Patent Application
20090054292
The present invention relates to encapsulated granulates of phthalocyanine compounds, to a process for the preparation thereof, and to washing agent formulations comprising such granulates.
Water-soluble phthalocyanine compounds, especially zinc and aluminium phthalocyanine sulfonates, are frequently used as photoactivators in washing agent preparations. A compilation of such formulations and their preparation, properties and use is to be found, for example, in WO 04/022693.
A further development for improved bleaching and whiteness build-up consists, for example, of mixtures of phthalocyanine compounds with at least one azo dye and/or a triphenyl-methane dye, as mentioned in WO 05/014769. Further improvements are obtained by the use of a phthalocyanine system that comprises at least one phthalocyanine to which at least one dye is covalently bonded.
As is furthermore described in the mentioned documents, suitable solid commercial forms can be produced using such phthalocyanine compounds. Such granulates meet the requirement of very rapid solubility in water in order, as a result, to avoid staining of the textile with the coloured phthalocyanine during application to the textile. A disadvantage of such granulates can be that when they are incorporated in the washing agent they can, depending on the storage conditions and the composition of the washing agent, start to dissolve and, as a result, stain the washing agent.
It has now been found that the stability of such granulates in the washing agent can be improved and, as a result, staining of the washing agent prevented, if the granulates are coated with a non-aqueous coating agent comprising at least one finely particulate solid. The finely particulate solid is present in the coating agent and, in addition thereto, may be admixed with the already coated granulate (dusting). In the embodiment of the invention, the rapid solubility of the phthalocyanine granulate in water and, as a result, the advantageous use profile of the granulates are retained.
The present invention accordingly relates to encapsulated granulates G of phthalocyanine compounds wherein the encapsulating layer consists of at least one finely particulate solid and at least one hydrophobic coating material.
The present invention relates preferably to encapsulated granulates G which are distinguished by the fact that the granulate does not contain enzymes.
The granulates do not contain any enzymes, whether in the core or in or on the encapsulation.
The present invention relates preferably to encapsulated granulates Go of phthalocyanine compounds containing
The sum of the percentages by weight (% by weight) is always 100%.
The granulates G0 preferably contain no enzymes, whether in the core or in or on the encapsulation.
The present invention relates preferably to encapsulated granulates G1 of phthalocyanine compounds containing
The granulates G1 preferably contain no enzymes, whether in the core or in or on the encapsulation.
As the phthalocyanine compound for the granulates G0 and G1 there come into consideration phthalocyanine complexes with di-, tri- or tetra-valent metals (complexes having a d0 or d10 configuration) as the central atom.
Such complexes are especially water-soluble Zn(II), Fe(II), Ca(II), Mg(II), Na(I), K(I), Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI) phthalocyanines, aluminium and zinc phthalocyanines being especially preferred.
The granulate G and G1 advantageously comprises at least one phthalocyanine compound of formula
wherein
R6 is branched or unbranched C1-C8alkylene; or 1,3- or 1,4-phenylene;
X2 is —NH—; or —N—C1-C5alkyl-; X3+ is a group of formula —N—R8; (CH+—N A; —COCH2—NA1; or —COCH2—N—R8; and, in the case where R6═C1-C8alkylene, may also be a group of formula —NNN A; or —S+N Al —N Bi H′z R//N—R12R13R15
Y1+ is a group of formula
t is 0 or 1;
in which above formulae
R7 and R8 are each independently of the other C1-C6alkyl;
R9 is C1-C6alkyl; C5-C7cycloalkyl; or NR11R12;
R, O and R1, are each independently of the other C1-C5alkyl;
R12 and R13 are each independently of the other hydrogen or C1-C5alkyl;
R14 and R15 are each independently of the other unsubstituted or hydroxy-, cyano-, carboxy-,
C1-C6alkoxy-carbonyl-, C1-C6alkoxy-, phenyl-, naphthyl- or pyridyl-substituted C1-C6alkyl;
u is from 1 to 6;
A1 is the balance of an aromatic 5- to 7-membered nitrogen heterocycle which may contain one or two further nitrogen atoms as ring members, and B1 is the balance of a saturated 5- to 7-membered nitrogen heterocycle which may contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms as ring members;
Q2 is hydroxy; C1-C22alkyl; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl or a mixture thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of formula
a branched alkoxy radical of formula
an alkylethyleneoxy unit of formula
-(T1)d-(CH2)b(OCH2CH2)a—B3 or an ester of formula COOR23,
wherein
The number of substituents Q1 and Q2 in formula (1a) and in formula (1b), respectively, which substituents may be identical or different, is from 1 to 8 and, as is usual with phthalo-cyanines, the number need not be a whole number (degree of substitution). If other, non-cationic substituents are also present, the sum of the latter and the cationic substituents is from 1 to 4. The minimum number of substituents that need to be present in the molecule is governed by the water-solubility of the resulting molecule. An adequate water solubility is achieved when the amount of phthalocyanine compound that dissolves is sufficient to cause photodynamically catalysed oxidation on the fibres. A solubility as low as 0.01 mg/l may be sufficient, but generally a solubility of from 0.001 to 1 g/l is expedient.
Halogen is fluorine, bromine or, especially, chlorine.
As groups
there come into consideration especially:
Preference is given to the group
As heterocyclic rings in the group
there likewise come into consideration the groups mentioned above, but with the bond to the remaining substituents being made by way of a carbon atom.
In all substituents, phenyl, naphthyl and aromatic hetero rings may be substituted by one or two further radicals, for example by C1-C6alkyl, C1-C6alkoxy, halogen, carboxy, C1-C6alkoxy-carbonyl, hydroxy, amino, cyano, sulfo, sulfonamido etc.
