening agents and cosmetically acceptable auxiliaries.
Depending on the form in which the bodycare composition is present, as well as the fluorescent whitening agents, it also has further constituents, such as, for example, sequestering agents, dyes, perfume oils, thickening or setting agents (consistency regulators), emollients, UV-absorbers, skin protectants, antioxidants, additives which improve the mechanical properties, such as dicarboxylic acids and/or Al, Zn, Ca, Mg salts of C14-C22 fatty acids and optionally preservatives.
The bodycare composition according to the invention can be formulated as a water-in-oil emulsion or oil-in-water emulsion, as an alcoholic or alcohol-containing formulation, as a vesicular dispersion of an ionic or nonionic amphiphilic lipid, as a gel, solid stick or as an aerosol formulation.
As a water-in-oil or oil-in-water emulsion, the cosmetically acceptable auxiliary preferably comprises 5 to 50% of an oil phase, 5 to 20% of an emulsifier and 30 to 90% of water. The oil phase can comprise any oil suitable for cosmetic formulations, such as, for example, one or more hydrocarbon oils, a wax, a natural 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.
Cosmetic formulations according to the invention are used in various fields. In particular, the following compositions, for example, are considered:
An antimicrobial, whitening soap has, for example, the following composition:
A shampoo has, for example, the following composition:
A deodorant has, for example, the following composition:
The invention further provides an oral composition comprising 0.01 to 15% by weight, based on the total weight of the composition, of the compound of the formula (1) and orally acceptable auxiliaries.
Example of an oral composition:
The oral composition according to the invention can be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).
In addition, the oral composition according to the invention can comprise compounds which release fluoride ions, which are effective against the formation of caries, e.g. inorganic fluoride salts, such as, for example, sodium fluoride, potassium fluoride, ammonium fluoride or calcium fluoride, or organic fluoride salts, such as, for example, amine fluorides, which are known under the trade name Olafluor.
In addition, the benzyl alcohol derivatives of the formula (1) used according to the invention are suitable for the treatment, in particular preservation, of textile fibre materials. The fibre materials are undyed and dyed or printed and are made of, for example, silk, wool, polyamide or polyurethanes, and in particular cellulosic fibre materials of all types. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, and also regenerated cellulose. Preferred suitable textile fibre materials are made of cotton.
The fluorescent whitening agents are also suitable for the treatment, in particular for the antimicrobial finishing or preservation, of plastics, such as, for example, polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex etc. Fields of use for these are, for example, floor coverings, plastic coatings, plastic container and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains; sponges, bathroom mats), latex, filter materials (air and water filters), plastic articles used in the medical sector, such as, for example, bandaging materials, syringes, catheters etc., so-called medical devices, gloves and mattresses.
Paper too, such as, for example, hygiene papers, can be antimicrobially finished with the benzyl alcohols according to the invention.
In addition, nonwovens, such as, for example, nappies, sanitary towels, panty liners, wipes for the hygiene and household sector, can be antimicrobially finished according to the invention.
In addition, the fluorescent whitening agents are used in washing and cleaning formulations, such as, for example, in liquid and powder detergents or fabric softeners.
The fluorescent whitening agents can be used, in particular, also in household and all-purpose cleaners for the cleaning, whitening and disinfection of hard surfaces. A cleaner has, for example, the following composition:
As well as the preservation and whitening of cosmetics and household products, the whitening, preservation and antimicrobial finishing of technical products and also use as biocide in technical processes is also possible, such as, for example, in the treatment of paper, in particular in paper-treatment liquors, printing thickeners made of starch or cellulose modifications, surface coatings and paints.
The fluorescent whitening agents are also suitable for the antimicrobial treatment of wood and also for the antimicrobial treatment, preservation and finishing of leather.
In addition, the compounds according to the invention are suitable for protecting cosmetic products and household products against microbial decay.
The fluorescent whitening agents which can be used according to the invention are known compounds.
Solution A: 0.5% by weight of compound of formula (26) is solved in 100 g anhydrous ethanol.
Solution B: 0.1 g % by weight of compound of formula (26) is solved in 100 g anhydrous ethanol.
Solution C: 0.01% by weight of compound of formula (26) is solved in 100 g anhydrous ethanol.
