DE102020215677A1 - Photoactivated bleach for detergents - Google Patents

Abstract

Photoexcitable chemical compounds having the following properties:shows a maximum of absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm;has a molar attenuation coefficient in the range from 100 m2mol-1 to 100 000 m2mol-1;has a triplet energy in the range from has a singlet-triplet transition quantum yield in the range of 5% to 100%; has a reduction potential versus a standard ferrocene electrode in the range of -0.5V to -4V; exhibits an excited state redox potential in the range of +0.1 V to +11 V; andhas a water solubility of 4 mg/l to 1000 g/l.are suitable for enhancing the bleaching effect of detergents when used in aqueous washing liquids for washing soiled textiles.

Description

The present invention relates to detergent compositions containing a photoactivator which is effective as an oxidative bleaching agent on irradiation. The present invention also relates to the photoactivator substances and methods of cleaning and/or bleaching textiles using the photoactivators.

Detergents often include ingredients that act on stains and soils to be removed from fabrics via oxidation reactions. Common examples of such bleach oxidants are hydrogen peroxide, which can be used mainly in liquid detergents, and sodium percarbonate, which can be used mainly in solid detergent formulations. The bleaching power of these oxidizing agents is regularly increased by so-called bleach activators, for example by substances that react with the bleaching agents to form more reactive species, such as organic peroxoacids. Detergent manufacturers have always strived to develop bleaching systems that are less susceptible to deactivation during storage and cause less oxidative damage to other detergent ingredients.

From the international patent application WO 2015/112671 A1 are consumer product compositions containing water-soluble organic photoactivators such as 1,1-biphenyl-4,4'-diamine, 1,1'-biphenyl-4-amine, benzophenone, 1,1'-biphenyl-4,4'-diol, 1, 1'-biphenyl-4-amine, 1,1'-biphenyl-4-ol, 1,1':2',1"-terphenyl, 1,1':3',1"-terphenyl, 1,1':4',1":4",1"'-quaterphenyl,1,1':4',1''-terphenyl, 1,10-phenanthroline, 1,1'-biphenyl, 1,2,3,4 -Dibenzanthracene, 1,2-Benzenedicarbonitrile, 1,3-Isobenzofuranedione, 1,4-Naphtoquinone, 1,5-Naphthalenediol, 10H-Phenothiazine, 10H-Phenoxazine, 10-Methylacridone, 1-Acetonaphthone, 1-Chloroanthraquinone, 1-Hydroxyanthraquinone , 1-naphthalenecarbonitrile, 1-naphthalenecarboxaldehyde, 1-naphthalenesulfonic acid, 1-naphthalenol, 2(1H)-quinolinone, 2,2'-biquinoline, 2,3-naphthalenediol, 2,6-dichlorobenzaldehyde, 21H,23H-porphine, 2 -aminoanthraquinone, 2-benzoylthiophene, 2-chlorobenzaldehyde, 2-chlorothioxanthone, 2-ethylanthraquinone, 2H-1-benzopyran-2-one, 2-methoxythioxanthone, 2-methyl-1,4-naphthoquinone, 2-methyl-9(10 -methyl)-acridinone, 2-methylanthraquinone n, 2-Methylbenzophenone, 2-Naphthalenamine, 2-Naphthalenecarboxylic acid, 2-Naphthalenol, 2-Nitro-9(10-methyl)-acridinone, 9(10-ethyl)-acridinone, 3,6-acridinediamine, 3,9- Dibromoperylene, 3,9-dicyanophenanthrene, 3-benzoylcoumarin, 3-methoxy-9-cyanophenanthrene, 3-methoxythioxanthone, 3'-methylacetophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-bromobenzophenone, 4-chlorobenzophenone , 4'-Fluoroacetophenone, 4-Methoxybenzophenone, 4'-Methylacetophenone, 4-Methylbenzaldehyde, 4-Methylbenzophenone, 4-Phenylbenzophenone, 6-Methylchromanone, 7-(Diethylamino)coumarin, 7H-Benz[de]anthracene-7-one, 7H-Benzo[c]xanthen-7-one, 7H-Furo[3,2-g][1]benzopyran-7-one, 9(10H)-acridinone, 9(10H)-anthracenone, 9(10-methyl )-acridinone, 9(10-phenyl)-acridinone, 9,10-anthracenedione, 9-acridinamine, 9-cyanophenanthrene, 9-fluorenone, 9H-carbazole, 9H-fluoren-2-amine, 9H-fluorene, 9H-thioxanthene -9-ol, 9H-thioxanthen-9-one, 9H-thioxanthen-2,9-diol, 9H-xanthen-9-one, acetophenone, acridene, acridine, acridone, anthracene, anthraquinone, anthrone, α-tetralone, benz[a]anthracene, benzaldehyde, benzamide, benzo[a]coronene, benzo[a]pyrene, benzo[f]quinoline, benzo[ghi]perylene, benzo[rst]pentaphene, benzophenone, 2, 3,5,6-Tetramethylbenzoquinone, chrysene, coronene, dibenz[a,h]anthracene, dibenzo[b,def]chrysene, dibenzo[c,g]phenanthrene, dibenzo[def,mno]chrysene, dibenzo[def,p] chrysene, DL-tryptophan, fluoranthene, fluoren-9-one, fluorenone, isoquinoline, methoxycoumarin, methylacridone, Michler's ketone, naphthacene, naphtho[1,2-g]chrysene, N-methylacridone, p-benzoquinone, 2,3,5 ,6-Tetrachloro-p-benzoquinone, pentacene, phenanthrene, phenanthrenequinone, phenanthridine, phenanthro[3,4-c]phenanthrene, phenazine, phenothiazine, p-methoxyacetophenone, pyranthrene, pyrene, quinoline, quinoxaline, riboflavin 5'-(dihydrogen phosphate) , thioxanthone, thymidine, xanthen-9-one, xanthone and derivatives thereof are known.

