WO2013151970A1 - Laundry detergent composition comprising water-soluble phthalocyanine compound - Google Patents

Laundry detergent composition comprising water-soluble phthalocyanine compound Download PDF

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Publication number
WO2013151970A1
WO2013151970A1 PCT/US2013/034905 US2013034905W WO2013151970A1 WO 2013151970 A1 WO2013151970 A1 WO 2013151970A1 US 2013034905 W US2013034905 W US 2013034905W WO 2013151970 A1 WO2013151970 A1 WO 2013151970A1
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WIPO (PCT)
Prior art keywords
alkyl
group
alkoxy
substituted
hydroxy
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PCT/US2013/034905
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French (fr)
Inventor
Patrick Christopher Stenger
Andrew Philip MOON
Gregory Scot Miracle
Ullrich Menge
Gunther Schlingloff
Frank Bachmann
Andreas Lindenmaier
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CN201380017490.XA priority Critical patent/CN104204178A/en
Priority to EP13715874.7A priority patent/EP2834340B1/en
Publication of WO2013151970A1 publication Critical patent/WO2013151970A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • 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 washing agent additive formulations.
  • Water-soluble phthalocyanine complex compounds especially zinc and aluminium
  • phthalocyanine sulphonates are frequently used as photo-activators in washing agent preparations.
  • the invention relates to a laundry detergent composition, which comprises
  • At least one water-soluble phthalocyanine compound At least one water-soluble phthalocyanine compound
  • At least one hydrophilic binding agent At least one hydrophilic binding agent; and, optionally,
  • compositions according to the invention may be liquid, solid, paste-like or gel-like.
  • the compositions especially washing agent compositions but also washing agent additives or additive concentrates, for example pre- and/or after-treatment agents, stain-removing salt, washing-power enhancers, fabric conditioners, bleaching agents, UV-protection enhancers etc.
  • a preferred embodiment of the invention relates to a composition, which comprises
  • composition which comprises a) 0.1 - 10.0 wt.- of a water-soluble phthalocyanine compound
  • Suitable phthalocyanine compounds are water-soluble or at least water-dispersible
  • phthalocyanine complex compounds with di-, tri- or tetra-valent coordination centres, particularly metal ions (complexes having a d° or d 10 configuration), as the central atom, to which the substituent of at least one mono-azo dye is attached.
  • Such phthalocyanine complex compounds correspond to the formula
  • PC represents the Zn(II), Fe(II), Ca(II), Mg(II), Na(I), K(I), Al(III), Si(IV), P(V), Ti(IV) or Cr(VI) metal-containing phthalocyanine structure;
  • D represents the substituent of a mono-azo dye
  • R 20 represents hydrogen, Ci-Csalkyl, Ci-Csalkoxy or halogen
  • R 21 represents D, hydrogen, OH, CI or F, provided that at least one of R 2 i is D;
  • R 100 represents Ci-Csalkylene
  • Ci-Csalkyl is linear or branched alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or isopropyl.
  • Ci-Csalkoxy is linear or branched, for example methoxy, propoxy or octyloxy.
  • Halogen is F, CI, Br or I, preferably CI.
  • Ci-Csalkylene is, for example, linear or branched methylene, ethylene, propylene, butylene or pentylene.
  • the phthalocyanine complex compound of the formula (1) wherein the phthalocyanine backbone is substituted by at least one sulpho groups and to which the substituent of at least one mono-azo dye is attached by the linking group L, are characterized by rapid photo degradation, which has the effect that discolouration on the treated fabric is avoided, even after repeated treatment.
  • the phthalocyanine complex compounds of the formula (1) are characterized by improved shading and exhaustion onto the fabrics.
  • the phthalocyanine complex compounds of the formula (1) are also highly efficient photo catalysts by additional light absorption and energy transfer to the phthalocyanine part of the molecule.
  • the water-soluble phthalocyanine complex compound (1) corresponds to the formula
  • PC represents the phthalocyanine 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, Al-Zi, Si(IV)-(Z 1 ) 2 , Ti(IV)-(Z! 2 and SnOVMZ z;
  • Zj represents C C 8 alkanolate, OH “ , R 0 COO “ , C10 4 “ , BF 4 “ , PF 6 “ , R 0 SO 3 “ , S0 4 2” , N0 3 “ , F “ , CI “ , Br “ , ⁇ , citrate, tartrate or oxalate, wherein Ro is hydrogen or Ci-Cisalkyl;
  • r represents 0 or a numeral from 1 to 3, preferably 1 to 2;
  • r' represents a numeral from 1 to 3, preferably 1 to 3;
  • each Q 2 independently of one another represents -SO3 M "1" or the group -(CH 2 ) m -COO " M + ; wherein M + is H + , 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
  • D represents the substituent of a mono-azo dye
  • R20 represents hydrogen, Ci- Csalkyl, Ci-Csalkoxy or halogen
  • R21 represents D, hydrogen, OH, CI or F, provided that at least one is D;
  • R100 represents d-Csalkylene
  • the sum of r and r' is preferably from 1 - 4.
  • Me represents the central metal atom or central metal group coordinated to PC, which is selected from the group consisting of Zn, Al-Zi and Ti(IV)-(Zi)2, wherein Zi is as defined above, preferably halogen, e.g. chlorine, or hydroxy.
  • Me preferably represents Zn.
  • the water-soluble phthalocyanine complex compound (1) corresponds to the formu
  • each k is independently selected from 0 and 1
  • j is independently selected from 0 and 1- k
  • Me represents Zn, Al-Zi, Si(IV)-(Z 1 ) 2 or Ti(IV)-(Z 1 ) 2 , wherein Zi is chloride, fluoride, bromide or hydroxide Ci-C 4 alkoxide;
  • each Q 2 independently of one another represents -SO 3 M "1" or the group -(CH 2 ) m -COO M + , wherein M + is H + , 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
  • L represents a group
  • R 21 represents D, hydrogen, OH, CI or F, provided that at least one of R 2 i is D, preferably two of R 21 are D;
  • the groups D independently of one another, represent the substituents of a mon - azo dye of the partial formulae Xa, Xb, Xc or Xd:
  • R a represents hydrogen, Ci-C4alkyl, Ci-C2alkyl which is substituted by at least one
  • Ci-C4alkyl independently of one another represent hydrogen, hydroxy, Ci-C4alkyl, Ci-C 2 alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, Ci-C4alkoxy, Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C4
  • G represents the direct bond, -COOCi-C 4 alkylene, arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N0 2 , SO 3 H, NH 2 , carboxy, carbo-Ci-C 4 alkoxy, Ci-C 4 alkoxy and Ci-C 4 alkyl, Ci-C 4 alkylene,
  • Ci-C 4 -alkylene substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N0 2 , SO 3 H, NH 2 , carboxy, carbo-Ci-C 4 alkoxy, Ci- C 4 alkoxy and Ci-C 4 alkyl, or represents -CO-arylene;
  • n 0; 1; 2 or 3;
  • n' represents 0; 1 or 2;
  • each M independently of one another represents hydrogen; an alkali metal ion or an ammonium ion.
  • the substituents in the naphthyl groups in the event they are not attached in a fixed position to an individual carbon atom, can be attached in either ring of the naphthyl radical. This is expressed by the horizontal line going through both rings in, for example, in structural formula Xa, Xb and Xc.
  • Ci-C 4 alkylene is methylene, ethylene, propylene or butylene.
  • Arylene in the context of the description of the instant invention means phenylene or naphthylene, preferably phenylene.
  • the groups D independently of one another, represent the substituents of a mo - azo dye of the partial formulae XIa, Xlb, XIc or Xld:
  • Z 2 represents Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci- C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci-C 2 alkoxy, Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkyl, phenyl, naphthyl and pyridyl, or represents OH;
  • Z3 represents hydrogen, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one
  • Z 4 represents hydrogen, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci-C 2 alkoxy, Ci- C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, N0 2 , NH 2 , NHCi-C 2 alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH 2 , C C 2 alkyl, CN and COOH
  • Z5 represents hydrogen, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl;
  • G represents the direct bond, COOCi-C 2 alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N0 2 , SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy and Ci-C 2 alkyl, Ci-C 2 alkylene or Ci-C 2 -alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N0 2 , SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy and Ci-C 2 alkyl;
  • Z 2 represents Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo- Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci-C 2 alkoxy, Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkyl, phenyl, naphthyl and pyridyl or represents OH;
  • Z5 represents hydrogen, Ci-C 2 -alkyl or Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl;
  • G represents the direct bond, COOCi-C 2 alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano,
  • Z 2 represents hydrogen, hydroxy, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci- C 2 alkoxy or Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci- C 4 alkoxy, Ci-C 4 alkyl, phenyl, naphthyl and pyridyl, or represents N0 2 ;
  • Z 3 represents hydrogen, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci- C 2 alkoxy, Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkyl, phenyl, naphthyl and pyridyl, OH, N0 2 , NH 2 , NHCi-C 2 alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH 2 , Ci-C 2 alkyl, CN and CO
  • Z 4 represents hydrogen, Ci-C 2 -alkyl, Ci-C 2 -alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy, phenyl, naphthyl and pyridyl, Ci- C 2 alkoxy or Ci-C 2 alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH 2 , carboxy, carbo-Ci- C 4 alkoxy, Ci-C 4 alkyl, phenyl, naphthyl and pyridyl, OH, N0 2 , NH 2 , NHCi-C 2 alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH 2 , Ci-C 2 alkyl, CN and CO
  • G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N0 2 , SO 3 H, NH 2 , carboxy, carbo-Ci-C 2 alkoxy, Ci-C 2 alkoxy and Ci-C 2 alkyl, Ci- C 2 alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO 3 H, N3 ⁇ 4, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
  • n 0, 1, 2 or 3;
  • n' 0, 1 or 2;
  • Z3 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, N3 ⁇ 4, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents
  • Z4 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
  • Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO 3 H, N3 ⁇ 4, carboxy, carbo-Ci-C 4 alkoxy, Ci-C 4 alkyl, phenyl, naphthyl and pyridyl, OH, NO2, NH 2 , NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH 2 , Ci-C2alkyl, CN and COOH, or represents NHCOCi-C
  • Z 6 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
  • G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO 3 H, N3 ⁇ 4, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci-C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO 3 H, NH 2 , carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl; n represents 0, 1, 2 or 3;
  • n' 0, 1 or 2;
  • each M independently of one another represents hydrogen, Na + or K + .
  • D is selected from the group consisting of compounds, wherein the partial formulae 10, 11, 12, 13 and 14:
  • the sulphonic acid groups of the dyes represented by -SO 3 H may also be in the form of their salts, in particular of alkali metal salts, such as Na, K or Li salts or as ammonium salts. Also mixtures of the free acid and the corresponding salts are embraced.
  • a particularly suitable individual phthalocyanine is represented by the following formula wherein the degree of sulphonation is between 1 and 3 in the phthalocyanine ring:
  • the water-soluble phthalocyanine complex compound (1) corresponds to the formula
  • PC, L and D are as defined above (including the preferences);
  • Me is Zn or Al-Zi, Ziis chlorine, fluorine, bromine or hydroxy
  • Y 3 ' is hydrogen; an alkali metal ion or ammonium ion;
  • r is zero or a numeral from 1 -3 ;
  • r' is a numeral from 1 to 4.
  • the amount of water-soluble phthalocyanine complex compounds (1) present in the agglomerates, particularly granules, may vary within wide limits.
  • a preferred range is from about 0.01-20.0 wt.- , particularly 0.1-20 wt.- , especially from 0.1 -10.0 wt.- , based on the total weight of the agglomerates.
  • Lower weight ranges are from about 0.01-0.5 wt.- , particularly 0.05-0.3 wt.- , based on the total weight of the agglomerates.
  • water-soluble phthalocyanine complex compounds (1) For the synthesis of the water-soluble phthalocyanine complex compounds (1), two different reaction sequences are available: either by initial synthesis of a metal-free phthalocyanine derivative and subsequent complexation with a metal salt or by synthesis of a phthalocyanine ring system from a simple benzenoid precursor by concomitant incorporation of the metal ion. Substituents can be introduced before or after the formation of the phthalocyanine ring structure.
  • a suitable method to obtain water-soluble phthalocyanine complex compounds (1) is the introduction of sulphonate groups, for example by sulphonation of the unsubstituted metal phthalocy
  • the sulphonated phthalocyanine complex compounds are mixtures of different structure and different positional isomers.
  • the -SC ⁇ H-group can be located at positions 3, 4, 5 or 6. Also the degree of sulphonation is varying.
  • a tetra sodium salt of the zinc phthalocyanine can be prepared after known procedure; /. Griffiths et al, Dyes and Pigments, Vol. 33, 65-78 (1997) and the literature cited therein.
  • Another method to obtain a sulphonated metal phthalocyanine is reacting a sulpho phthalic acid with a metal salt, urea and a molybdate catalyst in a melt condensation. The position of the sulphonation is determined by the corresponding phthalic acid reactant. If 4-sulphophthalic acid is used, a tetrasulphonated metal phthalocyanine with sulphonic acid groups exclusively in position 4 or 5 is obtained.
  • the content of sulphonic acid groups can be adjusted by addition of phthalic acid.
  • the phthalocyanine complex is being linked with a mono-azo dye molecule corresponding to D via specific linking groups L.
  • a convenient way to realize this linkage is the synthesis of a metal phthalocyanine sulphonyl chloride by a sulphochlorination reaction after known procedures (DE 2812261, DE 0153278).
  • the desired degree of sulpho chloride content can be adjusted.
  • the sulphochlorination reaction of phthalocyanines generally leads to a main product, but as by-products small amounts of lower or higher degree of sulphonyl chloride groups are detected.
  • the resulting reactive phthalocyanine-sulphonyl chloride can then be reacted further with a suitable dye having an amino group.
  • a suitable dye having an amino group For illustrate the synthesis, the following synthetic examples leading to zinc and aluminium phthalocyanines linked with amino-functionalized azo dyes are given. The syntheses are performed as shown in the following scheme. From the possible positional isomers, only one is shown. The formation of the side products (degree of -SO 3 R and SO2CI) is not shown.
  • R H or Na dye
  • the synthesis of metal phthalocyanines with lower degree of sulphonation can also be performed by a modified sulphonation reaction, for example by shortening of reaction time and/or reduction of reaction temperature (WO 2009068513 and WO 2009069077).
  • the cross-linked polyvinylpyrrolidone component b) is insoluble in water.
  • the insoluble cross- linked polyvinylpyrrolidone is characterized in that it contains less than or equal to 1.5% water- soluble substances, more preferably less than or equal to 1 % water-soluble substances, cf. Biihler, V. Kollidon: Polyvinylpyrrolidone Excipients for the Pharmaceutical Industry; 9th ed. Ludwigshafen, Germany BASF; 2008:145 ctd.
  • Suitable products belong to the group of super disintegrants and are known under the generic terms Crospovidone, crospovidonum, insoluble polyvinylpyrrolidone, cross-linked PVP and (inadequate chemical term) polyvinylpolypyrroli- done (PVPP).
  • Such products are items of commerce and are available from BASF SE under the product designations Kollidon®CL, KOLLIDON CL-F, -SF and -M or from ISP under the product designations Polyplasdone®XL and XL- 10.
  • soluble polyvinylpyrrolidone are widely used as auxiliary material (e.g. as binder, rheology modifier or complexing agent), for example in pharmaceutical industry and also in detergent additives.
  • auxiliary material e.g. as binder, rheology modifier or complexing agent
  • Such materials are commercially available in different average molecular weight and can be obtained as solutions in water or as free-flowing powders.
  • powders from BASF SE for the pharmaceutical industry are available under the product designations Kollidon® 12 PF, Kollidon® 25, Kollidon® 30 and Kollidon® 90 F.
  • Sokalan ® HP 165 For detergent and cleaners, a selection of products from BASF SE are Sokalan ® HP 165, Sokalan ® HP 50, Sokalan ® HP 53, Sokalan ® HP 59, and from ISP under the product designation PVP K-15, PVP K-30, PVP K-60 and PVP K-90. Soluble polyvinylpyrrolidones are not preferred materials for component b) in the context of this invention.
  • the cross-linked polyvinylpyrrolidone component b) has a swelling pressure [kpa] from about 25.0 to 200.0 and a hydration capacity from 2.0 to 10.0 g water per g of the cross-linked polyvinylpyrrolidone.
  • kpa swelling pressure
  • hydration capacity 2.0 to 10.0 g water per g of the cross-linked polyvinylpyrrolidone.
  • the insoluble grades of KOLLIDON have different specific surface areas from less than 1.0 m 2 /g to more than 6.0m 2 /g: Kollidon®CL: ⁇ 1.0 m 2 /g, KOLLIDON CL-F: ca. 1.5 m 2 /g, KOLLIDON CL-SF: ca. 3.0m 2 /g and KOLLIDON CL-M: > 6.0 m 2 /g.
  • the insoluble grades of KOLLIDON have different particle sizes in the range from ⁇ 15 ⁇ to ⁇ 250 ⁇ :
  • the amount of cross-linked polyvinylpyrrolidone according to component b) may vary within wide limits, particularly from 0.5 - 40.0 wt.-%, based on the total weight of the composition. According to a preferred embodiment, the amount of cross-linked polyvinylpyrrolidone is from about 0.5 - 30.0 wt.-%, based on the total weight of the composition.
