ES2271534T3 - PROCEDURE FOR THE TREATMENT OF TEXTILE FIBER MATERIALS. - Google Patents

Abstract

A detergent composition, comprising at least one compound of the formula wherein, R1 and R2, are, independently from each other, hydrogen or a C1-C8 alkyl, unsubstituted or substituted, X2 and X4 , are, independently of each other with respect to each other, -N (R3) R4, where R3 and R4 are hydrogen; cyano; C1-C8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and wherein, the C1-C8 alkyl group is uninterrupted or interrupted by ¿O-; C5-C7 cycloalkyl, unsubstituted or substituted by C1-C4 alkyl; or R3 and R4, together with the nitrogen atom that binds them, form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by C1-C4 alkyl; R5, is C1-C8 alkyl, which is unsubstituted, or substituted by hydroxy, and N, is hydrogen, an alkali metal or alkaline earth metal, or ammonium, preferably, sodium, and wherein, the detergent, contains a peroxide , a peroxide activator and / or a bleaching catalyst.

Description

Procedure for the treatment of materials of textile fibers.

The present invention relates to detergent formulations, which contain certain agents fluorescent bleaches, and a peroxide, an activator of peroxide and / or a bleaching catalyst.

It is commonly known, the fact of using fluorescent bleaching agents, in detergent formulations. These are depleted during the treatment on the material to be washing and, by virtue of its special absorption / emission of light, give as a result the elimination of yellowish hues.

However, there is still a need in as to finding fluorescent bleaching agents, improved, for this application. The fact of that, the compounds presented below, of the formula (1), they have superior properties, in terms of, for example, the solubility, the concentration properties, the light strength, the degree of whiteness, and also possess a excellent white spectra, in solid state. The properties of whiteness, such as maintaining whiteness, can even be improved by using the compounds of the formula (1), in detergents containing a peroxide, an activator of peroxide and / or a bleaching catalyst. Results are obtained favorable, even at low washing temperatures.

Correspondingly in accordance, the The present invention provides, as a first aspect, a detergent composition, comprising at least one compound of the formula

one

in where,

X1 and X2 are NH2,

R_ {1} and R2_, are, in a way independent from each other, hydrogen or an alkyl C_ {1} -C_ {8}, unsubstituted or substituted,

X_ {2} and X_ {4}, are, in a way independent from each other, -N (R 3) R 4, where R 3 and R 4 are hydrogen; cyano; C 1 -C 8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and wherein, the alkyl group C_ {1} -C_ {8}, is it uninterrupted or interrupted by -O-; C 5 -C 7 cycloalkyl, unsubstituted or substituted by alkyl C 1 -C 4; or R 3 and R 4, together with the nitrogen atom that bonds them, they form a ring morpholino, piperidine or pyrrolidine, unsubstituted or substituted by C 1 -C 4 alkyl;

R5 is alkyl C_ {1} -C_ {8}, which is unsubstituted, or substituted by hydroxy, and

N, is hydrogen, an alkali metal or alkaline earth, or ammonium;

and where the detergent contains a peroxide, a peroxide activator and / or a bleaching catalyst.

Within the scope of the previous definition, C 1 -C 8 alkyl, may be methyl, ethyl, n- or isopropyl, n-sec.- or tert.-butyl, or pentyl, hexyl, heptyl or octyl, linear or branched. The ones are preferred C 1 -C 4 alkyl groups. In the case in the that, the alkyl groups provided for R 1 and R 2, are find substituted, examples of possible substituents, are hydroxyl, halogen, such as fluorine, chlorine or bromine, sulfo, sulfate, carboxy, and C 1 -C 4 alkoxy, as methoxy and ethoxy. Other substituents of such alkyl groups are, by example, cyano, CONH2, and phenyl. Preferred substituents, they are hydroxy, carboxy, cyano, -CONH2 and phenyl, especially, hydroxyl and carboxy. Additionally, highly substituents Preferred are hydroxy and C 1 -C 4 alkoxy, especially hydroxy. The alkyl groups can also be uninterrupted or interrupted by -O- (in case of alkyl groups containing two or more carbon atoms).

Examples for cycloalkyl groups C 5 -C 7, are cyclopentyl and, especially, cyclohexyl These groups can be substituted by C 1 -C 4 alkyl, as methyl. They prefer the corresponding unsubstituted cycloalkyl groups.

In the scope of the above definitions, of above, C 1 -C 4 alkyl, may be methyl, ethyl, n- or isopropyl, n-sec.- or tert.-butyl, especially methyl.

If R 3 and R 4, together with the atom of nitrogen, they form a morpholino, piperidine or pyrrolidine ring, such type of ring system, may be unsubstituted or substituted by C 1 -C 4 alkyl, especially methyl. Ring systems are preferred unsubstituted

The cation M, is an alkali metal atom, a alkaline earth metal atom, or ammonium. Be they prefer Na, Ka, Ca, Mg, ammonium, mono-, di-, tri-, or C 1 -C 4 tetra-alkylammonium, mono-, di- or tri-hydroxyalkylammonium C 2 -C 4, or ammonium that is di- or tri-substituted with a mixture of alkyl groups C 1 -C 4 and hydroxyalkyl C_ {2} -C_ {4}. Sodium is highly favorite.

R1 and R2 are, preferably, hydrogen or C 1 -C 4 alkyl.