We have now found that when optimizing a photoactivated oxidative bleaching system that can be used in fabric laundering, certain chemical compound parameters need to be considered. According to our invention, relevant parameters are the wavelength of maximum absorption of electromagnetic radiation, the molar attenuation coefficient, the triplet energy, the singlet-triplet transition quantum yield, the reduction potential of the ground state and the redox potential of the excited state.

A first aspect of the invention relates to a photoexcitable chemical compound with the following properties: it shows a maximum in the absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm; it has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 100,000 m ² mol ^-1 ; it has a triplet energy in the range of 1.5 eV to 5 eV; it has a singlet-triplet transition quantum yield ranging from 5% to 100%; it exhibits a ground state reduction potential relative to a standard ferrocene electrode in the range of -0.5V to -4V on; it has an excited state redox potential in the range of +0.1 V to +11 V; and it has a solubility in water of pH 6.3 at 20°C from 4 mg/l to 1000 g/l.

Absorption occurs when energy from an electromagnetic radiation source is absorbed by a material. Absorption is determined by measuring the energy fraction transmitted through the material. Depending on the nature of the chemical compounds that form the material, the fraction of the incident radiation absorbed by the material is typically not the same for all wavelengths over a range of wavelengths. Radiation is more likely to be absorbed at wavelengths that correspond to the energy difference between two quantum mechanical states of the irradiated molecules. For most chemical compounds there is a specific wavelength (λ _max ) of strongest absorption of electromagnetic radiation. It can be determined by known spectroscopic methods, the radiation intensity being measured after passing through a sample of the material and being compared with the radiation intensity before passing through the sample. A compound according to the invention shows a maximum of the absorption of electromagnetic radiation in the wavelength range from 200 nm to 700 nm, preferably in the range from 300 nm to 500 nm.

In quantum mechanics, a triplet is a quantum state of a system with a spin of quantum number 1, so there are three allowed values of the spin component, -1, 0, and +1. In a system with two electrons that are spin 1/2 particles, each particle can be either spin up or spin down measured on a given axis. This system can have the three states top-top, top-bottom=bottom-top and bottom-bottom. According to the Pauli exclusion principle, a pair of electrons in the same energy level must have opposite spins, two electrons in the triplet quantum state cannot have the same energy level. From a singlet ground state, absorption of energy from electromagnetic radiation leads to a singlet excited state in which both electrons still have opposite spins. Via Intersystem Crossing (ISC), the system enters the triplet excited state, in which two unpaired electrons have the same spin. The triplet energy is the lowest vibrational energy level of the system in the cold triplet state. A compound according to the invention has a triplet energy in the range from 1.5 eV to 5 eV, preferably in the range from 1.5 eV to 4.5 eV.

The molar attenuation coefficient (ε) is a measure of how much a chemical compound attenuates light at the wavelengths of maximum absorption. It is defined as the molar concentration of the compound times the length of path the radiation travels through the compound sample divided by the absorbance. A compound ^according to the invention has a molar attenuation coefficient in the range from 100 m ² mol ^-1 to 100,000 m ² mol ^-1 , preferably in the range from 100 m ² mol ^-1 to 10,000 m ² mol ^-1 .

The quantum yield (Φ) is the probability that a certain quantum state will be formed from the system originally produced in another quantum state. Accordingly, the quantum yield of the singlet-triplet transition (Φ _1-3 ) is the fraction of molecules that transition from a singlet state to the triplet state after photoexcitation. You can by triplet determination, z. B. quenching with triplet atmospheric oxygen. A compound of the invention exhibits a singlet-triplet transition quantum yield in the range of 5% to 100%, preferably in the range of 50% to 100%.

Reduction potentials can easily be determined by cyclic voltammetry or other electrochemical methods. Conveniently, reduction potentials are defined relative to a reference electrode. Reduction potentials of aqueous solutions are determined by measuring the potential difference between an inert measuring electrode in contact with the solution and a stable reference electrode (e.g. ferrocene or standard H electrode). A compound of the invention has a reduction potential versus a standard ferrocene electrode in the range of -0.5V to -4V, preferably in the range of -0.5V to -2.5V.

The excited-state redox potential can be measured by phase-modulated voltammetry or calculated from the sum of the ground-state redox potential and the excitation energy or triplet energy. A compound of the invention has an excited state redox potential in the range of -1V to +11V, preferably in the range of +0.1V to +2.5V.