  • the hydrophilic binding agent of component c) is a water-soluble or at least water-dispersible polymer or wax-type polymer selected from the group consisting of gelatines, polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), vinyl acetates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohols, hydrolysed and non-hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons and also mixed polymerization products of the mentioned polymers.
  • gelatines polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), vinyl acetates, copolymers of styrene and acrylic acid, polycar
  • copolymers of ethylene oxide with propylene oxide MW > 3500
  • condensation products block polymerization products of alkylene oxide, especially propylene oxide, ethylene oxide-propylene oxide addition products with diamines, especially ethylenediamine, polystyrenesulphonic acid,
  • polyethylenesulphonic acid copolymers of acrylic acid with sulphonated styrenes, gum arabic, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl
  • methylcellulose phthalate methylcellulose phthalate, maltodextrin, sucrose, lactose, enzymatically modified and subsequently hydrated sugars, as are obtainable under the name "Isomalt”, cane sugar, polyaspartic acid and tragacanth.
  • binding agents special preference is given to sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, polyacrylamides, polyvinyl alcohols, gelatines, hydrolysed polyvinyl acetates, maltodextrin, polyaspartic acid and also polyacrylates and polymethacrylates.
  • the amount of binding agent according to component c) may vary within wide limits, particularly from 3.0 - 40.0 wt.- , based on the total weight of the composition.
  • the amount of binding agent is from about 3.0 - 20.0 wt.- , based on the total weight of the composition.
  • the agglomerates, particularly the granules, according to the invention contain from 5.0 - 95.0 wt.- , preferably from 20.0 - 90.0 wt.- , of at least one further additive (component d)), based on the total weight of the granule.
  • Such further additives may be anionic dispersing agents; inorganic salts, aluminium silicates such as zeolites, and also compounds such as talc, kaolin; further disintegrants such as, for example, powdered or fibrous cellulose, microcrystalline cellulose; fillers such as, for example, dextrin, starch as for example corn starch or potato starch; water-insoluble or water-soluble dyes or pigments; and also optical brighteners.
  • Ti0 2 , Si0 2 or magnesium trisilicate may also be used in small amounts, for example 0.0 to 10.0% by weight, based on the weight of the total composition.
  • the anionic dispersing agents used are, for example, the commercially available water-soluble anionic dispersing agents for dyes, pigments etc.
  • condensation products of aromatic sulphonic acids and formaldehyde condensation products of aromatic sulphonic acids with unsubstituted or chlorinated biphenyls or biphenyl oxides and optionally formaldehyde, (mono-/di-) alkylnaphthalenesulphonates, sodium salts of polymerized organic sulphonic acids, sodium salts of polymerized alkylnaphthalenesulphonic acids, sodium salts of polymerized
  • alkylbenzenesulphonic acids alkylarylsulphonates, sodium salts of alkyl polyglycol ether sulphates, polyalkylated polynuclear arylsulphonates, methylene-linked condensation products of arylsulphonic acids and hydroxyarylsulphonic acids, sodium salts of dialkylsulphosuccinic acids, sodium salts of alkyl diglycol ether sulphates, sodium salts of
  • Especially suitable anionic dispersing agents are condensation products of naphthalenesulphonic acids with formaldehyde, sodium salts of polymerized organic sulphonic acids, (mono-/di-) alkylnaphthalenesulphonates, polyalkylated polynuclear arylsulphonates, sodium salts of polymerized alkylbenzenesulphonic acid, lignosulphonates, oxylignosulphonates and condensation products of naphthalenesulphonic acid with a poly chlorome thy lbiphenyl.
  • the agglomerates, particularly the granules, according to the invention may contain residual moisture. This water level may range from 3.0 to 15.0 wt.- , based on the total weight of the granule.
  • the invention also relates to a process for the preparation of the agglomerates, particularly the granules described above, which comprises mixing simultaneously or subsequently
  • At least one water-soluble phthalocyanine compound At least one water-soluble phthalocyanine compound
  • At least one hydrophilic binding agent At least one hydrophilic binding agent; and, optionally,
  • the agglomerates are prepared according to known methods. Any known method is suitable to produce granules comprising the inventive mixture. Continuous or discontinuous methods are suitable. Continuous methods, such as spray drying or fluidised bed granulation processes are preferred. Such methods are for instance described in WO
  • the invention also relates to solid agglomerates, particularly granules, which comprise
  • At least one water-soluble phthalocyanine compound At least one water-soluble phthalocyanine compound
  • At least one hydrophilic binding agent At least one hydrophilic binding agent; and, optionally,
  • the agglomerates particularly the granules, have an average particle size of ⁇ 500 ⁇ .
  • the agglomerates particularly the granules, have an average particle size of 50 to 200 ⁇ .
  • Laundry detergent composition The laundry detergent composition may be in liquid, solid or unit dose form such as a tablet or a pouch, preferably a water-soluble pouch. When in unit dose form, the composition may be at least partially, preferably completed enclosed by a water-soluble film such as polyvinyl alcohol. Preferably, the composition is in solid form.
  • Solid laundry detergent composition typically, the composition is a fully formulated laundry detergent composition, not a portion thereof such as a spray-dried or agglomerated particle that only forms part of the laundry detergent composition.
  • an additional rinse additive composition e.g. fabric conditioner or enhancer
  • a main wash additive composition e.g. bleach additive
  • the composition comprises a plurality of chemically different particles, such as spray-dried base detergent particles and/or agglomerated base detergent particles and/or extruded base detergent particles, in combination with one or more, typically two or more, or three or more, or four or more, or five or more, or six or more, or even ten or more particles selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes; polymer particles such as cellulosic polymer particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol polymer particles; builder particles, such as sodium carbonate and sodium silicate co- builder particles, phosphate particles, zeolite particles, silicate salt particles, carbonate salt particles; filler particles such as sulphate salt particles; dye transfer inhibitor particles; dye fixative particles; bleach particles, such as percarbonate particles, especially coated percarbonate particles, such as percarbonate coated with carbonate
  • composition typically comprises detergent ingredients.
  • Suitable detergent ingredients include; detersive surfactants including anionic detersive surfactants, non-ionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof; polymers including carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio of 1 :4:1, hexamethylenediamine derivative polymers, and any combination thereof; builders including zeolites, phosphates, citrate, and any combination thereof; buffers and alkalinity sources including carbonate salts and/or silicate salts; fillers including sulphate salts and bio-filler materials; bleach including bleach activators, sources of available oxygen, pre-formed peracids, bleach
  • Detersive surfactant The composition typically comprises detersive surfactant. Suitable detersive surfactants include anionic detersive surfactants, non-ionic detersive surfactant, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof.
  • Anionic detersive surfactant Suitable anionic detersive surfactants include sulphate and sulphonate detersive surfactants.
  • Suitable sulphonate detersive surfactants include alkyl benzene sulphonate, such as C 10-13 alkyl benzene sulphonate.
  • Suitable alkyl benzene sulphonate (LAS) is obtainable, or even obtained, by sulphonating commercially available linear alkyl benzene (LAB);
  • suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2- phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • Another suitable anionic detersive surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
  • Suitable sulphate detersive surfactants include alkyl sulphate, such as C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
  • the alkyl sulphate may be derived from natural sources, such as coco and/or tallow.
  • the alkyl sulphate may be derived from synthetic sources such as C 12-15 alkyl sulphate.
  • alkyl alkoxylated sulphate such as alkyl ethoxylated sulphate, or a C 8-18 alkyl alkoxylated sulphate, or a C 8-18 alkyl ethoxylated sulphate.
  • the alkyl alkoxylated sulphate may have an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to 10.
  • the alkyl alkoxylated sulphate may be a C 8-18 alkyl ethoxylated sulphate, typically having an average degree of ethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5 or from 0.5 to 3.
  • alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted.
  • the anionic detersive surfactant may be a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate.
  • the mid-chain branches are typically C 1-4 alkyl groups, such as methyl and/or ethyl groups.
  • Another suitable anionic detersive surfactant is alkyl ethoxy carboxylate.
  • the anionic detersive surfactants are typically present in their salt form, typically being complexed with a suitable cation.
  • Suitable counter-ions include Na + and K + , substituted ammonium such as Ci-C 6 alkanolammnonium such as mono-ethanolamine (MEA) tri- ethanolamine (TEA), di-ethanolamine (DEA), and any mixture thereof.
  • Non-ionic detersive surfactant Suitable non-ionic detersive surfactants are selected from the group consisting of: Cs-Cis alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C 6 -Ci2 alkyl phenol alkoxylates wherein optionally the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -Ci2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C14-C22 mid-chain branched alcohols; C14-C22 mid-chain branched alkyl alkoxylates, typically having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, such as alky lpoly glycosides; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixture
  • Suitable non-ionic detersive surfactants are alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, such as C 8-18 alkyl alkoxylated alcohol, or a C 8-18 alkyl ethoxylated alcohol.
  • the alkyl alkoxylated alcohol may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10.
  • the alkyl alkoxylated alcohol may be a C 8-18 alkyl ethoxylated alcohol, typically having an average degree of ethoxylation of from 1 to 10, or from 1 to 7, or from 1 to 5, or from 3 to 7.
  • the alkyl alkoxylated alcohol can be linear or branched, and substituted or un- substituted.
  • R 2 linear or branched, substituted or unsubstituted, saturated or unsaturated C 2- j alkyl
  • R 1 + R 2 moieties wherein the total number of carbon atoms present in R 1 + R 2 moieties is in the range of from 7 to 13;
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, or mixtures thereof, optionally the EO/PO alkoxyl moieties are in random or block configuration;
  • n is the average degree of alkoxylation and is in the range of from 4 to 10.
  • non-ionic detersive surfactants include EO/PO block co-polymer surfactants, such as the Plurafac ® series of surfactants available from BASF, and sugar-derived surfactants such as alkyl N-methyl glucose amide.
  • Cationic detersive surfactant Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
  • Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R ! )(R 2 )(R 3 )N + X wherein, R is a linear or branched, substituted or unsubstituted C 6 -i8 alkyl or alkenyl moiety, Ri and R 2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, suitable anions include: halides, such as chloride; sulphate; and sulphonate.
  • Suitable cationic detersive surfactants are mono-C6-is alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Suitable cationic detersive surfactants are mono-Cs-io alkyl mono-hydroxyethyl di- methyl quaternary ammonium chloride, mono-Cio-i 2 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
  • Suitable zwitterionic and/or amphoteric detersive surfactants include amine oxide such as dodecyldimethylamine N-oxide, alkanolamine sulphobetaines, coco-amidopropyl betaines, HN + -R-C0 2 " based surfactants, wherein R can be any bridging group, such as alkyl, alkoxy, aryl or amino acids.
  • Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio of 1 :4: 1 ,
  • hexamethylenediamine derivative polymers and any combination thereof.
  • Carboxylate polymer Suitable carboxylate polymers include maleate/acrylate random copolymer or polyacrylate homopolymer.
  • the carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000 Da.
  • Other suitable carboxylate polymers are co-polymers of maleic acid and acrylic acid, and may have a molecular weight in the range of from 4,000 Da to 90,000 Da.
  • carboxylate polymers are co-polymers comprising: (i) from 50 to less than 98 wt structural units derived from one or more monomers comprising carboxyl groups; (ii) from 1 to less than 49 wt structural units derived from one or more monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II):
  • Ro represents a hydrogen atom or CH 3 group
  • R represents a C3 ⁇ 4 group, CH2CH2 group or single bond
  • X represents a number 0-5 provided X represents a number 1-5 when R is a single bond
  • Ri is a hydrogen atom or Ci to C2 0 organic group
  • Ro represents a hydrogen atom or CH 3 group
  • R represents a CH2 group, CH2CH2 group or single bond
  • X represents a number 0-5
  • Ri is a hydrogen atom or Ci to C2 0 organic group.
  • Polyethylene glycol polymer include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) hydrophobic side chain(s) selected from the group consisting of: C4-C25 alkyl group,
  • Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains.
  • the average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da.
  • the molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1 : 1 to 1 :5, or from 1 : 1.2 to 1 :2.
  • the average number of graft sites per ethylene oxide units can be less than 1 , or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4.
  • a suitable polyethylene glycol polymer is Sokalan HP22.
  • Polyester soil release polymers Suitable polyester soil release polymers have a structure as defined by one of the following structures (I), (II) or (III):
  • a, b and c are from 1 to 200;
  • d, e and f are from 1 to 50;
  • Ar is a 1 ,4-substituted phenylene
  • sAr is 1,3-substituted phenylene substituted in position 5 with SC ⁇ Me;
  • Me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are Ci-Cis alkyl or C2-C1 0 hydroxyalkyl, or any mixture thereof;
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from H or Ci-Cis n- or iso-alkyl; and R 7 is a linear or branched Ci-Cis alkyl, or a linear or branched C2-C 30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C 30 aryl group, or a C6-C 30 arylalkyl group.
  • Suitable polyester soil release polymers are terephthalate polymers having the structure of formula (I) or (II) above.
  • Suitable polyester soil release polymers include the Repel-o-tex series of polymers such as Repel-o-tex SF2 (Rhodia) and/or the Texcare series of polymers such as Texcare SRA300 (Clariant).
  • Suitable amine polymers include polyethylene imine polymers, such as alkoxylated poly alky leneimines, optionally comprising a polyethylene and/or polypropylene oxide block.
  • the composition can comprise cellulosic polymers, such as polymers selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl, and any combination thereof. Suitable cellulosic polymers are selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl
  • carboxymethyl cellulose and mixtures thereof.
  • the carboxymethyl cellulose can have a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da.
  • Another suitable cellulosic polymer is hydrophobically modified carboxymethyl cellulose, such as Finnfix SH-1 (CP Kelco).
  • suitable cellulosic polymers may have a degree of substitution (DSub) of from 0.01 to 0.99 and a degree of blockiness (DB) such that either DSub+DB is of at least 1.00 or DB+2DSub-DSub 2 is at least 1.20.
  • the substituted cellulosic polymer can have a degree of substitution (DSub) of at least 0.55.
  • the substituted cellulosic polymer can have a degree of blockiness (DB) of at least 0.35.
  • the substituted cellulosic polymer can have a DSub + DB, of from 1.05 to 2.00.
  • a suitable substituted cellulosic polymer is carboxymethylcellulose.
  • Another suitable cellulosic polymer is cationically modified hydroxyethyl cellulose.
  • Dye transfer inhibitor polymer Suitable dye transfer inhibitor (DTI) polymers include polyvinyl pyrrolidone (PVP), vinyl co-polymers of pyrrolidone and imidazoline (PVPVI), polyvinyl N-oxide (PVNO), and any mixture thereof.
  • the dye transfer inhibitor polymers are not present in the same particle as the water-soluble phthalocyanine compound, cross-linked polyvinylpyrrolidone component, or hydrophilic binding agent.
  • Hexamethylenediamine derivative polymers Suitable polymers
  • X " is a suitable counter-ion, for example chloride
  • R is a poly(ethylene glycol) chain having an average degree of ethoxylation of from 20 to 30.
  • the poly(ethylene glycol) chains may be independently capped with sulphate and/or sulphonate groups, typically with the charge being balanced by reducing the number of X " counter-ions, or (in cases where the average degree of sulphation per molecule is greater than two), introduction of Y + counter- ions, for example sodium cations.
  • Suitable builders include zeolites, phosphates, citrates, and any combination thereof.
  • Zeolite builder The composition may be substantially free of zeolite builder.
  • Substantially free of zeolite builder typically means comprises from 0wt% to 10wt , zeolite builder, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt zeolite builder.
  • Substantially free of zeolite builder preferably means "no deliberately added" zeolite builder.
  • Typical zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite X and zeolite Y.
  • Phosphate builder The composition may be substantially free of phosphate builder.
  • Substantially free of phosphate builder typically means comprises from 0wt to 10wt phosphate builder, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt phosphate builder.
  • Substantially free of zeolite builder preferably preferably means "no deliberately added" phosphate builder.
  • a typical phosphate builder is sodium tri-polyphosphate (STPP).
  • citrate is sodium citrate. However, citric acid may also be incorporated into the composition, which can form citrate in the wash liquor.
  • Buffer and alkalinity source Suitable buffers and alkalinity sources include carbonate salts and/or silicate salts and/or double salts such as burkeitte.
  • a suitable carbonate salt is sodium carbonate and/or sodium bicarbonate.
  • the composition may comprise bicarbonate salt. It may be suitable for the composition to comprise low levels of carbonate salt, for example, it may be suitable for the composition to comprise from 0wt% to 10wt% carbonate salt, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt carbonate salt.
  • the composition may even be substantially free of carbonate salt; substantially free means "no deliberately added".
  • the carbonate salt may have a weight average mean particle size of from 100 to 500 micrometers. Alternatively, the carbonate salt may have a weight average mean particle size of from 10 to 25 micrometers.
  • Silicate salt The composition may comprise from 0wt to 20wt silicate salt, or to 15wt , or to 10wt , or to 5wt , or to 4wt , or even to 2wt , and may comprise from above 0wt , or from 0.5wt , or even from lwt silicate salt.
  • the silicate can be crystalline or amorphous. Suitable crystalline silicates include crystalline layered silicate, such as SKS-6. Other suitable silicates include 1.6R silicate and/or 2.0R silicate.
