Phthalocyanine-containing granules to decrease phthalocyanine deposition on textiles

Abstract

The present invention relates to compositions comprising granules of phthalocyanine compounds, to a process for the preparation thereof, and to the use thereof in washing agent and additive formulations. The composition comprises a) At least one water-soluble phthalocyanine compound; b) At least one cross-linked polyvinylpyrrolidone component; c) At least one hydrophilic binding agent; and, optionally, d) Further additives suitable for the preparation of solid agglomerates; and may be liquid, solid, paste-like or gel-like.

Claims

1. A washing agent composition comprising I) 5.0 to 70.0 wt.-% A) of at least one surfactant selected from the group of anionic surfactants, based on the total weight of the washing agent formulation; II) 0.0 to 60.0 wt.-% B) of at least one builder substance, based on the total weight of the washing agent formulation; III) 0.0 to 30.0 wt.-% C) of at least one peroxide and, optionally, at least one activator and/or at least one catalyst, based on the total weight of the washing agent formulation; IV) 0.001 to 5.0 wt.-% D) of granules, based on the total weight of the washing agent formulation, which granules comprise a) at least one water-soluble phthalocyanine compound; b) at least one cross-linked polyvinylpyrrolidone component; c) at least one hydrophilic binding agent selected from the group consisting of sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, polyacrylamides, polyvinyl alcohols, gelatines, hydrolyzed polyvinyl acetates, maltodextrin, polyaspartic acid, polyacrylates and polymethacrylates, and, optionally, d) further additives suitable for the preparation of granules, V) 0.0 to 60.0 wt.-% E) of at least one further additive, based on the total weight of the washing agent formulation; and VI) 0.0 to 5.0 wt.-% F) water, based on the total weight of the washing agent formulation; provided that the sum of the weight percentages of components I)-VI) in the composition is 100%.

2. A composition according to claim 1, wherein the granules D) comprise a) 0.1-20.0 wt.-% of the water-soluble phthalocyanine compound; b) 0.5-40.0 wt.-% of the cross-linked polyvinylpyrrolidone component; c) 3.0-40.0 wt.-% of the hydrophilic binding agent; and, optionally, d) 5.0-95.0 wt.-% of further additives suitable for the preparation of granules; and e) 3.0-15.0 wt.-% of water; provided that the sum of components a), b), c), d) and e) amounts up to 100 wt.-%.

3. The composition according to claim 1, wherein the granules D) comprise a) 0.1-10.0 wt.-% of the water-soluble phthalocyanine compound; b) 0.5-30.0 wt.-% of the cross-linked polyvinylpyrrolidone component; c) 3.0-20.0 wt.-% of the hydrophilic binding agent; and, optionally, d) 20.0-90.0 wt.-% of further additives suitable for the preparation of granules; and e) 3.0-15.0 wt.-% of water; provided that the sum of components a), b), c), d) and e) amounts up to 100 wt.-%.

4. The composition according to claim 1, which comprises, as water-soluble phthalocyanine component a), at least one phthalocyanine complex compound of the formula
(PC)-L-(D)(1), to which the substituent of at least one mono-azo dye is attached by the linking group L, Wherein PC represents the Zn(II), Fe(II), Ca(II), Mg(II), Na(I), K(I), Al, Si(IV), P(V), Ti(IV) or Cr(VI) metal-containing phthalocyanine structure; D represents the substituent of a mono-azo dye; and L represents a group ##STR00022## Wherein R.sub.20 represents hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy or halogen; R.sub.21 represents D, hydrogen, OH, Cl or F, provided that at least one is D; R.sub.100 represents C.sub.1-C.sub.8alkylene; * marks the point of attachment of PC; and # marks the point of attachment of the substituent D of the mono-azo dye.