A chromophore with such photochemical properties is preferably attached to a functional group that provides water solubility in the required range. Suitable functional groups are, for example, carboxylic acid groups, sulfonic acid groups or phosphonic acid groups, which can be present in acid form or in the form of their sodium, potassium or ammonium salts. Photoexcitable chemical compounds according to the invention may comprise one or more such functional groups, where the functional group is attached directly to the chromophore or is attached via a spacer, for example an alkylene group. The presence of one or more such functional groups provides the photoexcitable chemical compounds of the invention preferably with a water solubility of from 4 mg/l to 1000 g/l, more preferably from 5 mg/l to 150 g/l in water with a pH value of 6, 3 ready at 20 °C.

ausgewählt,
wobei R¹ für eine Alkylengruppe mit 1 bis 20 C-Atomen, vorzugsweise 2 bis 6 C-Atomen, und R² und R³ unabhängig voneinander für eine optional substituierte aromatische Gruppe stehen. R² und R³ können auch verbunden sein, um nur eine aromatische Gruppe auszubilden, wie eine Benzol- oder eine Naphthalengruppe. Unter den letztgenannten Verbindungen werden Derivate von 1,8-Naphthalimid (ebenfalls bekannt als Benzo[de]isochinolin-1,3-dion) bevorzugt. Optionale Substituenten der aromatischen Gruppen werden vorzugsweise aus Halogenen ausgewählt. In Verbindungen der Formel I kann die an R¹ gebundene Carbonsäuregruppe auch in ihrer Salzform vorliegen, beispielsweise als Natrium-, Kalium- oder Ammoniumsalz.Suitable photoexcitable chemical compounds that meet the above parameters are preferably selected from the compounds of general formula I,

selected,
where R ¹ is an alkylene group having 1 to 20 carbon atoms, preferably 2 to 6 carbon atoms, and R ² and R ³ are each independently an optionally substituted aromatic group. R ² and R ³ can also be linked to form only one aromatic group, such as a benzene or a naphthalene group. Among the latter compounds, derivatives of 1,8-naphthalimide (also known as benzo[de]isoquinoline-1,3-dione) are preferred. Optional substituents on the aromatic groups are preferably selected from halogens. In compounds of the formula I, the carboxylic acid group attached to R ¹ can also be in its salt form, for example as the sodium, potassium or ammonium salt.

und

Preferred photoexcitable chemical compounds include

and

The compounds identified above can be prepared by general aromatic substitution chemistry.

A further aspect of the present invention is the use of the photoexcitable chemical compounds defined above for enhancing the bleaching action of detergents when used in aqueous wash liquors for washing soiled fabrics.

Yet another aspect of the invention is a method of washing soiled fabrics in an aqueous wash liquor comprising a surfactant and a photoexcitable chemical compound as defined above, wherein the aqueous wash liquor is irradiated with electromagnetic radiation of a wavelength range that includes Amax of the photoexcitable chemical compound .

The washing liquid used in the method according to the invention and in the application aspects is preferably irradiated with electromagnetic radiation with wavelengths from 250 nm to 700 nm, in particular from 300 nm to 500 nm. Such electromagnetic radiation can be generated, for example, by blue, purple light and UV LEDs. The device generating the electromagnetic radiation is preferably located inside a washing machine. In one embodiment of the invention, a portion of the washing liquid comprising the photoexcitable chemical compound is flowed continuously or intermittently through a tube containing the source of electromagnetic radiation inside it. The device that generates the electromagnetic radiation can preferably be switched off and on again during the wash cycle, taking into account that the increased bleaching power is not required for the entire time.

The use according to the invention and the method according to the invention are preferably carried out at temperatures in the range from 10.degree. C. to 95.degree. C., in particular 20.degree. C. to 60.degree. C. and particularly preferably at temperatures below 40.degree. The water hardness of the water used for the production of the aqueous liquid is preferably in the range from 0°dh to 21°dh, in particular 0°dh to 3°dh. The water hardness in the washing liquid is preferably in the range from 0°dh to 23°dh, in particular 0°dh to 6°dh, which can be achieved, for example, by using conventional builder substance materials or water softeners. The use according to the invention and the method according to the invention are preferably carried out at pH values in the range from pH 2 to pH 13 and in particular from pH 7 to pH 11.

The concentration of the photoexcitable chemical compound in the aqueous washing liquid is preferably in the range from 1 µmol/l to 30,000 µmol/l and in particular from 5 µmol/l to 10,000 µmol/l, more preferably from 7 µmol/l to 7500 µmol/l and even more preferably from 10 µmol/l to 5000 µmol/l. The photoexcitable chemical compound can be introduced into the wash liquid in addition to a conventional detergent; preferably, however, it can be part of the detergent used in the method of the invention and within the scope of the use of the invention. Thus a further aspect of the invention is a laundry detergent comprising a photoexcitable chemical compound as defined above.

In addition to the photoexcitable chemical compound, which is preferably present in the detergent in amounts of from 0.01% by weight to 50% by weight and in particular from 0.03% by weight to 25% by weight, a laundry detergent, used within the scope of the present invention include conventional ingredients compatible with that component.

Laundry detergents, which can be present in particular in the form of powdered solids, in post-compacted particle form or preferably as liquids, more preferably aqueous liquids, can in principle comprise all known ingredients customary in such detergents in addition to the active ingredient used according to the invention. The agents according to the invention can include in particular builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries such as optical brighteners, graying inhibitors, foam regulators, dyes and fragrances. The detergents are preferably free from peroxygen-based bleaching agents and customary bleach activators.

