EP0026744B2 - Means and process for the treatment and the improvement of the appearance of textiles - Google Patents

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 1372036, US Patent 3,927,967, German Offenlegungsschriften 2613936 and 2812278. 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 bleached fabrics soaked, washed, rinsed or otherwise cleaned. To develop the bleaching effect caused by the photodynamic effect, the textiles must be irradiated with light during the treatment. A corresponding lamp can be used for this purpose, or, particularly advantageously, in particular with regard to energy consumption, 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 can be achieved with the best combinations of photoactivators alone, still with selected optical brighteners alone, or with combinations of the photoactivators mentioned with the other known optical brighteners available on the market. 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 the 4,4 ^1- bis- (1,2,3-triazot-2-yl) -2.2 ^1- stilbene-sulfonic acids or their salts, it also being possible for mixtures of several brighteners to be present, and excluding those agents which are a combination of zinc phthalocyanitri- and tetrasulfonate and 4,4'-bis- ( Contain 2-sulfostyryl) biphenyl.

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 photoactivators can also be used, e.g. Mixtures of various phthalocyanine compounds, such as mixtures of water-soluble Zn and Al phthalocyanines.

in welchen Formeln

• X, Sauerstoff, den Rest -Nh- oder -N-Alkyl und
• R, 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,
• Y, 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 R₆ unabhängig voneinander einen gegebenenfalls substituierten Alkyl- oder Aralkylrest,
• R₇ eine gegebenenfalls substituierte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder Wasserstoff, M ein Alkalimetall- oderAmmoniumion,
• 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 / l 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 formols

in what formulas

• X, 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, oxygen, sulfur, the radical -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, unsubstituted or phenyl 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, a saturated 5- or 6-membered heterocyclic ring which additionally contains a nitrogen - or can contain oxygen atom as ring member,
• R ₅ and R ₆ independently of one another are an optionally substituted alkyl or aralkyl radical,
• R _{7 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 and Y 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 radical are preferred.

The number of substituents present in the molecule is determined by achieving sufficient water solubility. If there are several water-solubilizing groups 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 present in addition to the water-solubilizing groups, at most in a number such 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.

worin

• PC für das Phthalocyaninringsystem steht,
• v einen beliebigen Wert zwischen 1 und 4 hat,
• Me Zn, Fe (II), Ca, Mg, Na, K oder AI X, vorzugsweise Zn oder AI 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,
• R, 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 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,
• 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

wherein

• 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 is 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 is hydrogen, an alkali metal, ammonium or amine ion,
• R _' , hydrogen or alkyl having 1 to 4 carbon atoms,
• n _' an integer from 2 to 6,
• R, and R ₂ independently of one another 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 being} 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 ₄ together with the nitrogen atom to which they are attached are 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 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, und
• Me Zn, Fe(II), Ca, Mg, Na, K oder AI X, vorzugsweise Zn oder AI 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.

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

oder Mischungen von solchen AI-Phthalocyaninen, worin

• X ein Anion, insbesondere ein Halogenid-, Sulfat-, Hydroxyl-, oder Acetation, Y' Wasserstoff, ein Alkalimetall- oder Ammoniumion, R_I1 Fluor, Chlor, Brom, Jod oder Cyano, v' eine beliebige Zahl zwischen 1, 3 und 4 (Sulfonierungsgrad) und x_' null oder eine beliebige Zahl zwischen 0,5 und 4 bedeuten.

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 _{I1 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.