Preference is given to a substituent from the group C1-C6alkyl, C1-C6alkoxy, halogen, carboxy, C1-C6alkoxy-carbonyl and hydroxy.
As the group
there come into consideration especially:
All above-mentioned nitrogen heterocycles may, in addition, be substituted by alkyl groups, either at a carbon atom or at a further nitrogen atom located in the ring, with preference being given to a methyl group as the alkyl group.
As− in formula (1a) denotes, as counterion to the positive charge of the remainder of the molecule, any desired anion. It is generally introduced in the process of manufacture (quaternisation), in which case it preferably is a halogen ion, an alkylsulfate ion or an arylsulfate ion. Among the arylsulfate ions mention should be made of the phenylsulfonate, p-tolylsulfonate and p-chlorophenylsulfonate ions. It is also possible, however, for any other anion to function as the anion, since the anions can readily be interchanged in known manner; accordingly, As− may also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate or lactate ion or another anion of an organic carboxylic acid. In the case of monovalent anions, the index s is equal to r. In the case of polyvalent anions, s assumes a value ≦r but must be such, depending on the conditions, that it exactly balances the positive charge of the remainder of the molecule.
C1-C6Alkyl and C1-C6alkoxy are straight-chain or branched alkyl and alkoxy radicals, respectively, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl, and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy, respectively. C2-C22Alkenyl denotes, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
Preferred phthalocyanine compounds of formula (1a) of the granulates G and G1 correspond to formula
wherein
Me, q, PC, X2, X3 and R6 are as defined for formula (Ia),
M is hydrogen; or an alkali metal ion, ammonium ion or amine salt ion; and the sum of the numbers r1 and r2 is from 1 to 4, and
As− exactly balances the positive charge of the remainder of the molecule, and especially to formula
wherein
Me, q and PC are as defined for formula (Ia),
R6′ is C2-C6alkylene;
r is a number from 1 to 4;
X3′ is a group of formula
wherein
Further phthalocyanine compounds that can be used in the granulate G and G1 correspond to formula
wherein
Of those, very special preference is given to phthalocyanine compounds of formula (4) wherein
Z1 is a halide ion, sulfate ion, nitrate ion, acetate ion or hydroxy ion.
Further phthalocyanine compounds of interest that can be used in the granulate G and G′ correspond to formula
wherein
, R17
it being possible, when r>1, for the radicals
present in the molecule to be identical or different.
Further phthalocyanine compounds of interest that can be used in the granulate G and G1 correspond to formula
wherein
Where the central atom Me in the phthalocyanine ring is Si(IV), the phthalocyanines used in the granulate G and G1 may also contain, in addition to the substituents on the phenyl nucleus of the phthalocyanine ring, axial substituents (═R24). Such phthalocyanines correspond, for example, to formula
wherein
a branched alkoxy radical of formula
an alkylethyleneoxy unit of formula
R16, R17, R18, R19, R20, R21, R22, R23, B2, B3, M, M1, Q1, Q2, As, T1, X1, Y2, Z2, a, b, c, d, e, r, v and w therein are as defined for formulae (1a) and (1b).
Especially preferred phthalocyanine compounds are such compounds as are commercially available and used in washing agent compositions. Usually, the anionic phthalocyanine compounds are in the form of alkali metal salts, especially sodium salts.
These phthalocyanine compounds may be used on their own or in admixture with at least one azo dye and/or triphenylmethane dye. Preferred azo dyes and/or triphenylmethane dyes are described in WO 05/014769 (on pages 13-16). Especially preferred azo dyes and/or triphenylmethane dyes are compounds of the following structures
Mixtures of phthalocyanine compounds together with at least one azo dye and at least one triphenylmethane dye are, moreover, also suitable.
Further suitable phthalocyanine compounds are those which comprise at least one phthalocyanine to which at least one dye is covalently bonded. Preference is given to the use of compounds of the general structure (8a) and/or (8b)
wherein
and, when R26═C1-C8alkylene, X6+ may also be
—SO2(CH2)v—OSO3M; —SO2(CH2)v—SO3M;
an alkylethyleneoxy unit of formula
Halogen is fluorine, bromine or, especially, chlorine.
Especially suitable groups
are:
Preference is given to the group
As heterocyclic rings in the group
there likewise come into consideration the groups mentioned above, but with the bond to the remaining substituents being made by way of a carbon atom.
In all those substituents, phenyl, naphthyl and aromatic heterocyclic rings may be substituted by one or two further radicals, for example by C1-C6alkyl, C1-C6alkoxy, halogen, carboxy, C1-C6alkoxy-carbonyl, hydroxy, amino, cyano, sulfo, sulfonamido etc.
Preference is given to a substituent from the group C1-C6alkyl, C1-C6alkoxy, halogen, carboxy, C1-C6alkoxy-carbonyl and hydroxy.
Especially suitable groups
are:
etc., wherein
B1 and R31 are as defined hereinbefore.
All above-mentioned nitrogen heterocycles may, in addition, be substituted by alkyl groups, either at a carbon atom or at a further nitrogen atom located in the ring. The alkyl group is preferably a methyl group.