5. The composition according to claim 4, wherein the water-soluble phthalocyanine complex compound (1) corresponds to the formula ##STR00023## Wherein PC represents the porphyrine structure, Me represents the central metal atom or central metal group coordinated to PC, which is selected from the group consisting of Zn, Fe, Ca, Mg, Na, K, AlZ.sub.1, Si(IV)-(Z.sub.1).sub.2, Ti(IV)-(Z.sub.1).sub.2 and Sn(IV)-(Z.sub.1).sub.2; Z.sub.1 represents C.sub.1-C.sub.8alkanolate, OH.sup., R.sub.0COO.sup., ClO.sub.4.sup., BF.sub.4.sup., PF.sub.6.sup., R.sub.0SO.sub.3.sup., SO.sub.4.sup.2, NO.sub.3.sup., F.sup., Cl.sup., Br.sup., I.sup., citrate, tartrate or oxalate, wherein R.sub.0 is hydrogen or C.sub.1-C.sub.18alkyl; r represents 0 or a numeral from 1 to 3; r represents a numeral from 1 to 4; each Q.sub.2 independently of one another represents SO.sub.3.sup.M.sup.+ or the group (CH.sub.2).sub.mCOO M.sup.+; wherein M.sup.+ is H.sup.+ an alkali metal ion or the ammonium ion and m is 0 or a numeral from 1 to 12; each Q independently of one another represents the segment of the partial formula -L-D, Wherein D represents the substituent of a mono-azo dye; and L represents a group ##STR00024## Wherein R.sub.20 represents hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy or halogen; R.sub.21 represents D, hydrogen, OH, Cl or F, provided that at least one of R.sub.21 is D; R.sub.100 represents C.sub.1-C.sub.8alkylene; * marks the point of attachment of Me-PC; and # marks the point of attachment of the substituent D of the mono-azo dye.

6. The composition according to claim 4, wherein the water-soluble phthalocyanine complex compound (1) corresponds to the formula ##STR00025## Wherein Me represents Zn, AlZ.sub.1, Si(IV)-(Z.sub.1).sub.2 or Ti(IV)-(Z.sub.1).sub.2, wherein Z.sub.1 is chloride, fluoride, bromide or hydroxide; each Q.sub.2 independently of one another represents SO.sub.3.sup.M.sup.+ or the group (CH.sub.2).sub.mCOO M.sup.+, wherein M.sup.+ is H.sup.+, an alkali metal ion or the ammonium ion and m is 0 or a numeral from 1 to 12; D represents the substituent of a mono-azo dye; and L represents a group ##STR00026## Wherein R.sub.21 represents D, hydrogen, OH, Cl or F, provided that at least one is D; * marks the point of attachment of PC; # marks the point of attachment to D; r.sub.2 represents 0 or 1; r.sub.3 represents 0 or 1; and r.sub.4 represents 0 or 1.

7. The composition according to claim 6, wherein Me represents Zn.

8. The composition according to claim 4, wherein D represents the substituent of a mono-azo dye of the partial formulae Xa, Xb, Xc or Xd: ##STR00027## Wherein # marks the point of attachment of the bridging group L; R.sub. represents hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.2alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C.sub.3-C.sub.4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, aryl, aryl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy and C.sub.1-C.sub.4alkyl; Z.sub.2, Z.sub.3, Z.sub.4, Z.sub.5 and Z.sub.6 independently of one another represent hydrogen, hydroxy, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.2alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C.sub.3-C.sub.4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.4alkoxy, C.sub.1-C.sub.2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C.sub.3-C.sub.4-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy, phenyl, naphthyl and pyridyl, halogen, SO.sub.2CH.sub.2CH.sub.2SO.sub.3H, NO.sub.2, COOH, COOC.sub.1-C.sub.4alkyl, NH.sub.2, NHC.sub.1-C.sub.4alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.4alkyl, CN and COOH, N(C.sub.1-C.sub.4alkyl)C.sub.1-C.sub.4alkyl, wherein the alkyl groups may independently of one another be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.4alkyl, CN and COOH, NH-aryl, NH-aryl, wherein aryl is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl and C.sub.1-C.sub.4alkoxy, or represents NHCOC.sub.1-C.sub.4alkyl or NHCOOC.sub.1-C.sub.4alkyl; G represents the direct bond, COOC.sub.1-C.sub.4alkylene, arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy and C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkylene, C.sub.1-C.sub.4-alkylene substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkoxy and C.sub.1-C.sub.4alkyl, or represents CO-arylene; n represents 0; 1; 2 or 3; n represents 0; 1 or 2; and each M independently of one another represents hydrogen; an alkali metal ion or an ammonium ion.

