EP0026744A1 - Means and process for the treatment and the improvement of the appearance of textiles - Google Patents

Abstract

Agent for improving the appearance of brought textiles, which comprises a photoactivator and an optical brightener from the class of distyrylbiphenylsulfonic acids and their salts or / and 4,4'-bis- (1,2,3-triazol-2-yl) Contains -2,2'- stilbenesulfonic acids or their salts, soaking, washing or rinsing liquors containing such agents and a process for improving the appearance of used textiles with the aid of the agents or liquors according to the invention.

Description

The present invention relates to an agent for improving the appearance of used, in particular soiled textiles, especially soaking, washing or rinsing agents, and to a method for improving the appearance of textiles with the aid of the agents according to the invention.

It is known that photosensitizing compounds, i.e. especially dyes that catalyze oxidation processes under the influence of light can be used for bleaching textiles. These compounds can be contained in soaking, washing, rinsing or other cleaning agents or they are used in a separate bleaching process. See British Patent 1,372,036, U.S. Patent 3,927,967, German Offenlegungsschriften 26 13 936 and 28 12 278. To treat the textiles, the corresponding photosensitizing compound or a soaking, washing, rinsing or cleaning agent containing it is added to an aqueous liquor in which the textiles to be bleached are soaked , washed, rinsed or otherwise cleaned. To develop the bleaching effect caused by the photodynamic effect, the textiles must be treated with light

be irradiated. A corresponding lamp can be used for this purpose, or, particularly advantageously, in particular with regard to the energy consumption, the daylight can be used for the irradiation. Irradiation can take place during the treatment of the textiles in the bathroom (e.g. in the bleaching, soaking, washing or rinsing bath) or after the treatment outside the bath. Here the still damp textiles can be exposed to sunlight, e.g. while drying on a leash. Irradiation can also be carried out, if necessary, with repeated rewetting of the textiles.

It is also known that the appearance of textiles can be significantly improved if optical brighteners are added to the soaking, washing or rinsing bath in which the textiles are treated. See Eckhardt et al: "Fluorescent Whitening Agents in Detergents" in Environmental Quality and Safety, Suppl. Vol. IV, Ed. by Coulston & Korte, G. Thieme Verlag Stuttgart 1975. When optical brighteners are used in soaking, washing and rinsing baths, the degree of whiteness of white textiles and the color freshness of colored textiles are increased.

It has now surprisingly been found that a combination of photosensitizing compounds (photoactivators) used for bleaching textiles with very specific types of optical brighteners in the aforementioned textile treatment baths can achieve such a striking improvement in the aspect of soiled textiles, an improvement that neither with the best combinations of photoactivators alone, still with selected optical brighteners alone, still possible with combinations of the photoactivators mentioned with the other commercially available optical brighteners. The combination according to the invention thus leads to a synergistic bleaching and lightening effect.

The present invention accordingly consists first of all in a means of improving the appearance of used, in particular soiled, textiles, which comprises 0.0001 to 1%, preferably 0.001 to 0.1% of a photoactivator and 0.005 to 1.5%, preferably 0.01 to _0, 5%, based in each case on the total weight of the composition, sulfonic acids distyrylbiphenyl of an optical brightener of the class of acids and salts thereof and / or 4,4'-bis- (1,2,3-triazol-2-yl) Contains -2,2'-stilbene sulfonic acid or its salts, it also being possible for mixtures of several brighteners to be present.

All dyes known from the literature which have a photodynamic effect can be used as the photoactivator. Examples of such dyes are eosin, rose bengal, fluorescein, chlorophyll, metal-free porphyrin, methylene blue, but above all water-soluble phthalocyanine compounds, the latter being preferred in the agents according to the invention.

Both metal-free phthalocyanines and metal complexes of phthalocyanines can be used as water-soluble phthalocyanines. In particular, those of Al, Zn, Mg, Ca, Fe, Na, K, preferably Al and Zn, are used as metal complexes.

Of course, mixtures of photo actuators can also be used, e.g. Mixtures of various phthalocyanine compounds, such as mixtures of water-soluble Zn and Al phthalocyanine.

in welchen Formeln

• X₁ Sauerstoff, den Rest -NH- oder -N-Alkyl und
• R₁ und R₂ unabhängig voneinander Wasserstoff, die Sulfogruppe und deren Salze, die Carboxylgruppe und deren Salze oder die Hydroxylgruppe bedeuten, wobei mindestens einer der Reste R₁ und R₂ für eine Sulfo- oder Carboxylgruppe oder deren Salz steht,
• Y₁ Sauerstoff, Schwefel, den Rest -NH- oder -N-Alkyl,
• R₃ und R₄ unabhängig voneinander Wasserstoff, Alkyl, Hydroxyalkyl, Cyanoalkyl, Sulfoalkyl, Carboxyalkyl oder Halogenalkyl mit 1 bis 6 Kohlenstoffatomen im Alkylteil, unsubstituiertes oder mit Halogen, Alkyl oder Alkoxy mit 1 bis 4 Kohlenstoffatomen, Sulfo oder Carboxy substituiertes Phenyl oder R₃ und R₄ zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen gesättigten 5- oder 6-gliedrigen heterocyclischen Ring, der zusätzlich noch ein Stickstoff- oder Sauerstoffatom als Ringglied enthalten kann,
• R₅ und R unabhängig voneinander einen gegebenenfalls substituierten Alkyl- oder Aralkylrest,
• R eine gegebenenfalls substituierte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder Wasserstoff,
• M ein Alkalimetall- oder Ammoniumion,
• Z⊖ ein Anion wie z.B. ein Chlor-, Brom-, Alkyl- oder Arylsulfation,
• n eine ganze Zahl von 2 bis 12 und
• m 0 oder 1

