DE60308485T2 - PROCESS FOR THE TREATMENT OF TEXTILE FIBER MATERIALS - Google Patents

Description

The The present invention is directed to detergent formulations. the particular fluorescent brightener and a peroxide, a peroxide activator and / or a bleach catalyst.

It is well known, fluorescers in detergent formulations to use. They exhaust while Treatment on the material to be washed and force their special light absorption / emission characteristic to the elimination the yellowish tint.

It however, there is still a need for improved fluorescent brighteners for this Application. It has now been found that the following Compounds of formulas (1) superior Properties re for example, solubility, Own builder characteristics, light fastness of the whiteness and also one have excellent appearance in the solid state. The whiteness properties, How to maintain whiteness even through use of compounds of formula (1) are reinforced in detergents, which contain a peroxide, a peroxide activator and / or a bleach catalyst. Cheap Properties are obtained even at low wash temperatures.

worin X₁ und X₃ -NH₂ sind,
R₁ und R₂ unabhängig voneinander Wasserstoff oder unsubstituiertes oder substituiertes C₁-C₈-Alkyl sind,
X₂ und X₄ unabhängig voneinander -N(R₃)R₄ sind, worin R₃ und R₄ Wasserstoff; Cyano; C₁-C₈-Alkyl, das unsubstituiert oder substituiert ist durch Hydroxy, Carboxy, Cyano-, -CONH₂ oder Phenyl ist, und worin die C₁-C₈-Alkylgruppe nicht unterbrochen oder unterbrochen ist durch -O-; unsubstituiertes oder C₁-C₄-alkylsubstituiertes C₅-C₇-Cycloalkyl sind; oder R₃ und R₄ zusammen mit dem Stickstoffatom, welches sie verbindet, einen unsubstituierten oder C₁-C₄-alkylsubstituierten Morpholin-, Piperidin- oder Pyrrolidinring bilden;
R₅ C₁-C₈-Alkyl ist, das unsubstituiert oder durch Hydroxy substituiert ist, und M Wasserstoff, ein Alkali- oder Erdalkalimetall oder Ammonium ist, und worin das Reinigungsmittel ein Peroxid, einen Peroxidaktivator und/oder einen Bleichkataly-sator enthält.Accordingly, in a first aspect, the present invention provides a detergent composition comprising at least one compound of the formula

wherein X ₁ and X _{3 are} -NH ₂ ,
R ₁ and R _{2 are} independently hydrogen or unsubstituted or substituted C ₁ -C ₈ -alkyl,
X ₂ and X _{4 are} independently -N (R ₃ ) R ₄ , wherein R ₃ and R _{4 are} hydrogen; cyano; C ₁ -C ₈ alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH ₂ or phenyl, and wherein the C ₁ -C ₈ alkyl group is uninterrupted or interrupted by -O-; unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ cycloalkyl; or R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring;
R _{5 is} C ₁ -C ₈ alkyl which is unsubstituted or substituted by hydroxy, and M is hydrogen, an alkali or alkaline earth metal or ammonium, and wherein the cleaning agent comprises a peroxide, a peroxide activator and / or a bleach catalyst.

Within the above definitions, C ₁ -C ₈ -alkyl may be methyl, ethyl, n- or iso-propyl, n-, sec- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl. Preference is given to C ₁ -C ₄ -alkyl groups. In the case where the alkyl groups which are R ₁ and R ₂ are substituted, examples of possible substituents are hydroxyl, halogens such as fluorine, chlorine or bromine, sulfo, sulfato, carboxy and C ₁ -C ₄ alkoxy such as methoxy or ethoxy. Other substituents of such alkyl groups are, for example, cyano, -CONH ₂ and phenyl. Preferred substituents are hydroxy, carboxy, cyano, -CONH ₂ and phenyl, especially hydroxy and carboxy. Highly preferred substituents are furthermore hydroxy and C ₁ -C ₄ -alkoxy, in particular hydroxy. The alkyl groups can not be interrupted or (in case the alkyl groups contain two or more carbon atoms) be interrupted by -O-.

Examples of C ₅ -C ₇ -cycloalkyl groups are cyclopentyl and in particular cyclohexyl. These groups may be substituted by C ₁ -C ₄ -alkyl, such as methyl. Preference is given to the corresponding unsubstituted cycloalkyl groups.

In the above definitions, C ₁ -C ₄ -alkyl may be methyl, ethyl, n- or iso-propyl, n-, sec- or t-butyl, in particular methyl.

R ₃ and R ₄ together with the nitrogen atom form a morpholine, piperidine or pyrrolidine ring, Such a ring system may be unsubstituted or substituted by C ₁ -C ₄ -alkyl, in particular methyl. Preference is given to the unsubstituted ring systems.

The cation M is an alkali metal atom, an alkaline earth metal atom or ammonium. Preference is given to Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C ₁ -C ₄ -alkylammonium, mono-, di- or tri-C ₂ -C ₄ -hydroxyalkylarnmonium or ammonium, which are di- or trisubstituted with a mixture of C ₁ -C ₄ -alkyl and C ₂ -C ₄ -hydroxyalkyl groups. Highly preferred is sodium.

R ₁ and R ₂ are preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen.

R ₃ and R ₄ are preferably hydrogen; cyano; C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH ₂ or phenyl, in particular by hydroxy or carboxy, and in which the C ₁ -C ₈ -alkyl group is not interrupted or by -O - is interrupted; unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ cycloalkyl, in particular cyclohexyl; or R ₃ and R _{4 together} with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring.