The detergents preferably comprise one or more surfactants, it being possible in particular to use anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and/or propoxylation products of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. It is also possible to use corresponding ethoxylation and/or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to the long-chain alcohol derivatives described with regard to the alkyl moiety, and of alkylphenols having 5 to 12 carbon atoms in the alkyl group.

in der R¹CO einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen bezeichnet, R² Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen bezeichnet und [Z] einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen bezeichnet.Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, especially primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position, or linear and methyl branched residues in the mixture, such as are commonly present in oxo alcohol residues. In particular, however, preference is given to alcohol ethoxylates which comprise linear groups from alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol and an average of 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The levels of ethoxylation given represent statistical averages equivalent to an integer or fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. Especially in detergents for use in mechanical operations, highly foamable compounds are generally used. These preferably include C ₁₂ -C ₁₈ alkyl polyethylene glycol/polypropylene glycol ethers each having up to 8 moles of ethylene oxide and propylene oxide units in the molecule. It is also possible to use other known low-foaming nonionic surfactants such as C ₁₂ -C ₁₈ alkyl polyethylene glycol/polybutylene glycol ethers each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule, and end-capped alkyl polyalkylene glycol mixed ethers. The alkoxylated alcohols containing hydroxyl groups, which are known as hydroxy mixed ethers, are also particularly preferred. The nonionic surfactants also include alkyl glycosides of the general formula RO(G) _x , where R is a primarily straight-chain or methyl-branched, especially methyl-branched in the 2-position, aliphatic group having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose moiety 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of mono- and oligoglycosides, is any number which, as a variable to be determined analytically, can also assume fractional values between 1 and 10; x is preferably 1.2 to 1.4. Polyhydroxy fatty acid amides of the formula are also suitable

wherein R ¹ CO denotes an aliphatic acyl group having 6 to 22 carbon atoms, R ² denotes hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] denotes a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups .

in der R³ einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen bezeichnet, R⁴ eine lineare, verzweigte oder cyclische Alkylengruppe oder eine Arylengruppe mit 2 bis 8 Kohlenstoffatomen bezeichnet und R⁵ eine lineare, verzweigte oder cyclische Alkylgruppe oder eine Arylgruppe oder eine Oxyalkylgruppe mit 1 bis 8 Kohlenstoffatomen bezeichnet, wobei C₁-C₄-Alkyl- oder Phenylgruppen bevorzugt werden, und [Z] eine lineare Polyhydroxyalkylgruppe bezeichnet, deren Alkylkette mit mindestens zwei Hydroxylgruppen oder alkoxylierten, vorzugsweise ethoxylierten oder propoxylierten Derivaten dieser Gruppe substituiert ist. [Z] wird wiederum bevorzugt durch reduktive Aminierung eines Zuckers, wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können in der Gegenwart eines Alkoxids als der Katalysator in die erwünschten Polyhydroxyfettsäureamide umgewandelt werden, indem diese Verbindungen mit Fettsäuremethylestern umgesetzt werden. Eine weitere Klasse von nichtionischen Tensiden, die bevorzugt verwendet wird, die entweder als das alleinige nichtionische Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, verwendet werden können, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Cocoalkyl-N-N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und vom Typ der Fettsäurealkanolamide können ebenfalls geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Weitere mögliche Tenside sind sogenannte Gemini-Tenside. Darunter werden allgemein Verbindungen verstanden, die pro Molekül zwei hydrophile Gruppen umfassen. Diese Gruppen sind in der Regel durch einen sogenannten „Spacer“ voneinander getrennt. Dieser Spacer ist im Allgemeinen eine Kohlenstoffkette, die lang genug sein sollte, damit die hydrophilen Gruppen genügend Abstand voneinander haben, um unabhängig voneinander wirken zu können. Solche Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich niedrige kritische Micellenkonzentration und die Fähigkeit aus, die Oberflächenspannung des Wassers drastisch zu reduzieren. Unter dem Begriff „Gemini-Tenside“ werden in Ausnahmefällen nicht nur solche „dimeren“, sondern auch entsprechende „trimere“ Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkoholbis- und Trimeralkoholtrissulfate und -ethersulfate. Endgruppen-verkappte dimere und trimere Mischether werden insbesondere durch die Bi- und Multifunktionalität davon gekennzeichnet. Beispielsweise zeigen die vorstehend genannten Endgruppen-verkappten Tenside gute Benetzungseigenschaften bei gleichzeitig geringer Schaumbildung, wodurch sie insbesondere für die Verwendung in mechanischen Wasch- oder Reinigungsvorgängen geeignet sind. Es können jedoch auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide verwendet werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars containing 5 or 6 carbon atoms and in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R ³ denotes a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms, R ⁴ denotes a linear, branched or cyclic alkylene group or an arylene group having 2 to 8 carbon atoms and R ⁵ denotes a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl group having 1 to 8 carbon atoms, C ₁ -C ₄ alkyl or phenyl groups being preferred, and [Z] denotes a linear polyhydroxyalkyl group whose alkyl chain is substituted with at least two hydroxyl groups or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group is. [Z] is in turn preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can be converted to the desired polyhydroxy fatty acid amides in the presence of an alkoxide as the catalyst by reacting these compounds with fatty acid methyl esters. Another class of nonionic surfactants that is preferably used, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, especially together with alkoxylated fatty alcohols and/or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-NN-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamide type may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it. Other possible surfactants are so-called gemini surfactants. This is generally understood to mean compounds which comprise two hydrophilic groups per molecule. These groups are usually separated from each other by a so-called "spacer". This spacer is generally a carbon chain, which should be long enough to allow the hydrophilic groups to be spaced enough to act independently. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to drastically reduce the surface tension of water. In exceptional cases, the term "gemini surfactants" is understood to mean not only such "dimeric" but also corresponding "trimeric" surfactants. Examples of suitable gemini surfactants are sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol trissulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multifunctionality. For example, the above End group-capped surfactants have good wetting properties with low foam formation, which makes them particularly suitable for use in mechanical washing or cleaning processes. However, gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides can also be used.

Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups. Surfactants of the sulfonate type which can be used are preferably C ₉ -C ₁₃ alkyl benzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates such as those obtained from C ₁₂ -C ₁₈ monoolefins with a terminal or internal Double bond are obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation. Also suitable are alkane sulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are converted into the fatty acid molecule and subsequent neutralization to give water soluble monosalts. Preferably these are the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although it is also possible that sulfonation products of unsaturated fatty acids such as oleic acid may be present in minor amounts, preferably in amounts not exceeding about 2 to 3% by weight. In particular, α-sulfofatty acid alkyl esters comprising an alkyl chain having not more than 4 carbon atoms in the ester group such as methyl ester, ethyl ester, propyl ester and butyl ester are preferred. The methyl esters of α-sulfofatty acid (MES), but also the saponified disalts thereof, are particularly advantageously used. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are the monoesters, diesters and triesters and mixtures thereof, as obtained during manufacture by the esterification of a monoglycerol with 1 to 3 moles of fatty acid or during the transesterification of triglycerides with 0.3 to 2 moles Glycerol can be obtained. Alk(en)yl sulfates are the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ - to C ₁₈ -fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ - to C ₂₀ - Oxo alcohols and the half esters of secondary alcohols of these chain lengths are preferred. Furthermore, preference is given to alk(en)yl sulfates with the chain length described, which comprise a synthetic, straight-chain alkyl group produced on a petrochemical basis, which exhibit a degradation behavior analogous to that of the appropriate compounds based on oleochemical raw materials. From a washing point of view, the C ₁₂ to C ₁₆ alkyl sulfates, C ₁₂ to C ₁₅ alkyl sulfates and C ₁₄ to C ₁₅ alkyl sulfates are preferred. The sulfuric monoesters of C ₇ -C ₂₁ straight or branched chain alcohols ethoxylated with from 1 to 6 moles of ethylene oxide, such as C ₉ -C ₁₁ 2-methyl branched alcohols containing an average of 3.5 moles of ethylene oxide (EO) or C C ₁₂ -C ₁₈ fatty alcohols with 1 to 4 EO are also suitable. The suitable anionic surfactants also include the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates comprise C ₈ to C ₁₈ fatty alcohol groups or mixtures thereof. In particular, preferred sulfosuccinates comprise a fatty alcohol group derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants. In this context, sulfosuccinates which comprise fatty alcohol groups, those of ethoxylated fatty alcohols which have a restricted distribution of homologs, are particularly preferred. Likewise, it is also possible to use alk(en)ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof. Other possible anionic surfactants are fatty acid derivatives of amino acids, such as N-methyltaurine (tauride) and/or N-methylglycine (sarcoside). In particular, the sarcosides or sarcosinates are preferred, including in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids, such as oleyl sarcosinate. Other anionic surfactants that can also be used are, in particular, soaps. In particular, saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids such as coconut, palm kernel or tallow fatty acids are suitable. Along with these soaps or as a substitute for soaps, it is also possible to use the known alkenyl succinic acid salts.

The anionic surfactants, including soaps, may be present in the form of the sodium, potassium or ammonium salts thereof or as soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine. Preferably the anionic surfactants are in the form of the sodium or potassium salts thereof and more preferably in the form of the sodium salts. Surfactants are normally present in the laundry detergents at levels of from 1% to 50%, more preferably from 5% to 30% by weight.

A laundry detergent preferably comprises at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, especially citric acid, saccharic acids, monomeric and polymeric aminopolycarboxylic acids, especially glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, especially aminotris(methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysine tetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, the may also have minor fractions of polymerizable substances having no carboxylic acid functionality polymerized into it. The relative average molar mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g/mol and 200,000 g/mol, that of the copolymers between 2,000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, in each case based on free acid. A particularly preferred acrylic acid/maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers comprising as the monomers two unsaturated acids and/or the salts thereof and as the third monomer vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate. The first acidic monomer, the salt thereof, is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, especially from (meth)acrylic acid. The second acidic monomer or salt thereof may be a derivative of a C ₄ -C ₈ dicarboxylic acid, with maleic acid being particularly preferred. The third monomer unit is formed from vinyl alcohol and/or preferably an esterified vinyl alcohol. In particular, preference is given to vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example C ₁ -C ₄ -carboxylic acids, with vinyl alcohol. Preferred polymers comprise 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate and maleic acid or maleate, and 5 % to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate. Particularly preferred are polymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and in particular 2:1 and 2.5 :1 lies. Both the amounts and the weight ratios relate to the acids. The second acidic monomer or salt thereof may also be a derivative of an allylsulfonic acid substituted at the 2-position with an alkyl group, preferably a C ₁ -C ₄ alkyl group, or an aromatic group, preferably derived from benzene or benzene derivatives is. Preferred terpolymers comprise 40% by weight to 60% by weight, in particular 45% by weight to 55% by weight (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30 wt%, preferably 15 wt% to 25 wt% methallyl sulfonic acid or methallyl sulfonate; and as the third monomer, 15 wt% to 40 wt%, preferably 20 wt% to 40 wt% of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably introduces predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molar mass of between 1000 g/mol and 200,000 g/mol, preferably between 200 g/mol and 50,000 g/mol. Other preferred copolymers are those comprising acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions, in particular for the production of liquid detergents. All of the aforesaid acids are generally used in the form of the water-soluble salts thereof, particularly the alkali metal salts thereof.

Such organic builder substances may be present in amounts of up to 40%, more preferably up to 25% and preferably from 1% to 8% by weight if desired. For pasty or liquid, in particular water-based, agents, amounts close to the aforementioned upper limit are preferably used.