bedeuten.The necessary water solubility of the phthalocyanine compounds in question can be brought about by a wide variety of water-solubilizing substituents. Such substituents are known from the literature relating to phthalocyanine dyes, in particular Cu and Ni-phthalocyanine complexes. The water solubility of a phthalocyanine derivative is sufficient if enough of it dissolves in the treatment bath to cause photodynamically catalyzed oxidation on the fiber. A minimum solubility of 0.01 g / l may already be sufficient, in general that of 0.1 to 20 g / 1 is appropriate. Some of the water-solubilizing groups in question are listed below, but this list does not claim to be complete: sulfo and carboxyl groups and their salts and groups of the formulas

in what formulas

• X _{1 is} oxygen, the radical -NH- or -N-alkyl and
• R ₁ and R ₂ independently of one another denote hydrogen, the sulfo group and their salts, the carboxyl group and their salts or the hydroxyl group, at least one of the radicals R ₁ and R _{2 representing} a sulfo or carboxyl group or their salt,
• Y ₁ oxygen, sulfur, the rest -NH- or -N-alkyl,
• R ₃ and R ₄ independently of one another are hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulfoalkyl, carboxyalkyl or haloalkyl having 1 to 6 carbon atoms in the alkyl part, phenyl which is unsubstituted or substituted by halogen, alkyl or alkoxy having 1 to 4 carbon atoms, sulfo or carboxy or R ₃ and R ₄ together with the nitrogen atom to which they are attached form a saturated 5- or 6-membered heterocyclic ring, which can additionally contain a nitrogen or oxygen atom as a ring member,
• R ₅ and R independently of one another are an optionally substituted alkyl or aralkyl radical,
• R is an optionally substituted alkyl group having 1 to 6 carbon atoms or hydrogen,
• M is an alkali metal or ammonium ion,
• Z⊖ an anion such as a chlorine, bromine, alkyl or aryl sulfate ion,
• n is an integer from 2 to 12 and
• m 0 or 1

mean.

In the above formulas, X ₁ and Y _{1 are} preferably -NH- or -N-alkyl. Halogen is preferably chlorine or bromine, especially chlorine. Among the 5- or 6-membered heterocyclic rings (R ₃ ⁺ R ₄ ), the morpholine, piperidine, pyrazolidine, piperazine and oxazolidine radicals are preferred.

The number of substituents present in the molecule is determined by achieving sufficient water solubility. If - several water-solubilizing groups are present in the molecule, these can be the same or different. As is common in phthalocyanine chemistry, the degree of substitution does not necessarily have to be an integer, since the manufacturing method, e.g. Sulfonation does not always result in uniform products. In general, the total number of water-solubilizing substituents per molecule is between 1 and 4.

In addition to the water-solubilizing groups, the phthalocyanines which can be used in the agents according to the invention can also contain other substituents, for example reactive residues customary in dye chemistry, such as chloropyrazine, chloropyrimidine and especially Chlorotriazine residues. However, any other substituents can also be used in addition to _. be water-solubilizing groups, at most in a number that they do not fall below the required water solubility. However, they can also only be present in very small amounts, for example about 0.1 mol per mol of phthalocyanine compound. Examples of such substituents are: halogen atoms (including F and J), cyano, optionally substituted alkyl, alkoxy, optionally substituted phenyl and other substituents customary in phthalocyanine chemistry. Preferred additional substituents are fluorine, chlorine, bromine, iodine and cyano, especially chlorine.

• PC für das Phthalocyaninringsystem steht,
• v einen beliebigen Wert zwischen 1 und 4 hat,
• Me Zn, Fe(II), Ca, Mg, Na, K oder Al X, vorzugsweise Zn oder Al X, wobei X für ein Anion, insbesondere für ein Halogenid-, Sulfat-, Nitrat-, Acetat- oder Hydroxylion steht,
• m 0 oder 1,
• R eine Gruppe der Formel
  
  
  oder
  
  darstellen, worin
  • y Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminion,
  • R' Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen,
  • n' eine ganze Zahl von 2 bis 6,
  • R₁ und R₂ unabhängig voneinander Wasserstoff, die Sulfogruppe und deren Salze, die Carboxylgruppe und deren Salze oder die Hydroxylgruppe, wobei mindestens einer der Reste R und R₂ für eine Sulfo- oder Carboxylgruppe oder deren Salz steht und
  • R₃ und R₄ unabhängig voneinander Wasserstoff, Alkyl, Hydroxyalkyl, Cyanoalkyl, Sulfoalkyl, Carboxyalkyl oder Halogenalkyl mit jeweils 1 bis 6 Kohlenstoffatomen im Alkylteil oder Phenyl oder R₃ und R zusammen mit dem Stickstoffatom, an das sie gebunden sind, einen gesättigten 5- oder 6-gliedrigen heterocyclischen Ring, der zusätzlich noch ein Stickstoff- oder Sauerstoffatom als Ringglied enthalten kann,
  
  bedeuten, wobei, wenn mehrere Reste R im Molekül vorhanden sind, diese gleich oder verschieden sein können, und worin R₁₁ Fluor, Chlor, Brom, Jod oder Cyano und x einen beliebigen Wert zwischen 0,1 und 4 darstellen, wobei die im Molekül vorhandenen R₁₁ gleich oder verschieden sein können.