9. The composition according to claim 4, wherein D represents the substituent of a mono-azo dye of the partial formulae XIa, XIb, XIc or XId: ##STR00028## Wherein # marks the point of attachment of the bridging group L; Z.sub.2 represents C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkyl, phenyl, naphthyl and pyridyl, or represents OH; Z.sub.3 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN and COOH, or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.4 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN and COOH, or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.5 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl; G represents the direct bond, COOC.sub.1-C.sub.2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkylene or C.sub.1-C.sub.2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl; n represents 0, 1, 2 or 3; n represents 0, 1 or 2; and each M independently of one another represents hydrogen, Na.sup.+ or K.sup.+; ##STR00029## Wherein # marks the point of attachment of the bridging group L; Z.sub.2 represents C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkyl, phenyl, naphthyl and pyridyl or represents OH; Z.sub.3 is hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN or COOH or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.5 represents hydrogen, C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl; G represents the direct bond, COOC.sub.1-C.sub.2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkylene or C.sub.1-C.sub.2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl; n represents 0, 1, 2 or 3; N is 0, 1 or 2; and each M independently of one another represents hydrogen, Na.sup.+ or K.sup.+; ##STR00030## Wherein # marks the point of attachment of the bridging group L; Z.sub.2 represents hydrogen, hydroxy, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy or C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, or represents OH or NO.sub.2; Z.sub.3 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN and COOH, or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.4 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy or C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN and COOH, or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.5 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, or represents NO.sub.2; G represents the direct bond, COOC.sub.1-C.sub.2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkylene or C.sub.1-C.sub.2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl, n represents 0, 1, 2 or 3; n represents 0, 1 or 2; and each M independently of one another represents Na.sup.+ or K.sup.+; ##STR00031## Wherein # marks the point of attachment of the bridging group L; Z.sub.3 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, or represents SO.sub.2CH.sub.2CH.sub.2SO.sub.3H or NO.sub.2; Z.sub.4 represents C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, OH, or represents SO.sub.2CH.sub.2CH.sub.2SO.sub.3H, or NO.sub.2; Z.sub.5 represents hydrogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, OH, NO.sub.2, NH.sub.2, NHC.sub.1-C.sub.2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH.sub.2, C.sub.1-C.sub.2alkyl, CN and COOH, or represents NHCOC.sub.1-C.sub.2alkyl or NHCOOC.sub.1-C.sub.2alkyl; Z.sub.6 represents C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy, phenyl, naphthyl and pyridyl, C.sub.1-C.sub.2-alkoxy, C.sub.1-C.sub.2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.4alkoxycarbonyl, C.sub.1-C.sub.4alkyl, phenyl, naphthyl and pyridyl, or represents NO.sub.2; G represents the direct bond, COOC.sub.1-C.sub.2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2alkylene or C.sub.1-C.sub.2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO.sub.2, SO.sub.3H, NH.sub.2, carboxy, C.sub.1-C.sub.2alkoxycarbonyl, C.sub.1-C.sub.2alkoxy and C.sub.1-C.sub.2alkyl; n represents 0, 1, 2 or 3; n represents 0, 1 or 2; and each M independently of one another represents hydrogen, Na.sup.+ or K.sup.+.

10. The composition according to claim 4, wherein D is selected from the group consisting of compounds, wherein the partial formulae 10, 11, 12, 13 and 14: ##STR00032## are present and wherein # marks the point of attachment of the bridging group L.

11. The composition according to claim 1, wherein the cross-linked polyvinylpyrrolidone component b) is insoluble in water.

12. The composition according to claim 1, wherein the cross-linked polyvinylpyrrolidone component b) has a swelling pressure [kpa] from 25.0 to 200.0 and a hydration capacity from 2.0 to 10.0 g water per g of the cross-linked polyvinylpyrrolidone.