R 3 and R 4, are preferably hydrogen; cyano; C 1 -C 8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, especially by hydroxy or carboxy, and in where, the C 1 -C 8 alkyl group, is is uninterrupted or interrupted by -O-; cycloalkyl C_ {5} -C_ {7}, unsubstituted or substituted by C 1 -C 4 alkyl, especially cyclohexyl; or R 3 and R 4, together with the nitrogen atom that bind, form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by alkyl C 1 -C 4;

More preferably, R 3 and R 4, are hydrogen, unsubstituted C 1 -C 4 alkyl or substituted by hydroxy, cycloalkyl C_ {5} -C_ {7}, unsubstituted or substituted by C 1 -C 4 alkyl, or R 3 and R 4, together with the nitrogen atom that bonds them, they form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by C 1 -C 4 alkyl. They are highly preferred meanings, for R 3 and R 4, hydrogen, unsubstituted C 1 -C 4 alkyl or substituted by hydroxy, or R 3 and R 4 together with the nitrogen atom that bonds them, they form a morpholino ring, piperidine or pyrrolidine, unsubstituted or substituted by alkyl C_ {1} -C_ {4}. The most preferred are the morpholino, piperidine or pyrrolidine rings, especially from pyrrolidine, unsubstituted or substituted by alkyl C 1 -C 4, formed by R 3 and R 4, together with the nitrogen atom that binds them.

Examples of groups -N (R 3) R 4, are -NH 2 -, -NHCH 3, NHC 2 H 5, -NH (n-C 3 H_ {7}, -NH (i-C 3 H 7), -NH (i-C 4 H 9),
-N (CH 3) 2, -N (C 2 H 5) 2, -N (i-C 3 H 7) 2, - NH (CH 2 CH 2 OH), -N (CH 2 CH 2 OH) 2, -N (CH 3 CH (H) CH 3) 2 }, -NCH 3) CH 2 CH 2 OH), -N (C 2 H 5) (CH 2 CH 2 OH), -N (i-CH_ { 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 OHCH 3), -NH (CH 2 CH 2 OCH 2) CH 2 OH), -NH (CH 2 COOH), -NH (CH 2 CH 2 COOH), -NH (CH 3) (CH 2 COOH),
-NH (CN),

2

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3

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4

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5

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Preferred compounds are those of the formula (1), where;

R1 and R2 are hydrogen or alkyl C_ {1} -C_ {{}},

R 3 and R 4 are hydrogen; cyano; I rent C_ {1} -C_ {8}, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and in where, the C 1 -C 8 alkyl group, is is uninterrupted or interrupted by -O-; cycloalkyl C_ {5} -C_ {7}, unsubstituted or substituted by C 1 -C 4 alkyl; or R 3 and R 4, together with the nitrogen atom that bonds them, they form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by C1-C4 alkyl; Y

R5 is alkyl C_ {1} -C_ {8}, which is uninterrupted or interrupted by hydroxy.

For R 3, R 4 and R 5, the preferences cited above, above.

Of particular interest, the compounds of the formula (1), wherein X 1 and X 3, are amino, and X 2 and X 4, are a radical of the formula -N (R 3) R 4, wherein R 3 and R 4, are hydrogen, unsubstituted or substituted C 1 -C 8 alkyl or substituted by hydroxy, cyclopentyl or cyclohexyl, or substituted by C 1 -C 4 alkyl, or R 3 and R 4, together with the nitrogen atom that bonds them, form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by C 1 alkyl } -C_ {4}. The most interesting compounds of the formula (1), are those in which, or R 3 and R 4, together with the nitrogen atom that binds them, form a morpholino, piperidine or pyrrolidine ring, unsubstituted or substituted by C 1 -C 4 alkyl. As in R_ {3} and R_ {4}, the preferences mentioned above apply,
above.

The compounds of the formula (1), can occur proceeding to react, under conditions known reaction, cyanuric chloride, successively, in any desired sequence, with each of the acids 4,4'-diaminoestylbeno-2,2'-disulfonic, and amino compounds capable of introducing the X1 groups, X_ {2}, X_ {3} and X_ {4}. Preferably, they are made react, initially 2 moles of cyanuric chloride, with 1 mole of acid 4,4'-diaminoestylbeno-2,2'isulfonic acid and then reacting the obtained intermediary, in any order, with amino compounds, capable of introducing groups X_ {1}, X_ {2}, X_ {3} and X_ {4}. For the preparation of compounds wherein, X_ {2} and X_ {4}, have the same meaning, it is preferable to proceed to react the intermediate obtained, first, with an amino compound, capable of introducing X_ {1} and X_ {2} and finally with a compound amino, capable of introducing X 3 and X 4. It is also possible carry out the reaction, with the amino compounds, in one step, proceeding to react the intermediary, with a mixture of amino compounds; in that case, mixtures are usually obtained corresponding compounds of the formula (1).

The detergent composition used comprises, in a preferable way,

i)

1 - 70% of an anionic surfactant and / or nonionic surfactant;

ii)

0 - 75% of an improver;

iii)

0.5-30% of a peroxide;

iv)

0.5-10% of a peroxide activator and / or 0.1-2% of a bleaching catalyst;

v)

0.001-5% of a compound of the formula (one); Y

saw)

0.5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase

In a mostly preferable way, the detergent composition used, comprises,

vii)

5 - 70% of an anionic surfactant and / or surfactant nonionic;

viii)  

5 - 70% of an improver;

ix)

0.5-30% of a peroxide;

x)

0.5-10% of a peroxide activator and / or 0.1-2% of a bleaching catalyst;

xi)

0.01-5% of a compound of the formula (1); Y

xii)

0.05-5% of at least one enzyme selected between the group consisting of cellulase, protease, amylase and lipase

In general, a quantity of compounds of the formula (1), corresponding to a percentage of 0.001-5%, especially an amount corresponding to a 0.01-5% percentage. It is highly preferable, an amount corresponding to a percentage of 0.05-5%. In general, the quantities provided in percentages, should be understood as corresponding to percentages by weight, based on total weight, to Unless otherwise specified.