A water-soluble phthalocyanine of the formula is particularly suitable as a photosensitizer

• PC stands for the phthalocyanine ring system,
• v has any value between 1 and 4,
• Me Zn, Fe (II), Ca, Mg, Na, K or Al X, preferably Zn or Al X, where X represents an anion, in particular a halide, sulfate, nitrate, acetate or hydroxyl ion,
• m 0 or 1,
• R is a group of the formula
  
  
  or
  
  represent what
  • y hydrogen, an alkali metal, ammonium or amine ion,
  • R 'is hydrogen or alkyl having 1 to 4 carbon atoms,
  • n 'an integer from 2 to 6,
  • R ₁ and R ₂ independently of one another are hydrogen, the sulfo group and their salts, the carboxyl group and their salts or the hydroxyl group, at least one of the radicals R and R _{2 representing} a sulfo or carboxyl group or its salt and
  • R ₃ and R ₄ independently of one another are hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulfoalkyl, carboxyalkyl or haloalkyl, each having 1 to 6 carbon atoms in the alkyl part or phenyl, or R ₃ and R together with the nitrogen atom to which they are attached form a saturated 5- or 6-membered heterocyclic ring which may additionally contain a nitrogen or oxygen atom as a ring member,
  
  mean, where, if several radicals R are present in the molecule, these can be the same or different, and in which R _{11 is} fluorine, chlorine, bromine, iodine or cyano and x represents any value between 0.1 and 4, where in the molecule existing R _{11 may be the} same or different.

worin

• PC für das Pthalocyaninringsystem steht,
• Y' Wasserstoff, ein Alkalimetall- oder Ammoniumion,
• v' eine beliebige Zahl zwischen 1,3 und 4 (den Sulfonierungsgrad),
• m 0 oder 1, insbesondere 1, und
• Me Zn, Fe(II), Ca, Mg, Na, K oder Al X, vorzugsweise Zn oder Al X bedeuten, wobei X für ein Anion, insbesondere ein Halogenid-, Sulfat-, Hydroxyl- oder Acetation steht , sowie solche der Formel
  
  worin
  • PC für das Phthalocyaninringsystem steht,
  • Y' Wasserstoff, ein Alkalimetall- oder Ammoniumion,
  • v' eine beliebige Zahl zwischen 1,3 und 4 (den Sulfonierungsgrad),
  • m 0 oder 1, insbesondere 1,
  • R₁₁ Fluor, Chlor, Brom, Jod oder Cyano,
  • x eine beliebige Zahl zwischen 0,1 und 4, vorzugsweise zwischen 0,5 und 4, insbesondere zwischen 0,8 und 3, wobei die Reste R₁₁ gleich oder verschieden sein können, und
  • Me Zn, Fe (II), Ca, Mg, Na, K oder Al X, vorzugsweise Zn oder Al (X) bedeuten, wobei X für ein Anion, insbesondere ein Halogenid-, Sulfat-, Hydroxyl- oder Acetation steht.
  
  Weitere bevorzugte Photoaktivatoren in erfindungsgemässen Mitteln entsprechen der Formel
  
  
  oder Mischungen von solchen Al-Phthalocyaninen , worin
  X ein Anion, insbesondere ein Halogenid-, Sulfat-, Hydroxyl-, oder Acetation, Y' Wasserstoff, ein Alkalimetall- oder Ammoniumion, R₁₁ Fluor, Chlor, Brom, Jod oder Cyano, v' eine beliebige Zahl zwischen 1, 3 und 4 (Sulfonierungsgrad) und *' null oder eine beliebige Zahl zwischen 0,5 und 4 bedeuten.

Preferred photoactivators in agents according to the invention are acid-substituted phthalocyanine derivatives and their metal complexes, especially those which are substituted by sulfo and / or carboxyl groups, but especially sulfonated phthalocyanines and their metal complexes, in particular those of the formula

wherein

• PC stands for the pthalocyanine ring system,
• Y 'is hydrogen, an alkali metal or ammonium ion,
• v 'any number between 1.3 and 4 (the degree of sulfonation),
• m 0 or 1, in particular 1, and
• Me is Zn, Fe (II), Ca, Mg, Na, K or Al X, preferably Zn or Al X, where X is an anion, in particular a halide, sulfate, hydroxyl or acetate ion, and those of the formula
  
  wherein
  • PC stands for the phthalocyanine ring system,
  • Y 'is hydrogen, an alkali metal or ammonium ion,
  • v 'any number between 1.3 and 4 (the degree of sulfonation),
  • m 0 or 1, in particular 1,
  • R ₁₁ fluorine, chlorine, bromine, iodine or cyano,
  • x any number between 0.1 and 4, preferably between 0.5 and 4, in particular between 0.8 and 3, where the radicals R _{11 can be the} same or different, and
  • Me is Zn, Fe (II), Ca, Mg, Na, K or Al X, preferably Zn or Al (X), where X is an anion, in particular a halide, sulfate, hydroxyl or acetate ion.
  
  Further preferred photoactivators in agents according to the invention correspond to the formula
  
  
  or mixtures of such Al phthalocyanines, wherein
  X is an anion, in particular a halide, sulfate, hydroxyl or acetate ion, Y 'is hydrogen, an alkali metal or ammonium ion, R _{11 is} fluorine, chlorine, bromine, iodine or cyano, v' is any number between 1, 3 and 4 (degree of sulfonation) and * 'mean zero or any number between 0.5 and 4.

In the case of aluminum complexes, the molecule contains an anion X to saturate the third valence of the aluminum ion, which is not important for the bleaching effect. This anion is mostly identical to that of the aluminum compound used to make the complex.

Particularly preferred photoactivators are aluminum and zinc phthalocyanine di, tri and tetrasulfonates and their salts, which may also contain an additional substituent, e.g. contain a halogen, especially chlorine.

Methods for the preparation of all of the water-soluble phthalocyanine compounds mentioned above are described in German Offenlegungsschriften 28 12 261 and 28 12 278. All of the phthalocyanine compounds disclosed in these two published publications can be used as photoactivators in the agents according to the invention.