13. The composition according to claim 1, wherein the further additives of Component d) are selected from the group consisting of anionic dispersants, disintegrants, fillers, water-insoluble or water-soluble dyes or pigments; optical brighteners, zeolites, talcum, powdered cellulose, fibrous cellulose, microcrystalline cellulose, starch, dextrin, kaolin, TiO.sub.2 SiO.sub.2 and magnesium trisilicate.

14. The composition according to claim 1, wherein the granules have an average particle size of <500 m.

15. The composition according to claim 1, wherein the granules have an average particle size of 50 to 200 m.

16. The composition according to claim 1, which comprises A) 0.001 to 1.0 wt.-% granules D.

Description

EXAMPLES

1 Test Materials and Compositions

1.1 Preparation of zinc phthalocyanine sulphonic acid conjugates with 4,4-[[6-[(3-aminophenyl)amino]-1,3,5-triazine-2,4-diyl]diimino]bis[5-hydroxy-6-[2-(1-naphthalenyl)diazenyl]-2,7-naphthalenedisulphonic acid (CAS-No. 1159843-59-0)

1.1.1 Acetylation of H-acid

(1) 191.9 g (0.5 mol) 4-amino-5-hydroxy-naphthalene-2,7-disulphonic acid (83%, CAS-No. 90-20-0) are suspended in 500 ml water and dissolved at pH 7 by addition of 48.6 ml aqueous NaOH (30%). 92.1 g acetic acid anhydride are slowly added within 10 minutes. The reaction mixture is cooled to 10 C. by addition of 250.0 g ice. A pH-level of 7 is adjusted by addition of 118.3 ml aqueous NaOH (30%). 56.2 ml aqueous NaOH (30%) are added subsequently. A pH-level of 10.5 is maintained for 1 hour at a temperature of 30 C. by addition of 4.8 ml aqueous NaOH (30%). By addition of 32.9 ml aqueous HCl (32%) the solution is adjusted to a pH-level of 7.2. After cooling to 20 C. with 180 g ice, 1594 g solution of acetylated H-acid (ca. 0.5 mol) is obtained.

1.1.2 Diazotation and Coupling of 1-Naphthylamine

(2) 57.3 g (0.4 mol) 1-naphthylamine is added with stirring as a melt to a mixture of 800 ml water and 40.0 ml aqueous HCl (32%). Aqueous HCl (97.2 ml, 32%) is added, and the solution is cooled to 0 C. with 530 g ice. 90 ml of aqueous sodium nitrite (4N) is added within 15 minutes. During the addition, the temperature is maintained below 4 C. After further addition of 11 ml aqueous sodium nitrite, the reaction mixture is stirred for 30 minutes. 1 Mol of sulphamic acid is added subsequently to decompose any remaining nitrite.

(3) To the suspension thus obtained, 1275.0 g (0.4 mol) of the acetylated H-acid (pH 4.8) described above (1.1.1) is poured within a minute. A pH-level of 7.5 is adjusted with 327 ml of aqueous sodium carbonate solution (20% w/v). The solution is stirred at room temperature for 12 hours. The total volume of reaction solution is about 3.4 l. For hydrolysis, 340 ml aqueous NaOH (30%) are added to the reaction mixture, followed by heating to 90 C. for 3 hours. A pH-level of 7.5 is adjusted by the addition of 292.5 ml of aqueous HCl (32%). The violet suspension is stirred at room temperature for 12 hours. The volume of the reaction solution is about 4 l. The formed precipitate is filtered off to yield 518.7 g (84.4%) 5-amino-4-hydroxy-3-[2-(1-naphthalenyl)diazenyl]-2,7-naphthalenedisulphonic acid (CAS-No. 103787-67-3) as a paste.

1.1.3 Preparation of 4,4-[[6-[(3-aminophenyl)amino]-1,3,5-triazine-2,4-diyl]diimino]bis[5-hydroxy-6-[2-(1-naphthalenyl)diazenyl]-2,7-naphthalenedisulphonic acid (Dye, CAS-No. 1159843-59-0)

(4) An aqueous solution of 0.060 mol 5-amino-4-hydroxy-3(naphthalene-1-ylazo)-naphthalene-2,7-disulphonic acid is stirred at room temperature. A suspension consisting of 100 ml of ice water, 0.1 g disodium hydrogen tetraoxophosphate and 5.53 g (0.03 mol) cyanuric chloride is added. The reaction mixture is adjusted with aqueous NaOH (30%) and maintained at pH 7. After 30 minutes, the reaction mixture is heated to 70 C. and maintained at a pH-level of 7 for several hours until the coupling reaction with cyanuric chloride is complete as indicated by LC.