The detergent should be formulated as a solid, as an aqueous liquid comprising, for example, 5-50%, of a preferable form, 10-35% water, or a liquid detergent, non-aqueous, containing no more than 5%, by weight, of water, of a preferably 0-1%, by weight, of water, based on the suspension of an improver, in a non-ionic surfactant, such and as described, for example, in the British patent application GB-A-2 158 454.

The anionic surfactant component may be, for example, an alkylbenzene sulphonate, an alkyl sulfate, an alkyl ether sulfate, an olefin sulphonate, a sulphonate of alkene, a fatty acid salt, an alkyl or carboxylate of alkyl ether, or an α-sulfo acid salt fatty, or an ester of these. Sulfonates of alkyl benzene, having 10 to 20 atoms of carbon in the alkyl group, alkyl sulfates having from 8 to 18 carbon atoms, alkyl ether sulfates having 8 to 18 carbon atoms, and fatty acid salts that are derived from palm oil, or tallow oil, having 8 to 18 carbon atoms. The average molecular weight of the ethylene oxide added in the alkyl ether sulfate is preferably from 1 to 20, preferably from 1 to 10. The salts are derived preferably, alkali metals, such as sodium, and potassium, preferably, sodium. The highly carboxylates preferred, are the alkali metal sarcosinates of the formula R-CO (R 1) CCH 2 COOM 1, in which, R is alkyl or alkenyl, which has 9-17 atoms of carbon in the alkyl or alkenyl radical, R1 is alkyl C 1 -C 4 and M 1, is an alkali metal, Especially sodium.

The nonionic surfactant component may be, for example, ethoxylates of primary or secondary alcohols, especially ethoxylated aliphatic alcohols C_ {8} -C_ {20}, with an average of 1 to 20 moles of ethylene oxide per mole of alcohol and, in a more special way, ethoxylates of primary or secondary alcohols C 10 -C 15, with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Nonionic Surfactants non-ethoxylated, include alkyl polyglycosides, to glycerol monoethers, and to polyhydroxyamides (glucamide).

The total amount of anionic surfactant and non-ionic surfactant is preferably 5-50%, by weight, preferably, 5 - 40%, by weight and, in a more preferably, 5-30%, by weight. As for these surfactants, it is preferred that the lower limit be 10%, in weigh.

The improver component may be a phosphate of alkali metal, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate, an acid polycarboxylic, an organic phosphonate; or a aminoalkylene poly (alkylene phosphonate); or a mixture of these.

Preferred silicates are crystalline, layered sodium silicates, silicates of the formula NaHSi m O2m + 1.
pH 2 O, or NaSi m O 2m + 1. pH 2 O, in which, m, is a number from 1.9 to 4 and, p, is from 0 to 20.

Preferred aluminosilicates are the commercially obtainable synthetic materials in the market, designated as Zeolites A, B, X and HS, or mixture thereof. The Zeolite A, is preferred.

Preferred polycarboxylates include the hydroxypolycarboxylates, in a particular way, citrates, polyacrylates and their copolymers, with maleic anhydride.

Preferred polycarboxylic acids include to nitrilotriacetic acid, and ethylenediaminetetraacetic acid.

Organic phosphonates or aminoalkylene poly (alkylene phosphonates) preferred are ethane-1-hydroxy diphosphonates  of alkali metals, nitrile trimethylene phosphonates, ethylenediamine tetramethylene phosphonates and diethylenetriamine pentamethylene phosphonates.

The quantity of improvers is, in a way preferably, corresponding to a percentage of 5-7%, by weight, preferably, 5-60%, by weight and, in a way mostly preferable, from 10-60%, by weight. As for concerning the improvers, it is preferred that the lower limit, be 15%, by weight, especially 20%, by weight.

The appropriate peroxide components, include, for example, organic and inorganic peroxides (such as  sodium peroxides), known in the literature and commercially obtainable in the market, which bleach textile materials at conventional washing temperatures, for for example, at a temperature within a range of They range from 5 to 95 ° C.

In a particular way, peroxides organic, for example, monoperoxides or polyperoxides, which they have alkali chains of at least 3 carbon atoms, of a preferable form, from 6 to 20 carbon atoms; in a way In particular, diperoxycarboxylates that are of special interest are they have 6 to 12 carbon atoms, such as diperoxiperazelates, diperoxipersebacatos, diperoxiftalates and / or diperoxidedecanedioates, especially their corresponding free acids. It is preferred, however, to employ very active inorganic peroxides, such as persulfate, perborate and / or percarbonate. It is also possible, of course, to employ organic and / or inorganic peroxides.

The amount of peroxide is, in a way preferably, corresponding to a percentage of 0.5-30%, in weight, preferably, 1-20%, by weight, and in a way more preferable, 1-15%, by weight. In case a peroxide, the lower limit is, preferably, 2%, in weight, especially 5%, by weight.