Phthalocyanine compounds which are contained in agents according to the invention as a photoactivator and which contain other substituents in addition to the water-solubilizing groups can also be obtained by customary methods. For example, these substituents can already be present in the starting materials used for the construction of the phthalocyanine ring structure (for example phthalic anhydride, phthalodinitrile or imide). After the correspondingly substituted, possibly already metallized phthalocyanine has been built up, the water-solubilizing groups can be introduced (for example by sulfonation), provided that these were not already present in the starting materials. Some substituents can also be introduced into the already constructed phthalocyanine ring system, for example by chlorination, bromination or iodination (R ₁₁ = Cl, Br, J). The water-solubilizing substituents can be introduced before or preferably afterwards, for example by sulfonation. If the phthalocyanine ring system is built up from phthalic anhydride or phthalodinitrile in the presence of chlorides, for example AlCl ₃ , ZnCl ₂ and others, chlorinated phthalocyanines are formed, especially with a chlorine content of 0.5-1.5 mol chlorine per mol phthalocyanine. The water-solubilizing groups can also be introduced subsequently into such products, for example by sulfonation. The methods mentioned can be combined in a suitable manner for the production of mixed-substituted phthalocyanine compounds. All methods are well known in phthalocyanine chemistry and are described in detail there.

erwähnt, worin X₁ Wasserstoff, Chlor, Brom oder Alkyl oder Alkoxy mit jeweils 1 bis 4 C-Atomen, X₂ Wasserstoff oder Alkyl mit 1 bis 4 C-Atomen und M Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminsalzion bedeuten.Brighteners from the class of distyrylbiphenylsulfonic acids which are contained in the agents according to the invention are, above all, those of the formula

mentioned, wherein X _{1 is} hydrogen, chlorine, bromine or alkyl or alkoxy each having 1 to 4 carbon atoms, X _{2 is} hydrogen or alkyl having 1 to 4 carbon atoms and M is hydrogen, an alkali metal, ammonium or amine salt ion.

Of the alkali metal ions M in formula (20), Na and K are preferred. Suitable amine salt ions M are mainly those of the formula -HNR ₁ R ₂ R ₃ , in which R ₁ and R are hydrogen or optionally substituted alkyl and R _{3 is} optionally substituted alkyl. Of the substituted alkyl radicals, which preferably have 1 to 4 carbon atoms in the alkyl part, particular mention should be made of hydroxyalkyl, cyanoalkyl, haloalkyl and benzyl. M is preferably hydrogen, sodium, potassium or ammonium.

eingesetzt, worin X' Wasserstoff oder Chlor und M' Wasserstoff, Natrium, Kalium oder Ammonium bedeuten, insbesondere der Aufheller der Formel

worin M" Wassertoff, Natrium oder Kalium bedeutet.Brighteners of the formula are preferred

used, wherein X 'is hydrogen or chlorine and M' is hydrogen, sodium, potassium or ammonium, in particular the brightener of the formula

where M "means hydrogen, sodium or potassium.

worin M" Wasserstoff, Natrium oder Kalium bedeutet, liefert in den erfindungsgemässen Mitteln gute Ergebnisse.But also the brightener of the formula

where M "is hydrogen, sodium or potassium, gives good results in the agents according to the invention.

erwähnt, worin M Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminsalzion bedeutet. Für den Substituenten M gelten die oben angeführten Definitionen.As a brightener from the class of 4,4'-bis- (1,2,3-triazol-2-yl) -2,2'-stilbenesulfonic acids, which are also contained in agents according to the invention, the brightener of the formula in particular

mentioned, wherein M represents hydrogen, an alkali metal, ammonium or amine salt ion. The definitions given above apply to the substituent M.

Mixtures of the aforementioned brighteners can of course also be incorporated into the agents according to the invention, in particular mixtures of the brighteners of the formulas (22) and (24), but also mixtures of the brighteners of the formulas (22) and (23).

In addition to the mentioned brighteners essential to the invention, brighteners from other classes can also be included in the agents according to the invention.

The agents according to the invention, which are used to improve the appearance of used, in particular soiled, textiles are, for example, soaking, washing, rinsing or other cleaning agents. Accordingly, the agents according to the invention contain, in addition to brighteners and photoactivators, as a supplement to 100% constituents, as are customary in such agents. In general, such components are primarily anionic, non-ionic or mixtures of anionic and non-ionic surface-active substances.

Detergents according to the invention, which can be liquid or solid, preferably contain, in addition to brightener and photoactivator, an organic detergent or mixture of several detergents (preferably anionic and / or nonionic), so-called “builders” (in the case of solid detergents), redeposition inhibitors and, if appropriate, foam stabilizers, Enzymes, antimicrobials, perfumes, additional bleaches and / or additional optical brighteners and water (especially in the case of liquid detergents).

• Bekannte Mischungen von Waschaktivsubstanzen wie beispielsweise Seife in Form von Schnitzeln und Pulver, Synthetika, lösliche Salze von Sulfonsäurehalbestern höherer Fettalkohole, höher und/oder mehrfach alkylsubstituierten Arylsulfonsäuren, Sulfocarbonsäureester mittlerer bis höherer Alkohole, Fettsäureacylaminoalkyl- oder -aminoarylglycerinsulfonate, Phosphorsäureester von Fettalkoholen, nicht-ionische Tenside usw. Als Aufbaustoffe.für feste Waschpulver, sogenannte
• "Builders", kommen z.B. Alkylipoly- und -polymetaphosphate, Alkalipyrophosphate oder Aluminosilikate, Alkalisalze der Carboxymethylcellulose und andere "Soilredepositioninhibitoren", ferner Alkali- und Erdalkalisilikate, Alkalicarbonate, Alkalisulfate, Alkaliborate, Alkaliperborate, Alkalipercarbonate, Nitrilotriessigsäure, Aethylendiaminotetraessigsäure, Schaumstabilisatoren wie Alkanolamide höherer Fettsäuren, in Betracht. Ferner können in Waschmitteln beispielsweise enthalten sein: Bleichmittel wie Perverbindungen, z.B. Perborate, Percarbonate usw., chlorabspaltende Substanzen, antistatische Mittel, rückfettende Hautschutzmittel wie Lanolin, Enzyme, Antimikrobika, Parfüme, zusätzliche optische Aufheller und Bleich-Aktivatoren wie Tetraacetyläthylendiamin oder Tetraacetylglycoluril sowie Wasser.