R ₃ and R ₄ are further preferably hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₈ alkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ cycloalklyl, or R ₃ and R ₄ together with the linking thereof Nitrogen atom is an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring. Highly preferred meanings for R ₃ and R ₄ are hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₈ -alkyl, or R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ -alkyl-substituted morpholine, piperidine - or pyrrolidine ring. Most preferred are unsubstituted or C ₁ -C ₄ alkyl substituted morpholine, piperidine or pyrrolidine rings, especially morpholine formed by R ₃ and R ₄ together with the nitrogen atom linking them.

Examples of -N (R ₃ ) R ₄ groups are -NH ₂ , -NHCH ₃ , -NHC ₂ H ₅ , -NH (nC ₃ H ₇ ), -NH (iC ₃ H ₇ ), -NH (iC ₄ H ₉ ), -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -N (iC ₃ H ₇ ) ₂ , -NH (CH ₂ CH ₂ OH), -N (CH ₂ CH ₂ OH ) ₂ , -N (CH ₂ CH (OH) CH ₃ ) ₂ , -N (CH ₃ ) (CH ₂ CH ₂ OH), -N (C ₂ H ₅ ) (CH ₂ CH ₂ OH), -N ( iC ₃ H ₇ ) (CH ₂ CH ₂ CH ₂ OH), -NH (CH ₂ CH (OH) CH ₃ ), -N (C ₂ H ₅ ) (CH ₂ CH (OH) CH ₃ ), -NH ( CH ₂ CH ₂ OCH ₃ ), -NH (CH ₂ CH ₂ OCH ₂ CH ₂ OH), -NH (CH ₂ COOH), -NH (CH ₂ CH ₂ -COOH), -N (CH ₃ ) (CH ₂ COOH), -NH (CN);

Preference is given to compounds of the formula (1) in which
R ₁ and R _{2 are} hydrogen or C ₁ -C ₄ -alkyl,
R ₃ and R _{4 are} hydrogen; cyano; C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH ₂ or phenyl and in which the C ₁ -C ₈ -alkyl group is uninterrupted or interrupted by -O-; unsubstituted or C ₁ -C ₄ -alkyl-substituted C ₅ -C ₇ -cycloalkyl; or R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring; and
R _{5 is} C ₁ -C ₈ alkyl which is unsubstituted or substituted by hydroxy. As regards R ₃ , R ₄ and R ₅ , apply the above preferences.

Of particular interest are compounds of formula (1) wherein X ₁ and X _{3 are} amine and X ₂ and X _{4 is} a radical of formula -N (R ₃ ) R ₄ wherein R ₃ and R _{4 are} hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₈ -alkyl, unsubstituted or by C ₁ -C ₄ -alkyl-substituted cyclopentyl or cyclohexyl, or R ₃ and R ₄ together with the nitrogen atom linking them is an unsubstituted or C ₁ -C ₄ -alkyl-substituted morpholine, piperidine or form pyrrolidine ring. The most interesting compounds of formula (1) are those wherein R ₃ and R _4, together with the nitrogen atom linking them, form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring. As for R ₃ and R ₄ , the above preferences apply.

The Compounds of the formula (1) are known or can be prepared in analogy to known Process are produced.

Compounds of formula (1) may be prepared by reacting cyanuric chloride in any desired order under known reaction conditions with both 4,4'-diaminostilbene-2,2'-disulfonic acid and amino compounds capable of the groups X ₁ X ₂ , X ₃ and X _{4 are} introduced. Initially, preferably 2 moles of cyanuric chloride with 1 mole of 4,4'-diaminostilbene-2,2'-disulfonic acid and the resulting intermediate product then reacted in any order with amino compounds, which are capable of the groups X _1, X _2, X ₃ and X ₄ introduce. In the production of compounds in which X ₂ and X ₄ have the same meaning, the resulting intermediate is preferably reacted first with an amino compound which is capable of introducing X ₁ and X _3, and finally with an amino compound, which in capable of introducing X ₂ and X ₄ . The reaction with the amino compounds may also be accomplished in one step by reacting the intermediate with a mixture of amino compounds; In such a case, mixtures are usually obtained, which correspond to the compounds of formula (1).

• i) 1–70% eines anionischen Tensids und/oder eines nichtionischen Tensids;
• ii) 0–75% eines Builders;
• iii) 0,5–30% eines Peroxids;
• iv) 0.5–10% eines Peroxidaktivators und/oder 0,1–2% eines Bleichkatalysators;
• v) 0,001–5% einer Verbindung der Formel (1); und
• vi) 0–5% mindestens eines Enzyms, gewählt aus der Gruppe, bestehend aus Cellulase, Protease, Amylase und Lipase.

The detergent compositions used preferably comprise

• i) 1-70% of an anionic surfactant and / or a nonionic surfactant;
• ii) 0-75% of a builder;
• iii) 0.5-30% of a peroxide;
• iv) 0.5-10% of a peroxide activator and / or 0.1-2% of a bleach catalyst;
• v) 0.001-5% of a compound of formula (1); and
• vi) 0-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

• i) 5–70% eines anionischen Tensids und/oder eines nichtionischen Tensids;
• ii) 5–70% eines Builders;
• iii) 0,5–30% eines Peroxids;
• iv) 0,5–10% eines Peroxidaktivators und/oder 0,1–2% eines Bleichkatalysators;
• v) 0,01–5% einer Verbindung der Formel (1); und
• vi) 0,05–5% mindestens eines Enzyms, gewählt aus der Gruppe, bestehend aus Cellulase, Protease, Amylase und Lipase.

