GB2283980A

GB2283980A - Cationic aluminium-phthalocyanine dyestuffs

Info

Publication number: GB2283980A
Application number: GB9422469A
Authority: GB
Inventors: Helmut Anton Moser
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1993-11-10
Filing date: 1994-11-08
Publication date: 1995-05-24
Anticipated expiration: 2014-11-08
Also published as: GB9422469D0; CH688413A5; ES2096523A1; IT1273994B1; FR2712294B1; GB2283980B; ITRM940707A0; DE4439243A1; DE4439243B4; ITRM940707A1; FR2712294A1; ES2096523B1

Abstract

Cationic aluminium-phthalocyanine compounds correspond to formula I, <IMAGE> wherein the individual symbols are defined as in claim 1, as well as their salts and mixtures thereof. The compounds and their preparations are used for dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates by a known method. Preferred substrates are textile materials which consist of or contain cellulose, especially cotton, but also bast fibres, leather and preferably paper or paper products, especially wood-containing paper. The paper dyeings have perfect wet fastness.

Description

Cationic aluminium-phthalocyanine dyestuffs The invention relates to aluminium-phthalocyanine compounds which are linked via a nitrogen-containing bridge, a process for their production and their use in dyeing and printing processes.

Corresponding heavy metal-phthalocyanine dyestuffs, especially copper- or nickelphthalocyanine dyestuffs, are known. Previously, aluminium-phthalocyanines were mentioned in various instances in the literature, but in practice, they were of minimum significance in technical application / commercially. It was only the ecological considerations and demands based on environmental politics that led to considerations and work with the aim to replace the poisonous heavy metals, especially chromium, nickel, cobalt and copper, in the complex dyestuffs which the market could not do without, with less poisonous complex-forming metals.

The German patent application DE-A4 005 015 describes copper, nickel or cobalt complexes of dyestuffs of formula I of the present invention. These complexes show the above-mentioned ecological disadvantages. With respect to the corresponding aluminium complexes there existed the prejudice that these latter ones would not nearly provide an acceptable alternative regarding coloring strength or fastness properties. However, surprisingly it was now found that the new dyestuffs can well present a practically equivalent substitute for the heavy metal-phthalocyanine dyestuffs which are not in keeping with times any more.

The invention consequently relates to compounds of formula I,

wherein each Ra independently is chlorine or hydroxyl, each W1 independently is -A- eNR1R2R3 Ane or -A-NR2R3, R1 independently is hydrogen, unsubstituted C1-4alkyl; C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl; or C5.6cycloalkyl, each R2 and R3 independently is unsubstituted C1-4alkyl or C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl, or C5-6cycloalkyl, and each Ane is a non-chromophoric anion; each R4 independently is hydrogen or unsubstituted C14alkyl, or C1alkyl which is monosubstituted by hydroxy, each A independently is -C2.6alkylene-, or -C3 6alkylene which is monosubstituted by hydroxy, Y is a divalent bridge member, which is bonded on both ends via an aliphatic carbon atom, and each R5 and R6 independently is unsubstituted C1-4alkyl; or C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl; or C5.6cycloalkyl, each AlPc is the aluminium-phthalocyanine radical, the two m independently signify 0 or 1, the two n independently signify 1, 2 or 3, and p signifies 1 or 2, and mixtures of compounds of formula I, in which compounds each SO3H group is in free acid or in salt form, with the proviso that in a compound or mixture of compounds of formula I: (i) 1 < p < 2 and (ii) m + n + p < 4.

If not otherwise stated, the definition alkyl and alkylene includes both linear and branched aliphatic radicals. If not defined more precisely, the examples are understood to include only linear radicals.

In a hydroxy-substituted alkyl or alkylene group which is bonded to nitrogen, the hydroxy group is preferably located at the other end, preferably not at a C-atom which is directly attached to this nitrogen atom.

Halogen generally denotes fluorine, chlorine or bromine; preferably chlorine or bromine and in particular chlorine.

R, preferably signifies Ria as hydrogen, methyl, ethyl; Alkyl monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl; more preferably Rib as hydrogen, methyl, ethyl; C2.3alkyl monosubstituted by hydroxy; benzyl or cyclohexyl; most preferably Ric as hydrogen, methyl or ethyl.