In particular, polyphosphates, and preferably sodium triphosphate, can be used as water-soluble inorganic builder materials. Water-insoluble inorganic builder substance materials which are used are in particular crystalline or amorphous, water-dispersible alkali aluminosilicates in amounts not exceeding 25% by weight, preferably from 3% to 20% by weight and in particular in amounts from 5% to 15% by weight. Of these, the crystalline detergent grade sodium aluminosilicates, particularly zeolite A, zeolite P and zeolite MAP, and optionally zeolite X, are preferred. For solid, particulate compositions, preferably amounts close to the upper limit mentioned above are used. Suitable aluminosilicates include, in particular, no particles with a particle size of more than 30 μm and preferably contain at least 80% by weight of particles with a size of less than 10 μm. The calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to the water-insoluble aluminosilicates and alkali metal carbonates described, other water-soluble inorganic builder substance materials may be present. In addition to the polyphosphates such as sodium triphosphate, these include in particular the water-soluble crystalline and/or amorphous alkali silicate builders. Preferably, the detergent compositions comprise such water-soluble inorganic builder substance materials in amounts of from 1% to 20%, more preferably from 5% to 15%, by weight. The alkali metal silicates which can be used as builder substance materials preferably have a molar ratio of alkali metal oxide to SiO ₂ of less than 0.95, in particular from 1:1.1 to 1:12 and can be in amorphous or crystalline form. Preferred alkali metal silicates are sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O:SiO ₂ of 1:2 to 1:2.8. The crystalline silicates used, which can be present either alone or in a mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na ₂ Si _x O _2x+1 · y H ₂ O, where x, the so-called modulus, is a is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x in the general formula given above assumes the value 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Substantially anhydrous crystalline alkali silicates prepared from amorphous alkali silicates of the above general formula in which x denotes a number from 1.9 to 2.1 can also be used in the detergents. In a further preferred embodiment, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. In another embodiment, sodium silicates having a modulus in the range of 1.9 to 3.5 are used. In a preferred embodiment of such detergents, a granular compound consisting of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Enzymes which can be used in the detergents include those from the classes of amylases, proteases, lipases, cutinases, pullulases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Enzymatic active substances obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus are particularly suitable. The enzymes can be adsorbed on carrier substances and/or embedded in coating substances in order to protect them from premature inactivation. These are preferably present in the laundry detergents or cleaning agents according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the detergent according to the invention comprises protease, this preferably has a proteolytic activity in the range from approximately 100 PU/g to approximately 10,000 PU/g, in particular from 300 PU/g to 8000 PU/g. When several enzymes are to be used in the detergent composition of the present invention, this can be done by incorporating two or more enzymes formulated separately or separately in a known manner, or two or more enzymes formulated together in granular form.

The organic solvents that can be used in addition to water in the laundry detergents, especially when they are in liquid or paste form, include alcohols having 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert. Butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and the mixtures thereof and the ethers which can be derived from the classes of compounds mentioned above. Such water-miscible solvents are preferably present in the detergents according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

To set a desired pH value, which does not result by mixing the remaining components, the agents according to the invention can contain system-compatible and environmentally friendly acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also include mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are in the detergents according to the invention preferably in amounts of not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Graying inhibitors have the task of keeping the dirt loosened from the textile fibers suspended in the lye. Water-soluble colloids, mostly of an organic nature, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulphonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch are suitable for this purpose. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, starch derivatives other than those mentioned above can be used, for example aldehyde starches. The use of cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent, is preferred.

If desired, the compositions may comprise a conventional dye transfer inhibitor, preferably in amounts up to 2% by weight, and more preferably from 0.1% to 1% by weight, which in a preferred embodiment consists of the polymers of vinylpyrrolidone , vinylimidazole, vinylpyridine-N-oxide or their copolymers. Both polyvinylpyrrolidones with molecular weights of 15,000 g/mol to 50,000 g/mol and polyvinylpyrrolidones with higher molecular weights of more than 1,000,000 g/mol and in particular from 1,500,000 g/mol to 4,000,000 g/mol can be used , For example N-vinylimidazole/N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers and polyvinyl alcohols. However, enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which yields hydrogen peroxide in water can also be used. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenothiazine or phenoxazine, is preferred, it being possible in addition to use the polymeric dye transfer inhibitor agents mentioned above. Polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 g/mol to 60,000 g/mol and in particular in the range from 25,000 g/mol to 50,000 g/mol. Among the copolymers are those made from vinylpyrrolidone and vinylimidazole in a 5:1 to 1:1 molar ratio with an average molar mass in the range from 5,000 g/mol to 50,000 g/mol and in particular from 10,000 g/mol to 20,000 g/mol exist, preferred. In preferred embodiments of the invention, however, the laundry detergents are free from such added color transfer inhibitors.

Laundry detergents can comprise, for example, derivatives of diaminostilbene disulfonic acid or the alkali metal salts thereof as optical brighteners, and when used as color laundry detergents they are preferably free from optical brighteners. For example, salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'disulfonic acid or compositions with a similar structure which contain a diethanolamino group, a methylamino group , an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)biphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)biphenyl or 4-(4- chlorostyryl)-4'-(2-sulfostyryl)biphenyls. It is also possible to use mixtures of the optical brighteners mentioned above.