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 optionally also have 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 2812261 and 2812 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 may already be present in the starting materials used for the construction of the phthalocyanine ring structure (for example phthalic anhydride, phthalonitrile 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 before or before are preferably introduced subsequently, for example by sulfonation, provided that the phthalocyanine ring system is built up from phthalic anhydride or phthalodinitrile in the presence of chlorides, for example AICI ₃ , ZnC1 ₂ and others, chlorinated phthalocyanines are formed, especially with a chlorine content of 0.5-1.5 Moles of chlorine per mole of 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 X, 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, hydrogen, chlorine, bromine or alkyl or alkoxy each having 1 to 4 carbon atoms, X ₂ hydrogen or alkyl having 1 to 4 carbon atoms and M 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 _{2 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" Wasserstoff, Natrium oder Kalium bedeutet.Brighteners of the formula are preferred

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

where M "is 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 constituents are primarily anionic, non-ionic or mixtures of anionic and nonionic 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 mixtures 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. Alkalipoly-und -polymetaphosphate, Alkalipyrophosphate oder Aluminosilikate, Alkalisalze der Carboxymethylcellulose und andere «Soilredepositioninhibitoren», ferner Alkali- und Erdalkalisilikate, Alkalicarbonate, Alkalisulfate, Alkaliborate, Alkaliperborate, Alkalipercarbonate, Nitrilotriessigsäure, Äthylendiaminotetraessigsäure, 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 middle to higher alcohols, fatty acid acylaminoalkyl or aminoamino acid ester sulfonates, non-phosphonic ionophosphates Surfactants, etc. As builders for solid washing powders, so-called “builders”, there are, for example, alkali poly- and polymetaphosphates, alkali pyrophosphates or aluminosilicates, alkali salts of carboxymethyl cellulose and other “soil deposition inhibitors”, furthermore alkali and alkaline earth silicates, alkali metal carbonates, alkali metal borate sulfates. Alkali percarbonates, nitrilotriacetic acid, ethylenediaminotetraacetic acid, foam stabilizers such as alkanolamides of higher 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 Imidazoliniumderivate; 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 Wasch- . mitteln 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:

• One or more dialkylated di (lower alkyl) ammonium salts, preferably dialkyldimethylammonium salts, for example dimethyl distearylammonium chloride, and / or imidazolinium 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) (for example 0.1 to 1%), as they are also found in laundry detergents. medium can be used (see above). Optionally, perfume, a white pigment (eg Ti0 ₂ ), 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 salinity, 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.

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 powder, which can be dried by spray drying.

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 from the class of distyrylbiphenylsulfonic acids and their salts and / or 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, and excluding soaking, washing and rinsing liquors which contain a combination of zinc phthalocyanine tri and tetrasulfonate and 4,4'-bis (2- contain sulfostyryl) biphenyl.

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 achieved with an artificial light source that emits light e.g. supplies in the visible and / or infrared range (e.g. incandescent lamp, infrared lamp), whereby the bathroom can be directly irradiated, either by a light source inside the container in which the liquor is located (e.g. lamp in the washing machine), or by 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 in a moist state after treatment in the washing or bleaching bath. The textiles can preferably be exposed to daylight during drying, for example on a clothesline.

The ancestor 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.

example 1

Als Fotoaktivator wird das Aluminium-phthalocyanin-tetrasulfonat, im folgenden als AIPCS bezeichnet, in einer Konzentration von 0,03%, bezogen auf das Waschmittelgewicht, verwendet. In einigen Versuchen wird auch das Zinkphthalocyanin-tetrasulfonat, im folgenden als ZnPCS bezeichnet, in einer Konzentration von 0,07% eingesetzt.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 AIPCS, 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%.

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

(AI PC) - unsubstituted aluminum phthalocyanine)
used (concentration also 0.03%). The results with this photo activator are practically identical to those achieved with the use of AIPCS. In the following (Examples 1 to 6), the term AIPCS is always also to be understood as the compound of the formula (25).