Each R2 and R3 preferably denotes R2a and R3a, where each R2a and R3a independently signifies methyl, ethyl; C2.3alkyl monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl. R2 and R3 more preferably denote R2b and R3b, whereby each R2b and R3b, independently of one another, signifies methyl, ethyl; C2.3alkyl monosubstituted by hydroxy; benzyl or cyclohexyl. They most preferably denote R, and R3c, which independently of one another signify methyl or ethyl.

R4 preferably denotes R4a, where each R4a independently signifies hydrogen, methyl, ethyl or 2-hydroxyethyl. R4 more preferably denotes R4b, where each R4b independently signifies hydrogen or methyl. Most preferably each R4 signifies hydrogen.

A as alkylene preferably denotes a C2 4alkylene group, for example -(CH2)q- with q = 2, 3

it especially denotes -(CH2)ql- with q' = 2 or 3.

A as hydroxy-substituted alkylene preferably contains 3 or 4 C-atoms.

A preferably signifies Al, where each A1 independently denotes -C2.4alkylene- or monohydroxy-substituted -C3-4alkylene-; more preferably A2, where each A2 independently denotes -C2-4alkylene-; most preferably A3, where each A3 independently denotes -(CH2)q'-, wherein q' signifies 2 or 3.

W1 preferably denotes Wla, where each Wia independently signifies -A1-#NR1aR2aR3a Ane or -Al-NR2aR3a; more preferably Wib, where each Wib signifies -A2-#NR1bR2bR3b Ane or A2-NR2bR3b;; most preferably Wic, where each Wic independently signifies -A3-#NR1cR2cR3c Ane or -A3-NR2cR3c Y preferably denotes Y1 as -C2.6alkylene-, monohydroxy- or dihydroxy-substituted -C3-8alkylene-, a -C2.6alkylene chain which is interrupted by -O-, -NR7- or

or a monohydroxy- or dihydroxy-substituted -C3-8alkylene chain which is interrupted by -O-, -NR7- or

whereby R7 signifies hydrogen or C1.6alkyl and R8 signifies hydrogen, halogen, C1-4alkyl or C1-4alkoxy.

Y more preferably denotes Y2 as -C24alkylene-, monohydroxy-substituted -C34alkylene- or -T1-X-T2, wherein each T1 and T2 independently signifies -C1-3alkylene- or monohydroxysubstituted -C34alkylene-, and X signifies -NR7a- or

in which R7a denotes hydrogen or C1alkyl and Rga denotes hydrogen, chlorine, methyl or methoxy.

Y most preferably denotes Y3 as -C2-3alkylene-, monohydroxy-substituted -C3-4alkylene- or

Each R5 and R6 preferably signifies R5a and R6a, where each R5a and R6a independently signifies methyl, ethyl; C2-3alkyl which is monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl; R5 and R6 more preferably denote R5b and R6b, which independently signify methyl, ethyl; C2-3alkyl monosubstituted by hydroxy; benzyl or cyclohexyl. R5 and R6 most preferably denote R5c and R6c, which independently signify methyl or ethyl.

Preferred compounds correspond to formula Ia,

wherein each SO3H-group is in free acid or in salt form, and mixtures of compounds of formula Ia, Ra, R4b, R5b, R6b, W1b, A2 and Y2 being defined as above.

Further preferred are the compounds of formula Ia, wherein (1) each A2 independently is A3; (2) Y2 is Y3; (3) each Wib independently is Wic, (4) each R4b is hydrogen; (5) those of (1) to (4), wherein each R5b and R6b independently is R5C and R6c.

The invention also relates to a process for the production of the compounds of formula I, which is characterized in that two compounds of formula II

wherein AlPc, Rab A, Wl, R4, R5, R6, m, n and p are defined as above, which may be the same or different, are linked together by introducing the bridge Y, whereby the -NR5R6 group(s) of each compound of formula II is (are) quaternized. For the man skilled in the art it is evident that when Wl denotes -A-NR2R3, either -NR5R6 or -NR2R3 can be linked together with the bridge Y, whereby if -NR5R6 and -NR2R3 are not identical a mixture of compounds will be produced. For the man skilled in the art it is also evident that the number of linkages is determined by the relative amounts of reactants.

The linking of two compounds of formula II is conveniently carried out at an elevated temperature between 50 and 800C, preferably 60-700C, and in an alkaline medium, preferably at pH 8-10; water serves as the reaction medium, also when mixed with an organic solvent, e.g. dimethylformamide.