Particularly when used in washing machines, it can be advantageous to add customary foam inhibitors to the detergents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin with a high content of C ₁₈ -C ₂₄ fatty acids. Suitable foam inhibitors of the non-surfactant type are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silicic acid and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silicic acid or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes. The foam inhibitors, in particular silicone-comprising and/or paraffin-comprising foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. In particular, mixtures of paraffins and ethylene distearylamide are preferred.

Solid detergents are not difficult to produce and can be produced in a known manner, for example by spray drying or granulation, enzymes and any further heat-sensitive ingredients, such as bleaches, optionally being subsequently added separately. For the production of detergents with an increased bulk density, in particular in the range from 650 g/l to 950 g/l, a process which comprises an extrusion step is preferred.

In order to produce detergents in tablet form, which can be single-phase or multi-phase, monochromatic or multicolored and can consist in particular of one layer or of several, in particular two layers, the procedure is preferably such that all components - optionally of a respective layer - are mixed together in a mixer are mixed and the mixture is compressed using conventional tablet presses, such as eccentric or rotary tablet presses, using pressures in the range of about 50 to 100 kN, preferably 60 to 70 kN. In the case of multilayer tablets in particular, it can be advantageous if at least one layer is precompressed. This preferably takes place at pressures between 5 and 20 kN, in particular at 10 to 15 kN. This results in unbreakable tablets, which nevertheless dissolve sufficiently quickly under application conditions, with breaking and flexural strengths of normally 100 to 200 N, but preferably over 150 N. A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular from 15 g to 40 g. The physical shape of the tablets is arbitrary and may be round, oval or square, with intermediate shapes being possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cuboid tablets, which are mainly introduced via the dosing device of the washing machine, depends on the geometry and the volume of this dosing device. Preferred embodiments have, for example, a base area of (20 to 30 mm) x (34 to 40 mm) and in particular 26 x 36 mm or 24 x 38 mm.

Liquid or paste detergents in the form of solutions, comprising common solvents, are usually made by simply mixing the ingredients, which can be placed neat or as a solution in an automatic mixer.

examples

example 1

Amax [nm] 344 (H₂O) 341 (EtOH) 334 (MeOH) 340 (EtOH) Triplettenergie [eV] 2,31 2,21 3,0 3,22 ε [m²mol^-1] 1447,7 2031,3 15 750 Φ_1-3 Φ_F = 0,32 Φ_ISC = 0,68 Φ_F = 0,06 Φ_ISC = 0,94 Φ_ISC = 1,0 Φ_ISC = 1,0 Reduktionspotential vs. SCE [V] -1,28 -1,00 -1,72 -1,65 Redoxpotential des angeregten Zustands vs. SCE [V] 1,03 1,21 1,57 1,28 Wasserlöslichkeit (pH-Wert 6,3, 20 °C) 25 g/l 7,6 mg/l 23,9 mg/l (25 °C) 2,6 mg/l Table 1: Photoexcitable chemical compounds. connection

Amax [nm] 344 ( _H2O ) 341 (EtOH) 334 (MeOH) 340 (EtOH) triplet energy [eV] 2:31 2:21 3.0 3.22 ε [m ² mol ^-1 ] 1447.7 2031.3 15 750 _{Φ1-3 ΦF} = 0.32 _ΦISC = 0.68 _ΦF = 0.06 _ΦISC = 0.94 _ΦISC = 1.0 _ΦISC = 1.0 Reduction potential vs. SCE [V] -1.28 -1.00 -1.72 -1.65 Excited state redox potential vs. SCE [V] 1.03 1:21 1.57 1.28 Water solubility (pH 6.3, 20°C) 25g/l 7.6mg/l 23.9mg/l (25°C) 2.6mg/l

Values of the photochemical parameters of benzophenone and xanthone are given in N A. Romero, DA Nicewicz, Chem Rev. 2016, 116, 10075-10116; Values for compounds 1 and 2 were determined by UV-vis absorption spectroscopy in water or ethanol solutions (for λ _max and ε values), by triplet state calculations, by fluorescence spectroscopy and by standardized fluorescence quantum yield determination (for Φ values), by cyclic voltammography (in acetonitrile, for the determination of the V reduction potential) and calculated by calculation for the excited state redox potential (E* = E _red + E _T with E _red = ground state reduction potential and E _T = triplet state energy).

Synthesis of compound 1

A total of 23.8 g (120 mmol, 1.00 eq) of naphthalic anhydride and 63.0 g (480 mmol, 4.00 eq) of aminocaproic acid in 800 ml of H ₂ O were initially taken. 15.4 g (384 mmol, 3.20 eq) of NaOH were added to this suspension and the reaction mixture was refluxed at 120° C. for 5 h. After cooling to room temperature, the reaction mixture was acidified (pH=4) with concentrated HCl solution (37% by weight in H ₂ O). The precipitated solids were filtered off and washed with _H2O . After drying, a colorless solid (mp 136-137°C) was obtained.

Synthesis of compound 2

In 180 mL of EtOH was placed 4.00 g (14.4 mmol, 1.00 eq) of bromonaphthalic anhydride and 2.09 g (15.9 mmol, 1.10 eq) of aminocaproic acid was added. The reaction was heated to reflux at 90°C for 24 h. After cooling, the reaction mixture was poured onto ice. The solid was filtered off and washed with a little cold H ₂ O and EtOH before drying the solid in a desiccator over P ₄ O ₁₀ . A colorless solid (mp 166-168°C) was obtained.