As− in formula (8a) denotes, as counterion to the positive charge of the remainder of the molecule, any desired anion. It is generally introduced in the process of manufacture (quaternisation), in which case it preferably is an alkanolate ion; a hydroxyl ion; R25COO−; ClO4−; BF4−; PF6−; R25SO3−; SO42−; NO3−; F−; Cl−; Br−; I−; or a citrate, tartrate or oxalate ion (wherein R25 is hydrogen; or unsubstituted C1-C18alkyl; or C1-C18alkyl which is substituted by at least one substituent from the group hydroxy, cyano, carboxy, SO3H, —NH2, C1-C6alkoxy-carbonyl, C1-C6alkoxy, phenyl, naphthyl and pyridyl; unsubstituted aryl; or aryl which is substituted by at least one substituent from the group hydroxy, cyano, carboxy, —SO3H, —NH2, C1-C6alkoxy-carbonyl, C1-C6alkoxy and C1-C4alkyl). Among the arylsulfate ions mention should be made of the phenylsulfonate, p-tolylsulfonate and p-chlorophenylsulfonate ions. It is also possible, however, for any other anion to function as the anion, since the anions can readily be interchanged in known manner; accordingly, As− may also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate or lactate ion or another anion of an organic carboxylic acid. In the case of monovalent anions, the index s is equal to r. In the case of polyvalent anions, s assumes a value ≦r but must be such, depending on the conditions, that it exactly balances the positive charge of the remainder of the molecule.
C1-C6Alkyl and C1-C6alkoxy are straight-chain or branched alkyl and alkoxy radicals, respectively, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl, and methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy, respectively.
C2-C22Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
Me preferably is Zn, AlZ2, Si(IV)-(Z2)2 or Ti(IV)-(Z2)2, wherein Z2 is as defined hereinbefore.
Me especially is Zn, AlZ2, Si(IV)-(Z2)2 or Ti(IV)-(Z2)2, wherein Z2 is chlorine, fluorine, bromine or hydroxy.
R26 preferably is branched or unbranched C1-C4alkylene; or 1,3- or 1,4-phenylene.
X5 preferably is —NH— or —N(C1-C4alkyl)-.
R27 and R28 preferably are each independently of the other C1-C4alkyl.
R29 preferably is C1-C4alkyl; pentyl; hexyl or NR32R33.
R30 and R31 preferably are each independently of the other C1-C4alkyl.
R32 and R33 preferably are each independently of the other hydrogen or C1-C4alkyl.
R34 and R35 preferably are each independently of the other unsubstituted C1-C4alkyl, or
C1-C4alkyl which is substituted by at least one substituent from the group hydroxy, cyano,
SO3H, —NH2, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy, phenyl, naphthyl and pyridyl.
u preferably is 1; 2; 3 or 4.
A1 preferably is a unit which completes a pyrrole, imidazole, pyridine, pyrazine, pyrimidine or pyridazine ring.
B1 preferably is a unit which completes a morpholine, pyrrolidine, piperazine or piperidine ring.
L preferably is a direct bond; —SO2—; —(CH2)1-4—SO2—; —O—; —(CH2)1-4—O—; —OR44—; —(CH2)1-4—OR44—; —OR44O—; —(CH2)1-4—OR44O—; —OR44N(R45)—; —(CH2)1-4—OR44N(R45)—; —N(R45)—; —(CH2)1-4—N(R45)—; —(CH2CH2O—)n—; —C(O)—; —(CH2)1-4—C(O)—; —C(O)N(R45)—; —(CH2)1-4—C(O)N(R45)—; —N(R45)C(O)—; —(CH2)1-4—N(R45)C(O)—; —OC(O)—; —(CH2)1-4—OC(O)—; —C(O)O—; —(CH2)1-4—C(O)O—; —S—; —(CH2)1-4—S—; unsubstituted, straight-chain or branched C1-C18alkylene;
straight-chain or branched C1-C18alkylene which is substituted by at least one substituent from the group hydroxy, cyano, —SO3H, —NH2, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy, phenyl, naphthyl and pyridyl;
unsubstituted C5-C18arylene;
C5-C18arylene which is substituted by at least one substituent from the group hydroxy, cyano, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy and C1-C4alkyl;
unsubstituted straight-chain or branched C1-C18alkylene-C5-C18aryl; straight-chain or branched C1-C18alkylene-C5-C18aryl which is substituted by at least one substituent from the group hydroxy, cyano, —SO3H, —NH2, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy, C1-C4alkyl, phenyl, naphthyl and pyridyl;
unsubstituted straight-chain or branched C5-C18arylene-C1-C18alkyl or straight-chain or branched C5-C18arylene-C1-C18alkyl which is substituted by at least one substituent from the group hydroxy, cyano, —SO3H, —NH2, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy, C1-C4alkyl, phenyl, naphthyl and pyridyl,
wherein
wherein
Especially preferred dye radicals D correspond to the following formulae (I′)-(XIX′):
wherein
G is a direct bond; unsubstituted arylene; arylene which is substituted by at least one substituent from the group hydroxy, cyano, —NO2, —SO3H, —NH2, carboxy, C1-C2-alkoxy-carbonyl, C1-C2alkoxy and C1-C2alkyl; unsubstituted C1-C4alkylene, or C1-C4alkylene which is substituted by at least one substituent from the group hydroxy, cyano, —NO2, —SO3H, —NH2, carboxy, C1-C2alkoxy-carbonyl, C1-C2alkoxy and C1-C2alkyl,
m1 is 0 or 1,
wherein
wherein
wherein
Especially preferred dye radicals D are those of the following formulae (XXVI)-(XXVIII):
which is the radical of Bisazo Red 253,
The mixture of the dyes of formulae (XXI) and (XXII) is known as Pontamine.
Preferred phthalocyanine compounds of formula (8a) correspond to formula
wherein
Especially preferred phthalocyanine compounds of formula (8a) correspond to formula
wherein
wherein
Further photobleaching active ingredients that may be used in accordance with this invention correspond to formula
wherein
Very especially preferred phthalocyanine compounds correspond to formula (11a),
wherein
Further phthalocyanine compounds of interest that may be used in accordance with this invention correspond to formula
wherein
in the molecule may be the same or different.