In particular, the detergents according to the invention can contain:

• Known mixtures of detergent substances such as soap in the form of chips and powder, synthetics, soluble salts of sulfonic acid semiesters of higher fatty alcohols, higher and / or multiple alkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminoalkyl or aminoamino acid ester sulfonates, non-phosphonic ionophosphates, Surfactants etc. as builders for solid washing powder, so-called
• “Builders” include, for example, alkylipoly- and polymetaphosphates, alkali pyrophosphates or aluminosilicates, alkali salts of carboxymethyl cellulose and other “soil deposition inhibitors”, furthermore alkali and alkaline earth silicates, alkali carbonates, alkali sulfates, alkali borates, alkali diperborates, fatty acids, nitric acid aminotetraacids, fatty acids, nitralic acid aminotetraacids, alkali metal carboxylates, fatty acid tricarboxylic acids, alkali metal carboxylates, fatty acid tricarboxylates, fatty acids , into consideration. Detergents may also contain, for example: bleaching agents such as per compounds, for example perborates, percarbonates etc., chlorine-releasing substances, antistatic agents, lipid-replenishing skin protection agents such as lanolin, enzymes, antimicrobials, perfumes, additional optical brighteners and bleach activators such as tetraacetylethylenediamine or tetraacetylglycoluril and water.

Soaking agents according to the invention contain, in addition to brighteners and photoactivators, similar components to those mentioned above for the corresponding detergents. Soaking agents may contain enzymes in larger quantities than corresponding detergents.

• Als Aktivsubstanz (Weichmacher) ein oder mehrere dialkylierte Di-{nieder-alkyl)-ammoniumsalze, vorzugsweise Dialkyldimethylammoniumsalze, beispielsweise Dimethyl-distearylammoniumchlorid, oder/und Imidazolir.iumderivate, beispielsweise 1-Methyl-2-heptadecyl-3-ß- stearyl-amidoethyl-imidazolinium-methosulfat. Meist enthalten derartige Spülmittel etwa 5% eines derartigen Weichmachers. Ferner enthalten sie in der Regel ein oder mehrere nicht-ionogene(s) Tensid(e) (z.B. 0,1 bis 1%), wie sie auch in Waschmitteln verwendet werden (siehe oben). Fakultativ kann noch Parfüm, ein weisses Pigment (z.B. Ti02), Puffersubstanzen und ein Farbstoff (z.B. einige ppm) zugegeben werden. Im Falle der erfindungsgemässen Spülmittel kann der Fotoaktivator gleichzeitig als Farbstoff fungieren. Als Viskositätsregler wird den Spülmitteln meist noch ein Elektrolyt (z.B. ein Alkalimetallsalz) zugesetzt. Die Ergänzung auf 100% besteht in der Regel aus Wasser oder einer Mischung aus Wasser und einem Alkohol, vorzugsweise Isopropanol.

In addition to brighteners and photoactivators, detergents according to the invention contain components such as are used in conventional detergents, for example:

• As active substance (plasticizer) one or more dialkylated di (lower alkyl) ammonium salts, preferably dialkyldimethylammonium salts, for example dimethyl distearylammonium chloride, and / or Imidazolir.ium derivatives, for example 1-methyl-2-heptadecyl-3-ß-stearyl-amidoethyl-imidazolinium methosulfate. Such detergents usually contain about 5% of such a plasticizer. Furthermore, they usually contain one or more non-ionic surfactant (s) (eg 0.1 to 1%), as they are also used in detergents (see above). Optionally, perfume, a white pigment (eg Ti02), buffer substances and a dye (eg a few ppm) can also be added. In the case of the detergents according to the invention, the photoactivator can simultaneously act as a dye. An electrolyte (eg an alkali metal salt) is usually added to the detergents as a viscosity regulator. The addition to 100% usually consists of water or a mixture of water and an alcohol, preferably isopropanol.

It should also be mentioned that the salt content (e.g. Na sulfate) in the agents according to the invention has a certain influence on the effectiveness of the photoactivator. By varying the salt content, an optimal effect of the photoactivator can be set.

As already mentioned, further dirt removal agents in the agents according to the invention (such as perborate or enzymes) can increase the efficiency of the photoactivators.

trocknung getrocknet werden kann.The agents according to the invention can be produced without problems by all methods customary in the detergent industry, be they liquid formulations or powders or granules. In particular, the good heat resistance of the components essential to the invention also allows them to be added to the slurry of washing powders, which by

drying can be dried.

The invention further relates to aqueous soaking, washing or rinsing liquors which contain 0.001 to 100 ppm, preferably 0.01 to 10 ppm of a photoactivator and 0.05 to 150 ppm, preferably 0.1 to 50 ppm, in each case based on the total liquor, an optical brightener the class of the distyrylbiphenyl sulfonic acids and their salts or / and the 4,4'-bis (1,2,3-triazol-2-yl) -2,2'-stilbene sulfonic acids or their salts, including mixtures can be contained by several brighteners.

Brighteners and photoactivators in the fleets according to the invention are the same as those defined above for the agents according to the invention. The fleets according to the invention are e.g. obtained by dissolving or dispersing the agents according to the invention in water. Alternatively, however, the individual constituents can be dissolved or dispersed individually or in groups in water, whereupon the liquors according to the invention are formed. For example, a known soaking, washing or rinsing agent can be processed into a corresponding liquor and the photoactivator (s) and the brightener (s) added subsequently in the amount defined above. It is essential that the finished liquors contain photo activator and brightener in the specified concentration.

Finally, the invention also relates to a process for improving the appearance of used, in particular soiled, textiles, which is characterized in that the textiles are treated in the presence of oxygen with a liquor which contains an agent according to the invention and the textiles are directly in the liquor or in irradiated with light when wet outside the fleet.

For this purpose, the textiles are soaked, washed or rinsed in an aqueous liquor according to the invention (as described above).