(5) To this solution (ca. 0.030 mol intermediate), a solution of 5.59 g (0.0031 mol) m-phenylenediamine dihydrochloride in 50 ml water is added. The reaction mixture is heated to 95 C. A pH value of 8.5 is maintained by addition of aqueous NaOH (30%). The reaction is monitored by LC. After 3 hours, the reaction mixture is cooled to room temperature and a volume of 950 ml solution is obtained. For isolation of the product, 237.5 g sodium chloride is added. The reaction mixture is stirred for another 12 hours. The formed precipitate is filtered off and dried to give 42.2 g dye (UV.sub.vis .sub.max: 536 nm).

1.1.4 Sulphonation and Sulphonyl Chloride Formation of Zinc(II) Phthalocyanine (Bis- and Tris-Sulphonated Zinc Phthalocyanines)

(6) A mixture of 16.55 ml (31.4 g) fuming sulphuric acid (nominally 20% free SO.sub.3) and 12.8 ml (24.8 g) fuming sulphuric acid (65% free SO.sub.3) is stirred at 20 C. 12.5 g (0.0195 mol) zinc phthalocyanine (90% active) is added to this solution within 5-10 minutes. The reaction mixture is heated to 75 C. and maintained for 30 minutes at that temperature. The reaction mixture is poured within 10 minutes into 330.0 g of a mixture of ice and water. A pH-level of 7 is adjusted, and the temperature of the solution is maintained below 25 C. The crude zinc phthalocyanine sulphonic acid mixture is desalted by dialysis and freeze-dried to give 13 g of a dark blue solid to give a mixture of bis- and tris-sulphonated zinc phthalocyanine isomers.

(7) 1.5 g of this dry mixture is suspended in 14.94 g (0.128 mol) chlorosulphuric acid. The reaction mixture is heated to 87 C. and maintained at this temperature for 30 minutes. 1.05 ml (1.72 g, 0.014 mol) thionyl chloride is added dropwise within 45 minutes. The reaction mixture is maintained at 87 C. for two more hours. The solution is allowed to cool to 30 C. and poured within 10 minutes into 25.0 g of an ice/water mixture. The temperature of the solution is maintained at 0-5 C. by further addition of ice. The formed precipitate is filtered off and washed with aqueous sodium chloride solution (3%) to give a crude mixture of sulphonyl chlorides.

1.1.5 Sulphonation and Sulphonyl Chloride Formation of Zinc(II) Phthalocyanine (Mono- and Bis-Sulphonated Zinc Phthalocyanines)

(8) A solution of 30 ml (56.9 g) fuming sulphuric acid (nominally 20% free SO.sub.3) is warmed up and stirred at 40 C. 12.5 g (21.6 mmol) zinc phthalocyanine is added in portions within 5-10 minutes. The reaction mixture is heated to 60-65 C. and stirred for 90 minutes at that temperature. The dark reaction suspension is slowly poured into 330 g of an ice/water mixture. By the addition of sodium hydroxide solution (50%), the suspension is adjusted to pH 7, and the mixture is stirred for another two hours. The crude product is desalted by dialysis and freeze-dried to give 13 g dark blue powder to give a mixture of essentially mono- and bis-sulphonated zinc phthalocyanines.

(9) 1.35 g of this dry mixture is slowly added to 8.8 ml (14.94 g, 0.128 mmol) chlorosulphuric acid. The reaction mixture is heated to 87 C. and maintained at this temperature for 30 minutes. 1.05 ml (1.72 g, 0.014 mol) thionyl chloride is added drop wise within 30-45 minutes and stirring is continued for two hours. Within 45 minutes, the reaction solution is cooled to 25 C. and poured into 140 g of a water/ice mixture. The formed precipitate is filtered off and washed with sodium chloride solution (3%) to give a crude mixture of sulphonyl chlorides.