Further phthalocyanine compounds of interest which may be used in accordance with this invention correspond to formula
wherein
Where the central atom Me in the phthalocyanine ring is Si(IV), the phthalocyanines used in accordance with the invention may also contain, in addition to the substituents on the phenyl nucleus of the phthalocyanine ring, axial substituents (═R46). Such phthalocyanines correspond, for example, to formula
wherein
Especially preferred compounds of formulae (8a) and (8b) correspond to formulae
wherein
an alkylethyleneoxy unit of formula
unsubstituted straight-chain or branched C5-C18arylene-C1-C18alkyl, or straight-chain or branched C5-C18arylene-C1-C18alkyl which is substituted by at least one substituent from the group hydroxy, cyano, carboxy, C1-C4alkoxy-carbonyl, C1-C4alkoxy, C1-C4alkyl, phenyl, naphthyl and pyridyl,
The compounds of formulae (8a) and (8b) can be prepared by conventional synthesis methods customary in organic chemistry.
For synthesis of the Me-phthalocyanines there are two methods: either the phthalocyanine ring is prepared first and is subsequently complexed with a metal salt, or the phthalocyanine ring is synthesised from simple benzenic precursors with simultaneous incorporation of the metal ion.
The substituents on the phthalocyanine ring can be introduced before or after ring synthesis. If the substituents are introduced before ring formation, this results in substitution of all four rings. When the substituents are introduced after ring synthesis, the substitution can be varied.
As a result of introduction of suitable substituents, it is possible to obtain, for example, water-soluble phthalocyanines. Such synthesis methods are described in, inter alia, DE1569783, DE1569729, DE2021257 and DE1794298. The synthesis of metal-containing phthalocyanines and their use as photoactivators is known, for example, from DE0081462.
A suitable method of obtaining water-soluble phthalocyanines is the introduction of sulfonate groups. It is known that such sulfonated phthalocyanines are not pure substances but are a mixture of positional isomers. In addition, the degree of sulfonation will also vary and, as a result, frequently may not be a whole number. In J. Griffiths et al., Dyes and Pigments, Vol 33, 65-78 (1997) and the literature cited therein there is described a method for the preparation of a tetrasodium salt of a zinc phthalocyanine.
The phthalocyanines which carry a covalently bonded dye are prepared in customary manner. For example, the covalent bonding is achieved by reacting a metal-containing phthalocyanine substituted by sulfonyl chloride groups with a suitable dye containing amino groups.
Synthesis of a metal-containing phthalocyanine substituted by sulfonyl chloride groups is carried out by sulfochlorination as is described in, inter alia, DE2812261 or DE0153278. The degree of sulfochloride substitution can be modified by varying the starting materials. Sulfochlorination of phthalocyanines usually results in a main product which can, however, also contain amounts of phthalocyanines substituted by a greater or lesser number of sulfonyl chloride groups.
Granulates G and G1 contain from 2 to 50% by weight, based on the total weight of the granulate, of at least one of the mentioned phthalocyanine compounds (1a), (1b), (2a), (3), (4), (5), (6), (7), (8), (8a), (9), (9a), (10), (11), (11a), (12) and (13) and optionally a dye of formula (A), (B), (C), (D), (E), (F), (G), (H) and/or (I). Preferred granulates G and G1 contain from 4 to 30% by weight and especially preferred granulates contain from 5 to 20% by weight of at least one of the mentioned phthalocyanine compounds (1a), (1b), (2a), (3), (4), (5), (6), (7), (8), (8a), (9), (9a), (10), (11), (11a), (12) and (13) and optionally a dye of formula (A), (B), (C), (D), (E), (F), (G), (H) and/or (I), based on the total weight of the granulate.
The granulates G and G1 contain from 10 to 60% by weight, preferably from 12 to 60% by weight, especially from 12 to 55% by weight, based on the total weight of the granulate, of at least one anionic dispersing agent and/or at least one water-soluble organic polymer. In certain cases, less than 10% by weight or more than 70% by weight may also be used.
Such anionic dispersing agents and also the water-soluble organic polymers, which may also have dispersing properties, are described hereinbelow.
The anionic dispersing agents used are, for example, the commercially available water-soluble anionic dispersing agents for dyes, pigments etc. The following products, especially,
come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated biphenyls or biphenyl oxides and optionally formaldehyde, (mono-/di-)alkyl-naphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkylbenzene-sulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids, sodium salts of alkyl diglycol ether sulfates, sodium salts of polynaphthalenemethane-sulfonates, ligno- or oxyligno-sulfonates or heterocyclic polysulfonic acids.
Especially suitable anionic dispersing agents are condensation products of naphthalene-sulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethylbiphenyl.
Instead of or in addition to the dispersing agent or agents, the granulates according to the invention may comprise a water-soluble organic polymer, which may also have dispersing properties. Such polymers may be used singly or as mixtures of two or more polymers. As water-soluble polymers (which may, but need not, have film-forming properties), there come into consideration, for example, gelatins, polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), polyvinyl-pyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-chain olefins, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinyl-pyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethyl-aminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylamino-ethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, 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 polymerisation products of the mentioned polymers. Further suitable substances are polyethylene glycol (MW=4000−20 000), copolymers of ethylene oxide with propylene oxide (MW>3500), condensation products (block polymerisation products) of alkylene oxide, especially propylene oxide, copolymers of vinylpyrrolidone with vinyl acetate, ethylene oxide-propylene oxide addition products with diamines, especially ethylenediamine, polystyrene-sulfonic acid, polyethylenesulfonic acid, copolymers of acrylic acid with sulfonated styrenes, gum arabic, carboxymethyl cellulose, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose phthalate, maltodextrin, starch, sucrose, lactose, enzymatically modified and subsequently hydrogenated sugars, as are obtainable under the name “Isomalt”, cane sugar, polyaspartic acid, tragacanth and polyvinyl alcohols.