The detergent compositions used more preferably comprise

• i) 5-70% of an anionic surfactant and / or a nonionic surfactant;
• ii) 5-70% of a builder;
• iii) 0.5-30% of a peroxide;
• iv) 0.5-10% of a peroxide activator and / or 0.1-2% of a bleach catalyst;
• v) 0.01-5% of a compound of formula (1); and
• vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.

in the Generally, the compound of formula (1) is in an amount of 0.001-5% especially used in an amount of 0.01-5%. Highly preferred is an amount of 0.05-5%, in particular from 0.05 to 2%. Generally understood in percent given amounts as weight percent, based on the total weight, unless otherwise stated.

The Detergent may be used as a solid, as an aqueous liquid, e.g. B. 5-50, preferably 10-35% water, or as non-aqueous liquid Detergent containing not more than 5, preferably 0-1% by weight Water in the form of a suspension of a builder in a nonionic Tensid be formulated, such as. As described in GB-A 2158454.

The anionic surfactant component may, for. An alkylbenzenesulfonate, an alkylsulfate, an alkyl ether sulfate, an olefin sulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or a salt of an α-sulfofatty acid or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkyl sulfates having 8 to 18 carbon atoms, alkyl ether sulfates having 8 to 18 carbon atoms, and fatty acid salts having 8 to 18 carbon atoms derived from palm oil or talc. The The average ethylene oxide molar number added to the alkyl ether sulfates is preferably 1 to 20, preferably 1 to 10. The salts are preferably derived from an alkali metal such as sodium or potassium, in particular sodium. Highly preferred carboxylates are alkali metal sarcosinates of the formula R-CO (R ¹ ) CH ₂ COOM ¹ wherein R is an alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R ^{1 is} C ₁ -C ₄ alkyl and M ¹ is an alkali metal, especially sodium.

The nonionic surfactant component may, for. Example, a primary and secondary alcohol ethoxylate, in particular one with an average of 1 to 20 moles of ethylene oxide per mole of ethoxylated aliphatic C ₈ -C ₂₀ alcohol and more particularly with an average of 1 to 10 moles of ethylene oxide per mole of alcohol ethoxylated primary or secondary aliphatic C ₁₀ -C ₁₅ alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamine (glucamide).

The Total amount of anionic surfactant and nonionic surfactant is preferably 5-50% by weight, preferably 5-40 Wt .-% and more preferably 5-30 wt .-%. What these surfactants concerns the lower limit is preferably 10% by weight.

The builder component may be an alkali metal phosphate, in particular a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate, a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these. Preferred silicates are crystalline sodium layer silicates of the formula NaHSi _m O _{2m + 1} pH ₂ O or Na ₂ Si _m O _{2m + 1} · pH ₂ O, where m is a number from 1.9 to 4 and p is 0 to 20. Preferred aluminosilicates are the commercially available synthetic materials called zeolite A, B, X and HS or mixtures thereof. Zeolite A is preferred. Preferred polycarboxylates include hydroxypolycarboxylates, especially citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are the alkali metal ethane 1-hydroxy diphosphonates, nitrilotrimethylene phosphonates, ethylenediamine tetramethylene phosphonates and diethylene triamine pentamethylene phosphonates. The builder content is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. As for the builder, the lower limit is preferably 15% by weight, more preferably 20% by weight.

suitable Close peroxide components for example, the organic and inorganic peroxides (such as sodium peroxides) one which is known from the literature and commercially as a textile bleach for conventional Washing temperatures of, for example, 5 to 95 ° C are available. The organic ones For example, peroxides are especially monoperoxides or polyperoxides with alkyl chains having at least 3, preferably 6 to 20 carbon atoms, in particular diperoxydicarboxylates having 6 to 12 carbon atoms, such as diperoxyazelates, Diperoxypersebacates, diperoxyphthalates and / or diperoxydodecanedioates, in particular, their corresponding free acids are of interest. Preferably However, the very active inorganic peroxides such as persulfates, Perborates and / or percarbonates used. Of course, it can also be mixtures of organic and / or inorganic peroxides are used.

Of the Peroxide content is preferably 0.5-30 Wt .-%, preferably 1-20 % By weight and further preferably 1-15 Wt .-%. When a peroxide is used, the lower limit is preferably 2 wt .-%, in particular 5 wt .-%.

worin R eine Sulfonatgruppe, eine Carbonsäuregruppe oder eine Carboxylatgruppe ist, und worin R' ein lineares oder verzweigtes C₇-C₁₅-Alkyl ist; ebenso Aktivatoren, die unter den Bezeichnungen SNOBS, SLOBS, NOBS und DOBA bekannt sind; acetylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran und acetyliertes Sorbitol und Manitol sowie acetylierte Zuckerderivate, insbesondere Pentaacetylglucose (PAG), Saccharosepolyacetat (SUPA), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose; und acetyliertes, gegebenenfalls N-alkyliertes Glucamin sowie Gluconolacton. Es können auch die in der Deutschen Patentanmeldung DE-A 44 43 177 offen gelegten Kombinationen herkömmlicher Bleichaktivatoren verwendet werden. Nitrilverbindungen, die mit Peroxiden Peroxyimidsäuren bilden, sind ebenfalls als Bleichaktivatoren geeignet. Bevorzugt sind Tetraacetylethylendiamin und Nonoyloxybenzolsulfonat.The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of a bleach activator. Particular preference is given to those compounds which under perhydrolysis conditions give unsubstituted or substituted perbenzoic and / or peroxydicarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms. Suitable compounds include those bearing O- and / or N-acyl groups with said number of carbon atoms and / or unsubstituted or substituted benzoyl groups. Preference is given to the polyacylated alkylenediamines, in particular tetraacetylenediamine (TAED); acetylated glycolurils, especially tetraacetylglycoluril (TAGU); N, N-diacetyl-N, N-dimethylurea (DDU); acetylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); Compounds with the formula

wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R 'is a line ares or branched C ₇ -C ₁₅ -alkyl; as well as activators known under the names SNOBS, SLOBS, NOBS and DOBA; acetylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol, and acetylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose; and acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use the combinations of conventional bleach activators disclosed in German Patent Application DE-A 44 43 177. Nitrile compounds which form peroxyimidic acids with peroxides are also suitable as bleach activators. Preferred are tetraacetylethylenediamine and nonoyloxybenzenesulfonate.

Of the Blleichaktivatoranteil is preferably 0-10 Wt .-%, preferably 0-8 Wt .-%. When a bleach activator is used, the lower limit is preferably 0.5 wt .-%, in particular 1 wt .-%.

Bleach catalysts, which can be added shut down z. B. enzymatic peroxide precursors and / or Metal complexes. preferred metal complexes are manganese, cobalt or iron complexes such as the manganese or Eisenphthalo cyanine or the complexes described in EP-A 0 509 787. Becomes a bleach catalyst used is its content is preferably 0.005 to 2% by weight, more preferably 0.01 to 2 wt .-%, in particular 0.05 to 2 wt .-%. Highly preferred is a share of 0.1-2 Wt .-%.

• – WO-A 95/30681 (vgl. Formel (I) und die nachstehende Definition auf Seite 1, Zeile 7 bis 30; insbesondere Formel (I) und die auf Seite 2, Zeile 29 bis Seite 11, Zeile 11 gegebenen Definitionen). Bevorzugte Liganden sind die auf Seite 13, Zeile 12 bis Seite 26, Zeile 11 angegebenen.
• – WO-A 01/09276 (vgl. die Formeln (1), (2) und (3) und die auf den Seiten 2 und 3 gegebenen Definitionen);
• – WO-A 01/05925 (vgl. Formel (1) und die nachstehende Definitionen auf Seite 1, letzter Absatz bis Seite 2, erster Absatz. Bezüglich der zu verwendenden Metallkomplexe, denen der Vorzug gegeben wird, vgl. insbesondere jene mit der Formel (2) auf Seite 3 und jene mit der Formel (3) auf Seite 4);
• – WO-A 02/088289 (vgl. Formel (1) und die nachstehende Definition auf Seite 2. Bezüglich der zu verwendenden Metallkomplexe, denen der Vorzug gegeben wird, vgl. insbesondere die Liganden der Formel (3) und auch den auf Seite 3, Absatz 4 bis Seite 4, Absatz 7 bevorzugten).

As examples of bleach catalysts, the following are listed:

• WO-A 95/30681 (see formula (I) and the definition below on page 1, lines 7 to 30, in particular formula (I) and the definitions given on page 2, line 29 to page 11, line 11). Preferred ligands are those listed on page 13, line 12 to page 26, line 11.
• WO-A 01/09276 (see formulas (1), (2) and (3) and the definitions given on pages 2 and 3);
• - WO-A 01/05925 (see formula (1) and the definitions below on page 1, last paragraph to page 2, first paragraph) With regard to the metal complexes to be used, which are given preference, see in particular those having the formula (2) on page 3 and those with the formula (3) on page 4);
• WO-A 02/088289 (see formula (1) and the definition below on page 2. With regard to the metal complexes to be used, which are given preference, see in particular the ligands of the formula (3) and also those on page 3 , Paragraph 4 to page 4, paragraph 7 preferred).

The cleaning agent may further optionally contain enzymes. Enzymes can be added to stain removal detergents. The enzymes usually intensify the effect on stains based either on proteins or starch; like those caused by blood, milk, grass or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, in particular proteases. Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them to glucose, cellobiose, cellooligosaccharides, cellulases remove dirt and soften roughness on contact. Examples of useful enzymes include, but are in no way limited to, the following:
Proteases, reported in US Pat. No. 6,242,405 B, col. 14, lines 21 to 32;
Lipases, reported in US Pat. No. 6,242,405 B, column 14, lines 33 to 46;
Amylases, reported in US-A 6,242,405 B, column 14, lines 47 to 56 and
Cellulases, US-A 6,242,405 B, col. 14, lines 57-64.

The Enzymes can optionally present in the detergent. Are enzymes used they usually lie in a proportion of 0.01-5 Wt%, preferably 0.05-5% and more preferably from 0.1-4 Wt .-% before, based on the total weight of the cleaning agent.

preferred Additives for the cleaning agents according to the invention are still polymers, which during the washing of textiles prevent staining caused by dyes in the wash liquor caused by the textiles under washing conditions have been released (dye fixatives, dye transfer inhibitors). Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides, which by the incorporation of anionic or cationic substituents, may have been modified, in particular those having a molecular weight in the range of 5,000 to 60,000, very special from 10,000 to 50,000. Such polymers usually become in a proportion of 0.01 to 5%, preferably 0.05 to 5% by weight, in particular from 0.1 to 2% by weight, based on the total weight of the cleaning agent used. Preferred polymers are those in WO-A 02/02865 (see in particular page 1, last paragraph and page 2, first paragraph).