Different types of brighteners have been used tests, all in a concentration of 0.134% 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 Extrakt werden Baumwollstreifen behandelt (2 Stunden kochend, dann 17 Stunden im abkühlenden Bad), gospult, zontrifugiert und warm gotrocknot. 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), gospult, zontrifuged and warm Gotrocknot. 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 lists the composition of the detergent with regard to photoactivator and optical brightener (photoactivator / brightener combinations).

bis (₇; geprüft. Für alle Gewebe mit den oben genannten Anschmutzungen ergeben die Versuche folgendes Bild:

• Mit Versuch
  
  (ohne Zusatz) werden mehr oder weniger bescheidene Schmutzentfernungen erreicht.
• Versuch
  
  (mit AIPCS, ohne Aufheller) ergibt deutliche Bleicheffekte.
• Versuche
  
  , und
  
  (mit AIPCS und diversen Aufhellern, die üblicherweise in der Waschmittelindustrie verwendet werden) ergeben gegenüber Versuch (₇) bei jeder Anschmutzungsart eine bestimmte Nuancen-Änderung, die als eine Spur bis mässig heller bezeichnet werden kann. Untereinander verglichen, sind keine nennenswerten Unterschiede zwischen den Versuchen
  
  ,
  
  und
  
  festzustellen.
• Die Versuche @ und
  
  dagegen liefern bei jeder Anschmutzungsart die deutlich besten Resultate in bezug auf Farbentfernung und Helligkeit der behandelten Testgewebe.

In the context of example 1, only the combinations

to ( ₇ ; checked. For all fabrics with the above-mentioned soiling, the tests give the following picture:

• With an attempt
  
  (without addition) more or less modest dirt removal is achieved.
• attempt
  
  (with AIPCS, without brightener) produces clear bleaching effects.
• tries
  
  , and
  
  (with AIPCS and various brighteners that are commonly used in the detergent industry) result in a specific change in nuance for each type of soiling compared to experiment ( ₇ ), which can be described as a trace to moderately brighter. Compared to each other, there are no significant differences between the tests
  
  ,
  
  and
  
  ascertain.
• The attempts @ and
  
  on the other hand, the best results in terms of color removal and brightness of the treated test fabrics provide the best results for every 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 with a brown dye in accordance with Example 9 of German Offenlegungsschrift 2812278. Because of the coloration achieved in this way, bleaching results which are very reproducible are obtained.

• - Nur mässig aufgehellt: Kombination
  
  (ohne Zusatz)
• - gut aufgehellt: Kombination
  
  (nur AlPCS)
• - gut aufgehellt, mit etwas hellerer Nuance als @: Kombinationen
  
  ,
  
  und (AIPCS + diverse Aufheller)
• - bei weitem beste Aufhellungen: Kombinationen @ und @.

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
  
  (without addition)
• - well lightened: combination
  
  (AlPCS only)
• - well lightened, with a slightly lighter shade than @: combinations
  
  ,
  
  and (AIPCS + various brighteners)
• - By far the best brightening: combinations @ and @.

Example 3

Es ist deutlich ersichtlich, dass die in erfindungsgemässen Waschmitteln vorhandenen Kombinationen deutlich höhere Resultate ergeben, als wenn entweder der Fotoaktivator allein oder der optische Aufheller allein im entsprechenden Waschmittel enthalten ist.With the aim of quantifying the effects, different 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 whitening 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

Die Resultate in Tabelle III zeigen deutlich, dass die in erfindungsgemässen Mitteln enthaltenen Kombinationen zu deutlich besseren Resultaten führen, als Kombinationen mit anderen handelsüblichen Waschmittelaufhellern.Combinations with a photo activator, but different brighteners, are tested this time under the same conditions as in Example 3. The results are shown 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

Während beim Aufheller C keine Beeinflussung des Grundweisses festzustellen ist, ergeben dagegen überraschenderweise die beiden Aufheller, die in erfindungsgemässen Mitteln enthalten sind, zusätzliche Bleichwirkung, die deutlich über jener der durch den Fotoaktivator erzielten liegt.The rags from Example 4 are also examined for their basic white in order to check the actual dirt removal. 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 44983. The brightener is therefore not excited and only the basic white is determined. The results are shown in the following table IV specified.