The compounds of formula I thus obtained may be isolated from the reaction mixture in known manner as presscakes, or after drying, in powder or granulate form. However, isolation may also be omitted, and the compound of formula I may then be used further without separating it from the reaction mixture.

The compounds of formula II used as starting material are new and therefore similarly form the subject matter of the invention. As copper-phthalocyanine compounds they are known e.g. from DE-PS 10 61 010 (US Patent 5,084,064), and the corresponding aluminium-phthalocyanin compounds may be obtained from known starting substances analogously to the production process described therein. Thus, the production of the new aluminium-phthalocyanine compounds of formula II is characterized in that 1 mol of an aluminium-phthalocyanine compound of formula m

wherein Hal are exchangeable halogen atoms, is condensed with p mols of a compound of formula IVa HN(R4)-A-NRsR6 (IVa) and n mols of a compound of formula IVb HN(R4)-Wl (IVb).

This condensation process is effected under the conditions described in DE-PS 10 61 010 (US Patent 5,084,064).

The aluminium-phthalocyanine sulfonic acid halogenides of formula m are produced by known methods such as heating of aluminium-phthalocyanine in halogen sulfonic acid to temperatures between 110 and 145 C. When heating for three hours at about 115"C a product containing 3 substituents per molecule is produced and when heating above 135"C a product containing 4 substituents per molecule is produced. The substituents are to a major part sulfohalogenide groups and to a lesser part sulfonic acid groups. By reacting with e.g. thionyl halogenide the sulfonic acid groups can be converted partially or wholly into the sulfohalogenide groups. The sulfohalogenides can be isolated by discharging into a water-ice mixture and subsequent filtration.

The compounds of formula I are generally present as water-soluble salts. The following anions may be considered for example as anions An, which are introduced by reacting protonatable N-atoms and/or quaternary ammonium groups with organic or inorganic acids: Chloride, bromide, iodide, sulphate, bisulphate, methyl sulphate, ethyl sulphate, amino sulphate, hydrogen sulphate, perchlorate, benzene sulphonate, oxalate, maleinate, acetate, methoxy acetate, formate, propionate, lactate, succinate, tartrate, malate, methane sulphonate; furthermore, the anions of acids such as boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid, or addition products of ortho-boric acid with polyalcohols such as cis-polyols.

The compounds of formula I in water-soluble salt form are dyestuffs and may be used for dyeing or printing hydroxy-group-containing or nitrogen-containing organic substrates.

They are thus suitable for dyeing or printing cationically dyeable materials, e.g. homo- or co-polymers of acrylonitrile, acid-modified polyamide or polyester fibres; leather, cotton, bast fibres, e.g. hemp, flax, sisal, jute, coir fibres and straw; regenerated cellulose fibres, glass fibres and paper.

The compounds of formula I are used for example for dyeing or printing fibres, filaments or textiles produced therefrom, which consist of or contain cellulose material, e.g. cotton, in accordance with known methods. Cotton is preferably dyed by a conventional exhaust process, for example from a long or short bath and at room temperature to boiling temperature. One preferred method for effecting printing employs impregnation with a printing paste that is prepared by a known method.

The compounds according to the invention may also be used for dyeing or printing leather, advantageously low-affinity types of leather, which have undergone vegetable re-tanning, in accordance with known methods.

However, the compounds of formula I are especially suited for dyeing or printing paper or paper products, e.g. for the production of sized or unsized, wood-free or wood-containing paper (so-called mechanical wood pulp) in pulp form, as well as on the size press. They may also be used for dyeing paper by the dipping process. Paper is dyed and printed in accordance with known methods.

The dyeings and prints obtained, and in particular the dyeings and prints on paper, have good fastness to use, which is not surpassed in quality by the equivalent heavy metavphthalocyanines.

The compounds of formula I may be used directly (in isolated powder form or as a solution) as dyestuffs, but may also be employed in the form of dye preparations. The processing into stable liquid, preferably aqueous, and also solid dye preparations may be carried out in a generally known manner. Suitable liquid preparations may be advantageously obtained by dissolving in suitable solvents such as mineral acids or organic acids, e.g. hydrochloric acid, sulphuric acid, phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, methanesulphonic acid and citric acid; or further solvents such as formamide, dimethylformamide, urea; glycols and ethers thereof, which are used in a mixture with water, optionally in the presence of an assistant, e.g. a stabilizer. Such preparations may be produced for example analogously to the processes known from French Patent Specification no. 1.572.030.