  • a suitable silicate salt is sodium silicate. Another suitable silicate salt is sodium metasilicate.
  • the composition may comprise from 0wt to 70% filler.
  • Suitable fillers include sulphate salts and/or bio-filler materials.
  • a suitable sulphate salt is sodium sulphate.
  • the sulphate salt may have a weight average mean particle size of from 100 to 500 micrometers, alternatively, the sulphate salt may have a weight average mean particle size of from 10 to 45 micrometers.
  • Bio-filler material A suitable bio-filler material is alkali and/or bleach treated agricultural waste.
  • the composition may comprise bleach.
  • the composition may be substantially free of bleach; substantially free means "no deliberately added".
  • Suitable bleach includes bleach activators, sources of available oxygen, pre-formed peracids, bleach catalysts, reducing bleach, and any combination thereof. If present, the bleach, or any component thereof, for example the pre-formed peracid, may be coated, such as encapsulated, or clathrated, such as with urea or cyclodextrin.
  • Suitable bleach activators include: tetraacetylethylenediamine (TAED); oxybenzene sulphonates such as nonanoyl oxybenzene sulphonate (NOBS),
  • Iso-NOBS hexanoyloxybenzene sulphonate
  • LOBS dodecyl oxybenzene sulphonate
  • caprolactams pentaacetate glucose (PAG); nitrile quaternary ammonium
  • imide bleach activators such as N-nonanoyl-N-methyl acetamide; and any mixture thereof.
  • a suitable source of available oxygen is a source of hydrogen peroxide, such as percarbonate salts and/or perborate salts, such as sodium
  • the source of peroxygen may be at least partially coated, or even completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or any mixture thereof, including mixed salts thereof.
  • Suitable percarbonate salts can be prepared by a fluid bed process or by a crystallization process.
  • Suitable perborate salts include sodium perborate mono-hydrate (PB1), sodium perborate tetra-hydrate (PB4), and anhydrous sodium perborate which is also known as fizzing sodium perborate.
  • Other suitable sources of AvOx include persulphate, such as oxone. Another suitable source of AvOx is hydrogen peroxide.
  • Pre-formed peracid A suitable pre-formed peracid is ⁇ , ⁇ -pthaloylamino peroxycaproic acid (PAP).
  • PAP ⁇ , ⁇ -pthaloylamino peroxycaproic acid
  • Bleach catalyst Suitable bleach catalysts include oxaziridinium-based bleach catalysts, transition metal bleach catalysts and bleaching enzymes.
  • Oxaziridinium-based bleach catalyst A suitable oxaziridinium-based bleach catalyst has the formula:
  • R 1 is selected from the group consisting of: H, a branched alkyl group containing from 3 to 24 carbons, and a linear alkyl group containing from 1 to 24 carbons;
  • R 1 can be a branched alkyl group comprising from 6 to 18 carbons, or a linear alkyl group comprising from 5 to 18 carbons,
  • R 1 can be selected from the group consisting of: 2-propylheptyl, 2-butyloctyl, 2- pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n- octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl;
  • R 2 is independently selected from the
  • Transition metal bleach catalyst The composition may include transition metal bleach catalyst, typically comprising copper, iron, titanium, ruthenium, tungsten, molybdenum, and/or manganese cations. Suitable transition metal bleach catalysts are manganese-based transition metal bleach catalysts.
  • the composition may comprise a reducing bleach. However, the composition may be substantially free of reducing bleach; substantially free means "no deliberately added". Suitable reducing bleach include sodium sulphite and/or thiourea dioxide (TDO).
  • the composition may comprise a co-bleach particle.
  • the co-bleach particle comprises a bleach activator and a source of peroxide. It may be highly suitable for a large amount of bleach activator relative to the source of hydrogen peroxide to be present in the co-bleach particle.
  • the weight ratio of bleach activator to source of hydrogen peroxide present in the co-bleach particle can be at least 0.3:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8: 1, or at least 0.9:1, or at least 1.0:1.0, or even at least 1.2:1 or higher.
  • the co-bleach particle can comprise: (i) bleach activator, such as TAED; and (ii) a source of hydrogen peroxide, such as sodium percarbonate.
  • the bleach activator may at least partially, or even completely, enclose the source of hydrogen peroxide.
  • the co-bleach particle may comprise a binder.
  • Suitable binders are carboxylate polymers such as polyacrylate polymers, and/or surfactants including non-ionic detersive surfactants and/or anionic detersive surfactants such as linear Cn-C ⁇ alkyl benzene sulphonate.
  • the co-bleach particle may comprise bleach catalyst, such as an oxaziridium-based bleach catalyst.
  • Suitable chelants are selected from: diethylene triamine pentaacetate, diethylene triamine penta(methyl phosphonic acid), ethylene diamine-N'N'-disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid), hydroxyethane di(methylene phosphonic acid), and any combination thereof.
  • a suitable chelant is ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP).
  • the laundry detergent composition may comprise ethylene diamine-N'N'- disuccinic acid or salt thereof.
  • the ethylene diamine-N'N'-disuccinic acid may be in S,S enantiomeric form.
  • the composition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt.
  • Suitable chelants may also be calcium crystal growth inhibitors.
  • the composition may comprise a calcium carbonate crystal growth inhibitor, such as one selected from the group consisting of: 1- hydroxyethanediphosphonic acid (HEDP) and salts thereof; N,N-dicarboxymethyl-2- aminopentane-l,5-dioic acid and salts thereof; 2-phosphonobutane-l,2,4-tricarboxylic acid and salts thereof; and any combination thereof.
  • HEDP 1- hydroxyethanediphosphonic acid
  • N,N-dicarboxymethyl-2- aminopentane-l,5-dioic acid and salts thereof 2-phosphonobutane-l,2,4-tricarboxylic acid and salts thereof; and any combination thereof.
  • Photobleach Suitable photobleaches are zinc and/or aluminium sulphonated
  • Additional hueing agents are typically formulated to deposit onto fabrics from the wash liquor so as to improve fabric whiteness perception, for example producing a relative hue angle of from 200° to 320° on a garment. Additional hueing agents are typically blue or violet. It may be suitable that the additional hueing dye(s) have a peak absorption wavelength of from 550nm to 650nm, or from 570nm to 630nm. The additional hueing agents may be a combination of dyes which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester of from 550nm to 650nm, or from 570nm to 630nm. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
  • Dyes are typically coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes maybe selected from the classes of basic, acid, hydrophobic, direct and polymeric dyes, and dye-conjugates. Suitable polymeric hueing dyes are commercially available, for example from Milliken, Spartanburg, South Carolina, USA.
  • Suitable dyes are, direct violet 7 , direct violet 9 , direct violet 11 , direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, direct violet 99, acid violet 50, acid blue 9, acid violet 17, acid black 1 , acid red 17, acid blue 29, acid blue 80, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3 , basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, thiazolium dyes, reactive blue 19, reactive blue 163, reactive blue 182, reactive blue 96, Liquitint® Violet CT (Milliken, Spartanburg, USA), Liquitint® Violet DD (Milliken,
  • a particularly suitable hueing agent is a combination of acid red 52 and acid blue 80, or the combination of direct violet 9 and solvent violet 13.
  • Another suitable hueing dye is described in more detail in WO2010/151906.
  • Brightener Suitable brighteners are stilbenes, such as C.I. fluorescent brightener 351.
  • the brightener may be in micronized particulate form, having a weight average particle size in the range of from 3 to 30 micrometers, or from 3 micrometers to 20 micrometers, or from 3 to 10 micrometers.
  • the brightener can be alpha or beta crystalline form.
  • a preferred brightener is C.I. fluorescent brightener 260 having the following structure:
  • the C.I. fluorescent brightener 260 is either: (i) predominantly in alpha-crystalline form; or (ii) predominantly in beta-crystalline form and having a weight average primary particle size of from 3 to 30 micrometers.
  • predominantly typically means “comprises greater than 50wt to 100wt , or greater than 60wt , or greater than 70wt , or greater than 80wt , or greater than 90wt to 100wt , or even comprises 100wt .
  • Enzyme Suitable enzymes include proteases, amylases, cellulases, lipases, xylogucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof.
  • accession numbers and IDs shown in parentheses refer to the entry numbers in the databases Genbank, EMBL and/or Swiss-Prot.
  • standard 1- letter amino acid codes are used with a * representing a deletion.
  • Accession numbers prefixed with DSM refer to micro-organisms deposited at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, 38124 Brunswick (DSMZ).
  • the composition may comprise a protease.
  • Suitable proteases include metalloproteases and/or serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62).
  • Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin.
  • the suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases.
  • the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease.
  • suitable neutral or alkaline proteases include:
  • subtilisins EC 3.4.21.62
  • Bacillus lentus Bacillus alkalophilus
  • Bacillus subtilis Bacillus amyloliquefaciens
  • P00782, SUBT_BACAM Bacillus pumilus
  • DSM14391 Bacillus gibsonii
  • trypsin-type or chymotrypsin-type proteases such as trypsin (e.g. of porcine or bovine origin), including the Fusarium protease and the chymotrypsin proteases derived from
  • metalloproteases including those derived from Bacillus amyloliquefaciens (P06832, NPRE_BACAM).
  • Suitable proteases include those derived from Bacillus gibsonii or Bacillus Lentus such as subtilisin 309 (P29600) and/or DSM 5483 (P29599).
  • Suitable commercially available protease enzymes include: those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark); those sold under the tradename Maxatase®, Maxacal®,
  • Amylase Suitable amylases are alpha- amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included.
  • a suitable alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSMZ no. 12649, KSM API 378, KSM K36 or KSM K38.
  • Suitable amylases include:
  • alpha-amylase derived from Bacillus licheniformis P06278, AMY_BACLI
  • variants thereof especially the variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.
  • AA560 amylase CBU30457, HD066534
  • variants thereof especially the variants with one or more substitutions in the following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, optionally that also contain the deletions of D183* and G184*.
  • variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus SP722 (CBU30453, HD066526), especially variants with deletions in the 183 and 184 positions.
  • Suitable commercially available alpha-amylases are Duramyl®, Liquezyme® Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, Stainzyme Plus®, Fungamyl® and BAN® (Novozymes A/S), Bioamylase® and variants thereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. m.b.H, Austria), Rapidase® , Purastar®, Optisize HT Plus®, Enzysize®, Powerase® and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM® (KAO, Japan).
  • Suitable amylases are Natalase®, Stainzyme® and Stainzyme Plus®.
  • the composition may comprise a cellulase.
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
  • cellulases include Celluzyme®, and Carezyme® (Novozymes A/S), Clazinase®, and Puradax HA® (Genencor International Inc.), and KAC-500(B)® (Kao Corporation).
  • the cellulase can include microbial-derived endoglucanases exhibiting endo-beta-1,4- glucanase activity (E.C. 3.2.1.4), including a bacterial polypeptide endogenous to a member of the genus Bacillus sp. AA349 and mixtures thereof. Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
  • the composition may comprise a cleaning cellulase belonging to Glycosyl Hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
  • a cleaning cellulase belonging to Glycosyl Hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
  • Suitable cellulases may also exhibit xyloglucanase activity, such as Whitezyme®.
  • Lipase The composition may comprise a lipase.
  • Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g., from H. lanuginosa (T. lanuginosus), or from H. insolens, a Pseudomonas lipase, e.g., from P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P. fluorescens, Pseudomonas sp. strain SD 705, P.
  • the lipase may be a "first cycle lipase", optionally a variant of the wild-type lipase from Thermomyces lanuginosus comprising T231R and N233R mutations.
  • the wild-type sequence is the 269 amino acids (amino acids 23 - 291) of the Swissprot accession number Swiss-Prot 059952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)).
  • Suitable lipases would include those sold under the tradenames Lipex®, Lipolex® and Lipoclean® by
  • composition may comprise a variant of Thermomyces lanuginosa (059952) lipase having >90 identity with the wild type amino acid and comprising substitution(s) at T231 and/or N233, optionally T231R and/or N233R.
  • Suitable xyloglucanase enzymes may have enzymatic activity towards both xyloglucan and amorphous cellulose substrates.
  • the enzyme may be a glycosyl hydrolase (GH) selected from GH families 5, 12, 44 or 74.
  • the glycosyl hydrolase selected from GH family 44 is particularly suitable.
  • Suitable glycosyl hydrolases from GH family 44 are the XYG1006 glycosyl hydrolase from Paenibacillus polyxyma (ATCC 832) and variants thereof.
  • Pectate lyase Suitable pectate lyases are either wild-types or variants of Bacillus-derived pectate lyases (CAF05441, AAU25568) sold under the tradenames Pectawash®, Pectaway® and X-Pect® (from Novozymes A/S, Bagsvaerd, Denmark).
  • Mannanase Suitable mannanases are sold under the tradenames Manna way® (from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).
  • Suitable bleach enzymes include oxidoreductases, for example oxidases such as glucose, choline or carbohydrate oxidases, oxygenases, catalases, peroxidases, like halo-, chloro-, bromo-, lignin-, glucose- or manganese -peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases).
  • oxidases such as glucose, choline or carbohydrate oxidases
  • oxygenases catalases
  • peroxidases like halo-, chloro-, bromo-, lignin-, glucose- or manganese -peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases).
  • Suitable commercial products are sold under the Guardzyme® and Denilite® ranges from Novozymes.
  • organic compounds especially aromatic compounds
  • these compounds interact with the bleaching enzyme to enhance the activity of the oxidoreductase (enhancer) or to facilitate the electron flow (mediator) between the oxidizing enzyme and the stain typically over strongly different redox potentials.
  • Suitable bleaching enzymes include perhydrolases, which catalyse the formation of peracids from an ester substrate and peroxygen source.
  • Suitable perhydrolases include variants of the Mycobacterium smegmatis perhydrolase, variants of so-called CE-7 perhydrolases, and variants of wild-type subtilisin Carlsberg possessing perhydrolase activity.
  • Cutinase Suitable cutinases are defined by E.C. Class 3.1.1.73, optionally displaying at least 90%, or 95%, or most optionally at least 98% identity with a wild-type derived from one of Fusarium solani, Pseudomonas Mendocina or Humicola Insolens.
  • the relativity between two amino acid sequences is described by the parameter "identity”.
  • the alignment of two amino acid sequences is determined by using the Needle program from the EMBOSS package (http://emboss.org) version 2.8.0.
  • the Needle program implements the global alignment algorithm described in Needleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453.
  • the substitution matrix used is BLOSUM62, gap opening penalty is 10, and gap extension penalty is 0.5.
  • Suitable fabric-softening agents include clay, silicone and/or quaternary ammonium compounds.
  • Suitable clays include montmorillonite clay, hectorite clay and/or laponite clay.
  • a suitable clay is montmorillonite clay.
  • Suitable silicones include amino- silicones and/or polydimethylsiloxane (PDMS).
  • a suitable fabric softener is a particle comprising clay and silicone, such as a particle comprising montmorillonite clay and PDMS.
  • Suitable flocculants include polyethylene oxide; for example having an average molecular weight of from 300,000 Da to 900,000 Da.
  • Suitable suds suppressors include silicone and/or fatty acid such as stearic acid.
  • Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume/polymer complexes, starch-encapsulated perfume accords, perfume-loaded zeolites, blooming perfume accords, and any combination thereof.
  • a suitable perfume microcapsule is melamine formaldehyde based, typically comprising perfume that is encapsulated by a shell comprising melamine formaldehyde. It may be highly suitable for such perfume microcapsules to comprise cationic and/or cationic precursor material in the shell, such as polyvinyl formamide (PVF) and/or cationically modified hydroxyethyl cellulose (catHEC).
  • PVF polyvinyl formamide
  • catHEC cationically modified hydroxyethyl cellulose
  • Suitable aesthetic particles include soap rings, lamellar aesthetic particles, geltin beads, carbonate and/or sulphate salt speckles, coloured clay particles, and any combination thereof.
  • the method of laundering fabric typically comprises the step of contacting the composition to water to form a wash liquor, and laundering fabric in said wash liquor, wherein typically the wash liquor has a temperature of above 0°C to 90°C, or to 60°C, or to 40°C, or to 30°C, or to 20°C, or to 10°C, or even to 8°C.
  • the fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry detergent composition with water.
  • the composition can be used in pre-treatment applications.
  • the wash liquor is formed by contacting the laundry detergent to water in such an amount so that the concentration of laundry detergent composition in the wash liquor is from above Og/1 to lOg/1, or from lg/1, and to 9g/l, or to 8.0g/l, or to 7.0g/l, or to 6.0g/l, or to 4g/l, or even to 3. Og/1, or even to 2.5g/l.
  • the method of laundering fabric may be carried out in a top-loading or front- loading automatic washing machine, or can be used in a hand-wash laundry application.
  • the wash liquor formed and concentration of laundry detergent composition in the wash liquor is that of the main wash cycle. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor.
  • the wash liquor may comprise 80 litres or less of water, or 60 litres or less, or 40 litres or less, or 20 litres or less, or 8 litres or less, or even 6 litres or less of water.
  • the wash liquor may comprise from above 0 to 15 litres, or from 2 litres, and to 12 litres, or even to 8 litres of water.
  • 150g or less, lOOg or less, 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even lOg or less of the composition is contacted to water to form the wash liquor.