Among those water-soluble organic polymers, special preference is given to carboxymethyl cellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatins, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, maltodextrins, polyaspartic acid and also polyacrylates and polymethacrylates.
The granulates G and G1 contain from 15 to 75% by weight, preferably from 20 to 75% by weight, especially from 25 to 70% by weight, based on the total weight of the granulate, of at least one inorganic salt and/or at least one low-molecular-weight organic acid and/or a salt thereof. In certain cases, less than 15% by weight or more than 75% by weight may also be used.
The mentioned components are described in detail hereinbelow:
For use as inorganic salts there come into consideration carbonates, hydrogen carbonates, phosphates, polyphosphates, sulfates, silicates, sulfites, borates, halides and pyro-phosphates, preferably in the form of alkali salts. Preference is given to water-soluble salts such as, for example, alkali metal chlorides, alkali phosphates, alkali carbonates, alkali polyphosphates and alkali sulfates and water-soluble salts used in washing agent formulations.
As low-molecular-weight organic acids there come into consideration, for example, mono- or poly-carboxylic acids. Of special interest are aliphatic carboxylic acids, especially those having a total number of from 1 to 12 carbon atoms. Preferred acids are aliphatic C1-C12-mono- or -poly-carboxylic acids, the monocarboxylic acids being especially those having at least 3 carbon atoms in total. As substituents of the carboxylic acids there come into consideration, for example, hydroxy and amino, especially hydroxy. Special preference is given to aliphatic C2-C12polycarboxylic acids, especially aliphatic C2-C6polycarboxylic acids. Very special preference is given to hydroxy-substituted aliphatic C2-C6polycarboxylic acids. These compounds may be used in the form of the free acid or a salt, especially an alkali salt. There may also be used aminopolycarboxylates (e.g. sodium ethylenediaminetetraacetate), phytates, phosphonates, aminopolyphosphonates (e.g. sodium ethylenediaminetetra-phosphonate), aminoalkylenepoly(alkylenephosphonates), polyphosphonates, polycarb-oxylates or water-soluble polysiloxanes.
As examples of low-molecular-weight organic acids and salts thereof there may be mentioned oxalic acid, tartaric acid, acetic acid, propionic acid, succinic acid, maleic acid, citric acid, formic acid, gluconic acid, p-toluenesulfonic acid, terephthalic acid, benzoic acid, phthalic acid, acrylic acid and polyacrylic acid.
The granulates G and G1 may comprise further additives, for example wetting agents, disintegrants such as, for example, powdered or fibrous cellulose, microcrystalline cellulose, fillers such as, for example, dextrin, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, and optical brighteners such as, for example, bis(triazinyl-amino)stilbene disulfonic acid, bis(triazolyl)stilbene disulfonic acid, bis(styryl)biphenyl or bis(benzofuranyl)biphenyl, a bis(benzoxalyl) derivative, bis(benzimidazolyl) derivative, a coumarin derivative or a pyrazoline derivative. Suitable optical brighteners are described in WO 05/014769 on pages 26-47. Aluminium silicates such as zeolites, and also compounds such as talc, kaolin, TiO2, SiO2 or magnesium trisilicate may also be used in small amounts. Such additives are present in an amount of from 0 to 10% by weight, preferably from 0 to 5% by weight, based on the total weight of the granulate. In certain cases, more than 10% by weight may also be used.
As especially preferred additives, special emphasis is to be given to powdered or fibrous cellulose and to aluminium silicates. These are present in an amount of from 0 to 10% by weight, preferably from 0 to 5% by weight, based on the total weight of the granulate.
The granulates G and G1 may contain from 3 to 15% water by weight, based on the total weight of the granulate.
The granulates G and G1 contain from 1 to 60% by weight, based on the total weight of the granulate, of an encapsulation material consisting of at least one finely particulate solid and at least one hydrophobic coating material. Preferred granulates G and G1 contain from 3 to 55% by weight, more preferred granulates contain from 3 to 50% by weight and especially preferred granulates contain from 4 to 50% by weight, based on the total weight of the granulate, of an encapsulation material consisting of at least one finely particulate solid and at least one hydrophobic coating material.
The granulates G and G1 are encapsulated with a layer consisting of at least one hydrophobic coating material and at least one finely particulate solid. The finely particulate solid may both be present in the hydrophobic coating material and also be applied onto the hydrophobic coating material. The content of hydrophobic coating material is from 2 to 98% by weight, preferably from 15 to 98% by weight, very preferably from 40 to 95% by weight and more preferably from 50 to 95% by weight, based on the total weight of the encapsulating layer, and the content of the finely particulate solid is from 2 to 98% by weight, preferably from 2 to 85% by weight, very preferably from 5 to 60% by weight and more preferably from 5 to 50% by weight, based on the total weight of the encapsulating layer. The components are described in detail hereinbelow.
Meltable hydrophobic materials which are described in the literature for the encapsulation of washing agent components are suitable as the hydrophobic coating material of the encapsulating layer as understood by this invention. These coating materials are usually not present in chemically pure form and are therefore distinguished by a melting/solidification range. It may furthermore be advantageous to use a mixture of a plurality of coating materials. The mixture used has a solidification point range preferably above 30° C., especially above 40° C. It may furthermore be advantageous for solidification from the liquid phase to occur within a narrow temperature range of <5 Kelvin. In this context, the determination of melting/solidification ranges can be carried out using established test procedures such as differential thermal analysis, as is described, for example, in “The Analyst, 87 (1962), p. 420 ff.”.