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

If in Examples 1 to 5 aluminum phthalocyanine tetrasulfonate or the compound of the formula (25) (AIPCS) is replaced by a photoactivator 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 (ZnPC) J (SO ₃ H) _{3, 5-4} replaced (AIPC and ZnPC means the Al- and Zn-phthalocyanine ring system), you get similar results as those given in Examples 1 and 2 and in Tables II to IV.

Example 6

(= 0,03% AIPCS und 0,13% des Aufhellers D) gemäss Tabelle I, werden gebleichte, nicht voraufgehellte, unverschmutzte Lappen aus dickem Baumwollgewebe unter folgenden Bedingungen gewaschen:

• Je 6 der genannten Baumwollappen (ä 10 g) werden bei einem Flottenverhältnis von 1:10 bei 30°C bzw. bei 60°C in einer Waschflotte gewaschen, die 5 g/I 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.

Using the detergent defined in Example 1, containing the combinations 0 (= 0.03% AIPCS and 0.13% of brightener A) or the combination

(= 0.03% AIPCS and 0.13% of 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 (according 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 (5), shows an unsightly yellowish aspect (both after washing at 30 ° C. and after washing at 60 ° C.).

(= erfindungsgemässe Kombination) enthaltenden Waschmittel gewaschen wurde, eine helle, als «Gletscherschimmer» beschriebene Weissnuance, die dem Waschgut ein ausgesprochen sauberes Aussehen verleiht. Dieser enorme Vorteil wird sowohl bei der Wäsche bei 30°C als auch bei der Wäsche bei 60°C erzielt. Besonders deutlich wird der beschriebene Effekt, wenn unter UV-armem Licht (Glühlampe) beobachtet wird, das auch in der Praxis bei der Entnahme von Waschgut aus der Waschmaschine in der Regel vorherrscht.In contrast, the corresponding bundle shows that with the combination

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

It also shows here that the combination contained in the agents according to the invention surprisingly leads to significantly better results than the combination with another commercial detergent brightener. Preparation of the compound referred to in the examples as AIPCS of the formula 25 given in example 1

128 g of phthalodinitrile, 40 g of AICI ₃ 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, the suspension is poured into 400 ml of water containing 100 g of trisodium phosphate with stirring. The mixture is then evaporated to dryness on a rotary evaporator, the crude product is stirred with 750 ml of water, 60 g of 50% NaOH are added, the mixture is 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 32% HCl (2 hours at 90-95 ° C.), filtered hot and washed.

(AIPC) = unsubstituiertes Aluminiumphthalocyanin.20 g of the product thus obtained 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. Then it is washed with 300 ml of HCI 10%. The product is dried at 80 ° C in a vacuum. It corresponds to the formula

(AIPC) = unsubstituted aluminum phthalocyanine.

Claims (18)

1. A composition for improving the appearance of used, in particular soiled, textiles, said composition comprising 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 based on the total weight of the composition, of a fluorescent whitening agent selected from the class of distyrylbiphenylsulfonic acids or their salts and/or of 4,4'-bis-(1,2,3-triazol-2-yl)-2,2'- stilbenesulfonic acids or their salts, which composition may also contain a mixture of several fluorescent whitening agents, excluding such composition which contains a combination of zinc phthalocyaninetri- and -tetrasulfonate and 4,4'-bis(2-sulfostyryl)-biphenyl.

2. A soaking, detergent or rinsing composition according to claim 1, wherein the photoactivator is a water-soluble phthalocyanine or a mixture of several water-soluble phthalocyanines.

3. A soaking, detergent or rinsing composition according to claim 2, wherein the photoactivator is a sulfonated phthalocyanine of the formula

or

or a mixture of such phthalocyanines, wherein

PC denotes the phthaloxyanine ring system,

X is an anion,

Y' is hydrogen, an alkali metal ion or an ammonium ion, and

v' is any number from 1.3 to 4 (degree of sulfonation).