Example 2: bleaching tests

Aqueous solutions of 3.1 g / l of a commercial, bleach-free liquid detergent were brought to a pH of 8.3 by addition of sodium citrate buffer and as such (C1) or after addition of the sodium salt of compound 1 of Example 1 to a concentration of 1.0 x 10 ^-4 mol/l (11) or 1.0 x 10 ^-3 mol/l (12). Cotton swatches contaminated with standardized impurities given in Table 2 were added and the aqueous mixtures were exposed to light (with a wavelength of 360 nm and with the electric power of 45 kg.m ² .s- ³ ) for 1 hour at room temperature irradiated. The samples were removed, air dried and their reflectivity measured. Table 2 gives the measured reflectivity values (mean values of 15 experiments each) with their standard deviations. Table 2 tea tea standard dev. blueberry Blueberry standard dev. blackberry Blackberry standard dev. C1 62.4 0.45 51.2 0.38 69.1 0.32 I1 64.2 0.70 54.0 1.57 70.6 0.58 I2 67.2 0.48 58.3 0.48 73.3 0.29

QUOTES INCLUDED IN DESCRIPTION

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Patent Literature Cited

• WO 2015/112671 A1 [0003]

Claims (10)

Photoexcitable chemical compound having the following properties: shows a maximum absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm; has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 100,000 m ² mol ^-1 ; has a triplet energy in the range of 1.5 eV to 5 eV; exhibits a singlet-triplet transition quantum yield in the range of 5% to 100%; exhibits a reduction potential versus a standard ferrocene electrode in the range of -0.5 V to -4 V; exhibits an excited state redox potential in the range of +0.1 V to +11 V; and has a water solubility of pH 6.3 at 20°C from 4 mg/l to 1000 g/l. Use of a photoexcitable chemical compound having the following properties: shows a maximum absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm; has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 100,000 m ² mol ^-1 ; has a triplet energy in the range of 1.5 eV to 5 eV; exhibits a singlet-triplet transition quantum yield in the range of 5% to 100%; exhibits a reduction potential versus a standard ferrocene electrode in the range of -0.5 V to -4 V; exhibits an excited state redox potential in the range of +0.1 V to +11 V; and has a water solubility of pH 6.3 at 20°C from 4 mg/l to 1000 g/l; for increasing the bleaching effect of detergents when used in aqueous washing liquids for washing soiled textiles. A method of washing soiled fabrics in an aqueous wash liquor comprising a surfactant and a photoexcitable chemical compound having the following properties: exhibits a maximum absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm; has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 100,000 m ² mol ^-1 ; has a triplet energy in the range of 1.5 eV to 5 eV; exhibits a singlet-triplet transition quantum yield in the range of 5% to 100%; exhibits a reduction potential versus a standard ferrocene electrode in the range of -0.5 V to -4 V; exhibits an excited state redox potential in the range of +0.1 V to +11 V; and has a water solubility of pH 6.3 at 20°C from 4 mg/l to 1000 g/l; wherein the aqueous washing liquid is irradiated with electromagnetic radiation of a wavelength range that includes λ _max from the photoexcitable chemical compound. use after claim 2 or procedures claim 3 , characterized in that the washing liquid is irradiated with electromagnetic radiation with wavelengths from 250 nm to 700 nm, in particular from 300 nm to 500 nm. Use or method according to any preceding claim, characterized in that it is carried out at temperatures in the range from 10°C to 95°C, in particular 20°C to 60°C and particularly preferably at temperatures below 40°C. Use or method according to one of the preceding claims, characterized in that the concentration of the photoexcitable chemical compound in the aqueous washing liquid is in the range from 1 µmol/l to 30000 µmol/l and in particular from 5 µmol/l to 10000 µmol/l. A laundry detergent comprising a photoexcitable chemical compound having the following properties: exhibits a maximum absorption of electromagnetic radiation in the wavelength range from 250 nm to 700 nm; has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 100,000 m ² mol ^-1 ; has a triplet energy in the range of 1.5 eV to 5 eV; exhibits a singlet-triplet transition quantum yield in the range of 5% to 100%; exhibits a reduction potential versus a standard ferrocene electrode in the range of -0.5 V to -4 V on; exhibits an excited state redox potential in the range of +0.1 V to +11 V; and has a water solubility of pH 6.3 at 20°C from 4 mg/l to 1000 g/l. Use or method according to any of claims 2 until 6 or detergent claim 7 , characterized in that the photoexcitable chemical compound is present in the detergent in amounts of 0.01% by weight to 50% by weight and in particular 0.03% by weight to 25% by weight. A compound, use, method or detergent according to any one of the preceding claims, characterized in that the photoexcitable chemical compound exhibits a maximum in the absorption of electromagnetic radiation in the wavelength range from 300 nm to 500 nm; has a molar attenuation coefficient in the range of 100 m ² mol ^-1 to 10,000 m ² mol ^-1 ; has a triplet energy in the range of 1.5 eV to 4.5 eV; has a singlet-triplet transition quantum yield in the range of 50% to 100%; has a reduction potential versus a standard ferrocene electrode in the range of -0.5 V to -2.5 V; has an excited state redox potential in the range of +0.1 V to +2.5 V; and/or has a water solubility of pH 6.3 at 20°C from 5 mg/l to 150 g/l. Compound, use, method or detergent according to any one of the preceding claims, characterized in that the photoexcitable chemical compound is selected from compounds of the general formula I,

in which R ¹ represents an alkylene group having from 1 to 20 carbon atoms and R ² and R ³ independently represent an optionally substituted aromatic group, it also being possible for R ² and R ³ to be linked to form only one aromatic group, such as a benzene or form naphthalene group.