Peroxides, especially peroxides inorganic, they are activated, preferably, by inclusion of a bleach activator. Compounds are preferred, which, under perhydrolysis conditions,            provide perbenzo- and / or acids peroxo-carboxylic, having 1 to 10 atoms of carbon, especially 2 to 4 carbon atoms. The compounds appropriate, include those who carry O- and groups N-acyl, having the aforementioned number of atoms of carbon and / or benzoyl groups, unsubstituted or substituted. Is granted preference, to polycylated alkylenediamines, especially the tetraacetylenediamine (TAED), acylated glycolurils, especially, tetraacetylglucolcolyl (TAGU), N, N-diacetyl-N, N-dimethyl-urea  (DDU), acetylated triazine derivatives, especially the 1-5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine  (DADHT), compounds of the formula

6

where, R, is a sulfonate group, a carboxylic acid group, or a carboxylate group, and wherein, R ', is a linear (C 7 -C 15) alkyl or branched; also the activators that are known by the names  of SNOBS, SLOBS, NOBS AND DOBA, acylated polyhydric alcohols, especially, triacetin, ethylene glycol diacetate and the 2-diacetoxy-2,5-dihydrofuran and hydroxylated sorbitol and mannitol and derivatives of acetylated sugar, especially, pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylfructose, tetraacetylxylose and octaacetyl-lactose, and glucamine and gluconolactone acetylated, optionally N-alkylated. They can bleach activator combinations also be used conventional, disclosed in the German patent application DE-A-44 43 177. Compounds of nitrile that form polyximidic acids with peroxides, are also suitable as bleach activators. They prefer the tetraacetylethylenediamine and sulfonate nonyloxybenzene.

The amount of bleach activator is one preferably, 0-10%, by weight, preferably, 0 - 8%, by weight. In the event that a trigger activator is used bleaching, the lower limit is preferably a 0.5%, by weight, especially 1%, by weight.

Catalysts that may be added include, for example, to enzymatic precursors of peroxides, and / or of metal complexes Preferred metal complexes are, of a preferable form, manganese, cobalt or iron complexes, such such as manganese or iron phthalocyanines, or complexes described in the European patent application EP-A-0 509 787. In the event that use a bleaching catalyst, the amount to be used is, of a preferable way, of a percentage comprised within about margins ranging from 0.005 to 2%, by weight, in a more preferably from 0.01 to 2%, by weight, especially 0.05 at 2%, by weight. It is highly preferred, an amount corresponding to a percentage of 0.1-2%, by weight.

As examples for bleaching catalysts, The following may be mentioned:

- International patent application WO-A-95/30 681 (see, to said effect, formula (I), and the following definitions, on the page 2, lines 29 to page 11, line 11). Preferred ligands are those provided on page 13, lines 12 to page 26, line 11.

- International patent application WO-A-01/09 276 (see, to said effect, formulas (1), (2) and (3), and the following definitions, provided on pages 2 and 3).

- International patent application WO-A-01/05 925 (see, to said effect, formula (1) and the following definition, on page 1, last paragraph, until page 2, first paragraph. They apply here the preferences provided for metal complexes, being able to see, for that purpose, those of the formula (2), in the page 3, and those of the formula (3) on page 4.

- International patent application WO-A-02/088 289 (see, to said effect, formula (1), and the following definition, on page 2. The preferences provided for complexes apply here  metallic, being able to see, especially, the ligands of the formula (3), and also, the preferences provided in the page 3, fourth paragraph, to page 4, paragraph 7).

Additionally, the detergent, in a way Optional, may contain enzymes. Enzymes can be added to detergents, for the removal of stains. Enzymes, usually improve performance, on spots that are either protein base or starch base, such as those caused by blood, milk, fat, or fruit juices. Enzymes Preferred are cellulases, proteases, amylases and lipases. The cellulases, are enzymes that act on cellulose and its derivatives, and hydrolyze them into glucose, cellobiose, celoligosaccharide.  Cellulases, remove dirt and have the effect of mitigating roughness to the touch. Examples of enzymes to be used, include, but not limited to, at all following:

proteases, as provided in US Pat. No. 6,242,405, column 14, lines 21
to 32;

the ligases, as provided in the US patent US-B-6,242,405, column 14, lines 33 to 46;

the amylases, as provided in the US patent US-B-6,242,405, column 14, lines 47 to 56; Y

cellulases, as provided in US Pat. No. 6,242,405, column 14, lines 57
to 64.

Enzymes can optionally be found present in the detergent. When they are used, enzymes, they they are usually present in an amount corresponding to a percentage of 0.01-5%, by weight, preferably, of 0.05-5%, by weight and, more preferably, 0.1-4%, in weight, based on the total weight of the detergent.

Additional preferred additives for detergents in accordance with the present invention are polymers, which, during textile washing, inhibit stains caused by dyes in the washing liquor that has been released by the textiles, under washing conditions (agents color fixation, transfer inhibitors). Such types of polymers are, preferably, polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides, which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight within a range from 5,000 to
60,000, in a more special way, from 10,000 to 50,000. Such types of polymers are usually used in an amount ranging from 0.01 to 5%, by weight, preferably, 0.05 to 5%, by weight, especially 0.1 to 2%, by weight, based on the total weight of the detergent. Preferred polymers are those disclosed in patent application WO-A-02/02 865 (see, especially, page 1, last paragraph, and page 2, first paragraph).