  • a further aspect of the invention is a shading process for textile fibre materials characterized in that the textile fibre material is treated with a composition, which comprises
  • At least one water-soluble phthalocyanine compound At least one water-soluble phthalocyanine compound
  • At least one hydrophilic binding agent At least one hydrophilic binding agent; and, optionally,
  • compositions of the invention are typically used in a detergent or washing agent composition.
  • the amount of the compounds used is, for example, from 0.0001 to 1% by weight, preferably from 0.001 to 0.5% by weight, based on the weight of the textile material.
  • 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.
  • 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.
  • a solution of 30 ml (56.9 g) fuming sulphuric acid (nominally 20% free S03) 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.
  • 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.
  • 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.
  • the reaction mixture is heated to 50°C to ensure complete conversion.
  • 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 + ]: 1767 and 1847 along with minor amounts of 1927).
  • the aqueous zinc phthalocyanine dye conjugate solution can be used directly for granule formation or it can be desalted by dialysis and lyophilized.
  • Alternative co- solvents to dimethoxyethane (e.g. alcoholic) solvents are also suitable.
  • compositions are prepared as indicated in Table 1. Solid content of the materials is measured by IR balance operated at 140°C.
  • 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 ⁇ particle size.
  • the resulting agglomerates contain 7.2% of the ZnPcDC photo catalyst with respect to dry matter of the material.
  • Example 1.2.1 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.
  • the ZnPcDC solution (1.1.6) is blended in water 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 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 4 A 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.
  • binder solution portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to Example 1.2.1.
  • 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.
  • 26.0g 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.
  • portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to 1.2.1.
  • 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.
  • Example 1.2.4 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.
  • the zinc(II) phthalocyanine dye conjugate II solution obtained from (1.1.7) is blended with the sodium salt of a condensate of naphthalenesulphonic acid with fomaldehyde 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.
  • 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.
  • binder solution portions of binder and powdering agent are subsequently blended with the dry powder mix analogous to Example 1.2.1.
  • 0.7 g of fine hydrophobic silica Sipernat® D17, EVONIK
  • Further processing of the agglomerates is analogous to 1.2.1.
  • 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
  • a level of 0.3 wt.- of the granule is chosen for all tests.
  • the spotting test used for evaluation of the agglomerates is outlined in
  • WO 2003/018740 Six 15x15 cm pieces of white bleached woven non- mercerised cotton are placed flat on the bottom of a bowl containing 1 1 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.
  • 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.
  • composition 1.2.2 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.
  • 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 consumer detergents.
  • Anionic detersive surfactant (such as alkyl benzene from 8wt to sulphonate, alkyl ethoxylated sulphate and mixtures thereof) 15wt
  • Non-ionic detersive surfactant (such as alkyl ethoxylated from 0.5wt to alcohol) 4wt%
  • Cationic detersive surfactant (such as quaternary from 0 to 4wt% ammonium compounds)
  • detersive surfactant such as zwiterionic detersive from 0wt% to surfactants, amphoteric surfactants and mixtures thereof
  • Carboxylate polymer (such as co-polymers of maleic acid from lwt to and acrylic acid) 4wt%
  • Polyethylene glycol polymer (such as a polyethylene glycol from 0.5wt% to polymer comprising poly vinyl acetate side chains) 4wt%
  • Polyester soil release polymer (such as Repel-o-tex and/or from 0.1 to 2wt% Texcare polymers)
  • Cellulosic polymer (such as carboxymethyl cellulose, methyl from 0.5wt% to cellulose and combinations thereof) 2wt%
  • polymer such as amine polymers, dye transfer from 0wt% to inhibitor polymers, hexamethylenediamine derivative 4wt%
  • Zeolite builder and phosphate builder (such as zeolite 4A from 0wt% to and/or sodium tripolyphosphate) 4wt%
  • Carbonate salt (such as sodium carbonate and/or sodium from 15wt to bicarbonate) 30wt
  • Silicate salt (such as sodium silicate) from 0wt% to
  • 10wt% Filler (such as sodium sulphate and/or bio-fillers) from 10wt% to
  • Source of available oxygen (such as sodium percarbonate) from 10wt% to
  • Bleach activator such as tetraacetylethylene diamine from 2wt to (TAED) and/or nonanoyloxybenzenesulphonate (NOBS) 8wt%
  • Bleach catalyst (such as oxaziridinium-based bleach catalyst from 0wt% to and/or transition metal bleach catalyst) 0.1 wt%
  • Chelant such as ethylenediamine-N'N'-disuccinic acid from 0.2wt% to (EDDS) and/or hydroxyethane diphosphonic acid (HEDP) lwt%
  • Photobleach (such as zinc and/or aluminium sulphonated from 0wt% to phthalocyanine) 0.1 wt%
  • Hueing agent such as direct violet 99, acid red 52, acid blue from 0wt to 80, direct violet 9, solvent violet 13 and any combination lwt%
  • Inventive particle comprising a phthalocyanine complex from 0.0001wt to
  • Brightener (such as C.I. Fluorescent Brightener 260 and/or from 0.1 wt to C.I. Fluorescent Brightener 351) 0.4wt
  • Protease such as Savinase, Savinase Ultra, Purafect, FN3, from 0.1 wt to FN4 and any combination thereof
  • Amylase such as Termamyl, Termamyl ultra, Natalase, from 0.05wt to Optisize, Stainzyme, Stainzyme Plus and any combination 0.2wt
  • Cellulase (such as Carezyme and/or Celluclean) from 0.05wt to
  • Lipase (such as Lipex, Lipolex, Lipoclean and any from 0.2 to lwt% combination thereof)
  • enzyme such as xyloglucanase, cutinase, pectate from 0wt to lyase, mannanase, bleaching enzyme
  • 2wt% from 0wt% to
  • Fabric softener such as montmorillonite clay and/or
  • Flocculant (such as polyethylene oxide) from 0wt% to
  • Suds suppressor (such as silicone and/or fatty acid) from 0wt% to
  • Perfume such as perfume microcapsule, spray-on perfume, from 0.1 wt% to
  • Aesthetics such as coloured soap rings and/or coloured from 0wt to

Abstract

The present invention relates to compositions having granules of phthalocyanine compounds, to a process for the preparation thereof, and to the use thereof in washing agent and additive formulations. The composition has: 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.

Description

LAUNDRY DETERGENT COMPOSITION COMPRISING WATER-SOLUBLE
PHTHALOCYANINE COMPOUND
FIELD OF THE INVENTION
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 washing agent additive formulations.
BACKGROUND OF THE INVENTION
Water-soluble phthalocyanine complex compounds especially zinc and aluminium
phthalocyanine sulphonates are frequently used as photo-activators in washing agent preparations.
A problem is seen in the fact that such photo-activators, despite their water-solubility, dissolve too slowly in water. Especially, in the event of inadequate mixing of the washing liquor, coloured photo-activators tend to stain the laundry.
It has now been found that the rate at which agglomerates, particularly granules, of phthalocyanine compounds dissolve in water can be improved by the addition of disintegrants, such as cross-linked polyvinylpyrrolidone. SUMMARY OF THE INVENTION
The invention relates to a laundry detergent composition, which 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) Detersive surfactant; and
e) Optionally additional detergent ingredients.
DETAILED DESCRIPTION OF THE INVENTION
The compositions according to the invention may be liquid, solid, paste-like or gel-like. The compositions, especially washing agent compositions but also washing agent additives or additive concentrates, for example pre- and/or after-treatment agents, stain-removing salt, washing-power enhancers, fabric conditioners, bleaching agents, UV-protection enhancers etc., may be in any known and customary form, especially in the form of powders, (super-)compact powders, in the form of single- or multi-layer tablets (tabs), bars, blocks, sheets or pastes, or in the form of pastes, gels or liquids used in capsules or in pouches (sachets). Powders may also be used in suitable sachets or pouches.
A preferred embodiment of the invention relates to a composition, which comprises
a) 0.1 - 20.0 wt.- of a water-soluble phthalocyanine compound;
b) 0.5 - 40.0 wt.- of a cross-linked polyvinylpyrrolidone component
c) 3.0 - 40.0 wt.- of a hydrophilic binding agent; and, optionally,
d) 5.0 - 95.0 wt.- of further additives suitable for the preparation of solid agglomerates, 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.-%.
A particularly preferred embodiment of the invention relates to composition, which comprises a) 0.1 - 10.0 wt.- of a water-soluble phthalocyanine compound;
b) 0.5 - 30.0 wt.- of a cross-linked polyvinylpyrrolidone component;
c) 3.0 - 20.0 wt.- of a hydrophilic binding agent; and, optionally,
d) 20.0 - 90.0 wt.- of further additives suitable for the preparation of solid agglomerates, 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.- .
Suitable phthalocyanine compounds are water-soluble or at least water-dispersible
phthalocyanine complex compounds with di-, tri- or tetra-valent coordination centres, particularly metal ions (complexes having a d° or d10 configuration), as the central atom, to which the substituent of at least one mono-azo dye is attached.
Such phthalocyanine complex compounds correspond to 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(III), Si(IV), P(V), Ti(IV) or Cr(VI) metal-containing phthalocyanine structure;
D represents the substituent of a mono-azo dye; and
Figure imgf000004_0001
Wherein
R20 represents hydrogen, Ci-Csalkyl, Ci-Csalkoxy or halogen;
R21 represents D, hydrogen, OH, CI or F, provided that at least one of R2i is D;
R100 represents Ci-Csalkylene;
* marks the point of attachment of PC; and
# marks the point of attachment of the substituent D of the mono-azo dye. Ci-Csalkyl is linear or branched alkyl, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or isopropyl.
Ci-Csalkoxy is linear or branched, for example methoxy, propoxy or octyloxy.
Halogen is F, CI, Br or I, preferably CI.
Ci-Csalkylene is, for example, linear or branched methylene, ethylene, propylene, butylene or pentylene.
The phthalocyanine complex compound of the formula (1), wherein the phthalocyanine backbone is substituted by at least one sulpho groups and to which the substituent of at least one mono-azo dye is attached by the linking group L, are characterized by rapid photo degradation, which has the effect that discolouration on the treated fabric is avoided, even after repeated treatment. The phthalocyanine complex compounds of the formula (1) are characterized by improved shading and exhaustion onto the fabrics. The phthalocyanine complex compounds of the formula (1) are also highly efficient photo catalysts by additional light absorption and energy transfer to the phthalocyanine part of the molecule. According to a preferred embodiment the water-soluble phthalocyanine complex compound (1) corresponds to the formula
Figure imgf000005_0001
Wherein
PC represents the phthalocyanine 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, Al-Zi, Si(IV)-(Z1)2, Ti(IV)-(Z!)2 and SnOVMZ z;
Zjrepresents C C8alkanolate, OH", R0COO", C104 ", BF4 ", PF6 ", R0SO3 ", S04 2", N03 ", F", CI", Br", Γ, citrate, tartrate or oxalate, wherein Ro is hydrogen or Ci-Cisalkyl;
r represents 0 or a numeral from 1 to 3, preferably 1 to 2;
r' represents a numeral from 1 to 3, preferably 1 to 3;
each Q2 independently of one another represents -SO3 M"1" or the group -(CH2)m-COO" M+; wherein M+ is H+, 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
Figure imgf000005_0002
Figure imgf000006_0001
Wherein
R20 represents hydrogen, Ci- Csalkyl, Ci-Csalkoxy or halogen;
R21 represents D, hydrogen, OH, CI or F, provided that at least one is D;
R100 represents d-Csalkylene;
* marks the point of attachment of Me-PC; and
# marks the point of attachment of the substituent D of the mono-azo dye.
In the phthalocyanine complex compound that corresponds to the formula (la) of above, the sum of r and r' is preferably from 1 - 4.
Me represents the central metal atom or central metal group coordinated to PC, which is selected from the group consisting of Zn, Al-Zi and Ti(IV)-(Zi)2, wherein Zi is as defined above, preferably halogen, e.g. chlorine, or hydroxy.
Me preferably represents Zn.
According to a preferred embodiment the water-soluble phthalocyanine complex compound (1) corresponds to the formu
Figure imgf000006_0002
wherein each k is independently selected from 0 and 1, j is independently selected from 0 and 1- k, Wherein
Me represents Zn, Al-Zi, Si(IV)-(Z1)2 or Ti(IV)-(Z1)2, wherein Zi is chloride, fluoride, bromide or hydroxide Ci-C4alkoxide;
each Q2 independently of one another represents -SO3 M"1" or the group -(CH2)m-COO M+, wherein M+ is H+, 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
Figure imgf000007_0001
Wherein
R21 represents D, hydrogen, OH, CI or F, provided that at least one of R2i is D, preferably two of R21 are D;
* marks the point of attachment of PC;
# marks the point of attachment to D;
According to a preferred embodiment, the groups D, independently of one another, represent the substituents of a mon - azo dye of the partial formulae Xa, Xb, Xc or Xd:
(Xb)
Figure imgf000007_0002
Figure imgf000008_0001
(S03M)n (S03M)n,
# marks the point of attachment of the bridging group L;
Ra represents hydrogen, Ci-C4alkyl, Ci-C2alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci- C4alkoxy, phenyl, naphthyl and pyridyl, aryl, aryl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy and Ci-C4alkyl;
Z2, Z3, Z4, Z5 and Z6
independently of one another represent hydrogen, hydroxy, Ci-C4alkyl, Ci-C2alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, Ci-C4alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, halogen, -S02CH2CH2S03H, N02, COOH, -COOCi-C4alkyl, NH2, NHCj- C4alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C4alkyl, CN and COOH, N(Ci-C4alkyl)Ci- C4alkyl, wherein the alkyl groups may independently of one another be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C4alkyl, CN and COOH, NH-aryl, NH-aryl, wherein aryl is substituted by at least one substituent se- lected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-
C4alkoxy, C C4alkyl and C C4alkoxy, or represents NHCOC C4alkyl or NHCOOC C4alkyl;
G represents the direct bond, -COOCi-C4alkylene, arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy and Ci-C4alkyl, Ci-C4alkylene,
Ci-C4-alkylene substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci- C4alkoxy and Ci-C4alkyl, 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.
The substituents in the naphthyl groups, in the event they are not attached in a fixed position to an individual carbon atom, can be attached in either ring of the naphthyl radical. This is expressed by the horizontal line going through both rings in, for example, in structural formula Xa, Xb and Xc.
For example Ci-C4alkylene is methylene, ethylene, propylene or butylene.
Arylene in the context of the description of the instant invention means phenylene or naphthylene, preferably phenylene.
According to a preferred embodiment, the groups D, independently of one another, represent the substituents of a mo - azo dye of the partial formulae XIa, Xlb, XIc or Xld:
Figure imgf000009_0001
Wherein
# marks the point of attachment of the bridging group L; Z2 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, or represents OH;
Z3 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci- C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi- C2alkyl;
Z4 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci- C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, C C2alkyl, CN and COOH, or represents NHCOC C2alkyl or NHCOOC
C2alkyl;
Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci-C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
n represents 0, 1, 2 or 3; n' represents 0, 1 or 2; and
each M
Figure imgf000011_0001
Wherein
# marks the point of attachment of the bridging group L;
Z2represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo- Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl or represents OH;
Z3IS hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo- Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN or COOH or represents NHCOCi-C2alkyl or NHCOOCi- C2alkyl;
Z5 represents hydrogen, Ci-C2-alkyl or Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano,
N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci- C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
n represents 0, 1, 2 or 3; n' is 0, 1 or 2; and
each K+;
Figure imgf000012_0001
Wherein
# marks the point of attachment of the bridging group L;
Z2represents hydrogen, hydroxy, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy or Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents N02;
Z3represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Z4represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy or Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl; Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy, Ci-C2alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents NO2;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci- C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, N¾, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
n represents 0, 1, 2 or 3;
n' represents 0, 1 or 2; and
each M indep
Figure imgf000013_0001
Wherein
# marks the point of attachment of the bridging group L;
Z3 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents
Figure imgf000013_0002
Z4 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci- C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, or represents SO2CH2CH2SO3H, or N02;
Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, NO2, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Z6 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci- C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents NO2;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci-C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl; n represents 0, 1, 2 or 3;
n' represents 0, 1 or 2; and
each M independently of one another represents hydrogen, Na+ or K+.
According to a particularly preferred embodiment, D is selected from the group consisting of compounds, wherein the partial formulae 10, 11, 12, 13 and 14:
Figure imgf000015_0001
are present and wherein # marks the point of attachment of the bridging group L.
The sulphonic acid groups of the dyes represented by -SO3H may also be in the form of their salts, in particular of alkali metal salts, such as Na, K or Li salts or as ammonium salts. Also mixtures of the free acid and the corresponding salts are embraced.
A particularly suitable individual phthalocyanine is represented by the following formula wherein the degree of sulphonation is between 1 and 3 in the phthalocyanine ring:
Figure imgf000016_0001
According to another preferred embodiment, the water-soluble phthalocyanine complex compound (1) corresponds to the formula
Figure imgf000016_0002
Wherein
PC, L and D are as defined above (including the preferences);
Me is Zn or Al-Zi, Ziis chlorine, fluorine, bromine or hydroxy;
Y3' is hydrogen; an alkali metal ion or ammonium ion;
r is zero or a numeral from 1 -3 ; and
r' is a numeral from 1 to 4.