1.1.6 Preparation of Zinc(II) Phthalocyanine Dye Conjugate I

(10) Freshly prepared (1.1.4) moist zinc phthalocyanine sulphonyl chloride (about 0.0195 mol) is dissolved in ice-cold water. An aqueous solution (ca. 0.0195 mol) of the dye (1.1.3) is added within 5 minutes. The reaction mixture is adjusted with aqueous NaOH (32%) to a pH-level of 7. The reaction mixture is heated to 50 C. and stirred for 2 hours, cooled to 25 C. and stirred for another eight hours. The reaction mixture is maintained at a pH-level of 7 with aqueous NaOH (32%). The completion of the reaction is monitored by TLC. The crude reaction mixture is desalted by nanofiltration to give a product containing about 10% active zinc(II) phthalocyanine dye conjugate (main conjugate signal in ESI-MS [M+]: 1927), which is used for further formulation processing.

1.1.7 Preparation of Zinc(II) Phthalocyanine Dye Conjugate II

(11) The crude filter cake (1.1.5; approx. 1.95 mmol) is suspended in a freshly prepared ice-cold water/dimethoxyethane 1:1 (v/v) mixture. The reaction solution is immediately adjusted to pH 4-5 with sodium hydroxide solution (50%). The dye (1.1.3, approx. 1.95 mmol) is dissolved in 20 ml water and added drop wise within 5-10 minutes. The reaction mixture is stirred for 25 C. for 12 hours. The reaction mixture is maintained at a pH-level of 7 with aqueous NaOH (32%). The reaction mixture is monitored by TLC. Optionally, the reaction mixture is heated to 50 C. to ensure complete conversion.

(12) The mixture is evaporated under vacuum at 60-70 C. to remove organic volatiles to the desired spectroscopic strength (main conjugate signals in ESI-MS [M.sup.+]: 1767 and 1847 along with minor amounts of 1927).

(13) The aqueous zinc phthalocyanine dye conjugate solution can be used directly for granule formation or it can be desalted by dialysis and lyophilized. Alternative cosolvents to dimethoxyethane (e.g. alcoholic) solvents are also suitable.

1.2 Preparation of Agglomerates

(14) The following compositions are prepared as indicated in Table 1. Solid content of the materials is measured by IR balance operated at 140 C.

(15) TABLE-US-00004 TABLE 1 No. of Composition Components [wt.-%] 1.2.1 1.2.2.sup.1) 1.2.3 1.2.4 1.2.5.sup.1) 1.2.6 ZnPcDC.sup.2) 6.7 6.8 6.8 4.2 4.2 7.1 Cross-linked PVP 10.8 11.0 11.3 8.5 Corn Starch 37.8 49.2 29.8 38.4 51.2 30.6 Zeolite 4A 32.2 32.4 32.7 33.8 33.8 27.7 Gelatin 5.5 5.6 5.6 5.8 5.8 8.2 Anionic Dispersant 6.9 7.0 Hydrophobic Silica 0.7 0.4 0.8 Water 7.0 6.0 6.5 6.1 5.0 10.1 .sup.1)Referential Composition .sup.2)Zinc-Phthalocyanine Dye Conjugate I: 1.2.1, 1.2.2, 1.2.3, 1.2.4; 1.2.5 Zinc-Phthalocyanine Dye Conjugate II: 1.2.6

1.2.1 Composition with Cross-Linked PVP

(16) The solution of zinc(II) phthalocyanine dye conjugate I obtained from (1.1.6) is dried into a powder with a solid content of 97 wt.-%. 5.0 g of this powder is dry-blended in a mixer with 27.0 g of corn starch (Cargill, solid content 88 wt.-%) and 25.0 g of Zeolite 4A (Silkem, solid content 93 wt.-%). 20.0 g of a 20 wt.-% solution of gelatine (Gelita, type A) in water is prepared as binder solution, and a blend of 4.0 g of corn starch and 8.0 g of cross-linked PVP powder (KOLLIDON CL-F, BASF, solid content of 98 wt.-%) as powdering agent. 4.0 g of the binder solution are blended with the solids in the mixer, and then 3.0 g of the powdering agent is added and thoroughly mixed. This procedure is repeated for three times. Then the final portion of the binder solution is added and the wet powder is further blended in the mixer for homogenization and agglomeration. The material obtained is dried at 80 C. and sieved to 100-160 m particle size. The resulting agglomerates contain 7.2% of the ZnPcDC photo catalyst with respect to dry matter of the material.