The detergents used usually contain one or more auxiliaries, such as dirt suspending agents, such as carboxymethylcellulose; Salts for pH adjustment, such as alkali or alkaline earth metal silicates; Foam control agents such as soaps; Salts for adjusting the spray-drying and granulating properties, such as sodium sulfate; Fragrances; and, if necessary, anti-static and softening agents such as smectite clays; Photobleaching agents; pigments; and / or tinting agents. Of course, these ingredients should be stable to all bleach systems used. Such auxiliaries may be present in a proportion of, for example, from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight, based on the total weight of the detergent.

The Detergent compositions can be a variety of physical Take forms, shooting in those of powders, granules, tablets and liquid forms. Examples of this are conventional powdery All-purpose cleaner, compact and super-compact all-purpose cleaner and tablets such as general purpose detergent tablets. An important physical form is designed for the addition to the washing machine so-called concentrated granule form.

From Importance is also the so-called compact (or super compact) cleaners. In the field of detergent production has again a trend towards the production of compact detergents formed, which increased Content of active substance included. To the energy costs during the Washing is minimized by the compact detergents Requires that they be at temperatures as low as 40 ° C or even at room temperature, d. H. at 25 ° C, work effectively. Such detergents usually contain only small amounts of fillers or processing aids such as sodium sulfate or sodium chloride, The proportion of such fillers is usually 0-10% by weight, preferably 0-5 Wt .-%, in particular 0-1 Wt .-%, based on the total weight of the cleaning agent. Such Detergents usually have a bulk density from 650-1000 g / l, preferably from 700-1000 g / l and in particular from 750-1000 g / l.

• – Schäummittel wie Carbonat/Hydrogencarbonat/Citronensäure;
• – Quellmittel wie Cellulose, Carboxymethylcellulose, vernetztes Poly(N-vinylpyrrolidon;
• – schnell lösliche Materialien wie Na(K)acetat oder Na(K)citrat;
• – schnell wasserlösliche spröde Beschichtungen wie Dicarbonsäuren.

The cleaning agents may also be in the form of tablets. The relevant properties of tablets are the ease of dosage and the ease of handling. Tablets are the most compact form of solid detergent and have a substance density of, for example, 0.9 to 1.3 kg / liter. In order to facilitate a rapid disintegration, laundry detergents generally contain special disintegrating agents:

• Foaming agents such as carbonate / bicarbonate / citric acid;
• - Swelling agents such as cellulose, carboxymethyl cellulose, crosslinked poly (N-vinylpyrrolidone;
• - rapidly soluble materials such as Na (K) acetate or Na (K) citrate;
• - Fast water-soluble brittle coatings such as dicarboxylic acids.

The Tablets can also any combinations of the above disintegrating agents contain.

The Detergent may also be formulated as an aqueous fluid comprising 5-50, preferably 10-35% Water or as a non-aqueous liquid Cleaning agent containing not more than 5, preferably 0-1 wt .-% Water. non-aqueous liquid Detergent compositions may use other solvents as a carrier contain. Suitable are low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol. monovalent Alcohols are used to solve the Surfactants are preferred; it can however, polyols containing from 2 to about 6 carbon atoms can also be used and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, Glycerin and 1,2-propanediol). The compositions can be 5% to 90%, typically 10% to 50% of such carriers. The cleaning agents can also in the form of a so-called "disposable fluid dose".

The Cleaning treatment of textiles can be done in the household with a normal Washing machine done.

The textile fabrics to be treated may be made of natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, flax, rayon or linen, preferably cotton, and animal fibers such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. Preferred textile fibers are cotton, polyamide and wool fibers, in particular cotton fibers. Textile fabrics which are treated by the process according to the invention preferably have a density of less than 200 g / m ² .

In accordance with the method, an amount of 0.01 to 3.0% by weight, in particular 0.05 to 3.0% by weight of a compound of formula (1), based on the weight of the textile fabric material.

The Procedure becomes common in the temperature range from 5 to 100 ° C, in particular from 5 to 60 ° C. Prefers is a temperature range of 5 to 40 ° C, especially 5 to 35 ° C and more preferably from 5 to 30 ° C.

The Detergent compositions herein are preferably so formulated that the wash water during their use at aqueous Cleaning process a pH between about 6.5 and about 11, preferably between about 7.5 and 11. Own laundry products typically a pH of 9-11. Techniques for adjusting the pH to a recommended level of use shut down the use of buffers, alkalis, acids, etc. and are the Expert well known.

• – Obenbeladung, Waschmaschine von U.S.-Typ mit vertikaler Achse, die etwa 45 bis 83 Liter Wasser im Wasserbad, einen Waschzyklus von etwa 10 bis etwa 14 Minuten und eine Waschwassertemperatur von etwa 10 bis etwa 50°C verwendet;
• – Frontbeladung, Waschmaschine vom Europäischen Typ mit horizontaler Achse, welche etwa 8 bis 15 Liter Wasser im Wasserbad, einen Waschzyklus von etwa 10 bis etwa 60 Minuten und eine Waschwassertemperatur von etwa 30 bis etwa 95°C verwendet;
• – Obenbeladung, Waschmaschine von Japanischen Typ mit vertikaler Achse, welche etwa 26 bis 52 Liter Wasser im Wasserbad, einen Waschzyklus von etwa 8 bis etwa 15 Minuten und eine Waschwassertemperatur von etwa 5 bis etwa 25°C verwendet.