The amount of water-soluble phthalocyanine complex compounds (1) present in the agglomerates, particularly granules, may vary within wide limits. A preferred range is from about 0.01-20.0 wt.- , particularly 0.1-20 wt.- , especially from 0.1 -10.0 wt.- , based on the total weight of the agglomerates. Lower weight ranges are from about 0.01-0.5 wt.- , particularly 0.05-0.3 wt.- , based on the total weight of the agglomerates.
For the synthesis of the water-soluble phthalocyanine complex compounds (1), two different reaction sequences are available: either by initial synthesis of a metal-free phthalocyanine derivative and subsequent complexation with a metal salt or by synthesis of a phthalocyanine ring system from a simple benzenoid precursor by concomitant incorporation of the metal ion. Substituents can be introduced before or after the formation of the phthalocyanine ring structure. A suitable method to obtain water-soluble phthalocyanine complex compounds (1) is the introduction of sulphonate groups, for example by sulphonation of the unsubstituted metal phthalocy
Figure imgf000017_0001
The sulphonated phthalocyanine complex compounds are mixtures of different structure and different positional isomers. The -SC^H-group can be located at positions 3, 4, 5 or 6. Also the degree of sulphonation is varying. For example, a tetra sodium salt of the zinc phthalocyanine can be prepared after known procedure; /. Griffiths et al, Dyes and Pigments, Vol. 33, 65-78 (1997) and the literature cited therein.
Another method to obtain a sulphonated metal phthalocyanine is reacting a sulpho phthalic acid with a metal salt, urea and a molybdate catalyst in a melt condensation. The position of the sulphonation is determined by the corresponding phthalic acid reactant. If 4-sulphophthalic acid is used, a tetrasulphonated metal phthalocyanine with sulphonic acid groups exclusively in position 4 or 5 is obtained.
Figure imgf000018_0001
The content of sulphonic acid groups can be adjusted by addition of phthalic acid. With this melt process sulphonated zinc phthalocyanine derivatives having a degree of sulphonation between DS= 1 - 4 can be prepared.
Figure imgf000018_0002
11 = 1 , 2, 3, 4
In the compositions according to the present application, the phthalocyanine complex is being linked with a mono-azo dye molecule corresponding to D via specific linking groups L. A convenient way to realize this linkage is the synthesis of a metal phthalocyanine sulphonyl chloride by a sulphochlorination reaction after known procedures (DE 2812261, DE 0153278). By varying the amount of the sulphochlorination agent, the desired degree of sulpho chloride content can be adjusted. The sulphochlorination reaction of phthalocyanines generally leads to a main product, but as by-products small amounts of lower or higher degree of sulphonyl chloride groups are detected.
The resulting reactive phthalocyanine-sulphonyl chloride can then be reacted further with a suitable dye having an amino group. To illustrate the synthesis, the following synthetic examples leading to zinc and aluminium phthalocyanines linked with amino-functionalized azo dyes are given. The syntheses are performed as shown in the following scheme. From the possible positional isomers, only one is shown. The formation of the side products (degree of -SO3R and SO2CI) is not shown.
Figure imgf000019_0001
R = H or Na dye
DS 3-4
Figure imgf000019_0002
synthesis of zinc phthalocyanine complex compounds with a lower degree of sulphonation and analogous activation and coupling to the corresponding zinc phthalocyanine azo dyes is also possible.
The synthesis of exactly tris-sulphonated zinc phthalocyanine derivatives is known from literature [J.E. van Lier, Journ. Med. Chem. (1997), 40 (24) 3897] as a product from ring expansion reaction of boron tri(4-sulpho)sub-phthalocyanine.
The synthesis of metal phthalocyanines with lower degree of sulphonation can also be performed by a modified sulphonation reaction, for example by shortening of reaction time and/or reduction of reaction temperature (WO 2009068513 and WO 2009069077).
Figure imgf000020_0001
DS 1 -3
Figure imgf000020_0002
The cross-linked polyvinylpyrrolidone component b) is insoluble in water. The insoluble cross- linked polyvinylpyrrolidone is characterized in that it contains less than or equal to 1.5% water- soluble substances, more preferably less than or equal to 1 % water-soluble substances, cf. Biihler, V. Kollidon: Polyvinylpyrrolidone Excipients for the Pharmaceutical Industry; 9th ed. Ludwigshafen, Germany BASF; 2008:145 ctd. Suitable products belong to the group of super disintegrants and are known under the generic terms Crospovidone, crospovidonum, insoluble polyvinylpyrrolidone, cross-linked PVP and (inadequate chemical term) polyvinylpolypyrroli- done (PVPP). Such products are items of commerce and are available from BASF SE under the product designations Kollidon®CL, KOLLIDON CL-F, -SF and -M or from ISP under the product designations Polyplasdone®XL and XL- 10.
In contrast, soluble polyvinylpyrrolidone are widely used as auxiliary material (e.g. as binder, rheology modifier or complexing agent), for example in pharmaceutical industry and also in detergent additives. Such materials are commercially available in different average molecular weight and can be obtained as solutions in water or as free-flowing powders. For example, powders from BASF SE for the pharmaceutical industry are available under the product designations Kollidon® 12 PF, Kollidon® 25, Kollidon® 30 and Kollidon® 90 F. For detergent and cleaners, a selection of products from BASF SE are Sokalan ® HP 165, Sokalan ® HP 50, Sokalan ® HP 53, Sokalan ® HP 59, and from ISP under the product designation PVP K-15, PVP K-30, PVP K-60 and PVP K-90. Soluble polyvinylpyrrolidones are not preferred materials for component b) in the context of this invention.
One of the most prominent property of cross-linked polyvinylpyrrolidone is the build-up of swelling-pressure in water without forming a gel.
According to a preferred embodiment, the cross-linked polyvinylpyrrolidone component b) has a swelling pressure [kpa] from about 25.0 to 200.0 and a hydration capacity from 2.0 to 10.0 g water per g of the cross-linked polyvinylpyrrolidone. The methods for determination of these properties can be found in the literature (hydration capacity: S.Kornblum, S.Stoopak, J. Pharm.
Sci. 62 (1973) 43 - 49; swelling pressure: a compilation of methods is given in: Biihler, V.
Kollidon: Polyvinylpyrrolidone Excipients for the Pharmaceutical Industry. 9th ed.;
Ludwigshafen, Germany: BASF; 2008:152-153 ctd.).
Some specific insoluble grades of KOLLIDON have the following swelling pressure and time to reach 90% of the maximum swelling pressure [s] :
KOLLIDON KOLLIDON KOLLIDON KOLLIDON CL CL-F CL-SF CL-M
Swelling presca. 170 ca. 30 ca. 25 Ca. 70
sure [kPa]
Time to reach <10 < 15 < 35 >100 90% of the
maximum
swelling pressure [s]
Some specific insoluble grades of KOLLIDON have the following hydration capacity which is calculated as the quotient of the weight after hydration and the initial weight:
Figure imgf000022_0001
The insoluble grades of KOLLIDON have different specific surface areas from less than 1.0 m2/g to more than 6.0m2/g: Kollidon®CL: < 1.0 m2/g, KOLLIDON CL-F: ca. 1.5 m2/g, KOLLIDON CL-SF: ca. 3.0m2/g and KOLLIDON CL-M: > 6.0 m2/g.
The insoluble grades of KOLLIDON have different particle sizes in the range from < 15 μιη to < 250 μιη:
Figure imgf000022_0002
The amount of cross-linked polyvinylpyrrolidone according to component b) may vary within wide limits, particularly from 0.5 - 40.0 wt.-%, based on the total weight of the composition. According to a preferred embodiment, the amount of cross-linked polyvinylpyrrolidone is from about 0.5 - 30.0 wt.-%, based on the total weight of the composition.
The hydrophilic binding agent of component c) is a water-soluble or at least water-dispersible polymer or wax-type polymer selected from the group consisting of gelatines, polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), vinyl acetates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohols, hydrolysed and non-hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons and also mixed polymerization products of the mentioned polymers. Further suitable substances are polyethylene glycol (MW = 2000 - 20 000), copolymers of ethylene oxide with propylene oxide (MW > 3500), condensation products (block polymerization products) of alkylene oxide, especially propylene oxide, ethylene oxide-propylene oxide addition products with diamines, especially ethylenediamine, polystyrenesulphonic acid,
polyethylenesulphonic acid, copolymers of acrylic acid with sulphonated styrenes, gum arabic, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl
methylcellulose phthalate, maltodextrin, sucrose, lactose, enzymatically modified and subsequently hydrated sugars, as are obtainable under the name "Isomalt", cane sugar, polyaspartic acid and tragacanth.
Among those binding agents, special preference is given to sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, polyacrylamides, polyvinyl alcohols, gelatines, hydrolysed polyvinyl acetates, maltodextrin, polyaspartic acid and also polyacrylates and polymethacrylates.
The amount of binding agent according to component c) may vary within wide limits, particularly from 3.0 - 40.0 wt.- , based on the total weight of the composition.
According to a preferred embodiment, the amount of binding agent is from about 3.0 - 20.0 wt.- , based on the total weight of the composition.
The agglomerates, particularly the granules, according to the invention contain from 5.0 - 95.0 wt.- , preferably from 20.0 - 90.0 wt.- , of at least one further additive (component d)), based on the total weight of the granule.
Such further additives may be anionic dispersing agents; inorganic salts, aluminium silicates such as zeolites, and also compounds such as talc, kaolin; further disintegrants such as, for example, powdered or fibrous cellulose, microcrystalline cellulose; fillers such as, for example, dextrin, starch as for example corn starch or potato starch; water-insoluble or water-soluble dyes or pigments; and also optical brighteners. Ti02, Si02 or magnesium trisilicate may also be used in small amounts, for example 0.0 to 10.0% by weight, based on the weight of the total composition.
The anionic dispersing agents used are, for example, the commercially available water-soluble anionic dispersing agents for dyes, pigments etc.
The following products are listed as examples: condensation products of aromatic sulphonic acids and formaldehyde, condensation products of aromatic sulphonic acids with unsubstituted or chlorinated biphenyls or biphenyl oxides and optionally formaldehyde, (mono-/di-) alkylnaphthalenesulphonates, sodium salts of polymerized organic sulphonic acids, sodium salts of polymerized alkylnaphthalenesulphonic acids, sodium salts of polymerized
alkylbenzenesulphonic acids, alkylarylsulphonates, sodium salts of alkyl polyglycol ether sulphates, polyalkylated polynuclear arylsulphonates, methylene-linked condensation products of arylsulphonic acids and hydroxyarylsulphonic acids, sodium salts of dialkylsulphosuccinic acids, sodium salts of alkyl diglycol ether sulphates, sodium salts of
polynaphthalenemethanesulphonates, ligno- or oxyligno-sulphonates or heterocyclic
polysulphonic acids.
Especially suitable anionic dispersing agents are condensation products of naphthalenesulphonic acids with formaldehyde, sodium salts of polymerized organic sulphonic acids, (mono-/di-) alkylnaphthalenesulphonates, polyalkylated polynuclear arylsulphonates, sodium salts of polymerized alkylbenzenesulphonic acid, lignosulphonates, oxylignosulphonates and condensation products of naphthalenesulphonic acid with a poly chlorome thy lbiphenyl.
The agglomerates, particularly the granules, according to the invention may contain residual moisture. This water level may range from 3.0 to 15.0 wt.- , based on the total weight of the granule.
The invention also relates to a process for the preparation of the agglomerates, particularly the granules described above, which comprises mixing simultaneously or subsequently
a) At least one water-soluble phthalocyanine compound;
b) At least one cross-linked polyvinylpyrrolidone component; and
c) At least one hydrophilic binding agent; and, optionally,
d) Further additives suitable for the preparation of agglomerates,
converting the mixture into a workable mass, and drying.
The agglomerates, particularly the granules, are prepared according to known methods. Any known method is suitable to produce granules comprising the inventive mixture. Continuous or discontinuous methods are suitable. Continuous methods, such as spray drying or fluidised bed granulation processes are preferred. Such methods are for instance described in WO
2004/022693.
The invention also relates to solid agglomerates, particularly granules, which comprise
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.
According to a preferred embodiment, the agglomerates, particularly the granules, have an average particle size of < 500 μιη.
According to a particularly preferred embodiment, the agglomerates, particularly the granules, have an average particle size of 50 to 200 μιη. Laundry detergent composition: The laundry detergent composition may be in liquid, solid or unit dose form such as a tablet or a pouch, preferably a water-soluble pouch. When in unit dose form, the composition may be at least partially, preferably completed enclosed by a water-soluble film such as polyvinyl alcohol. Preferably, the composition is in solid form.
Solid laundry detergent composition: Typically, the composition is a fully formulated laundry detergent composition, not a portion thereof such as a spray-dried or agglomerated particle that only forms part of the laundry detergent composition. However, it is within the scope of the present invention for an additional rinse additive composition (e.g. fabric conditioner or enhancer), or a main wash additive composition (e.g. bleach additive) to also be used in combination with the laundry detergent composition during the method of the present invention. Although it may be preferred for no bleach additive composition to be used in combination with the laundry detergent composition during the method of the present invention.
Typically, the composition comprises a plurality of chemically different particles, such as spray-dried base detergent particles and/or agglomerated base detergent particles and/or extruded base detergent particles, in combination with one or more, typically two or more, or three or more, or four or more, or five or more, or six or more, or even ten or more particles selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes; polymer particles such as cellulosic polymer particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol polymer particles; builder particles, such as sodium carbonate and sodium silicate co- builder particles, phosphate particles, zeolite particles, silicate salt particles, carbonate salt particles; filler particles such as sulphate salt particles; dye transfer inhibitor particles; dye fixative particles; bleach particles, such as percarbonate particles, especially coated percarbonate particles, such as percarbonate coated with carbonate salt, sulphate salt, silicate salt, borosilicate salt, or any combination thereof, perborate particles, bleach catalyst particles such as transition metal bleach catalyst particles, or oxaziridinium-based bleach catalyst particles, pre-formed peracid particles, especially coated pre-formed peracid particles, and co-bleach particles of bleach activator, source of hydrogen peroxide and optionally bleach catalyst; bleach activator particles such as oxybenzene sulphonate bleach activator particles and tetra acetyl ethylene diamine bleach activator particles; chelant particles such as chelant agglomerates; hueing dye particles; brightener particles; enzyme particles such as protease prills, lipase prills, cellulase prills, amylase prills, mannanase prills, pectate lyase prills, xyloglucanase prills, bleaching enzyme prills, cutinase prills and co-prills of any of these enzymes; clay particles such as montmorillonite particles or particles of clay and silicone; flocculant particles such as polyethylene oxide particles; wax particles such as wax agglomerates; perfume particles such as perfume microcapsules, especially melamine formaldehyde-based perfume microcapsules, starch encapsulated perfume accord particles, and pro-perfume particles such as Schiff base reaction product particles; aesthetic particles such as coloured noodles or needles or lamellae particles, and soap rings including coloured soap rings; and any combination thereof.
Detergent ingredients: The composition typically comprises detergent ingredients.
Suitable detergent ingredients include; detersive surfactants including anionic detersive surfactants, non-ionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof; polymers including carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio of 1 :4:1, hexamethylenediamine derivative polymers, and any combination thereof; builders including zeolites, phosphates, citrate, and any combination thereof; buffers and alkalinity sources including carbonate salts and/or silicate salts; fillers including sulphate salts and bio-filler materials; bleach including bleach activators, sources of available oxygen, pre-formed peracids, bleach catalysts, reducing bleach, and any combination thereof; chelants; photobleach; hueing agents; brighteners; enzymes including proteases, amylases, cellulases, lipases, xylogucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and any combination thereof; fabric softeners including clay, silicones, quaternary ammonium fabric-softening agents, and any combination thereof; flocculants such as polyethylene oxide; perfume including starch encapsulated perfume accords, perfume microcapsules, perfume loaded zeolites, schif base reaction products of ketone perfume raw materials and polyamines, blooming perfumes, and any combination thereof; aesthetics including soap rings, lamellar aesthetic particles, geltin beads, carbonate and/or sulphate salt speckles, coloured clay, and any combination thereof: and any combination thereof.
Detersive surfactant: The composition typically comprises detersive surfactant. Suitable detersive surfactants include anionic detersive surfactants, non-ionic detersive surfactant, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof.
Anionic detersive surfactant: Suitable anionic detersive surfactants include sulphate and sulphonate detersive surfactants.
Suitable sulphonate detersive surfactants include alkyl benzene sulphonate, such as C 10-13 alkyl benzene sulphonate. Suitable alkyl benzene sulphonate (LAS) is obtainable, or even obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2- phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®. Another suitable anionic detersive surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
Suitable sulphate detersive surfactants include alkyl sulphate, such as C8-18 alkyl sulphate, or predominantly C12 alkyl sulphate. The alkyl sulphate may be derived from natural sources, such as coco and/or tallow. Alternative, the alkyl sulphate may be derived from synthetic sources such as C 12-15 alkyl sulphate.
Another suitable sulphate detersive surfactant is alkyl alkoxylated sulphate, such as alkyl ethoxylated sulphate, or a C8-18 alkyl alkoxylated sulphate, or a C8-18 alkyl ethoxylated sulphate. The alkyl alkoxylated sulphate may have an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to 10. The alkyl alkoxylated sulphate may be a C8-18 alkyl ethoxylated sulphate, typically having an average degree of ethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5 or from 0.5 to 3.