A preferred liquid preparation is for example as follows (parts are parts by weight): 100 parts of a compound of formula I, 1-100, preferably 1-10 parts of an inorganic salt, 1-100 parts of an organic acid, such as formic, acetic, lactic, citric, propionic, methoxyacetic acid, 100-800 parts of water, 0-500 parts of a dissolving assistant (e.g. glycols such as ethylene glycol, propylene glycol, di- or triethylene glycol, hexylene glycol; glycol ethers such as methyl cellosolve, methyl carbitol, butyl polyglycol; urea, formamide and dimethylformamide).

Similarly, the compounds of formula I may be processed in known manner into solid, preferably granulated dye preparations, advantageously by means of granulation, as described in French Patent Specification No. 1.581.900.

A preferred solid preparation is for example as follows (parts are by weight): 100 parts of a compound of formula I, 1-100, preferably 1-10 parts of an inorganic salt, 0-800 parts of a standardizing agent (preferably non-ionic, such as dextrin, sugar, grape sugar and urea).

The solid preparations may contain up to 10% residual moisture.

The compounds of formula I have good solubility properties, and are especially notable for their good solubility in cold water. As a result of their high substantivity, the dyestuffs are absorbed practically quantitatively, and thereby have good build-up. During the produciton of sized and unsized paper, the waste water is practically colourless or is only negligibly coloured. The dyestuffs may be added to the paper pulp directly, i.e. without previously dissolving them, as a dry powder or as granules, without incurring any reduction in brilliance or yield of colour.

However, the compounds of formula I are preferably used as a solution or as liquidaqueous dye preparations.

Compared with an unsized paper dyeing, the sized paper dyeing shows no reduction in depth of colour. Dyeing may also be effected using the present dyestuffs in soft water, with a full yield of colour. The dyestuffs do not mottle, especially when dyed on woodcontaining paper, they do not tend to produce two-sided effects on paper, and are substantially insensitive towards fillers and pH variations.

The dyed papers have a high level of fastness to bleeding, and have very good wet fastness properties, not only to water, but also to milk, fruit juices, sweetened mineral water, soap water, tonic water, sodium chloride solution, urine, perspiration, etc.; in addition, they have good alcohol fastness.

Paper that has been dyed with the compounds of formula I may be bleached both by oxidation and by reduction, which is important for the re-use of waste paper.

Fibrous materials containing mechanical wood pulp are dyed by the compounds according to the invention in a good and even quality.

The following examples serve to illustrate the invention. If not otherwise stated, all parts and percentages given in the examples are by weight; the temperatures are given in degrees celsius.

Example 1 10.5 parts of the dyestuff of formula 1

in 200 parts of dimethylformamide and 50 parts of water are reacted at 70" and at pH 8.5 with 1.12 parts (20% excess) of epichlorohydrin. The pH is maintained at 8.5 - 9 with 30% sodium hydroxide solution. After stirring for ca. one hour, the pH remains unchanged. The resultant condensation product is precipitated from the alkaline medium by adding water, and after filtration, is isolated as a moist presscake. The dyestuff of formula

is obtained. In its salt form it dyes paper in greenish-turquoise shades. The paper dyeings have especially outstanding wet fastness.

Example la Instead of the 10.5 parts of the chloro-aluminium-phthalocyanine compound of formula la, 10.4 parts of the corresponding hydroxy-aluminium-phthalocyanine compound may also be employed. In this way, a dyestuff having practically the same properties is obtained.

Example 2 Using the method described in example 1, if 2.1 parts (20% excess) of a,a'-dichloro-pxylene are used instead of epichlorohydrin, the corresponding phthalocyanine dyestuff is obtained with the bridge

It dyes paper in a bluish-turquoise shade, and the dyeings have perfect wet fastness.

Examples 3-20 / Table Further compounds of formula I may be obtained analogously to the method described in examples 1 and 2, using corresponding starting materials.

These compounds correspond to formula (A),

the individual variables of which are summarised in the following table.

The symbols used in this table under column 3 for the bridge Y have the following significances: Ya denotes Yb denotes

and Yc denotes -CH2CH2 The numerical values given for p, m and n are to be regarded as average values, which result from the correspondingly prepared mixtures of compounds of formula (A); for each dyestuff in the table, m has the value 0.5.