The exposure required to develop the effect of the photoactivator can be carried out with an artificial light source which provides light, for example in the visible and / or infrared range (for example incandescent lamp, infrared lamp), it being possible for the bathroom to be irradiated directly, either by a Light source inside the container in which the liquor is located (e.g. lamp in the washing machine), be it from a light source outside the container. Likewise, the irradiation can also take place only after the textiles have been removed from the treatment bath. In this case, however, the textiles should still be damp or they must be moistened again afterwards. However, sunlight can also serve as the light source, the textiles preferably being exposed to the sunlight after treatment in the washing or bleaching bath in a moist state. The textiles can preferably be exposed to daylight during drying, for example on a clothesline.

The process according to the invention is expediently carried out at temperatures in the range from about 10 to 100, in particular from 10 to 85 ° C., for a period of from 15 minutes to 5 hours, preferably from 15 minutes to 60 minutes.

The following examples serve to further explain the invention, but without restricting it thereto.

Example 1: A detergent slurry consisting of 50 parts of deionized water and 50 parts of a detergent of the following composition is produced:

The aluminum phthalocyanine tetrasulfonate, hereinafter referred to as A1PCS, is used as the photoactivator in a concentration of 0.03%, based on the weight of the detergent. In some experiments, the zinc phthalocyanine tetrasulfonate, hereinafter referred to as ZnPCS, is used in a concentration of 0.07%.

(Al PC) = unsubstituiertes Aluminiumphthalocyanin) eingesetzt (Konzentration ebenfalls 0,03%). Die Ergebnisse mit diesem Photoaktivator sind praktisch identisch mit jenen, die beim Einsatz von A1PCS erzielt werden. Im folgenden (Beispiele 1 bis 6) ist unter der Bezeichnung A1PCS immer auch die Verbindung der Formel (25) zu verstehen.An aluminum phthalocyanine of the formula is also used as the photoactivator instead of aluminum phthalocyanine tetrasulfonate

(Al PC) = unsubstituted aluminum phthalocyanine) (concentration also 0.03%). The results with this Photoactivators are practically identical to those that can be achieved when using A1PCS. In the following (Examples 1 to 6), the term A1PCS always also means the compound of the formula (25).

Different types of brighteners are tested, all in a concentration of 0.13% active substance, based on the weight of the detergent.

The photoactivator and brightener are added to the above-defined detergent slurry, which does not yet contain these two components, with largely no light and dried in a drying box and a vacuum of approx. 400 torr at 80 ° C. for 4 hours. The detergent crusts obtained are then pressed through a sieve, beneath which another sieve is located, so that a uniform-grain washing powder is produced.

• a) 1 Teil Fruchtsaft aus dem Handel (unvergoren, ohne Zuckerzusatz, ohne Wasserzusatz, pasteurisiert) wird mit 1 Teil deionisiertem Wasser verdünnt. Das Baumwollgewebe wird darin während 45 Minuten in einem Flottenverhältnis von 1:20 behandelt und ohne Spülung bei 60°C getrocknet. Als Fruchtsäfte wurden verwendet: Kirschen-, Holunder-, Brombeer-, Johannisbeer- und Heidelbeersaft.
• b) 10 g Tee werden in 1 Liter deionisiertem Wasser gekocht und filtriert. Im Exktrakt werden Baumwollstreifen behandelt (2 Stunden kochend, dann 17 Stunden im abkühlenden Bad), gespült, zentrifugiert und warm getrocknet. Nach 1 Woche Lagerung werden die Testlappen für die Prüfung benutzt.
• c) EMPA-Testgewebe (Art. 103, Serie 23) = mit Blut angeschmutztes Baumwollgewebe.
• d) EMPA-Testgewebe (Art. 103, Serie 23) = mit Rotwein angeschmutztes Baumwollgewebe.

Rags made of bleached cotton fabric that had been soiled as follows are used as test substrates:

• a) 1 part of fruit juice from the trade (not fermented, without added sugar, without added water, pasteurized) is diluted with 1 part of deionized water. The cotton fabric is treated in a liquor ratio of 1:20 for 45 minutes and dried at 60 ° C without rinsing. The following were used as fruit juices: cherry, elderberry, blackberry, currant and blueberry juice.
• b) 10 g of tea are boiled in 1 liter of deionized water and filtered. In the extract, cotton strips are treated (boiling for 2 hours, then 17 hours in a cooling bath), rinsed, centrifuged and dried warm. After 1 week of storage, the test rags are used for the test.
• c) EMPA test fabric (Art. 103, Series 23) = cotton fabric soiled with blood.
• d) EMPA test fabric (Art. 103, Series 23) = cotton fabric soiled with red wine.

Test strips from the soiled fabrics just described are each washed in a liquor containing 4 g per liter of the detergent defined above at a liquor ratio of 1:20 for 30 minutes at 50 ° C., then rinsed briefly and suspended on a leash in the daylight and then Let dry for 6 hours (equivalent to about 250 Langley). An alkaline solution (pH 9, corresponds to that of the wash liquor) is sprayed every 40 minutes. This is a typical application for photo activators. The washing tests are carried out by varying the photoactivator and / or the optical brightener, with all tests to be compared being carried out in parallel and simultaneously for each type of soiling. The following Table I shows the composition of the detergent with regard to photoactivator and optical brightener (photoactivator / brightener combinations).

• Mit Versuch ① (ohne Zusatz) werden mehr oder weniger bescheidene Schmutzentfernungen erreicht.

In Example 1, only the combinations up to ⑦ were checked. The tests give the following picture for all fabrics with the soiling mentioned above:

• Experiment ① (without addition) achieves more or less modest dirt removal.

Trial (with A1PCS, without brightener) gives clear bleaching effects.

Experiments ④, and ⑥ (with A1PCS and various brighteners, which are usually used in the detergent industry) result in a certain change in nuance compared to experiment ⑦ for each type of soiling, which can be described as a trace to moderately lighter. Compared to each other, there are no significant differences between the experiments ④, ⑤ and ⑥.

The trials ② and ③, on the other hand, deliver the best results in terms of color removal and brightness of the treated test fabrics for each type of soiling.