Suitable coating materials are particular hydrocarbons (paraffins), long-chain saturated carboxylic acids or alcohols having fewer than 24 carbon atoms, their comparable esters and wax esters of natural or synthetic origin, fatty acid glycerides and also fatty acid alkanolamides and fatty alcohol ethers, with special preference being given to fatty acids and fatty acid blends, alkali metal salts of stearic or palmitic acid, glycerol monostearates or palmitates, solid fatty alcohols, PEG fatty alcohols or PEG stearates having a lipophilic character, solid paraffin, microcrystalline waxes, condensation products of stearic acid, triethanolamine and acrylamide, fatty acid mono-, di- or tri-esters or fatty acid mono-, di- or tri-glycerides, especially of stearic or palmitic acid, solid and semi-solid waxes such as beeswax or carnauba wax and their PEG derivatives.
As very especially preferred coating materials mention should be made of fatty acids and mixtures thereof, PEG ethoxylates of stearic acid, glyceryl monostearates, triglycerides and PEG derivatives of beeswax and mixtures of those substances.
A finely particulate solid is present in the encapsulating layer. As understood by the invention, finely particulate herein means an average particle size of <100 μm, preferably <50 μm and especially <10 μm. The solid is mixed together with the meltable material in suitable manner, and the resulting solid-containing melt is applied to the granulates according to the invention. The finely particulate solid may be present in the melt on its own or in admixture with a plurality of finely particulate solids.
To that applied encapsulating layer, which may not necessarily have solidified completely, it may furthermore be advantageous to apply further finely particulate solid. According to our understanding, finely particulate solid so applied contributes to a further improvement in storage stability of the washing agent composition because it reduces the number of direct contact points between the granulates according to the invention and the washing agent particles. In that case it is desirable for the superficially applied finely particulate solid to adhere sufficiently firmly for it not to be rubbed off during incorporation into the washing agent. The finely particulate solid in the encapsulating layer may have, but need not have, the same composition as the superficially applied finely particulate solid and likewise may also consist of a mixture of a plurality of finely particulate solids.
Suitable finely particulate solids include, for example, those disclosed in EP-A-133 562, for example the water-soluble inorganic and organic salts which may be textile washing agent constituents customary per se, but preferably excluding salt-type surfactants. They are primarily the customary washing agent builder substances, for example the alkali metal silicates, carbonates, hydrogen carbonates and borates also known as washing alkalis and also the alkali metal polyphosphates. Also suitable, however, are alkali metal sulfates, which are practically inert in the washing process, for example sodium sulfate, and also water-soluble salts of organic acids, especially alkali salts of hydroxycarboxylic acids, for example citric acid and tartaric acid, and also salts of polymeric polycarboxylates, for example homo- and co-polymerisation products of acrylic acid, hydroxyacrylic acid, maleic acid, methylenemalonic acid, and copolymerisation products of those acids with vinyl methyl ether or methacrylic acid.
A further class of finely particulate solids that can be used includes finely particulate organic solids that are capable of swelling or are partially soluble in water and absorbent polymeric powders, for example of the cellulose, methylcellulose or starch type, especially carboxymethyl starch, dextrins and also polyester, polyethylene and polyacrylonitrile.
Finally, a third class of suitable materials consists of very finely dispersed inorganic compound mixtures which are insoluble in water. These include the bentonites, such as sodium montmorillonite, layered silicates and also kieselguhr, talc, kaolin, mica, fuller's earth, feldspar and zeolites, and also hydrosodalite. Mention should also be made of very finely dispersed metal oxides or metal hydroxides or mixed oxides of silicon, aluminium, magnesium, zinc and titanium, and also the very finely particulate silicic acids produced by precipitation or pyrogenic means. Examples of suitable metal oxides include very finely dispersed magnesium oxide, titanium oxide, zinc oxide and aluminium oxide. Further suitable materials are finely particulate alkaline earth metal salts, for example calcium chloride and calcium sulfate. Further suitable materials are finely particulate alkali metal silicates, carbonates, polyphosphonates and sulfates.
Preferred finely particulate solids are alkali metal silicates, carbonates, polyphosphates and sulfates, layered silicates, talc, kaolin, zeolite, alkaline earth salts and titanium dioxide which are <50 μm.
A very preferred granulate G2 consists of
Preferably, the granulate G2 does not contain any enzymes, whether in the core or in or on the encapsulation.
A likewise very preferred granulate G3 consists of
Preferably, the granulate G3 does not contain any enzymes, whether in the core or in or on the encapsulation.
An especially preferred granulate G4 consists of
Preferably, the granulate G4 does not contain any enzymes, whether in the core or in or on the encapsulation.
An especially preferred granulate G5 consists of
Preferably, the granulate G5 does not contain any enzymes, whether in the core or in or on the encapsulation.
A particularly preferred granulate G6 consists of
Preferably, the granulate G6 does not contain any enzymes, whether in the core or in or on the encapsulation.
A particularly preferred granulate G7 consists of
Preferably, the granulate G7 does not contain any enzymes, whether in the core or in or on the encapsulation.
The granulates G, G1, G2, G3, G4, G5, G6 and G7 according to the invention are prepared by drying an aqueous solution or suspension of the phthalocyanine compound, as a result of which solid particles (granulates) are formed. That drying step, the procedures employed and also examples of granulates obtainable thereby and their characteristics are described in detail in WO 04/022693 and form part of, but do not limit, this invention. The granulates are resistant to abrasion, low in dust, free-flowing and can be readily metered and they are distinguished by very rapid solubility in water. However, depending on the composition of the washing agent and the prevailing storage conditions, those granulates can start to dissolve in the washing agent, which is associated with undesirable staining of the washing agent.
For that reason, in a further step, the granulates are encapsulated with a solid-containing melt. Established procedures are used for application of the encapsulating layer, for example batch-wise mixing of the granulate together with the solid-containing melt in a temperature-controlled mixer (e.g. a ploughshare mixer) or spraying the melt onto the granulate in a fluidised layer. Continuous procedures are also possible for forming the encapsulation, for example mixing together the melt and granulate in a continuous mixer or spraying the melt in a fluidised bed. Uniformity of the encapsulated granulate and control of its composition are benefited if the solid-containing melt is prepared separately and metered into the granulate.