The non-chromophoric anion Ane is acetate, optionally in the presence of chloride.

The dyestuffs of examples 3-20 dye paper in bluish- to greenish-turquoise shades. The paper dyeings obtained have perfect wet fastness.

Table / Compounds of formula (A)

Ex. Y A R R4 R5 R6 p n No.

3 Ya -(CH2)3- -N(CH3)2 H CH3 CH3 1 2 4 Ya Ya do. do. CH3 do. do. 1 2 5 Ya -(CH2)2- -N(C2Hs)2 H C2H5 C2H5 1 2 6 Ya do. -N(CH3)2 H CH3 CH3 1.5 2 7 Yb -(CH2)3- do. CH3 do. do. 1.5 2 8 Yc do. do. H do. do. 1.5 2 9 Ya -(CH2)2- -N(C2Hs)2 CH3 C2H5 C2H5 1 2.5 10 Yb -(CH2)3- -N(CH3)2 H CH3 CH3 1 2.5 11 Ya do. -#N(CH3)3 H do. do. 1 2.5 12 Ya -(CH2)2- do. CH3 do. do. 1.5 2 13 Ya do. -#N(C2H5)2 H C2H5 C2H5 1.5 2 CH3 14 Ya -(CH2)3- -#N(CH3)3 CH3 CH3 CH3 1 2.5 15 Yb do. do. H. do. do. 1 2.5 16 Ya do. -N(CH3)2 H do. do. 1 2.5 17 Yc -(CH2)2- do. H do. do. 1 2.5 18 Ya do. -N(C2Hs)2 H C2H5 C2H5 1 2.5 19 Ya -(CH2)3- -N(CH3)2 H CH3 CH3 1 2.5 20 Yc do. -#N(CH3)3 H do. do. 1 2.5 Also, in examples 2 to 20, instead of the chloro-aluminium-phthalocyanine, the corresponding hydroxy-aluminium-phthalocyanines may be used.

The possibilities of use of the described dyestuffs are illustrated in the following application examples.

Application Example A 70 parts of chemically bleached sulphite cellulose of pinewood and 30 parts of chemically bleached sulphite cellulose of birchwood are ground in a Holllinder beater in 2000 parts of water. 0.1 parts of the dyestuff of example 1 are added to this mass. After mixing for 20 minutes, paper is produced therefrom. The absorbent paper obtained in this way is dyed bluish-turquoise. The waste water is colourless.

Application Example B 0.2 parts of the dyestuff of example 1 are added to 100 parts of chemically bleached sulphite cellulose, which have been ground in a Holliinder beater with 2000 parts of water.

After thorough mixing for 15 minutes, sizing is carried out in the usual way with rosin size and aluminium sulphate. Paper which is produced from this material is dyed bluishturquoise and has perfect wet fastness; the waste water is colourless.

Application Example C An absorbent length of unsized paper is drawn through a dyestuff solution of the following composition at 40-50 : 0.2 parts of the dyestuff of example 1 0.5 parts of starch and 99.3 parts of water.

The excess dye liquor is squeezed out through two rollers. The dried length of paper is dyed turquoise and has a high level of wet fastness.

Dyeing may also take place in a similar manner to that of examples A to C using the dyestuffs of examples 2-20. The bluish- to greenish-turquoise dyed paper dyeings obtained show good fastness properties.

Application Example D 1.0 part of the dyestuff of example 1 is dissolved in 4000 parts of demineralised water at 400. 100 parts of pre-moistened cotton fabric are placed in the bath and heated in 30 minutes to boiling temperature. The bath is maintained at boiling temperature for one hour, whereby the water which evaporates is replaced from time to time. The dyed fabric is then removed from the liquor, rinsed with water and dried. The dyestuff is absorbed practically quantitatively onto the fibres; the dye bath is colourless. A turquoise-coloured dyeing with good fastness is obtained.

The dyestuffs of examples 2-20 may be used analogously for dyeing cotton.

Application Example E 100 parts of freshly tanned and neutralised chrome grain leather are drummed for 30 minutes in a vat containing a dye liquor of 250 parts of water of 55" and 0.5 parts of the dyestuff of example 1, and then treated for a further 30 minutes in the same bath with 2 parts of an anionic fat liquor based on sulphonated train oil. The leathers are dried and finished in the usual way. An evenly dyed leather in a turquoise shade is obtained.

Leather may be dyed in analogous manner using the dyestuffs of examples 2-20.