The detergents used will contain one usual form, one or more auxiliaries, such as suspending agents from dirt, for example, sodium carboxymethylcellulase; you go out for pH value adjustment, for example, alkali metal silicates or alkaline earths; foam regulators, for example, soap; salts for adjustment of spray drying properties sprayed (spray), and granulation properties, by example, sodium sulfate; perfumes; and also, if appropriate, antistatic or softening agents; such as clays smectite, photoblanking agents; and / or toning agents. These constituents must, of course, be stable to any bleaching system used. Such types of auxiliaries can be present in an amount of, for example, 0.1 to a 0.20%, by weight, preferably 0.5 to 10%, in weight, especially 0.5 to 5%, by weight, based on weight Total detergent.

Detergent compositions can take a variety of forms, including powdered matter forms, granular, tablet and liquid forms. Examples of these are conventional detergents in powder form, detergent tablets high performance, high performance detergents and tablets, compact and super-compact, such as detergent tablets high performance. An important physical form is called concentrated granular form, adapted to be added to machines washed.

They are also of importance, the so-called compact (or supercompact) detergents. In the sector of the detergent manufacturing, recently, a trend towards the production of compact detergents, which They contain increased amounts of active substances. With in order to minimize energy expenditure during the process of washing, compact detergents are required, in order to operate efficiently at temperatures as low as corresponding to a level of 40 ° C, or even at temperatures corresponding to the ambient temperature, such as a temperature of 25 ° C. Such types of detergents contain usually only small amounts of cargo or processing aids, such as sodium sulfate or chloride sodium The amount of such types of charges is usually the corresponding to a percentage within a range 0-10%, by weight, preferably 0-5%, by weight and, in a special way, from 0 - 1%, by weight, based on the total weight of detergent. Such types of detergents usually have a bulk density of 640 - 1000 g / l, preferably 700 - 1000 g / l and, in a special way, 750 - 1000 g / l.

Detergents can also be found present in the form of tablets. The relevant characteristics of tablets, are the ease of dispensing and convenience of its handling. The tablets correspond to the forms of delivery more compact than solid detergents, and have a density apparent of, for example, 0.9-1.3 kg / liter. With the object of facilitate rapid disintegration, detergent tablets Laundry, contain special disintegrants:

-

          effervescent, such as carbonate / hydrogen carbonate / acid citric;

-

          swelling agents, such as cellulose, carboxymethyl cellulose, cross-linked poly (N-vinyl pyrrolidone);

-

          fast dissolving materials, such as Na acetate (or Ka), or Na (or K) citrate;

-

          Rigid coatings quickly soluble in water, such as dicarboxylic acids.

The tablets may also contain combinations of any of the disintegrants above cited above.

Detergents can also be formulated as an aqueous liquid comprising a percentage of 5 - 50%, by weight, preferably 10-35%, by weight, or as a detergent non-aqueous liquid, which does not contain more than 5%, by weight, of a preferable form, which does not contain more than 0-1%, by weight, of Water. Non-aqueous liquid detergent compositions may contain other solvents as supports or carriers. They are appropriate, primary or secondary low-weight alcohols molecular, exemplified by methanol, ethanol, propanol, and isopropanol As solubilizing surfactants, the monohydric alcohols, such as those containing 2 to 6 carbon atoms, and 2 to 6 atoms of hydroxy groups (for example,  1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol). The compositions may contain from 5% to 90% of such carriers or supports. Detergents, they can also be present in the form called form of "unit liquid dose".

This treatment of detergents with liquids, can be conducted as a domestic treatment, in machines normal wash.

The treated textile fibers can be natural or synthetic, or mixtures thereof. Fiber examples natural, include plant fibers, such as cotton, viscose, linen, rayon or thread, preferably cotton and animal fibers, such as wool, mohair, cashmere, angora and silk, preferably wool. Synthetic fibers, include polyester, polyamide and fibers of pliacrylonitrile. Preferred textile fibers are the fibers of cotton, polyamide and wool, especially the fibers of cotton. Preferably, the textile fibers treated in concordance with the process of the present invention, have a density of less than 200 g / m2.

In accordance with this procedure, it usually use an amount corresponding to a percentage comprised within margins ranging from 0.01 to 3.0%, in weight, especially 0.05 to 3.0%, by weight, based on the weight of the textile fiber material, of a compound of the formula (1).

The procedure usually leads to a temperature within a range of 5 to 100 ° C, especially at a temperature ranging from 5 to 60 ° C. Be prefers a temperature within a range that they range from 5 to 40 ° C, especially from 5 to 35 ° C and, in a way mostly preferable, from 5 to 30 ° C.

The detergent compositions presented here, they will be formulated, preferably, in such a way that, during its use, in water wash operations, wash water, have a pH value within ranges between about 6.5 and about 11, preferably, between 7.5 and 11. laundry products are, in a way typical, of a pH 9 - 11. Techniques for controlling pH, at Recommended levels of use, including the use of buffers, alkalis, acids, etc., and are well known, by those people specialized in this art of technique.

The machine-laundering procedures referred to herein typically comprise treating dirty laundry (laundry), with an aqueous washing solution, in a washing machine, which has an effective amount of one dissolved or dispensed therein. detergent composition of machine laundry, in accordance with the invention. By means of an effective amount of the detergent composition, it is meant, for example, an amount ranging from 20 to 300 g of product, dissolved or dispensed in a wash solution of a volume of 5 to 85 liters, dosages these the which are typical dosages of typical products and volumes of solution, commonly used in conventional machine laundry procedures. They are examples,
following:

- automatic washing machines, loading upper, vertical axis, typical in the United States of America,  that use about 45 to about 83 liters of water in the wash bath, a wash cycle of approximately 10 at about 14 minutes and a wash temperature of about 10 to about 50 ° C;

- automatic washing machines, loading front, horizontal axis, typical in Europe, which use of about 8 to about 15 liters of water in the bathroom washing, a cycle of about 10 to about 60 minutes, and a wash temperature of about 30 to approximately 95 ° C.