Example 2: The same detergent compositions are used under the same test conditions as in Example 1. However, a cotton fabric is washed which has been soiled in accordance with Example 9 of German Offenlegungsschrift 28 12 278 with a brown dye. Because of the coloration achieved in this way, bleaching results which are very reproducible are obtained.

• - Nur mässig aufgehellt: Kombination ① (ohne Zusatz)
• - gut aufgehellt: Kombination ⑦ (nur A1PCS)
• - gut aufgehellt, mit etwas hellerer Nuance als ⑦ : Kombinationen ④ , @ und ⑥ (A1PCS + diverse Aufheller)
• - bei weitem beste Aufhellungen: Kombinationen (2) und ③ .

The results correspond to the results from Example 1 with the other types of soiling. The rags can be divided into 4 groups after washing:

• - Only moderately brightened: combination ① (without addition)
• - well lightened: combination ⑦ (only A1PCS)
• - well brightened, with a slightly lighter shade than ⑦: combinations ④, @ and ⑥ (A1PCS + various brighteners)
• - By far the best brightening: combinations (2) and ③.

Example 3: With the aim of quantifying the effects, various variants are tested under the same conditions as in Example 2 using a brightener compound contained in agents according to the invention, namely the brightener B (see Table I). However, the evaluation is not only visual, but also colorimetric. The rags are measured after washing on the RFC 3 color measuring device (from Zeiss) with the 21 filters. The degree of whiteness according to the whiteness formula of Ganz (see Fluorescent Whitening Agents, Chapter V / 2 in Environmental Quality and Safety, Ed. By Coulston & Korte, G. Thieme Verlag Stuttgart) is determined. The combinations listed in Table II below are tested (see also Table I). The degrees of whiteness achieved are also summarized in Table II below.

It is clearly evident that the combinations present in detergents according to the invention give significantly higher results than if either the photoactivator alone or the optical brightener alone is contained in the corresponding detergent.

Example 4: Under the same conditions as in Example 3, combinations with a photo activator but different brighteners are tested this time. The results are given in Table III below.

The results in Table III clearly show that the combinations contained in agents according to the invention lead to significantly better results than combinations with other commercial detergent brighteners.

Example 5: The cloth from Example 4 are further tested for their intrinsic white to the actual removal of dirt to kontrollie- _r s. This is done by measuring the reflection at 460 nm (R value) with xenon lighting with the addition of a UV blocking filter, in accordance with DIN 44 983. The brightener is thus not excited and only the basic white is determined. The results are shown in Table IV below.

While there is no influence on the base whiteness of the brightener C, on the other hand, surprisingly, the two brighteners contained in the agents according to the invention surprisingly result in an additional bleaching effect which is significantly higher than that achieved by the photoactivator.

If aluminum phthalocyanin or the compound of formula (25) (A1PCS) through a one _Pho toaktivator in the Beispielel 1 to 5 of the formula (ALPC) Br (SO ₃ H) _3.5-4 (ALPC) F (SO ₃ H) _3.5-4 , (AlPC) J (SO ₃ H) _3.5-4 , (ZnPC) Br (SO ₃ H) _3.5-4 or (ZnPG) J (SO ₃ H) _3.5-4 replaced (A1PC and ZnPC means the Al- and Zn-phthalocyanine ring system), the results are similar to those given in Examples 1 and 2 and in Tables II to IV.

• Je 6 der genannten Baumwollappen (a 10 g) werden bei einem Flottenverhältnis von 1:10 bei 30°C bzw. bei 60°C in einer Waschflotte gewaschen, die 5 g/l des oben genannten Waschmittels enthält. Die Waschzeit beträgt 15 Minuten, anschliessend werden die Lappen 30 Sekunden in fliessendem Wasser gespült und anschliessend 15 Sekunden geschleudert. Hernach werden die Lappen bei Tageslicht (bis zu 200 Langley) an der Leine getrocknet. Der eben beschriebene Waschzyklus (inklusive Trocknen) wird 9 Mal wiederholt.

Example 6: Using the detergent defined in Example 1, containing the combinations ② (= 0.03% AlPCS and 0.13% of the brightener A) or the combination ⑤ (= 0.03% A1PCS and 0.13% of the Brightener D) 'according to Table I, bleached, not pre-lightened, soiled rags made of thick cotton fabric are washed under the following conditions:

• 6 of the cotton rags mentioned (10 g each) are washed at a liquor ratio of 1:10 at 30 ° C. or at 60 ° C. in a washing liquor which contains 5 g / l of the above-mentioned detergent. The wash time is 15 minutes, then the rags are rinsed in running water for 30 seconds and then spun for 15 seconds. The rags are then dried on a line in daylight (up to 200 Langley). The washing cycle just described (including drying) is repeated 9 times.

The 6 cotton flaps are then subjected to a 10th wash cycle (as described), which is however stopped after spinning.

The 6 spin-damp cloths are now observed in bundle form, also looking into the bundle (corresponding to the process when the housewife takes the washed bundle of laundry from the washing machine and looks at it).

The damp bundle of the 6 cotton flaps, which was washed with the detergent containing the combination, shows an unsightly yellowish aspect (both after washing at 30 ° C and after washing at 60 ° C).

In contrast, the corresponding bundle, which was washed with the detergent containing the combination ② (= combination according to the invention), shows a light shade of white, described as a "glacial shimmer", which gives the items to be washed a particularly clean appearance. This enormous advantage is achieved both when washing at 30 ° C and when washing at 60 ° C. The effect described is particularly clear when it is observed under low-UV light (incandescent lamp), which generally also prevails in practice when laundry is removed from the washing machine.

It also shows here that the combination contained in agents according to the invention surprisingly leads to significantly better results than the combination with another commercially available detergent brightener.