Further low-affinity, vegetable-tanned leathers may similarly be dyed by known methods.

Application Example F A dry pulp consisting of 60% mechanical wood pulp and 40% unbleached sulphite cellulose is beaten in a Holländer beater with sufficient water and up to a grinding degree of 40"SR (Schopper-Riegler degrees) for the dry content to be at a little above 2.5%; the mixture is subsequently adjusted with water to exactly 2.5% dry content of thick pulp.

200 parts of this thick pulp are mixed with 5 parts of a 0.25% acetic-acid-containing solution of the dyestuff of example 1, and stirred for ca. 5 minutes. After adding 2% rosin size and 4% alum (based on dry substance), stirring is again effected for a few minutes until a homogeneous mixture is obtained. The mass is diluted with ca. 500 parts of water to 700 parts by volume, and paper sheets are formed therefrom in known manner, by drawing it through a sheet former. The paper sheets have an intense turquoise shade.

Application Example G 15 parts of waste paper (containing wood), 25 parts of bleached mechanical wood pulp and 10 parts of unbleached sulphate cellulose are defibrated in a pulper to form a 3% aqueous pulp slurry. This stock suspension is diluted to 2% in a dyeing chest. To this diluted suspension are then added in succession, whilst stirring, 5% (based on total dry fibres) of kaolin and 0.6 parts of a 5% acetic-acid-containing solution of the dyestuff of example 1. After 20 minutes, the pulp is mixed in a mixing chest with 1% (based on total dry weight of the fibres) of a rosin size dispersion. The homogeneous pulp slurry is adjusted to pH 5 with alum in the paper machine shortly before starting up.

A 80git2 mill-finished bag paper of turquoise colour is produced on the paper machine.

The resulting dyed paper exhibits very good fastness properties to bleeding according to DIN 53 991..

The paper obtained may be practically completely bleached with hypochlorite.

Any one of the dyestuffs of examples 2 to 20 may be used in place of that of example 1 in any one of application examples F and G. In all cases, the waste water exhibits a substantially low residual dyestuff concentration.

Claims

Patent Claims

1. The cationic aluminium-phthalocyanine dyestuffs of formula I,

wherein each Ra independently is chlorine or hydroxyl, each W1 independently is -A- sNR,R2R3 Ane or -A-NR2R3, R, independently is hydrogen, unsubstituted C,4alkyl; C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl; or Cs 6cycloalkyl, each R2 and R3 independently is unsubstituted C1-4alkyl or C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl, or C5.6cycloalkyl, and each Ane is a non-chromophoric anion; each R4 independently is hydrogen or unsubstituted C14alkyl, or C1-4alkyl which is monosubstituted by hydroxy, each A independently is -C2.6alkylene-, or -C3.6alkylene which is monosubstituted by hydroxy, Y is a divalent bridge member, which is bonded on both ends via an aliphatic carbon atom, and each R5 and R6 independently is unsubstituted C.4alkyl; or C1-4alkyl which is monosubstituted by halogen, cyano, hydroxy or phenyl; or C5-6cycloalkyl, each AlPc is the aluminium-phthalocyanine radical, the two m independently signify 0 or 1, the two n independently signify 1, 2 or 3, and p signifies 1 or 2, and mixtures of compounds of formula I, in which compounds each SO3H group is in free acid or in salt form, with the proviso that in a compound or mixture of compounds of formula I: (i) 1 # p # 2 and (ii) m + n + p < 4.

2. Compounds according to claim 1, wherein each R4 denotes R4a and each R4a independently signifies hydrogen, methyl, ethyl or 2-hydroxyethyl.

3. Compounds according to claim 1 or 2, wherein each A denotes A1 and each A1 independently signifies -C24alkylene- or monohydroxy-substituted -C34alkylene-.

4. Compounds according to one of claims 1 to 3, wherein each W1 denotes Wia and each Wia independently signifies -A1-#NR1aR2aR3a Ane or -A-NR2aR3a, in which A, is defined as in claim 3, Ria denotes hydrogen, methyl, ethyl; C2-3alkyl which is monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl, each R2a and R3a independently is methyl, ethyl; C23alkyl which is monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl, and An is a non-chromophoric anion.