Machine wash processes herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine containing therein an effective amount of a machine laundry detergent composition according to the invention dissolved or dispersed. An effective amount of detergent composition means e.g. B. 20 to 300 g of product which is dissolved or dispersed in a washing solution having a volume of 5 to 85 liters, corresponding to typical product doses and wash solution volumes in commonly used conventional machine laundry methods. Examples are:

• Top load, vertical-axis US-type washing machine using about 45 to 83 liters of water in a water bath, a wash cycle of about 10 to about 14 minutes, and a wash water temperature of about 10 to about 50 ° C;
• Front loading, horizontal axis type European washing machine using about 8 to 15 liters of water in a water bath, a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30 to about 95 ° C;
• Top load, vertical axis Japanese type washing machine using about 26 to 52 liters of water in a water bath, a washing cycle of about 8 to about 15 minutes, and a washing water temperature of about 5 to about 25 ° C.

The Wash liquor ratio is preferably 1: 4 to 1:40, in particular 1: 4 to 1:15. Highly preferred is a wash liquor ratio from 1: 4 to 1:10, especially from 1: 5 to 1: 9.

A Another object of the present invention is a method to provide for the washing treatment of textile fabric material in the home, wherein the textile fabric material with an aqueous solution of a cleaning agent in touch comprising a compound as defined above Formula (1), and wherein the cleaning agent is a peroxide, a peroxide activator and / or a bleach catalyst, and wherein the temperature the solution while of the whole procedure between 5 ° C and 40 ° C, preferably between 5 ° C and 30 ° C located.

What both the compounds of Formal (1) and the detergent and the washing process, the above apply Definitions and preferences.

The used according to the invention Compounds are particularly advantageous in that they do not only extraordinary high degrees of whiteness but also deliver in many cases highly desirable water solubilities and also an excellent white appearance in the solid state have. Another advantage of the present invention is in that the detergent composition improved White effect and provide grip. The compounds continue to show very good Results regarding the exploitation characteristics.

The Compounds have the advantage that they are also active in the presence of Chlorine donors, such as hypochlorite, substantially without Loss of effect in washing baths with nonionic detergents such as alkylphenol polyglycol ethers can be used. The compounds are both in powdered detergents as well in washing baths in the presence of perborate or peracids and activators, such as Example tetraacetylglycoluril or ethylenediaminetetraacetic acid resistant. Additionally lend they look brilliant in daylight.

The the following examples serve to illustrate the invention; Parts and percents are by weight unless otherwise stated specified otherwise.

Production Example 1

mit 600 ml Wasser gemischt und auf eine Temperatur von 60°C erwärmt. Anschließend werden 9,2 g 2-Ethylaminoethanol zugegeben und das Reaktionsgemisch auf eine Temperatur von 98°C aufgeheizt; Während des Aufheizens wird der pH durch Zugabe einer 4-molaren wässrigen Natriumhydroxidlösung auf einem Wert zwischen 8,5 und 9 gehalten. Die Reaktionsmischung wird auf 50°C abgekühlt und der pH durch Zugabe einer 6-molaren wässrigen Salzsäurelösung auf einen Wert von 4,5 eingestellt. Der Niederschlag wird abfiltriert, mit 100 ml 10% wässriger Natriumchloridlösung gewaschen und im Vakuum getrocknet. Auf diese Weise werden 30,5 g eines gelblichen Produkts erhalten.In a 1 liter flask, 0.05 moles of the compound of the formula

mixed with 600 ml of water and heated to a temperature of 60 ° C. Subsequently, 9.2 g of 2-ethylaminoethanol are added and the reaction mixture heated to a temperature of 98 ° C; During heating, the pH is maintained at between 8.5 and 9 by the addition of a 4 molar aqueous sodium hydroxide solution. The reaction mixture is cooled to 50 ° C and the pH is adjusted by the addition of a 6-molar aqueous hydrochloric acid solution to a value of 4.5. The precipitate is filtered off, washed with 100 ml of 10% aqueous sodium chloride solution and dried in vacuo. In this way, 30.5 g of a yellowish product are obtained.

Preparation Examples 2 to 15

können analog dem für die Herstellung von Beispiel 1 angegebenen Verfahren hergestellt werden, indem 9,2 g 2-Ethylaminoethanol durch eine äquivalente Menge des entsprechenden Amins ersetzt werden. X entspricht der Definition in der nachstehenden Tabelle 1. Verbindungen, welche nach dem Abkühlen auf 50°C ausfallen, werden ohne Zusatz von Salzsäure direkt als Natriumsalze isoliert und dann unter Vakuum getrocknet.The following compounds of the formula

can be prepared analogously to the procedure given for the preparation of Example 1 by replacing 9.2 g of 2-ethylaminoethanol with an equivalent amount of the corresponding amine. X is as defined in Table 1 below. Compounds which cool to 50 ° C after cooling are directly isolated as sodium salts without the addition of hydrochloric acid and then dried under vacuum.