- automatic washing machines, loading upper, vertical axis, typical in Japan, which use approximately 26 to approximately 52 liters of water in the bathroom wash, a wash cycle of about 8 to about 15 minutes and a wash temperature of approximately 5 to approximately 25 ° C.

The relationship value of the liquor is, in a way preferably from 1: 4 to 1: 40, especially from 1: 4 to 1: 15. From a highly preferred form, a relationship value of liquor from 1: 4 to 1: 10, especially from 1.5 to 1.9.

A further object of the present invention is that of providing a procedure for domestic washing of a textile fiber material, where the fiber material textiles, is contacted with an aqueous solution of a detergent comprising a compound of the formula (1), as has been defined above, above, and where, the detergent, it contains a peroxide, a peroxide activator and / or a catalyst of  Whitening,

and where, the temperature of the solution is a value within margins between 5ºC and 40 ° C, preferably, between 5 and 30 ° C, in the entire procedure, from the beginning to the end.

As regards the compounds of the formula (1), as well as in relation to detergents and the washing procedure, the definitions and preferences provided above, above.

Compounds used in accordance with the present invention, are particularly advantageous, due to the fact that, these, exhibit not only an extremely high bleaching capacity, but also, in many cases, these they also exhibit desirably high water solubilities, and they also have excellent aspects of whiteness in state solid. An additional advantage of the present invention resides in the fact that the detergent composition provides some enhanced whiteness benefits, and an improved touch of textiles Additionally, the compounds show good results, with respect to depletion properties.

The compounds have the advantage that, these, they are also effective, in the presence of active chlorine donors, such as, for example, hypochlorite, and can be used without a substantial loss of effects, in washing baths with agents nonionic washing agents, such as, for example, ethers of alkylphenol polyglycol. Also in the presence of perborate or peracids and activators, for example, tetraacetyl glycoluryl or acid ethylenediamine tetraacetic, are the compounds stable in both, the washing agent in powder form, and the wash baths Additionally, they impart an appearance Bright in daylight.

The examples given below, they serve to illustrate the invention; the parts and percentages, it refer to weight, unless expressly specified by another mode.

Preparation Example one

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7

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In a 1 l capacity flask, they are mixed 0.05 moles of the compound of the formula

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8

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with 600 ml of water, and proceed to heat at a temperature of 60 ° C. Then, 9.2 g are added of 2-ethylaminoethanol and, the reaction mixture, is heats at a temperature of 98; during heating, the pH, is maintained at a value between 8.5 and 9, by means of addition of a 4 molar aqueous solution of sodium hydroxide. The reaction mixture is cooled to a temperature of 50 ° C and the pH is adjusts to a value of 4.5, by adding a solution 6-molar aqueous hydrochloric acid. The precipitate, filtered, washed with 100 ml of a 10% aqueous solution of sodium chloride, and dried under vacuum. In this way, 30.5 are obtained g of a product yellowish.

Preparation Examples 2 a fifteen

The examples of the formula

9

can be prepared in a way analogous to the procedure provided in the preparation example 1, proceeding to replace 9.2 g of 2-ethylaminoethanol with an equimolar amount of the corresponding amine. X, is as defined in the following Table 1. Compounds that precipitate after cooling to a temperature of 50 ° C, they are isolated directly with sodium salts, without the addition of hydrochloric acid and then dried at empty.

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(Table goes to page next)

TABLE 1

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10

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Example Preparation 16

(Not according to the invention)

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eleven

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In a 1 l capacity flask, they are mixed 0.05 moles of the compound of the formula

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12

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with 600 ml of water, and proceed to heat at a temperature of 60 ° C. Then, 9.5 g are added of morpholine and the reaction mixture is heated to a temperature of 98 ° C; during heating, the pH is maintained at a value between 8.5 and 9, by adding a 4 molar aqueous solution of sodium hydroxide. The reaction mixture, it is cooled to a temperature of 40 ° C and, the precipitate, filtered, wash with 100 ml of a 10% aqueous solution of sodium chloride, and It dries under vacuum. In this way, 30 g of a product are obtained yellowish.

Preparation Examples 17 a 19

(Not according to the invention)

The examples of the formula

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13

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can be prepared in a way analogous to the procedure provided in the preparation example 16, proceeding to replace 9.5 g of morpholine, with an amount equimolar of the corresponding amine. X, is as defined in the following table 2. The compounds that have a high solubility, treated with a 6 molar aqueous acid solution hydrochloric, in order to adjust the pH to a value of 4.5, before cool down 50 ° C

14

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Preparation Example twenty

(Not according to the invention)

fifteen

In a 2-liter flask, 130 ml of methyl ethyl ketone, 80 ml of deionized water, 150 g of ice and 18.5 g of cyanuric chloride are mixed. Over a period of 30 minutes, 185 ml of a solution of 4,4'-diaminoestylbeno-2,2'-disulfonic acid (as disodium salt) in water (100 g / l concentration) is added dropwise , being, the temperature, of a value between -8 and + 5ºC. The pH value is maintained at a value between 4.5 and 5, by the addition of an aqueous solution of sodium carbonate. A yellowish solution is obtained. Then, by using a drip funnel, 27.2 g of ethanolamine (99%) are added. The pH is increased to a value of 10 and then drops to a lower value, whereby the temperature is increased from 10 to 15 ° C. Then, the reaction mixture is heated to a temperature of 45 ° C and maintained at this temperature, over a period of 20 minutes. During heating at a temperature of 98 ° C, in a time of 30 minutes, a mixture of methyl ethyl ketone and water is distilled off; the pH is maintained at a value within ranges between 8.5 and 9, by the addition of an aqueous solution of sodium hydroxide. After no additional addition of aqueous sodium hydroxide solution is necessary, to maintain the pH at a constant value, the reaction mixture is cooled to a value of 50 ° C. The pH is adjusted to a value of 5.5 and a yellow crystalline precipitate can be filtered. After drying, 29 g of product are obtained
yellowish.