1.2.2 Referential Example, Control

(17) Analogous to Example 1.2.1. 28.0 g of corn starch, 25.0 g of Zeolite 4A and 5.0 g of dried ZnPcDC photo catalyst powder obtained from the solution of zinc(II) phthalocyanine dye conjugate I (1.1.6) are blended with 20.0 g of the binder solution. The powdering agent consists of 12.0 g of corn starch only. No cross-linked PVP is present in the composition. Processing of the agglomerates analogous to 1.2.1.

1.2.3 Composition with Cross-Linked PVP

(18) Analogous to 1.2.1. The ZnPcDC solution (1.1.6) is blended in water with the sodium salt of a condensate of naphthalenesulphonic acid with formaldehyde as the anionic dispersant, and dried into a powder that contains equal amounts of ZnPcDC and dispersant at 93 wt.-% solid content. 10.5 g of the formulated ZnPcDC powder, 20.0 g of corn starch and 25.0 g of Zeolite 4A are blended with 20.0 g of the binder solution. A mixture of 4.0 g of corn starch and 8.0 g of cross-linked PVP powder (KOLLIDON CL-F, BASF) is used as powdering agent. Starting with the binder solution, portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to Example 1.2.1. After adding half of the powdering agent, 0.5 g of fine hydrophobic silica (Sipernat D17, EVONIK) is blended with the remaining powdering agent. Further processing of the agglomerates is analogous to 1.2.1.

1.2.4 Composition with Cross-Linked PVP

(19) 26.0 g of corn starch (Cargill) is dry-blended with 25.0 g of Zeolite 4A and 3.0 g of dried ZnPcDC photo catalyst powder obtained from the solution of zinc (II) phthalocyanine dye conjugate I (1.1.6). 20.0 g of a 20 wt.-% aqueous gelatine solution (Gelita, type A) is prepared as binder solution, and a blend of 4.0 g of corn starch and 8.0 g of cross-linked PVP powder (KOLLIDON CL-F, BASF) as powdering agent. Starting with the binder solution, portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to 1.2.1. After adding half of the powdering agent, 0.3 g of fine hydrophobic silica (Sipernat D17, EVONIK) is blended with the remaining powdering agent. Further processing is analogous to 1.2.1.

1.2.5 Referential Composition, Control

(20) Analogous to Example 1.2.4. 28.0 g of corn starch, 25.0 g of Zeolite 4A and 3.0 g of dried ZnPcDC photo catalyst powder obtained from the solution of zinc(II) phthalocyanine dye conjugate I (1.1.6) are blended with 20.0 g of the binder solution. The powdering agent consists of 12.0 g of corn starch only. No cross-linked PVP is present in the composition. Processing of the agglomerates analogous to 1.2.1.

1.2.6 Composition with cross-linked PVP

(21) The zinc(II) phthalocyanine dye conjugate II solution obtained from (1.1.7) is blended with the sodium salt of a condensate of naphthalene-sulphonic acid with formaldehyde as the anionic dispersant, and dried into a powder that contains equal amounts of zinc(II) phthalocyanine dye conjugate II and the dispersant at 95 wt.-% solid content. 12.0 g of this powder, 20.0 g of corn starch and 24.0 g of Zeolite 4A are dry-blended in a mixer. 33.0 g of a 20 wt.-% aqueous gelatine solution (Gelita, type A) is prepared as binder solution, and a blend of 8.0 g of corn starch and 7.0 g of cross-linked PVP powder (KOLLIDON CL-F, BASF) is used as powdering agent. Starting with the binder solution, portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to Example 1.2.1. After adding half of the powdering agent, 0.7 g of fine hydrophobic silica (Sipernat D17, EVONIK) is blended with the remaining powdering agent. Further processing of the agglomerates is analogous to 1.2.1.