Table 1

Preparation Example 16 (not according to the invention)

mit 600 ml Wasser gemischt und auf eine Temperatur von 60°C erwärmt. Dann werden 9,5 g Morpholin zugesetzt und die Reaktionsmischung auf eine Tempe ratur von 98°C aufgeheizt; Während des Aufheizens wird der pH durch Zugabe einer 4-molaren wässrigen Natriumhydroxidlösung auf einem Wert zwischen 8,5 und 9 gehalten. Die Reaktionsmischung wird auf 40°C abgekühlt, der Niederschlag abfiltriert, mit 100 ml 10% wässriger Natriumchloridlösung gewaschen und unter Vakuum getrocknet. Auf diese Weise werden 30 g eines gelben Produkts erhalten.In a 1 liter flask, 0.05 moles of the compound of the formula

mixed with 600 ml of water and heated to a temperature of 60 ° C. Then 9.5 g of morpholine are added and the reaction mixture is heated to a Tempe temperature of 98 ° C; During heating, the pH is maintained at between 8.5 and 9 by the addition of a 4 molar aqueous sodium hydroxide solution. The reaction mixture is cooled to 40 ° C, the precipitate is filtered off, washed with 100 ml of 10% aqueous sodium chloride solution and dried under vacuum. In this way, 30 g of a yellow product are obtained.

Preparation Examples 17 to 19 (not according to the invention)

können analog dem für die Herstellung von Beispiel 16 angegebenen Verfahren hergestellt werden, indem 9,5 g Morpholin durch eine äquivalente Menge des entsprechenden Amins ersetzt wird. X entspricht der Definition in der nachstehenden Tabelle 2. Verbindungen mit einer hohen Löslichkeit werden mit einer 6-molaren wässrigen Salzsäurelösung behandelt, um den pH vor dem Abkühlen auf 50°C auf einen Wert von 4,5 einzustellen.The following compounds of the formula

can be prepared analogously to the procedure given for the preparation of Example 16 by replacing 9.5 g of morpholine with an equivalent amount of the corresponding amine. X is as defined in Table 2 below. High solubility compounds are treated with a 6 molar aqueous hydrochloric acid solution to adjust the pH to 4.5 before cooling to 50 ° C.

Table 2

Preparation Example 20 (not according to the invention)

In To a 2 liter flask is added 130 ml of methyl ethyl ketone, 80 ml of deionized Water, 150 g of ice and 18.5 g of cyanuric chloride mixed. During one Period of 30 minutes, 185 ml of a solution of 4,4'-diaminostilbene-2,2'-disulfonic acid (as sodium salt) in water (Concentration 100 g / l) at a temperature between -8 and + 5 ° C dropwise added. The pH is raised by adding an aqueous sodium carbonate solution a value between 4.5 and 5 held. It becomes a yellowish suspension receive. Then, using a dropping funnel, add 27.2 g of ethanolamine (99%) added. The pH rises to a value of 10 and then drops to a lower value, with the temperature rising to 10 to 15 ° C. Subsequently the reaction mixture is heated to a temperature of 45 ° C and held at this temperature for 20 minutes. During heating to 98 ° C within for 30 minutes is a mixture of methyl ethyl ketone and water distilled off. The pH is raised by adding an aqueous sodium hydroxide solution a value between 8.5 and 9 held. After no further addition of watery sodium hydroxide more is needed to keep the pH at a constant level, the reaction mixture is at 50 ° C cooled. The pH is adjusted to a value of 5.5, whereupon a yellowish crystalline precipitate can be filtered off. After drying 29 g of a yellowish product are obtained.

Preparation Example 21 (not according to the invention)

In a 1 liter pressure vessel 0.037 mole of N, N'-bis (4-morpholino-6-chloro-1,3,5-triazin-2-yl) -4,4'-diaminostilbene-2,2'-disulfonic acid (as Sodium salt) in 500 ml of water. It will be 15 g of a aqueous ethylamine (70%) added and the reaction mixture to a temperature of 100 up to 105 ° C heated and stirred for 4.5 hours. The reaction mixture is at 25 ° C chilled and the precipitate filtered off, with 100 ml of 10% aqueous Sodium chloride solution washed and in vacuo at 70 ° C. dried. In this way, 25.8 g of a yellowish powder receive.

Preparation Example 22 (not according to the invention)

The Compound of formula (107) may be prepared analogously to that described in Example 21 Be prepared by adding 15 g of the aqueous ethylamine solution (70%). through an appropriate solution be replaced, which is an equimolar Contains amount of diethylamine.

Preparation Example 23 (not according to the invention)

In a 1 liter flask, 0.05 mole of N, N'-bis (4-morpholino-6-chloro-1,3,5-triazin-2-yl) -4,4'-diamino nostilbene-2,2'-disulfonic acid (as the sodium salt) suspended in 600 ml of water and heated to a temperature of 60 ° C. 6.4 g of ethanolamine are added and the reaction mixture is heated to a temperature of 98.degree. The pH is maintained at between 8.5 and 9 by the addition of an aqueous 4 molar sodium hydroxide solution. The reaction mixture is cooled to 25 ° C and 10% of the volume of sodium chloride added. The precipitate is filtered off, washed with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuo at 70 ° C. In this way, 41.8 g of a yellowish powder are obtained.