The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted.
The anionic detersive surfactant may be a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate. The mid-chain branches are typically C1-4 alkyl groups, such as methyl and/or ethyl groups.
Another suitable anionic detersive surfactant is alkyl ethoxy carboxylate.
The anionic detersive surfactants are typically present in their salt form, typically being complexed with a suitable cation. Suitable counter-ions include Na+ and K+, substituted ammonium such as Ci-C6 alkanolammnonium such as mono-ethanolamine (MEA) tri- ethanolamine (TEA), di-ethanolamine (DEA), and any mixture thereof.
Non-ionic detersive surfactant: Suitable non-ionic detersive surfactants are selected from the group consisting of: Cs-Cis alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C6-Ci2 alkyl phenol alkoxylates wherein optionally the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C12-C18 alcohol and C6-Ci2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C14-C22 mid-chain branched alcohols; C14-C22 mid-chain branched alkyl alkoxylates, typically having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, such as alky lpoly glycosides; polyhydroxy fatty acid amides; ether capped poly(oxyalkylated) alcohol surfactants; and mixtures thereof.
Suitable non-ionic detersive surfactants are alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, such as C8-18 alkyl alkoxylated alcohol, or a C8-18 alkyl ethoxylated alcohol. The alkyl alkoxylated alcohol may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10. The alkyl alkoxylated alcohol may be a C8-18 alkyl ethoxylated alcohol, typically having an average degree of ethoxylation of from 1 to 10, or from 1 to 7, or from 1 to 5, or from 3 to 7. The alkyl alkoxylated alcohol can be linear or branched, and substituted or un- substituted.
Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants having the formula:
Figure imgf000028_0001
wherein R1 = linear or branched, substituted or unsubstituted, saturated or unsaturated C2-j alkyl;
wherein R2 = linear or branched, substituted or unsubstituted, saturated or unsaturated C2-j alkyl,
wherein the total number of carbon atoms present in R1 + R2 moieties is in the range of from 7 to 13;
wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, or mixtures thereof, optionally the EO/PO alkoxyl moieties are in random or block configuration;
wherein n is the average degree of alkoxylation and is in the range of from 4 to 10.
Other suitable non-ionic detersive surfactants include EO/PO block co-polymer surfactants, such as the Plurafac® series of surfactants available from BASF, and sugar-derived surfactants such as alkyl N-methyl glucose amide.
Cationic detersive surfactant: Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R!)(R2)(R3)N+ X wherein, R is a linear or branched, substituted or unsubstituted C6-i8 alkyl or alkenyl moiety, Ri and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, suitable anions include: halides, such as chloride; sulphate; and sulphonate. Suitable cationic detersive surfactants are mono-C6-is alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Suitable cationic detersive surfactants are mono-Cs-io alkyl mono-hydroxyethyl di- methyl quaternary ammonium chloride, mono-Cio-i2 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
Zwitterionic and/or amphoteric detersive surfactant: Suitable zwitterionic and/or amphoteric detersive surfactants include amine oxide such as dodecyldimethylamine N-oxide, alkanolamine sulphobetaines, coco-amidopropyl betaines, HN+-R-C02 " based surfactants, wherein R can be any bridging group, such as alkyl, alkoxy, aryl or amino acids.
Polymer: Suitable polymers include carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio of 1 :4: 1 ,
hexamethylenediamine derivative polymers, and any combination thereof.
Carboxylate polymer: Suitable carboxylate polymers include maleate/acrylate random copolymer or polyacrylate homopolymer. The carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000 Da. Other suitable carboxylate polymers are co-polymers of maleic acid and acrylic acid, and may have a molecular weight in the range of from 4,000 Da to 90,000 Da.
Other suitable carboxylate polymers are co-polymers comprising: (i) from 50 to less than 98 wt structural units derived from one or more monomers comprising carboxyl groups; (ii) from 1 to less than 49 wt structural units derived from one or more monomers comprising sulfonate moieties; and (iii) from 1 to 49 wt structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II):
formula (I): Ro
I
c
CH2
CH2
O-R wherein in formula (I), Ro represents a hydrogen atom or CH3 group, R represents a C¾ group, CH2CH2 group or single bond, X represents a number 0-5 provided X represents a number 1-5 when R is a single bond, and Ri is a hydrogen atom or Ci to C20 organic group;
formula (II)
Figure imgf000030_0001
in formula (II), Ro represents a hydrogen atom or CH3 group, R represents a CH2 group, CH2CH2 group or single bond, X represents a number 0-5, and Ri is a hydrogen atom or Ci to C20 organic group.
Polyethylene glycol polymer: Suitable polyethylene glycol polymers include random graft co-polymers comprising: (i) hydrophilic backbone comprising polyethylene glycol; and (ii) hydrophobic side chain(s) selected from the group consisting of: C4-C25 alkyl group,
polypropylene, polybutylene, vinyl ester of a saturated Ci-C6 mono-carboxylic acid, Ci_C 6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof. Suitable polyethylene glycol polymers have a polyethylene glycol backbone with random grafted polyvinyl acetate side chains. The average molecular weight of the polyethylene glycol backbone can be in the range of from 2,000 Da to 20,000 Da, or from 4,000 Da to 8,000 Da. The molecular weight ratio of the polyethylene glycol backbone to the polyvinyl acetate side chains can be in the range of from 1 : 1 to 1 :5, or from 1 : 1.2 to 1 :2. The average number of graft sites per ethylene oxide units can be less than 1 , or less than 0.8, the average number of graft sites per ethylene oxide units can be in the range of from 0.5 to 0.9, or the average number of graft sites per ethylene oxide units can be in the range of from 0.1 to 0.5, or from 0.2 to 0.4. A suitable polyethylene glycol polymer is Sokalan HP22. Polyester soil release polymers: Suitable polyester soil release polymers have a structure as defined by one of the following structures (I), (II) or (III):
Figure imgf000031_0001
(II) -[(OCHR3-CHR4)b-0-OC-sAr-CO-]e
(III) -[(OCHR5-CHR6)c-OR7]f
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50;
Ar is a 1 ,4-substituted phenylene;
sAr is 1,3-substituted phenylene substituted in position 5 with SC^Me;
Me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are Ci-Cis alkyl or C2-C10 hydroxyalkyl, or any mixture thereof;
R1, R2, R3, R4, R5 and R6 are independently selected from H or Ci-Cis n- or iso-alkyl; and R7 is a linear or branched Ci-Cis alkyl, or a linear or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group. Suitable polyester soil release polymers are terephthalate polymers having the structure of formula (I) or (II) above.
Suitable polyester soil release polymers include the Repel-o-tex series of polymers such as Repel-o-tex SF2 (Rhodia) and/or the Texcare series of polymers such as Texcare SRA300 (Clariant).
Amine polymer: Suitable amine polymers include polyethylene imine polymers, such as alkoxylated poly alky leneimines, optionally comprising a polyethylene and/or polypropylene oxide block.
Cellulosic polymer: The composition can comprise cellulosic polymers, such as polymers selected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkyl carboxyalkyl, and any combination thereof. Suitable cellulosic polymers are selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl
carboxymethyl cellulose, and mixtures thereof. The carboxymethyl cellulose can have a degree of carboxymethyl substitution from 0.5 to 0.9 and a molecular weight from 100,000 Da to 300,000 Da. Another suitable cellulosic polymer is hydrophobically modified carboxymethyl cellulose, such as Finnfix SH-1 (CP Kelco).
Other suitable cellulosic polymers may have a degree of substitution (DSub) of from 0.01 to 0.99 and a degree of blockiness (DB) such that either DSub+DB is of at least 1.00 or DB+2DSub-DSub2 is at least 1.20. The substituted cellulosic polymer can have a degree of substitution (DSub) of at least 0.55. The substituted cellulosic polymer can have a degree of blockiness (DB) of at least 0.35. The substituted cellulosic polymer can have a DSub + DB, of from 1.05 to 2.00. A suitable substituted cellulosic polymer is carboxymethylcellulose.
Another suitable cellulosic polymer is cationically modified hydroxyethyl cellulose.
Dye transfer inhibitor polymer: Suitable dye transfer inhibitor (DTI) polymers include polyvinyl pyrrolidone (PVP), vinyl co-polymers of pyrrolidone and imidazoline (PVPVI), polyvinyl N-oxide (PVNO), and any mixture thereof. Preferably, the dye transfer inhibitor polymers are not present in the same particle as the water-soluble phthalocyanine compound, cross-linked polyvinylpyrrolidone component, or hydrophilic binding agent.
Hexamethylenediamine derivative polymers: Suitable polymers
includehexamethylenediamine derivative polymers, typically having the formula:
R2(CH3)N+(CH2)6N+(CH3)R2. 2X~
wherein X" is a suitable counter-ion, for example chloride, and R is a poly(ethylene glycol) chain having an average degree of ethoxylation of from 20 to 30. Optionally, the poly(ethylene glycol) chains may be independently capped with sulphate and/or sulphonate groups, typically with the charge being balanced by reducing the number of X" counter-ions, or (in cases where the average degree of sulphation per molecule is greater than two), introduction of Y+ counter- ions, for example sodium cations.
Builder: Suitable builders include zeolites, phosphates, citrates, and any combination thereof.
Zeolite builder: The composition may be substantially free of zeolite builder.
Substantially free of zeolite builder typically means comprises from 0wt% to 10wt , zeolite builder, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt zeolite builder. Substantially free of zeolite builder preferably means "no deliberately added" zeolite builder. Typical zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite X and zeolite Y.
Phosphate builder: The composition may be substantially free of phosphate builder. Substantially free of phosphate builder typically means comprises from 0wt to 10wt phosphate builder, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt phosphate builder. Substantially free of zeolite builder preferably preferably means "no deliberately added" phosphate builder. A typical phosphate builder is sodium tri-polyphosphate (STPP).
Citrate: A suitable citrate is sodium citrate. However, citric acid may also be incorporated into the composition, which can form citrate in the wash liquor. Buffer and alkalinity source: Suitable buffers and alkalinity sources include carbonate salts and/or silicate salts and/or double salts such as burkeitte.
Carbonate salt: A suitable carbonate salt is sodium carbonate and/or sodium bicarbonate. The composition may comprise bicarbonate salt. It may be suitable for the composition to comprise low levels of carbonate salt, for example, it may be suitable for the composition to comprise from 0wt% to 10wt% carbonate salt, or to 8wt , or to 6wt , or to 4wt , or to 3wt , or to 2wt , or even to lwt carbonate salt. The composition may even be substantially free of carbonate salt; substantially free means "no deliberately added".
The carbonate salt may have a weight average mean particle size of from 100 to 500 micrometers. Alternatively, the carbonate salt may have a weight average mean particle size of from 10 to 25 micrometers.
Silicate salt: The composition may comprise from 0wt to 20wt silicate salt, or to 15wt , or to 10wt , or to 5wt , or to 4wt , or even to 2wt , and may comprise from above 0wt , or from 0.5wt , or even from lwt silicate salt. The silicate can be crystalline or amorphous. Suitable crystalline silicates include crystalline layered silicate, such as SKS-6. Other suitable silicates include 1.6R silicate and/or 2.0R silicate. A suitable silicate salt is sodium silicate. Another suitable silicate salt is sodium metasilicate.
Filler: The composition may comprise from 0wt to 70% filler. Suitable fillers include sulphate salts and/or bio-filler materials.
Sulphate salt: A suitable sulphate salt is sodium sulphate. The sulphate salt may have a weight average mean particle size of from 100 to 500 micrometers, alternatively, the sulphate salt may have a weight average mean particle size of from 10 to 45 micrometers.
Bio-filler material: A suitable bio-filler material is alkali and/or bleach treated agricultural waste.
Bleach: The composition may comprise bleach. Alternatively, the composition may be substantially free of bleach; substantially free means "no deliberately added". Suitable bleach includes bleach activators, sources of available oxygen, pre-formed peracids, bleach catalysts, reducing bleach, and any combination thereof. If present, the bleach, or any component thereof, for example the pre-formed peracid, may be coated, such as encapsulated, or clathrated, such as with urea or cyclodextrin.
Bleach activator: Suitable bleach activators include: tetraacetylethylenediamine (TAED); oxybenzene sulphonates such as nonanoyl oxybenzene sulphonate (NOBS),
caprylamidononanoyl oxybenzene sulphonate (NACA-OBS), 3,5,5-trimethyl
hexanoyloxybenzene sulphonate (Iso-NOBS), dodecyl oxybenzene sulphonate (LOBS), and any mixture thereof; caprolactams; pentaacetate glucose (PAG); nitrile quaternary ammonium; imide bleach activators, such as N-nonanoyl-N-methyl acetamide; and any mixture thereof.
Source of available oxygen: A suitable source of available oxygen (AvOx) is a source of hydrogen peroxide, such as percarbonate salts and/or perborate salts, such as sodium
percarbonate. The source of peroxygen may be at least partially coated, or even completely coated, by a coating ingredient such as a carbonate salt, a sulphate salt, a silicate salt, borosilicate, or any mixture thereof, including mixed salts thereof. Suitable percarbonate salts can be prepared by a fluid bed process or by a crystallization process. Suitable perborate salts include sodium perborate mono-hydrate (PB1), sodium perborate tetra-hydrate (PB4), and anhydrous sodium perborate which is also known as fizzing sodium perborate. Other suitable sources of AvOx include persulphate, such as oxone. Another suitable source of AvOx is hydrogen peroxide.
Pre-formed peracid: A suitable pre-formed peracid is Ν,Ν-pthaloylamino peroxycaproic acid (PAP).
Bleach catalyst: Suitable bleach catalysts include oxaziridinium-based bleach catalysts, transition metal bleach catalysts and bleaching enzymes.
Oxaziridinium-based bleach catalyst: A suitable oxaziridinium-based bleach catalyst has the formula:
Figure imgf000034_0001
wherein: R1 is selected from the group consisting of: H, a branched alkyl group containing from 3 to 24 carbons, and a linear alkyl group containing from 1 to 24 carbons; R1 can be a branched alkyl group comprising from 6 to 18 carbons, or a linear alkyl group comprising from 5 to 18 carbons, R1 can be selected from the group consisting of: 2-propylheptyl, 2-butyloctyl, 2- pentylnonyl, 2-hexyldecyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n- octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; R2 is independently selected from the group consisting of: H, a branched alkyl group comprising from 3 to 12 carbons, and a linear alkyl group comprising from 1 to 12 carbons; optionally R2 is independently selected from H and methyl groups; and n is an integer from 0 to 1. Transition metal bleach catalyst: The composition may include transition metal bleach catalyst, typically comprising copper, iron, titanium, ruthenium, tungsten, molybdenum, and/or manganese cations. Suitable transition metal bleach catalysts are manganese-based transition metal bleach catalysts.
Reducing bleach: The composition may comprise a reducing bleach. However, the composition may be substantially free of reducing bleach; substantially free means "no deliberately added". Suitable reducing bleach include sodium sulphite and/or thiourea dioxide (TDO).
Co-bleach particle: The composition may comprise a co-bleach particle. Typically, the co-bleach particle comprises a bleach activator and a source of peroxide. It may be highly suitable for a large amount of bleach activator relative to the source of hydrogen peroxide to be present in the co-bleach particle. The weight ratio of bleach activator to source of hydrogen peroxide present in the co-bleach particle can be at least 0.3:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8: 1, or at least 0.9:1, or at least 1.0:1.0, or even at least 1.2:1 or higher.
The co-bleach particle can comprise: (i) bleach activator, such as TAED; and (ii) a source of hydrogen peroxide, such as sodium percarbonate. The bleach activator may at least partially, or even completely, enclose the source of hydrogen peroxide.
The co-bleach particle may comprise a binder. Suitable binders are carboxylate polymers such as polyacrylate polymers, and/or surfactants including non-ionic detersive surfactants and/or anionic detersive surfactants such as linear Cn-C^ alkyl benzene sulphonate.
The co-bleach particle may comprise bleach catalyst, such as an oxaziridium-based bleach catalyst.
Chelant: Suitable chelants are selected from: diethylene triamine pentaacetate, diethylene triamine penta(methyl phosphonic acid), ethylene diamine-N'N'-disuccinic acid, ethylene diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid), hydroxyethane di(methylene phosphonic acid), and any combination thereof. A suitable chelant is ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The laundry detergent composition may comprise ethylene diamine-N'N'- disuccinic acid or salt thereof. The ethylene diamine-N'N'-disuccinic acid may be in S,S enantiomeric form. The composition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt. Suitable chelants may also be calcium crystal growth inhibitors.
Calcium carbonate crystal growth inhibitor: The composition may comprise a calcium carbonate crystal growth inhibitor, such as one selected from the group consisting of: 1- hydroxyethanediphosphonic acid (HEDP) and salts thereof; N,N-dicarboxymethyl-2- aminopentane-l,5-dioic acid and salts thereof; 2-phosphonobutane-l,2,4-tricarboxylic acid and salts thereof; and any combination thereof.
Photobleach: Suitable photobleaches are zinc and/or aluminium sulphonated
phthalocyanines.