Preparation Example twenty-one

(Not according to the invention)

16

In a pressure vessel, 1 l of capacity, 0.037 mol of acid are suspended N, N'-bis- (4-morpholino-6-chloro-1,3,5-triazin-2-yl) -4,4'-diaminoestylbeno-2,2'-disulfonic  (as sodium salt), in 500 ml of water. 15 g of one are added aqueous ethylamine solution (70%) and, the reaction mixture, is heats to a temperature within a range that range from 100 to 105 ° C, and stir for a period of time of 4.5 hours The reaction mixture is cooled to a temperature of 25 ° C and, the precipitate, is filtered, washed with 100 ml of a 10% aqueous sodium chloride solution, and dried under vacuum, at a temperature of 70 ° C. Thus, in this way, 25.8 g of a yellowish powder.

Preparation Example 22

(Not according to the invention)

17

The compound of the formula (107), can be prepared in a manner analogous to the procedure provided  in preparation example 21, proceeding to replace 15 g of an aqueous solution of ethylamine (70%), with the corresponding solution containing an equimolar amount of diethylamine.

Preparation Example 2. 3

(Not according to the invention)

18

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

Application example one

General procedure

A wash liquor is prepared, dissolving 0.8 g of a washing powder in 200 ml of running water from tap. 10 g of bleached cotton fabric are added to the bathroom, and proceed to wash it, at a temperature of 40 ° C, during a course of 15 minutes time and then rinsed, dried by rotary procedure (centrifuge), and ironed to a temperature of 160 ° C.

Washing materials A and A are used B (amounts provided in Tables 3a and 3b, expressed in grams):

TABLE 3a Ingredients of washing powder A and B

TO B Sodium Laurylbenzenesulfonate (LAS) 10 g 10 g Sodium lauryl ether sulfate (AES) 3 g 3 g Dobanon 23-6.5 (non-ionic alcoholetoxylate) 4 g 4 g

TABLE 3a (continued)

TO B Sodium tripolyphosphate 30 g - - Zeolite TO - - 20 g Sodium carbonate 15 g 15 g Sodium silicate 5 g 5 g Sodium sulfate 11 g 17 g Sodium perborate mono-hydrated 10 g 10 g TAED 3 g 3 g Polycarbonate (co-improver) - - 4 g Carboxymethyl cellulose 2 g 2 g Fragrance 0.1 g 0.1 g Water 5 g 5 g Fluorescent bleach used X g X g

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TABLE 3b Washing powder used

Amount of bleach Matter in  powder fluorescent used from washed Prep compound Ex. one 0.2 g TO Compound of prep. Ex 2 0.1 g B Prep compound Ex 3 0.3 g TO Prep compound Ex 4 0.2 g TO Prep compound Ex. 5 0.4 g TO Compound of prep. Ex 12 0.15 g B Prep compound Ex 13 0.1 g B Prep compound Ex. 16 * 0.3 g B Compound  of prep. Ex. 18 * 0.2 g TO Prep compound Ex. 21 * 0.3 g TO Prep compound Ex. 22 * 0.2 g B Compound  of prep. Ex. 23 * 0.1 g TO Compound of the formula (109) * 0.3 g B * not according to the invention

Constitution of a compound of the formula (109)

19

Cotton fabrics washed with detergents shown in table 3b in accordance with the general procedure, exhibit good properties of whiteness.

Application example 2

General procedure

A wash liquor is prepared, dissolving 0.8 g of a washing powder in 200 ml of running water from tap. 10 g of bleached cotton fabric are added to the bathroom, and proceed to wash it, at a temperature of 30 ° C, during a course of 15 minutes time and then rinsed, dried by rotary procedure (centrifuge), and ironed to a temperature of 160 ° C.

Washing powder materials are used that They are cited below (the amounts provided in the Tables 4a and 4b, refer to percentage by weight, based on weight total detergent):

TABLE 4a Ingredients of washing powder C and D

C D Sodium Laurylbenzenesulfonate (THE) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanon 23-6.5 (alcoholetoxylate no ionic) 5% 5% Zeolite TO twenty% twenty% Polycarboxylate (co-improver) 5% 5% Soda ash 18% 18% Sodium silicate 4% 4% Sodium sulfate 5% 5% Hydroxyethanediphosphonic acid (agent complexing) 0.5% 0.5% Cellulase 1.5% - - Protease - - 1.5 Carboxymethyl cellulose one% one% Sodium perborate monohydrate fifteen% fifteen% TEAD 5% 5% Soap 2% 2% Fluorescent bleach used X% X%

TABLE 4b Washing powder used

Amount of bleach Matter in powder fluorescent used from washed Prep compound Ex. one 0.2% C Compound of prep. Ex 3 0.2% C Prep compound Ex 6 0.3% C Prep compound Ex. 7 0.2% D Compound of prep. Ex 8 0.2% C Prep compound Ex 9 0.4% C Prep compound Ex. 10 0.2% D Compound of prep. Ex 11 0.2% C Prep compound Ex 14 0.3% D Prep compound Ex. fifteen 0.2% C Compound of prep. Ex. 17 * 0.4% C Prep compound Ex. 19 * 0.3% C Compound of prep. Ex 20 * 0.5% C Compound of the formula (109) * 0.3% D * not according to the invention

As regards the constitution of the compound of the formula (109), see application example 1

Cotton fabrics washed with detergents shown in table 4b in accordance with the general procedure, exhibit good properties of whiteness.