4. A soaking, detergent or rinsing composition according to claim 2, wherein the photoactivator is a sulfonated phthalocyanine of the formula

or

or a mixture of such phthalocyanines, wherein PC is the phthalocyanine ring system, X is an anion, Y' is hydrogen, an alkali metal ion or ammonium ion, R11 is fluorine, chlorine, bromine, iodine or cyano, v' is any number from 1.3 to 4 (degree of sulfonation) and X is any number from 0.1 to 4, whilst the radicals R₁₁ present in the molecule can be the same of different.

5. A soaking, detergent or rinsing composition according to either of claims 3 or 4, wherein the photoactivator is a sulfonated aluminium phthalocyanine of the formula

or a mixture of such aluminium phthalocyanines, wherein X is an anion, especially a halide, sulfate, hydroxyl or acetate ion, Y' is hydrogen, an alkali metal ion or an ammonium ion, v' is any number from 1.3 to 4 (degree of sulfonation), and x' is 0 or any number from 0.5 to 4.

6. A soaking, detergent or rinsing composition according to any one of claims 1 to 5 which contains, as fluorescent whitening agent, one or more compounds of the formula

wherein X₁ is hydrogen, chlorine, bromine, or alkyl or alkoxy each containing 1 to 4 carbon atoms, X₂ is hydrogen or alkyl of 1 to 4 carbon atoms, and M is hydrogen, an alkali metal ion, ammonium ion or amine salt ion, preferably of the formula

wherein X₁' is hydrogen or chlorine and M' is hydrogen, sodium, potassium or ammonium.

7. A soaking, detergent or rinsing composition according to claim 6 which contains a fluorescent whitening agent of the formula

wherein M" is hydrogen, sodium or potassium.

8. A soaking, detergent or rinsing composition according to any one of claims 1 to 5 which contains, as fluorescent whitening agent, a compound of the formula

wherein M is hydrogen, an alkali metal ion, an ammonium ion or an amine salt ion.

9. A soaking, detergent or rinsing composition according to any one of claims 1 to 5 which contains, as fluorescent whitening agent, a mixture of the compounds defined in claims 7 and 8.

10. A detergent composition according to claim 1 which contains customary detergent ingredients in addition to photoactivator and fluorescent whitening agent.

11. A rinsing composition according to claim 1 which, in addition to containing photoactivator and fluorescent whitening agent, also contains constituents customarily employed in rinsing compositions.

12. A soaking composition according to claim 1 which, in addition to containing photoactivator and fluorescent whitening agent, also contains constituents customarily employed in soaking compositions.

13. A soaking, detergent 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 a fluorescent whitening agent selected from the class of the distyrylbiphenylsulfonic acids and salts thereof and/or 4,4'-bis-(1,2,3-triazol-2-yl)-2,2'-stilbenesulfonic acids or salts thereof, which liquor may also contain a mixture of several fluorescent whitening agents, excluding such soaking, detergent or rinsing liquor which contains a combination of zinc phthalocyaninetri- and -tetrasulfonate and 4,4'-bis(2-sulfostyryl)-biphenyl.

14. A method of improving the appearance of used, in particular soiled, textiles, which method comprises treating said textiles with a liquor which contains a composition as defined in claim 1, and irradiating the textiles direct in the liquor, or in the wet state outside the liquor, with light.

15. A method according to claim 14 which comprises soaking soiled textiles in a liquor which contains a composition as defined in any one of claims 2 to 9 or 12.

16. A method according to claim 14 which comprises washing soiled textiles in a liquor which contains a detergent composition as defined in any one of claims 2 to 10.

17. A method according to claim 14 which comprises rinsing already washed textiles with a liquor which contains a rinsing composition as defined in any one of claims 2 to 7 or 11.

18. A method according to anyone of claims 14 to 17, wherein the textiles, after removal from the liquor, are irradiated by exposure to daylight.