Additional hueing agent: Additional hueing agents (also defined herein as hueing dye) are typically formulated to deposit onto fabrics from the wash liquor so as to improve fabric whiteness perception, for example producing a relative hue angle of from 200° to 320° on a garment. Additional hueing agents are typically blue or violet. It may be suitable that the additional hueing dye(s) have a peak absorption wavelength of from 550nm to 650nm, or from 570nm to 630nm. The additional hueing agents may be a combination of dyes which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester of from 550nm to 650nm, or from 570nm to 630nm. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
Dyes are typically coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes maybe selected from the classes of basic, acid, hydrophobic, direct and polymeric dyes, and dye-conjugates. Suitable polymeric hueing dyes are commercially available, for example from Milliken, Spartanburg, South Carolina, USA.
Examples of suitable dyes are, direct violet 7 , direct violet 9 , direct violet 11 , direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, direct violet 99, acid violet 50, acid blue 9, acid violet 17, acid black 1 , acid red 17, acid blue 29, acid blue 80, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3 , basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, thiazolium dyes, reactive blue 19, reactive blue 163, reactive blue 182, reactive blue 96, Liquitint® Violet CT (Milliken, Spartanburg, USA), Liquitint® Violet DD (Milliken,
Spartanburg, USA) and Azo-CM-Cellulose (Megazyme, Bray, Republic of Ireland). A particularly suitable hueing agent is a combination of acid red 52 and acid blue 80, or the combination of direct violet 9 and solvent violet 13. Another suitable hueing dye is described in more detail in WO2010/151906.
Brightener: Suitable brighteners are stilbenes, such as C.I. fluorescent brightener 351. The brightener may be in micronized particulate form, having a weight average particle size in the range of from 3 to 30 micrometers, or from 3 micrometers to 20 micrometers, or from 3 to 10 micrometers. The brightener can be alpha or beta crystalline form. A preferred brightener is C.I. fluorescent brightener 260 having the following structure:
Figure imgf000037_0001
wherein the C.I. fluorescent brightener 260 is either: (i) predominantly in alpha-crystalline form; or (ii) predominantly in beta-crystalline form and having a weight average primary particle size of from 3 to 30 micrometers. As used herein, predominantly typically means "comprises greater than 50wt to 100wt , or greater than 60wt , or greater than 70wt , or greater than 80wt , or greater than 90wt to 100wt , or even comprises 100wt .
Enzyme: Suitable enzymes include proteases, amylases, cellulases, lipases, xylogucanases, pectate lyases, mannanases, bleaching enzymes, cutinases, and mixtures thereof.
For the enzymes, accession numbers and IDs shown in parentheses refer to the entry numbers in the databases Genbank, EMBL and/or Swiss-Prot. For any mutations, standard 1- letter amino acid codes are used with a * representing a deletion. Accession numbers prefixed with DSM refer to micro-organisms deposited at Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, 38124 Brunswick (DSMZ).
Protease. The composition may comprise a protease. Suitable proteases include metalloproteases and/or serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable protease may be of microbial origin. The suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease. Examples of suitable neutral or alkaline proteases include:
(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO) , Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM), Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391).
(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g. of porcine or bovine origin), including the Fusarium protease and the chymotrypsin proteases derived from
Cellumonas (A2RQE2).
(c) metalloproteases, including those derived from Bacillus amyloliquefaciens (P06832, NPRE_BACAM).
Suitable proteases include those derived from Bacillus gibsonii or Bacillus Lentus such as subtilisin 309 (P29600) and/or DSM 5483 (P29599).
Suitable commercially available protease enzymes include: those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark); those sold under the tradename Maxatase®, Maxacal®,
Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3® , FN4®,
Excellase® and Purafect OXP® by Genencor International; those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes; those available from Henkel/Kemira, namely BLAP (P29599 having the following mutations S99D + S101 R + S103A + V104I + G159S), and variants thereof including BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) all from Henkel Kemira; and KAP (Bacillus alkalophilus subtilisin with mutations A230V + S256G + S259N) from Kao.
Amylase: Suitable amylases are alpha- amylases, including those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A suitable alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM 9375, DSM 12368, DSMZ no. 12649, KSM API 378, KSM K36 or KSM K38. Suitable amylases include:
(a) alpha-amylase derived from Bacillus licheniformis (P06278, AMY_BACLI), and variants thereof, especially the variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.
(b) AA560 amylase (CBU30457, HD066534) and variants thereof, especially the variants with one or more substitutions in the following positions: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, optionally that also contain the deletions of D183* and G184*.
(c) variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus SP722 (CBU30453, HD066526), especially variants with deletions in the 183 and 184 positions.
Suitable commercially available alpha-amylases are Duramyl®, Liquezyme® Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, Stainzyme Plus®, Fungamyl® and BAN® (Novozymes A/S), Bioamylase® and variants thereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. m.b.H, Austria), Rapidase® , Purastar®, Optisize HT Plus®, Enzysize®, Powerase® and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM® (KAO, Japan). Suitable amylases are Natalase®, Stainzyme® and Stainzyme Plus®.
Cellulase: The composition may comprise a cellulase. Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g., the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum.
Commercially available cellulases include Celluzyme®, and Carezyme® (Novozymes A/S), Clazinase®, and Puradax HA® (Genencor International Inc.), and KAC-500(B)® (Kao Corporation).
The cellulase can include microbial-derived endoglucanases exhibiting endo-beta-1,4- glucanase activity (E.C. 3.2.1.4), including a bacterial polypeptide endogenous to a member of the genus Bacillus sp. AA349 and mixtures thereof. Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
The composition may comprise a cleaning cellulase belonging to Glycosyl Hydrolase family 45 having a molecular weight of from 17kDa to 30 kDa, for example the endoglucanases sold under the tradename Biotouch® NCD, DCC and DCL (AB Enzymes, Darmstadt, Germany).
Suitable cellulases may also exhibit xyloglucanase activity, such as Whitezyme®.
Lipase. The composition may comprise a lipase. Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g., from H. lanuginosa (T. lanuginosus), or from H. insolens, a Pseudomonas lipase, e.g., from P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P. fluorescens, Pseudomonas sp. strain SD 705, P. wisconsinensis, a Bacillus lipase, e.g., from B. subtilis, B. stearothermophilus or B. pumilus. The lipase may be a "first cycle lipase", optionally a variant of the wild-type lipase from Thermomyces lanuginosus comprising T231R and N233R mutations. The wild-type sequence is the 269 amino acids (amino acids 23 - 291) of the Swissprot accession number Swiss-Prot 059952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Suitable lipases would include those sold under the tradenames Lipex®, Lipolex® and Lipoclean® by
Novozymes, Bagsvaerd, Denmark.
The composition may comprise a variant of Thermomyces lanuginosa (059952) lipase having >90 identity with the wild type amino acid and comprising substitution(s) at T231 and/or N233, optionally T231R and/or N233R.
Xyloglucanase: Suitable xyloglucanase enzymes may have enzymatic activity towards both xyloglucan and amorphous cellulose substrates. The enzyme may be a glycosyl hydrolase (GH) selected from GH families 5, 12, 44 or 74. The glycosyl hydrolase selected from GH family 44 is particularly suitable. Suitable glycosyl hydrolases from GH family 44 are the XYG1006 glycosyl hydrolase from Paenibacillus polyxyma (ATCC 832) and variants thereof.
Pectate lyase: Suitable pectate lyases are either wild-types or variants of Bacillus-derived pectate lyases (CAF05441, AAU25568) sold under the tradenames Pectawash®, Pectaway® and X-Pect® (from Novozymes A/S, Bagsvaerd, Denmark).
Mannanase: Suitable mannanases are sold under the tradenames Manna way® (from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).
Bleaching enzyme: Suitable bleach enzymes include oxidoreductases, for example oxidases such as glucose, choline or carbohydrate oxidases, oxygenases, catalases, peroxidases, like halo-, chloro-, bromo-, lignin-, glucose- or manganese -peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases). Suitable commercial products are sold under the Guardzyme® and Denilite® ranges from Novozymes. It may be advantageous for additional organic compounds, especially aromatic compounds, to be incorporated with the bleaching enzyme; these compounds interact with the bleaching enzyme to enhance the activity of the oxidoreductase (enhancer) or to facilitate the electron flow (mediator) between the oxidizing enzyme and the stain typically over strongly different redox potentials.
Other suitable bleaching enzymes include perhydrolases, which catalyse the formation of peracids from an ester substrate and peroxygen source. Suitable perhydrolases include variants of the Mycobacterium smegmatis perhydrolase, variants of so-called CE-7 perhydrolases, and variants of wild-type subtilisin Carlsberg possessing perhydrolase activity. Cutinase: Suitable cutinases are defined by E.C. Class 3.1.1.73, optionally displaying at least 90%, or 95%, or most optionally at least 98% identity with a wild-type derived from one of Fusarium solani, Pseudomonas Mendocina or Humicola Insolens.
Identity. The relativity between two amino acid sequences is described by the parameter "identity". For purposes of the present invention, the alignment of two amino acid sequences is determined by using the Needle program from the EMBOSS package (http://emboss.org) version 2.8.0. The Needle program implements the global alignment algorithm described in Needleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. The substitution matrix used is BLOSUM62, gap opening penalty is 10, and gap extension penalty is 0.5.
Fabric-softener: Suitable fabric-softening agents include clay, silicone and/or quaternary ammonium compounds. Suitable clays include montmorillonite clay, hectorite clay and/or laponite clay. A suitable clay is montmorillonite clay. Suitable silicones include amino- silicones and/or polydimethylsiloxane (PDMS). A suitable fabric softener is a particle comprising clay and silicone, such as a particle comprising montmorillonite clay and PDMS.
Flocculant: Suitable flocculants include polyethylene oxide; for example having an average molecular weight of from 300,000 Da to 900,000 Da.
Suds suppressor: Suitable suds suppressors include silicone and/or fatty acid such as stearic acid.
Perfume: Suitable perfumes include perfume microcapsules, polymer assisted perfume delivery systems including Schiff base perfume/polymer complexes, starch-encapsulated perfume accords, perfume-loaded zeolites, blooming perfume accords, and any combination thereof. A suitable perfume microcapsule is melamine formaldehyde based, typically comprising perfume that is encapsulated by a shell comprising melamine formaldehyde. It may be highly suitable for such perfume microcapsules to comprise cationic and/or cationic precursor material in the shell, such as polyvinyl formamide (PVF) and/or cationically modified hydroxyethyl cellulose (catHEC).
Aesthetic: Suitable aesthetic particles include soap rings, lamellar aesthetic particles, geltin beads, carbonate and/or sulphate salt speckles, coloured clay particles, and any combination thereof.
Method of laundering fabric: The method of laundering fabric typically comprises the step of contacting the composition to water to form a wash liquor, and laundering fabric in said wash liquor, wherein typically the wash liquor has a temperature of above 0°C to 90°C, or to 60°C, or to 40°C, or to 30°C, or to 20°C, or to 10°C, or even to 8°C. The fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry detergent composition with water. The composition can be used in pre-treatment applications.
Typically, the wash liquor is formed by contacting the laundry detergent to water in such an amount so that the concentration of laundry detergent composition in the wash liquor is from above Og/1 to lOg/1, or from lg/1, and to 9g/l, or to 8.0g/l, or to 7.0g/l, or to 6.0g/l, or to 4g/l, or even to 3. Og/1, or even to 2.5g/l.
The method of laundering fabric may be carried out in a top-loading or front- loading automatic washing machine, or can be used in a hand-wash laundry application. In these applications, the wash liquor formed and concentration of laundry detergent composition in the wash liquor is that of the main wash cycle. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor.
The wash liquor may comprise 80 litres or less of water, or 60 litres or less, or 40 litres or less, or 20 litres or less, or 8 litres or less, or even 6 litres or less of water. The wash liquor may comprise from above 0 to 15 litres, or from 2 litres, and to 12 litres, or even to 8 litres of water.
Typically from 0.01kg to 2kg of fabric per litre of wash liquor is dosed into said wash liquor. Typically from 0.01kg, or from 0.05kg, or from 0.07kg, or from 0.10kg, or from 0.15kg, or from 0.20kg, or from 0.25kg fabric per litre of wash liquor is dosed into said wash liquor.
Optionally, 150g or less, lOOg or less, 50g or less, or 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even lOg or less of the composition is contacted to water to form the wash liquor.
A further aspect of the invention is a shading process for textile fibre materials characterized in that the textile fibre material is treated with a composition, which 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,
particularly granules; and
e) Water
In such a shading process the compositions of the invention are typically used in a detergent or washing agent composition. The amount of the compounds used is, for example, from 0.0001 to 1% by weight, preferably from 0.001 to 0.5% by weight, based on the weight of the textile material.
The following Examples illustrate the invention:
Examples
1 Test Materials and Compositions
1.1 Preparation of zinc phthalocyanine sulphonic acid conjugates with 4,4'-[[6-[(3- aminophenyl)amino]-l,3,5-triazine-2,4-diyl]diimino]bis[5-hydroxy-6-[2-(l-naph- thalenyl)diazenyl]-2,7-naphthalenedisulphonic acid (CAS-No. 1159843-59-0) 1.1.1 Acetylation of H-acid
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 HC1 (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
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 HC1 (32%). Aqueous HC1 (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.
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 1. 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 1. The formed precipitate is filtered off to yield 518.7 g (84.4%) 5-amino-4-hydroxy-3-[2- (l-naphthalenyl)diazenyl]-2,7-naphthalenedisulphonic acid (CAS-No. 103787-67-3) as a paste.
Preparation of 4,4'-[[6-[(3-aminophenyl)amino]-l,3,5-triazine-2,4-diyl]di- imino]bis[5-hydroxy-6-[2-(l-naphthalenyl)diazenyl]-2,7-naphthalenedisulphonic acid ("Dye", CAS-No. 1159843-59-0).
An aqueous solution of 0.060 mol 5-amino-4-hydroxy-3(naphthalene-l-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.
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 (UVvis λ^: 536 nm).
Sulphonation and sulphonyl chloride formation of zinc(II) phthalocyanine
(bis- and tris-sulphonated zinc phthalocyanines)
A mixture of 16.55 ml (31.4 g) fuming sulphuric acid (nominally 20% free SO3) and 12.8 ml (24.8 g) fuming sulphuric acid (65% free S03) 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. 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. Sulphonation and sulphonyl chloride formation of zinc(II) phthalocyanine
(mono- and bis-sulphonated zinc phthalocyanines)
A solution of 30 ml (56.9 g) fuming sulphuric acid (nominally 20% free S03) 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.
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.
Preparation of zinc(II) phthalocyanine dye conjugate I
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
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.
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+]: 1767 and 1847 along with minor amounts of 1927).
The aqueous zinc phthalocyanine dye conjugate solution can be used directly for granule formation or it can be desalted by dialysis and lyophilized. Alternative co- solvents to dimethoxyethane (e.g. alcoholic) solvents are also suitable.
1.2 Preparation of Agglomerates
The following compositions are prepared as indicated in Table 1. Solid content of the materials is measured by IR balance operated at 140°C.
Table 1
No. of 1.2.1 1.2.2 1.2.3 1.2.4 1.2.51' 1.2.6
Composition
Components
[wt.-%]
ZnPcDC1] 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
Referential Composition
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
Composition with cross-linked PVP
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 μιη particle size. The resulting agglomerates contain 7.2% of the ZnPcDC photo catalyst with respect to dry matter of the material.
Referential Example, Control
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.
Composition with cross-linked PVP
Analogous to 1.2.1. The ZnPcDC solution (1.1.6) is blended in water 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 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 4 A 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.
Composition with cross-linked PVP
26.0g 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.
Referential Composition, Control
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.
Composition with cross-linked PVP
The zinc(II) phthalocyanine dye conjugate II solution obtained from (1.1.7) is blended with the sodium salt of a condensate of naphthalenesulphonic acid with fomaldehyde 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.
Application tests
Spotting tests
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.
The spotting test used for evaluation of the agglomerates is outlined in
WO 2003/018740. Six 15x15 cm pieces of white bleached woven non- mercerised cotton are placed flat on the bottom of a bowl containing 1 1 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.
Exhaustion and spotting-in-use
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.
Release in the wash
Analogous to the procedure in 2.2, the washing experiments are performed with 6.9 mg/1 (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.
Results Table 2
Spotting tests
Figure imgf000050_0001
3.2 Table 3
Exhaustion and spotting in use (2.2)
Figure imgf000050_0002
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.
Table 4
Release in the wash
Figure imgf000050_0003
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 consumer detergents.