Claims (17)

1. A detergent composition, comprising at least one compound of the formula twenty in where, R_ {1} and R2_, are, in a way independent from each other, hydrogen or an alkyl C_ {1} -C_ {8}, unsubstituted or substituted, X_ {2} and X_ {4}, are, in a way independent from each other, -N (R 3) R 4, where R 3 and R 4 are hydrogen; cyano; C 1 -C 8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and wherein, the alkyl group C_ {1} -C_ {8}, is it uninterrupted or interrupted by -O-; C 5 -C 7 cycloalkyl, unsubstituted or substituted by alkyl C 1 -C 4; or R 3 and R 4, together with the nitrogen atom that bonds them, they form a ring morpholino, piperidine or pyrrolidine, unsubstituted or substituted by C 1 -C 4 alkyl; R5 is alkyl C_ {1} -C_ {8}, which is unsubstituted, or substituted by hydroxy, and N, is hydrogen, an alkali metal or alkaline earth, or ammonium, preferably, sodium, and where the detergent contains a peroxide, a peroxide activator and / or a bleaching catalyst. 2. A composition according to claim 1, where, R 3 and R 4, together with the atom of nitrogen that binds them, they form a morpholino, piperidine or pyrrolidine, unsubstituted or substituted by alkyl C 1 -C 4, preferably, a ring morpholino 3. A composition, according to any one of the claims 1 or 2, which comprises,

i)

1 - 70% of an anionic surfactant and / or surfactant nonionic;

ii)

0 - 75% of an improver;

iii)

0.5-30% of a peroxide;

iv)

0.5-10% of a peroxide activator and / 0.1-2% of a bleaching catalyst;

v)

0.001-5% of a compound of the formula (one); Y

saw)

0.5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase

4. A composition, according to any one of the claims 1 to 3, which comprises,

i)

5 - 70% of an anionic surfactant and / or nonionic surfactant;

ii)

5 - 70% of an improver;

iii)

0.5-30% of a peroxide;

iv)

0.5-10% of a peroxide activator and / 0.1-2% of a bleaching catalyst;

v)

0.01-5% of a compound of the formula (one); Y

saw)

0.05-5% of at least one enzyme selected between the group consisting of cellulase, protease, amylase and lipase

5. A composition according to any one of the claims 1 to 4, wherein the composition comprises minus one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 6. A composition according to claim 5, where, the enzyme, is a protease enzyme. 7. A composition, according to any one of the claims 1 to 6, wherein the composition comprises a peroxide. 8. A composition, according to any one of the claims 1 to 7, wherein the composition comprises a peroxide and a peroxide activator. 9. A composition according to claim 8, where, the peroxide activator is TAED. 10. A procedure for domestic washing of a textile fiber material, where the fiber material textiles, is contacted with an aqueous solution of a detergent comprising a compound of the formula twenty-one in where, R_ {1} and R2_, are, in a way independent from each other, hydrogen or an alkyl C_ {1} -C_ {8}, unsubstituted or substituted, X_ {2} and X_ {4}, are, in a way independent from each other, -N (R 3) R 4, where R 3 and R 4 are hydrogen; cyano; C 1 -C 8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and wherein, the alkyl group C_ {1} -C_ {8}, is it uninterrupted or interrupted by -O-; C 5 -C 7 cycloalkyl, unsubstituted or substituted by alkyl C 1 -C 4; or R 3 and R 4, together with the nitrogen atom that bonds them, they form a ring morpholino, piperidine or pyrrolidine, unsubstituted or substituted by C 1 -C 4 alkyl; R5 is alkyl C_ {1} -C_ {8}, which is unsubstituted, or substituted by hydroxy, and N, is hydrogen, an alkali metal or alkaline earth, or ammonium, preferably, sodium, and where the detergent contains a peroxide, a peroxide activator and / or a bleaching catalyst, and in where, the temperature of the solution is between 5 ° C and 40 ° C, preferably, between 5 ° C and 30 ° C, in the entire procedure, from beginning to end. 11. A method according to claim 10, where, R 3 and R 4, together with the atom of nitrogen that binds them, they form a morpholino, piperidine or pyrrolidine, unsubstituted or substituted by alkyl C 1 -C 4, preferably, a ring morpholino 12. A procedure according to any one of the claims 10 to 11, wherein the fiber materials textiles, are treated with 0.05 to 3.0%, by weight, based on weight of the textile fiber material, of the compound of the formula (one). 13. A procedure according to any one of the claims 10 to 12, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 14. A method according to claim 13, where, the enzyme, is a protease enzyme. 15. A procedure according to any one of the claims 10 to 14, wherein the detergent comprises a peroxide. 16. A procedure according to any one of the claims 10 to 15, wherein the detergent comprises a peroxide and a peroxide activator. 17. A composition according to claim 16, where, the peroxide activator is TAED.