5. Compounds according to one of claims 1 to 4, wherein Y denotes Y1 and Y1 signifies -C2.6alkylene-, monohydroxy- or dihydroxy-substituted -C3 8alkylene-, a -C2 6alkylene chain which is interrupted by -O-, -NR7- or

or a monohydroxyor dihydroxy-substituted -C3.8alkylene chain which is interrupted by -O-, -NR7- or

wherein R7 is hydrogen or C, 6alkyl and R8 is hydrogen, halogen, C1-4alkyl or C1-4alkoxy.

6. Compounds according to one of claims 1 to 5, wherein each R5 and R6 is R5a and R6a, and each R5a and R6a independently signifies methyl, ethyl; C2.3alkyl which is monosubstituted by chlorine, cyano or hydroxy; benzyl or cyclohexyl.

7. Compounds according to claim 1, which correspond to formula Ia,

or a mixture of compounds of formula Ia, in which each SO3H group is present in free acid or in salt form, AlPc, An m, n and p are defined as in claim 1, each R4b independently is hydrogen or methyl, and each Wib independently is -A2-#NR1bR2bR3b Ane or -A2-NR2bR3b, wherein A2 signifies -C24alkylene-, Rib independently signifies hydrogen, methyl, ethyl, monohydroxy-substituted C2.3alkyl, benzyl or cyclohexyl, each R2b and R3b independently signifies methyl, ethyl, monohydroxy-substituted C2 3alkyl, benzyl or cyclohexyl, and Y2 denotes -C2-4alkylene-, monohydroxy-substituted-C3-4alkylene- or -T1-X-T2-, wherein each T, and T2 independently signifies -C, 3alkylene- or monohydroxy substituted-C3-4alkylene, and X signifies -NR7a- or

in which R7a denotes hydrogen or C1alkyl and Rga denotes hydrogen, chlorine, methyl or methoxy, and each R5b and R6b independently is methyl, ethyl, monohydroxy-substituted C2.3alkyl, benzyl or cyclohexyl.

8. Compounds according to claim 7, wherein each Wib denotes Wic and each Wic independently signifies -A3-#NR1cR2cR3c Ane or -A3-NR2cR3c, in which A3 denotes -(CH2)q-, wherein q' signifies 2 or 3, Ric denotes hydrogen, methyl or ethyl, each R, and R3c independently is methyl or ethyl, and Ane is a non-chromophoric anion.

9. Compounds according to claim 7 or 8, wherein each A2 denotes A3 and each A3 independently is -(CH2)q'-, wherein q' is 2 or 3.

10. Compounds according to one of claims 7 to 9, wherein each R4b denotes hydrogen.

11. Compounds according to one of claims 7 to 10, wherein Y2 denotes Y3 and each Y3 denotes -C2-3alkylene-, monohydroxy-substituted -C34alkylene- or

12. Compounds according to one of claims 7 to 11, wherein each R5b and R6b denotes R5C and R6c and each R5c and R, independently is methyl or ethyl.

13. Process for the production of compounds of formula I according to claim 1, characterized in that two compounds of formula II,

wherein Al(Ra)Pc, A, Wl, R4, R5, R6, m, n and p are defined as in claim 1, which may be the same or different, are linked together by introducing the bridge Y, whereby the -NR5R6 group of each compound of formula II is quaternized.

14. Liquid-aqueous dye preparation which is stable in storage and contains a compound of formula I according to claim 1, or a mixture thereof, in water-soluble salt form.

15. Process for dyeing or printing hydroxy-group-containing or nitrogencontaining organic substrates, characterized in that dyeing or printing is effected using a compound of formula I according to claim 1, or a mixture thereof, or a preparation according to claim 14.

16. Process according to claim 15, for dyeing or printing leather or fibrous matter which consists of or contains natural or regenerated cellulose.

17. Process according to claim 16, for dyeing or printing paper or paper products, bast fibres, or textile material which consists of or contains cotton.

18. The compounds of formula II

wherein Al(Ra)Pc, A, Wl, R4, Rs, R6, m, n and p are defined as in claim 1.

19. Process for the production of compounds of formula II, according to claim 18, characterized in that 1 mol of an aluminium-phthalocyanine compound of formula m

wherein Hal are exchangeable halogen atoms, and R, m, n and p correspond to the significances given in claim 1, is condensed with p mols of a compound of formula IVa HN(R4)-A-NR5R6 (IVa) and n mols of a compound of formula IVb HN(R4)-W1 (IVb), wherein R4, R R6 and W1 correspond to the significances given in claim 1.