After the granulate has been covered with the melt and solid, the product is brought, in controlled manner, to a temperature below the solidification temperature of the encapsulation material. In batch operation this can be done, in the simplest case, by cooling the mixing vessel or discharging the material into a cooled mixer. Cooling can also be carried out continuously, for example by using a fluidised bed cooler. The cooling process is generally so carried out that significant granulate agglomeration of the mixture is avoided.
Further finely particulate solid can be applied to the surface of the granulate during or after formation of the encapsulating layer depending on the procedure selected. In a batch-wise process procedure, further finely particulate solid can be added after intimate mixing of the granulate with the melt and formation of the encapsulating layer. When this is done during the cooling phase of the granulate it is possible both to obtain products in which the post-dosed solid is an integral part of the coating (in the case of addition during the solidification phase of the encapsulating layer) and also to obtain products in which the solid adheres to the surface of the coated granulate (when the addition is made after the coating has substantially solidified). The characteristics of the product and the stability of the granulates according to the invention are benefited if the additional solid is added before the encapsulating layer has to a very large extent solidified, in order to obtain the adhesion of the solid to the granulate which is necessary for a non-dusty product.
The granulates G, G1, G2, G3, G4, G5, G6 and G7 preferably have a density in the range from 400 to 900 g/l and are rapidly soluble in water. They may be added directly to the washing agent formulation in the desired concentration of the phthalocyanine compound. Alternatively, the granulates according to the invention may be mixed with other washing agent components, such as phosphates, zeolites, brighteners or enzymes, for metering into a washing agent by means of a post-dosing step. Such a mixture for post-dosing of the granulates is distinguished by a homogeneous distribution of the granulates according to the invention in the mixture and may consist of, for example, from 1 to 50% granulate and from 99 to 50% sodium tripolyphosphate.
The granulates G, G1, G2, G3, G4, G5, G6 and G7 in the washing agent formulations according to the invention preferably have an average particle size of <500 μm. More preferably, the particle size of the granulates is from 40 to 400 μm.
As already mentioned, the granulates G, G1, G2, G3, G4, G5, G6 and G7 according to the invention are used especially as an additive in a washing agent formulation. Such a washing agent formulation may be in solid, liquid, gel-like or paste form, for example in the form of a liquid, non-aqueous washing agent composition containing not more than 5% by weight, preferably from 0 to 1% by weight, water and based on a suspension of a builder substance in a non-ionic surfactant, for example as described in GB-A-2 158 454.
The washing agent formulation may also be in the form of powders or (super-)compact powders, in the form of single- or multi-layer tablets (tabs), in the form of washing agent bars, washing agent blocks, washing agent sheets, washing agent pastes or washing agent gels, or in the form of powders, pastes, gels or liquids used in capsules or in pouches (sachets).
However, the washing agent formulations are preferably in the form of non-aqueous formulations, powders, tabs or granulates.
The present invention accordingly relates also to washing agent formulations containing
The sum of the percentages by weight of components I)-VI) in a formulation is always 100%.
All the preferences mentioned hereinbefore apply to the granulates G, G1, G2, G3, G4, G5, G6 and G7.
The anionic surfactant A) may be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture of those surfactants. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, where appropriate in combination with alkyl ethoxysulfates having from 10 to 20 carbon atoms in the alkyl radical. Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical and/or alkylnaphthalenesulfonates having from 6 to 16 carbon atoms in the alkyl radical in question. The cation in the anionic surfactant is preferably an alkali metal cation, especially sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R—CO—N(R1)—CH2COOM1, wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal.
The non-ionic surfactant B) may be, for example, a condensation product of from 3 to 8 mol of ethylene oxide with 1 mol of primary alcohol containing from 9 to 15 carbon atoms.
As builder substance C) there come into consideration, for example, alkali metal phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates, especially the sodium salts thereof, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds. Especially suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSitO2t+1.pH2O or Na2SitO2t+1.pH2O, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20. Among the aluminium silicates, preference is given to those obtainable commercially under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of those components.
Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylene-diamine disuccinate either in racemic form or in the enantiomerically pure S,S form. Phosphonates and aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylene-phosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriamine-pentamethylenephosphonic acid.
As the peroxide component D) there come into consideration, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95° C. The organic peroxides are, for example, mono- or poly-peroxides, especially organic peracids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxy-dodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof. Preferably, however, inorganic peroxides are used, such as, for example, persulfates, perborates, percarbonates and/or persilicates. It will be understood that mixtures of inorganic and/or organic peroxides can also be used. The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability. The peroxides are added to the washing agent composition preferably by mixing the components, for example using a screw metering system and/or a fluidised bed mixer.
The washing agent compositions may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the classes bis(triazinylamino)stilbene disulfonic acid, bis(triazolyl)stilbene disulfonic acid, bis(styryl)-biphenyl and bis(benzofuranyl)biphenyl, a bis(benzoxalyl) derivative, bis(benzimidazolyl) derivative, coumarin derivative or a pyrazoline derivative.
The washing agent compositions may also comprise suspending agents for dirt, e.g. sodium carboxymethyl cellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, fragrances and, optionally, antistatic agents and fabric conditioners, enzymes, such as amylase, bleaching agents, pigments and/or toning agents. It will be understood that such constituents must be stable towards the bleaching agent used.
Further preferred additives to the washing agent compositions according to the invention are polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor which have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones which may have been modified by the incorporation of anionic or cationic substituents, especially those polyvinylpyrrolidones having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are preferably used in an amount of from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent composition.