Application example 1

General procedure:

It is a wash by dissolving made of 0.8 g of a washing powder in 200 ml of tap water. The bath is charged with 10 g of bleached cotton fabric and this at 40 ° C while Washed for 15 minutes, then pouring rinsed, spun and at 160 ° C flattened.

Tabelle 3b (verwendete Waschpulver)

• * nicht erfindungsgemäß

The following washing powders A and B are used (the amounts given in Tables 3a and 3b below are in grams): TABLE 3a (Ingredients of washing powders A and B)

Table 3b (washing powder used)

• * not according to the invention

Constitution of the compound of formula (109):

The Cotton fabric, which with the cleaning agents specified in Table 4b were washed by the general method, had good whiteness.

Application Example 2

General procedure:

It is a wash by dissolving made of 0.8 g of a washing powder in 200 ml of tap water. The bath is charged with 10 g of bleached cotton fabric and this at 30 ° C while Washed for 15 minutes, then pouring rinsed, spun and at 160 ° C flattened.

The following washing powders are used (the amounts given in Tables 4a and 4b below are percentages by weight, based on the total weight of the cleaning agent): Table 4a (components of washing powders C and D)

In Each of the above detergents will be 100% sufficient Used amount of water.

Table 4b (washing powder used)

• * not according to the invention

to Constitution of the compound of formula (109) compare the application of Example 1.

The Cotton fabric, which with the cleaning agents specified in Table 4b were washed by the general method, have good whiteness.

Claims (17)

A detergent composition comprising at least one compound of the formula

wherein R ₁ and R _{2 are} independently hydrogen or unsubstituted or substituted C ₁ -C ₈ alkyl, X ₂ and X _{4 are} independently -N (R ₃ ) R ₄ , wherein R ₃ and R _{4 are} hydrogen; cyano; C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, CONH ₂ or phenyl, and wherein the C ₁ -C ₈ -alkyl group is unbroken or interrupted by -O-; unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ cycloalkyl; or R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring; R _{5 is} C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, and M is hydrogen, an alkali or alkaline earth metal or ammonium, preferably sodium, and wherein the cleaning agent comprises a peroxide, a peroxide activator and / or a bleach catalyst. A composition according to claim 1 wherein R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolid ring, preferably a morpholine ring. Composition according to at least one of claims 1 to 2, comprising i) 1-70% an anionic surfactant and / or a nonionic surfactant; ii) 0-75% a builder; iii) 0.5-30% a peroxide; iv) 0.5-10% a peroxide activator; and / or 0.1-2% of a bleach catalyst; v) 0.001-5% a compound of formula (1); and vi) 0-5% of at least one enzyme, chosen from the group consisting of cellulase, protease, amylase and lipase. Composition according to at least one of claims 1 to 3, comprising i) 5-70% an anionic surfactant and / or a nonionic surfactant; ii) 5-70% a builder; iii) 0.5-30% a peroxide; iv) 0.5-10% a peroxide activator; and / or 0.1-2% of a bleach catalyst; v) 0.01-5% a compound of formula (1); and vi) 0.05-5% at least an enzyme chosen from the group consisting of cellulase, protease, amylase and lipase. Composition according to at least one of claims 1 to 4, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. A composition according to claim 5, wherein the enzyme is a protease enzyme. Composition according to at least one of claims 1 to 6, wherein the composition comprises a peroxide. Composition according to at least one of claims 1 to 7, wherein the composition is a peroxide and a peroxide activator includes. A composition according to claim 8, wherein the peroxide activator TAED is. A method of household laundry of a textile fiber material wherein the textile fiber material is treated with an aqueous solution of a detergent comprising a compound of the formula

wherein R ₁ and R _{2 are} independently hydrogen or unsubstituted or substituted C ₁ -C ₈ alkyl, X ₂ and X _{4 are} independently -N (R ₃ ) R ₄ , wherein R ₃ and R _{4 are} hydrogen; cyano; C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano-, -CONH ₂ or phenyl, and wherein the C ₁ -C ₈ -alkyl group is unbroken or interrupted by -O-; unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₇ cycloalkyl; or R ₃ and R ₄ together with the nitrogen atom linking them form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine, or pyrrolidine ring; R _{5 is} C ₁ -C ₈ -alkyl which is unsubstituted or substituted by hydroxy, and M is hydrogen, an alkali or alkaline earth metal or ammonium, preferably sodium, and wherein the cleaning agent comprises a peroxide, a peroxide activator and / or a bleach catalyst, and wherein the temperature of the solution throughout the process between 5 ° C and 40 ° C, preferably between 5 ° C and 30 ° C, is. The process of claim 10 wherein R ₃ and R _4, together with the nitrogen atom linking them, form an unsubstituted or C ₁ -C ₄ alkyl-substituted morpholine, piperidine or pyrrolidine ring, preferably a morpholine ring. Method according to at least one of claims 10 to 11, wherein the textile fiber materials with 0.05 to 3.0 wt .-%, based on the weight of the textile fiber material, the compound of the formula (1). Method according to at least one of claims 10 to 12, wherein the cleaning agent comprises at least one enzyme selected from the group consisting of the group consisting of cellulase, protease, amylase and lipase. The method of claim 13, wherein the enzyme comprises Protease enzyme is. Method according to at least one of claims 10 to 14, wherein the cleaning agent comprises a peroxide. Method according to at least one of claims 10 to 15, wherein the cleaning agent is a peroxide and a peroxide activator includes. The method of claim 16, wherein the peroxide activator TEAD is.