Process a):
The hydroxyapatite substrate (seize ⅜″×0.06″, supplier Clarkson Chemical Co., USA) is given in the solution A (as given above), for 5 minutes. Then the hydroxyapatite substrate is taken out of the solution, shaken for removing the remaining solution and then dried at room temperature for 2 hours. For analytical purpose the hydroxyapatite substrate is then washed with distilled waster and dried in the air at room temperature for 18 hours.
Process b):
The process a) is repeated, with the proviso the solution A is exchanged by solution B.
Process c):
The process a) is repeated, with the proviso the solution A is exchanged by solution C.
The fluorescence of the hydroxyapatite substrate prepared according to example 1 is determined with UV-light (254 nm). There is a fluorescence visible on the substrate. The intensity of the fluorescence is proportional to the used concentration of the solution A, B or C. The fluorescent whitening agent has affinity to the hydroxyapatite substrate since fluorescence is visible though the substrate is washed.
For evaluating the whiteness, the whiteness of the treated hydroxyapatite substrate is determined and than compared with that of the untreated hydroxy apatith substrate. There is a significant whitening visible, which is proportional to the used concentration of the solution A, B or C.
Test Principle:
1% stock solutions of the substances are prepared in an appropriate solvent and diluted in serial dilutions 1:2 (to yield end concentrations in the agar of 500-1.9 ppm). 0.3 ml of each dilution step is mixed with 15 ml of nutrient medium while the latter is still liquid. After the nutrient medium has solidified, 10 μl of each test strain in 0.85% NaCl solution are spotted onto the agar medium.
The plates are incubated at 37° C. for 24 hours and then the highest dilution (lowest concentration) of the test substance at which growth is no longer observable is determined.
Test Organisms:
Staphylococcus aureus ATCC 6583
Staphylococcus epidermidis ATCC 12228
Corynebacterium xerosis ATCC 373
Propionibacterium acnes ATCC
Escherichia coli ATCC 10536
Salmonella choleraesuis ATCC
Klebsiella pneumoniae ATCC
*Candida albicans ATCC 10231
*Aspergillus niger ATCC 6275
Test Principle:
1500 ppm stock solutions of the substances are prepared in ethanol and pipetted into the growth medium to yield concentrations between 0.94 and 15 ppm. Bacteria are taken from blood agar plates with cotton swabs and adjusted in the appropriate growth medium to yield an optical density corresponding to McFarland 0.5. This suspension is directly used in the case of F. nucleatum and P. nigrescens. For the other strains, the suspension is diluted 1:20. 0.1 ml of these bacterial suspensions are added to 2 ml of the substance solutions. After the incubation time, the tubes are assessed for growth (turbidity).
Test Organisms:
*Actinobacillus actinomycetemcomitans ATCC 43718
*Stretococcus gordonii ATCC 10558
*Streptococcus mutans ATCC 33402
Actinomyces viscosus ATCC 43146
Fusobacterium nucleatum subsp. polymorphum ATCC 10953
Porphyromonas gingivalis ATCC 33277
Prevotella nigrescens ATCC 33563
Test Principle:
1 g stock solution with an appropriate concentration of test products are mixed with 8 g water and then inoculated with 1 ml of the selected test organisms. After a given contact period, aliquots are taken, inactivated and diluted. The number of surviving bacteria per ml incubation assay is determined by plate count. Proper inactivation by the inactivating medium used was checked each time.
Diluent: tryptone water for microorganisms
Incubation time: 24 h at 37° C.
Test Principle:
Hydroxyapatite discs are incubated in artificial saliva (German Dental Magazine DZZ 5/2002) for 4 hrs under stirring, rinsed in NaCl, dried over night, and then incubated in ethanolic solutions of the test substances. Then all treated discs are put in 12 well Nucleon surface titre plates (one disc per well), and Caso Broth inoculated with the test strain. The titre plates are incubated at 37° C., samples are taken after 6 and 24 hrs and the colony count is determined by plate count.
The illustrations show the growth inhibition of Actinomyces viscosus by the bis-styryl benzenes of formula (24) and (33) after adsorption of the substances on hydroxyapatite discs, that were pretreated with artificial saliva in comparison to an untreated control.
| Number | Date | Country | Kind |
|---|---|---|---|
| 0410380.8 | Aug 2004 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/53780 | 8/3/2005 | WO | 2/6/2007 |