In addition, the washing agent compositions according to the invention may also comprise so-called perborate activators, such as, for example, TAED or TAGU. Preference is given to TAED, which is preferably used in an amount of from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent composition.
The percentages of components 1) to VI) in the washing agent formulations hereinbelow are in all cases based on the total weight of the washing agent formulation.
A preferred washing agent formulation according to the invention consists of
V) from 0 to 60% F) of further additives from the group consisting of optical brighteners; suspending agents for dirt; pH regulators; foam regulators; salts for regulating the spray-drying and granulating properties; fragrances; antistatic agents; fabric conditioners; enzymes; bleaching agents; pigments; toning agents; polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor which have been released from the textiles under the washing conditions; and perborate activators, and
The content of granulates G, G1, G2, G3, G4, G5, G6 and G7 in accordance with the invention in the washing agent composition is from to 0.001 to 1% by weight, preferably from 0.001 to 0.05% by weight and very especially from 0.005 to 0.03% by weight.
As already mentioned, the washing agent formulation may be in solid or liquid form.
Preferably, however, the washing agent formulations are in the form of powders, tabs or granulates. These can be prepared, for example, by first preparing an initial powder by means of spray-drying an aqueous slurry comprising all of the afore-mentioned components except for components D) and E) and then adding the dry components D) and E) and mixing them all together. It is also possible to start from an aqueous slurry which, although comprising components A) and C), comprises none of or only some of component B). The slurry is spray-dried; component E) is then mixed with component B) and added; and then component D) is mixed in dry. The components are preferably mixed with one another in such amounts that a solid compact washing agent composition in granule form is obtained, having a specific weight of at least 500 g/l.
In another preferred embodiment, the production of the washing agent composition is carried out in three steps. In the first step a mixture of anionic surfactant (and, where appropriate, a small amount of non-ionic surfactant) and builder substance is prepared. In the second step the major portion of the non-ionic surfactant is sprayed onto that mixture and then, in the third step, peroxide and, where appropriate, catalyst, and the granulate according to the invention are added. That method is usually carried out in a fluidised bed. In a further preferred embodiment, the individual steps are not carried out completely separately, so that there is a certain amount of overlap between them. Such a method is usually carried out in an extruder, in order to obtain granulates in the form of “megapearls”.
The following Examples serve to illustrate the invention, but do not limit the invention thereto. Unless otherwise specified, parts and percentages are based on weight. Temperatures are, unless otherwise specified, in degrees Celsius.
1500 g of an FSD granulate consisting of 13% (dry content) photocatalyst active ingredient (zinc and aluminium phthalocyanine compounds), 42% of an inorganic dispersing agent, 37% inorganic and organic salts, 3% of a toning dye (azo compound) and a residual moisture content of 5% are heated to 65° C. in a heatable Lödige ploughshare mixture. 375 g of a triglyceride (Edenor NHTI V, Cognis) are melted at 70° C. and homogeneously mixed together with 125 g of finely particulate talc (particle size: 600 mesh). The solid-containing melt is added to the granulate, with slow continuous mixing by means of the Lödige, and homogeneously distributed within 10 minutes. The encapsulated granulate is discharged continuously into a fluidised bed and cooled to room temperature using cold air. The desired particle size fraction obtained (50-400μ) is separated off by sieving. A product containing 10% photocatalyst and an encapsulating layer of 19% triglyceride and 6% talc, each based on the total weight of the product, is obtained.
Using the same procedure, granulates comprising phthalocyanine compounds are encapsulated with an encapsulating layer comprising solid and coating agent, cooled and classified. Table 1 gives the percentage contents of the respective components in the encapsulated granulate.
For preparation of the spraying liquid, 400 g of a stearic acid (Cutina FS45, Cognis) are melted at 70° C. 100 g of finely particulate talc (Talc TPM, d(50)=4μ, Scheruhn) are introduced and homogeneously mixed in. The mixture is transferred to the spray reservoir of the fluidised bed apparatus and held at 70° C. The melting range of this mixture is around 58° C., and the solidification temperature around 52° C.
1000 g of a granulate containing 14% active ingredient (dry content) and having an average particle size of 180 μm are introduced into a laboratory fluidised bed apparatus provided with a heatable binary nozzle. The active ingredient contained in the granulate is a zinc phthalocyanine covalently bonded to Direct Violet 99. The temperature of the bed air is regulated to 70° C. As soon as the temperature of the granulate bed has reached 70° C. spraying of the fluidised bed with the spray mixture is started. The spraying rate is about 10 g/min. After spraying 90 g of the melt onto the granulate, the apparatus is switched over to cold air supply and the granulate in the fluidised bed is cooled down to room temperature. After the oversized product (>400μ) has been sieved off, a free-flowing product having an average particle size of 190μ, a coating amount of about 8% and an active ingredient content of 12.8% is obtained.
Using the same procedure, granulates comprising phthalocyanine compounds are encapsulated with an encapsulating layer comprising solid and coating agent, cooled and classified. Table 2 gives the percentage contents of the respective components in the encapsulated granulate.
Examples 23-32 illustrate, but do not limit, the use of the granulates according to the invention in washing agent preparations.
Small amounts of further additives (foam inhibitors etc.) and the residual moisture content of the washing agent make the composition up to 100%.
The granulates from Examples 2-22 may also be used instead of the granulate from Example 1.
Small amounts of further additives and the residual moisture content of the washing agent make the composition up to 100%.
The granulates from Examples 2-22 may also be used instead of the granulate from Example 1.
| Number | Date | Country | Kind |
|---|---|---|---|
| 05103718.2 | May 2005 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2006/061771 | 4/24/2006 | WO | 00 | 10/30/2007 |