Table 5 - Granular Detergent Formulations Comprising the Inventive Particle Comprising a Phthalocyanine Complex
Ingredient Amount (in wt%)
Anionic detersive surfactant (such as alkyl benzene from 8wt to sulphonate, alkyl ethoxylated sulphate and mixtures thereof) 15wt
Non-ionic detersive surfactant (such as alkyl ethoxylated from 0.5wt to alcohol) 4wt%
Cationic detersive surfactant (such as quaternary from 0 to 4wt% ammonium compounds)
Other detersive surfactant (such as zwiterionic detersive from 0wt% to surfactants, amphoteric surfactants and mixtures thereof) 4wt%
Carboxylate polymer (such as co-polymers of maleic acid from lwt to and acrylic acid) 4wt%
Polyethylene glycol polymer (such as a polyethylene glycol from 0.5wt% to polymer comprising poly vinyl acetate side chains) 4wt%
Polyester soil release polymer (such as Repel-o-tex and/or from 0.1 to 2wt% Texcare polymers)
Cellulosic polymer (such as carboxymethyl cellulose, methyl from 0.5wt% to cellulose and combinations thereof) 2wt%
Other polymer (such as amine polymers, dye transfer from 0wt% to inhibitor polymers, hexamethylenediamine derivative 4wt%
polymers, and mixtures thereof)
Zeolite builder and phosphate builder (such as zeolite 4A from 0wt% to and/or sodium tripolyphosphate) 4wt%
Other builder (such as sodium citrate and/or citric acid) from 0wt% to
3wt%
Carbonate salt (such as sodium carbonate and/or sodium from 15wt to bicarbonate) 30wt
Silicate salt (such as sodium silicate) from 0wt% to
10wt% Filler (such as sodium sulphate and/or bio-fillers) from 10wt% to
60wt
Source of available oxygen (such as sodium percarbonate) from 10wt% to
20wt
Bleach activator (such as tetraacetylethylene diamine from 2wt to (TAED) and/or nonanoyloxybenzenesulphonate (NOBS) 8wt%
Bleach catalyst (such as oxaziridinium-based bleach catalyst from 0wt% to and/or transition metal bleach catalyst) 0.1 wt%
Other bleach (such as reducing bleach and/or pre-formed from 0wt% to peracid) 10wt%
Chelant (such as ethylenediamine-N'N'-disuccinic acid from 0.2wt% to (EDDS) and/or hydroxyethane diphosphonic acid (HEDP) lwt%
Photobleach (such as zinc and/or aluminium sulphonated from 0wt% to phthalocyanine) 0.1 wt%
Hueing agent (such as direct violet 99, acid red 52, acid blue from 0wt to 80, direct violet 9, solvent violet 13 and any combination lwt%
thereof)
Inventive particle comprising a phthalocyanine complex from 0.0001wt to
(according to the present invention) lwt%
Brightener (such as C.I. Fluorescent Brightener 260 and/or from 0.1 wt to C.I. Fluorescent Brightener 351) 0.4wt
Protease (such as Savinase, Savinase Ultra, Purafect, FN3, from 0.1 wt to FN4 and any combination thereof) 0.4wt
Amylase (such as Termamyl, Termamyl ultra, Natalase, from 0.05wt to Optisize, Stainzyme, Stainzyme Plus and any combination 0.2wt
thereof)
Cellulase (such as Carezyme and/or Celluclean) from 0.05wt to
0.2wt
Lipase (such as Lipex, Lipolex, Lipoclean and any from 0.2 to lwt% combination thereof)
Other enzyme (such as xyloglucanase, cutinase, pectate from 0wt to lyase, mannanase, bleaching enzyme) 2wt% from 0wt% to
Fabric softener (such as montmorillonite clay and/or
4wt%
polydimethylsiloxane (PDMS)
Flocculant (such as polyethylene oxide) from 0wt% to
lwt%
Suds suppressor (such as silicone and/or fatty acid) from 0wt% to
0.1 wt%
Perfume (such as perfume microcapsule, spray-on perfume, from 0.1 wt% to
starch encapsulated perfume accords, perfume loaded zeolite, lwt%
and any combination thereof)
Aesthetics (such as coloured soap rings and/or coloured from 0wt to
speckles/noodles) lwt%
Miscellaneous balance
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

CLAIMS What is claimed is:
1. A laundry detergent composition, which comprises
a) At least one water-soluble phthalocyanine compound;
b) At least one cross-linked polyvinylpyrrolidone component;
c) At least one hydrophilic binding agent;
d) Detersive surfactant; and
e) optionally additional detergent ingredients.
2. A laundry detergent 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
Figure imgf000054_0001
Wherein
R20 represents hydrogen, Ci-Csalkyl, Ci-Csalkoxy or halogen;
R21 represents D, hydrogen, OH, CI or F, provided that at least one is D;
R100 represents Ci-Csalkylene; * marks the point of attachment of PC; and
# marks the point of attachment of the substituent D of the mono-azo dye.
3. A laundry detergent composition according to claim 2, wherein the water-soluble
phthalocyanine complex compound (1) corresponds to the formula
Figure imgf000055_0001
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, Al-Zi, Si(IV)-(Z1)2, Ti(IV)-(Z!)2 and SnOVMZ z;
Zjrepresents Ci-C8alkanolate, OH", R0COO", C104 ", BF4 ", PF6 ", R0SO3 ", S04 2", N03 ", F", CI", Br", Γ, citrate, tartrate or oxalate, wherein Ro is hydrogen or Ci-Cisalkyl;
r represents 0 or a numeral from 1 to 3;
r' represents a numeral from 1 to 4;
each Q2 independently of one another represents -SO3 M"1" or the group -(CH2)m-COO" M+; wherein M+ is H+, 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
Figure imgf000055_0002
Figure imgf000056_0001
Wherein
R20 represents hydrogen, Ci- Csalkyl, Ci-Csalkoxy or halogen;
R21 represents D, hydrogen, OH, CI or F, provided that at least one is D;
R100 represents d-Csalkylene;
* marks the point of attachment of Me-PC; and
# marks the point of attachment of the substituent D of the mono-azo dye.
4. A laundry detergent composition according to claim 2, wherein the water-soluble
phthalocyanine complex compound (1) corresponds to the formula
Figure imgf000056_0002
wherein each k is independently selected from 0 and 1 , j is independently selected from 0 and 1-k,
Wherein
Me represents Zn, Al-Zi, Si(IV)-(Z1)2 or Ti(IV)-(Z1)2, wherein Zi is chloride, fluoride, bromide or hydroxide; each Q2 independently of one another represents -SO3 M or the group -(CH2)m-COO M+, wherein M+ is H+, 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
Figure imgf000057_0001
Wherein
R21 represents D, hydrogen, OH, CI or F, provided that at least one is D;
* marks the point of attachment of PC;
# marks the point of attachment to D;
5. A laundry detergent composition according to claim 2, wherein Me represents Zn, Al or mixtures thereof.
6. A laundry detergent composition according to claim 2, wherein D represents the
substituent of a mono- azo dye of the partial formulae Xa, Xb, Xc or Xd
(Xb)
Figure imgf000057_0002
Figure imgf000058_0001
Wherein
# marks the point of attachment of the bridging group L;
Ra represents hydrogen, Ci-C4alkyl, Ci-C2alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci- C4alkoxy, phenyl, naphthyl and pyridyl, aryl, aryl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy and Ci-C4alkyl;
Z2, Z3, Z4, Z5 and Z6
independently of one another represent hydrogen, hydroxy , Ci-C4alkyl, Ci-C2alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, Ci-C4alkoxy, Ci-C2alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, straight chain or branched C3-C4-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy, phenyl, naphthyl and pyridyl, halogen, OH, -S02CH2CH2S03H, N02, COOH, -COOCi-C4alkyl, NH2, NHCj- C4alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, d-C4alkyl, CN and COOH, N(d-C4alkyl)Ci- C4alkyl, wherein the alkyl groups may independently of one another be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C4alkyl, CN and COOH, NH-aryl, NH-aryl, wherein aryl is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C4alkoxy, C C4alkyl and C C4alkoxy, or represents NHCOC C4alkyl or NHCOOC C4alkyl;
G represents the direct bond, -COOCi-C4alkylene, arylene; arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkoxy and Ci-C4alkyl, Ci-C4alkylene, Ci-C4-alkylene substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, d- C4alkoxy and Ci-C4alkyl, 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.
7. A composition according to claim 2, wherein D represents the substituent of a mono- azo dye of the partial formulae XIa, Xlb, XIc or Xld:
Figure imgf000059_0001
Wherein
# marks the point of attachment of the bridging group L;
Z2 represents Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, Ci-C2-alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, or represents OH;
Z3 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, C1-C2- alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, NO2, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi- C2alkyl;
Z4 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, C1-C2- alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, NO2, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi- C2alkyl;
Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci-C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
n represents 0, 1, 2 or 3;
n' represents 0, 1 or 2; and
each M independently of one another represents hydrogen, Na+ or K+;
Figure imgf000061_0001
Wherein
# marks the point of attachment of the bridging group L;
Z2 represents Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo- Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, Ci-C2- alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl or represents OH;
Z3 is hydrogen, Ci-C2-alkyl, Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo- Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, Ci-C2- alkoxy, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN or COOH or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Z5 represents hydrogen, Ci-C2-alkyl or Ci-C2-alkyl, which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, C C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl;
n represents 0, 1, 2 or 3;
N' is 0, 1 or 2; and
each M independently of one another represents hydrogen, Na+ or K+; (Xlc)
(S03M)n Z5 (S03M)n,
Wherein
# marks the point of attachment of the bridging group L;
Z2represents hydrogen, hydroxy, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2-alkoxy or Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci- C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents OH or N02;
Z3represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2- alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Z4represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2- alkoxy or Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, N02, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, NH2, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Zsrepresents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2- alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents N02;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, C C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, N02, SO3H, NH2, carboxy, carbo-Ci- C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl,
n represents 0, 1, 2 or 3;
n' represents 0, 1 or 2; and
each M indep
Figure imgf000063_0001
(SQ3M)n (S03M)n,
Wherein
# marks the point of attachment of the bridging group L;
Z3 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents S02CH2CH2S03H or N02;
Z4 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2-alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, or represents S02CH2CH2S03H, or N02; Z5 represents hydrogen, Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci-C2-alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, OH, NO2, NH2, NHCi-C2alkyl, wherein the alkyl group may be substituted by at least one substituent selected from the group consisting of OH, N¾, Ci-C2alkyl, CN and COOH, or represents NHCOCi-C2alkyl or NHCOOCi-C2alkyl;
Z6 represents Ci-C2-alkyl, Ci-C2-alkyl which is substituted by at least one
substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy, phenyl, naphthyl and pyridyl, Ci- C2-alkoxy, Ci-C2-alkoxy which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, SO3H, N¾, carboxy, carbo-Ci-C4alkoxy, Ci-C4alkyl, phenyl, naphthyl and pyridyl, or represents N02;
G represents the direct bond, COOCi-C2alkylene, arylene, arylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, N¾, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl, Ci-C2alkylene or Ci-C2-alkylene which is substituted by at least one substituent selected from the group consisting of hydroxy, cyano, NO2, SO3H, NH2, carboxy, carbo-Ci-C2alkoxy, Ci-C2alkoxy and Ci-C2alkyl; n represents 0, 1, 2 or 3;
n' represents 0, 1 or 2; and
each M independently of one another represents hydrogen, Na+ or K+.
8. A laundry detergent composition according to claim 2, wherein D is selected from the group consisting of compounds, wherein the partial formulae 10, 11, 12, 13 and 14:
Figure imgf000065_0001
are present and wherein # marks the point of attachment of the bridging group L.
9. A laundry detergent composition according to claim 1, wherein the cross-linked
polyvinylpyrrolidone component b) is essentially insoluble in water.
10. A laundry detergent 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.
11. A laundry detergent composition according to claim 1 , wherein the hydrophilic binding agent of component c) is a water-soluble or at least water-dispersible polymer or wax-type polymer selected from the group consisting of gelatines, polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), vinyl acetates copolymers of styrene and acrylic acid, polycarboxylic acids,
polyacrylamides, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl alcohols, hydrolyzed and non-hydrolyzed polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons, polyethylene glycol (MW = 2000 - 20 000), copolymers of ethylene oxide with propylene oxide (MW > 3500), condensation products (block polymerization products) of alkylene oxide, especially propylene oxide, copolymers of vinylpyrrolidone with vinyl acetate, ethylene oxide -propylene oxide addition products with diamines, especially ethylenediamine, polystyrenesulphonic acid, polyethylenesulphonic acid, copolymers of acrylic acid with sulphonated styrenes, gum arabic, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose phthalate, maltodextrin, starch, sucrose, lactose, enzymatically modified and subsequently hydrated sugars, cane sugar, polyaspartic acid and tragacanth; and also mixed
polymerization products of the mentioned polymers.
12. A laundry detergent composition according to claim 1, wherein the hydrophilic binding agent of component c) is selected from the group consisting of sodium carboxymethyl cellulose, hydroxypropyl methylcellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatines, hydrolyzed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, maltodextrin, polyaspartic acid, polyacrylates and polymethacrylates .
13. A laundry detergent composition according to claim 1, wherein the further additives of Component e) 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, Ti02 Si02 and magnesium trisilicate.
14. A laundry detergent composition according to claim 1, wherein the composition comprises a particle, wherein the particle comprises:
a) At least one water-soluble phthalocyanine compound;
b) At least one cross-linked polyvinylpyrrolidone component;
c) At least one hydrophilic binding agent;
15. A laundry detergent composition according to claim 14, wherein the particles have an
average particle size of from 20 μιη to 200 μιη.
16. A laundry detergent composition according to any preceding claim, wherein the composition is substantially free of zeolite builder and phosphate builder.
17. A laundry detergent composition according to any preceding claim, wherein the detersive surfactant comprises:
(i) alkoxylated alkyl sulphate anionic detersive surfactant having an average degree of alkoxylation of from 0.5 to 5; and/or
(ii) predominantly C12 alkyl sulphate anionic detersive surfactant.
18. A laundry detergent composition according to any preceding claim, wherein the composition comprises a clay and soil removal/anti-redeposition agent selected from the group consisting of:
(a) random graft co-polymers comprising:
(i) hydrophilic backbone comprising polyethylene glycol; and
(ii) hydrophobic side chain(s) selected from the group consisting of: C4-C25 alkyl group, polypropylene, polybutylene, vinyl ester of a saturated Ci-C6 mono-carboxylic acid, Ci_C 6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof;
(b) cellulosic polymers having a degree of substitution (DSub) of from 0.01 to 0.99 and a degree of blockiness (DB) such that either DSub+DB is of at least 1.00 or DB+2DSub-DSub2 is at least 1.20;
(c) co-polymers comprising:
(i) from 50 to less than 98 wt structural units derived from one or more monomers comprising carboxyl groups;
(ii) from 1 to less than 49 wt structural units derived from one or more monomers comprising sulfonate moieties; and
(iii) from 1 to 49 wt structural units derived from one or more types of monomers selected from ether bond-containing monomers represented by formulas (I) and (II): formula (I): Ro
I
c
CH2
CH2
O-R! wherein in formula (I), Ro represents a hydrogen atom or CH3 group, R represents a CH2 group, CH2CH2 group or single bond, X represents a number 0-5 provided X represents a number 1-5 when R is a single bond, and Ri is a hydrogen atom or Ci to C20 organic group; formula (II)
Figure imgf000068_0001
in formula (II), Ro represents a hydrogen atom or CH3 group, R represents a CH2 group, CH2CH2 group or single bond, X represents a number 0-5, and Ri is a hydrogen atom or Ci to C20 organic group;
(d) polyester soil release polymers having a structure according to one of the following structures (I), (II) or (III):
Figure imgf000068_0002
(II) -[(OCHR3-CHR4)b-0-OC-sAr-CO-]e
(III) -[(OCHR5-CHR6)c-OR7]f
wherein:
a, b and c are from 1 to 200;
d, e and f are from 1 to 50; Ar is a 1 ,4-substituted phenylene;
sAr is 1,3 -substituted phenylene substituted in position 5 with SC^Me;
Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, or tetraalkylammonium wherein the alkyl groups are Ci-Cis alkyl or C2-C10 hydroxyalkyl, or any mixture thereof;
R\ R2, R3, R4, R5 and R6 are independently selected from H or Ci-Cig n- or iso-alkyl; and
R7 is a linear or branched Ci-Cis alkyl, or a linear or branched C2-C30 alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C8-C30 aryl group, or a C6-C30 arylalkyl group; and
(e) any combination thereof.
19. A laundry detergent composition according to any preceding claim, wherein the composition comprises an enzyme selected from the group consisting of:
(a) a variant of thermomyces lanuginosa lipase having >90 identity with the wild type amino acid and comprises substitution(s) at T231 and/or N233
(b) a cleaning cellulase belonging to Glycosyl Hydrolase family 45.
(c) a variant of AA560 alpha amylase endogenous to Bacillus sp. DSM 12649 having:
(i) mutations at one or more of positions 9, 26, 149. 182, 186, 202, 257, 295, 299, 323, 339 and 345; and
(ii) one or more substitutions and/or deletions in the following positions: 118, 183, 184, 195, 320 and 458; and
(d) any combination thereof.
20. A laundry detergent composition according to any preceding claim, wherein the composition comprises an oxaziridinium-based bleach catalyst having the formula:
Figure imgf000070_0001
wherein: R1 is selected from the group consisting of: H, a branched alkyl group containing from 3 to 24 carbons, and a linear alkyl group containing from 1 to 24 carbons; R2is independently selected from the group consisting of: H, a branched alkyl group comprising from 3 to 12 carbons, and a linear alkyl group comprising from 1 to 12 carbons; and n is an integer from 0 to 1.
A laundry detergent composition according to any preceding claim, wherein the composition comprises a perfume microcapsule.
22. A laundry detergent composition according to any preceding claim, wherein the composition comprises from 30 to 60% of a fillers selected from sulphate salts and/or bio-filler materials.
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US8809251B2 (en) 2014-08-19

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