2 Application Tests

2.1 Spotting Tests

(22) The compositions 1.2.1-1.2.5 are weighted into a detergent powder containing no photo catalyst active and are then thoroughly mixed using a turbula laboratory mixer until a homogenous distribution in the detergent is achieved. ECE 77 detergent (ECE reference detergent 77, from EMPA Test Materials) is used, and a level of 0.3 wt.-% of the granule is chosen for all tests.

(23) The spotting test used for evaluation of the agglomerates is outlined in WO 2003/018740. Six 1515 cm pieces of white bleached woven non-mercerised cotton are placed flat on the bottom of a bowl containing 1 l of tap water. 10 g of ECE 77 detergent containing the particle compositions are spread on the cloth and then left for 10 minutes. Then the cloth is thoroughly rinsed, dried and then evaluated on a scale ranging from 0 (no discoloration of the fabric, no spots) to 4 (full spotting). The results of the spotting evaluations are reported in Table 2.

2.2 Exhaustion and Spotting-in-Use

(24) Bleached cotton is washed for 15 minutes at 30 C. with ECE 77 detergent at a 20 g/kg fabric and a liquor ratio of 1:20, in the presence of composition 1.2.1, 1.2.2 and 1.2.3 (concentration of 20 mg/1) in LINITEST equipment (Atlas). Before the addition of cotton, the composition is allowed to stand for 1 minute at ambient temperature. After rinsing with tap water, spin-drying and ironing, the exhaustion of the active dye on the fabric is measured by reflectance spectroscopy by using the Kubelka/Munk formula K/S. The higher the K/S-value, the higher the exhaustion of the active dye on the cotton fabric. The results are reported in Table 3.

2.3 Release in the Wash

(25) Analogous to the procedure in 2.2, the washing experiments are performed with 6.9 mg/l (average of 7 independent washing runs) of composition 1.2.6. The CIELAB D65/10b* value of the cotton fabric is measured in order to determine the hueing ability (blue shift) of the composition. For comparative purposes, the experiment is modified in such a way that the composition is gently swirled for 20 minutes at ambient temperature. This ensures complete dissolution of the solid composition before starting the washing. The results are reported in Table 4.

3 Results

(26) TABLE-US-00005 TABLE 2 Spotting tests (2.1) No. of Composition Components [wt.-%] 1.2.1 1.2.2.sup.1) 1.2.3 1.2.4 1.2.5.sup.1) ZnPcDC 7.2 7.2 7.3 4.5 4.5 Cross-linked PVP 11.6 11.8 12.1 Spotting Result on Fabric 1-2 2-3 2 1 2 .sup.1)Referential Composition

(27) TABLE-US-00006 TABLE 3 Exhaustion and spotting in use (2.2) K/S (680 nm) vs. zero Relative Composition amount of composition K/S (680 nm) 1.2.1 0.202 123% 1.2.2 0.0164 100% 1.2.3 0.0200 122%

(28) The results reported in Table 3 show that the two compositions that contain cross-linked PVP give rise to a higher exhaustion of active dye on the fabric as compared with agglomerates that contain no disintegrant PVP (composition 1.2.2). This indicates an excellent release of the dye, and no exhaustion inhibiting interaction of disintegrant and dye in the wash liquor is found. Two thirds of the fabric washed in the presence of composition 1.2.2 show blueish-violet stains caused by incomplete disintegration, whereas no stains are visible when inventive compositions 1.2.1 and 1.2.3 are tested.

(29) TABLE-US-00007 TABLE 4 Release in the wash Composition b * average Standard deviation 1.2.6 1.8 0.23 1.2.6 dissolved in wash 1.9 0.22 liquor prior to wash

(30) The addition of compositions in the form of particles has no negative effect on the hueing performance as compared with agglomerates completely dissolved when beginning with the wash. The spotting performance remains within the expected acceptable range for use in consumer detergents.