Preparation of the compound referred to in the examples as A1PCS of the formula 25 given in example 1:

128 g of phthalodinitrile, 40 g of A1C1 and 650 g of 1,2-dichlorobenzene are placed in an autoclave. After flushing with nitrogen, the reaction mass is heated to about 170 ° C. for 26 hours. After cooling and venting, dig suspension is poured into 400 ml of water containing 100 g of trisodium phosphate while stirring. Then it is evaporated to dryness on a rotary evaporator Crude product mixed with 750 ml of water, mixed with 60 g of 50% NaOH, heated to 75 ° C. and kept at this temperature for 2 hours. Finally, the crude product is filtered off, stirred in 500 ml of water with 80 g of HC1 32% (2 hours at 90-95 ° C), filtered hot and washed.

(AlPC) = unsubstituiertes Aluminiumphthalocyanin.20 g of the product obtained in this way are stirred in 240 ml of 33% oleum at 73-75 ° C. for 7 hours. The reaction mixture, cooled to 25 ° C., is discharged onto a mixture of 1000 g of ice and 200 g of NaCl. The suspension is filtered and the filter residue is washed neutral with a 10% NaCl solution and then washed with 300 ml of 10% HCl. The product is dried at 80 ° C in a vacuum. It corresponds to the formula

(AlPC) = unsubstituted aluminum phthalocyanine.

Claims (18)

1. Means for improving the appearance of used, in particular soiled textiles, containing 0.0001 to 1%, preferably 0.001 to 0.1% of a photoactivator and 0.005 to 1.5%, preferably 0.01 to 0.5% in each case on the total weight of the agent, an optical brightener from the class of the distyrylbiphenylsulfonic acids and their salts and / or the 4,4'-bis (1,2,3-triazol-2-yl) -2,2'- stilbene sulfonic acids or their salts, which may also contain mixtures of several brighteners. 2. Soaking, washing or rinsing agent according to claim 1, characterized in that it contains a water-soluble phthalocyanine or mixtures of several water-soluble phthalocyanines as a photoactivator. 3. Soaking, washing or rinsing agent according to claim 2, characterized in that it is a sulfonated phthalocyanine of the formula as a photoactivator

or mixtures of these phthalocyanines, wherein PC stands for the Phrhalocyaninringsystem, X is an anion, in particular a halide, sulfate, hydroxyl or acetate ion, Y 'is hydrogen, an alkali metal or ammonium ion and v 'stands for any number between 1.3 and 4 (degree of sulfonation). 4. Soaking, washing or rinsing agent according to claim 2, characterized in that it is a sulfonated phthalocyanine of the formula as a photoactivator

or mixtures of these phthalocyanines, in which PC represents the phthalocyanine ring system, X is an anion, Y 'is hydrogen, an alkali metal or ammonium ion, R _{11 is} fluorine, chlorine, bromine, iodine or cyano, v "is any number between 1.3 and 4 (Degree of sulfonation) and X are any number between 0.1 and 4, it being possible for the R ₁₁ present in the molecule to be the same or different. 5. Soaking, washing or rinsing agent according to claim 3 or 4, characterized in that it is a sulfonated Al-phthalocyanine of the formula as a photoactivator

or mixtures of such Al phthalocyanines, in which X is an anion, Y 'is hydrogen, an alkali metal or ammonium ion, R _{11 is} fluorine, chlorine, bromine, iodine or cyano, v' is any number between 1.3 and 4 (degree of sulfonation ) and x 'mean zero or any number between 0.5 and 4. 6. Soaking, washing or rinsing agent according to one of claims 1 to 5, characterized in that it is an optical brightener one or more compound (s) of the formula

wherein X is hydrogen, chlorine, bromine or alkyl or alkoxy each having 1 to 4 carbon atoms, X _{2 is} hydrogen or alkyl having 1 to 4 carbon atoms and M is hydrogen, an alkali metal, ammonium or amine salt ion, in particular of the formula

wherein X ' _{l is} hydrogen or chlorine and M' is hydrogen, sodium, potassium or ammonium. 7. Soaking, washing or rinsing agent according to claim 6, characterized in that it is an optical brightener of the formula

where M "is hydrogen, sodium or potassium. 8. Soaking, washing or rinsing agent according to one of claims 1 to 5, characterized in that it is a compound of the formula as an optical brightener

wherein M represents hydrogen, an alkali metal, ammonium or amine salt ion. 9. Soaking, washing or rinsing agent according to one of claims 1 to 5, characterized in that it contains as an optical brightener a mixture of the compounds defined in claims 7 and 8. 10. Detergent according to claim 1, which contains the usual detergent components in addition to photoactivator and optical brightener. 11. Dishwashing liquid according to claim 1, which in addition to photoactivator and optical brightener also contains common detergent ingredients. 12. Soaking agent according to claim 1, which in addition to photoactivator and optical brightener also contains conventional components for soaking agents. 13. Soaking, washing or rinsing liquor containing 0.001 to 100 ppm, preferably 0.01 to 10 ppm of a photoactivator and 0.05 to 150 ppm, preferably 0.1 to 50 ppm, in each case based on the total liquor, of an optical brightener from the class of distyrylbiphenyl sulfonic acids and their salts or / and the 4,4'-bis (1,2,3-triazol-2-yl) -2,2'-stilbene sulfonic acids or their salts, where Mixtures of several brighteners can also be included. 14. A method for improving the appearance of used, in particular soiled textiles, characterized in that the textiles are treated with a liquor which contains an agent defined in claim 1 and the textiles directly in the liquor or in the wet state outside the liquor with light irradiated. 15. The method according to claim 14, characterized in that soiled textiles are soaked in a liquor which contains a agent defined in one of claims 2 to 9 or 12. 16. The method according to claim 14, characterized in that soiled textiles are washed in a liquor which contains a detergent as defined in claims 2 to 10. 17. The method according to claim 14, characterized in that optionally already washed textiles are rinsed with a liquor which contains a detergent defined in claims 2 to 7 or 11. 18. The method according to any one of claims 14 to 17, characterized in that the irradiation or exposure of the textiles takes place in daylight after removal from the bathroom.